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Notes: Summary The blood levels of serotonin (5-HT) and substance P (SP) in the portal vein were studied after splanchnic nerve stimulation in the cat. The portal levels of both substances were studied before, during and after splanchnic nerve stimulation. There was a twofold increase in 5-HT during stimulation whilst the SP concentration remained unchanged. These results suggest that the nervous control of the amine release into the portal stream and the mechanism that regulates the release of the polypeptide is not the same.

Notes: Summary Neuronal responses to moving visual stimuli were recorded in the lateral geniculate nucleus (LGN) and area 17 of cats. Response duration (DE), number of spikes (NT), and mean frequency (FM) were estimated from the response histograms and analysed for their dependence on stimulus velocity. In the LGN, for about 2/3 of cells these response parameters changed monotonically with velocity up to about 100 °/s. In 1/3 of the cells, the response frequency was tuned to velocity. The speed at which individual cells reached a peak or plateau firing rate was correlated with their receptive field size. In area 17, most neurones were tuned to velocity. Nine out of 59 cells were insensitive to stimulus speed in that they responded equally well at stimulus velocities up to about 10 °/s. The results suggest that at higher levels in the nervous system information about velocity is represented in discrete groups of neurones. It is pointed out that different response parameters may be relevant for different perceptual phenomena associated with movement. The significance of integrational properties and lateral inhibition of nerve cells for the development of complex response properties is discussed.

Notes: Summary In anaesthetized cats, sensory vagal units were recorded in the nodose ganglion by means of extracellular glass microelectrodes. In the antrum and the duodenum we have found receptors tonically activated by warm (38–51 ° C with an optimum at 46–49 ° C) or cold (36–10 ° C with an optimum at 12–10 ° C) solutions. These receptors did not respond to mechanical stimuli (compression and distension of the viscera) and to chemical ones (perfusion with glucose and acid solutions). Thus they did not belong to polymodal type, but they must be considered as true thermoreceptors, specifically sensitive to warm or cold stimulations. The gastro-duodenal thermoreceptors were connected to non-medullated vagal fibres (conduction velocity: 0.8–1.4 m/s). On the other hand, the role of the gastro-duodenal vagal thermoreceptors in the regulation of the digestive motility was studied. By using several electromyographic recordings, it was possible to show that the cold and warm stimulations of the duodenum which elicited thermoreceptor responses, induced an inhibition of the electrical activity of the antrum. The changes persisted after bisplanchnectomy, but disappeared completely after bivagotomy. From these facts it was concluded that the vagal thermoreceptors were involved in the nervous regulations of the gastro-duodenal motility.

Notes: Summary Five cats were trained to perform a forelimb ballistic flexion on a reaction time paradigm including an upper limit of about 400 ms for reinforcement (food pellets). They were implanted with a cyrogenic probe thermically insulated, except at the tip, by a vacuum jacket (outer diameter, 1.1 mm). Four cats had the probe inserted into the ventrolateral thalamic nucleus (VL), contralateral to the moving limb. During cooling they showed increased reaction times, which remained constant throughout daily sessions performed during many weeks, independent of the foreperiod but varying from 25 to 100 ms according to the subject. The temperatures used to upset the reaction times varied from +10 ° C to −8 ° C, depending on the localisation of the probe and on the insulation of the silver tip used to prevent nervous tissue reaction, but for each subject the reaction times always increased when the temperature was lowered. The fifth cat, with a probe inserted between VL and the Centre Median, showed a decrease of reaction times on cooling to 0 ° C and an increase of the reaction times for a cooling at −10 ° C. For one of the four cats with a probe properly inserted into the VL, strain-gauges were stuck on the lever to measure the latency of the decrease of the pressure exerted by the subject when the subject initiated the forelimb flexion in response to the CS. Reaction times and latencies of pressure changes were closely correlated with the movement onset, and they were equally delayed during cooling. This result demonstrates that it is not by slowing down movement velocity that reaction times are upset during VL cooling but by delaying the movement onset.

Notes: Summary Motoneurones innervating the retractor bulbi muscle in the cat have been identified by retrograde labelling with horseradish peroxidase, by intracellular recording and by intracellular staining with horseradish peroxidase. Their somata are found in an accessory abducens nucleus, analogous to that described in some other species, which consists of a narrow column of cells situated in the lateral tegmental reticular field, above the superior olive and medial to the facial nerve. This column of cells extends over approximately 1.5 mm from P 5.5 to P 7. The retractor bulbi motoneurones number from 80 to 120 and have large, elongated somata which give rise to five or six major dendrites. Their axons cross the reticular formation in a dorso-medial direction to pass through the principal abducens nucleus before turning to leave the brain stem in the 6th nerve. Antidromic latencies ranged from 0.4 to 0.7 ms. Some retractor bulbi motoneurones could also be activated antidromically by stimulation of the lateral rectus muscle nerve.

Notes: Summary A contrast reversal (alternating phase) stimulus was used to study the responses of 150 retinal ganglion cells from 15 adult cats. Because the majority of the cells did not show perfect linear spatial summation, a ratio of the firing rates at two time periods was used to express the degree of nonlinearity. Y-cells showed a high degree of nonlinearity, and their mean null ratio was significantly lower than that of X-cells. With the stimulus at the null position, X-cells had an unmodulated discharge rate which was significantly higher than maintained activity, while the firing rate of Y-cells was lower than maintained activity. With the stimulus placed at an eccentric position in the receptive field, X-cells responded in a sustained manner, while Y-cells respond transiently. Because of these observations, we conclude that X-cells correspond to the sustained cells, while Y-cells correspond to the transient cells.

Notes: Summary The retrograde labeling of cortical neurons with horseradish peroxidase (HRP) was used to investigate the morphological features of neurons in various cortical areas projecting to the superior colliculus in the cat. Corticotectal cells were found to be labeled in layer V of the entire cerebral cortex. The number of labeled cells and their locations varied according to the sites of injections of HRP in the colliculus. Most of the Corticotectal cells identified in the present study were small (9–20 μm in diameter, 66%) and medium (20–40 urn, 30%) pyramidal neurons and only 4% of them were large (more than 40 μm). The labeled cells, 261 in total number, had somal diameters of 20.8±8.0 μm (mean and SD). The range of sizes of the labeled neurons was different in different cortical areas. For example, the labeled neurons in the Clare-Bishop area had a greater proportion of large diameter cells than in other areas. The present findings are largely in agreement with the previous data of anterograde degeneration methods with respect to the topographical correlation of the Corticotectal projections. However, in some cortical areas, e.g., the sensorimotor and the first visual (area 17) cortex of the lateral surface of the hemisphere, relatively small numbers of Corticotectal neurons appear to have been labeled by retrogradely transported HRP. The sparsity of the labeled neurons in certain cortical areas may reflect the existence of Corticotectal neurons with axon collaterals supplying brain structures other than the superior colliculus.

Notes: Summary Horseradish peroxidase (HRP) injections in various portions of the cat pontine nuclei resulted in retrograde labeling of neurons in layer V of the ipsilateral cerebral cortex. Corticopontine neurons, pyramidal in type, have been found to be labeled in the entire cortex, confirming the previous findings of anterograde degeneration studies. Most (91%) of the labeled cells were 14–26 μm in diameter (mean 19.4±4.5 μm SD). Small (10–20 μm) and medium (20–40 μm) cells represent 51.5% and 47.7%, respectively, of the total number of the labeled neurons. The populations of the neurons of various sizes were almost identical in different cortical areas, and were different from the populations of corticoreticular and corticospinal cells. Corticopontine cells were well labeled in experimental cases of 3-days' survival time, confirming the topographical organization established previously by degeneration studies for this projection system. However, in cases of shorter survival time (20–27 h), the number of labeled neurons was very small. The relative paucity of labeled Corticopontine neurons in the sigmoid and lateral gyri is discussed with reference to other cortical descending neurons (e.g., the corticotectal, corticoreticular and corticospinal) which have hitherto been identified morphologically as well as physiologically.

Notes: Summary Cat phrenic motoneurons, labeled by intradiaphragmatic injection of horseradish peroxidase, formed a tight cluster in the most ventral portion of the ventral horn in lamina IX of the lower cervical cord. Cell counts were symmetrically distributed for 17 to 21 mm along the longitudinal axis of the cord with a unimodal peak at the junction of segments C5 and C6. The phrenic nucleus was bilaterally organized on either side of the cord with anatomical symmetry and in no case was there evidence for the crossing of phrenic axons in the cord. Assessment of cellular geometry and intercellular relationships demonstrated that phrenic cell diameters approximated a normal distribution with a single peak at 26 μm while longitudinal cell lengths averaged 76 μm. Cells of different size were mixed randomly at all levels of the nucleus. The minimum distance between cells was about 10 μm and the maximum cell packing density approached 2 cells per 106 μm3. The results confirm the location of the cat phrenic nucleus, extend the knowledge of phrenic motoneuronal geometry, and provide an anatomical basis for the understanding of recruitment and synchronization phenomena within the phrenic nucleus.

Notes: Summary We have studied the suppression of firing in single LGN cells of cat and monkey in response to visual stimulation of the nondominant eye. In the cat LGN most of the cells of each of the main laminae show this nondominat suppression. X cells having their dominant input from the ipsilateral eye were suppressed to a significantly greater degree than any other cell type in the cat LGN. In the monkey LGN nondominant suppression was absent in all 19 X-like cells studied, whereas 6 of 21 Y-like cells showed nondominant suppression. Thus nondominant suppression is present in the magnocellular laminae of the monkey LGN, where the Y-like cells are found, but appears to be absent from the parvocellular laminae, where the X-like cells are found.

Notes: Summary The behavioural thermosensitivity of cat paws was examined before and/or after restricted uni- and/or bilateral lesions had been made in the spinal cord between the first and fifth cervical segments. Unilateral lesions of the lateral funiculus, which involved at least its whole width at the level of the central canal, reproducibly were found to interfere with the contralateral sensitivity for temperature increases and/or decreases. No corresponding thermosensory deficiencies were found after unilateral lesions involving the ventral spinal quadrant or the dorsal funiculus. Various bilateral and combined lesions were made, but no cat ever developed thermoanaesthesia. The bilateral lesions included bilateral transections of: the middle parts of the lateral funiculi, the dorsal halves of the lateral funiculi, the dorsal funiculi, and the ventral spinal half. Most of our knowledge about peripheral behavioural thermosensitivity after spinal cord injury is based on observations of human patients, especially after anterolateral chordotomies. The present finding of contralateral thermosensory deficiencies after lesions of the middle part of the lateral funiculus fits with some of the clinical reports. The present failure to cause thermoanaesthesia, on the other hand, is inconsistent with the theory of a single ascending spinal pathway for behavioural thermo-sensitivity, which has emanated mainly from the clinical observations.

Notes: Summary Single unit recordings from 220 units were obtained from the nuclei praetectalis anterior (NPA) and posterior (NPP) of 30 immobilized, anesthetized cats. Quantitative analysis of pretectal (PT) visual activity was mainly based on recordings from the NPP. For comparison, 160 collicular (CS) neurons were studied. A strong sensitivity for moving objects was evident in both samples. The following main types of PT activity were categorized: (A) slow movement, direction-selective units (21%); (B) slow movement, nondirection-selective units (19%); (C) units nonselective for stimulus velocity and direction (24%); (D) jerk movement selective, nondirection-selective units (36%). Latency measurements following single shocks to optic chiasm (OX) and tract (OT) showed mainly slow conducting fiber input to the PT and CS which can be divided into two different groups by conduction properties and synaptic delay: direct W-input and delayed W-input. Fast Y-fiber input of both types, direct and indirect, was recorded at both sites, PT and CS.

Notes: Summary Single unit recording has revealed the same orientation sensitive cell classes in cat area 18 as are to be found in area 17. These include particularly the various types of hypercomplex cell belonging to the S, C, and B cell families.

Notes: Summary Unrestrained cats performed ballistic forelimb flexion movements triggered by an auditory stimulus (CS) on a simple reaction time (RT) paradigm. During the variable foreperiod the subject was required to hold down a lever and to release it on presentation of the CS. The RTs ranged from 200 to 300 ms. The activity of single neurons of the ventrolateral nucleus of the thalamus (VL) was recorded bilaterally. More than 40% of the 166 units recorded in the VL contralateral to the performing limb presented, after the CS, changes of activity with a latency less than 100 ms and were classified into three types: (1) Twenty-five units had a short latency transient increase of activity 10 to 30 ms after the CS, followed by a longer increase or decrease in activity. Short latency increase as well as subsequent increase of the firing rate were not correlated to the RTs. (2) Twenty-nine units showed a 40–60 ms latency increase of activity which lasted long enough to continue during the forelimb movement. These units displayed a correlation between the RTs and the mean firing rate measured in the 40–100 ms period after the CS. The more the cells were activated, the shorter the RTs. (3) Fifteen units presented a reciprocal pattern of discharge with respect to the type (2) units. The firing rate decreased with latencies ranging from 20 to 90 ms after the CS. Only 14,5% of the 96 units recorded in the VL ipsilateral to the performing limb presented changes of activity starting in the 100 ms period following the CS. Background firing levels as well as phasic activity were rather low compared to those observed contralaterally. Sixteen units showed burst activity while the cat was performing but burst pattern was not time-related to the task. In an unconditioned animal, a very low level of activity and an absence of modulations were observed in both VLs.

Notes: Summary In the developing kitten, the alignment of the pupils changes from strongly divergent to almost parallel. The visual axes, however, seem to stay almost parallel throughout this period. The influence of early visual experience on this development is examined in the present study. The results suggest that the development of eye alignment is not controlled by visual experience, but depends on maturational processes, and that normal visual input serves only to halt these processes at the appropriate time.

Notes: Summary Primary vestibular projections to the ipsilateral abducens nucleus were found in cats by injecting anterograde tracer substances (radioactive proline and fucose) into Scarpa's ganglion. Labelling was observed in the rostral and middle portion of the abducens nucleus.

Notes: Summary Climbing and mossy fibre activity in Purkinje cells of cat cerebellum (vermis part of lobules V and VI) were recorded by means of extracellular microelectrodes. Responses were obtained by stimulation of different types of mechanoreceptors in the gastro-intestinal tract: muscular receptors connected with C fibres, peritoneal movement receptors connected with Aγδ or B fibres, Pacinian corpuscules connected with Aβ fibres. The characteristics of the splanchnic fibre projections on this cerebellar area were defined. Splanchno-somatic, splanchno-visceral, and splanchno-cortical convergences were demonstrated.

Notes: Summary The orientation domain in the cortical visual areas of anesthetized cats has been investigated by employing the 14C-Deoxyglucose technique (Sokoloff et al., 1977). Orientation subunits (OS) are seen in the first (V1), the second (V2) and the third visual area (V3) as well as in the visual areas of the suprasylvian sulcus. In the latter regions OS are less elaborated than in V1, V2, and V3. The OS are continuous through all cortical layers; in V1 however, only weak label is detected in layer 4C. In V1, V2, and V3 the width of the OS is about 0.4 mm and the average distance between two OS centers is 0.9 mm. The spatial pattern of the OS seems to be more regular in the visual field periphery than in regions representing the vertical meridian.

Notes: Summary Corrosion casts of the complete vascular network of the choroid plexus of the lateral ventricle in the cat brain were studied in SEM using the injection-replication method. The villi of this plexus are located only on its supero-anterior and infero-posterior parts, being most densely packed in the former region, close to the interventricular foramen. The capillaries of the villi display small nodular thickenings, which suggest the presence of small, sinusoidal dilatations. The main vessel supplying the plexus with blood is the anterior choroidal artery. The plexus is also characterized by a particularly rich venous network, which is drained by a prominent (main) choroid vein. The vascular organization of the choroid plexus of the lateral ventricle in cat is compared to that of the corresponding plexuses in other mammals.

Notes: Summary Lafora-like bodies in an 8-year-old cat were studied light and electron microscopically and histochemically. In addition to Lafora-like bodies composed of branching filaments, glycogen granules and electron-dense materials, abnormal accumulations of glycogen granules attracted attention. The most remarkable features were the developmental processes of the branching filaments originating directly from glycogen granules. Lafora-like bodies in the present study showed ultrastructural, histochemical, and enzymatic similarities to those described in the previous reports in Lafora's disease, glycogenosis and other cases. From these results, a certain disturbance of the glycogen metabolism is considered to be probably related to the productive mechanism of Lafora-like bodies.

Notes: Summary Visual cortex, including areas 17, 18, and sometimes 19, was injected with tritiated leucine. Terminal labelling could be detected by autoradiography in the dorsocaudal part of the ipsilateral claustrum in all cases.

Notes: Summary A central network of neurones in the spinal cord has been shown to produce a rhythmic motor output similar to locomotion after suppression of all afferent inflow. The experiments were performed mainly in acute spinal cats (th. 12), which had received DOPA i.v. and the monoamine oxidase inhibitor Nialamide. In some preparations all dorsal roots supplying the spinal cord were transected, in others phasic afferent activity was suppressed by curarization. The activity was recorded as neurograms from nerve filaments or as electromyograms. It is concluded that: 1. alternating activity between flexors and extensors of foot, ankle, knee, and hip of one limb can still occur 2. the duration of the flexor discharges vary less with the cycle duration than the extensor discharges 3. different flexor muscles may retain individual patterns 4. the activity at different joints can be dissociated 5. there is at least one network for each limb 6. the coordination between the two hindlimbs can be alternating as in walking or be more closely spaced as in galloping 7. alternating activity in the ankle remains even when only segments L6, L7 and S1 are intact.

Notes: Abstract The effects of cerebellectomy on the semi-circular canal evoked responses recorded from individual vertical and oblique eye muscles were studied in cats anesthetized with Ketamine. The phase lag relative angular acceleration of the electromyographic response was consistantly smaller over the frequency range tested (0.02–1.0 Hz) in cerebellectomized than in intact animals. This finding indicates that the time constant of the central, neural integrator was shifted towards smaller values by the lesion. This was also suggested when the vertical eye movements generated by rotation about the pitch axis were recorded in the fully alert animal. In addition, the EOG data show that the phase of the VOR in the low frequency range was not altered following cerebellectomy suggesting that the macular influences were still present. When the EMG responses of the superior oblique (SO) and superior rectus (SR) muscles were studied in their presumed main mode, i.e. roll-canal and pitch-canal, respectively, no difference was noted in hemicerebellectomized animals when compared to intact control animals. However, when SO and SR were studied in pitch-canal and roll-canal rotation, respectively, dramatic changes in the response pattern were noted in lesioned animals.

Notes: Abstract Cats were trained to choose between two levers of an operant chamber using interoceptive cues provided by d-amphetamine or saline as the discriminative stimuli. Following training, stimulus generalization was observed to additional doses of d-amphetamine and cocaine, but not to morphine. Clozapine blocked the generalization of the drug discrimination response to d-amphetamine, but had no effect on generalization to cocaine. These data indicate that discriminative stimulus properties of psychomotor stimulants, previously described in rats, are similar in cats.

Notes: Summary Afferent connections to the ventrobasal complex (VB) of the thalamus were studied by means of retrograde transport of horseradish peroxidase (HRP) and by the Golgi-method. After HRP-injection into the VB, peroxidase-positive cells were observed contralaterally in the dorsal column nuclei (DCN), in the trigeminal nuclei and in the lateral cervical nucleus (LCN), and ipsilaterally in the somatosensory I (SI) and II (SII) cortical areas. Labeled cells of different shape and size were compared with neurons impregnated by the Golgi-technique. On the basis of HRP-labeling it is concluded that cells projecting to the VB are different in size and shape even within one region and that they correspond to the relay or efferent neurons observed in the Golgimaterial.

Notes: Summary The early auditory evoked responses have been studied in bilaterally hearing cats, and in animals with hereditary unilateral anacusis. Cross-over stimulation of the hearing ear occurs at an interaural attenuation of 50-50 dB, and all six waves of the responsare present at supra-threshold stimulus levels.

Notes: The title compound, an analogue of [Leu5]-enkephalin with L-o-carboranylalanine replacing L-phenylalanine in position 4, was prepared by fragment condensation. The analogue has a 3-fold higher affinity for rat brain opiate receptors in the [3H]naloxone competition assay than natural [Leu5]-enkephalin. Like [Leu5]-enkephalin and Na-acetyl-[Leu5]-enkephalin, the N-terminal tripeptide fragment, H · Tyr-Gly-Gly · OH, had no melanotropic activity in the Rana pipiens frog skin assay.A convenient, direct synthesis of methyl t-butoxycarbonyl-L-propargylglycinate is described, and the 13C-NMR. spectra of L-o-carboranylalanine recorded. The procedure was extended to the preparation of BOC · Car-Leu · OMe from BOC · Pra-Leu · OMe. A number of new propargylglycine derivatives are reported.

Notes: The conversion of primary, secondary and vinylic halides to the two C-atoms homologated phenylselenomethyl ketones 8 is described. The method involves addition of the readily available phenylselenoacetaldehyde 5 to the Grignard reagents 9 and oxidation of the resulting β-hydroxy-selenides 10 (Scheme 3).

Notes: Preparation of Stilbenyl Derivatives of 1,2,4-OxadiazolesSchiffs bases derived from 3- and 5-(p-formylphenyl)-phenyl-1,2,4-oxadiazoles and chloroanilines are reacted with various p-tolyl substituted aromatic heterocycles in the presence of dimethylformamide and potassium hydroxide to yield the corresponding heterocyclic substituted stilbenes (‘Anil synthesis’). The reactivity of 5-[4-(chlorophenylimino-methyl)phenyl]-3-phenyl-1,2,4-oxadiazoles is very low and side reactions will predominate.

Notes: (Perhalomethylthio)heterocycles. XIX. Mitt.: s. [1]. . Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activitiesIn the presence of C4F9SO3H the (perhalomethylthio)pyrroles 1a-c react with Cl3-nFnCSCl (n = 1-3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a-f and 3a-h. 2a and 3a react with CF3SCl (catalyst CF3SO3H) yielding 2,3,5-tris (trifloromethylthio)pyrrole (4a), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole (5). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole (4b) is formed. The pyrroles 2a, 4a and 5 form the mercury salts 6a-c; compound 5 yields also a silver salt 7. The 1H- and 19F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.

Notes: A new way to vinylic ethers from acetalsAcetals react at low temperatures in presence of a Lewis acid (aluminium chloride or magnesium bromide) with tertiary amine to give in good yields the vinylic ethers corresponding to the elimination of one molecule of alcohol.

Notes: Addition Reaction of 3-Dimethylamino-2,2-dimethyl-2H-azirine with Phenylisocyanate and Diphenylketene3-Dimethylamino-2,2-dimethyl-2H-azirine (1a) reacts with carbon disulfide and isothiocyanates with splitting of the azirine N(1), C(3)-double bond to give dipolar, fivemembered heterocyclic 1:1 adducts. In some cases, these products can undergo secondary reactions to yield 1:2 and 1:3 adducts. In this paper it is shown that the reaction of 1a with phenylisocyanate also takes place by cleavage of the N(1), C(3)-bond, whereas with diphenylketene N(1), C(2)-splitting is observed.The reaction of 1a and phenylisocyanate in hexane at room temperature yields the 1:3 adduct 2 in addition to the trimeric isocyanate 3 (Scheme 1). A mechanism for the formation of 2 is given in Scheme 5. Hydrolysis experiments with the 1:3 adduct 2, yielding the hydantoins 4-6 and the ureas 7 and 8 (Schemes 3 and 5), show that the formation of this adduct via the intermediates d, e and f is a reversible reaction.The aminoazirines 1a and 1b undergo an addition reaction with diphenylketene to give the 3-oxazolines 14 (Scheme 8), the structure of which has been established by spectral data and oxidative degradation of 14a to the 3-oxazolin-2-one 15 (R1 — R2 — CH3, Scheme 9).

Notes: 1H-NMR. Spectroscopic Analysis of Prochiral Allenic Esters Using Optically Active Europium Shift ReagentsThe prochiral allenic methyl esters 1-4 (cf. Scheme) show in the presence of 1 mol-equiv. tris[3-(heptafluorobutyryl)-(+)-camphorato]europium (III) (Eu (hfc)3) in 1,1,2-trichloro-1,2,2-trifluoroethane (TCFE) induced unlike 1H-NMR. shift differences (ΔΔδ) for the enantiotopic protons and methyl groups on C(4), respectively (cf. Fig. 2 and 3). This effect allows to determine directly the 2JH,H coupling constants of the geminal protons on C(4) of the allenic esters 1 (15.5 Hz) and 2 (14.5 Hz) (cf. Table 2).

Notes: Heterocyclic anellated derivatives of strychnine: Imidazo-, oxazolo- and (1,3-dioxolo)strychnineThe synthesis of imidazo-, oxazolo- and dioxolo-strychnine derivatives, anellated at the 2,3-position of the aromatic nucleus is described. The spectroscopic properties of these compounds and of some intermediates are given.

Notes: UV.-irradiation of pivalic and isobutyric acid and their methyl esters as well as of α-hydroxy isobutyric and malonic acid in solution lead to chemically induced dynamic nuclear polarization (CIDNP.) of parent compounds and of various reaction products. CIDNP.-effects and product distributions confirm α-cleavage of the C(α), CO bond to be the major mode of photodecomposition. Scavenger experiments indicate that decomposition of the molecules from a triplet excited state is roughly equally or more probable than from a singlet excited state. Quantum yields of educt disappearance are also given for the methyl esters of pivalic and isobutyric acid.

Notes: Sodiumthiophenoxide and sodiumphenylselenide react with N-benzyl- and N-hexyl-di-p-toluenesulfonamides (1 and 2) via displacement at the C-atom to afford the corresponding organosulfides and selenides in yields of 68-96%. In contrast, sodium cyanide converts disulfonamides to monosulfonamides by attack on the S-atom. The different selectivities of phenylsulfide and selenide as compared to cyanide anions with respect to attack on the C- and S-atoms are rationalized on the grounds of the HSAB (hard and soft acids and bases) principle of Pearson.

Notes: The recently proposed structure of the carotenoid pigment prolycopene as the 7,9,7′,9′-tetra-cis isomer of lycopene has been unambiguously confirmed by a series of homonuclear Overhauser 1H-NMR. experiments at 270 MHz. Comparative measurements are reported for lycopene.

Notes: The racemic sesquiterpene isocomene (1) has been synthesized starting from 1,7-octadien-3-one (2) in a stereoselective manner (Scheme 2). In the key step 4 → 5 the C(7), C(8)-bond was formed by an intramolecular thermal ene reaction. Further elaboration of 5 involved the ring contraction 6 → 7, the elimination 8 → 9 and the final olefin isomerization 9 → 1.

Notes: Metabolites of Microorganisms. The Aspochalasins A, B, C, and DThe structures of the antibiotic aspochalasin B (asposterol) and its inactive co-metabolites aspochalasin A, C, and D from Aspergillus microcysticus (Tü 502) were elucidated by extended spectroscopic studies and chemical degradation. The structures are: aspochalasin A = 10-isopropyl-14-methyl[11]cytochalasa-6, 13-dien-1, 17, 18, 21-tetrone (32), aspochalasin B = 17-hydroxy-10-isopropyl-14-methyl-[11]cytochalasa-6, 13, 19-trien-1, 18, 21-trione (11), and aspochalasin C = 17, 18-dihydroxy-10-isopropyl-14-methyl[11]cytochalasa-6, 13, 19-trien-1, 21-dione (29). Aspochalasin D (1) is a diastereomer of aspochalasin C (different configuration at C (17) or C (18)).

Notes: Metabolites of Microorganisms. Synthesis of 3-Isobutyl-4,5-dimethylisoindolin-1-one, a Degradation Product of Aspochalasin D3-Isobutyl-4,5-dimethylisoindolin-1-one (1) and 3-isobutyl-6, 7-dimethyl-isoindolin-1-one (6) were synthesized in a non-regioselective way. The structures could be assigned unequivocally by spectroscopic means. Compound 1 was identical with a degradation product of Aspochalasin D.

Notes: Complexation in anhydrous methanol of Cu (II) and Zn (II) with diaza-polyoxamacrocyclic ligandsProtonation of five diaza-polyoxamacrocyclic ligands, (L = [2.1], [2.2], [2.1.1.], [2.2.1], [2.2.2]), and their complexing properties towards Cu2+ and Zn2+ cations have been studied in anhydrous methanolic solutions.Potentiometric measurements have been carried out at 25°, using 5 · 10-2MEt4N+ClO4- as support-electrolyte, in order to determine the nature of the species formed upon complexation and their stability constants. The results were confirmed by spectrophotometry, for the cupric complexes of [2.1] and [2.2.2], and the electronic spectra of the different complexes were calculated.Comparison between complexation in aqueous and methanolic solutions have been made: as in water, ML2+ species and sometimes protonated MHL3+ species, with higher stability constants, are present in methanol; but the main difference is the formation of dinuclear complexes M2L4+, between Cu2+ and all ligands except [2.1]. In these complexes the Cu2+ cations cannot be both ‘encaged’ in the ligand cavity because of its small size. The different possible structures are discussed in terms of the stability constants values. The protonation constants values and the existence of the binuclear complexes may indicate a possible conformational change in the complexing ligand on changing the solvent from water to methanol.

Notes: rac-1,2,10-Trimethoxy-aporphine (14) and rac-2-ethoxy-10,11-dimethoxyaporphine (27) have been synthesized from the 3-phenylphenethylamines 9 and 22 by a new route. The 8-phenyl-3,4-dihydroisoquinolines 11 and 24, the oxo-aporphines 12 and 25 and the rac-nor-aporphines 13 and 26 were obtained as intermediates.

Notes: (6aR)-1,2-(Methylenedioxy)aporphine-10, 11-diol (8) and (6aR)-aporphine-1, 1, 10, 11-tetrol (16) have been prepared from natural (S)-bulbocapnine (4). For both compounds, the partial synthesis included racemic intermediates which have been resolved into their enantiomers. Both compounds 8 and 16 showed dopaminergic activity in rats, although to a lower extent than (R)-apomorphine (1) itself.

Notes: The self-ordered supramolecular structures formed by 5′-guanosine monophosphate (disodium salt) in aqueous solution at pH 7.8 show pronounced interaction with ammonium ions. Rather than competing with potassium ions for the central cavity in hydrogen-bonded guanine tetramers, ammonium ions bring about - in synergism with potassium ions - further aggregation. Glycine appears to destroy the aggregates, by competing with potassium ions for the core positions within the tetramers. Conversely, alanine does not interact significantly with the system. These conclusions follow from analysis, at various concentrations, of the microdynamics and of the mole fractions of sodium ions bound to self-assembled 5′-GMP--, obtained from relaxation rate measurements for the 23Na nucleus, as the 5′-GMP-- counter-ion.

Notes: Synthetic application of epoxynitrones. II. Syntheses of steroidal α-methylidene-γ-lactonesThis communication describes the application of the epoxynitrone/CF3SO3SiR3 → 1,2-oxazine annelation-reaction [1] to the syntheses of steroidal α-methylidene-γ-lactones from olefines, e.g. 12 → 14a/b → 16a/b → 18a/b → 20 → 22 (Scheme 2).

Notes: Evidence is presented which demonstrates that 13C-NMR. spectroscopy can be used with confidence in evaluating the configuration of R1R2CHOH centers at C(6) and C(8) of iridoid glucosides.

Notes: XPS. and 1H-NMR. spectra of 1,3-diaryltriazenes complexes of Hg(II)The core binding energies C 1s, N 1s, Hg 4f7/2, Hg 4f5/2 in 7 symmetrical p-substituted 1,3-diphenyltriazenes complexes of Hg(II) have been measured by XPS. Within the limits of experimental error (± 0.2 eV) only one N 1s signal could be detected. This indicates the equivalence of the 3 N-atoms. Invariance of C 1s, N 1s, Hg 4f7/2, Hg 4d5/2 signals with the para substituents on the phenyl ring is explained on the basis of ionic character in the Hg, N bond. These results are corroborated by the 1H-NMR. spectra.

Notes: Synthesis and reactivity of 3-aryl-1-(3,4-dimethyl-5-isoxazolyl)-triazenes and 4-arylazo-3,4-dimethylisoxazol-5-onesAccording to the experimental conditions and the nature of the substituents on the aromatic ring, aryldiazonium salts react with 5-amino-3,4-dimethylisoxazole (3) leading to either 3-aryl-1 (3,4-dimethyl-5-isoxazolyl)-triazenes (1A) or 4-arylazo-3,4-dimethylisoxazol-5-ones (4). Analyses of the products resulting from thermal decomposition of these triazenes in aromatic substrates and in DMSO and their behaviour in acidic medium show that it is essentially the arylazo form 1B which is reactive.

Notes: The neurotoxin α-kainic acid (7) was synthesized from 1 via the thermal key step 5 → 6 in 41% overall yield.

Notes: Stereospecific synthesis of 6β,7β-methylene-20-spirox-4-ene-3,21-dioneA stereospecific synthesis of the highly active 6β,7β-methylene-20-spirolactone 4 (Prorenone) is described.

Notes: Chiral 2,2′-polyoxaalkano-9,9′-spirobifluorenesFrom 2,2′-diacetyl-9,9′-spirobifluorene (2), twelve chiral polyethers have been prepared as potential ion- and enantiomer-selective ionophores. The absolute configuration of the polyethers 15-17, 19-22, and 25 has been determined by chemical correlation with vespirenes [11] [29], by circular dichroism, and by X-ray analysis. The circular dichroism of 15-17, 19 and 21 depends on the size of the macrocycle and indicates that the fluorene chromophores of 19 and 21 with 13- and 16-membered rings respectively deviate considerably from orthogonality.

Notes: Favorskii-rearrangement in the presence of 3,4-dimethoxyfuran: preparation of 3,4-dimethoxy 11endo-oxo-tricyclo [4.3.1.12,5]undec-3-en-10-one and any derivativesOn treatment with sodiumhydride of 2-chloro-cyclohexanone in the presence of 3,4-dimethoxyfuran, a possible intermediate of the Favorskii-rearrangement has been trapped as 3,4-dimethoxy-11endo-oxa-tricyclo [4.3.1.12,5]undec-3-en-10-one (3). This new compound contains a highly nucleophilic double bond. It can be cleaved in high yield by ozonolysis to 2exo, 4exo-bis (methoxycarbonyl)-3-oxabicyclo [3.3.1]nonan-9-one (4). Addition of chlorine to 3 occurs in stereoselective exo-cis-manner to the crystalline 3exo, 4exo-dichloro-3endo,4endo-dimethoxy 11endo-oxa-tricyclo [4.3.1.12,5]undecan-10-one (5). Silver ion assisted hydrolysis of 5, followed by thermal treatment of the intermediate hydrates, leads to the red 11endo-oxa-tricyclo [4.3.1.12,5]undecan-3,4, 10-trione (6), and methanolysis to 3,3,4,4-tetramethoxy-11endo-oxa-tricyclo [4.3.1.12,5]undecan-10-one (8). By photolytic decarbonylation, 8 is converted into 3,3,4,4-tetramethoxy-10-oxa-tricyclo-[4.3.12,5.0]decan (9).

Notes: Activated quinones: O- versus C-addition of phenols. New regiospecific syntheses of xanthones, thioxanthones and N-methyl-9-acridonesThe acid catalyzed reaction of phenols with activated quinones, e.g. 2-methoxycarbonyl-1, 4-benzoquinone or 2-acetyl-1, 4-benzoquinone, leads to substituted biphenylderivatives (C, C-addition) as has been previously described [1]. O, C-Addition of phenols has now been achieved by using 2-methoxypyridin or 4-dimethyl-aminopyridin [4] as basic catalysts. The resulting substituted diphenylethers can serve as convenient starting materials for regiospecific syntheses of substituted xanthones, especially for 1, 4-dimethoxyxanthones.Arylthiols and N-methyl-N-arylamines also react readily with activated quinones to give substituted di-aryl-thioethers and N-methyl-N, N-diarylamines respectively; both types of compounds are convenient materials for regiospecific syntheses of substituted thioxanthones and N-methyl-9-acridones.

Notes: Cob(I)alamin as Catalyst. 5. Communication [1]. Enantioselective Reduction of α,β-Unsaturated Carbonyl DerivativesThe cob(I)alamin-catalyzed reduction of an α,β-unsaturated ethyl ester in aqueous acetic acid produced the (S)-configurated saturated derivative 2 with an enantiomeric excess of 21%. The starting material 1 is not reduced at pH = 7.0 in the presence of catalytic amounts of cob(I)alamin (see Scheme 2). It is shown that the attack of cob(I)alamin and not of cob(II)alamin, also present in Zn/CH3COOH/H2O, accounts for the enantioselective reduction observed. All the (Z)-configurated starting materials 1, 3, 5, 7, 9 and 11 have been transformed to the corresponding (S)-configurated saturated derivatives 2, 4, 6, 8, 10 and 12, respectively. The highest enantiomeric excess revealed to be present in the saturated product 12 (32,7%, S) derived from the (Z)-configurated methyl ketone 11 (see Scheme 3 and Table 1). The reduction of the (E)-configurated starting materials led mainly to racemic products. A saturated product having the (R)-configuration with a rather weak enantiomeric excess (5.9%) has been obtained starting from the (E)-configurated methyl ketone 23 (see Scheme 5 and Table 2). The allylic alcohols 16 and 24 have been reduced to the saturated racemic derivative 17.

Notes: Total Synthesis of Natural α-TocopherolTwo independent syntheses of (S)-6-hydroxy-2,5,7,8-tetramethylchroman-2-yl-methanol (8b), (Scheme 6 resp. 9) as optically active chroman moiety for the preparation of natural vitamin E via (S)-6-acetoxy-2,5,7,8-tetramethylchroman-2-carboaldehyde (2a) (Scheme 1) and a corresponding side chain are described. Both reaction sequences use trimethyl-hydroquinone as starting material; one approach employs an optically active C4 unit (10a) (Schemes 5 and 6) to introduce the required configuration at C(2), the other uses an optically active C5-synthon (11a) (Schemes 8 and 9) to build the optically active chroman unit. The correct configuration and optical purity of the chroman synthesized is established by correlation with optically pure material of known configuration from which natural vitamin E had already been derived [2].

Notes: The crystal structure of the antibiotic hedamycin (1) has been solved by direct method and refined by least squares techniques to R = 0.091 for 2289 of 2643 independent reflexions. Crystals of C41H50N2O11 are orthorhombic, space group P212121 with lattice parameters a = 24.239 (12), b = 21.440 (10), c = 7.369 (4) Å, Z = 4. The structural features of hedamycin derived earlier by chemical and spectroscopical means are confirmed. Optical rotation and circular dichroism indicate that hedamycin (1) has the absolute configuration of the related antibiotic kidamycin (3). The conformation of ring F is a chair form with the aryl substituent almost axial. The bioxirane part of the antibiotic is in a synclinal conformation.

Notes: Synthesis and Chirality of (5R, 6R)-5,6-Dihydro-β, ψ-carotene-5,6-diol, (5R, 6R, 6′R)-5,6-Dihydro-β, ε-carotene-5,6-diol, (5S, 6R)-5,6-Epoxy-5,6-dihydro-β,ψ-carotene and (5S, 6R, 6′R)-5,6-Epoxy-5,6-dihydro-β,ε-caroteneWittig-condensation of optically active azafrinal (1) with the phosphoranes 3 and 6 derived from all-(E)-ψ-ionol (2) and (+)-(R)-α-ionol (5) leads to the crystalline and optically active carotenoid diols 4 and 7, respectively. The latter behave much more like carotene hydrocarbons despite the presence of two hydroxylfunctions. Conversion to the optically active epoxides 8 and 9, respectively, is smoothly achieved by reaction with the sulfurane reagent of Martin [3]. These syntheses establish the absolute configurations of the title compounds since that of azafrin is known [2].

Notes: ESR. and ENDOR. studies are reported for the radical anions of 1,2-diphenylcyclopentene (3) and its di(pe+deuteriophenyl)-derivative (3-D10). Comparison of the coupling constants of the phenyl protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. with the analogous values for the radical anions of 1,2-diphenyl substituted cyclopropene (1) and cyclobutene (2) reveals regular changes in the sequence 1\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 2\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}, which are caused by an increasing twist of the phenyl groups about the C(1), C(1′)- and C(2), C(1″)-bonds linking them to the ethylene fragment. Such a twist is shown to be also responsible for the large difference in the coupling constants of the methylene β-protons in 3\documentclass{article}\pagestyle{empty}\begin{document}$ ^{\ominus \atop \dot{}} $\end{document}. (0.659 and 0.293 mT). It is suggested that - in order to minimize the losses caused by this twist in the π-delocalization energy - the 2 pz-axes at the centres 1 and 2 deviate from a perpendicular orientation to the mean plane of the cyclopentene ring. A deviation by 19° from such an orientation is required to account for the observed β-proton coupling constants in terms of their conventional cos2-dependence on the dihedral angles θ.

Notes: Sorelline and Hobartine, Two New Indole Alkaloids from Aristotelia peduncularis (LABILL.) HOOK. F.From Aristotelia peduncularis (LABILL.) HOOK. F. two new indole alkaloids, sorelline (1) and hobartine (2), have been isolated. Their structures were elucidated on the basis of spectroscopic data (the formulae represent their relative configurations). The alkaloids 1 and 2 have closely related structures with a monosubstituted indole moiety and an unrearranged monoterpene unit in the aliphatic part.

Notes: Synthesis and configuration of some spiro [indan-2,2′-pyrrolidine] and spiro [pyrrolidine-2,2′-tetraline] derivativesCatalytic hydrogenation of the nitrosoindan and nitrosotetralin derivatives 8 yielded trans-1-hydroxy-spiro [indan-2,2′-pyrrolidin]-5′-one (9) and trans-1′-hydroxy-spiro [pyrrolidine-2,2′-tetralin]-5-one (10) respectively, whilst the corresponding cis compounds 12 and 15 were prepared via the chlorides 11 and 14.The configurations of 10 and 13 were determined by X-Ray analysis.

Notes: Reactions of valencepolaromeric ketenes of mesoionic heterocyles with 3-dimethylamino-2H-azirinesReactions of the 3-dimethylamino-2H-azirines 1a and 1b with the mesoionic oxazole 5 and the mesoionic dithiole 6 in acetonitrile at room temperature yield the 1:1 adducts 11, 12, 19 and 20, respectively (Schemes 5 and 8). These products can be formulated as adducts of the aminoazirines and the ketenes 5a and 6a, which are valence polaromeric forms of the mesoionic heterocycles 5 and 6 (Scheme 2).The structure of the adducts has been elucidated by spectral data and their comparison with the data of (Z)-11, the structure of which has been established by X-ray [19]. Oxidation of the 1:1 adducts with KMnO4 in a two-phase system yields 4-dimethylamino-3-oxazolin-2-ones (cf. Scheme 6) by clevage of the exocyclic C,C-double bond. A mechanism for the formation of the adducts is given in Scheme 9: Nucleophilic attack of 1 on the ketene leads to a primary adduct of type a, which undergoes clevage of the former N(1), C(2)-azirine bond to give adducts of type 11 or 19. The N(1), C(2)-ring opening of 1a in the reaction with ketenes contrasts with the N(1), C(3)-opening of 1a in the addition with, for instance, isothiocyanates. These different ring openings are explained by the difference in nucleophilicity of the heteroatoms X and Y in a′ (Scheme 10).

Notes: The spironaphthalen-2-ones 2, 10 and 18 were prepared by N-bromosuccinimide (NBS) oxidation of 1, 9 and 17 respectively, whereas spironaphthalen-1-ones 24 and 25 were obtained by treating 23 with NBS.The stereoisomeric reduction products 29, 30 and 32 obtained from 24 and 25, gave the pentacyclic compound 33 on treatment with polyphosphoric acid.

Notes: Cyclopeptide antibiotics from Aspergillus species. Structure of echinocandins C and DThe echinocandins B, C and D are antifungal antibiotics produced by a strain of Aspergillus rugulosus. All three metabolites are closely related representing cyclic oligopeptides composed of six amino acids and a linolic acid residue in an amide linkage. The complete structure of echinocandin B (1) has recently been established by X-ray analysis. Structural assignments to the new minor metabolites C and D have now been made by hydrolytic and oxidative cleavage reactions, formation of N-acyl-α-aminoethers as well as by chemical correlations and extensive NMR. examinations. Echinocandin C (2), C52H81N7O15, contains 3-hydroxyhomotyrosine in the place of 3, 4-dihydroxyhomotyrosine present in 1. Echinocandin D (3), C52H81N7O13, differs in two amino acids: 3, 4-dihyroxyhomotyrosine and 4, 5-dihydroxyornithine, unusual units of 1 being replaced by 3-hydroxyhomotyrosine and ornithine.

Notes: Compounds 2, 5 and 9 represent the first examples of isolable dichlorooxiranes formed by formal addition of dichloro carbene to a carbonyl group under phase transfer conditions. On heating, 2, 5 and 9 rearrange into α-chloroacid chlorides 3, 6 and 10, respectively.

Notes: Aminoisoxazoles C-nucleosidesUpon treatment with bromocyanomethylenetriphenylphosphorane, a series of aldehydosugar derivatives gave in good to excellent yields the corresponding terminal gem-bromocyanoenoses 3, 7-10 and 16. Reacted with hydroxylamine, these unsaturated sugars led to the expected [3] 5-amino-3-glycosylisoxazoles 4, 11, 12 and 17, whereas using hydroxyurea as a binucleophile they gave the corresponding 3-amino-5-glycosylisoxazoles 13 and 14 as previously described in other series [3]. The major interest of these compounds rests in their being close analogs (or enantiomers of analogs) of important biological compounds as f.e. AICAR.

Notes: Irradiation of 4-Allylated 2,6-Dimethylanilines in Methanol4-Allyl-, 4-(1′-methylallyl)-, 4-(2′-butenyl)-, and 4-(1′,1′-dimethylallyl)-2,6-dimethylaniline (14-17; cf. Scheme 3) were obtained by the acid catalysed, thermal rearrangement of the corresponding N-allylated anilines in good yields. Aniline 14, when irradiated with a high pressure mercury lamp through quartz in methanol, yielded as main product 4-(2′-methoxypropyl)-2,6-dimethylaniline (22; cf. Scheme 4) and, in addition, 2,6-dimethyl-4-propylaniline (18) and 4-cyclopropyl-2,6-dimethylaniline (23). The analogous products, namely erythro- and threo-4-(2′-methoxy-1′-methylpropyl)-2,6-dimethylaniline (erythro- and threo-24), 2,6-dimethyl-4-(1′-methylpropyl)aniline (19), trans- and cis-2,6-dimethyl-4-(2′-methylcyclopropyl)aniline (trans- and cis-25), as well as small amounts of 4-ethyl-2,6-dimethylaniline (26), were formed by irradiation of 15 in methanol (cf. Scheme 5). When this photoreaction was carried out in O-deuteriomethanol, erythro- and threo-24 showed an up-take of one deuterium atom in the side chain. The mass spectra of erythro- and threo-24 revealed that in 50% of the molecules the deuterium was located at the methyl group at C(1′) and in the other 50% at the methyl group at C(2′) (cf. Scheme 6). This is a good indication that the methanol addition products arise from methanolysis of intermediate spiro[2.5]octa-4,7-dien-6-imines (cf. Scheme 7). This assumption is further supported by the photoreaction of 17 in methanol (cf. Scheme 8) which led to the formation of 4-(2′-methoxy-1′,2′-dimethylpropyl)-2,6-dimethylaniline (28) as main product. The occurrence of a rearranged side chain in 28 can again be explained by the intervention of a spirodienimine 31 (cf. Scheme 9). In comparison with 14, 15 and 17, the 2′-butenylaniline 16 reacted only sluggishly on irradiation in methanol (cf. Scheme 10). It is suggested that all photoproducts - except for the cyclopropyl derivatives which are formed presumably via a triplet di-π-methane rearrangement - arise from an intramolecular singlet electron-donor-acceptor complex between the aniline and ethylene chromophor of the side chain. Protonation of this complex at C(3′) or C(2′) will lead to diradicals (e.g. 33 and 34, respectively, in Scheme 11). The diradicals of type 33 undergo ring closure to the corresponding spirodienimine intermediates (e.g. 31) whereas the diradicals of type 34 take up two hydrogen atoms to yield the photo-hydrogenated compounds (e.g. 21) or undergo to a minor extent fragmentation to side chain degraded products (e.g. 30; see also footnote 7).-Irradiation of 4-ally-2,6-dimethylaniline (14) in benzene or cyclohexane yielded the corresponding azo compound 38 (cf. Scheme 12), whereas its N,N-dimethyl derivative 41 was transformed into the cyclopropyl derivative 42. The allyl moiety in 14 is not necessary for the formation of azo compounds since 2,4,6-trimethylaniline (39) exhibited the same type of photoreaction in benzene solution.

Notes: Conjugated cyclic divinyl ketones containing fifteen and seventeen membered rings have been prepared in a single step by condensation of 1,3-bis (dimethylphosphono)-2-propanone (10) with the dialdehydes 14, 17, 20, and 42 in the presence of hydrogencarbonate in aqueous t-butyl alcohol at reflux without using high dilution techniques. The more highly unsaturated aldehydes give better yields and ketones 34 and 36, or mixtures of the two, were transformed to muscone (1) and Exaltone® by standard procedures. Civetone (2) was prepared by hydrogenation of 43 in pyridine solution. Dienone 29 appears to be the first α, β-unsaturated ketone in which one of the β-vinyl proton resonates at higher field than the corresponding α-proton.

Notes: Mechanism of the Photochemical Addition of Methanol to 2-Allylated AnilinesWe studied in methanol the photoreaction of the 2-allylated anilines, given in Scheme 3 (cf. also [1]). Irradiation of N-methyl-2-(1′-methylallyl)aniline (15) with a high pressure mercury lamp yielded trans- and cis-1,2,3-trimethylindoline (trans- and (cis-34) as well as erythro- and threo-2-(2′-methoxy-1′-methylpropyl)-N-methylaniline (erythro- and threo-35; Scheme 7). When the corresponding aniline d3-15, specifically deuterated in the 1′-methyl group, was irradiated in methanol, a mixture of trans- and cis-d3-34, and of erythro- and threo-d3-35 was obtained. Successive dehydrogenation of the mixture of cis/trans-d3-34 by Pd/C in boiling xylene and by MnO2 in boiling benzene lead to the corresponding indole d3-36 (cf. Scheme 9), the 1H- and 2H-NMR. spectra of which showed that both cis-d3- and trans-d3-34 had bound the deuterium labeled methyl group exclusively at C(3). The 1H- and 2H-NMR. analyses of the separated methanol addition products revealed that erythro-d3-35 contained the deuterium label to at least 95% in the methyl group at C(1′), and threo-d3-35 to 50% in CH3—C(1′) and to 50% in CH3—C(2′) (cf. Scheme 9). To confirm these results 2-(1′-ethylallyl)aniline (16) was irradiated in methanol, whereby a complex mixture of at least 6 products was obtained (cf. Scheme 11). Two products were identified as trans- and cis-3-ethyl-2-methylindoline (trans- and cis-37). The four other products represented erythro- and threo-2-(1′-ethyl-2′-methoxypropyl)aniline (erythro- and threo-39) as major components, and erythro- and threo-2-(2′-methoxy-1′-methylbutyl)aniline (erythro- and threo-40). These results clearly demonstrate that the methanol addition products must arise from spirodienimine intermediates of the type of trans-9 and cis-11 (R1 = CD3 or C2H5, R2 = CH3 or H; Scheme 2) which are opened solvolytically with inversion of configuration by methanol. Thus, cis-11 (R1 = CD3, R2 = CH3) must lead to a 1:1 mixture of threo-13 and threo-14 (i.e.) a 1:1 distribution of the deuterium labelled methyl group between C(1′) and C(2′) in threo-35) The formation of erythro-d3-35 with at least 95% of the deuterium label in the methyl group at C(1′) indicates that trans-9 (R1 = CD3, R2 = CH3) reacts with methanol regioselectively (〉 95%) at the C(2), C(3) bond. Similarly, the formation of the methanol addition products in the photoreaction of 16 (Scheme 11) can be explained. Since the indolines, formed in both photoreactions, show no alteration in the position of the subsituent at C(1′) with respect to the starting material we suppose that the diradical 7 (R1 = CD3 or C2H5, R2 = CH3 or H; Scheme 2) is a common intermediate which undergoes competetive 1.3 and 1.5 ring closure yielding the spirodienimines and the indolines.This conception is supported by irradiation experiments with N, 3,5-trimethyl-2-(1′-methylally)aniline (17) and 2-(2′-cyclohexenyl)-N-methylaniline (18) in methanol. In the former case the formation of spirodienimines is hindered by the methyl group at C(3) for steric reasons, thus leading to a ratio of the indoline to the methoxy compounds of about 6.3 as compared with ca. 1.0 for 15 (cf. Scheme 12). On the other hand, no methoxy compounds could be detected in the reaction mixture of 18 (cf. Scheme 13) which indicates that in this case the 1.3 ring closure cannot compete with the 1.5 cyclization in the corresponding cyclic diradical of the type 7 (R1-C(1′)-C(2′) is part of a six-membered ring; Scheme 2).We suppose that the diradicals of type 7 are formed by proton transfer in an intramolecular electron-donor-acceptor (EDA) complex arising from the excited single state of the aniline chromophor and the allylic side chain. This idea is supported by the fluorescence specta of 2-allylated N-methylanilines (cf. Fig.1-4) which show pronounced differences with respect to the corresponding 2-alkylated anilines. Furthermore, the anilines 18 and 20 when irradiated in methanol in the presence of an excess of trans-1,3-pentadiene undergo preferentially an intermolecular addition to the diene, thus yielding the N-(1′-methyl-2′-butenyl)anilines 52 and 51, respectively (Scheme 15), i.e. as one would expect the diene with its low lying LUMO is a better partner for an EDA complex than the double bond of the allylic side chain.

Notes: A new strategy for the synthesis of muscone (1) using the OH-assisted Prins reaction for macrocyclic ring closure has been developed. The monoacetal 4 of (Z,E)-4,8-dodecadienedial (3), easily obtainable from (Z,E,E)-1,5,9-cyclododecatriene (2), is treated with methallylmagnesium chloride, and the resulting C16-precursor 5 is subjected to acid-catalyzed cyclization in dilute (≤1%) solutions. This results in formation of the bicyclic dihydropyran derivatives 6 which directly yield muscone (1) on heating with a noble metal catalyst saturated with hydrogen. The five-step pathway proceeds with readily available starting materials in conventional steps and excellent overall yield (∼40%). This new principle of macrocyclic ring formation has also been used successfully for the preparation of 3-methylcyclotridecanone (34) and should be generally applicable for other suitable ring systems.

Notes: A synthesis of (6 R, 7 R)-7-acylamino-2-oxocephem-4-carboxylic acids from penicillins is reported based on the formation of the 2-oxocephem system in an intramolecular Wittig condensation. An interesting steric effect of the acylamino grouping on the course of this key step was used to advantage. Some physical and biological properties of this new type of Δ3-cephem are described.

Notes: The chiral aminoethers 1-4, accessible from tartaric acid, are tested as complexing ligands in organolithium reactions. The tetramine 4 turns out to cause highest inductions [see Table 2 and Equations (1)-(4)].

Notes: Diglycosyl Derivatives. Preliminary communicationNovel types of diglycosyl compounds, some of them bearing a resemblance to natural di- or tri-saccharides are described: a diglycosyldiyne (1), a diglycosylthiophene (2), a diglycosylaziridine (3), a diglycosyldioxolane (4), as well as six C,N-diglycosylnitrones, 9b-9f and 14. These C,N-diglycosylnitrones, on treatment with an acetylenic Grignard reagent, led to the expected acetylenic diglycosyl-hydroxylamine 11, whereas diglycosylisoxazolines (f. ex. 10) were obtained when these nitrones underwent 1,3-dipolar cycloaddition to acetylenic compounds.

Notes: Cob(I)alamin as Catalyst. 4. Communication. Reduction of α,β-Unsaturated NitrilesUsing catalytic amounts of cob (I)alamin and an excess of metallic zinc as source of electrons 1-naphthonitril (5) has been reduced to (1-naphthyl)methylamin (6) and in small amounts to (1-naphthyl)methanol (7) and (1,2,3,4-tetrahydro-1-naphthyl)methanol (8) (5 ½ h, CH3COOH/H2O; s. Scheme 3). Starting from cyclododecylideneacetonitrile (15) similar conditions (68 h, CH3COOH/H2O) produced the amines 16-19 as well as the nitrogen free saturated aldehyde 20, the corresponding allylic alcohol 21 and the saturated derivative 22 (s. Scheme 6). It is deduced that the first attack of cob (I)alamin on an α,β-unsaturated nitrile might occur on both the nitrile dipole as well as on the carbon atom in β-position. Cob (I)alamin in aqueous acetic acid saturates the isolated double bonds in allylic alcohols and amines. In a slow reaction the two different aromatic rings of (1-naphthyl)methanol (7) have been reduced giving the corresponding tetrahydronaphthalene derivatives 8 and 12, and in one case the production of the octahydroderivative 14 has been observed in a low yield (s. Scheme 5).

Notes: The wavelength range of the CD. spectra of some cyclohexapeptides containing different sequences of glycine, L- and D-alanine is extended down to 170 nm. This allows a relatively complete recording of the (n - π*) and (π° - π*) Cotton effects. Some striking spectral changes are observed on going from one molecule to another. The relative influence of L- and D-alanyl residues is discussed: Some spectra may be qualitatively related to each other by considering the effect of an L-residue at position q in the ring to cancel partially with the effect of a D-residue at position q ± 3. Assuming these cyclopeptides to occur in a hydrogen-bonded pleated sheet structure, certain dominant changes in the spectra are interpreted as reflecting a transition of the overall backbone conformation from one which is closer to the (optically inactive) symmetry Ci to another which is closer to the (optically active) symmetry C2. An attempt is made to relate the influence of L- and D-substituents within hairpin bends of the pleated sheet structure to an amide sector rule.

Notes: Lincomycin analogues. I. Chain-extensions of [1,2:3,4]-di-O-isopropylidene-α-D-galacto-hexodialdo-1,5-pyranoseThe title aldehydosugar 1 treated with Wittig reagents led in good to excellent yields to the unsaturated sugar derivatives 3-7 and 10-15, 8 having been prepared by condensation of 1 with malonic acid. The configuration (Z or E) of each compound obtained has been established by 1H-NMR. These chain-extensions constitute the first synthetic step towards the preparation of lincomycin analogues.

Notes: The photochemistry of optical active λ, δ-epoxy-enones. Racemization and cyclization of (-)-4-methylidene-5,6-epoxy-5,6-dihydro-β-ionone and of (-)-4-oxo-5,6-epoxy-5,6-dihydro-β-iononeUV.-irradiation (λ ≥ 347 nm as well as λ = 254 nm) converts the conjugated λ, δ-epoxy-enones (-)-2 and (-)-4 by cleavage of the C,C-oxirane bond to an intermediate ketonium ylide f which cyclizes giving the racemic starting materials. The degree of racemization depends on the length of the irradiation time.The formation of the optical active products (-)-3 and (+)-5 in these irradiations gives evidence, that the photocyclization of (-)-2 und (-)-4, respectively, is a one step reaction of a state g.

Notes: The photoinduced cleavage of the C,C-oxirane bond of γ, δ-epoxy-enones: UV.-irradiation of 4-methylidene-5,6-epoxy-5,6-dihydro-β-iononeOn 1n, π*-excitation (λ ≥ 347 nm, pentane) 5 gives the isomeric bicyclic ether 10 in 75% yield (s. Scheme 2). In methanol the photoconversion of 5 to 10 is strongly reduced (12%) in favour of the formation of the methanol adduct 11 (43%). On photolysis in aqueous acetonitrile 5 is converted to the bicyclic ether 10 (9%), the dihydrofurane 12 (18%) as well as to the triketones 13A and 13B (7%), and 14 (23%).On 1π, π*-excitation (λ = 254 nm) in pentane no 10 is formed, but 5 isomerizes to the tricyclic cyclopropyl compound 16 (59%), the allenic product 17 (10%), and the cyclopropene compound 18 (12%; s. Scheme 3). Photolysis in methanol furnishes 11 (63%), and 18 (4%), but no tricyclic cyclopropyl compound 16. In a secondary photoreaction (λ = 254 nm) the dihydrofurane 12 is isomerized to the bicyclic cyclopropyl compound 20.Evidence is given that the products 11 and 13 are formed by solvent addition to an intermediate ketonium ylide b (s. Scheme 12). The presence of b is further proven by the formation of 12, a product of an electrocyclization of b. On photofragmentation of b carbenoids d and e are presumably formed (s. Scheme 14). 1,2-Hydrogen shift in d yields the allene derivative 17, and cyclization of d gives the cyclopropene compound 18. On the other hand, e cyclizes to the non isolated cyclopropene compound 69 which is transformed to 16 by an intramolecular [4 + 2]-cycloaddition.The present investigation shows that the photochemistry of 5 is determined by photoinduced C,C-bond cleavage of the oxirane ring. This is in sharp contrast to the photochemistry of conjugated γ, δ-epoxy-enones without the additional double bond in ε, ζ-position, where selective photocleavage of the C(λ), O-bond is observed.

Notes: Enantioselective 1,2-addition of Li-, Mg-, Zn-, and Cu-organic compounds and of Li-enolates to carbonyl derivatives in the chiral medium DDBDDB = 1,4-Dimethylamino-2,3-dimethoxybutan (= 2,3-Dimethoxy-N,N,N′,N′-tetramethyl-1,4-butandiamin).The (+)-enantiomer of the methoxyamine DDB is used as a chiral cosolvent in the title reactions. As evident from the results listed in the table, enantiotopic faces are generally differentiated with preferences ranging from 55:45 to 60:40.

Notes: The influence of twenty substituents R on the solvolysis rates and products of tertiary chlorides R - CH2CH2C(CH3)2Cl (7) has been studied. H, CH3, (CH3)2NCH2, ClCH2, Cl, CN and NO2 exert an inductive effect only, as the good correlation of the rates with the corresponding inductive substituent constants σIq shows. Bulkier alkyl groups, i.e. isopropyl and t-butyl, lower the rate due to a Baker-Nathan effect, while the n-electron donors CH3S, CH3O, HO and (CH3)2N and the σ-electron donors (CH3)3Sn and HOCH2 cause rate increases based on σIq constants. These accelerations are attributed to C,C-hyperconjugative and inductomeric effects which arise in the transition state for ionization. A comparison of the reactivity of the acyclic chlorides 7 and the corresponding 1-R-substituted 3-bromoadamantanes 1a shows that polar substituent effects are more strongly transmitted in the rigid bicyclic compounds 1a than in the flexible acyclic compounds 7.

Notes: The intramolecular and dimensionless equilibrium constant, K′, for the equilibrium between open and aromatic-ring stacked isomers of ternary complexes formed between adenosine 5′-triphosphate, inosine 5′-triphosphate, or uridine 5′-triphosphate, Mg2+ or Zn2+, and L-tryptophanate, 2,2′-bipyridyl (bipy), or 1,10-phenanthroline (phen) have been estimated by 1H-NMR. shift measurements in D2O (I = 0.1M, NaNO3; 27°). The approximate equilibrium constants K′ are ≥ 20, ≥ 20, 1.2, 0.9, 0.7, 0.5, and 0.3 for the ternary complexes Zn (phen) (ATP)2-, Mg (phen) (ATP)2-, Zn (bipy) (ATP)2-, Zn (bipy) (ITP)2-, Zn (bipy) (UTP)2-, Zn (trp) (ATO) 3-, and Mg (trp) (ATP)3-, respectively. The percentages of the stacked isomers decrease in the order Zn (phen) (ATP)2- (≥ 95%) ≫ Zn (bipy) (ATP)2- (55%) 〉 Zn (bipy) (ITP)2- (48%) 〉 Zn (bipy) (UTP)2- (∼ 40%), which coincides with the order of stability of the binary metal-free adducts (phen) (ATP)4- 〉 (bipy) (ATP)4- ≃ (bipy) (ITP)4- 〉 (bipy) (UTP)4-; the corresponding stability constants are KABA = 28.2 ± 4.7, 8.1 ± 2.6, 8.8 ± 1.8, and ∼ 1 (M-1), respectively (D2O; I = 0.1 M, NaNO3; 27°): these series reflect the decreasing size of the aromatic-ring systems forming the stacks. The indole moiety of tryptophan resembles 2,2′-bipyridyl rather than 1,10-phenanthroline and K(trp)(ATP)(trp) = 6.2 ± 1.8 M-1 for (trp) (ATP)4-. Implications with respect to the stability of ternary complexes, and to biological systems are indicated briefly.

Notes: Structural Modifications of Vitamin D3. Synthesis and Properties of the SO2-Adducts with (5Z)- and (5E)-Vitamin D3Treatment of (5Z)- and (5E)-vitamin D3 (4) with sulfur dioxide yields each quantitatively the cyclic sulfones 1a and 1b. Thermally induced elimination of sulfur dioxide leads to either isotachysterol3 (3) alone or mixtures of isotachysterol3 (3) and isovitamin D3 (2). On the other hand the extrusion of SO2 can be brought about by means of KOH/CH3OH or on an alumina surface affording (5E)-vitamin D3 (4). On treatment with CD3UD/tBuOK/D2O 1a and 1b are transformed (5E)-6, 19, 19′-trideuteriovitamin D3 (4a).

Notes: (E)-3α-Acetoxy-5, 10-seco-1(10)-cholesten-5-one (3) was synthesized by fragmentation of 3α-acetoxy-5α-cholestan-5-ol (1) using the photochemical version [3] of the lead tetraacetate reaction [4], and transformed into the corresponding 3-oxo-compound (5). Two conformations (A2α and B1α) were deduced for the 10-membered ring of 3 by analysis of the 1H- and 13C-NMR. spectra in toluene. The major conformation (A2α) corresponds to that found in the solid state by X-ray analysis. According to its NMR. spectra in toluene, the medium-sized ring of the diketone 5 exists also predominantly in two conformations, the major one being analogous to A1β (the solid-state conformation of the 3β-acetoxy isomer (9) [1]) and the minor one to A2α (see above). The stereochemistry of the acidcatalyzed and thermal cyclisations of 3 as well as of the corresponding 5-oxime is discussed in terms of conformational factors.

Notes: The crystal structures of PdCl2[(-)-DIOP], PtCl2[(-)-DIOP] and of NiCl2-[(-)-DIOP] have been determined by X-ray analysis and refined by least-squares methods [(-)-DIOP=(-)-2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolane]. The coordination around the nickel atom is tetrahedral, the coordination around palladium and platinum is square planar. The unit cell of the palladium complex contains two non-equivalent molecules with different conformations of the seven-membered chelate ring involving the metal and the two phosphorus atoms. PtCl2[(-)-DIOP] is isostructural with the corresponding palladium complex.

Notes: 1H-NMR. Spectroscopic Determination of Enantiomeric Purities of Allenic Esters Using Optically Active Europium Shift ReagentsThe racemic allenic methyl esters 3--7 and the racemic allenic diesters 8--10 (cf. Scheme 2) in 1,1,2-trichloro-1,2,2-trifluoroethane (TCFE) and CCl4 in the presence of optically active tris[3-(heptafluorobutyryl)-(+)-camphorato]europium(III) (Eu(hfc)3) have induced unlike 1H-NMR. shift differences (ΔΔδ) for the protons of the methoxycarbonyl groups of their enantiomers. In some allenic esters the shift reagent causes additional separation of resonance signals; thus, further substituents on the allenic framework may be differentiated in the racemic mixture. This finding provides a widely applicable method for the determination of absolute enantiomeric purities of allenic esters and their corresponding acids. Accordingly we found for optically pure (+)-(S)-2-methyl-2,3-pentadienoic acid ((+)-(S)-13; cf. Fig. 2) a calculated [α]58920 value of + 73.3 ± 1.8°. Finally, the substituent effects on ΔΔδ-values (cf. Table 1--3) are discussed.

Notes: Stereospecific Fragmentations in the Mass Spectra of Cyclohexanediamines and Bis(aminomethyl)cyclohexanesThe mass spectral behaviour, especially loss of NH3, of the six isomeric cyclohexanediamines 1--3 (cis and trans each, Scheme 1) as well as of the six isomeric bis(aminomethyl)cyclohexanes 4--6 (cis and trans each, Scheme 6) has been investigated. The cis- and trans-compounds of the 1,2-isomers 1 and 4 show very similar spectra, because of the ease of ring cleavage at C(1)--C(2) and the similar geometrical relations in all ring conformations. The cis- and trans-compounds of both the 1,3- and 1,4-isomers 2, 3, 5 and 6 show striking differences in their mass spectra due to stereospecific elimination of NH3 from the molecular ion.

Notes: The Mass Spectral Decomposition of Isomeric Diacetamido-cyclohexanes, their N-Phenethyl-Derivatives and Bis(acetamidomethyl)cyclohexanesIn the mass spectra of the six isomeric diacetamidocyclohexanes 2--4 (cis and trans each, Scheme 2) as well as of the six isomeric bis(acetamidomethyl)cyclohexanes 6--8 (cis and trans each, Scheme 5) are clear differences between the constitutional isomers, whereas cis/trans isomers show very similar spectra. The lack of stereospecific fragmentations is explained by loss of configurational integrity of the molecular ion before fragmentation.However, the mass spectral fragmentation of epimeric diamidocyclohexanes becomes very stereospecific by the introduction of a phenethyl group on one of the nitrogen atoms: this group avoids epimerization of the molecular ion prior to fragmentation. In the N-phenethyl derivatives 10, 11, 13 and 14 (Scheme 8) the typical fragmentations of the cis-isomer after loss of ·C7H7 from the molecular ion are the elimination of CH2CO by formation of cyclic ions, and the loss of p-toluenesulfonic acid or benzoic acid, respectively, with subsequent elimination of CH3CN (Scheme 9). In the trans-isomer the typical fragmentations are the loss of the side chain bearing a tertiary nitrogen atom, and the elimination of the tosyl or benzoyl radical, respectively, with subsequent loss of CH3CONH2 (Scheme 10).

Notes: The potentiometric study of the complexation of Cu2+ with 1,4,7-triazacyclononane (1), 1,4,8-triazacyclodecane (2) 1,5,9-triazacyclododecane (3) has shown that CuL, CuL2 and (CuLOH)2 are the main species present in solution. Their stabilities (Table 1) and their absorption spectra (Table 2) indicate facial coordination of the cyclic triamines in a distorted octahedral geometry.The formation and dissociation kinetics have been measured by stopped-flow techniques. The formation in acetate buffer can be described by the reaction of Cu2+ and CuAcO+ with the monoprotonated species of the ligand. The bimolecular rate constants for these complexations (Table 3) decrease when the ring size increases. In contrast the dissociation induced by acid is only little affected by the ring size. Thus for these complexes the rate of formation and not that of the dissociation determines the overall stability.

Notes: The absolute configuration of the title compound, a minor constituent of civet, is shown to be S,S.

Notes: Synthesis of 22,23-methano-24-nor-cholest-5-en-3β-ol and comparison with cystosterol22,23-Methano-24-nor-cholest-5-en-3β-ol, a novel cyclopropane-containing sterol was synthesized from stigmasterol and found to be different from the isomeric, naturally occurring marine sterol cystosterol.

Notes: The synthesis of the spin-labeled uridine and 2′-deoxyridine analogues RUGT 2, DUGT 3, l-RUGT 4, and l-DUGT 5 is described. DUGT 3 showed some activity against the leukemia P388 cell line.

Notes: The unique stabilization of the ester link in dialkyl succinyl succinates is explained and a facile route to known as well as to hitherto inaccessible succinyl succinates is suggested. New representatives of this series are described.

Notes: The kinetics of ethylene oxidation by air over a supported silver catalyst were investigated in the temperature range 490-620 K. The reaction network was found to be triangular. Under virtually constant oxygen partial pressure (0.2 bar), the following rate relationships, (in mol g-1s-1) were found: (formulae in curved brackets denote partial pressures) where R is expressed in J · mol-1 · K-1.The given rate expressions are discussed in the framework of earlier kinetic investigations.

Notes: Enantioselective 1,4-additions of organometallic compounds to conjugated systems in the chiral medium DDBDDB = 1,4-Dimethylamino-2,3-dimethoxybutan (= 2,3-Dimethoxy-N,N,N′,N′-tetramethyl-1,4-butandiamin).The chiral methoxyamine DDB is used as a cosolvent to add achiral Li-, Cu-, and Zn-organic compounds enantioselectively to prochiral β-carbon atoms of α, β-unsaturated aldehydes, ketones, nitro compounds and ketene-thioacetals (Tables 1 and 2). The selectivity generally ranges from 55:45 to 63:27, in one case (9b) an enantiomeric excess of 43% was obtained.

Notes: The study of 16, 17, 18, 19, 28, 29-hexahydrorifamycin S by 1H-NMR. spectroscopy using INDOR at 100 MHz and homodecoupling at 270 MHz has shown that the conformation of the ansa fragment C(20)-C(27) and the position of this fragment relative to the naphthoquinone chromophore are practically the same as those of rifamycin S. This finding rules out the hypothesis that the lower activity of the hydrogenated rifamycins could be due to a different conformation.

Notes: Pyrazolo[1,5-a]indolesTreatment of 1-(2-heteroaroyl or aroyl-phenyl)-pyrazoles (3) with potassium hydroxide in 95% ethanol or with sodium ethanolate in ethanol produces a novel ring closure to new 4-hydroxy-4-(4-heteroaryl or aryl)-4H-pyrazolo [1,5-a]indoles 5 and 6 (Table 1). A 2, 3, or 4-pyridyl at position 4 is easily reduced yielding the 4-(2, 3, or 4-piperidyl)-derivatives 7 and 8 (Table 2). Water is split off from these piperidyl-derivatives 7 or 8 to give the piperidylidene derivatives 9 or 10 (Table 3) which may be considered as heterocyclic analogues to known tricyclic psychopharmaceuticals with antidepressant or neuroleptic activities.