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31.
Enantiomerically pure N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(phenyl)cinnamylsulfoximines as well as the corresponding crotylsulfoximines have been prepared from N-methyl-, N-benzyl-, and N-(methoxyethyl)-S-(lithiomethyl)sulfoximines and carbonyl compounds by an addition-elimination-isomerization reaction sequence. Under basic conditions, complete isomerization of the vinylic sulfoximines, obtained as intermediates, to the corresponding allylic sulfoximines takes place. Chromatographically separable mixtures of (E) and (Z) allylic sulfoximines were isolated in the case of beta,gamma-disubstituted allylic sulfoximines. The (E/Z) ratio depends on the nature of the substituents in the beta- and gamma-positions, and the equilibrium amount of the (Z) isomer varies from 68% to nil. The allylic N-methylsulfoximines do not racemize thermally, and their rearrangement to the corresponding allylic sulfinamides is negligible. Upon prolonged treatment with boron trifluoride at low temperatures allylic N-methylsulfoximines are recovered unchanged. The crystal structure of S-(3,4-dihydronaphthalen-2-ylmethyl)-N-methyl-S-phenylsulfoximine was determined. Reaction of the allylic sulfoximines with butylcopper in the presence of lithium iodide and boron trifluoride leads with very high gamma-selectivities and moderate to high enantioselectivities to the corresponding chiral alkenes. Their configuration was determined by chemical correlation through ozonolysis to the corresponding carbonyl compounds. The asymmetric induction exerted by the chiral N-methyl-S-phenylsulfoximine group strongly depends on the double bond configuration and the substituents in the beta- and gamma-positions. The (E) allylic sulfoximines are substituted with low to moderate enantioselectivities (2-66%), whereas the (Z) allylic sulfoximines react with much higher enantioselectivities (69-92%). Interestingly, substitution of the beta-methyl-gamma-phenyl-substituted (Z) allylic sulfoximine and its beta-phenyl-gamma-methyl isomer proceeded with almost the same degree of asymmetric induction but with the opposite sense. Replacement of the N-methyl group by a benzyl or a methoxyethyl group has no significant influence on the regio- and enantioselectivity of the substitution. 相似文献
32.
The oxidative cyclization of 5-(2-amino-5-methoxycarbonylphenyl)-substituted tricarbonyl[η4-cyclohexa-1,3-diene]iron complexes by air in protic medium provides the corresponding tricarbonyl[η4-4a,9a-dihydro-9H-carbazole]iron complexes. This procedure is applied to the total synthesis of the 3-methoxycarbonylcarbazole alkaloids mukonine and mukonidine. 相似文献
33.
Hans-Joachim Böhm 《Journal of computer-aided molecular design》1992,6(1):61-78
Summary A new computer program is described, which positions small molecules into clefts of protein structures (e.g. an active site of an enzyme) in such a way that hydrogen bonds can be formed with the enzyme and hydrophobic pockets are filled with hydrophobic groups. The program works in three steps. First it calculates interaction sites, which are discrete positions in space suitable to form hydrogen bonds or to fill a hydrophobic pocket. The interaction sites are derived from distributions of nonbonded contacts generated by a search through the Cambridge Structural Database. An alternative route to generate the interaction sites is the use of rules. The second step is the fit of molecular fragments onto the interaction sites. Currently we use a library of 600 fragments for the fitting. The final step in the present program is the connection of some or all of the fitted fragments to a single molecule. This is done by bridge fragments. Applications are presented for the crystal packing of benzoic acid and the enzymes dihydrofolate reductase and trypsin. 相似文献
34.
For the determination of flouride, chloride and bromide, a suitable metal ion is added in a modified graphite tube atomizer. After drying and ashing, the substances are vaporized and diatomic molecules between the metal and nonmetal are formed. These molecules are excited by a pulsed dye laser and the resulting fluorescence is measured. At constant metal concentration, the fluorescence is proportional to the halide concentration. The diatomic molecules used are MgF, InCl and AlBr. The detection limits are 11 pg of fluoride, 15 pg of chloride and 70 pg of bromide in the 10-μl injections, corresponding to 6 x 10?8 mol l?1 fluoride, 4 x 10?8 mol l?1 chloride and 9 x 10?8 mol l?1 bromides. 相似文献
35.
Clarissa Müller Tim Ortmann Akram Abi Dave Hartig Stephan Scholl Hans-Joachim Jördening 《Applied biochemistry and biotechnology》2017,182(1):197-215
Immobilization methods and carriers were screened for immobilization of Euglena gracilis extract with laminaribiose phosphorylase activity. The extract was successfully immobilized on three different carriers via covalent linkage. Suitable immobilization carriers were Sepabeads EC-EP/S and ECR 8209M with epoxy groups and ECR 8309M with amino groups as functional units. Immobilization on Sepabeads EC-EP/S resulted in highest retained activity (65%). The immobilizates were characterized for pH, temperature, and buffer molarity preferences. The immobilized enzyme lost 48% of its activity when used seven times. Together with sucrose phosphorylase, laminaribiose phosphorylase was successfully applied for bienzymatic production of laminaribiose from sucrose and glucose with a final laminaribiose concentration of 14.3 ± 2.1 g/L (20% yield). 相似文献
36.
37.
Hans-Joachim Knlker Helmut Goesmann Rüdiger Klauss 《Angewandte Chemie (International ed. in English)》1999,38(5):702-705
The photochemical exchange of all three carbonyl ligands with acetonitrile converts tricarbonyliron–diene complexes into the very labile triacetonitrile-iron–diene complexes. These easily demetalate in high yields to the corresponding free ligands on injection of air at −30°C [Eq. (1)]. The novel demetalation procedure is applied to the tricarbonyliron complexes of cyclopentadienones, cyclohexa-1,3-dienes, and buta-1,3-dienes. 相似文献
38.
Karsten Haas J. Feldmann Rainer Wennrich Hans-Joachim Stärk 《Analytical and bioanalytical chemistry》2001,370(5):587-596
The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP–TOFMS) as a detector
for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated.
A cryotrapping GC–ICP–TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the
suitability of the TOF mass analyzer for multi-elemental speciation analysis and multi-isotope ratio determinations was studied
in terms of accuracy and precision. Isotope ratios 118Sn/120Sn and 121Sb/123Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for
different elemental species (SnH4, MeSnH3, Me2SnH2, Me3SnH, BuSnH3, SbH3, and MeSbH2). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10
ng mL–1) and cadmium (40 ng mL–1) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias
correction (by measuring the 111Cd/113Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established
for Me2SnH2 (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD
if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more
than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations.
A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their
isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough
to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination
of cryotrapping GC and ICP–TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments
and isotope dilution methodology.
Received: 23 November 2000 / Revised: 19 February 2001 / Accepted: 24 February 2001 相似文献
39.
Alfred Kreutzberger Elfriede Kreutzberger Hans-Joachim Saltler Hayriye Aml Aysel Gürsoy 《Journal of heterocyclic chemistry》1982,19(4):753-755
The three-component reaction comprising the interaction of 2-amino-4-antipyrinyl-5-ethylthiazole (1) with s-triazine (2) and pyrrolidine leads to 4-anitpyrinyl-5-ethyl-2-[(4-pyrrolidinyl)methyleneamino]thiazole (5). Structure 5 is supported by 1H- and 13C-NMR spectroscopy. 相似文献
40.
Summary The calculation of electronically excited states with the internally contracted multiconfiguration-reference configuration interaction (CMRCI) method is discussed. A straightforward method, in which contracted functions for all states are included in the basis, is shown to be very accurate and stable even in cases of narrow avoided crossings. However, the expense strongly increases with the number of states. A new method is proposed, which employs different contracted basis sets for each state, and in which eigensolutions of the Hamiltonian are found using an approximate projection operator technique. The computational effort for this method scales only linearly with the number of states. The two methods are compared for various applications.Dedicated in honor of Prof. Klaus Ruedenberg 相似文献