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  • transformation
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  • 1
    ISSN: 1573-4889
    Keywords: Fe–Cr–Al alloy ; oxidation ; molybdenum ; breakaway oxidation ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thin foils of Fe–20Cr–5Al alloys are susceptible to breakawayoxidation once the aluminum content of the substrate has fallen below somecritical value. The combined addition of 0.1 wt.% lanthanum and 0, 1, or 2wt% molybdenum has a beneficial effect on the high-temperature oxidation ofsuch foils. Lanthanum has the well-known reactive-element effect on adhesionof the protective alumina scale, thereby increasing the time to onset ofbreakaway oxidation, while, for alloys containing molybdenum, breakawayoxide spreads relatively slowly over the specimen in comparison to alloysthat contain no molybdenum. In particular, molybdenum-containing alloys areable to develop a protective Cr2O3 layer at the breakawayoxide–substrate interface. Conversely, molybdenum-free alloys form aninternal-oxide zone in the substrate adjacent to this interface, rather thana Cr2O3 layer, so breakaway oxide spreads rapidly. A martensitic phase isobserved in the substrate adjacent to the breakaway oxide formed on Fe–20Cr–5Al–La specimens, which means that theα-phase has transferred to the γ -phase at the temperature ofthe oxidation test (1150°C). Conversely, α-phase is retained inthe molybdenum-containing alloy, even after breakaway takes place, sincemolybdenum, which is a strong ferrite former, is enriched in the alloyadjacent to areas of breakaway oxide. The diffusion rate of chromium isslower in the γ than in the α-phase so a continuouschromium-rich oxide layer, which is effective in inhibiting breakawayoxide from spreading, cannot be established at the breakawayoxide–substrate interface for the molybdenum-free alloys.
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  • 2
    ISSN: 1573-9368
    Keywords: Hyoscyamus muticus ; particle bombardment ; transformation ; tropane alkaloids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We report an efficient whole plant transformation system for Hyoscyamus muticus, an important medicinal plant of the Solanaceous family. We developed a system using a plasmid carrying the nptII and gusA genes, which was delivered into leaf explants by particle bombardment. Ten percent of bombarded leaf explants formed kanamycin-resistant callus, from which putative transgenic plants were recovered. The nptII gene conferring kanamycin resistance was found to be incorporated into the genome of all transgenic plants screened. Over 50% of the kanamycin resistant plants showed strong expression of the non-selected gusA gene. The majority of transgenic plants reached maturity, could be self pollinated, and produced fertile seed. A simple and efficient whole plant transformation system for this medicinal plant is an important step in furthering our understanding of tropane alkaloid production in plants.
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  • 3
    ISSN: 1573-9368
    Keywords: inheritance ; Rubisco small subunit promoters ; sonication ; sulphur nutrition ; sunflower albumin ; transformation ; white clover
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract With the aim of increasing the rumen-protected level of the sulphur amino acids cysteine and methionine in Trifolium repens, we introduced the coding sequence of the sunflower seed albumin (SSA) into T. repens by Agrobacterium tumefaciens-mediated transformation. The SSA gene was modified such that the protein would be localised to the endoplasmic reticulum (ER). Four different T-DNA constructions all containing the SSA gene driven by either the promoter of a gene encoding the small subunit of ribulose bisphosphate carboxylase (Rubisco) from Arabidopsis thaliana (A ssu), the promoter of the gene encoding the small subunit of Rubisco of Medicago sativa (L ssu), or the Cauliflower Mosaic Virus 35S promoter (CaMV35S), were transferred to T. repens cv. Haifa. Transgenic T 0-plants and inter-transgenic hybrids were analysed for the level of SSA accumulation in the leaves by western blotting. The highest observed level of SSA accumulation was 0.1% of total extractable leaf protein. We observed that the promoter had a substantive effect on the level of SSA accumulation with A ssu〉CaMV35S〉L ssu. Results from the inter-transgenic hybrids showed that the capacity to synthesise SSA was inherited. However the level of SSA accumulation in the leaves generally appears not to be additive with extra transgenic loci. During this work, we attempted to improve the efficiency of A. tumefaciens-mediated transformation of T. repens using the SAAT-method (Sonication Assisted Agrobacterium-mediated Transformation) on cotyledons of T. repens. T-DNA transfer was in general not enhanced by sonication compared to traditional A. tumefaciens-mediated transformation. Furthermore, Southern blot analyses of plants regenerated from the same cotyledon after A. tumefaciens treatment and under selection, indicated that multiple shoots were usually derived from the same transformation event. We concluded from these results that only one plant from each A. tumefaciens-treated cotyledon should be taken to avoid transgenic clones.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Transgenic research 9 (2000), S. 405-415 
    ISSN: 1573-9368
    Keywords: Manihot esculenta ; transformation ; Agrobacterium tumefaciens ; mannose ; hygromycin ; selection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In order to improve the efficiency of cassava (Manihot esculenta Crantz) transformation, two different selection systems were assessed, a positive one based on the use of mannose as the selective agent, and a negative one based on hygromycin resistance encoded by an intron-containing hph gene. Transgenic plants selected on mannose or hygromycin were regenerated for the first time from embryogenic suspensions cocultivated with Agrobacterium. After the initial selection using mannose and hygromycin, 82.6% and 100% of the respective developing embryogenic callus lines were transgenic. A system allowing plant regeneration from only transgenic lines was designed by combining chemical selection with histochemical GUS assays. In total, 12 morphologically normal transgenic plant lines were produced, five using mannose and seven using hygromycin. The stable integration of the transgenes into the nuclear genome was verified using PCR and Southern analysis. RT-PCR and northern analyses confirmed the transgene expression in the regenerated plants. A rooting test on mannose containing medium was developed as an alternative to GUS assays in order to eliminate escapes from the positive selection system. Our results show that transgenic cassava plants can be obtained by using either antibiotic resistance genes that are not expressed in the micro-organisms or an antibiotic-free positive selection system.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Transgenic research 9 (2000), S. 471-486 
    ISSN: 1573-9368
    Keywords: Arabidopsis thaliana ; Agrobacterium tumefaciens ; floral spray ; SOD ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In this study, floral spray and floral dip were used to replace the vacuum step in the Agrobacterium-mediated transformation of a superoxide dismutase (SOD) gene into Arabidopsis. The transgene was constructed by using a CaMV 35S promoter to drive a rice cytosolic CuZnSOD coding sequence in Arabidopsis. The transgene construct was developed in binary vectors and mobilized into Agrobacterium. When Arabidopsis plants started to initiate flower buds, the primary inflorescence shoots were removed and then transformed by floral spray or floral dip. More than 300 transgenic plants were generated to assess the feasibility of floral spray used in the in planta transformation. The result indicates that the floral spray method of Agrobacterium can achieve rates of in planta transformation comparable to the vacuum-infiltration and floral dip methods. The floral spray method opens up the possibility of in planta transformation of plant species which are too large for dipping or vacuum infiltration.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1573-4986
    Keywords: Cancer ; caveolae ; caveolin ; cholesterol ; glucosylceramide ; multidrug resistance ; rafts ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The carcinogenic process involves a complex series of genetic and biochemical changes that enables transformed cells to proliferate, migrate to secondary sites and, in some cases, acquire mechanisms that make cancer cells resistant to chemotherapy. This phenomenon in its most common form is known as multidrug resistance (MDR). It is usually mediated by overexpression of P-glycoprotein (P-gp) or other plasma membrane ATPases that export cytotoxic drugs used in chemotherapy, thereby reducing their efficacy. However, additional adaptive changes are likely to be required in order to confer a full MDR phenotype. Recent studies have shown that acquisition of MDR is accompanied by up-regulation of lipids and proteins that constitute lipid rafts and caveolar membranes, notably glucosylceramide and caveolin. These changes may be related to the fact that in MDR cells a significant fraction of cellular P-gp is associated with caveolin-rich membrane domains, they may be involved in drug transport and they could have an impact on drug-induced apoptosis and on the phenotypic transformation of MDR cancer cells.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1572-9788
    Keywords: Choline oxidase ; glycinebetaine ; transformation ; Brassica juncea ; salt stress
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The codA gene for biosynthesis of glycinebetaine from Arthrobacter globiformis was used for transforming Brassica juncea cv. Pusa Jaikisan (which lack any means to synthesize glycinebetaine) through Agrobacterium mediated transformation. The stable insertion of the codA gene in the shoots obtained on medium with kanamycin and hygromycin was confirmed by PCR analysis of the nptII gene. Southern hybridization with a codA probe further demonstrated its successful integration. Immunoblot analysis revealed the presence of choline oxidase demonstrating that the bacterial codA gene had been successfully transcribed and translated. The seeds of transgenic lines showed enhanced capacity to germinate under salt stress as compared to that of the wild type. Further, the seedlings of transgenic plants that expressed codA gene showed significantly higher growth than that of the wild type under salt stress conditions. These results demonstrated that the introduction of a biosynthetic pathway for glycinebetaine into Brassica juncea significantly enhanced their salt tolerance. Hence, homozygous genotypes of selected transformed lines can be exploited for improving the salt tolerance of the desirable cultivars of Brassica juncea through breeding programmes.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1572-9788
    Keywords: antisense DNA ; co-transformation ; nucleocapsid gene ; pathogen-derived resistance ; somatic embryogenesis ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Peanut (Arachis hypogaea L.) lines transgenic for the antisense nucleocapsid (N) gene of a Tomato spotted wilt virus (TSWV) strain isolated from peanut were generated by microprojectile-mediated transformation of repetitive somatic embryos of cultivars VC1 and AT120. The selectable marker (hygromycin resistance) and the N gene were on separate plasmids. A total of 207 VC1 and 120 AT120 hygromycin-resistant lines were produced. Of all the VC1 plants recovered 71% were cotransformed with the N gene (N+), but all plants were sterile. For AT120, 48 of the transgenic cell lines converted into plants. Polymerase chain reaction (PCR) screening showed 15 of the lines were transgenic for the N gene (N+), and two of these lines were fertile. A field test was conducted in 1998 at Ashburn, GA, using seeds from each fertile line, along with segregated and non-transgenic controls. Plants from four randomly selected field plots were examined for symptoms and analyzed by double-antibody sandwich enzyme-linked immunoabsorbent assay and PCR at 10 and 14 weeks after planting. At 14 weeks, 76% of the N+ plants were symptomless, while 2% were severely symptomatic or dead. In contrast, only 42% of the plants lacking the N gene were symptomless and 50% were severely symptomatic or dead. Northern blot analysis of selected field-resistant plants detected transgene RNA, and the transcript level appeared undiminished after viral exposure.
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  • 9
    ISSN: 1572-9788
    Keywords: bar ; cry3A ; Eucalyptus ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Transgenic Eucalyptus camaldulensis containing both the insecticidal cry3A gene and the bar gene (conferring tolerance to the herbicide glufosinate ammonium) have been produced by Agrobacterium tumefaciens-mediated transformation of seedling explants. Transgenic plants from two lines tested were resistant to first instars of chrysomelid beetles that are important pests of commercial Australian eucalypt plantations. Both lines also exhibit tolerance to the broad-spectrum herbicide Liberty® at 6 l/ha (1.2 kg active ingredient per hectare), twice the field application rate. Transgenic insect- and herbicide-resistant eucalypts like these are likely to provide better insect and weed control options in plantations, particularly during the vulnerable establishment phase, provided that any adverse ecological impacts of releasing transgenic trees into the environment can be assessed and minimized.
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  • 10
    ISSN: 1572-9788
    Keywords: choline oxidase ; glycinebetaine ; Japanese persimmon ; salt tolerance ; transformation ; woody plant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This report describes the first successful genetic engineering of tolerance to salt in an agriculturally important species of woody plants by Agrobacterium-mediated transformation with the codA gene of Arthrobacter globiformis. This gene encodes choline oxidase, which catalyzes the oxidation of choline to glycinebetaine. The binary plasmid vector pGC95.091, containing a kanamycin-resistance gene (nptII), a gene for β-glucuronidase (gusA) and the codA gene in its T-DNA region, was used with a disarmed strain of Agrobacterium tumefaciens, EHA101, to transform Japanese persimmon (Diospyros kaki Thunb. `Jiro') by the leaf disk transformation method. The pRS95.101 plasmid that included only nptII and gusA in the T-DNA region was used as a control. We selected eight transgenic lines with one or two copies of the T-DNA after transformation with pGC95.091 (PC lines) and three lines after transformation with pRS95.101 (PR lines). The eight PC lines produced choline oxidase and glycinebetaine whereas neither was found in untransformed `Jiro' and in the control PR lines. Transgenic plants grew normally, resembling wild-type plants both in vitro and ex vitro. The activity of photosystem II in leaves of the transgenic Japanese persimmon plants under NaCl stress was determined in terms of the ratio of the variable (F v) to the maximum (F m) fluorescence of chlorophyll (F v/F m). The rate of decline in (F v/F m under NaCl stress was lower in the PC lines than in the control PR lines. These results demonstrated that genetic engineering of Japanese persimmon, which allowed it to accumulate glycinebetaine, enhanced the tolerance to salt stress of this plant.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Molecular breeding 6 (2000), S. 185-194 
    ISSN: 1572-9788
    Keywords: Agrobacterium ; transformation ; pea ; Pisum sativum L. ; PCR analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Factors influencing the efficiency of Agrobacterium-mediated transformation of pea were tested using highly efficient, direct regeneration system. The virulence of three Agrobacterium strains (octopine LBA 4404, nopaline C58C1 and succinamopine, hypervirulent EHA 105) clearly varied giving 1 transgenic plant per 100 explants for LBA 4404, 2.2 for C58C1 and 8.2 for EHA 105. To test the efficacy of selection agents we used the hypervirulent EHA 105 strain carrying pGPTV binary vector with one of four different selection genes: nptII, hpt, dhfr or bar. The mean number of transgenic, kanamycin-resistant plants for two cultivars tested was 4.2 per 100 explants and was slightly higher than the number of phosphinothricin-resistant plants (3.6 plants per 100 explants). The proportion of transgenics among kanamycin-selected plants was also higher than among phosphinothricin-resistant plants (35% and 28% respectively). There was no regeneration on hygromycin or methotrexate media (transformation with hpt and dhfr genes). Acetosyringone had no apparent influence on efficiency of transformation with hypervirulent EHA 105 strain, however it did affect the rate of transformation when moderately virulent C58C1 was used. Recovery of transgenic plants was enhanced after application of 5-azacytidine. The presence of integrated T-DNA was checked by PCR and confirmed by Southern hybridization. T-DNA was stably transmitted to the next generation.
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  • 12
    ISSN: 1572-9788
    Keywords: heterologous protein accumulation ; phytate phosphorus digestibility ; phytase ; phytic acid ; transformation ; Triticum aestivum L.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The Aspergillus niger phytase-encoding gene (phyA) has been constitutively expressed in wheat. Transgenic wheat lines were generated by microprojectile bombardment of immature embryos, using the bar-Bialaphos selection system. The bar and the phyA gene expression were controlled by the maize ubiquitin-1 promoter. To ensure secretion and glycosylation of the microbial phytase, an expression cassette was designed (Ubi-SP-Phy) where an α-amylase signal peptide sequence was inserted between the promoter and the phytase coding region. A similar cassette was constructed without the signal peptide sequence (Ubi-Phy). Five lines of fertile wheat transformed with the Ubi-SP-Phy were generated and two lines with the Ubi-Phy construct. The inheritance of the phyA gene was monitored through three generations. Western blotting of leaf and seed derived protein revealed the presence of an immunoreacting polypeptide of the size expected for the Aspergillus phytase. Up to 25 days after pollination, the heterologous phytase was exclusively present in the pericarp-seed coat-aleurone fraction. Thereafter, it accumulated in the endosperm in amounts exceeding that found in the seed coat and aleurone. The phyA mRNA and derived protein could at no stage be detected in the embryo. The Ubi-SP-Phy transgenic seeds exhibited up to 4-fold increase of phytase activity while up to 56% increase was found in Ubi-Phy plants. It is concluded that a functional Aspergillus phytase can be produced in significant amounts in wheat grains. This may be of relevance for improving the phytate-phosphorus digestibility when wheat grains are used for non-ruminant animal feed.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Pituitary 3 (2000), S. 117-122 
    ISSN: 1573-7403
    Keywords: Cushing's disease ; silent ; pituitary ; tumour ; macroadenoma ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Silent pituitary adenomas occur in 25–40% of all clinically apparent pituitary tumours. However, the subsequent development of florid Cushing's disease in a patient with a previous non-functioning tumour is extremely rare. We describe a 47 year-old woman presenting initially with a large, invasive and recurrent, non-functioning pituitary tumour. Histopathologic study of the initial tissue did not stain for any hormones. Six years after the initial presentation, she manifested florid ACTH dependent Cushing's syndrome. A recurrent invasive pituitary macroadenoma necessitated a third transphenoidal surgery. The resected specimen, in this instance, revealed positive staining for ACTH, FSH, prolactin, and growth hormone on immunocytochemistry. An incomplete response to surgical, radiation and medical therapy necessitated a bilateral adrenalectomy to control the hypercortisolism, which resulted in remarkable clinical improvement. We also review five previous case reports from the revision literature of similar transformations from non-secreting pituitary adenomas to Cushing's disease. This subset of patients may represent yet another entity in the widening spectrum of Cushing's syndrome.
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Systemic practice and action research 13 (2000), S. 475-501 
    ISSN: 1573-9295
    Keywords: reflection ; transformation ; self-society dynamics ; critical systems thinking ; systemic intervention ; critical self-reflection ; ideology-critique ; critical appreciation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Sociology
    Notes: Abstract This paper sets out to uncover some relationships between reflection, discourse and action. By challenging and synthesizing some polemical arguments concerning the creation, maintenance, and transformation of self and society, a model of self-society dynamics that operates through reflection, discourse, and action is developed. The model of self-society dynamics brings together aspects of self-reflection and ideology-critique (explored in the paper), which it is suggested are required for any intervention (transformative action) to be grounded in locally meaningful ways. By creating a dialog community in which self- and group assumptions can be subjected to validation through discourse, it is proposed that a dynamic balance between individual needs and broader societal aims may be achieved. If individuals can be open to such discourse (i.e., they can become critically self-reflective), then it is argued that possibilities for achieving sustainable change will be significantly enhanced.
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  • 15
    ISSN: 1573-5060
    Keywords: conifers ; salgareño pine ; tissue culture ; transformation ; transient gene expression ; uidA expression ; vir gene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Cotyledons from dissected sterile embryos of salgareño pine (Pinus nigra Arn. ssp. salzmannii (Dunal) Franco) were inoculated with different disarmed Agrobacterium tumefaciens strains harbouring the binary vector p35SGUSint. The transient expression of a β-glucuronidase gene (uidA) was studied, using a histochemical staining procedure. Nineteen days after inoculation, the activity of β-glucuronidase was detected in epidermal and subepidermal layers of cotyledonary explants. The EHA105 strain harbouring a disarmed agropine-type Ti-plasmid (pTiBO542) was the most effective for gene transfer of the uidA gene. The effects of exudates and extracts from 0-day-old embryos on induction of vir gene expression in A. tumefaciens were also examined. The results of this study showed that salgarño pine embryo exudates contain a substance(s) that induce vir gene expression, in similar way to that observed with 100 μM acetosyringone (AS).All these findings suggest that T-DNA processing and transfer might take place when Agrobacterium infects suitable tissues of salgareño pine.
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  • 16
    ISSN: 1573-5060
    Keywords: cell suspension ; monocotyledon ; selection ; somatic embryogenesis ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The successful application of plant biotechnology to Alstroemeria improvement will largely depend on the availability of an efficient regeneration/transformation system. Regeneration in Alstroemeria is accomplished from nodular embryogenic callus initiated from zygotic embryos. Histological studies of embryogenic callus initiation from 4-weeks old cultured ovules revealed that the outermost layers of the protoderm of the embryogenic nodules divided to form either a new nodule or aproembryo. Transient gene expression after particle bombardment of nodular embryogenic callus was optimized using DNA of pAHC25. The highest β-glucuronidase expression was found when the GUS gene was under control of the maize ubiquitin promoter, the target tissue was placed 5 cm below the microcarrier launch assembly and when the rupture disc-breakage point was between 650–900 psi. Kanamycin blocked regeneration of somatic embryos, however, did not block growth of nodular embryogenic callus. With phosphinothricin both callus growth and regeneration were blocked. Bombardment of nodular embryogenic callus with DNA of pAHC25 combined with selection on medium containing phosphinothricin resulted in putative transgenic chimeric. Friable calli were selected from nodular embryogenic callus and used to initiate suspensions. These cell suspensions were subjected to transformation by particle bombardment using DNA of pAHC25 and resulted in a stable transformed friable callus line after selection based on luciferase activity. Even after 2 years of maintenance this callus line was luciferase positive and the Polymerase Chain Reaction analysis demonstrated the presence of the introduced gene in this friable callus line.
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  • 17
    ISSN: 1573-5087
    Keywords: alfalfa ; cell division cycle ; somatic embryogenesis ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Two simple, rapid and efficient protocols for theregeneration of transformed tetraploid lines ofalfalfa (Medicago falcata L.) have beendeveloped and compared. Leaf explants fromembryogenic lines 47/1-150 and 47/1-5 were inoculatedwith Agrobacterium tumefaciens containingconstructs carrying the nptII selectable markergene and promoter:gusA gene fusions under thecontrol of the CaMV 35S or Arabidopsis cdc2a,CycB1 and CycA2 promoters. In the firstregeneration system (the MSH system), inoculated leafexplants were incubated on MS medium supplemented with2,4-D and kinetin and then subcultured onto plantgrowth regulator-free MS medium in order to inducedirect somatic embryogenesis. In the secondregeneration system (the B5h system), the inoculatedexplants were incubated on B5h medium to induceindirect production of somatic embryos viaembryogenic callus. In both systems, an effectivekanamycin selection regime was employed and wasmaintained when the embryos were subcultured onto arecovery medium (Boi2Y) to promote further embryodevelopment. The use of Boi2Y medium was particularlyimportant for shortening the regeneration time andpromoting a higher frequency of healthy plantletproduction from the somatic embryos. The maturesomatic embryos were finally transferred to plantgrowth regulator-free MS medium for plantletformation. Transgenic plantlets were produced within10–14 weeks in the MSH system and 12–16 weeks in theB5h system. The MSH system appears to be the fastesttransformation system reported for leguminous speciesto date. Confirmation of transformation was obtainedusing a re-callusing assay on kanamycin and subsequentSouthern blot hybridisation and PCR analysis. Theability to induce expression of GUS activity in leafexplants containing the cell division cycle genepromoter:gusA constructs by 2,4-D treatment alsoproved to be a reliable indicator of transformation.
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  • 18
    ISSN: 1573-5028
    Keywords: Agrobacterium tumefaciens ; sorghum ; transformation ; transgenic plants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Agrobacterium tumefaciens was used to genetically transform sorghum. Immature embryos of a public (P898012) and a commercial line (PHI391) of sorghum were used as the target explants. The Agrobacterium strain used was LBA4404 carrying a `Super-binary' vector with a bar gene as a selectable marker for herbicide resistance in the plant cells. A series of parameter tests was used to establish a baseline for conditions to be used in stable transformation experiments. A number of different transformation conditions were tested and a total of 131 stably transformed events were produced from 6175 embryos in these two sorghum lines. Statistical analysis showed that the source of the embryos had a very significant impact on transformation efficiency, with field-grown embryos producing a higher transformation frequency than greenhouse-grown embryos. Southern blot analysis of DNA from leaf tissues of T0 plants confirmed the integration of the T-DNA into the sorghum genome. Mendelian segregation in the T1 generation was confirmed by herbicide resistance screening. This is the first report of successful use of Agrobacterium for production of stably transformed sorghum plants. The Agrobacterium method we used yields a higher frequency of stable transformation that other methods reported previously.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    GeoJournal 52 (2000), S. 253-262 
    ISSN: 1572-9893
    Keywords: map sheets ; GIS ; seamless spatial database ; transformation ; computational procedure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography
    Notes: Abstract Map sheets have been often used as a basic spatial unit for managing spatial data produced from paper maps. This often results in incompatibility between adjacent map sheets, because spatial objects do not cross the boundaries smoothly and even the boundaries themselves do not match their neighbors exactly. To solve the problem this paper proposes a computational procedure for joining separate map sheets to obtain seamless spatial data. Line objects digitized separately in different map sheets are considered, which are frequently used to represent road networks, gas pipelines, and boundaries of polygon objects. The procedure consists of three steps: (1) extraction of end nodes, (2) detection of matching nodes, and (3) transformation of the map sheet. Each step goes interactively so that unexpected errors can be avoided by human observation. To test the validity of the procedure, map sheets are combined containing the road network data of Tokyo 23-ku area, Japan.
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    GeoJournal 50 (2000), S. 97-100 
    ISSN: 1572-9893
    Keywords: disease ; health ; morbidity ; mortality ; pollution ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography
    Notes: Abstract In general, the health of Poles improved markedly in the thirty years after the Second World War, but there was some deterioration after 1989 before improvement resumed. Only in the case of cancer is there an upward trend and so Poles are now healthier than they have been at any time in the past. However there are sharp regional variations well exemplified by the incidence of tuberculosis, where there appears to be some correlation with poorer housing and atmospheric pollution. High death rates in Lodz (consistently the highest in the country at the voivodship level between 1989 and 1996), may also be linked with environmental pollution as well as the ageing of the population. Variations between town and country are small, but Poland shows up in a poor light when compared with other European countries. These are important issues for the administration and financing of the welfare services.
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    GeoJournal 50 (2000), S. 151-155 
    ISSN: 1572-9893
    Keywords: demography ; experts ; rural ; Romania ; rural development ; social issues ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography
    Notes: Abstract There is no standard model of transformation for post- socialist countries and each country encounters specific problems rooted in the geographical characteristics of the areas concerned. The human resources are of the greatest importance because it really matters how people (especially the decision-makers) perceive system change and continually reformulate their expectations and strategies; so investigations into the views of people caught up in the transformation can provide a deeper understanding of the background to structural change. Working the national, regional level and local levels in Romania, experts were asked to consider the advantages and disadvantages arising out of the transformation, the most important problems and constraints for future rural development and the policies needed. The paper examines the responses on demographic and social issues. It emerges the most detailed responses were supplied by local-level representatives while respondents at the regional level steered a middle course between the need to address local problems and the prime importance of stimulating the Romanian economy so as to generate resources for welfare programmes (with the latter issue the overriding concern of interviewees at national level). There was general agreement on the importance of foreign investment and European integration for economic development, with local actors taking only small steps in line with the existing opportunities.
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  • 22
    ISSN: 1573-5060
    Keywords: Barley ; Hordeum vulgare ; transformation ; particle bombardment ; particle gun
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Immature embryos of the spring barley variety GoldenPromise, were bombarded with three different particledelivery systems and both transient and stabletransformation examined. In addition, a range oftechniques for the preparation of the DNA coated goldparticles was examined. Fertile transgenic barleyplants were obtained using three particle preparationtechniques which differed in the amount of gold andDNA used for each bombardment. However, only one ofthe particle delivery systems, the PDS 1000/He device,appeared to be effective in yielding transformedbarley plants.
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  • 23
    ISSN: 1573-6776
    Keywords: casein hydrolysate ; Coleus forskohlii ; forskolin ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Casein hydrolysate at 2.0 g l−1 significantly enhanced forskolin content (2.3 mg g−1 cell dry wt) in a rhizogenic tumourous line, GCO-RCH-2 of Coleus forskohlii. In rooty teratoma line, RC-ST-2/4, forskolin content enhanced to 1.7 mg g−1 cell dry wt in presence of 2.5 g l−1 casein hydrolysate. Unlike untransformed calli and rhizogenic/root cultures, all the forskolin yielding transformed cultures of C. forskohlii have been maintained for over 5 years.
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  • 24
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    Applied mathematics and mechanics 21 (2000), S. 1423-1431 
    ISSN: 1573-2754
    Keywords: nonlinear differential equations ; transformation ; algorithm ; analytical solution ; O175.29
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract The idea of AC=BD was applied to solve the nonlinear differential equations. Suppose that Au=0 is a given equation to be solved and Dv=0 is an equation to be easily solved. If the transformation u=Cv is obtained so that v satisfies Dv=0, then the solutions for Au=0 can be found. In order to illustrate this approach, several examples about the transformation C are given.
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  • 25
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    World journal of microbiology and biotechnology 16 (2000), S. 177-182 
    ISSN: 1573-0972
    Keywords: Conjugation ; metal resistance ; plasmid DNA ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Heavy metal concentrations in soil treated with industrial wastewater of Aligarh City (U.P.), India were determined. The analysis of test samples revealed high levels of Fe, Zn, Ni and Cu. A total of 45 Pseudomonas spp. were isolated from soil and were characterized on the basis of morphological, cultural and biochemical characteristics. MICs of Hg2+, Cd2+, Cu2+, Cr3+, and Zn2+ for each isolate were determined. Eighty percent of the strains isolated from soil harboured resistance to copper, whereas 73.3% of the isolates exhibited resistance to cadmium, 71.1% to chromium and zinc and 48.8% to mercury. A maximum MIC of 200 μg/ml for mercury and 1600 μg/ml for other metals was observed. Metal resistance was found to be plasmid mediated as evidenced by transformation studies. Further, the transmissible nature of chromium resistance was confirmed by conjugation. Agarose gel electrophoresis using the miniprep method for plasmid isolation revealed that these isolates harboured plasmids of molecular weights (45 & 47 kb) using EcoRI and HindIII digests of λDNA and undigested λDNA as standard markers.
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  • 26
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    Journal of applied psychoanalytic studies 2 (2000), S. 109-115 
    ISSN: 1573-3459
    Keywords: James Joyce ; “The Dead” ; fiction ; reading ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Psychology
    Notes: Abstract The author offers a personal reading of James Joyce's “The Dead.” She focuses on how the sounds of the language are used to portray the main character's deadness and his beginning to come to life once the barriers to inner self and self-knowledge are broken.
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  • 27
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    Chemistry of natural compounds 36 (2000), S. 137-139 
    ISSN: 1573-8388
    Keywords: 1,1′,6,6′,7,7′-hexahydroxy-3,3′-dimethyl-5,5′-diisopropyl-2,2′-dinaphthylidene-8,8′-dibarbituric acid ; transformation ; DMSO
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Transformations of 1,1′,6,6′,7,7′-hexahydroxy-3,3′-dimethyl-5,5′-diisopropyl-2,2′-dinaphthylidene-8,8′-dibarbituric acid (batridene) in DMSO are studied.
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  • 28
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    Current genetics 16 (1989), S. 369-372 
    ISSN: 1432-0983
    Keywords: Bialaphos ; Neurospora crassa ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Conidia of Neurospora crassa are sensitive to the herbicide bialaphos at concentrations of 160 mg/1 in Westergaard's or Fries' minimal media. Plasmid pJA4 was constructed by inserting a truncated bar gene from Streptomyces hygroscopicus fused to the his-3 promoter from N. crassa into pUC19. The bar gene in plasmid pJA4 confers resistance to bialaphos when transformants are selected on a medium containing bialaphos. The bar gene can be used as an additional dominant selectable marker for transformation of fungi.
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  • 29
    ISSN: 1436-6215
    Keywords: γ-Tocopherol ; Transformation ; α-Tocopherol ; Ratten ; Generationsversuch ; γ-tocopherol ; transformation ; α-tocopherol ; rats ; generation-experiment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Summary The biosynthesis of α-tocopherol, the most effective vitamer among the vitamin E-group, is found only in higher plants and microorganisms. Due to the lack of the shikimate pathway, animals are not able to synthesize α-tocopherol. Also not found is a whole enterai synthesis; only the conversion of dimethyletocol to trimethyletocol seems to be possible. Using four generations of rats, we sought to determine: Is a transformation of γ-tocopherol to α-tocopherol in the animal body possible? Are there any differences in the transformation rates in organs, tissues, or in the entire body along the generations? Does gut flora play any role in the conversion of γ-tocopherol? Is it possible to increase the efficiency of the transformation by supplying additional CH3-groups? Wistar rats were fed a semisynthetic basal diet, supplemented with 78.8 mg DL-γ-tocopherol/kg in the first three generations (F1–F3). In the fourth generation (F4), some of the animals were fed a vitamin E-free diet and γ-tocopherol (approx. 1.5 mg on alternate days) was injected s.c. Two other groups of animals received the basal diet containing additional methionine (0.25 %) or choline (0.45 %), as well as γ-tocopherol (as in F1–F3). α- and γ-tocopherol were analyzed by HPTLC in the whole body and in serum, liver, heart, lung, gut, gonads, and feces. The ratio of α-/γ-tocopherol (μg/μg) as transformation rate and vitamin E-biopotency (μg α-tocopherol equivalents/g) were calculated. Growth and fertility were normal until the fourth generation; no abnormal developments could be recognized. α-tocopherol was found in the whole-body as well as in all tissues and organs. In the whole-body, vitamin E-biopotency decreased 25–70 % in F2 and F3. On the other hand, the increase of the transformation rate of γ- to α-tocopherol amounted to 23 % (F2) and 168 % (F3). Highest conversion rates were found in F2 and F3 for feces, followed by gonads and lungs; the lowest rates were found for serum and liver. Due to the s.c.-injection of γ-tocopherol, feces showed a four-times lower transformation rate in F4 than in F3. There was an increase in heart, gut, lung and serum for both transformation rate and vitamin E-biopotency. These parameters could be improved also by the additional supplements of methionine and choline. Both methyl-group-donators revealed nearly the same positive effect. The results show that the animal organism can adapt to γ-tocopherol supply over generations. γ-tocopherol seems to be a direct precursor for the α-tocopherol synthesis. The methylation of γ-tocopherol in the organs and tissues occurs, presumably, according to their specific α-tocopherol requirement.
    Notes: Zusammenfassung Die Biosynthese des α-Tocopherols, des wirksamsten Vitamins innerhalb der Vitamin-E-Gruppe, ist beschränkt auf höhere Pflanzen und Mikroorganismen. Wegen des Fehlens des Shikimatweges vermag der tierische Organismus das α-Tocopherol nicht zu bilden. Auch eine vollständige enterale Synthese ist nicht bekannt. Es wird angenommen, daß die Umwandlung im Tierkörper von Dimethyltocol zum Trimethyltocol möglich sei. In einem Experiment an Ratten über vier Generationen wurde folgenden Fragen nachgegangen: Findet eine Umwandlung von γ- zu α-Tocopherol statt? Ändert sich die Effizienz der Transformation auf Gewebs- und Organebene bzw. im gesamten Körper über die Generationen? Welche Rolle spielt die Darmflora? Kann die Effizienz der Transformation durch zusätzliche Gaben an CH3-Gruppen verbessert werden? Über vier Generationen erhielten Wistarratten eine halbsynthetische Grunddiät mit 78,8 mg DL-γ-Tocopherol/kg (F1–F3). In F4 erhielt ein Teil der Tiere die tocopherolfreie Grunddiät, γ-Tocopherol (ca. 1,5 mg, alle zwei Tage) wurde den Tieren subkutan verabreicht. Weitere zwei Kollektive bekamen mit dem Grundfutter γ-Tocopherol (wie in F1–F3) und zusätzlich Methionin (0,24 %) bzw. Cholin (0,45 %) oral verabreicht. In einer Ganzkörperanalyse in F1–F3 und in Serum, Erythrozyten, Leber, Herz, Lunge, Darm, Gonaden und Kot wurden α- und γ-Tocopherol mittels HPTLC bestimmt. Das Verhältnis α-γ-Tocopherol (μg/μg) und die Vitamin-E-Wirksamkeit (μg α-Tocopheroläquivalente/ml bzw. g FS od. g TS) wurden errechnet. Bis zur 4. Filialgeneration waren Wachstum und Fortpflanzungsfähigkeit normal; keine äußeren oder anatomischen Abnormitäten wurden beobachtet. Im Gesamtkörper und in Geweben und Organen der Generationen F1–F4 wurde α-Tocopherol gefunden. Gemessen an den Ergebnissen der Ganzkörperanalyse nahm die Vitamin-E-Wirksamkeit in F2 um 25 % und in F3 um 70 % ab. Die Effizienz der γ-Tocopheroltransformation stieg dagegen um 23 % in F2 und 168 % in F3. Höchste Transformationsraten wurden in F2 und F3 für Kot, gefolgt von Gonaden und Lunge, festgestellt, die niedrigsten für Serum und Leber. Durch die subkutane γ-Tocopherolapplikation war die Transformationsrate im Kot in F4 um Faktor 4 schlechter als in F3. Die Effizienz der Transformation und die Vitamin-E-Wirksamkeit nahmen in Herz, Dickdarm, Lunge und Serum zu. Ebenso besser fielen die Werte für diese Parameter unter der Mehrzufuhr an Methionin und Cholin, wobei sich mit beiden Methylgruppendonatoren die gleiche positive Wirkung erzielen ließ. Die Ergebnisse zeigten, daß sich der Körper an eine γ-Tocopherolzufuhr über Generationen adaptieren kann. γ-Tocopherol dient auch im tierischen Organismus als unmittelbare Vorstufe der α-Tocopherolsynthese. Dieser Syntheseschritt erfolgt wahrscheinlich über eine Transmethylierungsreaktion in den verschiedenen Geweben und Organen gemäß ihrem spezifischen Bedarf an α-Tocopherol.
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  • 30
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    Methods in cell science 12 (1989), S. 127-133 
    ISSN: 1573-0603
    Keywords: polyethylene glycol ; transformation ; protoplasts ; Nicotiana
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Polyethylene glycol can be used to induce DNA uptake into plant protoplasts. Procedures for isolation, culture and transformation ofN. tabacum protoplasts are described and can be adapted for other dicot and monocot species. Criteria for proof of transformation are discussed.
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  • 31
    ISSN: 1573-5028
    Keywords: Agrobacterium rhizogenes ; border sequence ; T-DNA ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A Charon 4A phage library, containing insert DNA isolated from a morning glory (Convolvulus arvensis) plant genetically transformed by Ri T-DNA from Agrobacterium rhizogenes strain A4, was used to isolate a lambda clone that contains part of the Ri TL-DNA and the complete TR-DNA. The two Ri T-DNAs were recovered adjacent to each other in a tail-to-tail configuration (i.e. with the TR-DNA inverted with respect to the TL-DNA). Comparison of nucleotide sequences from this lambda clone with the corresponding sequences from the Ri plasmid allowed us to determine the location of the T-DNA/plant junction for the right end of the TL-DNA and the left and right ends of the TR-DNA. We located, near each of these borders, a 24 bp sequence that is similar to the 24 bp consensus sequence found near the pTi T-DNA extremities. In addition, sequences similar to the “core” overdrive sequence from pTi are located near each right border. Hybridization and nucleotide sequence analysis of the DNA adjacent to the TL/TR junction shows that no plant DNA is located between the TL and TR-DNAs and suggests that the plant DNA adjacent to the end of the TR-DNA may have been rearranged during the integration into the plant genome.
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  • 32
    ISSN: 1573-4943
    Keywords: conformational energy ; amino acid substitution ; P21 protein ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Substitutions of amino acids for Gly 12 or Gly 13 in theras oncogene-encoded P21 proteins have been demonstrated to produce unique structural changes in these proteins that correlate with their ability to produce cell transformation. For example, the P21 proteins with Arg 12 or Val 13 are both known to be actively transforming. Recent site-specific mutagenesis experiments on the transforming Arg 12 protein have found that the substitution of Val for Gly 10 has no effect on transforming activity whereas the substitution of Val for Gly 13 led to a loss of transforming activity. In this study, we examine the structural effects of these substitutions on the amino terminal hydrophobic decapeptide (Leu 6-Gly 15) of P21 using conformational energy analysis. The results show that the transforming proteins with Gly 10 and Arg 12 or Val 10 and Arg 12 can both adopt the putative malignancy-causing conformation, whereas, for the nontransforming protein with Arg 12 and Val 13, this conformation is energetically disallowed. These results further support the theory that due to structural changes the transforming P21 proteins are unable to bind to some regulatory cellular element which may be the recently identified binding protein responsible for the induction of increased GTPase activity in normal P21 compared with transforming mutants.
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  • 33
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    Plant molecular biology 13 (1989), S. 151-161 
    ISSN: 1573-5028
    Keywords: β-glucuronidase (gusA) gene ; maize ; protoplasts ; stable co-transformation ; transformation ; Zea mays L.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract An efficient co-transformation protocol using polyethylene glycol was developed for Zea mays L. (cv. A188 × BMS) protoplasts isolated from suspension culture cells. Co-transformation was accomplished by using plasmid constructions containing β-glucuronidase (gusA) or neomycin phosphotransferase (neo) gene coding sequences; both were under control of the CaMV 35S promoter. Protoplast culture and transformation conditions were optimized to assure efficient recovery of transformed cells. The overall efficiency of transformation was 1 × 10−4 (calculated per viable protoplast plated). Among kanamycin-resistant lines, 50% showed a high level of GUS activity (above one unit). Southern blot hybridization confirmed the presence of numerous gusA and neo coding sequences in the maize genome. In two analyzed lines, integrated sequences appeared to be organized in tandem head-to-tail repeats. Results also indicated that the integrated sequences were partially methylated.
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  • 34
    ISSN: 1573-5028
    Keywords: Agrobacterium tumefaciens ; adventitious shoot regeneration ; transformation ; homozygous potato
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Transformed potato (Solanum tuberosum) plants were obtained from homozygous diploid potato by using a transformation procedure in combination with an adventitious shoot regeneration method. Leaf and stem explants were inoculated with an Agrobacterium tumefaciens strain which contained a binary vector (pVU 1011) carrying the neomycin phosphotransferase gene. Shoot regeneration most effectively on stem explants, occurred within six weeks directly from the explants without introducing a callus phase. A strong seasonal influence on transformation efficiencies was observed. Analysis of a number of randomly selected regenerated shoots for their ability to root and form shoots on kanamycin-containing medium shows that over 90% of the regenerated shoots obtained are transformed. In a number of shoots transformation was confirmed by a test for the presence and expression of the NPT-II gene.
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  • 35
    ISSN: 1573-5028
    Keywords: herbicide ; mutant ; photosystem II ; psbA gene ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Mutations conferring herbicide resistance in 3 mutant strains of the cyanobacterium Synechocystis 6714 have been characterized by gene cloning and sequencing. The mutants display very different phenotypes: DCMU-IIA is DCMU-resistant and atrazine-resistant, DCMU-IIB is DCMU-resistant and atrazine-sensitive, and Az-V is DCMU-sensitive, atrazine-resistant and presents particular photoinhibition properties. These mutants were originally obtained either by one-step selection (DCMU-IIA) or by two-step selection (DCMU-IIB and Az-V). psbA copies carrying herbicide resistance have been identified by transformation experiments as psbAI in all cases. Sequences of the psbAI copy of each mutant have been compared to the wild-type sequence. In the single mutant DCMU-IIA, a point mutation at codon 264 (Ser→Ala) results in resistance to both DCMU and atrazine. In the double mutants DCMU-IIB and Az-V, two point mutations were found. DCMU-IIB was derived from DCMU-IIA and had acquired a second mutation at codon 255 (Phe→Leu) resulting in a slight increase in DCMU resistance and complete abolition of atrazine resistance. Az-V contains two changes at codons 211 (Phe→Ser) and 251 (Ala→Val) resulting in high atrazine resistance but only slight DCMU resistance.
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  • 36
    ISSN: 1573-5028
    Keywords: Agrobacterium tumefaciens ; C4 photosynthesis ; Flaveria ; regeneration ; ribulose bisphosphate carboxylase/oxygenase ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We report the successful transformation, via Agrobacterium tumefaciens infection, and regeneration of two species of the genus Flaveria: F. brownii and F. palmeri. We document the expression of a C3 plant gene, an abundantly expressed ribulose 1,5-bisphosphate carboxylase/oxygenase small subunit gene isolated from petunia, in these C4 plants. The organ-specific expression of this petunia gene in Flaveria brownii is qualitatively identical to its endogenous pattern of expression.
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  • 37
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    Methods in cell science 12 (1989), S. 135-138 
    ISSN: 1573-0603
    Keywords: transformation ; Agrobacterium tumefaciens ; vectors ; cocultivation ; leaf disc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Agrobacterium tumefaciens naturally transfers DNA into plant cells and is clearly one of the most effective methods of directed DNA transfer presently available. Two kinds of vectors are commonly used. Cointegrative vectors have the foreign genes incorporated directly into the Ti plasmid. Binary vectors carry two plasmids; the main Ti plasmid where most of the T-DNA has been removed, and a second plasmid containing the foreign genes between the usual border sequences. The vir genes on the main plasmid function to mobilize the foreign genes into a plant cell. Most plant transformation methods follow the procedure of cocultivating wounded tissue with vir-gene-induced bacteria. The cocultivation step is followed by transfer to a selective medium containing antibiotics to kill the bacterium and to allow only growth of transformed tissue. Several selectable markers are available that include resistance to antibiotics, herbicides, or drugs. In addition, several scorable markers such as the bacterial glucuronidase, chloramphenicol acetyl transferase, and the Agrobacterium opine genes are used to verify transformation. Southern blotting and inheritance of transferred genes are ultimately used to demonstrate stable transformation.
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  • 38
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    Plant cell, tissue and organ culture 18 (1989), S. 281-296 
    ISSN: 1573-5044
    Keywords: maize cells ; transformation ; kanamycin electroporation ; nurse cells ; hygromycin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Two chimaeric genes, containing the promoter of the 35S gene of cauliflower mosaic virus coupled to neomycin phosphotransferase (35S-NPT-NOS) or to hygromycin phosphotransferase (35S-HPT-NOS) have been stably transferred to maize (Zea mays cv. Black Mexican sweet) cells by electroporation. Transformation frequencies of 7.6×10-4 and 8×10-4, respectively, (based on the number of surviving cells that divided) were obtained with four pulses of 1 ms duration using 400 V capacitive discharge. Cells transformed to kanamycin-resistance and hygromycin-resistance subsequently multiplied to form callus. Southern blot analysis demonstrated the integration of the selectable marker genes, neomycin or hygromycin phosphotransferase, with single or multiple copy numbers. The blots from DNA of hygromycin-resistant calli also suggested the formation of plasmid concatemers.
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  • 39
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 19-24 
    ISSN: 0009-2940
    Keywords: Bis(diorganoboryl)chalcogenides ; Pyrazaboles ; Pyrazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Neuartige Substituierte B2ElVIN2 HeterocyclenDie Bis(diorganoboryl)chalkogenide (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], und (R2B)2Se [R2 = 1,5-C8H14 (7)] reagieren mit Pyrazol (Pz) und dessen Derivaten 3-Methylpyrazol (3-MePz) und Indazol (benzo-Pz) in hohen Ausbeuten (65-92%) zu stabilen 1:1-Additionsverbindungen [z. B. 2 (El = O), 4 (El = O), 6 (El = S), 8 (El = Se)]. 1H-, 13C-, 11B-NMR-Spektren und Röntgenstrukturanalysen (von 2 und 6) zeigen eine Grundstruktur mit einem zentralen B2ElN2-Heterocyclus (El = O, S, Se). Die Reaktion von 2 mit R2BH und die Thermolyse von 4 führen zu den dimeren 1-Pyrazolylboranen 9a bzw. 9b.
    Notes: The bis(diorganoboryl) chalcogenides (R2B)2O [R = C2H5 (3); R2 = 1,5-C8H14 (1)], (R2B)2S [R2 = 1,5-C8H14 (5)], and (R2B)2Se [R2 = 1,5-C8H14 (7)] react with pyrazole (Pz) and its derivatives 3-methylpyrazole (3-MePz) and indazole (benzo-Pz) to form in high yields (65-92%) stable 1:1 adducts [e.g. 2 (El = O), 4 (El = O), 6 (El = S) and 8 (El = Se)]. 1H-, 13C-, 11B-NMR spectra and X-ray analyses (of 2 and 6) show a basic structure with a central B2ElN2 (El = O, S, Se) heterocycle. The reaction of 2 with R2BH and the thermolysis of 4 give the dimeric 1-pyrazolylboranes 9a and 9b, respectively.
    Additional Material: 3 Ill.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 31-36 
    ISSN: 0009-2940
    Keywords: Mercury - mercury contacts ; Naphthalenediylmercury compounds ; Organomercury compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Extremely Short Mercury-Mercury Contacts in peri-Dimercurated Naphthalene Compounds1-Naphthylmercury chloride (1) and 1,8-naphthalenediylbis(mercury chloride) (2) were prepared from the corresponding naphthyllithium precursors and HgCl2 in ca. 80% yield. In an alternative route, 2 can be obtained from 1,8-naphthalenediyldiboric acid anhydride and HgCl2 in 85% yield. The structure of 2·DMSO has been determined by X-ray diffraction methods. The lattice contains discrete adducts in which the two mercury atoms are bridged by the DMSO oxygen atom. The HgCl moieties are bent away from each other through distortions of the naphthalene framework and of the C—Hg—Cl axes, which results in a Hg ‥ Hg distance of 3.102(1) Å. - Symmetrization of 2, induced by treatment with NaI in aqueous ethanol, affords bis(μ-1,8-naphthalenediyl)dimercury (3). In the X-ray structure determination of this compound the shortest „non-bonding“ Hg·Hg contact reported in the literature has been detected: Hg1··Hg2 = 2.797(1) Å. The molecule also shows distortions in the naphthalene framework and in the C—Hg—C axes [C—Hg—C = 173.3(5)°].
    Notes: 1-Naphthylquecksilberchlorid (1) und 1,8-Naphthalindiylbis-(quecksilberchlorid) (2) werden aus den zugehörigen Naphthyllithium-Verbindungen und HgCl2 mit ca. 80% Ausbeute erhalten. Alternativ kann 2 auch aus 1,8-Naphthalindiyldiborsäureanhydrid und HgCl2 gewonnen werden (Ausbeute 85%). Von 2·DMSO wurde die Kristallstruktur bestimmt. Es liegen diskrete Addukte vor, in denen die beiden Hg-Atome durch das O-Atom des DMSO überbrückt werden. Die HgCl-Einheiten sind durch Verzerrungen im Naphthalingerüst, durch Winkelung der Achsen C—Hg—Cl und durch deren Auslenkung aus der Naphthalinebene voneinander weggebogen, so daß ein Hg·· Hg-Kontakt von 3.102(1) Å resultiert. - 2 symmetrisiert sich bei der Einwirkung von NaI in wäßrigem Ethanol unter Bildung von Bis(μ-1,8-naphthalindiyl)diquecksilber (3). Bei der Strukturanalyse dieser im Kristall zentrosymmetrischen Verbindung wurde der bisher kürzeste „nichtbindende“ Hg··Hg-Kontakt von 2.797(1) Å gefunden. Auch in 3 sind die C—Hg—C-Achsen abgewinkelt [C—Hg—C = 173.3(5)°], und das Naphthalingerüst ist verzerrt.
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  • 41
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 59-61 
    ISSN: 0009-2940
    Keywords: N-Butyl-N′-dansylthiourea ; Complexing agent, fluorescent ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Butyl-N′-dansylthiourea as Fluorescent Broad-Band Complexing AgentN-Butyl-N′-dansylthiourea (2) [dansyl = 5-(dimethylamino)-1-naphthylsulfonyl] is obtained by the reaction of dansylamide (1) with butyl isothiocyanate. The compound is a stable, fluorescent complex agent for a broad spectrum of metal ions. The UV spectra and fluorescence of the ligand and some metal complexes are discussed. The fluorescence of the dansyl group is strongly affected by metal ions.
    Additional Material: 3 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 83-94 
    ISSN: 0009-2940
    Keywords: Enaminecarbaldehydes ; Enamino ketones ; hetero Diels-Alder reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Struktur von Enaminecarbaldehyden und Enamino KetonenDie Synthese der Enamincarbaldehyde 1a-s und 17a-c sowie der Enamino-Ketone 2a-k und deren N-Acyl-Derivate 19a-k und 21-t mit Elektronenacceptor-Substituenten an C-2 bzw an der CO-Gruppe wird beschrieben. Kondensation von 2-Formyl-3-oxopropansäure-methylester (13) mit Ammoniak und den Aminen 14b-s ergab die Enamincarbaldehyde 1a bzw. 1b-s in einer Ausbeute von 72-93%. Die Enamincarbaldehyde 17 konnten durch Formylierung von 15 mit dem gemischten Ameisensäureessigsäureanhydrid erhalten werden. Die Synthese der Enamino-Ketone 2a-k erfolgte mit einer Ausbeute von 61-97% durch Kondensation von Ammoniak und Aminen mit den Enolethern 24a-f, die durch Umsetzung reaktiver Acylchloride 23 mit Ethylvinyl-ether dargestellt wurden. Die für hetero-Diels-Alder-Reaktionen benötigten N-Acyl-Derivate 19a-k und 21-t wurden durch Acylierung des Enamincarbaldehyds 1a und der Enamino-Ketone 2a-k gebildet.
    Notes: The synthesis of enaminecarbaldehydes 1a-s and 17a-c as well as enamino ketones 2a-k, and their N-acyl derivatives 19a-k and 21-t with electron accepting substituents at C-2 and at the CO group, respectively, is described. Condensation of methyl 2-formyl-3-oxopropanoate (13) with ammonia and the amines 14b-s gave the enaminecarbaldehydes 1a and 1b-s, respectively, in 72-93% yield. The enaminecarbaldehydes 17 were obtained by formylation of 15 with acetic formic anhydride. The synthesis of the enamino ketones 2a-k was accomplished in 61-97% yield by reaction of ammonia and amines with the enol ethers 24a-f, which were formed by treatment of reactive acyl chlorides 23 with ethyl vinyl ether. The enaminecarbaldehyde 1a as well as the enamino ketones 2a-k could be acylated to give 19a-k and 2l-t, respectively, which can be used in the hetero Diels-Alder reaction.
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  • 43
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 119-122 
    ISSN: 0009-2940
    Keywords: Bis(phosphonium) salts ; Pyridylphosphonium salts, tri-n-butyl- and triphenyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Triphenyl-(or Tri-n-butyl-)pyridylphosphonium salts, 2. - 2,4-Pyridinediylbis(phosphonium) Salts2,4-Pyridinediylbis(phosphonium) salts 1 react with nucleophiles to give 4-substituted products 6-8. Under radical reaction conditions the 5-position in 1a is attacked to yield 9. sodium azide transforms 1a into 8. This salt is used as starting material for 11. The removal of the phosphonium groups in 1 and in the resulting products can be carried out selectively.
    Notes: 2,4-Pyridindiylbis(phosphoniumsalze) 1 lassen sich mit nucleophilen Reaktionspartnern in die 4-substituierten Produkte 6-8 überführen. Unter radikalischen Bedingungen wird selektiv die 5-Position in 1a unter Bildung von 9 angegriffen. Nach Umsetzung mit Natriumazid entsteht zunächst das Salz 8, das als Ausgangsverbindung für 11 dient. Die Substitution der Phosphoniumgruppen aus den Edukten 1 und Produkten kann selektiv durchgeführt werden.
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  • 44
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 145-149 
    ISSN: 0009-2940
    Keywords: Cycloalkenes, 1-methyl- ; Ozonolysis ; Peroxyhemiacetals, cyclic ; Rubber, natural ; Tetrahydrofurans, 2-hydroperoxy- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ozonolyses of 1-Methylcyclopentene, 1-Methylcyclobutene, 5-Hexen-2-one and Natural Rubber in the Presence of MethanolOzonolyses of 1-methylcyclopentene (8a) and of 1-methylcyclobutene (8b) in methanol proceeded in each case in the two possible directions. The resulting methoxyperoxides 13 and 14 afforded the corresponding peroxyhemiacetals 15 and 19 by intramolecular reactions of the OOH with the corresponding carbonyl groups. Ozonolysis of 1-methylcyclobutene (8b) additionally gave the corresponding ozonide 17b and 2-hydroperoxy-5-methoxy-2-methyl-as well as 5-hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b and 18b). The mode of formation of these hydroperoxy compounds has been elucidated by ozonolyses of 5-hexen-2-one (25) and of natural rubber (28) in the presence of methanol.
    Notes: Ozonolysen von 1-Methylcyclopenten (8a) und von 1-Methylcyclobuten (8b) in Methanol verliefen jeweils nach beiden möglichen Spaltungsrichtungen. Die dabei gebildeten Methoxyhydroperoxide 13 und 14 ergaben durch intramolekulare Reaktionen der OOH- mit den Carbonylgruppen die entsprechenden Peroxyhalbacetale 15 bzw. 19. Bei der Ozonolyse von 1-Methylcyclobuten (8b) wurden zusätzlich das entsprechende Ozonid 17b sowie 2-Hydroperoxy-5-methoxy-2-methyl- und 5-Hydroperoxy-2-methoxy-2-methyltetrahydrofuran (16b und 18b) gebildet. Die Bildungsweise dieser Hydroperoxy-Verbindungen wurde durch Ozonolysen von 5-Hexen-2-on (25) und von Naturkautschuk (28) im Beisein von Methanol aufgeklärt.
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  • 45
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 169-174 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of New 3-substituted PyrrolesThe synthesis of 3-alkyl- (4), 3-(ω-bromoalkyl)- (5), 3-iodo- (6), 3-formyl- (9a), 3-acetyl-1-(triisopropylsilyl)pyrrole (9b), of 2-[1-(triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(triisopropylsilyl)-3-pyrrolecarboxylic acid (8), and 7-[1-(triisopropylsilyl)-3-pyrrolyl]heptanoic acid (10) as well as the desilylation of these products to the corresponding 3-substituted pyrroles 11 is described. Intermediates in these syntheses are 1-(triisopropylsilyl)pyrrole (1), 3-bromo- (2), and 3-lithio-1-(triisopropylsilyl)pyrrole (3).
    Notes: Die Synthese von 3-Alkyl- (4), 3-(ω-Bromalkyl)- (5), 3-Iod- (6), 3-Formyl- (9a) und 3-Acetyl-1-(triisopropylsilyl)pyrrol (9b), von 2-[1-(Triisopropylsilyl)-3-pyrrolyl]-2-propanol (7), 1-(Triisopropylsilyl)-3-pyrrolcarbonsäure (8) und 7-[1-(Triisopropylsilyl)-3-pyrrolyl]heptansäure (10) sowie die Desilylierung dieser Produkte zu den entsprechenden 3-substituierten Pyrrolen 11 wird beschrieben. Zwischenstufen der Darstellung sind 1-(Triisopropylsilyl)pyrrol (1), 3-Brom- (2) und 3-Lithio-1-(triisopropylsilyl)pyrrol (3).
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 47
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 223-230 
    ISSN: 0009-2940
    Keywords: Gold(I) silyl complexes ; Transition-metal silyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition-Metal Silyl Complexes, 26. - Gold(I) Silyl ComplexesComplexes of type L-Au-SiR3 with L = PR′3 or PhNC and SiR3 = Si(aryl)3, Si(SiMe3)3, or SiPh2Me are prepared by reaction of L-Au-Cl with LiSiR3. Depending on L and R, their stability decreases, in the order R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Reaction of R′3P-Au-CH3 or R′3P-Au-OAc with HSiR3 does not yield silyl complexes. However, using chlorinated silanes like HSiR2Cl, CH3/Cl or OAc/Cl exchange takes place. The Mössbauer spectrum of MePh2P-Au-SiPh3 (6) and NMR- and IR-spectroscopic investigations show that silyl groups act as strong σ donors towards the gold atom. MePh2P-Au-SiPh3 (6) and MePh2P-Au-Si(SiMe3)3 (7) have been characterized by X-ray structure analyses [Au—Si 235.4(4) and 235.6(2) pm]. The Au-Si bond in MePh2P-Au-SiPh2Tol (5) is cleaved by X2 (X = Cl, Br, I), HCl or MeI, but not by H2O or MeOH.
    Notes: Komplexe des Typs L-Au-SiR3 mit L = PR′3 oder PhNC und SiR3 = Si(aryl)3, Si(SiMe3)3 oder SiPh2Me wurden durch Umsetzung von L-Au-Cl mit LiSiR3 dargestellt. Ihre Stabilität sinkt in Abhängigkeit von L und R in der Reihenfolge R′3P-Au-Si(aryl)3 〉 R′3P-Au-Si(SiMe3)3 〉 R′3P-Au-SiPh2Me ≈ PhNC-Au-SiR3. Umsetzung von R′3P-Au-CH3 oder R′3P-Au-OAc mit HSiR3 ergibt keine Silyl-Komplexe, bei Verwendung chlorierter Silane, HSi-R2Cl, findet lediglich CH3/Cl- bzw. OAc/Cl-Austausch statt. Das Mößbauer-Spektrum von MePh2P-Au-SiPh3 (6) sowie NMR- und IR-spektroskopische Untersuchungen zeigen, daß Silylreste als starke σ-Donor-Liganden gegenüber dem Goldatom wirken. MePh2P-Au-SiPh3 (6) und MePh2P-Au-Si(SiMe3)3 (7) wurden durch Röntgenstrukturanalysen charakterisiert [Au—Si 235.4(4) und 235.6(2) pm]. Die Au—Si-Bindung in MePh2P-Au-SiPh2 Tol (5) wird durch X2 (X = Cl, Br, I), HCl oder MeI, nicht aber durch H2O oder MeOH gespalten.
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  • 48
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 245-252 
    ISSN: 0009-2940
    Keywords: Germylenes ; Germanium nitrogen compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Germylenes with Azides: Iminogermanes, Azidogermanes, Tetrazagermoles and HexaazadigermadispirododecanesGermylenes, X2Ge, stabilized by steric blocking and/or incorporation into five-membered ring systems, react with azido compounds YN3 depending on the steric requirements of the substituents X and Y to give iminogermanes, X2Ge=NY (1, 2) azidogermanes X2Ge(N3)NY2 (6-8) tetrazagermoles, X2Ge(— NY — N =)2 (10-16), and hexaazadigermadispirododecanes, [(— NR — CH2 — CH2 — NR —)Ge(μ-NY -)]2 (17, 18). NMR (1H, 13C, 14N, 15N, and 29Si), MS data, and X-ray structure analyses of the compounds 8, 9, 16, and 18 are reported.
    Notes: Durch sterische Blockierung und/oder Einbau in fünfgliedrige Ringsysteme stabilisierte Germylene, X2Ge, reagieren mit Azidoverbindungen, YN3, in Abhängigkeit von der Raumerfüllung der Substituenten X und Y zu Iminogermanen X2 Ge=NY (1, 2), Azidogermanen, X2Ge(N3)NY2 (6′8), Tetrazagermolen, X2Ge-(-NY-N=)2 (10-16), bzw. Hexaazadigermadispirododecanen, [(—NR—CH2—CH2—NR— )Ge(μ-NY-)]2 (17, 18). NMR-(1H, 13C, 14N, 15N und 29Si), MS-Daten und Röntgenstrukturanalysen für die Verbindungen 8, 9, 16 und 18 sind angegeben.
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  • 49
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 271-277 
    ISSN: 0009-2940
    Keywords: Chalcogenogermanes, (trifluoromethyl)- ; Disilaselenanes ; Germachalcogenanes, bis(trifluoromethyl)- ; Germanes, (trifluoromethyl)- ; Germatranes, (trifluoromethyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (Trifluormethyl)germanes, III. - Preparation of New (Trifluormethyl)germanium Chalcogene CompoundsStarting with the dihalogenobis(trifluoromethyl)germanes (CF3)2-GeX2 (X = Cl, or I), halogen-chalcogen exchange leads to corresponding chalcogen derivatives of the general type [(CF3)2GeE]n (6, 7) (E = O, NH, S, or Se). The resulting compounds differ in their degree of polymerisation. [(CF3)2GeO]x and the corresponding sesquioxane [(CF3)GeO1, 5]x are highly polymeric, quite in contrast to the corresponding germathianes and -selenanes. The crystal structure of [(CF3)2GeO]x (6a) was determined by X-ray single crystal diffraction. The reaction of CF3GeCl3 with triethanolamine results in the formation of 1-(trifluoromethyl)germatrane (13). Disilaselenane (10) reacts at low temperatures with chloro-(trifluoromethyl)germanes (CF3)nGeCl4-n under retention of one Si—Se bond to give (CF3)nGe(SeSiH3)4-n (11) and H3SiCl. Compounds with n = 3 and 2 could be isolated. Exchange of iodine by ECF3 takes place with iodogermanes (CF3)nGeI4-n and Hg(ECF3)2 (E = S, Se) with formation of a complete series of (trifluoromethyl)(trifluoromethylchalcogeno)germanes (CF3)nGe-(ECF3)4-n (3, 5).
    Notes: Durch Halogen-Chalkogen-Austauschreaktionen an (CF3)2)GeX2 (X = Cl, I) wurden Bis(trifluormethyl)germachalkogenane [(CF3)2GeE]n (6, 7) E = O, NH, S, Se) von unterschiedlichem Oligomerisierungsgrad erhalten. Die Germoxane [(CF3)2GeO]x und (CF3GeO1,5)x sind im Gegensatz zu den homologen Germathianen und -selenanen polymer, wobei die Struktur von [(CF3)2GeO]x (6a) durch eine Kristallstrukturanalyse ermittelt wurde. Durch Umsetzung von CF3GeCl3 mit Triethanolamin wird 1-(Trifluormethyl)germatran (13) erhalten. Disilaselenan (10) reagiert bei tiefen Temperaturen mit den Chlor (trifluormethyl)-germanen (CF3)nGeCl4-n monofunktionell unter Erhalt einer Si—Se-Bindung zu (CF3)nGe(SeSiH3)4-n (11) und H3SiCl, von denen die Verbindungen mit n = 3 und 2 isoliert werden konnten. Reaktionen der Iodgermane (CF3)nGeI4-n(1) mit Hg(ECF3)2) (E = S, Se) führen unter Substitution des Iods gegen die ECF3-Gruppen zur vollständigen Reihe der (Trifluormethyl)(trifluormethylchalkogeno)germane (CF3)nGe(ECF3)4-n (3, 5).
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  • 50
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 291-292 
    ISSN: 0009-2940
    Keywords: (Phthalocyaninato)copper complex, substituted with crown ethers ; Alkali metal extraction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A soluble (phthalocyaninato)copper(II) complex containing eight symmetrical benzo-15-crown-5 substituents, namely {2,3,9,10,16,17,23,24-octakis[[benzo-15-crown-5)-4′ -yl]oxymethyl]phthalocyaninato}copper(II) (2) from 1,2-bis{[benzo-15-crown-5)-4′-yl]oxymethyl}-4,5-dibromobenzene (1) and CuCN in quinoline or pyridine was synthesized. The crown-ether groups in 2 were shown to prefer intramolecular complexation with alkali metal ions.
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  • 51
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 463-466 
    ISSN: 0009-2940
    Keywords: C—C Rotation ; Sterical hindrance by SF5 groups ; Rotational barriers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterical Hindrance of the C—C Rotation by two SF5 GroupsAddition of SF5Cl to SF5CH=CF2 gives products carrying two SF5 groups on one carbon atom. As a consequence, C—C single bond rotation is strongly hindered. The highest rotational barrier observed is 61.7 kJ mol-1, rotational isomers are hence detectable at room temperature.
    Notes: Die Addition von SF5Cl an SF5CH=CF2 ergibt Produkte, die zwei SF5-Gruppen an einem Kohlenstoff tragen. In diesen kommt es zu einer starken Hinderung der Rotation um die C—C-Einfachbindung. Die höchste Rotationsbarriere wird mit 61.7 kJ mol-1 gefunden, d. h. Rotationsisomere sind bei Raumtemperatur getrennt nachweisbar.
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  • 52
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 467-472 
    ISSN: 0009-2940
    Keywords: Tetracarbonylchromium complexes ; 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure, and Reactions of 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborine DerivativesThe 1,2,3,6-tetrahydro-1,2,3,6-diphosphadiborine derivatives 3a and 3b are obtained by cyclocondensation of 1,2-bis[chloro(dialkylamino)boryl]ethenes 2 and 1,2-dipotassium 1,2-di-tert-butyldiphosphanediide. As in the case of 2,5-dihydro-1H-1,2,5-phosphadiborole derivatives 1 the temperature-dependent 1H-NMR spectra of 3b exhibit a lowered barrier of inversion at phosphorus. The X-ray structure analysis of 3b shows, that the six-membered C2B2P2 ring is nonplanar and the P atoms are coordinated pyramidally. Attempts to substitute the dialkylamino groups at the boron atoms of 3a and 3b with HCl·Et2O or tBuLi lead to cleavage of the B—P bonds. Reaction between 3a or 3b and Cr(CO)3(MeCN)3 does not result in the formation of tricarbonylchromium complexes but of tetracarbonylchromium complexes 6a and 6b with pentahapto-bonded ligands 3a and 3b.
    Notes: Die 1,2,3,6-Tetrahydro-1,2,3,6-diphosphadiborin-Derivate 3a und 3b entstehen durch Cyclokondensation aus 1,2-Bis[chlor(dialkylamino)boryl]ethenen 2 und 1,2-Dikalium-1,2-di-tert-butyldiphosphandiid. Die Temperaturabhängigkeit der 1H-NMR-Spektren von 3b dokumentiert wie bei 2,5-Dihydro-1H-1,2,5-phosphadiborol-Derivaten 1 eine erniedrigte Phosphor-Inversionsbarriere. Die Röntgenstrukturanalyse von 3b zeigt, daß der C2B2P2-Sechsring im Kristall nicht eben ist und daß die P-Atome pyramidal koordiniert sind. Versuche zur Substitution der Dialkylaminogruppen an den Boratomen von 3a und 3b mit HCl·Et2O oder tBuLi führen zur Spaltung der B—P-Bindungen. Die Umsetzung von 3a bzw. 3b mit Cr(CO)3(MeCN)3 ergibt keine Tricarbonylchrom-Komplexe, sondern die Tetracarbonylchrom-Komplexe 6a bzw. 6b, in denen die Liganden 3a und 3b pentahapto gebunden sind.
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  • 53
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Synthesis via Transition Metal Complexes, 34. - Novel Formation of C=C Bonds by Condensation of Acid Amides with Carbene Complexes Involving an Insertion of C2 Units into M=C BondsCarben complexes LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] and acid amides RCH2CONMe2 2 undergo a novel condensation reaction in presence of POCl3/Et3N to give alkenyl aminocarbene complexes 3. The reaction involves an insertion of a C2 unit of 2 into the M=C bond of 1 to give a C=C bond. It can be achieved with open-chain and cyclic amides like N-methyl-2-pyrrolidone (8). the structures of the complexes have been determined spectroscopically. A mechanism of the reaction is suggested.
    Notes: Carbenkomplexe LnM=C(OEt)C6H5 1 [LnM = Cr(CO)5, Mo(CO)5, W(CO)5] lassen sich mit Säureamiden RCH2CONMe2 2 und POCl3/Et3N zu Alkenyl-Aminocarben-Komplexen 3 kondensieren. Dabei wird eine C2-Einheit von 2 in die M=C-Bindung von 1 eingeschoben und eine C=C-Bindung neu geknüpft. Die Reaktion gelingt mit offenkettigen und cyclischen Amiden wie N-Methyl-2-pyrrolidon (8). Die Strukturen der Komplexe wurden spektroskopisch ermittelt und Vorschläge zur Deutung des Reaktionsablaufs gemacht.
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  • 54
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 711-714 
    ISSN: 0009-2940
    Keywords: Azulenes ; 1,6-Methano[10]annulenes ; 1,2,4,5-Tetrazine ; [4 + 2] Cycloadditions, „inverse“ ; Pyridazines, annulated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azulene and 1,6-Methano[10]annulene as Dienophiles in the Diels-Alder Reaction with 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazineThe LUMO-diene-controlled [4 + 2] cycloadditions of azulene (2) and 1,6-methano[10]annulene (14) with the electron-deficient s-cisfixed diazadiene system of 3,6-bis(trifluoromethyl)-1,2,4,5-tetrazine (1) are described. Contrary to expectation, 1 reacts under unusually mild conditions with 2 (or its valence tautomer 3) to yield the adduct 4 which after N2 elimination rearranges to the benzo[f]phthalazine 11. The Diels-Alder reaction of 1 with 14 (or its valence tautomer 13) leads to the annulated dihydropyridazines 15 and 16, which can be dehydrogenated by silver(I) oxide to the methano-bridged aromatic cyclodecapyridazine 17 and the olefinic phthalazino[5,6-f]phthalazine 18, respectively. Besides, the methano-bridged cyclodeca[d]pyridazine 24 is prepared.
    Notes: LUMO-Dien-kontrollierte [4 + 2]-Cycloadditionen von Azulen (2) und 1,6-Methano[10]annulen (14) an das elektronenarme, s-cis-fixierte Diazadiensystem von 3,6-Bis(trifluoromethyl)-1,2,4,5-tetrazin (1) werden beschrieben. Wider Erwarten reagiert 1 unter ungewöhnlich milden Bedingungen mit 2 (oder dessen Valenztautomerem 3) zum Addukt 4, das nach N2-Eliminierung und nachfolgender Umlagerung das Benzo[f]phthalazin 11 liefert. Die Diels-Alder-Reaktion von 1 mit 14 (oder dessen Valenztautomer 13) führt zu den beiden anellierten Dihydropyridazinen 15 und 16, die mit Silber(I)-oxid zu dem Methano-überbrückten aromatischen Cyclodecapyridazin 17 bzw. dem olefinischen Phthalazino[5,6-f]phthalazin 18 dehydriert werden können. Daneben wird das Methano-überbrückte Cyclodeca[d]pyridazin 24 dargestellt.
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  • 55
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 715-719 
    ISSN: 0009-2940
    Keywords: Alkyne ; Carbene ; Cycloisomerization ; Pyrolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Über die thermische Cycloisomerisierung langkettiger Alkylacetylene in der GasphaseDie thermische Cycloisomerisierung einiger Alkylacetylene wurde in einem Laborrohrreaktor aus Quarzglas untersucht. 1-Hexin (1) wird dabei durch 1,2-H-Verschiebung und 1,5-C,H-Insertion des intermediär gebildeten Pentylidencarbens (vgl. Schema 1) in 3-Methyl-1-cyclopenten (5) umgelagert. 5-Methyl-1-hexin (2) reagiert analog; es entsteht 3,3-Dimethyl-1-cyclopenten (6). Im Gegensatz zur Bildung von in 3-Stellung methylierten Cyclopentenen aus 1-Alkinen ensteht aus 2-Hexin (3) 1-Methyl-1-cyclopenten (7). Offenbar ist die Acetylen-Vinyliden-Umlagerung nicht auf 1,2-H-Verschiebung beschränkt. Der Mechanismus der Cycloisomerisierung von Alkylacetylenen wird durch Untersuchungen mit D-markierten Alkinen bestätigt. Die Ergebnisse lassen den Schluß zu, daß die Cycloisomerisierung ohne weiteres mit dem überwiegend nach einem Radikalketten-Mechanismus verlaufenden thermischen Zerfall konkurrieren kann.
    Notes: The thermal cycloisomerization of some alkylacetylenes was investigated in a tubular quartz reactor. At 570°C 1-hexyne (1) rearranges to 3-methyl-1-cyclopentene (5) with a selectivity of about 27 by a reaction sequence including an acetylene-vinylidene rearrangement and 1,5-C,H insertion of the intermediately formed alkylidenecarbene species. 5-methyl-1-hexyne (2) behaves analogously forming 3,3-dimethyl-1-cyclopentene (6), while 2-hexyne (3) provides 1-methyl-1-cyclopentene (7) indicating that the acetylene-vinylidene rearrangement is obviously not restricted to 1,2-H shifts. The mechanism of the cycloisomerization of alkylacetylenes is investigated by means of D-labeled parent alkynes. The results show that the unimolecular cycloisomerization via alkylidenecarbenes obviously can be an important channel despite the dominance of a radical chain course.
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  • 56
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 745-748 
    ISSN: 0009-2940
    Keywords: Flash Pyrolysis ; Matrix IR spectroscopy ; Photolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Methoxy- und AminoisocyanatMethoxyisocyanat (1) kann durch Photolyse von Azidoameisensäure-methylester (3) oder Pyrolyse von N-Methoxycarbonyl-O-methylhydroxylamin (4) dargestellt werden. Aminoisocyanat (2) ist auf ähnliche Weise durch Photolyse von Carbamoylazid (12) und Pyrolyse von Carbazinsäure-methylester (13) oder 3,4-Diaminofurazan (14) zugänglich. Die IR-Spektren von 1 und 2, aufgenommen in einer Argon-Matrix bei 10 K, werden diskutiert.
    Notes: Methoxyisocyanate (1) can be prepared by photolysis of methyl azidoformate (3) or pyrolysis of N-methoxycarbonyl-O-methyl-hydroxylamine (4). Aminoisocyanate (2) is similarly formed on photolysis of carbamoyl azide (12) and pyrolysis of either methyl carbazate (13) or 3,4-diaminofurazan (14). The infrared spectra of 1 and 2 in an argon matrix at 10 K have been measured, and some of their properties are discussed.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 749-752 
    ISSN: 0009-2940
    Keywords: Matrix isolation ; Photochemistry ; Theoretical vibrational spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Infrarot-Spektren und Photochemie von Isodiazen und seinen deuterierten IsotopomerenDie Matrixisolation von Aminoisocyanat eröffnet einen neuen ergiebigen Weg zur Darstellung von Isodiazen (Aminonitren). Damit ist es möglich geworden, nicht nur sein IR-Spektrum eindeutig festzulegen und mit Hilfe von ab-initio-Rechnungen zu interpretieren, sondern auch seine Photochemie zu untersuchen.
    Notes: The matrix isolation of aminoisocyanate opens a new efficient route for the preparation of isodiazene (aminonitrene). Its infrared spectrum can now, with the help of ab initio calculations, be interpreted, and its photochemistry can be studied.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 795-796 
    ISSN: 0009-2940
    Keywords: Thiochalcones ; Thienylchalcones ; Fries rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four new thienylchalcones (1, 4, 5, and 6) were synthesized by condensing hydroxy-nitroacetophenones with 2-thiophene and 3-thiophenecarboxaldehydes in the presence of dilute NaOH.
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  • 59
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 767-779 
    ISSN: 0009-2940
    Keywords: Molecular twisting ; cis-9,10-Dihydronaphthalenes, persubstituted ; Valence isomerizations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Valence Isomerizations, 17. - Persubstituted cis-9,10-Dihydronaphthalenes and their Valence IsomerizationsThe tricyclic diester 10 is available from 2-butyne in a six-step synthesis with an overall yield of 10%. Thermolysis of 10 gives the bicyclic diester 11 which upon UV irradiation yields 12 as the first persubstituted cis-9,10-dihydronaphthalene. X-ray analysis of 12 shows the molecule considerably twisted along the central bond. In addition, the planes of the ester groups are at an angle of approximately 60° to the „planes“ of the six-membered rings so that conjugation of the diene systems with the carbonyl functions is virtually interrupted, an effect which is reflected by the unusual spectroscopic properties of 12. The same structural features can be found in decamethyl-cis-9,10-dihydronaphthalene (16). When heated slightly, 12 is converted to the tetracyclic valence isomer 34. On reduction of 12 with diisobutylaluminum hydride both, dihydronaphthalene dicarbinol 25 as well as its unexpected positional isomer 26, are formed depending on the reaction conditions. Etherification of the reduction products with CH2N2/Et2O—BF3 furnishes a mixture of the three isomeric bis(methoxymethyl) compounds 31, 32 and 33. They can be separated by chromatography in the cold, but revert to the mixture of the three isomers at room temperature. We consider diradical 38 to be the intermediate of this intriguing valence isomerization.
    Notes: Der tricyclische Diester 10 ist in sechs Stufen in einer Gesamtausbeute von 10% aus 2-Butin zugänglich. Thermolyse von 10 liefert den Bicyclus 11, bei dessen UV-Bestrahlung das erste persubstituierte cis-9,10-Dihydronaphtalin 12 gebildet wird. Eine Röntgenstrukturanalyse von 12 beweist die starke Verdrillung des Moleküls um die zentrale Bindung. Die Ebenen der Ester-Gruppen stehen ungefähr in einem 60°-Winkel zu den Sechsring-„Ebenen“, so daß die Konjugation der Dien-Systeme mit den Carbonyl-Funktionen praktisch unterbrochen ist, ein Effekt, der sich in den ungewöhnlichen spektroskopischen Eigenschaften von 12 widerspiegelt. Analoge Strukturmerkmale gelten auch für das Decamethyl-cis-9,10-dihydronaphthalin (16). Bicyclus 12 wandelt sich bei leichtem Erwärmen in den valenzisomeren Tetracyclus 34 um. Reduktion von 12 mit Diisobutylaluminiumhydrid gibt je nach den Reaktionsbedingungen das Dihydronaphthalindicarbinol 25 bzw. das unerwartete Stellungsisomere 26. Veretherung der Reduktionsprodukte mit CH2N2/Et2O—BF3 liefert ein Gemisch der drei isomeren Bis(methoxymethyl)-Verbindungen 31, 32 und 33, die chromatographisch in der Kälte trennbar sind, aber schon bei Raumtemperatur wieder das Gemisch der drei Isomeren zurückbilden, wobei das Diradikal 38 als Zwischenprodukt dieser erstaunlichen Valenzisomerisierung anzunehmen ist.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 803-808 
    ISSN: 0009-2940
    Keywords: Bismuth organic compounds ; Fluorinated aromatic rings ; Square pyramidal bismuth ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structures of Pentaarylbismuth CompoundsPentaarylbismuth compounds were synthesized by the known reaction Ar3BiX2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2. Whenever possible they were characterized by single-crystal X-ray structure determination. In two cases almost ideal square-pyramidal geometry was found, in a third case there were two different molecules in the unit cell, both again with square-pyramidal geometry. None of these novel bismuth pentaaryls exhibit the deep coloration and the dichroism of Bi(C6H5)5.
    Notes: Pentaarylbismut- Verbindungen wurden durch die bekannte Reaktion BiAr3X2 + 2 Ar′Li → 2 LiX + BiAr3Ar′2 hergestellt und, soweit möglich, durch Röntgenbeugung an Einkristallen strukturell untersucht. In zwei Fällen erwies sich die Struktur als nahezu ideal quadratisch-pyramidal, in einem dritten Fall wurden zwei unterschiedliche Moleküle im Kristall gefunden, die aber beide wiederum quadratisch-pyramidal sind. Keines der hier vorgestellten neuen Bismutpentaaryle zeigt die tiefe Färbung und den Dichroismus von Bi(C6H5)5.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 533-535 
    ISSN: 0009-2940
    Keywords: Free radicals ; Triphenylmethyl radicals ; ESR measurements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sterically Hindered Free Radicals, XIX. - Stable 4,4′,4″-Trisubstituted Triphenylmethyl RadicalsThe title radicals (4-R—C6H4)3C. (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, have been prepared, the latter four for the first time, and the ESR spectra have been recorded. aoH, amH, and apR are listed. The intensities of the ESR signals remain constant within the accessible range of -30 to + 100°C. Within this range these radicals are kinetically stable and do not dimerize like other trityls by, e.g., α,p-, α,o-, α,α -recombinations.
    Notes: Die Titelradikale (4-R—C6H4)3C· (1), R = F, Cl, Ph, OMe, NO2, tBu, OEt, SMe, CN, CF3, wurden dargestellt, davon die vier letzten erstmalig, und mittels ESR-Spektroskopie vermessen. aoH, amH und apR werden angegeben. Die ESR-Signale bleiben im gesamten zugänglichen Temperaturbereich - 30 bis + 100°C in ihrer Intensität unverändert. Daraus folgt, daß alle diese Radikale im genannten Temperaturbereich kinetisch stabil sind, also nicht wie andere Trityle zu Dimerisierungen, etwa α,p-, α,o-, α,α-, neigen.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 523-531 
    ISSN: 0009-2940
    Keywords: Dicyclopenta-s-indacene ; 2-Osxa[3.3.3]propellane derivatives ; Pentalene derivatives ; [3.3.3]Propellane-3,7-dione ; Weiss reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Products in the Weiss Reaction of 1,2-Cyclopentanedione. Improved Preparation of [3.3.3]Propellane-3,7-dioneThe reaction of 1,2-cyclopentanedione (1c, 9) with the 3-oxoglutarate 4 in methanol/water in the presence of sodium bicarbonate followed by hydrolysis and decarboxylation of the product mixture affords the oxa[3.3.3]propellane ester 11c in addition to the [3.3.3]propellanedione 6c. The alkali enolates of 4 react with 9 in boiling methanol to yield the yellow, poorly soluble alkali dihydropentalenolates 12M and the [3.3.3]propellane tetraester 5c, which on hydrolysis and decarboxylation yields 53% of 6c. The dihydropentalenol 12H equilibrates with the tautomeric β-oxodiester 13, the proportion of which increases with solvent polarity. In methanol solutions, 12H and 13 add diastereoselectively forming the dicyclopenta-s-indacene tetraester syn-14, which is derived from a novel pentacyclic ring system. The configuration of syn-14 is determined by X-ray diffraction analysis. The mechanisms of formation are discussed for 11c, 12M, and syn-14.
    Notes: Nach Umsetzung von 1,2-Cyclopentandion (1c, 9) mit dem 3-Oxoglutarsäureester 4 in Methanol/Wasser in Gegenwart von Natriumhydrogencarbonat, saurer Hydrolyse und Decarboxylierung des Produktgemischs erhält man neben dem [3.3.3]Propellandion 6c den Oxa[3.3.3]propellanester 11c. Die Alkali-Enolate von 4 reagieren mit 9 in siedendem Methanol zu den gelben, schwer löslichen Dihydropentalenolaten 12M und dem [3.3.3]Propellantetraester 5c, der nach Hydrolyse und Decarboxylierung 53% 6c ergibt. Das Dihydropentalenol 12H liegt im Gleichgewicht mit dem tautomeren β-Oxodiester 13 vor, dessen Anteil mit der Polarität des Lösungsmittels zunimmt. In Methanol addieren sich 12H und 13 diastereoselektiv und bilden den Dicyclopenta-s-indacentetraester syn-14, der sich von einem neuartigen, pentacyclischen Ringsystem ableitet. Die Konfiguration von syn-14 wird durch Röntgenstrukturbestimmung aufgeklärt. Die Mechanismen der Bildung von 11c, 12M und syn-14 werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 553-559 
    ISSN: 0009-2940
    Keywords: Amino acids ; Diastereoselective addition ; 1-(Methacryloyl)proline derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 15. - Diastereoselective Addition of Thiocarboxylic Acids to 1-(Methacryloyl)proline and-prolinol DerivativesThiocarboxylic acids 6 add to 1-(methacryloyl)-substituted proline and prolinol derivatives stereoselectively to give the 1-[3-(acylthio)-2-methylpropionyl]proline and -prolinol derivatives 7,7′ and 9. The less soluble (2S,2′R)-diastereomers are obtained in optical yields ≥ 98% by digestion of the crude products, the configuration of which was determined by acid hydrolysis of (2S,2′R)-7,7′ to (R)-3-mercapto-2-methylpropionic acid [(R)-8]. The stereoselectivity of the additions may be explained by a sevenmembered ring intermediate with an intramolecular H bridge, to which the S-nucleophiles add preferentially to give the compounds with the (2′R)-configuration.
    Notes: Thiocarbonsäuren 6 addieren stereoselektiv mit hohen optischen Ausbeuten an 1-(Methacryloyl)-substituierte Prolin- und Prolinol-Derivate zu den 1-[3-(Acylthio)-2-methylpropionyl]prolin-und -prolinol-Derivaten 7,7′ und 9. Durch Digerieren der Rohprodukte mit Diethylether werden die schwerer löslichen (2S,2′R)-Diastereomeren in optischen Ausbeuten ≥98% erhalten, deren Konfiguration durch Acidolyse von (2S,2′R)-7,7′ zu (R)-3-Mercapto-2-methylpropansäure [(R)-8] bewiesen wurde. Die Stereoselektivität der Additionen wird über einen Siebenring mit intramolekularer H-Brücke als Zwischenstufe, an die Schwefelnucleophile bevorzugt unter Bildung der (2′R)-Konfiguration addieren, gedeutet.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 545-551 
    ISSN: 0009-2940
    Keywords: Amino acids ; Diastereoselective addition ; 1-Acryloylproline esters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Amino Acids, 14. - Diastereoselective Addition of Benzenesulfenyl Chloride to 1-Acryloylproline Esters(S)-Proline esters (S)-1 react with acryloyl chloride (2) to give 1-acryloylproline esters (S)-3 in good yields. Addition of benzenesulfenyl chloride (6) to (S)-3 at -95°C in dichloromethane results in 1-[2-chloro-3-(phenylthio)propionyl]proline esters (2S,2′R/2S,2′S)-7. The diastereoselectivity of the addition depends on the conformer ratio 3′/3″ of the starting material (S)-3. The diastereomers are separated by MPLC. Configuration at C-2′ of the resulting main products (2S,2′S)-7 was proved by independent synthesis. The diastereoselectivity of the addition of 6 to (S)-3 is interpreted to result from formation of a complex of the benzenesulfenyl cation with the proline ester group and subsequent electrophilic addition to a thiiranium intermediate B with (2S,2′R) configuration; the (2S,2′S) diastereomeric adduct 7 then results by nucleophilic attack of chloride at C-2′ under ring opening.
    Notes: Die 1-Acryloylprolinester (S)-3 werden durch N-Acylierung der Prolinester (S)-1 mit Acryloylchlorid (2) in guten Ausbeuten hergestellt; sie addieren Benzolsulfenylchlorid (6) bei -95°C in Dichlormethan mit hoher Diastereoselektivität zu 1-[2-Chlor-3-(phenylthio)propionyl]prolinestern (2S,2′R/2S,2′S)-7, die mittels MPLC getrennt werden. Die Diastereoselektivität der Addition hängt vom Konformerenverhältnis 3′/3″ der Edukte (S)-3 ab. Der Beweis der Konfiguration an C-2′ der als Hauptprodukte anfallenden Diastereomeren (2S,2′S)-7 wird durch eine unabhängige Synthese erbracht. Die Diastereoselektivität der Addition von 6 an (S)-3 wird über eine Komplexbildung des Phenylsulfenylkations mit der Prolinestergruppe und eine sich anschließende elektrophile Reaktion zu einer Thiiranium-Zwischenstufe B mit (2S,2-R)-Konfiguration gedeutet; das (2S,2′S)-diastereomere Additionsprodukt 7 entsteht dann durch nucleophilen Angriff des Chlorids an C-2′ unter Ringöffnung.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 851-855 
    ISSN: 0009-2940
    Keywords: Diphosphines ; Tungsten - tungsten quadruple bond ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Struktur von W2Cl4{μ(iPr2PCH2CH2CH2PiPr2)}2: Eine durch sperrige, chelatisierende Diphosphane überbrückte Wolfram - Wolfram-VierfachbindungDie Reduktion von WCl4 in THF durch zwei Äquivalente Na/Hg in Gegenwart des sperrigen, chelatisierenden Diphosphinopropans iPr2PCH2CH2CH2PiPr2 (dippp) liefert den violetten, zweikernigen Komplex W2Cl4(μ-dippp)2. Der Komplex besitzt eine W-W-Vierfachbindung und β-Struktur, d.h. die chelatisierenden Diphosphinopropan-Liganden verbrücken die beiden Metall-Zentren. Die 1H-NMR-spektroskopischen Daten zeigen Tieffeldverschiebungen für die dippp-Liganden, die im Einklang mit der β-Struktur stehen. Das 31P{1H}-NMR-Spektrum besteht aus einem Singulett mit 183W-Satelliten. Die Röntgen-Stukturanalyse ergibt für die β-Struktur einen Torsionswinkel P-W-W-P von 75.9° und eine W-W-Bindungslänge von 2.297(1) Å. Aus den Molekülstruktur-Daten und den 1H-NMR-Tieffeldverschiebungen kann die diamagnetische Anisotropie χ der W-W-Vierfachbindung mit - 3000 ± 300 × 10-36 m3/Molekül abgeschätzt werden. Die für den festen Zustand beobachtete Chiralität wird auch in Lösung beibehalten.
    Notes: The reduction of WCl4 in THF by two equivalents of Na/Hg in the presence of the bulky chelating diphosphine iPr2PCH2-CH2CH2PiPr2 (dippp) generates the purple, binuclear complex W2Cl4(μ-dippp)2. The quadruply-bonded molecule has a β structure, that is, the chelating diphosphine bridges the two metal centers. 1H-NMR spectral data show downfield shifts for the ligand protons consistent with the β structure. The 31P{1H}-NMR spectrum consists of a singlet with 183W satellites. The X-ray crystal structure has a twist angle (P-W-W-P torsion angle) of 75.9°, and the W-W bond length is 2.297(1) Å. Using the solidstate data and the observed downfield shifts in the 1H-NMR spectrum, the diamagnetic anisotropy χ has been estimated as - 3000 ± 300 × 10-36 m3/molecule. The chiral structure observed in the solid phase is retained in solution.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 861-864 
    ISSN: 0009-2940
    Keywords: Aminoiminophosphanes ; 1,3,2λ5,4-Thiazaphosphaboretidines ; 1,2,4,3,5-Trithiadiborolanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Characterization of 1, 3, 2λ5, 4-ThiazaphosphaboretidinesThe reaction of 1,2,4,3,5-trithiadiborolanes with silylated aminoiminophosphanes leads to the 1,3,2λ5,4-thiazaphosphaboretidines 1a-i. The formation of 1h, i is accompanied by an exchange of the substituents bonded to the N atoms. 1H-, 11B-, 13C-, 29Si-, 31P-NMR, and mass spectra are discussed.
    Notes: Die Umsetzung von 1,2,4,3,5-Trithiadiborolanen mit silylierten Aminoiminophosphanen führt zu den 1,3,2λ5,4-Thiazaphosphaboretidinen 1a-i. Die Bildung von 1h, i wird von einem Austausch der N-ständigen Substituenten begleitet. 1H-, 11B-, 13C-, 29Si-, 31P-NMR- und Massenspektren werden diskutiert.
    Additional Material: 3 Tab.
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 857-860 
    ISSN: 0009-2940
    Keywords: Alkenylboranes ; Alkenylstannanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Convenient Route from Alkenylboranes to AlkenylstannanesAlkenyldialkylboranes 1 with various substituents at the C=C double bond, including organometallic groups such as the trimethylstannyl or trimethylsilyl group, react in hexane solution with (diethylamino)- or (dimethylamino)trimethylstannane (2) in the presence of a catalytic amount of lithium dimethyl- or diethylamide (3) to give aminodialkylboranes 4 and alkenyltrimethylstannanes 5 in high yields with retention of the configuration at the C—C double bond. With (diethylamino)trimethylplumbane (2c) the less stable alkenes 5Pb are obtained. A mechanism is proposed, and 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-data are reported.
    Notes: Alkenyldialkylborane 1 mit verschiedenen Substituenten an der C=C-Doppelbindung, einschließlich organometallischer Gruppen wie dem Trimethylstannyl- oder dem Trimethylsilyl-Rest, reagieren in Hexan mit (Diethylamino)- oder (Dimethylamino)trimethylstannan (2) in Gegenwart einer katalytischen Menge von Lithium-diethylamid (3b) oder -dimethylamid (3a) in hoher Ausbeute unter Beibehaltung der Konfiguration an der C—C-Doppelbindung zu den entsprechenden Alkenylstannanen 5 und Aminoboranen 4. Durch Einsatz von (Diethylamino)trimethylplumban (2c) lassen sich die weniger stabilen Alkene 5Pb erhalten. Ein Mechanismus wird vorgeschlagen, und 1H-, 13C-, 29Si-, 119Sn- und 207Pb-NMR-Daten werden mitgeteilt.
    Additional Material: 1 Tab.
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  • 68
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1919-1924 
    ISSN: 0009-2940
    Keywords: Hydrogen transfer ; Ziegler catalysis ; Dihydroarenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ziegler Nickel Catalysts for Hydrogen Transfer ReactionsCatalysts prepared from Ni(acac)2 and AlEt3 show high catalytic activity in the hydrogen transfer between dihydroarenes, but hardly any isomerisation and H/D scrambling is observed. The active form of the catalyst is produced only in the presence of the starting material. Kinetic experiments, especially those concerning the introduction periods and the inhibition, are indicative of a complex reaction mechanism. The first hydrogen is preferentially abstracted from the 2-position, the second with complete cis selectivity.
    Notes: Der aus Ni(acac)2 und AlEt3 dargestellte Katalysator zeigt eine hohe Aktivität beim H-Transfer zwischen Dihydroarenen, neben dem Isomerisierungen und H/D-Austausch kaum ablaufen. Die aktive Form entsteht erst in Gegenwart des Edukts. Kinetische Untersuchungen, vor allem zur Induktionsperiode und zur Hemmung, deuten auf einen komplexen Ablauf. Der Wasserstoff wird cis-selektiv abgespalten, primär bevorzugt aus der 2-Position.
    Additional Material: 1 Ill.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1925-1927 
    ISSN: 0009-2940
    Keywords: Hydrogen transfer ; Olefin isomerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydrogen Transfer Reactions, 13.  -  Catalysis of Disproportionation by (Dinitrogen)hydridotris(triphenylphosphine)cobalt(I)For both C—H activation and olefin isomerization, CoH(N2)(PPh3)3 (1) is a more powerful catalyst than the Wilkinson complex. In 1,2-dihydronaphthalene (2), a two-step cis abstraction of the hydrogen atoms is found with small regioselectivity in the first step.
    Notes: Die Aktivität des Komplexes CoH(N2)(PPh3)3 (1) liegt bei der C—H-Aktivierung deutlich höher als beim Wilkinson-Katalysator. Noch effektiver wird aber eine Olefin-Isomerisierung induziert. Die zweistufige H-Abstraktion erfolgt beim 1,2-Dihydronaphthalin (2) cis-selektiv, der Primärschritt aber kaum regioselektiv.
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  • 70
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1935-1938 
    ISSN: 0009-2940
    Keywords: as-Triazinium salt, fused ; Ring transformation ; Solvatochromy, negative ; Zwitterion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Ringtransformation von neuen kondensierten as-Triazinium-SalzenDie Reaktion des 1,2-Diaminopyridinium-Salzes 1 mit dem Furandion 2 ergab ein Pyrido-as-triazinon 3, das zum tricyclischen Furo[2,3-e]pyrido[1,2-b]-as-triazinium-Salz 5 cyclisiert wurde. Die Reaktion von 5 mit Nucleophilen führte zu unterschiedlichen Produkten: mit wäßriger Base entstand das bicyclische Triazinon 4, mit dem Methoxid-Ion und sekundären Aminen wurden die stabilen Zwitter-Ionen 7a, b erhalten, wohingegen Ammoniak und Hydrazine unter Transformation des Furanringes die neuen tricyclischen kondensierten Pyrrole 10, 11 bzw. Pyridazine 13, 14a, b ergaben.
    Notes: The 1,2-Diaminopyridinium salt 1 was treated with furandione 2 to give pyrido-as-triazinone 3, which could be cyclized to the tricyclic furo[2,3-e]pyrido[1,2,-b]-as-triazinium salt 5. Reaction of 5 with nucleophiles resulted in different types of products. Thus, aqueous base afforded bicyclic triazinone 4, methoxide ion or secondary amine led to stable zwitterions 7a, b, whereas ammonia and hydrazines resulted in ring transformation of the furan moiety, and gave new fused tricyclic pyrroles (10, 11) and pyridazines (13, 14), respectively.
    Additional Material: 1 Ill.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1947-1953 
    ISSN: 0009-2940
    Keywords: Enol ethers ; [n](2,4)Phloroglucinophanes ; Autoxidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations of the Autoxidation and the Rearrangement of [n](2,4)PhloroglucinophanesIn the autoxidation of [n](2,4)phloroglucinophanes 3 hydroperoxides 7 are isolated in several cases as the first oxidation products; they react to the more stable monohydroxylated compounds 8 with different rates. Acylphloroglucinophanes 5, however, react with oxygen to give the dihydroxylated compounds 9. The autoxidation rate of the phloroglucinophanes 3, 5 is markedly larger than that of diethylphloroglucinols 6. In alkaline solution the hydroxy compounds 8 rearrange to the dihydroxycyclopentenones 12; the rate of rearrangement correlates with the decrease of ring strain.
    Notes: Bei der Autoxidation von [n](2,4)Pholoroglucinophanen 3 können in einigen Fällen Hydroperoxide 7 als erste Oxidationsprodukte isoliert werden, die unterschiedlich rasch in die stabileren monohydroxylierten Verbindungen 8 übergehen. Aclphloroglucinophane 5 reagieren mit Luftsauerstoff dagegen zu den zweifach hydroxylierten Verbindungen 9. Die Geschwindigkeit der Autoxidation ist bei den Phloroglucinophanen 3, 5 deutlich größer als bei den 2,4-Diethylphloroglucinen 6. Im alkalischen Medium lagern sich die Hydroxyverbindungen 8 in die Dihydroxycyclopentenone 12 um, wobei für die Geschwindigkeit der Umlagerung eine Korrelation mit der Abnahme an Ringspannung gefunden wird.
    Additional Material: 3 Tab.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1963-1967 
    ISSN: 0009-2940
    Keywords: Allenyl azides, ring closure of ; Propargyl azides, rearrangement, base-induced ; Triazafulvenes, nucleophilic addition to ; 1,2,3-Triazoles, preparation of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Unsaturated Azides, 7.  -  Base-catalyzed Formation of Allenyl Azides from Propargyl Azides: New Syntheses for 1,2,3-TriazolesThe propargyl azides 10, 14, 17, 20, and 28 undergo a base-catalyzed (prototropic) rearrangement to short-lived allenyl azides. These intermediates rapidly cyclize to triazafulvenes, which can be trapped by nucleophiles (methanol, sodium hydroxide, ammonia) to give 1,2,3-triazoles. Starting with the precursors 9, 13, 16, 19, and 27 one-pot syntheses lead to the heterocycles 12, 15, 18, 21, and 29. Depending on the reaction conditions, compound 10 regioselectively yields 12c (75%) by prototropic rearrangement (path B) or by migration of the azide group (path A) the isomer 11c (62%).
    Notes: Die Propargylazide 10, 14, 17, 20 und 28 lagern sich basenkatalysiert (prototrop) zu kurzlebigen Allenylaziden um. Diese Zwischenstufen cyclisieren rasch zu Triazafulvenen, die mit Nucleophilen (Methanol, Natriumhydroxid, Ammoniak) als 1,2,3-Triazole abgefangen werden können. Ausgehend von den Vorläufern 9, 13, 16, 19 und 27 führen Eintopf-Synthesen zu den Heterocyclen 12, 15, 18, 21 und 29. In Abhängigkeit von den Reaktionsbedingungen liefert 10 über die prototrope Umlagerung (Weg B) regioselektiv 12c (75%) oder durch Azidwanderung (Weg A) die isomere Verbindung 11c (62%).
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2023-2025 
    ISSN: 0009-2940
    Keywords: Homoallylic alcohols ; [2,3] Sigmatropic rearrangement ; Stereoselective synthesis of alcohols ; [2,3] Wittig rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reductive cleavages of allyl [(phenylthio)methyl] ethers (8, 11) and an allyl [(tolylsulfonyl)methyl] ether (14) with lithium naphthalenide in THF furnish homoallylic alcohols (9, 12). The steric course of these transformations (E/Z selectivity in the case of 9, syn/anti selectivity for 12) is very similar to that of analogous Wittig-Still rearrangements.
    Additional Material: 1 Tab.
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  • 74
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2049-2054 
    ISSN: 0009-2940
    Keywords: Ligating properties ; Pentaphosphaferrocenes ; Sandwich and triple-decker complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pentaphospaferrocenes as Complex LigandsThe interaction of [Cp*Fe(P5)] (1a) with [Cr(CO)5(thf)] and [Cp(CO)2Mn(thf)], respectively, affords [Cp*Fe(P5){Cr(CO)5}2] (2) as well as [Cp*Fe(P5){Mn(CO)2Cp}n] (4a-d; n = 1-4; Cp* = η5-C5Me5). Irradiation of 1 and [CpFe(C6H6)]PF6 gives the cationic 30-VE triple-decker complexes [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5). In addition to the NMR studies 2 and 3b have been characterized by X-ray structure analyses.
    Notes: Die Umsetzung von [Cp*Fe(P5)] (1a) mit [Cr(CO)5(THF)] bzw. [Cp(CO)2Mn(THF)] ergibt [Cp*Fe(P5){Cr(CO)5}2] (2) sowie [HCp*Fe(P5){Mn(CO)2Cp}n] (4a-d; 1-4; Cp* = η5-C5Me5). Aus 1 und [CpFe(C6H6)]PF6 lassen sich photochemisch die kationischen 30-VE-Tripeldeckerkomplexe [CpFe(μ, η5-P5)Fe(C5Me4R)]PF6 (3a: R = CH3; 3b: R = C2H5; Cp = η5-C5H5) aufbauen. Zusätzlich zu den NMR-spektroskopischen Studien wurden von 2 und 3b Kristallstrukturanalysen angefertigt.
    Additional Material: 3 Ill.
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  • 76
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    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1139-1145 
    ISSN: 0009-2940
    Keywords: C-(Alkylideneamino)ketene imines ; Isocyanides, C=C coupling with aminocarbene ligands ; (2-Azaallenyl)chromium complexes ; 2-Imidazolin-5-ones ; α-Amino acids ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organic Syntheses via Transition Metal Complexes, 35. - (C-Amino) Ketene Imines, 2-Imidazolin-5-ones, and α-Amino Acids from Aminocarbene Chromium Complexes and IsocyanidesC-(Alkylidenamino)ketene imines 1,4-diaza-1,2,4-pentatrienes) 8 are easily accessible by C=C coupling of isocyanides R1 - NC (2, R1 = t-C4H9, c-C5H11, CH3) with the (alkylideneamino)carbene (= 2-azaallenyl-) ligand of (6). The tendency for an insertion of 2 into M=C bonds of aminocarbene complexes strongly depends on the electronic character of the aminocarbene ligand. Electron-rich aminocarbene chromium complexes like (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), show only little tendency for an insertion but mainly give cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) by substitution of CO. Electron-poor aminocarbene complexes like 6 (readily available on N-benzoylation of 1a) undergo a facile insertion of 2 into the M=C bond with smooth formation of 7. From 7 ketene imine 8 is spontaneously disengaged by a second equivalent of 2. The reaction works especially well with bulky isocyanides 2a, b. In the case of methyl isocyanide (2c) a [bis(imino)dihydropyrrol]chromium complex 15 is obtained as a minor product besides 8c. 15 results from a [4+1] cycloaddition of 2c at the ketene imine ligand of 7c. C-(Alkylideneamino)ketene imines 8 are easily accessible by our method. They prove to be very thermolabile in solution and spontaneously isomerize to give 2-imidazolin-5-ones 10 and C-amidoketene imines 11. Under the influence of wet silica gel keten imine derivatives 8 rapidly form α-amino acid amides 16 by hydrolysis with concomitant migration of a benzoyl group. Under the same conditions 11 also gives the „normal“ α-amino acid amides 17.
    Notes: C-(Alkylideneamino)ketenimine (1,4-Diaza-1,2,4-pentatriene) 8 wurden durch C=C-Kupplung von Isocyaniden R1-NC (2, R1 = t-C4H9, c-C5H11, CH3) mit dem (Alkylideneamino)carben-(= 2-Azaallenyl-)Ligand von (6) erstmals hergestellt. Die Bereitschaft zur Insertion von 2 in M=C-Bindungen von Aminocarbenkomplexen hängt stark von den elektronischen Eigenschaften der Aminocarbenliganden ab. Elektronenreiche (Aminocarben)chromkomplexe, wie z. B. (CO)5Cr=C(NR2)C6H5 (1, R = H, CH3), zeigen eine nur geringe Neigung zur Insertion von 2 und bilden bevorzugt cis-(R1-NC)(CO)4Cr=C(NR2C6H5 (3) unter Substitution von CO. Elektronenarme (Aminocarben)chromkomplexe hingegen, wie z. B. 6 (durch N-Benzoylierung von 1a leicht zugänglich), zeigen ausschließlich Insertion zu 7. Aus 7 wird spontan 8 freigesetzt durch Substitution mit einem zweiten Äquivalent 2. Sperrige Isocyanide 2a, c reagieren besonders einheitlich. Mit Methylisocyanid (2c) entsteht zusätzlich zu 8c der [Bis(imino)dihydropyrrol]-chromkomplex 15 unter [4+1]-Cycloaddition von 2c am Keteniminligand von 7c. C-(Alkylidenamino)ketenimine 8 sind nach unserem Verfahren einfach zugänglich; sie isomerisieren jedoch leicht zu 2-Imidazolin-5-onen 10 und C-Amidoketeniminen 11. An feuchtem Kieselgel entstehen aus 8 rasch α-Aminosäureamide 16 durch Hydrolyse unter Wanderung eines Benzoylrestes; aus 11 unter gleichen Bedingungen zusätzlich „normale“ α-Aminosäureamide 17.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2177-2181 
    ISSN: 0009-2940
    Keywords: Benzonitriles ; Hetero Diels-Alder reactions, “inverse” ; Pyrazines, annulated ; Triazines, benzofuro- and benzothieno- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Donor-Substituted Benzoitriles as Side-Chain Dienophiles in the Intramolecular [4+2] Cycloaddition with Inverse Electron DemandExpanding the scope of the intramolecular Diels-Alder reaction of 1,2,4,5-tetrazines to include donor-substituted benzonitriles as side-chain dienophiles we describe synthetic routes to novel fused heterotricycles such as the benzofuro[3,2-e]-1,2,4-triazines 11a, b and the benzothieno[3,2-e]-1,2,4-triazines 14a, b, and 17. The doubly annulated pyrazines 22 and 23 are constructed by a subsequent second intramolecular Diels-Alder cycloaddition of the benzonitrile moiety with the fused 1,2,4-triazine system, starting from 11a and 14a.
    Notes: Unter Einschluß donorsubstituierter Benzonitrile als Seitenkettendienophile haben wir die Anwendungsbreite der intramolekularen Diels-Alder-Reaktion von 1,2,4,5-Tetrazinen erweitert und beschreiben Synthesewege zu neuen anellierten Heterotricyclen wie den Benzofuro[3,2-e]-1,2,4-triazinen 11a, b und den Benzothieno[3,2-e]-1,2,4-triazinen 14a, b sowie 17. Die doppelt anellierten Pyrazine 22 und 23 lassen sich durch eine nachfolgende zweite intramolekulare Benzonitril/1,2,4-Triazin-Diels-Alder-Cycloaddition mit 11a bzw. 14a als Edukten herstellen.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2147-2157 
    ISSN: 0009-2940
    Keywords: 1,3-Dipolar cycloadditions, intramolecular ; Nitrile oxides ; Regioselectivity ; Furanophanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular Cycloadditions with Nitrile Oxides: Investigtions towards the Synthesis of HeterophanesThe intramolecular cycloaddition reactions of the nitrile oxides 30a-d, 35, 36, and 47, obtained in situ from the 2,5-difunctional furan hydroximoyl chlorides 12a, b, 18 and the nitro compounds 9c, d, 21, 29, are described. With 30c the expected isoxazolofuranophane of type 31 is formed in acceptable yield; the additionally formed regioisomer 32c and the dimer 34c are very minor products in this case. Whereas the highest homologue 30d gives a complex product mixture with small amounts of 31 d and the macrocycle 34d as the only identified compounds, the derivatives bearing a shorter side chain (30a, b; n = 1, 2) give rise to the exclusive reaction of the dipole with a double bond of the furan system (to give 33a, b). The same behavior is observed in the case of the electronically and sterically modified dipole systems 35/36 and 47, resp.; in spite of the much more favorable conditions for the formation of cyclophanes the cycloadditions result in the exclusive formation of the heterotricycles 41, 42 and 49. Possible preparative applications of the isomeric cycloaddition compounds are discussed.
    Notes: Die intramolekularen Cycloadditionsreaktionen der aus 2,5-difunktionellen Furan-Hydroximsäurechloriden (12a, b und 18) bzw. den Nitroverbindungen 9c, d, 21 und 29 in situ hergestellten Nitriloxide 30a-d, 35, 36 und 47 werden beschrieben. Eine Reaktion zu den angestrebten Isoxazolo-furanophanen des Typs 31 verläuft für 30c in brauchbarer Ausbeute; das Regioisomere 32c sowie das Dimere 34c treten hierbei nur in geringem Maße auf. Während das höchste Homologe 30d neben 31d und dem Makrocyclus 34d hauptsächlich Zersetzungsprodukte bildet, reagieren die Derivate mit kürzerer Seitenkette (30a, b; n = 1, 2) ausschließlich unter dipolarer Addition an eine Furandoppelbindung zu 33a, b. Für n = 1 entsprechen diesem Verhalten auch die elektronisch bzw. sterisch modifizierten Dipolsysteme 35/36 und 47, die trotz günstigerer Voraussetzungen für die Cyclophanbildung nur zu den Tricyclen 41, 42 bzw. 49 reagieren. Die präparativen Anwendungsmöglichkeiten der isomeren Cycloadditionsverbindungen als Synthesezwischenprodukte werden diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2183-2185 
    ISSN: 0009-2940
    Keywords: [4 + 2] Cycloaddition ; 3,5-Dihydroxytropone ; Singlet oxygen ; Y aromaticity ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von 3,5-DihydroxytroponWir beschreiben eine vierstufige Synthese des bisher unbekannten 3,5-Dihydroxytropons (6), die von Tropon ausgeht und eine [4 + 2]-Cycloaddition mit Singulett-Sauerstoff einschließt.
    Notes: Starting from tropone, the hitherto unknown 3,5-dihydroxytropone (6) is prepared in a four-step synthesis including a [4 + 2] cycloaddition reaction of singlet oxygen.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2207-2208 
    ISSN: 0009-2940
    Keywords: Allenes ; Hetero Diels-Alder reactions ; Catalysis, heterogeneous ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some examples of cycloadditions of 1-ethoxy-1,2-propadiene with 1-oxa-1,3-dienes, catalyzed by acid-free silica gel, are reported.
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    Berichte der deutschen chemischen Gesellschaft 122 (1989) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
    ISSN: 0009-2940
    Keywords: Bisporphyrinates, cerium(IV) ; Lanthanoid porphyrins ; Metalloporphyrins ; Tetrapyrrole complexes, sandwich-like ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallkomplexe mit Tetrapyrrol-Liganden, LIV.  -  Synthese, Spektren, Struktur und Redox-Chemie von Cer(VI)-Bisporphyrinaten mit gleichen und verschiedenen Porphyrin-Ringen im Sandwich-SystemWeitere symmetrische Cer(IV)-Bisporphyrinate werden aus Cer-(III)-acetylacetonat und Tetraphenylporphyrin, Tetra-p-chlorphenylporphyrin, und Hexadecahydrotetrabenzporphyrin hergestellt. Aus dem letzteren Porphyrin entsteht auch ein Biscer(III)-Tripeldecker; ein solcher bildet sich als einziges Produkt aus Octamethylporphyrin. Aus einem Gemisch zweier verschiedener Porphyrine, nämlich Octaethylporphyrin [H2(OEP)], und Tetraphenyl-porphyrin [H2(TPP)] oder Tetra-p-chlorphenylporphyrin [H2-(TClP)] erhält man neben den symmetrischen Spezies Ce(OEP)2 und Ce(TPP)2 die unsymmetrischen („gemischten“) Doppeldecker Ce(OEP)(TPP) oder Ce(OEP)(TClP), die verschiedene Porphyrin-Ringe im Sandwich-System haben und sich trennen lassen. Die Kristallstrukturanalyse von Ce(OEP)(TPP) zeigt CeIV in quadratisch-antiprismatischer Umgebung der Pyrrol-N-Atome der Porphyrin-Ringe. Während die IR- und NMR-Spektren der unsymmetrischen Doppeldecker-Überlagerungen der Spektren, die einzelnen Ringe darstellen, zeigen ihre UV/VIS-Spektren und die cyclischen Voltammogramme, daß die zwei unterschiedlichen Porphyrin-Ringe sich wie ein gemeinsames π-Elektronensystem verhalten. Die Darstellung der π-Kation-Radikal-Salze [Ce(OEP)2]-ClO4 und [Ce(OEP)(TPP)]SbCl6 wird ebenfalls beschrieben. In letzterem scheint sich das Defektelektron bevorzugt im OEP-Ring aufzuhalten.
    Notes: Further symmetrical cerium(IV) bisporphyrinates are prepared from cerium(III) acetylacetonate and tetraphenylporphyrin, tetra-p-chlorophenylporphyrin, and hexadecahydrotetrabenzporphyrin. In the latter case, a biscerium(III) triple-decker is also found which is the only product in the case of octamethylporphyrin. From a mixture of two different porphyrins, namely octaethylporphyrin [H2(OEP)] and either tetraphenylporphyrin [H2(TPP)] or tetra-p-chlorophenylporphyrin [H2(TClP)], besides the symmetrical species Ce(OEP)2 and Ce(TPP)2, the unsymmetrical (“mixed”) double-deckers Ce(OEP)(TPP) or Ce(OEP)(TClP) are obtained which have different porphyrin rings in the sandwich system and can be separated by chromatography. The crystal structure analysis of Ce(OEP)(TPP) shows CeIV in a square-antiprismatic geometry of the pyrrole N atoms of the porphyrin rings. While the IR and NMR spectra of the unsymmetrical double-deckers are superpositions of the spectra of the individual rings, their UV/VIS spectra and cyclic voltammograms indicate that the two porphyrin rings behave as a common π-electron system. The preparation of the π-cation radical salts [Ce(OEP)2]ClO4 and [Ce(OEP)(TPP)]SbCl6 is also described. In the latter, the defect electron seems to reside preferentially in the OEP ring.
    Additional Material: 5 Ill.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2261-2264 
    ISSN: 0009-2940
    Keywords: Iron, thiocarbonyl complex ; Iron-tin bond ; NMR, 13C-, 17O-, and 119Sn ; Dynamic molecules ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formation of Fe-Sn Bonds by the Reaction of Tris(trimethylstannyl)amine with Fe(CO)5 and Fe(CO)4CS; 13C-, 17O-, and 119Sn-NMR-Spectroscopic StudiesThe reaction between N(SnMe3)3 and Fe(CO)5 gives the known complex cis-Fe(CO)4(SnMe3)2 (1) in high yield. In the analogous reaction of Fe(CO)4CS the complex fac-Fe(CO)3(CS)(SnMe3)2 (2) is obtained together with small amounts of 1. In addition to the 13C-NMR data, the 17O- and 119Sn-NMR measurements proved particularly useful for studying the dynamic behaviour of 1 and 2.
    Additional Material: 3 Ill.
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  • 85
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2273-2274 
    ISSN: 0009-2940
    Keywords: Fluorine, application in organometallic chemistry ; Rhenocene(V)-trichloride ; Rhenocene(VII)-dichloride trication ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dichlorobis(η5-cyclopentadienyl)rhenium(VII) Tris(hexafluoroantimonate): Synthesis of the First Rhenocene(VII) Dichloride CationRhenocene trichloride ([Cp2ReCl2]⊕ Cl⊖, 1) reacts with one equivalent of AgSbF6 and three equivalents of SbF5 to provide [Cp2ReCl2]3⊕[SbF6]⊖3 (2) in high yield. 2 contains the first rhenocene(VII) dichloride cation and is the first member of a 16-electron group-7 species of the type [Cp2MCl2]n⊕ [EF6]n⊖ (M = Ti, Zr, Hf: n = 0; M = V, Nb: n = 1; M = Mo, W: n = 2; M = Re: n = 3; E = As, Sb).
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  • 86
    ISSN: 0009-2940
    Keywords: Manganese complexes ; Thiophosphinito complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXVII.  -  Stereochemical Impacts on the Transition of Monomeric Thiophosphinito Manganese Compounds to the Dimeric Complexes The η2-thiophosphinito manganese complexes (3d, e) and the dimeric complexes (4a-c, f) are obtained from BrMn(CO)5 (1) and the secondary phosphane sulfides R2P(S)H (2a-f) [R = Me (a), Et (b), n-Pr (c), i-Pr (d), Cy (e), Ph (f)] in the presence of the auxiliary base Et(i-Pr)2N with elimination of CO. For the kinetic stabilization of 3d, e sterically demanding substituents R at the phosphorus are suitable. The Mn—S bond in 3e is easily cleaved under CO pressure (100 bar) resulting in the formation of (5e). The reaction 3e ⇆ 5e is reversible.
    Additional Material: 1 Tab.
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2283-2287 
    ISSN: 0009-2940
    Keywords: Indium, trialkyl derivatives ; Dialkylchloroindium ; Alkyldichloroindium ; Alkylindium dialkylamides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Properties of iPr2InCl, iPrInCl2, and (iPr2InHRtBu)2The reactions of triisopropylindium (1) with half an equivalent or two equivalents of indium (III) chloride leads to iPr2InCl (2) and iPrInCl2 (3), respectively. (iPr2InNHtBu)2 (4) can be synthesized from 2 and LiNHtBu. According to NMR, IR, and RE studies, 2-4 from dimers in solution and solid state. The X-ray analysis of 4 is reported.
    Additional Material: 2 Ill.
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  • 88
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2311-2317 
    ISSN: 0009-2940
    Keywords: Allenes, 1,3-diamino- and 1-amino-3-thio- ; Propene iminium salts ; Propyne iminium salts ; MO calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Propyne Iminium Salts: Ambifunctional reactivity reactivity towards Sulfur and Nitrogen NucleophilesPropyne iminium ions 2a-d have been studied by both ab initio (3-21G//3-21G for 2a) and MNDO calculations (2a-d). It is found that the amino group stabilizes the propargyl cation structure at the expense of the allenyl cation structure. Furthermore, the highest positive charge density is located at the amino-substituted carbon atom.  -  Reactions of 2-propyne iminium triflates 6a, b with thiols, thiolates, morpholine, lithium morpholide, and phenylhydrazine have been investigated. C-1 attack at 6, expected under kinetically controlled conditions, is observed in a few cases only. In all other cases, products resulting from C-3 attack takes place leading either to 1,3-donorsubstituted allenes (8, 10, 12) in the absence of proton sources or to their C-2-protonated forms (9, 11, 13-15) otherwise.
    Notes: Für die Propiniminium-Ionen 2a-d werden ab-initio- (3-21G//3-21G für 2a) und MNDO-Rechnungen (2a-d) durchgeführt. Danach stabilisiert die Aminogruppe die Propargylkation- eindeutig gegenüber der Allenylkation-Struktur. Die höchste positive Ladungsdichte befindet sich am aminosubstituierten Kohlenstoffatom.  -  Umsetzungen der 2-Propiniminium-triflate 6a, b mit Thiolen, Thiolaten, Morpholin, Lithium-morpholid und Phenylhydrazin zeigen, daß nur in einigen Fällen unter kinetisch kontrollierten Bedingungen der erwartete C-1-Angriff erfolgt, ansonsten wird C-3-Angriff gefunden. Letzterer führt in Abwesenheit von Protonquellen zu 1,3-donorsubstituierten Allenen (8, 10, 12), andernfalls entstehen deren C-2-protonierte Formen (9, 11, 13-15).
    Additional Material: 3 Tab.
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  • 89
    ISSN: 0009-2940
    Keywords: Diels-Alder reactions, intramolecular ; Allenecarboxyamides, N-(hetarylmethyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloadditons, 17.  -  Influence of Methyl and Phenyl Groups in the Allenic ω-Position on the Thermally Induced Isomerizations of N-[2-Furanyl-(Thienyl-, Pyrrolyl-)methyl] allenecaboxamindesThe N-(2-hetarylmethyl)-1,2-alkadienecarboxamides 9a-q were synthesized by the ylide route, and their readiness to participate in the intramolecular Diels-Alder reaction was studied. Whereas the pyrrole derivatives 9p and 9q and the thiophene derivative 9o without directly bonded phenyl nuclei only decompose, the thiophene allenes 9m and 9n form the “normal” tricycles 12a and 12b by reaction of their amide phenyl nucleus (R1 = Ph). In all N-furfurylallenecarboxamides 9a-1 the furan nucleus is involved in the intramolecular Diels-Alder reaction, irrespective of the amine substituent R1. The furan nucleus reacts in all cases with the terminal allenic double bond to form the oxatricycles 10a-1 containing a six-membered lactam moiety. Reaction with the first allenic double bond (formation of 11c, d, and g) only takes place, when the reaction with the other double bond is slowed down by one or two methyl groups in the ω-position and the formation of 11 is not prevented by a methyl group in the furan 5-position.
    Notes: Die N-(2-Heteroarylmethyl)-1,2-alkadiencarboxamide 9a-q werden auf dem Ylid-Weg synthetisiert und auf ihre Bereitschaft zur intramolekularen Diels-Alder-Reaktion untersucht. Die Pyrrolderivate 9p und 9q und das Thiophen-Derivat 9o ohne direkt gebundenen Phenylkern zeigen lediglich Zersetzung, während die Thiophen-Allene 9m und 9n durch Reaktion ihrer Amid-Phenylkerne (R1 = Ph) die „normalen“ Tricyclen 12a und 12b bilden. In allen Furfuryl-allencarboxamiden (9a-1) geht der Furankern die intramolekulare Diels-Alder-Reaktion ein, unabhängig von der Art des Aminsubstituenten R1. Der Furankern reagiert in allen Fällen mit der endständigen Doppelbindung zu den Oxatricyclen 10a-1 mit sechsgliedrigem Lactamteil. Reaktion mit der ersten allenischen Doppelbindung (s. Bildung von 11c,d und g) wird daneben nur beobachtet, wenn durch Einbau von Methyl-gruppen in die ω-Position die Reaktion mit der endständigen Doppelbindung stark verlangsamt und die Bildung von 11 nicht durch eine Methylgruppe in der Furan-5-Position verhindert wird.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2377-2389 
    ISSN: 0009-2940
    Keywords: EPC syntheses ; Δ4-1,3-Oxazoline, derivatives ; Simmons-Smith reaction ; Sakurai reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloadditions to the Double Bond of Methyl (R)-2-tert-Butyl-Δs4-1,3-oxazoline-3-carboxylates1The title compounds (with or without an additional substituent, such as methyl or vinyl, in the 5-position) are allowed to react with peracids (→ dihydroxy derivatives 3), with cyclopropanation reagents (such as ICH2ZnEt, N2CHCOOEt, HCBr3, or HCCl3/NaOH → products 5-9), with tetracyanoethylene and OsO4 (see four- and five-membered rings in 19, 20), with dienophiles (maleic anhydride, see 23). The double bond of the oxazolines reacts in a highly diastereoselective manner, with the attack preferred from the face of the five-membered ring remote from the tert-butyl group. Some of the products obtained undergo or are subjected to further reactions (4, 12-18, 23, 29-33). Stereochemical and synthetic aspects of the reactions are discussed.
    Notes: Die Titelverbindungen (mit und ohne zusätzliche Substituenten wie z. B. Methyl oder Vinyl in der 5-Stellung) werden mit Persäuren (→ Dihydroxyderivate 3), mit Cyclopropanierungsreagentien (wie z.B. ICH2ZnEt, N2CHCOOEt, HCBr3 oder HCCl3/NaOH → Produkte 5-9), mit Tetracyanethylen und OsO4 (→ Produkte 19-20) und mit Dienophilen (Maleinsäureanhydrid, siehe 23) umgesetzt. Die Doppelbindung der Oxazoline reagiert hoch diastereoselektiv, wobei der bevorzugte Angriff von der der tert-Butylgruppe abgewandten Seite erfolgt. Einige der erhaltenen Produkte werden weiter umgesetzt (siehe 4, 12-18, 23, 29-33). Stereochemische und synthetische Aspekte der Reaktionen werden diskutiert.
    Additional Material: 2 Ill.
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  • 91
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2397-2398 
    ISSN: 0009-2940
    Keywords: Nucleophilic ring opening ; Regioselectivity ; Ambident nucleophiles ; Aziridines ; Tryptamine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions with Aziridines, 52.  -  branched-Chain Tryptamine Compounds from Indolyllithium and Activated AziridinesReaction of indolyllithium 1 with activated aziridines 2 in toluene provides the tryptamines 3 or 4 in good yields.
    Additional Material: 1 Tab.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 2407-2409 
    ISSN: 0009-2940
    Keywords: Organoantimony halides ; Aziridines, cycloaddition of, α-cleavage of ; Heterocumulenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of catalytic amounts of organoantimony(V) halides such as Ph4SbI, Ph4SbBr, Ph3SbBr2, and Ph3SbCl2, the cycloaddition of aziridines 1a-g with heterocumulenes (phenyl isothiocyanate, carbon disulfide, and carbon dioxide) selectively gave ring-expanded cycloadducts 3a-d, f, g, and 6e by α-cleavage of the aziridine rings.
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  • 93
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1263-1275 
    ISSN: 0009-2940
    Keywords: Rotational barriers ; Olefins, strained ; Heat of hydrogenation ; Force-field calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rotational Barriers of Strained OlefinesFor the olefins 1-8 heats of formation have been derived from heats of hydrogenation and force-field calculations, respectively. From the kinetics of their geometrical isomerisation the corresponding values for the transition states were obtained. The rotational barriers, which vary by nearly 30 kcal/mol, can be described by a unique torsional potential (65.9 ± 0.9 kcal/mol), which is independent of the degree of substitution, if a correction is made for the steric energy contribution in the ground- and transition-states.
    Notes: Für die Olefine 1-8 wurde durch Hydrierwärme-Messung bzw. Kraftfeld-Rechnung die Bildungsenthalpie der Grundzustände und durch kinetische Analyse der geometrischen Isomerisierung die der Übergangszustände ermittelt. Die um fast 30 kcal/mol variierenden Rotationsenthalpien lassen sich mit einer einheitlichen, vom Substitutionsgrad unabhängigen Torsionsbarriere (65.9 ± 0.9 kcal/mol) beschreiben, wenn um die sterischen Energiebeiträge der Grund- und Übergangszustand korrigiert wird.
    Additional Material: 5 Ill.
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  • 94
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1285-1290 
    ISSN: 0009-2940
    Keywords: 2-Cyclopropylidene-1,3-diones ; Hetero Diels-Alder reaction ; Cyclopropane derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [4+2] Cycloaddition reactions of 2-Cyclopropylidene-1,3-diones with Electron-Rich AlkynesCyclopropylidenedimedone 3, an unstable and highly reactive intermediate, is trapped in a Hetero Diels-Alder reaction by the addition of ynamines 7a-c, f, ynether 7d, or phenylacetylene (7e). Hydrolysis of the resulting cycloadducts 8a-d, f leads to carboxylic acid derivatives 9a-d, f. The latter may be regarded as the result of a twofold nucleophilic substitution at a cyclopropane system according to their synthesis by the sequence 17 → 5 → 8 → 9. An opening of the cyclopropane ring takes place during hydrolysis of cycloadduct 8e producing 11. Analogously, 2-cyclopropylidene-1,3-diones 13A-13C can be generated by aminocyclopropylation of CH acids 18A-18C and subsequent deamination induced by an acylation reaction. Trapping of 13A-13C by ethoxyacetylene (7d) or ethyl vinyl ether (4) provides the analogous cycloadducts 14A, B and 15C.
    Notes: Cyclopropylidendimedon 3, eine unbeständige und hochreaktive Zwischenstufe, kann durch Inamine 7a-c, f, Inether 7d oder Phenylacetylen (7e) in einer Hetero-Diels-Alder-Reaktion abgefangen werden. Die resultierenden Cycloaddukte 8a-d, f sind zu Carbonsäurederivaten 9a-d, f hydrolysierbar, die entsprechend ihrer Herstellung über die Reaktionssequenz 17 → 5 → 8 → 9 als Produkte einer zweifachen nucleophilen Substitution am Cyclopropan anzusehen sind. Das Cycloaddukt 8e läßt sich dagegen nur unter Öffnung des Dreirings zu 11 hydrolysieren. Analog können die 2-Cyclopropyliden-1,3-dione 13A-13C durch Aminocyclopropylierung von CH-Säuren 18A-18C und anschließende Desaminierung erzeugt und unter Zusatz von Ethoxyacetylen (7d) oder Ethylvinylether (4) zu den Cycloaddukten 14A, 14B und 15C abgefangen werden.
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  • 95
    ISSN: 0009-2940
    Keywords: Diels-Alder reaction ; Cyclopropanes ; Dienophile reactivity ; MNDO calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diels-Alder Reactions with Diacceptor-Substituted Methylene-cyclopropanes - A New Aspect for the Twofold Nucleophilic Substitution at Cyclopropanes(Diacylmethylene)cyclopropanes 3, generated from aminocyclopropanes 1 or 2 and acetyl chloride as highly reactive intermediates, are trapped by dienes 9a-c yielding the Diels-Alder products 10. Regioisomers 10Ab and 10Ac were isolated exclusively from the interaction of 1A with pentadiene 9b and isoprene (9c), respectively. Cycloadditions with bicyclic methylenecyclopropanes 3A and 3B stereospecifically generated the 1α,6α,7β-isomers 10A and 10B. Starting from 10 the products 16, 19, and 20 are obtained by a degradation reaction of the Meldrum's acid moiety or by an oxidative ring cleavage of the cyclohexene unit. An X-ray structural analysis is reported for 10Ac. Using MNDO calculations the reactivity of various (diacylmethylene)cyclopropanes 3 as dienophiles has been studied.
    Notes: (Diacylmethylen)cyclopropane 3, die als hochreaktive Zwischenstufen aus den Aminocyclopropanderivaten 1 bzw. 2 in Gegenwart von Acetylchlorid erzeugt werden, reagieren mit Dienen 9a-c zu Diels-Alder-Produkten 10. Aus der Umsetzung von 1A mit Pentadien 9b bzw. Isopren (9c) werden ausschließlich die Regioisomeren 10Ab und 10Ac isoliert. Die Cycloadditionen an die bicyclischen Methylencyclopropane 3A und 3B verlaufen stereospezifisch zu 1α,6α,7β-Isomeren 10A und 10B. Aus 10 lassen sich durch Abbau der Meldrumsäure bzw. durch oxidative Ringöffnung des Cyclohexens die Folgeprodukte 16,19 und 20 herstellen. Von 10Ac wurde eine Kristallstrukturanalyse angefertigt. Die Dienophil-Reaktivität von verschiedenen (Diacylmethylen)cyclopropanen 3 wird mit MNDO-Rechnungen untersucht.
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  • 96
    ISSN: 0009-2940
    Keywords: Nitriles ; Spiro compounds ; Propellanes ; Indan derivatives ; Cycloaddition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese with Nitriles, LXXXII1). - On spiro [indan-pyrans] and Indene-propellanes - Adducts of 2-(Diccyanomethylene)-1,3-indandione with 1,3-Dicarbonyl CompoundsThe reactivity of 2-(dicyanomethylene)-1,3-indandione (1) towards 1,3-dicarbonyl compounds depends strongly on the nature of the CH acidic component. While the reaction with dimedone yields a spiro[chromene-4,2′indan] (2), indene-propellanes (3) are formed with acetoacetic esters. Adducts of acetylacetone and benzoylacetic acid ethyl ester to 1 have been identified as spiro[indan-2,2′-pyrans] (4). The propellane structure 3 is proven by X-ray analysis. Adducts 6 of CH acidic components with 3-(dicyanomethylene)-2-indolones 5 are used for reference measurements.
    Notes: 2-(Dicyanmethylen)-1,3-indandion (1) zeigt gegenüber 1,3-Dicarbonylverbindungen ein überraschend differenziertes Reaktionsverhalten, das von der CH-aciden Komponente abhängt. Während mit Dimedon ein Spiro[chromen-4,2′-indan] (2) entsteht, führt die Reaktion mit Acetessigsäure-ethyl- bzw. -tert-butylester zur Bildung der Inden-propellane 3. Die Addukte von Acetylacaton und Benzoylessigsäure-ethylester an 1 erweisen sich als Spiro[indan-2,2′-pyrane] (4). Die Propellanstruktur 3 wird durch eine Röntgenkristallstrukturanalyse abgesichert. Addukte 6 CH-acider Komponenten an 3-(Dicyanmethylen)-2-indolone 5 werden für Vergleichsmessungen verwendet.
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  • 97
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    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1623-1627 
    ISSN: 0009-2940
    Keywords: Binuclear complexes ; Molybdenum complexes ; Rhodium complexes ; Sulfur dioxide bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sulfur(IV) Compounds as Ligands, IX.  -  Binuclear Molybdenum-Rhodium Complexes with Sulfur Dioxide as a Bridging LigandThe hetero-binuclear complexes [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) and [MoRh(CN)(CO)3(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) are the first compounds which contain sulfur dioxide as a bridging ligand connected to two metal atoms from different groups of the periodic table. The synthesis starts from Mo(CO)3(NCMe)3 (7), which reacts with the chelating ligands Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm), and Ph2AsCH2AsPh2 (daam) to give the mononuclear precursors Mo(CO)3-(η2-Ph2E1CH2E3 Ph2)(η1-Ph2E2CH2E4 Ph2) (9-12). With [Rh2Cl2(CO)4] these are converted to the binuclear complexes [MoRhCl(CO)4(μ-Ph2E1CH2E3 Ph2)(μ-Ph2E2CH2E4Ph 2)] (15-18). Reversible CO/SO2 exchange finally gives 1-4 and the analogous bromide 5, the cyanide complex 6 is obtained from 1 and NaCN in liquid ammonia.
    Notes: Die heteronuklearen Zweikernkomplexe [MoRhCl(CO)3(μ-SO2)(μ-Ph2E1CH2E3Ph2)(μ-Ph2E2CH2E4Ph2)] (E = P, As, 1-4), [MoRhBr(CO)3(μ-SO2)(μ-Ph2PCH2PPh2)2] (5) und [MoRh(CN)(CO)3-(μ-SO2)(μ-Ph2PCH2PPh 2)2] (6) sind die ersten Verbindungen, in denen Schwefeldioxid als Brückenligand an zwei Metallatome aus verschiedenen Gruppen des Periodensystems gebunden ist. Die Synthese geht von Mo(CO)3(NCMe)3 (7) aus, das mit den Chelatliganden Ph2PCH2PPh2 (dppm), Ph2AsCH2PPh2 (dapm) und Ph2AsCH2AsPh2 (daam) zu den einkernigen Vorstufen Mo(CO)3(η2-Ph2E1CH2E3 Ph2) (η1-Ph2E2CH2E4 Ph2) (9-12) umgesetzt wird. Daraus entstehen mit [Rh2Cl2(CC)4] die Zweikernkomplexe [MoRhCl(CO)4(μ-Ph2E1CH2E3Ph 2)(μ-Ph2E2CH2E4Ph2)] (15-18). Reversibler CO/SO2-Austausch ergibt schließlich 1-4 und das analoge Bromid 5, der Cyanokomplexe 6 wird aus 1 und NaCN in flüssigem Ammoniak erhalten.
    Additional Material: 1 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1825-1850 
    ISSN: 0009-2940
    Keywords: Organoboranes, unsaturated ; Organosilanes, unsaturated ; Aminotriorganoborates ; Cyclization ; 2,5-Dihydro-organo-1,2,5-azasilaboroles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organosubstituted 2,5-Dihydro-1,2,5-azasilaboroles - Methods of Preparation and Spectroscopic CharacterisationThe compounds (E)-R22R2′ElIVC(R3) = C(R4)BR25 [(E)-1a to -g] are prepared from Na[R34,5BC ≡ CR3] with ClElIVR22R2′ [ElIV = Si, Ge, Sn] or from R22R2′SiC ≡ CR3 with BR34,5 (R4,5 = CH3, C6H5). The substituted silol 1z is obtained from (CH3)2Si(C ≡ CCH3)2 and B(C2H5)3, the mixture of (Z/E)-1t from (CH3)3SiC ≡ CH and B(C2H5)3. - ClSi(CH3)2C(CH3)2C(CH3)=C(C2H5)B(C2H5)Cl (C) reacts with LiN(CH3)2 to form (CH3)2NSi(CH3) 2C(CH3)2 C(CH3)=C(C2H5) B(C2H5)N(CH3)2 (E)-1n. - (E)-1a to (E)-1g or (E)-1a or (E)-1aGe and (E)-1aSn add MNH2 (M = Na, K) to yield the compounds MNH2-1, which react to the solid alkaline metal heterocycles M-2 after liberating R2H. From. (E)-1a or (E)-1b with LiNH2 the compounds (E)-C2H5CH=CR4Si(CH3)3 (A, B) are obtained. - On heating M-2a to M-2g eliminate R5H (C2H6) and smoothly from the solid compounds M-3, from which the heterocycles (4a-f) are prepared with CH3I. The 1-phenyl derivatives 5a, b are obtained from 4a,b with aniline. M-2c,d react with HCl to give the compounds 6c,d from which 7c,d are formed after C2H6 elimination. The 5-chloro compound 4i is used for the preparation of the heterocycles 4 with R5 = H, C(CH3)3, and N(CH3)2. - All compounds 1-7 are characterized by multinuclear NMR spectroscopy, the volatile compounds 1 and 4-7 also by their mass spectra.
    Notes: Die Verbindungen (E)-R22R2′ElIVC(R3) = C(R4)BR25 [(E)-1a bis -g] stellt man aus Na[34,5BC ≡ CR3] mit ClElIVR22R2′ [ElIV = Si, Ge, Sn] oder aus R22R2′SiC ≡ CR3 mit B34,5 (R4,5 = CH3, C6H5) her. Aus (CH3)2Si(C ≡ CCH3)2 und B(C2H5)3 sind das substituierte Silol 1z, aus (CH3)3)SiC ≡ CH und B(C2H5)3 im Autoklaven u. a. (Z/E)-1t zugänglich. - ClSi(CH3)2C(CH3) = C(C2H5)B(C2H5)Cl (C) und LiN(CH3)2 bilden (E)-1n. - (E)-1a bis (E)-1g bzw. (E)-1aGe und (E)-1aSn reagieren mit MNH2 (M = Na, K) zu den Additionsverbindungen MNH2-1, aus denen unter R2H-Abspaltung die festen Alkalimetall-Heterocyclen M-2 gebildet werden. (E)-1a und (E)-1b liefern mit LiNH2 (E)-C2H5CH=CR4Si(CH3)3 (A, B). - Aus M-2a bis M-2g erhält man beim Erhitzen unter R5H(C2H6)-Abspaltung glatt M-3, die mit CH3I zu den Heterocyclen (4a-f) reagieren. Die 1-Phenyl-Derivate 5a,b gewinnt man aus 4a,b mit Anilin. Aus M-2c,d sind mit HCl die Verbindungen 6c, d zugänglich, die unter C2H6-Abspaltung 7c,d liefern. Aus der 5-Chlor-Verbindung 4i stellt man die Heterocyclen 4 mit R5 = H, C(CH3)3 und N(CH3)2 her. - Sämtliche Verbindungen werden mit Multikern-NMR-Spektroskopie, die flüchtigen Verbindungen 1 und 4-7 auch massenspektrometrisch charakterisiert.
    Additional Material: 18 Tab.
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  • 99
    ISSN: 0009-2940
    Keywords: Tris(diphenylphosphino)ethene derivatives ; 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadiene derivatives ; Molybdenum complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry and Structures of Tris(diphenylphosphino)enthen and 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadieneReaction of tris(diphenylphosphino)ethene (1), obtained by basecatalyzed hydrophosphorylation of Ph2PC≡CPPh2 with Ph2PH, with 2 equivalents of H3B · OC4H8 affords 1,1-bis(boranatodi-phenylphosphonio)-2-(diphenylphosphino)ethene (2). Methylation of 1 with MeI gives the monoquaternary salt 3, the molecular structure of which was determined by X-ray crystallography. A trisulfide 4 is available by treatment of 1 with elemental sulfur. - 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadiene (5) was isolated as a byproduct in the synthesis of 1. 1,1,4,4-substitution was established by X-ray analysis of the tetrasulfide 6, obtained by treatment of 5 with elemental sulfur. Reaction of 5 with 2 equivalents of Mo(CO)6 yields the symmetrical, dinuclear complex 7.
    Notes: Das durch basenkatalysierte Addition von Ph2PH an Ph2PC≡CPPh2 erhaltene Tris(diphenylphosphino)ethen (1) reagiert mit 2 Äquivalenten H3B · OC4H8 zu 1,1-Bis(boranatodiphenylphosphonio)-2-(diphenylphosphino)ethen (2). Die Behandlung von 1 mit Iodmethan liefert neben nicht näher untersuchten Spaltprodukten das Monoquartärsalz 3, in dem die Oniumfunktion am mittleren der drei Phosphoratome auftritt. Die Kristallstruktur wurde röntgenographisch bestimmt. Bei Behandlung von 1 mit Schwefel entsteht das Trisulfid 4.  -  Bei der Darstellung von 1 wird als Nebenprodukt 1,1,4,4-Tetrakis(diphenylphosphino)-1,3-butadien (5) gebildet. Die Substitution in den 1,1,4,4-Positionen wurde ebenfalls durch Röntgenstrukturanalyse des Tetrasulfids 6 bestätigt, das durch Reaktion von 5 mit elementarem Schwefel darstellbar ist. 5, dessen Bildungsmechanismus noch nicht geklärt ist, reagiert mit 2 Äquivalenten Mo(CO)6 zum zweikernigen Molybdänkomplex 7.
    Additional Material: 4 Tab.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1897-1900 
    ISSN: 0009-2940
    Keywords: Cyclooctatetraenyl complexes ; Cyclopentadienyl complexes ; Lanthanide amides ; Organolanthanides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Organometallic Compounds of the Lanthanides, 50.  -  N,N,N′ - Trimethylethylenediamine Derivatives of Yttrium, Holmium, and LutetiumThe reactions of LiN(CH3)CH2CH2N(CH3)2 with YCl3, HoCl3, LuCl3, as well as with (C5H5)2YCl and (C4H9C8H7)LuCl result in the formation of the amides Li[Ln{N(CH3)CH2CH2N(CH3)2}4] [Ln = Y (1), Ho (2), Lu (3)], Li[(C5H5)2Y{N(CH3)CH2CH2N-(CH3)2}2] (4), and Li[(C4H9C8H7)Lu{N(CH3)CH2CH2N(CH3)2}2] (5), respectively. The 1H- and 13C-NMR spectra of the new compounds as well as the X-ray crystal structure of 2 are reported and discussed.
    Notes: LiN(CH3)CH2CH2N(CH3)2 reagiert mit YCl3, HoCl3 und LuCl3, sowie mit (C5H5)2LuCl und (C4H9C8H7)LuCl unter Bildung der homoleptischen Amide Li[Ln{N(CH3)CH2CH2N(CH3)2}4] [Ln = Y (1), Ho (2), Lu (3)], sowie von Li[(C5H5)2Y{N(CH3)CH2-CH2N(CH3)2}2] (4) und Li[(C4H9C8H7)Lu{N(CH3)CH2CH2N-(CH3)2}2] (5). Die 1H- und 13C-NMR-Spektren der neuen Verbindungen und die Einkristall-Röntgenstrukturanalyse von 2 werden beschrieben und diskutiert.
    Additional Material: 1 Ill.
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