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  • 1980-1984
  • 1975-1979  (1,397)
  • 1976  (1,397)
  • Inorganic Chemistry  (739)
  • Physics  (492)
  • Engineering  (143)
  • Nuclear reactions
  • pharmacokinetics
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Material
Years
  • 1980-1984
  • 1975-1979  (1,397)
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Comparison of the half-life of antipyrine in plasma, whole blood and saliva of man (1976)
    Springer
    European journal of clinical pharmacology 9 (1976), S. 327-332 
    Details
    ISSN: 1432-1041
    Keywords: Antipyrine ; pharmacokinetics ; half-life ; blood ; plasma ; saliva ; individual variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A previously described GLC method has been modified and applied to measurement of antipyrine levels in plasma, blood and saliva of man following administration of a single oral dose (10 mg/kg). The levels in blood and saliva were comparable to those in plasma at every time studied. The half life of antipyrine determined in blood, plasma or saliva in any given individual was similar. The intersubject variation in half-life was about two-fold (n=5). Antipyrine levels in saliva were not affected by the rate of saliva flow when collections were made continuously for 20 minutes. This study has demonstrated that kinetic data about antipyrine comparable to that from plasma may also be obtained from readily accessible tissue fluids, such as saliva and capillary blood.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561668
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  • 2
    Electronic Resource
    Electronic Resource
    Interindividual differences in chlorthalidone concentration in plasma and red cells of man after single and multiple doses (1976)
    Springer
    European journal of clinical pharmacology 9 (1976), S. 319-325 
    Details
    ISSN: 1432-1041
    Keywords: Chlorthalidone ; diuretics ; drug plasma concentration ; protein binding ; red blood-cell concentration ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A gas chromatographic method has been employed to determine chlorthalidone in plasma and whole blood after therapeutic doses. Radioactively labelled chlorthalidone was used for in vitro studies of the uptake of chlorthalidone from plasma by red blood cells. Chlorthalidone was markedly concentrated in red cells and as a compartment they would account for at least 30% of total drug in the body after multiple doses. The ratio between the plasma and red cell concentration of chlorthalidone varied between individuals. After a single oral dose of 50 mg in 6 healthy volunteers chlorthalidone was eliminated with a half-life of 51 to 89 hours. The apparent volume of distribution varied between 3 and 13 1/kg and the clearance between 53 and 145 ml/min. The mean steady-state plasma concentrations during treatment with a standard dose of 50 mg daily (n=10) varied 5-fold between individuals. During the steady state approximately 50% of the daily dose was excreted unchanged in the urine during 24 hrs. The plasma levels observed in patients were higher than those predicted from the single oral dose studies in healthy volunteers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561667
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  • 3
    Electronic Resource
    Electronic Resource
    Observations on the efficacy and pharmacokinetics of sotalol after oral administration (1976)
    Springer
    European journal of clinical pharmacology 9 (1976), S. 367-372 
    Details
    ISSN: 1432-1041
    Keywords: Sotalol ; β-adrenoceptor blocking drugs ; exercise tachycardia ; efficacy ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effects of sotalol after oral administration were measured on the tachycardia induced by strenuous exercise in normal subjects. Plasma sotalol levels were also determined. The oral administration of sotalol (50, 100, 200 and 400 mg) to 6 subjects produced a progressive reduction in the tachycardia induced by severe exercise. This was similar to the effects of 25, 50, 100, 200, 400 and 800 mg given to different subjects. Each increase in sotalol dose produced a successively greater reduction in exercise tachycardia. This did not appear to be maximum even with 800 mg. Oral sotalol was rapidly absorbed and produced peak blood levels in 2 – 3 hours. The plasma levels of sotalol measured 2 hours after the oral administration of 25 to 800 mg showed never more than a six-fold variation between different subjects. The half-life of sotalol in plasma was 12.7 ± SE 1.6 hours. There was a significant correlation between the logarithm of the plasma sotalol concentration and the percentage reduction of exercise heart rate. It is concluded that the oral administration of sotalol either once or twice daily (depending on dose level) will provide satisfactory 24-hour blockade of β-adrenoceptors.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00606550
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  • 4
    Electronic Resource
    Electronic Resource
    Pharmacokinetics and relative bioavailability of cyclobarbital calcium in man after oral administration (1976)
    Springer
    European journal of clinical pharmacology 9 (1976), S. 443-450 
    Details
    ISSN: 1432-1041
    Keywords: Cyclobarbital calcium ; pharmacokinetics ; plasma concentration ; relative bioavailability ; oral administration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics and relative bioavailability of cyclobarbital calcium have been studied after oral administration of Phanodorm, of tablets according to the Formularium Nederlandse Apothekers (1968; FNA), and an aqueous solution. Six healthy volunteers participated in the investigation on three occasions and each received the three preparations. The dose administered was 300 mg cyclobarbital calcium. Plasma concentrations of cyclobarbital were determined at regular intervals. Absorption from the three preparations was rapid and was faster from the solution. Peak concentrations were usually attained within 1 h. The elimination of cyclobarbital could be described by a single first-order process with an average half-life of 11.6 h (range 8 – 17 h). There was little intra-subject variation of the half-life. Relative bioavailability for each volunteer was estimated by comparing the areas under the plasma concentration curves. The FNA-tablets and Phanodorm exhibited similar bioavailability, whereas the average bioavailability of the solution was 78% of that of FNA-tablets; the reason for this unexpected finding is unknown. It was concluded that cyclobarbital cannot be regarded as a uniformly suitable drug for the treatment of insomnia. The long half-life that was apparent in some of the volunteers (15 – 17 h) creates a substantial risk of residual effects on the following morning. In principle, however, the calcium salt of cyclobarbital may be used for induction of sleep, because of its rapid absorption.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00606563
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  • 5
    Electronic Resource
    Electronic Resource
    Clinical pharmacokinetics of sisomicin: Two-compartment model analysis of serum data after I.V. and I.M. administration (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 251-256 
    Details
    ISSN: 1432-1041
    Keywords: Sisomicin ; pharmacokinetics ; bioavailability ; two-compartment analysis ; man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of sisomicin, a new single component aminoglycoside antibiotic related to gentamicin c1a, were determined in four healthy volunteers after intravenous and intramuscular administration of a 1 mg/kg dose. The elimination profile of this antibiotic follows two-compartment model kinetics after I.V. administration. The fast (α) and slow (β) disposition rate constants averaged 0.072 and 0.004 min−1, respectively. The volume of distribution at the steady-state averaged 0.185 liters/kg which approximately corresponds to the volume of extracellular space. The physiological availability of an intramuscular dose appeared to be complete. A method of administration adapted to the kinetic properties of the drug is proposed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558337
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  • 6
    Electronic Resource
    Electronic Resource
    Studies on hydralazine (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 311-317 
    Details
    ISSN: 1432-1041
    Keywords: Hydralazine ; instability of impaired renal function ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Following a single 50 mg dose of hydralazine (Apresoline®) in 13 patients with impaired renal function, a decrease in glomerular filtration rate (GFR) was correlated with an increase in serum half-life (T1/2) of the drug (r=−0.69; p〈0.01). The T1/2 was 15.8 h in one patient with a GFR of 16 ml·min−1, as compared to a T1/2 of 1.7–3.0 h found previously in 16 healthy volunteers. In 49 patients on long-term antihypertensive treatment with hydralazine, the ratio between the minimum steady-state drug concentration and the daily dose of hydralazine (C SS min : Dose) increased as the GFR decreased. This accumulation of the drug was particularly evident in patients with a GFR less than 30 ml·min−1 (r=−0.63; p〈0.01; n=19). As renal excretion of unchanged hydralazine is generally regarded as unimportant, the slower elimination rate in chronic renal failure was probably caused by a slower rate of metabolic conversion. It was found, however, that the renal excretion of hydralazine could easily have been underestimated, as only 12.7% of an initial hydralazine concentration of 200 ng·ml−1 in urine could be recovered after storage of the samples at room temperature for 24 h.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00565619
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  • 7
    Electronic Resource
    Electronic Resource
    Influence of sex on the clinical pharmacology of flutiorex, a new anorectic drug (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 325-330 
    Details
    ISSN: 1432-1041
    Keywords: Flutiorex ; pharmacokinetics ; sex ; anorectic agent ; sympathetic stimulation ; CNS stimulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effects of flutiorex, a new anorectic agent, and of a placebo on food intake and the activity of the sympathetic and central nervous systems have been compared in a double blind trial in two groups of healthy volunteers, one of five males and the other of five females. Flutiorex 20 mg orally had a significant anorectic effect both in males and females, the observed reduction in food intake being 34.0 and 27.5%, respectively. It caused α-adrenergic stimulation (blood pressure and pupil diameter) and central nervous system excitation (critical flicker frequency), both of which were more marked in males than in females. Flutiorex was better tolerated by women than by men. Measurement of the blood level of flutiorex and its de-ethylated metabolite, norflutiorex, showed that both compounds were detectable in four of the five male subjects, but in only one of the five females. Sex-linked differences in the pharmacokinetics of flutiorex may explain the greater intensity of its effects in males.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00565621
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  • 8
    Electronic Resource
    Electronic Resource
    Serum concentrations of methaqualone after repeated oral doses of a combination formulation to human subjects (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 343-347 
    Details
    ISSN: 1432-1041
    Keywords: Methaqualone ; hypnotic ; pharmacokinetics ; combination formulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Concentrations of methaqualone have been measured in the serum of five male human subjects receiving five consecutive evening doses of a combination formulation containing methaqualone (250 mg), carbromal (300 mg) and benactyzine (0.33 mg) in each tablet. After administration of the first dose, mean peak serum concentrations of methaqualone (1.2 µg/ml) occurred at 3 h. After obtaining peak levels, mean concentrations of methaqualone declined rapidly during the next 6 h and there-after more slowly during the next 18 h. After administration of the last (fifth) dose, mean peak serum concentrations of methaqualone (1.9 µg/ml; 1.5 µg/ml above the predose level) occurred at 2 h. After attaining peak levels, mean concentrations of methaqualone declined rapidly during the next 6 h, and thereafter more slowly, with a half-life of approximately 10 h. Mean concentrations of methaqualone in serum samples 24 h after the second, third, fourth or fifth doses were not significantly different (0.3 µg/ml – 0.6 µg/ml) during this period of dosing. This suggests that significant accumulation of methaqualone in the serum did not occur during a period of five consecutive evening doses of the combination formulation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00565624
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  • 9
    Electronic Resource
    Electronic Resource
    Pharmacokinetics and bioavailability of indoprofen in man (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 257-262 
    Details
    ISSN: 1432-1041
    Keywords: Anti-inflammatory and analgesic drug ; indoprofen ; pharmacokinetics ; bioavailability ; man
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In a pharmacokinetic study of the new analgesic and anti-inflammatory drug indoprofen, plasma levels and urinary excretion were determined in four healthy volunteers after 100 mg and 200 mg iv, and after 100 mg (capsules) and 200 mg (tablets) oral doses. After iv administration, the mean biological half-life (t1/2 β) was about 2 h (range 1.4 to 3.2 h). The apparent volume of distribution Vdβ ranged between 11 to 17 % of body weight, indicating its limited extravascular distribution. Most of the drug was excreted in urine as glucuronide and a smaller proportion as unchanged indoprofen: the 24 h urinary excretion of these compounds accounted for 67 to 95 % of an iv dose. Peak plasma levels occurred between 30 and 120 minutes after oral administration of 100 mg as capsules or 200 mg as tablets. The mean biological half-life was about 2 h, as after iv administration. The bioavailability of oral doses was assessed using both plasma levels and urinary excretion data. The absorption of capsules and tablets was practically complete, that of the former being faster.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558338
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  • 10
    Electronic Resource
    Electronic Resource
    Effect of exchange transfusion on the elimination of digoxin in neonates (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 25-29 
    Details
    ISSN: 1432-1041
    Keywords: Digoxin ; exchange transfusion ; pharmacokinetics ; neonates ; 86Rb assay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary By means of an86Rb-uptake inhibition assay, changes in the plasma concentration of digoxin and the amount of the glycoside removed during exchange transfusion have been studied in two newborns. For comparison, the exchange procedure was simulated by a computer on the basis of a two-compartment open model and available pharmacokinetic constants. A rapid decrease in plasma digoxin concentration during exchange transfusion was found when the glycoside was administered intravenously or intramuscularly within 60 min before the procedure. The amount of digoxin removed by the exchange was less than 6 per cent of the given dose. Computer simulation of the procedure also showed removal of only a minor amount of digoxin. It is concluded that the decrease in plasma concentration and the removal of only a small amount of glycoside by the exchange transfusion can be attributed mainly to extensive tissue distribution of digoxin. The results imply that replacement of digoxin after an exchange transfusion seems unnecessary.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561545
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  • 11
    Electronic Resource
    Electronic Resource
    Comparison of the pharmacokinetics of diazepam after single and subchronic doses (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 121-126 
    Details
    ISSN: 1432-1041
    Keywords: Diazepam ; pharmacokinetics ; subchronic dosage in man ; desmethyldiazepam
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In seven healthy male volunteers the effects of the pattern of dosing on the pharmacokinetics of diazepam have been studied. A cross-over design was employed that consisted of three parts: a single intravenous dose (0.1 mg/kg), and oral dosing (10 mg/day) for six days followed by an intravenous bolus (0.1 mg/kg) on the seventh day, followed by re-examination of a single intravenous dose after diazepam (D) and its major metabolite desmethyldiazepam (DD) had been completely eliminated. Plasma levels of D and DD were monitored by a specific, sensitive GLC-method. In younger patients (n=5, age 29 – 35 years) the elimination half-life, T1/2 (β), of D was 33.9±10.6 h (mean±S.D.) after the single dose. The control study gave an almost identical result (35.7±12.1). After subchronic dosage in all patients T1/2 (β) showed a modest but significant prolongation (paired t-test p〈0.01) to 52.9±17.4 h. It was caused by a significant decrease (p=0.016) in total plasma clearance ( $$\overline {\user1{Cl}} $$ ), from 26.0±10.8 ml/min to 18.2±7.0 ml/min. Older patients (age 43–60 years) showed the same phenomenon. Blood/plasma ratios remained constant indicating no change in protein binding. Biliary excretion of D was measured in five patients with a T-tube. Only negligible amounts (0.3–0.4%) of administered D were excreted within 3 days after subchronic dosage, which demonstrates a lack of enterohepatic cycling of D. After multiple administration of D, there was accumulation of DD to levels approximately five times higher than after a single dose. The possibility that the slower elimination of D after subchronic treatment might be caused by DD was also supported by experiments in dogs and rabbits. After pretreating rabbits with DD and maintaining a high DD plasma level, there was prolongation of T1/2 (β) from 2.7 h to 5.2 h, with a corresponding decrease of $$\overline {\user1{Cl}} $$ from 101.6 ml/min to 23.4 ml/min. Similar results were obtained in dogs. It is concluded that the disposition of D is altered by subchronic use and may be regulated by the plasma DD concentration.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00609470
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  • 12
    Electronic Resource
    Electronic Resource
    Studies on hydralazine (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 183-187 
    Details
    ISSN: 1432-1041
    Keywords: Hydralazine ; bioavailability ; pharmacogenetics ; first pass effect ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary After oral administration of a single 50 mg dose of hydralazine (Apresoline®), the serum half-life (T1/2) and bioavailability (AUC0−∞) were assessed in 16 healthy volunteers. The half-life was 2.57±0.14 h (S.E.) in 10 slow acetylators of sulphadimidine, and 2.18±0.15 h in 6 fast acetylators (difference not statistically significant). AUC0−∞ was significantly higher in slow acetylators, at 1.04±0.10 µg·hour·ml−1, compared to 0.66±0.12 µg·hour·ml−1 in the fast acetylators (p〈0.025). Treatment with Apresoline® 25 mg tid produced minimum serum concentrations at steady-state of 57.3±7.3 ng·ml−1 and 33.4±4.2 ng·ml−1 in 8 slow and 5 fast acetylators, respectively (p〈0.05). The corresponding maximum concentrations were 228.8±20.3 ng·ml−1 and 147.6±15.0 ng·ml−1 in slow and fast acetylators, respectively (p〈0.025). First-pass metabolism of hydralazine could explain the difference in bioavailability of the drug between fast and slow acetylators, without any corresponding difference in the elimination rate of the drug in the post-distributive phase.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558327
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  • 13
    Electronic Resource
    Electronic Resource
    Pharmacokinetics of amitriptyline infused intravenously in man (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 337-341 
    Details
    ISSN: 1432-1041
    Keywords: Amitriptyline ; pharmacokinetics ; intravenous infusion ; two compartment model ; biological half-life
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Amitriptyline was given to four male volunteers by constant rate intravenous infusion. Blood samples were collected before, during and at various times after the infusion for estimation of the serum concentrations of amitriptyline. The level of nortriptyline never reached a detectable level. A two compartment open model was shown to be applicable to the data obtained. The meaning of the parameters obtained by a non-linear, least squares curve fitting procedure is discussed and the values are compared to those recently published for nortriptyline. The calculated biological half-life of amitriptyline was about 17 hours, a figure which differs considerably from previously calculated values for volunteers, but is in accordance with some newer results from patients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00565623
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  • 14
    Electronic Resource
    Electronic Resource
    Bioavailability of various preparations and doses of penicillin V (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 55-58 
    Details
    ISSN: 1432-1041
    Keywords: Penicillin V ; bioavailability ; pharmacokinetics ; dose ranging
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary An absorption study was performed in ten healthy volunteers to test the bioavailability of various doses of two penicillin V-K preparations: Isocillin® (Hoechst AG, Federal Republic of Germany), — tablets of 600 000 and 1.2 Mega U; V-Cillin® (Eli Lilly, USA), — tablets of 200 000, 400 000 and 800 000 U. The serum concentrations and elimination of the active substance in urine were measured for six hours after administration. Independently of the source of the preparation, a strict linear relation between the dose and the area under the serum curve (AUC), or between the dose and the urinary elimination, was demonstrated by regression analysis. The dose-dependent increase in the AUC was highly significant (p〈0.01) in the range tested, i.e. between 200 000 and 1.2 Mega U. The relative elimination of active substance in urine lay within narrow limits for all doses (35.7–41.3%). Thus, both compounds proved to have the same bioavailability.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561550
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  • 15
    Electronic Resource
    Electronic Resource
    Ampicillin: Comparison of bioavailability and pharmacokinetics after oral and intravenous administration of three brands (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 237-243 
    Details
    ISSN: 1432-1041
    Keywords: Ampicillin ; bioavailability ; pharmacokinetics ; branded products ; proprietary preparations ; capsule formulation ; tablet formulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics and bioavailability of three different brands of ampicillin were studied in 10 volunteers. After intravenous administration ampicillin can be described adequately by a two-compartment open pharmacokinetic model. The half-life during the α-phase was 9 min and the β-half-life was in the range 50–60 min, independent of the mode of administration. Absolute bioavailability was determined from the ratio of the areas under the serum concentration curves obtained after oral and intravenous administration of equal doses. Bioavailability was also estimated by analysis of variance. The results indicated absolute availability of the three products of 39–54%. One of the products, a capsule formulation, showed a significantly lower bioavailability than the others, which were tablet formulations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558335
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  • 16
    Electronic Resource
    Electronic Resource
    Pharmacokinetics of butobarbital after single and multiple oral doses in man (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 263-271 
    Details
    ISSN: 1432-1041
    Keywords: Butobarbital ; pharmacokinetics ; plasma concentration ; oral administration ; accumulation ; enzyme induction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A method is described for the assay of therapeutic levels of butobarbital (5-ethyl-5-n-butylbarbituric acid) in human plasma, which involves a single extraction step followed by gas chromatography with alkali flame ionization detection. The pharmacokinetics of butobarbital were studied in five healthy volunteers after oral administration of 200 mg. Plasma concentrations were determined at regular intervals up to 96 h and the data were fitted by non-linear, least squares regression analysis according to one-compartment kinetics. The average lag time was 0.11 h and the absorption half-life 0.21 h. The elimination half-life varied from 33.6 to 41.5 h with an average of 37.5 h. Four of the volunteers participated in a study of multiple dosing (every 24 h) during which substantial accumulation of butobarbital was observed. The elimination half-life after termination of drug administration had decreased to about 20–25% of its initial value, probably because of enzyme induction. It was concluded that butobarbital could not be regarded as a suitable drug for treatment of insomnia, since CNS depressant effects were likely to persist into the following day. Repeated administration of butobarbital should be avoided and its incidental use restricted to patients who require day-time sedation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558339
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  • 17
    Electronic Resource
    Electronic Resource
    A GLC assay for bendroflumethiazide. Preliminary data about its plasma level in man (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 293-295 
    Details
    ISSN: 1432-1041
    Keywords: Bendroflumethiazide ; diuretics ; GLC ; thiazides ; plasma level ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary A GLC method for determination of bendroflumethiazide has been developed, using extractive methylation. Cyclopenthiazide was used as internal standard. The maximal plasma concentration (56–107 ng/ml) after bendroflumethiazide 10 mg given orally to four healthy volunteers was seen at 2–2.5 h. On the slope between 4 and 10 h T1/2 averaged 2.7 h.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00558343
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  • 18
    Electronic Resource
    Electronic Resource
    The influence of hypoglycaemic sulphonylureas on elimination and efficacy of phenprocoumon following a single oral dose in diabetic patients (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 31-36 
    Details
    ISSN: 1432-1041
    Keywords: Diabetes mellitus ; drug interaction ; phenprocoumon ; pharmacokinetics ; pharmacodynamics ; sulphonylureas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The influence of various antidiabetic treatments on the kinetics and efficacy of a single oral dose of 12 mg phenprocoumon were studied in 71 hospitalized patients, 58 with adult-onset diabetes mellitus and 13 non-diabetic aged patients, and 13 healthy young volunteers. Treatment for one week or longer with insulin or the antidiabetic sulphonylureas tolbutamide, glibenclamide or glibornuride, altered neither the plasma level (1.29 – 1.40 µg/ml at zero time) nor the half-life of phenprocoumon (5.2 – 6.8 d) compared to treatment by diet alone. The mean half-life of phenprocoumon was significantly shorter in non-diabetic aged patients (4.2 d) than in diabetic patients of the same age (5.1 – 6.8 d), or in young healthy volunteers (5.7 d). The efficacy of a single dose of phenprocoumon (maximal reduction of Quick-values by 34 – 47% after 48 to 72 hrs) in diabetic patients treated with diet, or diet and antidiabetic drugs, was the same as in non-diabetic aged patients. In healthy young volunteers phenprocoumon was half as effective as in aged patients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561546
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  • 19
    Electronic Resource
    Electronic Resource
    Postoperative disappearance of phenazone from plasma in man (1976)
    Springer
    European journal of clinical pharmacology 10 (1976), S. 63-68 
    Details
    ISSN: 1432-1041
    Keywords: Phenazone ; pharmacokinetics ; injuries ; surgery ; operation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The elimination rate of phenazone after a single oral dose has been studied before and after elective operations. In a group of patients with different illnesses the elimination rate was increased on the fourth to seventh days after operation but was unchanged on the second and third days. The change in elimination rate was highly significant in a standardized group of nine patients with a ligament injury in one knee studied on the fourth or fifth postoperative day. Possible reasons for the changes are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00561552
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    Pharmacokinetics of the antiarrhythmic disopyramide in healthy humans (1976)
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 199-230 
    Details
    ISSN: 1573-8744
    Keywords: disopyramide ; antiarrhythmic ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pharmacokinetics of the antiarrhythmic disopyramide, 4-diisopropylamino-2-phenyl-2-(2-pyridyl)butyramide phosphate, and its monodealkylated metabolite were investigated in seven volunteers after intravenous (1 and 2 mg/kg) and oral (3 and 6 mg/kg) administration. Unchanged drug (52%) and the monodealkylated metabolite (25%) were renally excreted on intravenous administration. The pharmacokinetics of disopyramide were first order and dose independent only when referenced to the drug not bound to plasma proteins since this binding was dose dependent. The apparent half-lives of the α and β phases on intravenous administration were 2 min and 4.5 hr, respectively. The apparent volumes of distribution of the central and peripheral compartments, referenced to unbound disopyramide in the plasma, were 9 and 80 liters, respectively. The half-life of absorption of oral aqueous disopyramide phosphate was 30 min with a lag time of 16 min and an apparent first-pass metabolism of 16% of the absorbed dose, consistent with the hepatic efficiency of 14%. The renal and metabolic clearances were 125 and 111 ml/min, respectively. Graphical and computer analysis of the plasma and urine data showed dose-independent first-order pharmacokinetics of plasma unbound drug in a two-compartment-body model to give two metabolites and a first-pass transformation of a fraction of the oral dose. The absorption efficiency of unchanged drug was 83%.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01063614
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  • 21
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    Theoretical and computational basis for drug bioavailability determinations using pharmacological data. I. General considerations and procedures (1976)
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 337-353 
    Details
    ISSN: 1573-8744
    Keywords: bioavailability ; pharmacological data ; pharmacokinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The use of data deriving from monitoring the time variation of the intensity of pharmacological effect(s) following dosing can often present an advantageous alternative to the more conventional approach of using chemical or radiological assay of blood and/or urine level data for bioavailability evaluations of drug products: bioavailability studies can be performed with drugs where no assay exists. A relatively simplified discussion of the general theoretical principles on which the use of pharmacological data is based and a stepwise description of the approach for its routine application in bioavailability studies are presented. Approaches for computing rates and extents of drug bioavailability vs. time profiles on analog and digital computers are qualitatively described and quantitatively presented in a subsequent report. The concept of preabsorption (gastrointestinal bioavailability) is introduced and biophasic availability of drugs to local sites of action is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01063123
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  • 22
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    Theoretical and computational basis for drug bioavailability determinations using pharmacological data. II. Drug input ⇄ response relationships (1976)
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 355-375 
    Details
    ISSN: 1573-8744
    Keywords: deconvolution ; bioavailability ; pharmacokinetics ; modeling ; pharmacological data
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Mathematical expressions and approaches to the computation of rates and extents of drug bioavailability for implementation on analog and digital computers are derived. The equivalency of expressions derived on the basis of assuming compartment models to an approach based on using experimentally determined weighting functions is demonstrated. The relative merits of the two techniques are discussed: their application for use with temporal pharmacological data is emphasized. The applicability of the computational techniques to determining the availability of drugs at local sites of action (biophasic availability) and to computing preabsorptive drug release into the gastrointestinal contents (gastrointestinal bioavailability) is pointed out. An approach to computationally predicting in vivo blood level or pharmacological response vs. time profiles from in vitro dissolution testing results is presented and its limitations are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01063124
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  • 23
    Electronic Resource
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    Pharmacokinetic modeling of the dogfish shark (Squalus acanthias): Distribution and urinary and biliary excretion of phenol red and its glucuronide (1976)
    Springer
    Journal of pharmacokinetics and pharmacodynamics 4 (1976), S. 377-388 
    Details
    ISSN: 1573-8744
    Keywords: pharmacokinetics ; compartmental model ; phenol red ; phenol red glucuronide ; dogfish (Squalus acanthias)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A flow-limited multicompartment model simulates the distribution and disposition of phenol red in the dogfish after intravenous administration. Glucuronide conjugate, as well as parent compound, was found in urine and bile, but not in plasma, kidney, or liver tissue. An apparent 4-hr lag in phenol red appearance in the gall bladder was simulated using two stirred tanks connected in series to represent the bile ducts. The model should facilitate use of the dogfish in pharmacokinetic studies of drugs, environmental contaminants, and other xenobiotics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01062827
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  • 24
    Electronic Resource
    Electronic Resource
    Konformationsanalyse, XIII1) Umformung von 1,6-Anhydro-β-D-glucopyranose-Ringen in Bootkonformationen durch polare 1,3-diaxiale Wechselwirkungen. Synthese der 2,4-Diamino-1,6-anhydro-2,4-didesoxy-β-D-glucopyranose (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 104-111 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Conformational Analysis, XIII1) Conversion of 1,6-Anhydro-β-D-glucopyranose Rings to Boat Conformations by Means of Polar 1,3-Diaxial Interactions Synthesis of 2,4-Diamino-1,6-anhydro-2,4-dideoxy-β-D-glucopyranoseTreatment of 1,6:3,4-dianhydro-2-O-p-tolylsulfonyl-β-D-galactopyranose (5) with hydrazine followed by hydrogenation leads to 2, 4-diamino-1,6-anhydro-2,4-dideoxy-β-D-glucopyranose (8) with 85% yield. 1,6-Anhydro-2, 4-diazido-2, 4-dideoxy-β-D-glucopyranose (10) is obtained by reaction of 5 with sodium azide. Strong 1,3-diaxial interaction causes twisting of the pyranose ring in the 2,4-diazido compound 10 into the 1S0-Skew form 20, in the diammonium compound 9 into the 1.4B boat form 21
    Notes: 1.6:3,4-Dianhydro-2-O-p-tolylsulfonyl-β-D-galactopyranose (5) ergibt mit Hydrazin und anschließender Hydrierung 2,4-Diamino-1, 6-anhydro-2,4-didesoxy-β-D-glucopyranose (8) zu 85%. Mit Natriumazid ist aus 5 1.6-Anhydro-2.4-diazido-2.4-didesoxy-β-D-glucopyranose (10) gewinnbar. Durch starke polare 1,3-diaxiale Wechselwirkung ist der Pyranosering in der 2,4-Diazido-Verbindung 10 zur 1S0-Skew-Form 20 in der Diammonium-Verbindung 9 zur1.4 B-Boot-Form 21 verdreht.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090108
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  • 25
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    Darstellung und Eigenschaften von N3-(3-L-Amino-3-carboxypropyl)uridin-5′-monophosphat - einem modifizierten Nucleotid aus Transfer-RNA (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 82-89 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of N3-(3-L-Amino-3-carboxypropyl)uridine 5′-Monophosphate--a Modified Nucleotide from Transfer RNAN3-(3-L-Amino-3-carboxypropyl)uridine-5-monophosphate (5b), an α-L-aminobutyrate-modified uridine 5′-monophosphate (UMP), which is found at position 47 in the extra loop of Escherichia coli tRNAphe, was prepared from N3-(3-L-amino-3-carboxypropyl)uridine (5a) by phosphoryl chloride phosphorylation. Also described are the experimental conditions for the preparation of nucleoside 5a which was obtained by alkylation of isopropylideneuridine with ethyl α-L-benzamido-γ-bromobutyrate and after removal of the protecting groups from the intermediate 4. Comparison of the c. d. Spectra of 5b and UMP shows that the modified nucleotide under alkaline conditions has a geometry different from that in neutral or acidic media. This pH-dependent change, which is not observed with UMP itself, may influence the 3-dimensional structure of tRNA.
    Notes: N3-(3-L-Amino-3-carboxypropyl)uridin-5′-monophosphat (5b), ein durch den α-L-Aminobuttersäurerest modifiziertes Uridin-5′-monophosphat (UMP), das im Extraloop der Escherichia coli tRNAphe Position 47 einnimmt, wurde aus N3-(3-L-Amino-3-carboxypropyl)uridin (5a) durch Phosphorylierung mit Phosphoroxychlorid gewonnen. Die experimentellen Bedingungen für die Darstellung des Nucleosids 5a, das durch Alkylierung von Isopropylidenuridin mit α-L-Benzamido-γ-brombuttersäure-äthylester nach Abspaltung der Schutzgruppen aus der Vorstufe 4 erhalten wurde, werden beschrieben. Der Vergleich der CD-Spektren von 5b und UMP zeigt, daß das modifizierte Nucleotid im alkalischen eine andere Geometrie als im neutralen oder sauren Medium besitzt. Diese pH-abhängige Änderung, die bei UMP nicht beobachtet wird, beeinflußt vermutlich auch die räumliche Struktur der tRNA.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090106
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  • 26
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    Die Molekül- und Kristallstruktur von C7H7RuC7H9 - (1-5-ν-cycloheptadienyl)(1-5-ν-cycloheptatrienyl)-ruthenium(II) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 125-131 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal and Molecular Structure of C7H7RuC7H9 - (1-5-ν- Cycloheptadienyl)(1-5-ν-cyclohepatrienyl)ruthenium(II)The structure of the title compound 5 has been determined by X-ray diffraction. The compound crystallizes in the space group P21/n, a = 644.2 ± 0.1 pm, b = 01775.8 ± 0.2 pm., c = 989.9 ± 0.1 pm, β = 97.72 ± 0.02°, Z = 4 (R = 0.035). The ruthenium atom is coordinated by a cyclohephtadienyl and cycloheptatrienyl ligand, both functioning as five electron ligands. One double bond of the cycloheptarienyl ligand does not interact with the central atom.
    Notes: Mittels Röntgenanalyse wurde die Struktur der Titelverbindung 5 bestimmt. Der Komplex kristallisiert in der Raumgruppe p21/n, a = 644 ±0.1pm, b = 1775.8 ± 0.2pm, c = 989 ± 0.1pm, β = 97.72 ± 0.02°, Z = 4 (R + 0.035). Das Ruthenium ist im Komplex jeweils von einem Cycloheptadienyl- und Cycloheptarienylliganden koordiniert. Beide fungieren als 5-Elektronenliganden, wobei im Cycloheptarienylligand eine Doppelbindung nicht in Wechselwirkung mit dem Zentralatom ist.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090111
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  • 27
    Electronic Resource
    Electronic Resource
    Untersuchungen an Diazoverbindungen und Aziden, XXV1) Azid-Additionen an (Silyäthinyl)-, (Germyläthinyl)- und (Stannyläthinyl)amine (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 370-394 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on Diazo Compounds and Azides, XXV1) Azide Additions on (Silylethynyl)-, (Germylethynyl)- and (Stannylethynyl)aminesThe lithium acetylides 1 react with trialkyl- and triphenylmetal halides 2 to form the (silylethynyl)-, (germylethynyl)-, and (stannylethynyl)amines 3. The ynamines add aryl-and sulfonyl azides to the 5-amino-1, 2,3-triazoles 4,5, and 7, which in the case of the sulfonyl azide adducts 5 and 7 isomerize largely to the diazoacetamidines 6 and 8, respectively. Water or deuterium oxide hydrolyze the carbon-metal bond of the diazo compounds 8 with formation of the [2-H1] - and [2-D1]diazoacetamidines 9 and 10.
    Notes: Durch Umsetzung von Lithiumacetyliden 1 mit Trialkyl- und Triphenylmetallhalogeniden 2 werden (Silyläthinyl)-, (Germyläthinyl)- und (Stannyläthinyl)amine 3 synthetisiert. Diese Inamine addieren Aryl- und Sulfonylazide zu den 5-Amino-1,2,3-triazolen 4,5 und 7, die im Falle der Sulfonyladdukte (5 und 7)weitgehend zu den Diazoacetamidinen 6 bzw. 8 isomerisieren. Die Diazoverbindungen 8 spalten den Metallrest bei Einwirkung von Wasser oder Deuteriumoxid leicht ab unter Bildung der [2-H1]- und der [2-D1]Diazoacetamidine 9 und 10.
    Additional Material: 9 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090139
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  • 28
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    Nucleosidtransformationen, 1. Umwandlung von Adenosin in 2′- und 3′-azido-, -amino- sowie -chlor-substituierte Desoxyadenosine1) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 433-443 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nucleoside Transformations, 1 Transformation of Adenosine into 2′-and 3′-Azido, -Amino and -Chloro Substituted Deoxyadenosines1)Direct SN2-displacement of the 3′- or 2′-iodogroup in the iodohydrines 2b and 3b by chloride ions yields after removal of the protecting groups 3′-chloro-3′-deoxy- and 2′-chloro-2′-deoxyadenosine (4d and 5d). The 3′- and 2′-azidoadenosines 14b and 15b are obtained from the adenosinelyxoepoxide 11 with azide followed by inversion of configuration at the neighboring hydroxygroup. Their catalytical reduction yields the amines 16, 17.
    Notes: Direkte SN2-Substitution des 3′- oder 2′-Jodatoms in den Jodhydrinen 2b und 3b mit Chloridionen liefert nach Abspaltung der Schutzgruppen 3′-Chlor-3′-desoxy- bzw. 2′-Chlor-2′-desoxyadenosin (4d bzw. 5d). Die 3′- und 2′ -Azidoadenosine 14b, 15b, sind aus dem Adenosinlyxoepoxid 11 mit Azid und anschließende Konfigurationsumkehr an der benachbarten Hydroxylgruppe zugänglich. Ihre katalytische Reduktion ergibt die Amine 16, 17.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090204
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  • 29
    Electronic Resource
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    Synthese und Kristallstruktur eines zweikernigen Ylid-Komplexes mit Metall-Metall-Bindung zwischen Goldatomen der Oxidationsstufe + II1) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 466-472 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of a Binuclear Ylide Complex with Metal-Metal Bonding between Gold Atoms in the Oxidation State + II1)The [diethylphosphoniumbis(methylido)]gold(I) dimer 4 reacts with one equivalent of chlorine, bromine, or iodine to give a series of compounds 5a-c, for which a bicyclic structure with a remarkably short transannular gold-gold bond (259.7 pm) is demonstrated by means of analytical and spectral data as well as by an X-ray analysis of 5a. The two metals of formal oxidation state +II are separated by a very short distance.
    Notes: Die aus dem [Diäthylphosphonium-bis(methylido)]gold(I)-Dimeren 4 und äquimolaren Mengen Chlor, Brom oder Jod erhältlichen Verbindungen 5a-c besitzen nach analytischen und spektroskopischen Daten sowie nach einer an 5a durchgeführten Röntgenstrukturanalyse eine bicyclische Struktur mit transannularer, auffallend kurzer Gold-Gold-Bindung (259.7 pm). Die nur durch einen sehr kurzen Abstand getrennten Metalle besitzen formal die Oxidationsstufe +II.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090208
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  • 30
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    Electronic Resource
    Alkalische Carbonsäure-Eliminierung durch Nachbargruppeneffekt (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 459-465 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkaline Carboxylic Acid Elimination by Neighbouring Group Participation3-(2-Hydroxy-3,4,5-trimethylphenyl)-3-methylphthalide (1) und 3-(2-Hydroxyphenyl)-3-methylphthalide (2) react in alkali by way of intramolecular carboxylic acid elimination to give the 1,1-diphenylethylenes 3 and 4 in high yields. It is shown that this elimination reaction dominates over the saponification of the lactone ring by the neighbouring group effect of the phenolate oxygen. Only with higher concentrations of hydroxylic ions the saponification reaction becomes faster in the case of 2. This neighbouring group effect, though in a slow reaction, Causes β-elimination of water in the tert. alcohols 11 c, e yielding the 1,1-diphenylethylenes 12c, e.
    Notes: 3-(2-Hydroxy-3,4,5-trimethylphenyl)-3-methylphthalid (1) und 3-(2-Hydroxyphenyl)-3-methylphthalid (2) geben in Alkali unter intramolekularer Carbonsäure-Eliminierung in hohen Ausbeuten die 1,1-Diphenyläthylene 3 bzw. 4. Es wird gezeigt, daß diese Eliminierungsreaktionen durch den Nachbargruppeneffekt des Phenolat-Sauerstoffes schneller ablaufen als die Verseifung der Lactonringe. Erst bei höheren Hydroxylionen-Konzentrationen wird im Falle von 2 die Verseifungsreaktion schneller. Dieser Nachbargruppeneffekt ermöglicht ferner - wenn auch in langsamer Reaktion - alkalische β-Eliminierung von Wasser aus den tert. Alkoholen 11c, e unter Bildung der 1,1-Diphenyläthylene 12c, e.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090207
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  • 31
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    2,4,6-Tribrom-1,3,5-tris(dibromboryl)borazin (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 488-492 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 2,4,6,-Tribromo-1,3,5-tris(dibromoboryl)borazineThe title compound can be obtained by the reaction of N-chlorovanadium nitride trichloride, Cl3 VNCl, with excess boron tribromide. The compound is characterized by its spectra.
    Notes: Die Titelverbindung 1 entsteht durch Umsetzung von N-Chlorvanadinnitridtrichlorid. CL3 VNCl, mit überschüssigem Bortribromid. Die Verbindung wird spektroskopisch charakterisiert.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090211
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  • 32
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    Lichtinduzierte Reaktionen, X1) Die vier stereoisomeren 3,8-Diphenyl-1,2-diaza-1-cyclooctene (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 518-530 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Light-Induced Reactions, X1) The Four Stereo Isomeric 3,8-Diphenyl-1,2-diaza-1-cyclooctenesThe complete set of configurationally isomeric 3,8-diphenyl-1-cyclooctenes covers species 1, 2, 3, and 4. The up to now unknown compounds (2 and 3) were prepared and identified, together with compound 4 hitherto thought to be 3. The configuration of 2 and 4 was unambigously determined by nonempirical n. m. r. analysis and X-ray diffraction, respectively; 1 and 3 are sufficiently characterized as photo isomers (with regard to orientation of ligands at the azo group) of 2 or 4.  -  The stereoisomeric 1,2-diaza-1-cyclooctenes 5 and 6 have been obtained in different ways and determined n. m. r. spectroscopically.
    Notes: Der vollständige Satz der konfigurationsisomeren 3,8-Diphenyl-1,2-diaza-1-cyclooctene umfaßt die Individuen 1, 2, 3, und 4. Die bislang unbekannten Verbindungen (2 und 3) wurden dargestellt und, zusammen mit der bisher als 3 angesehenen Verbindung 4, identifiziert. Die eindeutige stereochemische Zuordnung geschah bei 2 durch nichtempirische NMR-Analyse, bei 4 durch Röntgenstrukturanalyse; 1 oder 3 sind als Photo-Isomere (in bezug auf die Liganden an der Azogruppierung) von 2 oder 4 sicher charakterisiert. Die stereoisomeren 1,2-Diaza-1-cyclooctene 5 und 6 sind aud verschiedene Weise dargestellt und NMR-spektroskopisch bestimmt worden.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090215
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  • 33
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    Topographie der Cyclodextrin-Einschlußverbindungen, VIIVI. Mitteil.:W. Saenger, K. Beyer und P. C. Manor, Acta Crystallogr., im Durck (1975). Entnommen aus der Diplomarbeit M. Noltemeyer, Institut für Organische Chemie der Universität Göttingen und Max-Planck-Institut für Experimentalle Medizin, Göttingen 1974. Kurzmitteil.: W. Saenger und M. Noltemeyer, Angew. Chem. 86, 594 (1974). Angew. Chem., Int. Ed. Engl. 13, 552(1974).. Röntgenstrukturanalyse des α-Cyclodextrin. Krypton-Pentahydrats. Zum Einschlußmechanismus des Modell-Enzyms (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 503-517 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Topography of Cyclodextrin Inclusion Complexes, VII* X-Ray Analysis of α-Cyclodextrin. Krypton Pentahydrate. On the Inclusion Mechanism of the Model EnzymeWhen crystallized from water under krypton pressures of 43 PSI (A) and 200 PSI(B), α-cyclodextrin (α-CD) yields inclusion compounds of composition α-CD·(0.78 H2O, 0.48 Kr)·5H2O (A) and α-CD·(0.28 H2O, 0.74 Kr)·5H2O (B). Both the adducts are isomorphous, space group P212121. The structures were determined from about 3900 X-ray data and refined to an R-factor of 8.8%. Although Kr has nearly the same van der Waals diameter as H2O (4Å), the structures of the Kr and of the recently determined α-CD·2H2O adduct are different. In the latter, the 5.0 Å wide cavity of α-CD is diminished by rotation of two glucoses, rendering the α-CD conformation strained. in the almost hexagonal Kr-adduct, all six glucoses are approximately equivalent, the cavity is 5 Å in diameter and the Kr is statistically disordered over five positions. It is concluded that α-CD adducts are stabilized through release of conformation- and hydrogen bonding energy when the “empty” α-CD·2H2O adduct transforms into any other adduct. This mechanism explains why so many different guest molecules are enclosed and bears some relation to enzyme-substrate interactions.
    Notes: α-Cyclodextrin (α-CD) liefert aus Wasser in Gegenwart von Krypton bei 3 und 14 atü kristalline Einschlußverbindungen der Zusammensetzung α-CD·(0.78H2O, 0.48 Kr)·5 H2O (A) und α CD·(0.28 H2O, 0.74 Kr)·5H2O (B). Beide sind isomorph, Raumgruppe P212121. Die Strukturen wurden aus etwa 3900 Röntgenreflexen gelöst und bis zu einem R-Faktor von 8.8% verfeinert. Obwohl Kr mit 4 Å van der Waals- Durchmesser etwa ebenso groß ist wie H2O3, sind die Strukturen der Kr-Addukte von der des reinen αCD·2H2O-Adduktes verschieden. Der 5.0 Å große Hohlraum im α-CD wird im H2O-Addukt durch Rotation zweier gegenüberliegender Glucosen zusammengezogen und dadurch gespannt. Im beinahe hexagonalen Kr-Addukt sind alle sechs Glucosen annähernd gleichwertig und das Kr besetzt statistisch fünf verschiedene Lagen, um den 5.0 Å weiten Innenraum auszufüllen. Es wird gefolgert, daß beim Austausch des Wassers gegen Gastmoleküle frei werdende Konformations- und Wasserstoffbrückenenergie die Addukte stabilisiert. Dieser Mechanismus erklärt, weshalb viele Gastmoleküle mit so unterschiedlichen Eigenschaften eingeschlossen werden und wird im Zusammenhang mit der Enzym-Substrat-Wechselwirkung diskutiert.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090214
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    Umsetzungen substituierter Aldehyde mit Diazoalkanen, IV1) Reaktionen von monosubstituierten Benzaldehyden mit Diazomethan (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 640-649 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Substituted Aldehydes with Diazoalkanes, IV1) Reactions of Monosubstituted Benzaldehydes with DiazomethaneThe step by step reaction of 2 molequiv. of o-cyano- and o-chlorobenzaldehydes 1 with diazo-methane gives besides 7b the ketones 3a, b and the β-ketols 4a, b. Whereas 4a isomerizes to the chalcone 5, dehydration of 5b yields the chalcone 6b. The m-substituted benzaldehydes 13 and diazomethane in the ratio 2:1 furnish the ketones 14a, b, the epoxides 15a, b and the β-ketols 16a, b; the last-named are dehydrated with acetic anhydride to the chalcones 17a, b. The p-substituted benzaldehydes 21 and half a molequiv. of diazomethane yield predominantly the ketones 24a, b and the β-ketols 22a, b and also small amounts of oxirane 25a, homologous β-ketol 27b and p-cyanophenylacetone 26a. With equivalent amounts of diazomethane and of two different aldehydes (o,m,p-cyanobenzaldehydes, chloral and p-nitrobenzaldehyde) one gets the “mixed” β-ketols 9, 12, 19, 29 as well as the oxiranes 20, 30, the “homogeneous” β-ketols 4a, 11, 16a, 22a and other ketones.
    Notes: Durch stufenweise Umsetzung von 2 Moläquivv. o-Cyan- bzw. o-Chlorbenzaldehyd 1 mit Diazomethan entstehen neben 7b die Ketone 3a, b und die β-Ketole 4a, b. Während 4a zum Chalkon 5 isomerisiert, dehydratisiert 4b zum Chalkon 6b. Die meta-substituierten Benzaldehyde 13 geben mit Diazomethan im Molverhältnis 2:1 die Ketone 14a, b, die Epoxide 15a, b und die β-Ketole 16a, b; die letzteren werden mit Acetanhydrid zu den Chalkonen 17a, b dehydratisiert. Die para-substituierten Benzaldehyde 21 lieferten mit einem halben Moläquiv. Diazomethan überwiegend die Ketone 24a, b und β-Ketole 22a, b neben kleinen Mengen von Oxiran 25a, homologem β-Ketol 27b und p-Cyanphenylaceton 26a. Aus äquivalenten Mengen Diazomethan und den äquivalenten Mengen zweier verschiedener Aldehyde (o,m,p-Cyanbenzaldehyde und Chloral bzw. p-Nitrobenzaldehyd) erhält man die “gemischten” β-Ketole 9, 12, 19, 29 sowie die Oxirane 20, 30 neben den “einheitlichen” β-Ketolen 4a, 11, 16a, 22a und anderen Ketonen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090227
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    Über Derivate des Hydrazins, 51) Darstellung und einige Eigenschaften trimethylsilylierter,-germylierter sowie -stannylierter Tosylhydrazine (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 710-722 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Derivatives of Hydrazine, 51) Preparation and Some Properties of Trimethylsilylated, -germylated, and -stannylated TosylhydrazinesWith the exception of TosN2H(SnMe3)2, all tosylhydrazines TosN2Hm(E′Me3)n(E″Me3)0-(E‴Me3)p(E′, E″, E‴= So, Ge, Sn; m + n + o + p = 3) have been synthesized and characterized. These were prepared mostly by silylation, germylation, or stannylation of tosylhydrazine, TosN2H3, with chlorides Me3ECl or amines Me3ENR2, and, in a few cases, by tosylation of hydrazines N2H2(EMe3)2 and N2H2(EMe3)3 with tosyl chloride. Amines Me3ENR2 react with these newly synthesized tosylhydrazines by an exchange of hydrogen or of E′Me3 for EMe3. The hydrazides TosN2Li(SiMe3)(EMe3), obtained by the reaction of LiN(SiMe3)2 with TosN2Li(SiMe3)(EMe3) (E=Si, Ge) decompose on heating into TosLi and the azo-compounds Me3Si—N=N—EMe3.
    Notes: Mit Ausnahme von TosN2H(SnMe3)2 konnten alle Tosylhydrazine TosN2Hm(E′Me3)n(E″Me3)0-(E‴Me3)p(E′, E″, E‴=Si, Ge, Sn; m + n + o + p = 3) synthetisiert und charakterisiert werden. Ihre Darstellung erfolgte in den meisten Fällen durch Silylierung, Germylierung oder Stannylierung von Tosylhydrazin, TosN2H3, mit Chloriden Me3 ECl oder Aminen Me3ENR2, in einigen Fällen durch Tosylierung von Hydrazinen N2H2(EMe3)2 und N2H(EMe3)3 mit Tosylchlorid. Amine Me3ENR2 reagieren mit den neu dargestellten Verbindungen unter Austausch sowohl von Wasserstoff als auch von E′Me3 gegen EMe3. Die aus TosN2H)SiMe3)(EMe3) (E=Si, Ge) mittels LiN(SiMe3)2 erhältlichen Hydrazide TosN2Li(SiMe3)(EMe3) liefern bei höheren Temperaturen unter TosLi-Abspaltung die Azoverbindungen Me3Si—N=N—EMe3.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090233
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  • 36
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    Darstellung und physikalische Eigenschaften mesoionischer 1,3-Dithiolone1) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 740-752 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Physical Properties of Mesoionic 1,3-Dithiolones1)1,3-Dithiolylium-4-olates 3a-1 are preparatively interesting mesoionic 6π Arenes. Their synthesis from the corresponding dithioester derivatives 1a-1 and their infrared, electronic, and mass spectra are described. 3a, b, and f possess as sydnone analogues compounds relatively high dipole moments of 5.00, 5.54, and 5.98 D, respectively.
    Notes: 1,3-Dithiolylium-4-olate 3a-1 sind präparativ interessante mesoionische 6π-Aromaten. Ihre Synthese aus den entsprechenden Dithiocarbonester-Derivaten 1a-1 sowie Infrarot-, Elektronen- und Massenspektren werden beschrieben. Als Sydnon-Analoga besitzen 3a, b und f relativ große elektrische Momente von 5.00, 5.54 bzw. 5.98 D.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090235
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  • 37
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    Zum Mechanismus der Reaktion von 1,6-Methano-[10]annulen mit Elektrophilen1) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 769-776 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Mechanism of the Reaction of 1,6-Methano-[10]annulene with Electrophiles1)Chlorosulfonyl isocyanate reacts with 1,6-methano-[10]annulene (1) to give only the substitution product 7; cycloaddtion products are not observed. The formation of the dibromo dichloro adduct 10 by bromination of 1 with Br2 in the presence of triethylbenzylammonium chloride as a competitive nucleophil provides evidence for a two-step addition via a cationic intermediate. Upon nitration of 1 with dinitrogen pentoxide at -110°C addition products are formed which can be characterized by n.m.r. spectroscopy. With collidine/nitronium trifluoromethanesulfonate, 1 is nitrated almost exclusively in the 2-position to form 5. With other nitration agents, however, mixtures of 5 and 6 are formed.
    Notes: Mit Chlorsulfonylisocyanat reagiert 1,6-Methano-[10]annulen (1) ausschließlich unter Bildung des Substitutionsproduktes 7; ein Cycloadditonsprodukt ist nicht nachzuweisen. Beweisend für eine zweistufige Additionsreaktion von Brom an 1 über kationische Zwischenverbindungen ist die Bildung des Dibrom-dichlor-Adduktes 10 in Gegenwart von Triäthylbenzylammoniumchlorid als Konkurrenznucleophil. Bei der Nitrierung von 1 mit Distickstoffpentoxid bei -110°C entstehen NMR-spektroskopisch nachweisbare Additionsprodukte. Mit Collidin/Nitronium-trifluormethansulfonat wird 1 nahezu ausschließlich in 2-Stellung nitriert, während mit anderen Nitrierungsagentien Gemische aus den Isomeren 5 und 6 entstehen.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090238
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  • 38
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    Natürlich vorkommende Terpen-Derivate, LIV1) Neue Terpenaldehydester aus Peucedanum luxurians Tamamsch (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 788-790 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, LIV1) New Terpene Aldehyde Esters from Peucedanum luxurians TamamschThe roots of Peucedanum luxurians Tamamsch contain besides already known terpenes five new aldehydes with mixed ester groups (3, 6-8, 10 and 13. Their structures have been elucidated by spectroscopic methods.
    Notes: Die Wurzeln von Peucedanum luxurians Tamamsch enthalten neben bereits bekannten Terpenen fünf neue Aldehyde mit gemischten Estergruppen (3, 6-8, 10, und 13), deren Strukturen durch spektroskopische Methoden geklärt werden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090240
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  • 39
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    Notiz zur Synthese des 1,4-Pentamethylen-Dewar-Benzols1, 2) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 793-795 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090242
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  • 40
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    Notiz über die Peptidsynthese mit Triphenylphosphin/Tetrachlorkohlenstoff als Kondensationsreagenz, II1) (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 801-804 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090245
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  • 41
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    Natürlich vorkommende Terpen-Derivate, LVI: Neue Furanoeremophilane aus mexikanischen Senecio-Arten (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 819-825 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occuring Terpene Derivatives, LVI: New Furanoeremophilanes from Mexican Senecio SpeciesThe investigation of two Mexican Senecio species yields, besides known sesquiterpenes, several new ones, their constitutions being elucidated mainly by spectroscopic methods (2, 3, 6-9, 14-16, 21, 22).
    Notes: Die untersuchung von zwei mexikanischen Senecio-Arten ergibt neben bekannten Sesquiterpenen mehrere neue, deren Konstitutionen hauptsächlich durch spektroskopische methoden geklärt werden (2,3,6-9, 14-16, 21, 22).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090304
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  • 42
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    Ringöffnende Cycloadditionen, II: Reaktion von Heterocumulenen mit 5-Äthoxy-3-phenylimino-3H-1,2,4-dithiazol (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 848-854 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ring-cleaving Cycloadditions, II: Reaction of Heterocumulenes with 5-Ethoxy-3-phenylimino-3H-1,2,4-dithiazoleReaction of acyl and imidoyl isothiocyanates with 5-ethoxy-3-phenylimino-3H-1,2,4-dithiazole (2) led to opening of the heterocyclic ring and formation of cycloadducts of the 1,2,4-dithiazolidine series (4,5). The corresponding reaction with two alkyl isocyanates afforded 1,2,4-thiadiazolidines (8).
    Notes: Reaktion von Acyl-und Imidoyl-isothiocyanaten mit 5-Äthoxy-3-phenylimino-3H-1,2,4-dithiazol (2) ergab unter Ringöffnung Cycloaddukte der 1,2,4-Dithiazolidinreihe (4,5). Die entsprechende Umsetzung mit zwei Alkylisocyananten führte zu Derivaten des 1,2,4-Thiadiazolidins (8).
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090307
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  • 43
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    Beiträge zur Chemie des Bors, LXXIV: Stabilisierung von Diborylaminen: (Borolanylamino)borane und (Diazaborolidinylamino)borane (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 884-895 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, LXXIV: Stabilisation of Diborylamines: (Borolanylamino)boranes and (Diazaborolidinylamino) boranesThe thermal decomposition of diborylamines into a borane and a borazine derivative becomes considerably more difficult when the boron atoms of diborylamines are incorporated into a five-membered ring system. This type of diborylamines is represented by (1-borolanylamino)-boranes as well as by (1,3-dimethyl-1,3,2-diazaborolidin-2-Ylamino)boranes whose structure and bonding are discussed on the basis of spectroscopic data.
    Notes: Durch Einbau der Boratome eines Diborylamins in ein fünfgliedriges Ringsystem wird die thermische Zersetzung der Diborylamine in ein Boran-und ein Borazin-Derivat beträchtlich erschwert. (1-Borolanylamino)borane und (1,3-Dimethyl-1,3,2-diazaborolidin-2-ylamino)borane repräsentieren diese Diborylamin-Typen, deren Struktur und Bindungsverhältnisse aufgrund spektroskopischer Daten diskutiert werden.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090310
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  • 44
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    Synthesen biologisch wichtiger Kohlenhydrate, 3: Sehr einfache Synthese von DL-Amicetose (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 896-900 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Biologically Important Carbohydrates, 3: Very Simple Synthesis of DL-AmicetoseSorbic acid (1) reacts with peracetic acid to form 4,5-epoxy-DL-threo-hex-2-enic acid (2). Ring fission yields 2,3,6-trideoxy-DL-erythro-hex-2-enoic acid (3) which after hydrogenation to 2,3,6-trideoxy hexonic acid 4 forms the amicetonolactone (5). Reduction of 5 by diisobutyl aluminium hydride gives an anomeric mixture of the furanoic and pyranoic antibiotic sugar DL-amicetose (2,3,6-trideoxy-erythro-hexose) (6).
    Notes: Sorbinsäure (1) reagiert mit Peressigsäure zur 4,5-Epoxy-DL-threo-hex-2-ensäure (2) Anm. b. d. Korr. (15. 1. 1975): Die Enantiomeren 2 lassen sich mit opt. akt. 1-Phenyläthylamin leicht trennen., die nach Ringöffnung zur 2,3,6-Tridesoxy-DL-erythro-hex-2-enonsäure (3) und Hydrierung zur 2,3,6-Tridesoxy-hexonsäure 4 das Amicetonsäurelacton (5) liefert. reduktion von 5 mit Diisobutylaluminiumhydrid führt zum Anomerengemisch des pyranoiden und furanoiden Antibiotikumzucker DL-Amicetose (2,3,6-Tridesoxy-erythro-hexose) (6).
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090311
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  • 45
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    Reaktionen an der α-Methylengruppe von (Glycinato)platin(II)-Chelat-Komplexen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 965-969 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of the α-Methylene Group in (Glycinato)platinum(II) Chelate ComplexesThe reaction of the glycinato complex (n-Bu3P)Pt(Cl)NH2CH2CO2) (1)with aldehydes or alkylating agents (dimethyl sulfate, benzyl chloride) affords the chelate compounds 3-6 with substituted α-amino acids.
    Notes: Der Glycinato-Komplex (n-Bu3P)Pt(Cl)NH2CH2CO2) (1) setzt sich mit Aldehyden oder Alkylierungsmitteln (Dimethylsulfat, Benzylchlorid) zu entsprechenden Chelat-Verbindungen 3-6 mit Höheren α-Aminosäuren um.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090317
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    Alkylierungsreaktionen an Thioamiden, II. Untersuchungen zur E/Z-Isomerie und innermolekularen Beweglichkeit in Thioimidsäureestern (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 922-946 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkylation reactions of Thioamides, II: Investigations of E/Z Isomerism and Intramolecular Mobility in ThioimidatesA Series of N-substituted thioimidates A was prepared and investigated by n. m. r. spectroscopy. It is shown by direct thermal stereomutation and dynamic n. m. r. spectroscopy that an inversion mechanism and an imine-enamine tautomerism are pathways of the E/Z isomerization in A (ΔG≠=51.5 to 92.9 kj/mol).
    Notes: Es wurde eine Anzahl N-substituierter Thioimidsäureester A dargestellt und NMR-spektroskopisch untersucht. Durch direkte thermische Isomerisierung und dynamische NMR-Messungen konnte nachgewiesen werden, daß der Inversionsmechanismus und die imin-Enamin-Tautomerie Wege der E/Z-Isomerisierung bei A(ΔG≠= 51.5 bis 92.9 kj/mol) darstellen.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090314
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  • 47
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    Selenoimidsäureester (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 956-964 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: SelenoimidatesThe new selenoimidates 3a-f were prepared and compared with imidates and thioimidates concerning their E/Z isomerism and barriers to isomerization.
    Notes: Die neuen Selenoimidsäureester 3a-f wurden dargestellt und hinsichtlich ihrer E/z-Isomerie und Isomerisierungsbarrieren mit Imidsäure- und Thioimidsäureestern verglichen.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090316
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  • 48
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    Neue Übergangsmetallkomplexe mit Nuclein-Basen und Nucleosiden (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 970-993 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Transition Metal Complexes with Nucleic Acid bases and NucleosidesThe isolation of carbonylmetal complexes W(CO)5L (1), [W(CO)5L]- (2), [Mo(CO)3enL]- (3), (π-CH3C5H4)Mn(CO)2L (4), Rh(CO)2(CI)L (5), (H)(CO)(PPh3)2L2 (6), M(CO)(PPh3)2L (M = Rh, Ir) (7,8) and of phosphine and amine containing monomeric and polynuclear palladium(II) and platinum(II) complexes (9-14 with various neutral and anionic nucleic acid bases and nucleosides L is reported. Using i. r. and 1H n. m. r. data a tentative assignment of the coordination sites of the ambidentate ligands is given. The reaction of 1,3,7,9-tetramethylxanthinium perchlorate with Hg11 acetate affords the C-8 mercurated complex 15.
    Notes: Die Darstellung von Carbonylmetallkomplexen W(CO)5L (1), [W(CO)5L]- (2), [Mo(CO)3enL] (3)-, (π-CH3C5H4)Mn(CO)2L (4), Rh(CO)2(Cl)L (5), Ir(H)(CO)(PPh3)2L2 (6), M(CO)(PPh3)2L (M = Rh, Ir) (7,8) und von phosphin- und amin-haltigen monomeren sowie mehrkernigen Palladium(II)-und Platin(II)-und Platin (II)-Komplexen (9-14) mit einer Reihe von neutralen und anionischen Purin und Pyrimidin-Basen und Nucleosiden L wird beschrieben. Mit Hilfe von IR- und 1H-NMR- Daten wird versucht, die Koordinationsstellen der ambidenten Nucleinbasen zu bestimmen. 1,3,7,9-Tetramethylxanthinium-perchlorat wird mit Quecksilber (II)-acetat am C-8 metalliert (15).
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090318
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    Sterische Wechselwirkungen im Innern cyclischer Verbindungen, XXIV: Konsequenzen beim Ersatz von CH2 durch Heteroatome in Ringverbindungen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1002-1010 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Steric Interactions of Inner Atoms in Cyclic Compounds, XXIV: Consequences of Replacing CH2-Groups by Hetero Atoms in Ring CompoundsThe method described allows to estimate the size of the cavity in crown ether type molecules. Dynamic 1H n. m. r. studies of the crown ether systems 2b, 2 and 3b, 3 show that by replacement of CH2 bridge members throught —S— as a rule the ring inversion barrier (ΔGC≠ decreases. In the ring system 2 replacing one CH2-group by one oxygen atom leads to higher (ΔGC≠-values. Whereas in 3b γ the barrier also is higher compared with 3aγ, 3bβ exhibits a lower (ΔGC≠-value than 3aβ. An interpretation is given in terms of several partly compensating effects, e. g. the loss of space filling hydrogen atoms proceeding from oligomethylene to hetero atom containing bridges, and repulsive steric interaction between the intraanular substituent X and the heteroatoms in the bridge.
    Notes: Die beschriebene Methode erlaubt eine vergleichende Abschätzung der Hohlraumgröße von Kronenäthern. Durch untersuchung der neuen Cyclen 2b, 2c und 3b, 3c mittels dynamischer protonenresonanz wird gefunden, daß bei Ersatz eines CH2- Brückenglieds durch —S— die Ringinversionsbarriere (ΔGC≠) abfällt. Ersatz einer einzelnen CH2-Gruppe durch —O— (vgl. 2aα, 2bα erhöht die Ringinversionsschwelle. Einführung zweier durch eine Äthylenbrücke getrennte Äther-Sauerstoffatome hat für X = NO2 (in 3b) einen Anstieg, für X = Cl (in 3bβ) jedoch eine Abnahme von ΔGC≠ zur Folge, Zur Deutung werden verschiedene sich teilweise kompensierende Effekte herangezogen: Am wichtigsten erscheinen der Wegfall der Raumbeanspruchung der H-Atome beim Übergang zu den heteroatom-haltigen Ringen sowie abstoßende sterische Wechselwirkungen zwischen dem intraanularen Substituenten X und Heteroatomen in der Brücke.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090320
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  • 50
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    Synthese von 6-Fluorbenz[a]anthracen-Derivaten (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1038-1045 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 6-Fluorobenz[a]anthracene Derivatives6-Fluoro-(12 and 6-Fluoro-12-methylbenz[a]anthracene(11) are prepared in several steps starting with 2-bromo-3-fluoronaphthalene (1). 6-Fluorobenz[a]anthracen-127H)-one (8) predominantly occurs in the enol form 9. Efforts to synthesize 6-fluoro-7,12-dimethylbenz[a]anthracene (10) are described.
    Notes: Ausgehend von 2-Brom-3-fluornapthalin (1) werden über mehrere Stufen 6-Fluor-(12) und 6-Fluor-12-methylbenz[a]anthracen (11) dargestellt. 6-Fluorbenz[a]anthracen-12(7 H)-on (8) liegt vorwiegend in der Enolform 9 vor. Syntheseversuche für 6-Fluor-7,12-dimethylbenz[a]anthracen (10) werden beschrieben.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090324
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  • 51
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    Komplexchemie polyfunktioneller Liganden, XXXVI: Über Halogeno- und Pseudohalogeno-kobalt(I)-Komplexe des tritertiären Phosphins 1,1,1-Tris(diphenylphosphinomethyl)äthan (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1095-1105 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Complex Chemistry of Polyfunctional Ligands, XXXVI: About Halogeno- and Pseudohalogeno-cobalt(I) Complexes of the Tritertiary Phosphine 1,1,1-Tris(diphenylphosphinomethyl)ethane\documentclass{article}\pagestyle{empty}\begin{document}$ [\mathop {{\rm Co}}\limits^{ + {\rm I}} ({\rm CO})_2 ({\rm R}_2 {\rm PCH}_2)_3 {\rm CCH}_3][\mathop {{\rm Co}}\limits^{ - {\rm I}} ({\rm Co})_4] $\end{document} (R = C6H5) 2 reacts with the alkali metal halides and pseudohalides MX(M = Na, K; X = Cl, Br, J) on ultraviolet irradiation to give the monomeric, paramagnetic (μeff ≍ 3 B.M.), tetrahedral cobalt(I) complexes XCo(R2PCH2)3CCH33 With CO the halogeno-cobalt(I) complexes 3a-c) yield the ionic, diamagnetic dicarbonyl compounds [Co(CO)2(R2PCH2)3]X(X = Cl, Br, J) 5. On the other hand the pseudohalogeno-cobalt(I) complexes 3d,e give with CO the non-ionic complex Co(NCO)(CO)2(R2PCH2C(CH3)CH2PR2 6. The potentially tridentate ligand CH3C(CH2PR2)3 Serves in it as a bidentate monometallic ligand. The halogeno- and pseudohalogeno-cobalt(I) complexes 3 are very air-sensitive. The forming of O2-complexes from the pseudohalogeno-cobalt(I) compounds 3d, e in the solid state has been shown qualitatively by the infrared spectra. In solution these O2complexes decompose to phosphine oxide-containing products. With 9,10-phenanthrenequinone, Co(NCO)(R2PCH2)3CCH3 (3d) gives also an oxidative addition product, the Paramagnetic Co(NCO)(C14H8O2(R2PCH2)2-C(CH3) CH2PR2 8 (μeff 2.97 B.M.). The compounds were characterized by their infrared and far infrared spectra.
    Notes: \documentclass{article}\pagestyle{empty}\begin{document}$ [\mathop {{\rm Co}}\limits^{ + {\rm I}} ({\rm CO})_2 ({\rm R}_2 {\rm PCH}_2)_3 {\rm CCH}_3][\mathop {{\rm Co}}\limits^{ - {\rm I}} ({\rm Co})_4] $\end{document} (R = C6H5) 2 setzt sich mit Alkalimetallhalogeniden und pseudohalogeniden MX (M = Na, K; X = Cl, Br, J, NCO, N3)unter UV-Bestrahlung zu den monomeren, paramagnetischen (μeff ≍ 3 B.M.), tetraedrischen Kobalt(I)-Komplexen XCo(R2PCH2CCH3 3um. Mit Co bilden die Halogeno-kobalt(I)-Komplexe 3a-c die ionischen, diamagnetischen Dicarbonylverbindungen [Co(CO)2(R2PCH2)CCH3]X (X = Cl, Br, J) 5. Die pseudohalogeno-kobalt(I)-Komplexe 3d, e reagieren dagegen mit CO jeweils zu dem nicht ionischen CO(NCO)(CO)2(R2PCH2C(CH3)CH2PR2 6 Der potentiell dreizähnige Ligand CH3C(CH2PR2)3 wirkt dabei lediglich zweifachkoordinierend-monometallisch. Die halogeno und Pseudohalogeno-kobalt(I) Komplexe 3 sind sehr oxidationsempfindlich. Bei den pseudohalogeno-kobalt(I)Komplexen 3d-e gelang es, im Festzustand die Bildung von O2-Komplexen qualitativ IR-spektroskopisch nachzuweisen. In Lösung zerfallen diese O2-Komplexe zu phosphinoxidhaltigen Produkten. 9,10-Phenanthrenchinon wird oxidativ an Co(NCO)(R2PCH2)3CCH3(3d) addiert. Es entsteht das paramagnetische Co(NCO)(C14H8O2)(R2PCH2)2C(CH3)CH2PR2 8 mit einem mittleren Spin von 2.97B. M. Die Verbindungen wurden IR- unf FIR- spektroskopisch untersucht.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090331
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    Rotationsbarriere der geometrischen Isomerisierung von cis-und trans-1,4-Dimethylbutatrien (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1158-1162 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rotational Barrier for the Geometrical Isomerization of cis-and trans-1,4-DimethylbutatrieneThe synthesis of cis(3a) and trans-1,4-dimethylbutatriene (3b) is described. The activation parameters for the mutual interconversion of the geometrical isomers have been determined: Ea = 31.8 ± 0.3 kcal/mol; A= 1.1 × 1013S-1 (ΔH125°C≠ = 31.0 kcal/mol; ΔH125°C≠ = -1.5 cal/grad × mol). The equilibrium constant was found to be K = 1 in the temperature range 100-150°C.
    Notes: Die Synthese von cis-(3a) und trans-1,4-Dimethylbutatrien (3b) wird beschrieben. Für die wechselseitige Umlagerung der geometrischen isomeren wurden Aktivierungsparameter von Ea = 31.8 ± 0.3 kcal/mol und A= 1.1 × 1013 S-1 (ΔH125°C≠ = 31.0 kcal/mol; ΔS125°C≠ = -1.5 cal/Grad × mol) bestimmt. Im bereich von 100-150°C ist die Gleichgewichtskonstante dieser Reaktion K=1.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090337
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  • 53
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    Anisotropieeffekte Konjugierter, cyclischer Systeme, I: NMR-Spektren mesityl- und (9-anthryl)-substituierter Aromaten (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1184-1194 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Anisotropy Effects of Conjugated Cyclic Systems, I: N.M.R. Spectra of Mesityl- and (9-Anthryl)-substituted Aromatic CompoundsThe chemical shift differences Δδ of the n. m. r. signals of o-and p-methyl-groups in mesityl-substituted ring system are a measure of the magnetic anisotropy of aromatic systems. The same applies to the Δδ of the 1-H and 4-H signals of (9-anthryl)-substituents, but to a greater extent. The Δδ values for benzene, mesitylene, and anthracene as well as for pyrimidine, pyrazole, and isoxazole are reported and discussed.
    Notes: Die Differenz der chemischen Verschiebung Δδ von o-und p-Methylgruppen-Signalen in den NMR-Spektren mesitylsubstituierter Ringsysteme ist ein brauchbares Maß für die magnetische Anisotropie aromatischer Verbindungen. Das gleiche gilt noch verstärkt für die 1-H- und 4-H-Signale eines (9-Anthryl)-Substituenten. Δδ-Werte für Benzol, Mesitylen und Anthracen sowie Pyrimidin, Pyrazol und isoxazol werden mitgeteilt und besprochen.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090341
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  • 54
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    Nuceophile Thioacylierung mit Thiocarbamoyllithium-Derivaten von sek. Aminen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1309-1323 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nucleophilic Thioacylation with Thiocarbamoyllithium Derivatives of sec. AminesThe possibilities of direct H/metal-exchange at formyl groups to give unmasked nucleophilic acylating reagents C are considered. In contrast to nitrosamines of sec. amines which show CH-acidity at the saturated carbon next to nitrogen, thioformamides 1 are smoothly metalated at the formyl carbon (lithium diisopropylamide, THF-solvent, -100°C). The title compounds 2 thus available react in good yields especially with carbonyl compounds to produce thioamides 3 and 4 of higher α-hydroxycarboxylic acids. We did not succeed in generating stable lithiocarbamoyls 2d and 2j derived from phenyl substituted thioformamides. As Shown in scheme 1, the diphenylthioformamide anion 2j could be trapped in situ, while it appears to dimerize to 9 in the absence of electrophiles. The isolated products 11-13 can be considered as derivatives of 9.
    Notes: Die Möglichkeiten des direkten H/Metall-Austauschs an Formylgruppen zu unmaskierten nucleophilen Acylierungsmitteln C werden erörtert. Im Gegensatz Nitrosaminen sekundärer Amine wie, F, die neben dem Stickstoff am gesättigten Kohlenstoff CH-acid sind, werden Thioformamide 1 bei Temperaturen um -100°C in Tetrahydrofuran von Lithiumdiisopropylamid glatt am Formyl-C-Atom metalliert. Die so zugänglichen Thiocarbamoyllithium-Verbindungen 2 setzen sich in guten Ausbeuten vor allem mit Carbonylverbindungen um. Bei phenylsubstituierten Thioformamiden gelingt es nicht, für kurze Zeit stabile Lithiumcarbamoyle wie 2d oder 2j zu erzeugen. Wie in Schema 1 gezeigt, kann man das Diphenylderivat 2j aber in situ abfangen; in Abwesenheit eines Elektrophils entsteht offensichtlich ein Dimeres 9. dessen Folgeprodukte 11-13 isoliert wurden.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090412
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  • 55
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    Lichtinduzierte Reaktionen, XI: Photochemische Öffnung linear-konjugierter Cyclohexadienone zu den seco-isomeren Dienylketenen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1332-1345 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Light-Induced Reactions, XI: Photochemical Cleavage of Linearly Conjugated Cyclohexadienones Affording seco-Isomeric Dienyl KetenesThe light-induced cyclo/seco-isomerization of linearly conjugated cyclohexadienones has been studied taking 6,6-dimethyl-2,4-cyclohexadienone (1) as an example. The dienyl ketene 4, kinetically unstable at room temperature, is produced in a spectroscopically simple reaction by u.v. irradiation of 1 in aprotic solvents and can be trapped at temperatures 〈 -60°C. The structure of the transient as well as the heat-induced seco/cyclo-isomerization reforming 1 is proved by means of i.r., n. m. r., and electronic absorption spectroscopy at 〈 -60°C. In addition to or instead of recyclizing 4 adds protic nucleophiles. When 1 is irradiated with u.v. light in the presence of water or cyclohexylamine, 2a or b is formed in a spectroscopically simple reaction in yields of 〉 95%. The constitution of 2a,b and the orientation of ligands at the doubly substituted double bond follow unambiguously from reaction products and spectroscopic data. Since 1* does not show any detectable emission other evidence has to be used to identify the photoreactive electronic isomer and the corresponding spin isomer. The quantum yield, which is independent of the wave length of the exciting light (313 nm: π*, π excitation; 365nm: π*,n excitation), is in accord with the formation of the energetically lower π*,n electronic isomer; the observation that the photoreaction is not quenched by piperylene indicates the occurrence of the singlet spin isomer, although an extremly short-lived triplet spin isomer cannot be rigorously excluded.  -  The equipment for the determination of quantum yields and the i.r. cell for use at variable temperatures are presented in detail.
    Notes: Am Beispiel von 6,6-Dimethyl-2,4-cyclohexadienon (1) wurde die lichtinduzierte Cyclo/seco-Isomerisierung linear-konjugierter Cyclohexadienone studiert. Durch UV-Bestrahlung von 1 in aprotischen Lösungsmitteln bei Temperaturen 〈-60°C läßt sich das in einer spektroskopisch einheitlichen Reaktion entstehende, bei Raumtemperatur kinetisch instabile Dienylketen 4 „einfrieren“. Ir-, NMR- und Elektronenabsorptions-Spektroskopie bei 〈-60°C belegen die Struktur des Transienten sowie die praktisch vollständig verlaufende, wärmeinduzierte seco/cyclo-Isomerisierung zu 1. Zusätzlich zu oder statt der Fähigkeit zu recyclisieren lagert 4 protische Nucleophile an. Wird 1 in Gegenwart von Wasser oder Cyclohexylamin mit UV-Licht bestrahlt, so erhält man in einer spektroskopisch einheitlichen Reaktion 2a oder b mit Ausbeuten von 〉 95%. Ihre Konstitution und Ligandenorientierung an der zweifach substituierten Doppelbindung wurden durch Folgeprodukte und Spektren sichergestellt. Da 1* keine nachweisbare Emission erkennen läßt, müssen für die Identifizierung des photoreaktiven Elektronenisomeren sowie des zugehörigen Spinisomeren andere Indizien herangezogen werden. die von der Wellenlänge des eingestrahlten Lichts (313 nm: π*, π-Anregung; 365 nm: π*, n-Anregung) unabhängige Quantenausbeute spricht für das Energetisch tiefer liegende π*, n-Elektronenisomere, die nicht stattfindende Reaktionslöschung durch Piperylen für das Auftreten des Singulett-Spinisomeren, Ohne daß ein extrem kurzlebiges Triplett-Spinisomeres ausgeschlossen werden kann. Die Apparatur zur Bestimmung der Quantenausbeute sowie die Küvette zur spektroskopischen Messung im IR-Bereich bei variabler Temperatur werden in einzelnen beschrieben.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090414
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    Nucleosidtransformationen, 2: Selektive Oxiranringöffnung von 9-(2,3-Anhydro-β-D-ribofuranosyl)- und 9-(2,3-Anhydro-β-D-lyxofuranosyl)adenin (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1395-1406 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nucleoside Transformations, 2: Selective Oxirane Ring Opening of 9-(2,3-Anhydro-β-D-ribofuranosyl)-and 9-(2,3-Anhydro-β-D-lyxofuranosyl)adenineOxirane ring opening of 9-(2,3-anhydro-β-D-ribofuranosyl)adenine (1) with hydrogen chloride or hydrogen bromide yields 3′-chloro-or 3′-bromo-3′-deoxy-xylo-adenosine (2 or 4). The corresponding 3′-iodo compound 6 was obtained by treating 1 with sodium iodide in the presence of boron trifluoride etherate. Treatment of 9-(2,3-anhydro-β-D-lyxofuranosyl)adenine (8) with boron trifluoride etherate/alkali metal halides gives mixtures of the 3′- and 2′-halogenonucleosides: lithium chloride yields 9 and 10, lithium bromide 11 and 12, sodium iodide 13 and 14. In the mixtures the 3′-halogeno isomers 9, 11 and 13 predominate. The best yield (18%)of a 2′-halogenonucleoside (12) was obtained using lithium bromide. The bromohydrines 11 and 12 can be converted into the epimers of 3′-deoxy- and 2′-deoxyadenosine 15, 16 by treatment with tributyl tin hydride.
    Notes: Oxiranringöffnung von 9-(2,3-Anhydro-β-D-ribofuranosyl)adenin (1) mit Chlor- bzw. Bromwasserstoff gibt 3′-Chlor- bzw. 3′-Brom-3′-desoxy-xylo-adenosin (2 bzw. 4) Die entsprechende 3′-Jodverbindung 6 wird aus 1 durch Einwirkung von Natriumjodid in Gegenwart von Bortrifluorid ätherat erhalten. Die Bortrifluorid-ätherat/Alkalihalogenid-Mischung, auf 9-(2,3-Anhydro-β-D-lyxofuranosyl)adenin (8) angewandt, führt zu einem Gemisch an 3′- und 2′-Halogennnucleosiden: Lithiumchlorid ergibt 9 und 10, Lithiumbromid 11 und 12 Natriumjodid 13 und 14. In den Gemischen überwiegen die 3′-Halogenisomeren 9, 11 bzw. 13 und der größte Prozentsatz (18%) an 2′-Halogennucleosid (12) entsteht mit Lithiumbromid. Die beiden Bromhydrine 11 und 12 lassen sich mit Tributylzinnhydrid in die Epimeren von 3′-Desoxy-und 2′-Desoxyadenosin 15, 16 überführen.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090422
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    Natürlich vorkommende Terpen-Derivate, 58: Über Inhaltsstoffe der Gattung Brickellia (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1436-1445 
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, 58: Constituents of the Genus BrickelliaBesides a dehydronerolidol derivative (2) and a benzofuran derivative (14) several new diterpenes (3, 9, 17, 18, 27, and 28) have been isolated. Their structures are elucidated by spectroscopic methods and some chemical reactions. 9 is an new type of degraded diterpene which, however, is closely related to 3.
    Notes: Neben einem Dehydronerolidol-Derivat (2) und eine, Benzofuran-Derivat (14) werden mehrere neue Diterpene (3, 9, 17, 18, 27 und 28) isoliert. Ihre Strukturen werden durch spektroskopische Methoden und einige chemische Reaktionen geklärt. 9 ist ein neuer Typ eines abgebauten Diterpens, der jedoch in enger Beziehung zu 3 steht.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090428
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  • 58
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    Methylkobaltverbindungen mit nicht chelatisierenden Liganden, III: Dimethyltris (trimethylphosphin)kobalt(II) und seine Derivate (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1453-1464 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Methylcobalt Compounds with NOn-Chelating Ligands, III: Dimethyltris(trimethylphosphine)cobalt(II)and its DerivativesSyntheses and properties of the pentacoordinated d7 -complexes CoX2L3 (L = (CH3)3 P; X = Cl, Br, I, CH3) are reported. Pentacoordination is also attributed to a hydride CoHL4⊕ Cl⊖. The title compound is oxidized by bromine or iodine to give methylcobalt(III) complexes. Weak acids HX cleave both Co-C bonds to form coordination polymers of the composition CoX2 (X = OCH3, OC6H5, acac). As Intermediates the methylcobalt (II) complexes [CoCH3(OCH3)L2]2 and CoCH3(acac)L2 (L = (CH3)3P) are isolated. From the reaction of the title compound with NO diamagnetic methylcobalt complexes are obtained. Primarily formed Co(CH3)2(NO)L2 rearranges via NO insertion into a Co—C bond to give [CoCH3(CH3NO)L2]2 (L = (CH3)3P), a dinuclear complex containing nitrosomethane bridge. The carbonylation reaction yields diamagnetic compounds Co(COCH3)(CO)2L2 and [Co(CO)2L2]2 (L = (CH3)3P) besides acetone.
    Notes: Es wird über Darstellung und Eigenschaften der pentakoordinierten d7-Komplexe CoX2L3 (L = (CH3)3P X = Cl, Br, J, CH3 berichtet. Pentakoordination wird auch einem Hydridkomplex CoHL4⊕Cl⊖ zugeschrieben. Die Oxidation der Titelverbindung mit Brom oder Jod führt zu Methylkobalt(III)-Komplexen. Schwache Säuren HX spalten beide Co—C-Bindungen und bilden Koordinationspolymere der Zusammensetzung CoX2 (X = OCH3, OC6H5, acac). Als Zwischen-stufen werden die Methylkobalt(II)-Komplexe [CoCH3(OCH3)L2]2 und CoCH3(acac)L2 (L = (CH3)3P) isoliert. Aus der Reaktion dr Titelverbindung mit NO erhält man diamagnetische Methylkobaltkomplexe. Primär gebildetes Co(CH3)2(NO)L2 lagert sich unter NO_Einschiebung in eine Co-C-Bindung zu [CoCH3(CH3NO)L2] (L = (CH3)3P) um, einem Zweikernkomplex mit brückenbildenden Nitrosomethan-Liganden. Die Carbonylierung ergibt die diamagnetischen Verbindungen Co(COCH3)(CO)2L2 und [Co(CO)2L2]2 neben Aceton.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090431
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    Metallkomplexe mit Tetrapyrrol- Liganden, XVII: Achtfach koordinierte Zirkonium (IV)- und Hafnium (IV)- Porphine mit axialen 1,3-Diketonat-Liganden (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1477-1485 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes of Tetrapyrrole Ligands, XVII: Octacoordinate Zirconium and Hafnium Porphines Containing Axial 1,3-Diketonate LigandsNew (1,3-diketonato)Metalloporphyrins Zr(OÄP)(acac)2 (3a), Hf(OÄP)-(dbm)2 3c, Hf(OÄP)(dbm)2 (3d), and Zr(OÄP)(acac)OPh (5)2 are prepared and characterized spectroscopically. By analogy to the structurally secured acetato complexes, e. g. Zr(OÄP)(OAc)2 (2a), the central metal ions in 3a-d are regarded as octacoordinate with bidentate axial ligands. This follows from the i.r. and 1H n.m.r. spectra. The cis-configurations 3A of 3a-d and 5A are compared with the configuration 1A, 2A, and 4A of related species.
    Notes: Neue (1,3-Diketonato)metallporphyrine Zr(OÄP)(acac)2 (3a), Hf(OÄP)(acac)2 (3b), Zr(OÄP)-(dbm)2 (3c), Hf(OÄP)(dbm)2 (3d) und Zr(OÄP)(acac)OPh (5) 2 werden dargestellt und spektroskopisch charakterisiert. In Analogie zu den strukturell gesicherten Acetatkomplexen, z. B. Zr(OÄP)(OAc)2 (2a), wird den Zentralmetall-lonen in 3a-d die Koordinationszahl 8 mit zweizähnig gebundenen Axial-Liganden zugeschrieben. Dies ergibt sich aus den IR- und 1H-NMR-Spektren. Die cis-Konfigurationen 3A von 3a-d und 5A werden mit den Konfigurationen 1A 2A und 4A einiger verwandter Spezies verglichen.
    Additional Material: 3 Tab.
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    Die Phosphoran-Phosphin-Umlagerung; Mechanismus und Stereochemie (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1497-1505 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Phosphorane-Phosphine-Rearrangement; Mechanism and StereochemistryOrganylbis(4,4′-dimethyl-2,2′-biphenylylene)phosphoranes 6 rearrange Thermally to two types of phosphines 7 and 13. Stereochemically these can be treated as bridged biphenyl system or tetrabenzophosphonine systems on the one hand and as biphenyl systems which are substituted in their 2,2′-position by large groupe on the other hand.
    Notes: Organylbis(4,4′-dimethyl-2,2′-biphenylylen)phosphorane 6 lagern thermisch zu zwei Phosphin Typen 7 und 13 um, die stereochemisch als verbrückte Biphenyl-Derivate oder Tetrabenzophosphonin-System einerseits und als mit großen Gruppen 2,2′-disubstituierte Biphenyl-Derivate andererseits behandelt werden können.
    Additional Material: 2 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090436
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  • 61
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    Natürlich vorkommende Terpen-Derivate, 59: Über neue Diterpene aus Dimorphotheca pluvialis Moench (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1446-1449 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Naturally Occurring Terpene Derivatives, 59: On New Diterpenes from Dimorphotheca pluvialis Moench.Besides small amounts of known acetylenes the investigated plant contains five new diterpenic acids (5, 7, 9, 11 and 12), their structures being elucidated by spectroscopic methods. The relationship to these compounds to the diterpenes in other genera of the same tribe are discussed.
    Notes: Neben kleinen Mengen bekannter Acetylene enthält die untersuchte Pflanze fünf neue Diterpen-säuren (5, 7, 9, 11 und 12 deren Strukturen durch spektroskopische Methoden geklärt werden. Die Beziehungen dieser Verbindungen zu den Diterpenen in anderen Gattungen der gleichen Tribus werden diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090429
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  • 62
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    Metall-Komplexe mit Tetrapyrrol-Liganden, XVI: Methoxonitrosyl(octaäthylporphinato)osmium (II) und verwandte Osmiumkomplexe des Octaäthylporphins (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1465-1476 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Complexes of Tetrapyrrole Ligands, XVI: Methoxonitrosyl(octaethylporphinato)osmium(II)and related Osmium Complexes of OctaethylporphineThe new diamagnetic nitrosyl(octaethylporphinato)osmium (II) derivatives Os(OÄP)NO· L′(2c-e; L′ = NO, OMe, or F)2 are prepared and characterized spectroscopically. According to the electronic absorption, i.r., and 1H n.m.r. spectra fo the bis(methoxo)osmium(IV) derivative Os(OÄP)(OMe)2 (2f) and of the nitrosyls 2d, e, the latter contain OsII with an linear N≡O⊕ group and an anion OMe⊖ or F⊖ in the trans position. The strong π-acceptor NO⊕ and the strong π-donator OMe⊖ (or F⊖) effect a push-pull stabilization of the system. The dinitrosyl 2c probably shows the rare trans-array of linear M — N ≡ O⊕ and an bent M — N = O⊖ unit. The porphine ligand acts as a probe of the π-acceptor capacity of the axial ligands; in the series Py 〈 N2 〈 CO 〈 NO⊕ an increasing bathochromic shift of the α-band in the spectral region from 510 to 580 nm obtains.
    Notes: Neue, diamagnetische Nitrosyl(octaäthylporphinato)osmium(II)-Derivate OS(OÄP)NO· L′(2c bis e; L′ = NO, OMe oder F)2 werden dargestellt und spektroskopisch charakterisiert. Nach einem Vergleich der Elektronenanregungs-, IR- und 1H-NMR-Spektren des Bis(methoxo)osmium(IV) Derivats Os(OÄP)(OMe)2 (2f) und der Nitrosyl 2d, e liegt in der letzteren Os11 mit linearer N ≡ O⊕-Gruppierung und trans-ständigem Anion OMe⊖ oder F⊖ vor. Der starke π-Acceptor NO⊕ und der starke π-Donator OMe⊖ (oder F⊖) bewirken eine „push-pull“ -Stabilisierung des Systems. Im Dinitrosyl 2c light wahrscheinlich die seltene trans-Anordnung einer Linearen M—N≡O⊕- und einer gewinkelten M—N=O⊖-Einheit vor. Der Porphin-Ligand wirkt als Sonde für die π-Acceptorstärke der axialen Liganden; in der Reihe Py 〈 N2 〈 CO 〈 NO⊕ erfolgt eine zunehmend bathochrome Verschiebung der α-Bande im Spektralbereich von 510 bis 580 nm.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090432
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    Reaktionen mit Cyclobutendionen, XLII: Umsetzung des Diphenylcyclobutendions mit Methylenphosphoranen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1506-1515 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Cyclobutenediones, XLII: Reactions of Diphenylcyclobutenedione with MethylenephosphoranesDiphenylcylobutenedione (1a) reacts with the methylenephosphoranes 4a-z to give the substituted 4-methylene-2,3-diphenyl-2-cyclobuten-1-ones 5a-p, t-z and 5u′-z. Structural proof of the products is given by spectroscopic methods. The unsubstituted compound 5r is not obtained. Wittig reaction of (2,5-dimethoxyphenyl)phenylcyclobutenedione (1d) with 4u proceeds nearly stereoselectively to give 9D.
    Notes: Diphenylcyclobutendion (1a) reagiert mit den Methylenphosphoranen 4a-z zu substituierten 4-Methylen-2,3-diphenyl-2-cyclobuten-1onen 5a-p, t-z bzw. 5u′-z, deren Struktur spektroskopisch gesichert wird. Die Synthese des Grundkörpers 5r gelingt nicht. Die Wittig-Reaktion am (2,5-Dimethoxyphenyl) phenylcyclobutendion (1d) mit 4u verläuft annähernd stereoselektiv zu 9D.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090437
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    Notiz zur Umwandlung schwefelverbrückter Carbonylkomplexe des Mangans und Rheniums mit CO unter Druck (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1569-1571 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090442
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  • 65
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    Notiz über zwei neue Cumarin-Derivate aus Machaeranthera scabrella (Greene) Shinners (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1584-1585 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090447
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  • 66
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    Stereospezifische Br/O Ac-Substitution an syn- und anti- 11- Brom-2,3-benzotricyclo[4.4.1.0]undecen-4-onen. Die Retentive Substitution am Dreiring (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1589-1600 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereospecific Br/O Ac-Substitution at syn- and anti-11-Bromo-2.3-benzotricyclo[4.4.1.0] undecen-4-one. The Retentive Substitution at CyclopropanePossible mechanisms A - G of the nucleophilic substitution at cyclopropane carbons are discussed. Special attention is given to the retentive replacements D and E which hitherto have not been observed. A smooth, stereospecific Br/OAc-substitution under typical SN2-type conditions is described for the syn/anti-isomers 6a and 7a. From the n.m.r. spectra of the four compounds 6a, b and 7a, b it is concluded that these substitutions occur under retention of configuration which is confirmed by X-ray analysis of the crystalline pair 7a, b.
    Notes: Mögliche mechanismen A - G der nucleophilen Substitution an Cyclopropanen werden unter besonderer Berücksichtigung der bisher nicht beobachteten Retention nach D oder E diskutiert. Am Beispiel der syn/anti-Isomeren 6a und 7a wird eine Br/OAc-Substitution beschrieben, die stereospezifisch unter typischen SN2-Bedingungen erfolgt. Aus den NMR-Spektren der vier Verbindungen 6a, b und 7a, b kann man schließen diese Substitutionen unter Retention der Konfiguration ablaufen. Die Röntgenstrukturanalyse des kristallinen Paares 7a, b bestätigt dies.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090501
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  • 67
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    Notiz über lie Darstellung von Carbenanalogen Germylenen mit Arylthio- und Alkylthioliganden (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1575-1576 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090444
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  • 68
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    Untersuchungen über Verbindungen mit Berban-Gerüst, III. Regiospezifische Synthese der Despyrroloyohimbinone durch Dieckmann-Kondensationen von ungesättigten Estern (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1724-1736 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation on the Chemistry of Berbans, III. Regiospecific Synthesis of Depyrroloyohimbinone by Dieckmann Condensation of unsaturated EstersDieckmann-ring closure of unsaturated-saturated esters (1-4) leads to products (6-10) whose stereochemistry is predominantly controlled by the configuration of the starting material. The reaction is useful for the regio-and stereoselective construction of berban derivatives.
    Notes: Untersuchungen des Dieckmann-Ringschlusses von gesättigt-ungesättigten Dicarbonsäureestern (1-4) zeigen, daß die Produkte (6-10) vor allem von der Konfiguration des Ausgangsmaterials abhängen. Die Reaktion ist zum regioselektiven und stereoselektiven Aufbau von Berban-Derivaten sehr nützlich.
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    URL: http://dx.doi.org/10.1002/cber.19761090516
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  • 69
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    Carben-Reaktionen, VI. Addition von Dimethoxycarben an Heterodiene (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1759-1768 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carbene Reactions, VI. Addition of Dimethoxycarbene to HeterodienesDimethoxycarbene (2) has been added to N-acylimines of hexafluoroacetone (6) forming oxazolines 7. It has been shown by competition experiments, that free dimethoxycarbene is generated in the reactions of 6 with trimethyl orthoformate (3).
    Notes: Dimethoxycarben (2) addiert sich an eine Reihe von N-Acyliminen des Hexafluoracetons (6) zu den Oxazolinen 7. Durch Konkurrenzversuche konnte gezeigt werden, daß bei der Einwirkung von 6 auf Orthoameisensäureester (3) freies Dimethoxycarben (2) auftritt.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090519
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  • 70
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    Umlagerung von bicyclo[5.1.0]octa-2,4-dien-Derivaten durch Säuren (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1856-1867 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement of Bicyclo[5.1.0]octa-2,4-diene Derivatives by AcidsThe addition of acids to bicyclo [5.1.0] octa-2,4-dienes mat proceed with rearrangement to bicyclo-[3.2.1] oct-2-enes. A donor substituent at C-8 is essential for this transformation, as shown by the decreasing tendency of 1 (NHCOCH3), 19 (OCH3), and (33) H) to form bicyclo [3.2.1] octenes. Cycloheptadienylmethyl derivatives are formed in a competing reaction. Regardless of the configuration of the starting material (19a, b), 4-exo-8-anti-substituted bicyclo [3.2.1] oct-2-enes are obtained. Configurations were established by n. m. r. and by unequivocal synthesis of 25. The reaction is thought to involve protolysis of the cyclopropane ring to a homoallyl cation 36 which undergoes cyclization to 38 (formally a 1,4 shift).
    Notes: Die Addition von Säuren an Bicyclo[5.1.0] octa-2,4-diene kann unter Umlagerung zu Bicyclo [3.2.1] oct-2-enen verlaufen. Ein Donor-Substituent an C-8 ist Voraussetzung für diese Umwandlung, wie aus der abnehmenden Tendenz von 1 (NHCOCH3), 19 (OCH3) und 33 (H) zur Bildung von Bicylo [3.2.1] octenen hervorgeht. In einer konkurrierenden Reaktion entstehen Cycloheptadienylmethyl-Derivate. Unabhängig von der Konfiguration des Ausgangsmaterials (19a, b) werden 4-exo-8-anti -substituierte Bicyclo [3.2.1.] oct-2-ene erhalten. Die Konfigurationen wurden durch NMR und eindeutige Synthese von 25 festgelegt. Die Reaktion beginnt wahrscheinlich mit der Protolyse des Cyclopropanrings zum Homoallylkation 36, das zu 38 cyclisiert (formal eine 1,4-Verschiebung).
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    URL: http://dx.doi.org/10.1002/cber.19761090528
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    [1,5]-Sigmatrope Esterverschiebung am Pentakis (methoxycarbonyl)cyclopentadien-System (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1918-1927 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [1,5]-Sigmatropic Ester Shift in the Pentakis(methoxycarbonyl)cyclopentadiene System5-Alkyl-pentakis(methoxycarbonyl)cyclopentadienes (1) equilibrate at 100°C with 1-alkyl-pentakis(methoxycarbonyl)cyclopentadienes (2) via 1,5-sigmatropic ester shifts. At higher temperatures a further ester shift generates the 2-alkyl-pentakis(methoxycarbonyl)cyclopentadienes (3). The intramolecular character of the rearrangement is demonstrated by crossover experiments.
    Notes: 5-Alkyl-pentakis(methoxycarbonyl)cyclopentadiene (1) äquilibrieren bei 100°C durch [1,5]-sigmatrope Esterverschiebung mit 1-Alkyl-pentakis(methoxycarbonyl)cyclopentadienen (2). Bei höheren Temperaturen führt eine weitere Esterverschiebung zu 2-Alkyl-pentakis(methoxycarbonyl)cyclopentadienen (3). Der intramolekular Verlauf der Umlagerung wurde durch Kreuzungsversuche gesichert.
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    URL: http://dx.doi.org/10.1002/cber.19761090533
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  • 72
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    Über Phosphazene, LIV. Synthese und Struktur von 2,2′-Dimethyl-octaphenyl-2,2′-bi[cyclotri(phosphazen)yl] (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1911-1917 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phosphazenes, LIV. Synthesis and Structure of 2,2′-Dimethyl-octaphenyl-2,2′-bi[cyclotri(phosphazen)yl]Metallation fo the hydrido-cyclophosphazene 1 and subsequent reaction with the chloro-cyclo-phosphazene 4 yields the title compounds 6. This is also obtained by reduction of 4 and from the disproportionation of the phosphino-cyclophosphazen 5. 6 has a centrosymmetric structure (determined by X-ray analysis), which may be compared to that of N3P3(C6H5)6 in respect to the phosphazene rings and to (CH3)4P2S4 as far as the central diphosphane part is concerned. I. r., 31 P, and 1 H n. m. r. spectra are discussed.
    Notes: Die Titelverbindung 6 wird aus dem Hydrido-cyclophosphazen 1 durch Metallieren und Umsetzen mit dem Chlor-cyclophosphazen 4 dargestellt. Sie bildet sich auch durch Reduktion von 4 und Disproportionieren des Phosphino-cyclophosphazens 5. 6 besitzt zentrosymmetrische Struktur (durch Röntgenstrukturanalyse bestimmt), die sich bezüglich des Ringgerüsts mit N3P3(C6H5)6 und bezüglich der zentralen Diphosphan-Gruppierung mit (CH3)4P2S2 vergleichen läßt. IR-, 31P- und 1H-NMR-Spektren werden diskutiert.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19761090532
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    Zur Synthese thioanaloger Cannabis-Derivate (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2164-2174 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Thio-CannabinoidsThe base-catalyzed reaction of pulegone (3) with the thiophenols 4a-d yields the γ-ketothioethers 5a-d, the cyclization of which produces the dibenzo[b,d]thiopyrans 6a-c. The cyclization of 5a and b also produces the thioxanthenes 7a, b as by-products. The thiopyrans 6a-c as well as 6a-c can be oxidized to the sulfones 10a-c with m-chloroperbenzoic acid. 6a-c can be demethylated to the free thio-analogous Δ6a(10a)-cannabinoid derivatives 11a-f by sodium ethanethiolate. Dehydrogenation of 11a-c by sulfur yields the analogous cannabinoids 15a-c. The structures of the compounds obtained are characterized by n. m. r., i. r., and mass spectra.
    Notes: Pulegon (3) wird basenkatalysiert an die Thiophenole 4a-d zu γ-Ketothioäthern 5a-d addiert, deren Cyclisierung Dibenzo[b,d]thiopyrane 6a-c liefert. Als Nebenprodukte entstehen bei der Cyclisierung von 5a und b auch die Thioxanthene 7a, b. Die Thiopyrane 6a-c lassen sich mit m-Chlorperbenzoesäure zu den Sulfonen 10a-c oxidieren. Sowohl 6a-c als auch 10a-c Können mit Natrium-äthanthiolat zu den freien thioanalogen Δ6a(10a)-Cannabis-Derivaten 11a-f demethyliert werden. Mit der Dehydrierung von 11a-c durch Schwefel erhält man die analogen Cannabinole 15a-c. Die Strukturen der erhaltenen Verbindungen werden durch NMR-, IR- und MS-Spektren Charakterisiert.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090623
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    Polycarbonylverbindungen, XVI. Darstellung und Struktur des Schwefelanalogons des Quadratsäure-Dianions K2[C4S4]·H2O (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2208-2215 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polycarbonyls, XVI. Synthesis and Structure of the Sulfur Analogue of Squaric Acid Dianion K2[C4S4·H2O]Sulfhydrolysis of 1,2- or 1,3-dithiosquaric acid diamides yields the sulfur analogue 4 of squaric acid dianion, the first member of the „thioxocarbons“. Spectroscopic data and intramolecular distances determined by X-ray diffraction indicate a symmetrical, delocalised electron system with C—C- and C—S-bond orders of n - 1.25 and 1.5, resp.
    Notes: Durch Sulfhydrolyse von 1,2- bzw. 1,3-Dithioquadratsäure-bisamiden entsteht das Schwefelanalogon 4 des Quadratsäure-Dianions, der erste Vertreter der „Thioxokohlenstoffe“. Spektroskopische Daten und die aus einer röntgenographischen Strukturbestimmung erhaltenen innermolekularen Bindungslängen weisen auf ein symmetrisches, delokalisiertes Elektronensystem mit C — C- bzw. C — S-Bindungsordnungen von n = 1.25 bzw. 1.5 him.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090627
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  • 75
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    Derivate des Borabenzols, VIII: Ein neuer Weg zu Alkalimetallborinaten. Synthesen von Ruthenium-, Osmium-, Rhodium- und Platin-Verbindungen mit Borinat-Liganden (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2382-2388 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Borabenzene Derivatives, VIII: A New Route to Alkalimetal Borinates. Syntheses of Ruthenium, Osmium, Rhodium, and Platinum Compounds with Borinate LigandsDegradation of bis(borinato)cobalt complexes Co(C5H5B — R)2(R = C6H5, CH3) with alkalimetal cyanides MCN (M = Na, K) yields alkalimetal borinates M[C5H5B — R]. These are versatile synthetic intermediates as demonstrated by the syntheses of Ru(C5H5B — R)2 (R = C6H5, CH3), Os(C5H5B — C6H5)2, Rh(1,5-C8H12)(C5H5B — R), and Pt(CH3)3(C5H5B — C6H5).
    Notes: Der Abbau von Bis(borinato)kobalt-Komplexen Co(C5H5B — R)2 (R = C6H5, CH3) mit Alkalimetallcyaniden MCN (M = Na, K) liefert Alkalimetallborinate M[C5H5B — R]. Diese sind vielseitige Synthesezwischenprodukte, wie mit der Darstellung von Ru (C5H5B — R)2 (R = C6H5,CH3), Os(C5H5B — C6H5)2, Rh(1,5-C8H12)(C5H5B — R) und Pt(CH3)3((C5H5B — C6H5) gezeigt wird.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090704
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  • 76
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    Kondensationsreaktionen von Schwefeltetrafluorid mit Iminophosphoranen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2442-2455 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensation Reactions of Sulfur Tetrafluoride with IminophosphoranesThe reaction of iminophosphoranes with SF4 is qualified for the syntheis of symmetric and unsymmetric substituted sulfur diimides 1a, b and bis(sulfur diimides) 4a - d, bis(iminosulfurdifluorids) 3a - e, cyclic sulfur diimides 6a - d, f, and 1,2,5-thiadiazoles 10a - e. Some reactions of the new substances are described.
    Notes: Die Umsetzung von Iminophosphoranen mit SF4 eignet sich zur Darstellung von symmetrisch und unsymmetrisch substituierten Schwefeldiimiden 1a, b und Bis(schwefeldiimiden) 4a - d, Bis(iminoschwefeldifluoriden)3a-e, cyclischen Schwefeldiimiden 6a -d, f und 1,2,5-Thiadiazolen 10a - e. Einige Reaktionen der neuen Substanzklassen werden hier beschrieben.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090711
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  • 77
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    Basisches Verhalten von Epoxiden in Gegenwart von Halogenid-Ionen, IV: gem-Difluorcyclopropane aus Chlordifluormethan und Alkanolat-Ionen in geringer Konzentration (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2351-2369 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Basic Behavior of Epoxides in the Presence of Halide Ions, IV. gem-Difluorocyclopropanes from Difluorocarbene, Generated from Chlorodifluoromethane and Alkoxide Ions in Small Concentrationgem-Difuorocyclopropanes are formed in high yields from chlorodifluoromethane, alkanolate ions, and reactive alkenes (table 1), provided that the concentration of alkanolate is small. Alkanolates of the necessary small concentration are found in a solution of halide ions in epoxides(eq. (3)). Suitable epoxides are (chloromethyl)oxirane and oxirane (ethylene oxide). The conversion is increased by increasing concentration of chloride ions (fig. 1, curve A) and decreased by increasing concentration of alcohol (tab. 4). With less reactive olefines are formed not only the desired gem-difluorocyclopropanes but also the products of reaction between difluorocarbene and alcohols (compounds 9, 11, 12). The structures both of the gem-difluorocyclopropanes and of the by-products are determined mainly by n.m.r. (1H, 13C, 19F).
    Notes: gem-Difluorcyclopropane entstehen in hohen Ausbeuten aus Chlordifluormethan, Alkanolat und reaktiven Alkenen (Tab. 1), sofern die Konzentration an Alkanolat sehr klein ist. Die Alkanolat-lonen in der erforderlichen geringen Konzentration enthält eine Lösung von Halogenid-Ionen in Epoxiden (Gi. (3)). Gebräuchliche Epoxide sind (Chlormethyl)oxiran und Oxiran (Äthylenoxid). Der Umsatz wird durch zunehmende Chlorid-Ionen-Konzentration erhöht (Abb. 1, Kurve A)und durch Zunehmende Alkohol-Konzentration Herabgesetzt (Tab. 4). Mit weniger reaktiven Alkenen erhält man nicht nur die gewünschten gem-Difluorcyclopropane, sondern auch Produkte der Umsetzung zwischen Difluorcarben und Alkoholen, wobei die Verbindungen 9, 11 und 12 entstehen. Die Strukturen der gem-Difluorcyclopropane und der Nebenprodukte werden hauptsächlich durch die NMR-Spektren (1H, 13C, 19F) belegt.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090702
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  • 78
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    Darstellung und Stereochemie von 1,2,3,4,9-Pentaphenyl-9H-tribenzo[b,d,f]phosphepin (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2405-2419 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Stereochemistry of 1,2,3,4,9-Pentaphenyl-9H-tribenzo[b,d,f]phosphepinThe synthesis of conformational isomeric tribenzo[b,d,f]phosphepin oxides (7A, B) has been achieved by transition metal-catalysed trimerisation of the triarylphosphinoxide bisacetylene 4. The use of dichlorobis(benzonitrile)palladium affords the novel palladium phosphinoxide complex 8. The free enthalpie of activation for the conformational change is determined in the case of the tribenzo[b,d,f]phosphepin oxides. Reduction with trichlorosilane affords the conformationally isomeric tribenzo[b,d,f]phosphepins 11A,B. The steric course of this reduction is discussed in detail. The kinetic data of the ringinversion are determined by the use of 31 P n.m.r. spectroscopy. With methyl iodide, the phosphonium salts 12A, B are formed from the tribenzo[b,d,f]phosphepins, which correspond formally to the tribenzotropylium cation. The lowered free enthalpie of activation of the ring inversion is interpretable by a cyclic conjugation in the transition state.
    Notes: Durch übergangssmetallkatalysierte Acetylen-Trimerisierung des Triarylphosphinoxid-Bisacetylens 4 mit Tolan gelingt die Darstellung konformationsisomerer Tribenzo[b,d,f]phosphepinoxide (7A,B). Die Verwendung von Bis(benzonitril)palladiumdichlorid führt zu dem bisher unbekannten Phosphinoxid-Palladium-Komplex 8. Die Freie Aktivierungsenthalpie für die Konformations-änderung der Tribenzo[b,df]phosphepinoxide wird bestimmt. Mit Trichlorsilan erhält man die konformationsisomeren Tribenzo[b,df,]phosphepine 11A, B wobei der sterische Reduktionsverlauf näher diskutiert wird. Die kinetischen Daten der Ringinversion werden mit Hilfe der 31P-NMR-Spektroskopie ermittelt. Die Tribenzo[b,d,f]phosphepine liefern mit Methyljodid Phosphoniumsalze (12A, B), die formal dem Tribenzotropylium-Kation entsprechen. Eine Erniedrigung der Freien Aktivierungsenthalpie bei der Ringinversion deutet auf eine cyclische Konjugation im Übergangszustand.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090707
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  • 79
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    Polycyanbenzole V: Ein einfacher Zugang zum Tetracyanhydrochinon. Darstellung der 1,4-Dihalogen-tetracyanbenzole (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2462-2468 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polycyanobenzenes, V: An Easy Access to Tetracyanohydroquinone. Preparation of the 1,4-Dihalogeno-tetracyanobenzenesChloranil (6), bromanil (1), 2,5-dibromo-3,6-dimethoxy-p-benzoquinone (4), and 2,3-dichloro-5,6-dicyano-p-benzoquinone (8) react with cyanide ions to give the corresponding ortho-dicyanosubstituted hydroquinones 2,5, and 7 as well as tetracyanohydroquinone (3). With phosphoryl halides/pyridine, 3, its dimethyl ether 3a, and its diacetate 3b yield 1,4-dichloro- (15) and 1,4-dibromo-2,3,5,6-tetracyanobenzene (16). Similarly 1,3,5-tricyano-2,4,6-trimethoxybenzene (17) is converted into 1,3,5-tribromo-24,6-tricyanobenzene (18). Reaction of 15 with potassium fluoride or potassium iodide yields 1,2,4,5-tetracyano-3,6-difluorobenzene (19) and 1,2,4,5-tetracyano-3,6-diiodobenzene (20), resp.
    Notes: Chloranil (6), Bromanil (1), 2,5-Dibrom-3,6-dimethoxy-p-benzochinon (4) und 2,3-Dichlor-5,6-dicyan-p-benzochinon (8) reagieren mit Cyanid-Ionen zu den entsprechenden ortho-dicyan-substituierten Hydrochinonen2,5 und 7 sowie zum Tetracyanhydrochinon (3). Durch Einwirkung von Phosphorylhalogenid/Pyridin auf 3, dessen Dimethyläther 3a oder das Diacetat 3b entsteht 1,4-Dichlor-(15) bzw. 1,4-Dibrom-2,3,5,6-tetracyanbenzol (16). Nach der gleichen Methode wird aus 1,3,5-Tricyan-2,4,6-trimethoxybenzol (17) das 1,3,5-Tribrom-2,4,6-tricyanbenzol (18) erhalten. Die Umsetzung von 15 mit Kaliumfluorid bzw. Kaliumjodid ergibt 1,2,4,5-Tetracyan-3,6-difluorbenzol (19) bzw. 1,2,4,5-Tetracyan-3,6-dijodbenzol (20).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090713
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    Untersuchungen an Stoffwechselprodukten von Mikroorganismen, XI: Flexirubin, ein neuartiges Pigment aus Flexibacter elegans (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2490-2502 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on Metabolites of Microorganisms, XI: Flexirubin, a Novel Pigment from Flexibacter elegansUp to now only carotinoid pigments have been found in ‘gliding bacteria’ of the Flexibacter/Cytophaga-type. The main pigment of Flexibacter elegans was now isolated by chromatographic separation and named flexirubin. Its structure was deduced to be 7. Flexirubin is the first member of a new class of bacterial pigments. In respect to the chemical structure this class is characterized by a polyene-carboxylic acid chromophore, which is esterified with a phenol carrying a long aliphatic side chain.
    Notes: Bisher wurden in den „Gleitenden Bakterien“ vom Typ Flexibacter/Cytophaga nur Carotinoide aufgefunden. Chromatographische Trennung des Farbstoffkomplexes aus Flexibacter elegans führte nun zur Isolierung des Hauptpigmentes Flexirubin, für das Struktur 7 abgeleitet wird. Flexirubin ist der erste Vertreter einer neuartigen Gruppe von Bakterienpigmenten, die sich strukturell durch einen Polyencarbonsäure-Chromophor in Esterbindung mit einem Phenol, das eine lange Alkyl-Seitenkette trägt, auszeichnet.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090717
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    Stabile Methylnickelverbindungen, VII: Reversible Überführung in Acetylnickelverbindungen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2524-2532 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stable Methylnickel Compounds, VII: Reversible Transformation into Acetylnickel CompoundsReaction of the methylnickel complexes trans-L2(CH3)NiX and L(CH3) Ni(acac) with carbon monoxide under normal conditions leads to the likewise square-planar σ-acetylnickel complexes trans-L2(CH3CO)NiX and L(CH3CO)Ni(acac), resp. (L = (CH3)3 P; X = Cl, Br, J, O2CCH3). Tetrakis(trimethylphosphine)nickel mobilizes and abstracts CO from the acetylnickel function with formation of carbonyltris(trimethylphosphine)nickel leading back to the corresponding methylnickel complexes. The rate of decarbonylation increases in the order acac 〈 O2CCH3 〈 Cl 〈 Br 〈 I. Strong protic acids liberate CO and CH4, from the NiCOCH3 group, but not acetaldehyde. The oxidative addition of acetyl chloride to trimethylphosphine complexes of zerovalent nickel is modified to give exclusively L2(CH3CO)NiCl.
    Notes: Die Reaktion der Methylnickelkomplexe trans-L2(CH3)NiX und L(CH3)Ni(acac) mit Kohlenmonoxid führt unter Normalbedingungen zu den gleichfalls quadratisch-planaren σ-Acetylnickelkomplexen trans-L2(CH3CO)NiX und L(CH3CO)Ni(acac) (L = (CH3)3P;X = Cl, Br, J, O2CCH3). Tetrakis(trimethylphosphin)nickel mobilisiert und übernimmt CO aus der Acetylnickelfunktion, wodurch neben Carbonyltris(trimethylphosphin)nickel der entsprechende Methylnickelkomplex zurückgebildet wird. Die Geschwindigkeit der Decarbonylierung wächst in der Reihe acac 〈 O2CCH3 〈 Cl 〈 Br 〈 J. Beim Angriff starker Protonensäuren auf die NiCOCH3-Gruppe entstehen CO und CH4, nicht aber Acetaldehyd. Die oxidative Addition von Acetylchlorid an Trimethylphosphinkomplexe des nullwertigen Nickels wird so modifiziert, daß nur L2(CH3CO)NiCl entsteht.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090721
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    Übergangsmetall-Carbin-Komplexe, XIII: Synthese und Eigenschaften von mer-Tricarbonylhalogeno-(methylcarbin)(trimethylphosphin bzw. -arsin, -stibin)-chrom-Komplexen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2547-2557 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition Metal Carbyne Complexes, XIII: Syntheses and Properties of mer-Tricarbonylhalogeno(methylcarbyne)(timethylphosphine or -arsine, -stibine)chromium Complexescis-Tetracarbonyl(methoxymethylcarbene)(trimethylphosphine or -arsine, -stibine)chromium(0) complexes react with boron trihalides BX3 (X = Cl, Br, I) under splitting off of the methoxy group and substitution of a CO ligand by a halide ion. In the resulting carbyne complexes the CO groups are meridionally arranged. The halogen atom is trans-positioned to the carbyne ligand. The spectroscopic data of the new compounds are discussed.
    Notes: cis-Tetracarbonyl(methoxymethylcarben)(trimethylphosphin bzw. -arsin, -stibin) chrom(0)-Komplexe reagieren mit Bortrihalogeniden BX3 (X = Cl, Br, J) unter Abspaltung der Methoxygruppe und Substitution eines CO-Liganden durch ein Halogenid-Ion. In den so erhältlichen Carbinkomplexen sind die CO-Gruppen meridional angeordnet, das Halogenatom befindet sich in trans-Stellung zum Carbinliganden. Die spektroskopischen Daten der neuen Verbindungen werden diskutiert.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19761090725
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    Mikrobiologische Umwandlungen nichtsteroider Strukturen, VIII: Mikrobiologische Umwandlungen von (±)-8-Hydroxy-6α, 11α-dimethyl-3-alkyl-oder-3-acyl-1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocinen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 2657-2669 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Microbiological Transformations of Nonsteroidal structures, VIII: Microbiological Transformations of (±)-8-Hydroxy-6α, 11α-dimethyl-3-alkyl-or-3-acyl-1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocins±-8-Hydroxy-6α, 11α-dimethyl-3-(3-methylbutyl)1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocin (1) is transformed microbiologically to the 3′-hydroxy-compound (2). The N-benzoate of the corresponding 3-desalkyl-compound is hydroxylated by several fungi in 1α-position (9). The hydroxylation of the 4- and 4′-position (11, 12), the oxidation to a 3- (3,4-epoxy-1,5-cyclohexadiene-carbonyl) structure (13) and the formation of a 8-pentosyl glycoside (10) are sidereactions. The fermentation of the N-cyclohexylcarbonyl derivative (14) leads to hydroxylations of the cyclohexylring in the axial 3′-and 4′(15 and 17) and in the euqatorial 4′ -position (16).
    Notes: ±-8-Hydroxy-6α, 11α-dimethyl-3-(3-methylbutyl)-1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocin (1) wird mikrobiologisch zur 3′-Hydroxyverbindung (2) umgewandelt. Das N-Benzoylderivat (8) der entsprechenden 3-Desalkylverbindung wird durch unterschiedliche Fungi in 1α-Stellung (9) hydroxyliert. Die Hydroxylierung der 4- und 4′-Stellung (11,12), die Oxidation zu einer 3-(3,4-Epoxy-1,7-cyclohexadiencarbonyl)-struktur (13) und die Bildung eines 8-Pentosylglycosids (10) treten als Nebenreaktionen auf. Bei der Fermentation des N-Cyclohexylcarbonyl-Derivates (14) entstehen Hydroxylierungsprodukte des Cyclohexylrestes in den axialen 3′- und 4′-Positionen (15 und 17) und in der äquatorialen 4′-Position (16).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090802
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    Redoxreaktionen zwischen Tri-tert-butylphosphin und Element(IVb)-tetrachloriden: Tri-tert-butylchlorphosphonium-Salze (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3017-3024 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Redox Reactions between Tri-tert-butylphosphine and Element(IVb)-Tetrachlorides: Tri-tert-butylchlorophosphonium SaltsTri-tert-butylphosphine reacts with equimolare amounts of germaniumtetrachloride or tintetrachloride yielding new compounds with the formula (t-C4H9)3PMCl4 (M=Ge, Sn). The Comparison of n. m. r., infrared-, and raman spectra as well as the conductivities with the corresponding data of tri-tert-butyldichlorophosphorane, prepared, using tri-tert-butylphosphine and Chlorine, indicates, that all these compounds are tri-tert-butylchlorophosphine salts. Tri-tert-butyl-chlorophosphonium salts are also available, by the reaction of tri-tert-butyldichlorophosphorane with various element chlorides.
    Notes: Tri-tert-butylphosphin reagiert mit Germaniumtetrachlorid und Zinntetrachlorid im Molverhältnis 1:1 zu neuen Verbindungen der Zusammensetzung (t-C4H9)3PMCl4 (M=Ge, Sn). Der Vergleich von Kernresonanz- und Schwingungsspektren sowie von Leitfähigkeiten mit den entsprechenden Daten von Tri-tert-butyldichlorphosphoran, das aus Tri-tert-butylphosphin mit elementarem Chlor erhalten wurde, zeigt, daß die Verbindungen als Tri-tert-butylchlor-phosphonium-Salze vorliegen. Weitere Verbindungen dieses Typs sind aus Tri-tert-butyldichlor-phosphoran mit verschiedenen Elementchloriden zugänglich.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090906
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  • 85
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    Notiz zur Synthese des [2,6-Bis(methoxycarbonyl)-5,6-dihydro-4H-pyran-4-yliden]essigsäure-methylesters (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3486-3488 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091028
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  • 86
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    Kernresonanzspektroskopische Untersuchungen an Bor-Verbindungen, XI. 14- und 11B-Kernresonanzstudien an Borazinen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3480-3485 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: N. M. R. Spectroscopic Investigations on Boron Compounds. XI14N- and 11B-Nuclear Magnetic Resonance Studies on Borazines14N and 11B chemical shifts of 30 borazines can be interpreted in terms of delocalised pz electron pairs of the nitrogen atoms in the ring system. Calculated π charge densities at the N-atoms correlate linearly with δ14N. Substituents effects are discussed.
    Notes: Die 14N- und 11B-chemischen Verschiebungen von 30 Borazinen lassen sich im Sinne einer Delokalisierung der pz-Elektronenpaare der Stickstoffatome im Ringsystem interpretieren. Berechnete π-Elektronendichten an den N-Atomen korrelieren linear mit δ14N. Substituenten. effekte werden diskutiert.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091027
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  • 87
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    Notiz über die Synthese von [2,2-2H2]-, [3,3-2H2]-, [2,2,4,4-2H4]- und [2,2,3,3,5,5-2H6]Cyclopentanon (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3492-3495 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091030
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  • 88
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    Reaktionen an Indolderivaten, XXXI Stereoselektive Totalsynthesen des Geissoschizins (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3825-3836 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Indole Derivatives, XXXI Stereoselective Total Syntheses of GeissoschizineStereoselective techniques of the construction of the sp2- as well as the sp3-hybridized centers of geissoschizine (1) are reported. The exocyclic E-configurated double bond may principally be installed by an elimination process, higher stereoselectivity is gained by an α-methylene lactame rearrangement.
    Notes: Es werden stereoselektive Techniken zum gezielten Aufbau der sp2 - und der sp3-hybridisierten Zentren des Geissoschizins (1) angegeben. Die exocyclische E-konfigurierte Doppelbindung kann prinzipiell über einen Eliminierungsprozeß, mit ausgeprägter Stereoselektivität jedoch über eine α-Methylen-Lactam-Umlagerung eingeführt werden.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091210
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  • 89
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    Protophane und Polyaromaten, XXII. Nucleophile Alkylierung und Arylierung des 2,2′-Bipyridyls (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3864-3868 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Protophanes and Polyaromatics, XXII Nucleophilic Alkylation and Arylation of 2,2′-Bipyridyl2,2′-Bipyridyl was alkylated by nucleophilic substitution for the first time. The reaction with methyl or n-butyllithium yielded very selectively either the 6-alkyl- or the 6,6′dialkyl compound (41 - 64%) depending on the conditions. Applying relatively low temperatures it was possible to prepare 6-aryl-2,2′-bipyridyls (aryl = phenyl, 2-pyridyl) in medium yields. In a competition experiment with n-butyllithium 2,2′bipyridyl was significantly more electrophilic than pyridine.
    Notes: 2,2′-Bipyridyl konnte erstmals nucleophil alkyliert werden. Bei der Umsetzung mit Methyl- und n-Butyllithium entstand je nach den Bedingungen sehr selektiv die 6-Alkyl- oder 6,6′-Dialkyl Verbindung (41 - 64%). Die Anwendung relativ tiefer Temperaturen erlaubte in mittlerer Ausbeute auch die Darstellung von 6-Aryl-Verbindungen (Aryl = Phenyl, 2-Pyridyl). Im Konkurrenzversuch zeigte 2,2′-Bipyridyl gegenüber n-Butyllithium deutlich höhere elektrophile Aktivität als Pyridin.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091214
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  • 90
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    Synthese von 3,6-Didesoxy-ulosen und 3,6-Didesoxy-3-halogen-ulosen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3907-3914 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 3,6-Dideoxy-uloses and 3,6-Dideoxy-3-halo-ulosesMethyl 2,3-anhydro-6-deoxy-α-D-ribo-hexopyranoside-4-ulose (1) reacts with sodium iodide in acetone under mild conditions to yield quantitatively methyl 3,6-dideoxy-α-D-erythro-hexopyranoside-4-ulose (2). By this general method α,β-epoxy-uloses can be transformed into α-deoxy-uloses as shown in the reactions of 13, 14 and 15. In contrast reaction of α,β-epoxy-uloses 1, 13, 14, and 15 with lithium halides in ether leads to α-halo-α,β-eno-uloses 8, 16, and 17.
    Notes: Methyl-2,3-anhydro-6-desoxy-α-D-ribo-hexopyranosid-4-ulose (1) reagiert mit Natriumiodid in Aceton nahezu quantitativ unter milden Bedingungen zu Methyl-3,6-didesoxy-α-D-erythro-hexopyranosid-4-ulose (2). Mit dieser allgemeinen Methode können α, β-Epoxy-ulosen in α-Desoxy-ulosen übergeführt werden, wie die Umsetzung von 13, 14, 15 zeigt. Mit Lithiumhalogeniden in Ether reagieren α,β-Epoxy-ulosen 1, 13, 14, 15 dagegen zu α-Halogen-α-β-eno-ulosen vom Typ 8, 16, 17.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091219
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  • 91
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    Organische Photochemie, X. Photoreaktionen von 3,3-Bis(arylthio)phthaliden, ihren isomeren Dithiophthalsäure-S,S'-diarylestern und von 3-(p-Tolylthio)-phthaliden in Lösung (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3915-3928 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Photochemistry, X Photoreactions of 3,3-Bis(arylthio)phthalides, of the Isomeric S, S'-Diaryl Dithiophthalates and of 3-(p-Tolylthio)Phthalides in SolutionU. v. irradiation of 3,3-bis(arylthio)phthalides 1, of the isomeric S, S'diaryl dithiophthalates 2, and of 3,3-bis(ethoxythiocarbonylthio)phthalide (12) leads to the formation of trans-Biphthalidylidene (4) via the photolabile intermediates 3,3-bis(arylthio)- or 3,3′bis(ethoxycarbonylthio)-3,3′-biphthalidyl (3 or 13), respectively. These intermediates can be isolated under certain conditions. 4. does not arise from reactions of the phthalidyl carbene C. Furthermore, a photochemical reversible isomerisation of 1 and 2 is described. U. v. irradiation of 3-mono-(p-tolylthio)phthalides 16 produces 3,3′-biphthalidyl derivatives 17 which are not transformed into 4. The phthalides 1, 2, 12, and 16 as well as the 3,3′-biphthalidyl derivatives 3 and 13 show parallel behaviour in their electron impact and photo inudced reactions.
    Notes: Die Bildung von trans-Biphthalidyliden (4) aus den 3,3-Bis(arylthio)phthaliden, ihren isomeren Dithiophthalsäure-S,S'-diarylestern 2 und 3,3-Bis(ethoxythiocarbonylthio)phthalid (12) im UV-Licht verläuft über die photolabilen Zwischenstufen 3,3′-Bis(arylthio)- bzw. 3,3′-Bis(ethoxythiocarbonylthio)-3,3′-biphthalidyl (3 bzw. 13), die unter bestimmten Bedingungen isolierbar sind. Die trans-Biphthalidyliden-Bildung erfolgt nicht über das Phthalidylcarben C. Ferner wird eine photochemisch reversible Isomerisierung von 1 und 2 beschrieben. Photolysen der 3-Mono(p-tolythio)phthalide 16, führen zu den 3,3′-Biphthalidyl-Derivaten 17, welche nicht zu 4 weiterreagieren. Die Phthalide 1, 2, 12 und 16 sowie die 3,3′-Biphthalidy-Derivate 3 und 13 zeigen Parallelität in ihren elektronenstoß- und photoinduzierten Reaktionen.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091220
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  • 92
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    Natürlich vorkommende Terpen-Derivate, 74 Notiz über ein neues Sesquiterpen-Glycosid aus Carthamus oxyacantha (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3953-3955 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091224
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  • 93
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    Notiz zur Darstellung von Siloxazanringen durch Spaltungsreaktionen an Zinn-Stickstoff-Verbindungen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3958-3963 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091226
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  • 94
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    Über selektive katalytisch Oxidationen, XXXVII Platin-Katalyse als Hydridmechanismus: Die katalytische Oxidation stickstoff- und sauerstoffhaltiger Heterocyclen (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3707-3727 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Selective Catalytic Oxidations, XXXVIIPlatinum Catalyses as Hydride Mechanism: Catalytic Oxidation of Nitrogen and Oxygen HeterocyclesThe reaction of model nitrogen and oxygen heterocycles with platinum catalyst and oxygen as dehydrogenating agent in liquid phase was investigated. Model compounds were piperidine (5), pyrrolidine (12), the piperidazines 16a, b, the cyclic ethers 19, 25, 31, 34, 40, and the cyclic acetals 44, 47, 50, 53, 56, 57, 59 and 60. The course and mechanism of the oxidations is discussed on the basis of product analyses. The experimental results are in agreement with a hydride transfer mechanism of the catalytic oxidation, platinum acting as a hydride abstractor. This has been substantiated by treating the dioxolane 60b with platinum and oxygen in the presence of BF3. It was possible to trap the ionic intermediate and to isolate the crystalline acetoxonium tetrafluoroborate 61b.
    Notes: Das Verhalten stickstoff- und sauerstoffhaltiger Heterocyclen bei der katalytischen Oxidation in flüssiger Phase mit Platin als Katalysator und Sauerstoff als Dehydrierungsmittel wurde an Modellsubstanzen untersucht. Als solche dienten Piperidin (5), Pyrrolidin (12), die Piperidazine 16a, b, ferner die cyclischen Äther 19, 25, 31, 34 sowie 40 und schließlich die cyclischen Acetale 44, 47, 50, 53, 56, 57, 59 sowie 60. An Hand der Produktanalyse der Oxidationsansätze wird der jeweilige Verlauf der Oxidation diskutiert und mechanistisch gedeutet. Die experimentellen Befunde lassen den Schluß zu, daß die katalytische Oxidation einem Hydridabspaltungsmechanismus folgt, wobei dem Platin die Funktion eines Hydridabstraktors zukommt. Dies konnte durch Behandlung des Dioxolans 60b mit Platin und Sauerstoff in Gegenwart von BF3 bestätigt werden. Es läßt sich die ionische Zwischenstufeabfangen und als kristallines Acetoxonium-tetrafluoroborat 61b isolieren.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091124
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  • 95
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    Die Kristall- und Molekülstruktur von 1,1,2,2-Tetrachlor-1,2-dimethyldisilan-2,2′-Bipyridyl (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3728-3734 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal and Molecular Structure of 1,1,2,2-Tetrachloro-1,2-dimethyldisilane-2,2′-BipyridylThe title compound crystallizes in the monoclinic space group P21/a (Z = 4). The monomeric complex molecule contains one tetrahedrally and one octahedrally bonded Si-atom Cl2MeSi-SiCl2MeN2. The bond lenghts Si - Si = 2.367 Ä and Si-CH3 = 1.90 Å correspond to normal tetrahedral bond lenghts. On the other hand the distances Si - Cl in the octahedral group (2.274 and 2.392 Å) are clearly lengthened compared with the distances Si - Cl in the tetrahedral group (2.081 Å). The two rings of the bipyridyl ligand are slightly bent against each other while the angles and distances correspond to those of the free bipyridyl molecule despite the transition from trans to cis configuration. - Per two of the complex molecules maximally one molecule of the solvent acetonitrile is incorporated.
    Notes: Die Titelverbindung kristallisiert monoklin in der Raumgruppe P21/a (Z = 4). Das monomere Komplex-Molekül besitzt ein tetraedrisch und ein oktaedrisch gebundenes Siliciumatom Cl2MeSi-SiCl2MeN2. Die Bindungslängen. Dagegen sind die Si - Si = 2.367 Ä und CH3 = 1.90 Å entsprechen den normalen tetraedrischen Bindungslängen. Dagegen sind die Si - Cl-Abstände in der Oktaedergruppe (2.274 und 2.392Å) gegenüber den Si - Cl-Abständen in der Tetraedergruppe (2.081 Å) deutlich verlängert. Die beiden Ringe des Bipyridyl-Linganden sind leicht gegeneinander geknickt, dabei entsprechen Winkel und Abstände trotz des Übergangs von der trans-zur cis-Konfiguration denen im freien Bipyridyl-Molekül - Pro zwei der Komplex-Moleküle ist maximal ein Molekül Acetonitril (Lösungsmittel) eingelagert.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091125
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  • 96
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    Organische Schwefelverbindungen, LXII Über die Äthinierung des Thiofluorenons und anderer aromatischer Thioketone (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3775-3780 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Sulfur Compounds, LXIIThe Reaction of Sodium Acetylide with Thiofluorenone and Other Aromatic ThioketonesMonosodium acetylide reacts with thiofluorenone (7) to yield 9,9′-bifluorenylidene (9) and dispiro-[fluorene-9,2′(3′H)-[1,4]dithiin-3′,9″-fluorene] (8). The mechanisms of the reactions between aromatic thioketones and monosodium acetylide are discussed.
    Notes: Bei der Äthinierung von Thiofluorenon (7) entsteht neben 9,9′-Bifluorenyliden (9) Dispiro[fluoren-9,2′(3′H)-[1,4]dithiin-3′,9″-fluoren] (8). Der Mechanismus der Äthinierung aromatischer Thioketone wird diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091204
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  • 97
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    Notiz über ein neues Curcumen-Derivat aus Elephantopus mollis HBK (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 3956-3957 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761091225
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  • 98
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    Notiz über die sterische Reaktions- und Rotationsbehinderung bei einigen Mesitylacetonderivaten (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1204-1207 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090343
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  • 99
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    Heterocyclische β-Enaminoester, 15: Zur Addition von 2-Amino-4,5-dihydro-3-furancarbonsäure-äthylestern an Acetylencarbonsäureester (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1269-1286 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterocyclic β-Enamino Esters, 15: The Addition of Ethyl 2-Amino-4,5-dihydro-3-furancarboxylates to AcetylenecarboxylatesEthyl 2-amino-4,5-dihydro-3-furancarboxylates (la-d) react with methyl propiolate (2a) to give the cyclopropanes 11a-c, the oxepines 4a, b, and the furo[2,3-b]pyridines 7a-c, 9a-c. Dimethyl acetylenedicarboxylate (2b) reacts with la-d to yield the 1:2-adducts 5a-d and the furo[2,3-b]pyridines 7d-k, 9d-f. The mechanisms of these reactions are discussed. The structures are proved unambigously by their spectra as well as by decomposition reaction (to 15-24. An independent synthesis of 9f has been performed.
    Notes: 2-Amino-4,5-dihydro-3-furancarbonsäure-äthylester (1a-d) reagieren mit Propiolsäure-methyl-ester (2a) zu den Cyclopropanen 11a-c, den Oxepinen 4a,b und den Furo[2,3-b]pyridinen 7a-c, 9a-c. Acetylendicarbonsäure-dimethylester (2b) reagiert in einer 1 : 2-Umsetzung zu den Addukten 5a-d und gleichfalls zu Furo[2,3-b]pyridinen (7d-k, 9d-f). Die Bildungsmechanismen werden erörtert und die Strukturen mit Hilfe der Spektren, durch Abbaureaktionen (zu 15-24) sowie durch unabhängige Synthese (9f) gesichert.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090408
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  • 100
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    Untersuchungen in der Cyclobutanreihe, XL: Umsetzung des 1-tert-Butylbenzocyclobutadien-Dimeren mit Brom und Umlagerung des erhaltenen Monobromids (1976)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 109 (1976), S. 1294-1300 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation in the Cyclobutane Series, XL: Reaction of the Dimer of 1-tert-Butylbenzocyclobutadiene with Bromine and the Rearrangement of the Resulting Monobromo DerivativeThe reaction of the dimer 2 with bromine is accompanied by a neopentylic rearrangement of the 5-tert-butyl group, yielding 6. In the presence of HBr 6 turns back to 2, this reaction involving a retroneopentylic rearrangement. Some reactions of 6 are described. Mechanistic aspects are discussed.
    Notes: Die Umsetzung des Dimeren 2 mit Brom schließt eine Neopentyl-Umlagerung der 5-ständigen tert-Butylgruppe ein, wobei das Monobromderivat 6 entsteht. Dessen Behandlung mit HBr führt unter Wiederherstellung der tert-Butylgruppe zurück zu 2. Das chemische Verhalten des Monobromids 6 und die Reaktionsmechanismen werden diskutiert.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19761090410
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