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1.
Peter G?rtner Martin Letschnig Max Knollmüller 《Monatshefte für Chemie / Chemical Monthly》2000,3(2):867-877
Eight O-substituted 1,2-diols and one O,N-substituted 1,2-aminoalcohol derived from 2-alkoxyoctahydro-7,8,8-trimethyl-4,7-methanobenzofurans
via a [1,2]-Witting rearrangement and subsequent substitution were synthesized and tested as additives for the enantioselective addition of butyllithium
and butylmagnesium chloride to benzaldehyde and for the reduction of acetophenone with lithium aluminum hydride. The selectivity
of the reactions was determined by GC of the obtained 1-phenyl-1-pentanol and 1-phenylethanol on a chiral phase. Best results
with regard to selectivity (52% ee and 94% ee, resp.) were achieved in the formation of 1-phenyl-1-pentanol by addition of the substituted 1,2-aminoalcohol to the organometallic
reagent and in the reduction of acetophenone using an α-alkoxyalcohol (62%ee). 相似文献
2.
Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers:
1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol.
Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G* and 6-311G** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds
of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH3, PhC(NOH)–C(O)CH3, and PhC(N–OH)C(O)CH3. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single
bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH3, PhC(N–O)C(OH)CH3, and PhC(NO)C(–OH)CH3. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone:
Ph–CH(NO)C(O)CH3, PhCH(–NO)C(O)CH3, and PhCH(NO)–C(O)CH3. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH2, PhC(N–OH)C(OH)CH2, PhC(NOH)–C(OH)CH2, and Ph-C(NOH)C(–OH)CH2. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH2, PhCH(–NO)C(OH)CH2, PhCH(NO)–C(OH)CH2, and PhCH(NO)C(–OH)CH2. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3
techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone
> 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding
appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated
λmax for the first excited singlet state (S1) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λmax of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental
spectra. 相似文献
3.
Martin Studer Christina Wedemeyer-Exl Felix Spindler Hans-Ulrich Blaser 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1335-1343
Summary. The first case of an enantioselective hydrogenation of monosubstituted pyridines and furans with homogeneous rhodium diphosphine
catalysts with low but significant enantioselectivities and catalyst activities is reported. Best enantioselectivities (ees of 24–27%) were obtained for the hydrogenation of 2- and 3-pyridine carboxylic acid ethyl ester and 2-furan carboxylic acid
with catalysts prepared in
situ from [Rh(nbd)2]BF4 and the chiral ligands diop, binap, or ferrocenyl diphosphines of the josiphos type. Turnover numbers (ton) were in the order of 10–20, turnover frequencies (tof) usually 1–2 h−1. Diphosphines giving 6- or 7-ring chelates led to higher ees than 1,2-diphosphines; otherwise, no clear correlation between ligand properties and catalytic performance was found. In
some experiments black precipitates were observed at the end of the reaction, indicating the decomposition of the homogeneous
catalysts for certain ligand/metal/substrate combinations.
Received April 5, 2000. Accepted (revised) May 2, 2000 相似文献
4.
Dr. Xi Chen Ting Mei Yunfeng Cui Qijia Chen Xiangtao Liu Prof. Jinhui Feng Prof. Qiaqing Wu Prof. Dunming Zhu 《ChemistryOpen》2015,4(4):483-488
Terminal vicinal diols are important chiral building blocks and intermediates in organic synthesis. Reduction of α-hydroxy ketones provides a straightforward approach to access these important compounds. In this study, it has been found that asymmetric reduction of a series of α-hydroxy aromatic ketones and 1-hydroxy-2-pentanone, catalyzed by Candida magnolia carbonyl reductase (CMCR) with glucose dehydrogenase (GDH) from Bacillus subtilis for cofactor regeneration, afforded 1-aryl-1,2-ethanediols and pentane-1,2-diol, respectively, in up to 99 % ee. In order to evaluate the efficiency of the bioreduction, lyophilized recombinant Escherichia coli whole cells coexpressing CMCR and GDH genes were used as the biocatalyst and α-hydroxy acetophenone as the model substrate, and the reaction conditions, such as pH, cosolvent, the amount of biocatalyst and the presences of a cofactor (i.e., NADP+), were optimized. Under the optimized conditions (pH 6, 16 h), the bioreduction proceeded smoothly at 1.0 m substrate concentration without the external addition of cofactor, and the product (S)-1-phenyl-1,2-ethanediol was isolated with 90 % yield and 99 % ee. This offers a practical biocatalytic method for the preparation of these important vicinal diols. 相似文献
5.
Derek R. Boyd David Clarke Marcel C. Cleij John T. G Hamilton Gary N. Sheldrake 《Monatshefte für Chemie / Chemical Monthly》2000,131(6):673-685
Summary. The bacterium Pseudomonas putida ML 2 was used in the oxidative biodegradation of the acyclic dienes isoprene, trans-piperylene, cis-piperylene, and 1,3-butadiene. Regioselective dioxygenase-catalyzed dihydroxylation of alkenes yielded vicinal diols in the
preferred sequence monosubstituted > cis-disubstituted > gem-disubstituted > trans-disubstituted. The isolated diol metabolites had an excess of the R configuration (9–97%ee), and further diol oxidation was controlled by addition of propylene glycol as an inhibitor. Stereoselectivity using the
ML2 strain resulted from both enzymatic asymmetric alkene dihydroxylation and kinetic resolution of diols. Enantioselective
oxidation of the allylic secondary alcohol group of R configuration yielded the corresponding unsaturated ketoalcohol; the residual diol was recovered with a large excess (≥ 93%ee) of the S configuration. In addition to the enzymatic diene oxidation steps yielding unsaturated diols and ketoalcohols, evidence was
also found of enzymatic alkene hydrogenation to yield saturated ketoalcohols and diols.
Received December 20, 1999. Accepted (revised) February 7, 2000 相似文献
6.
Nasir Ahmad Nasir Iqbal Christy Munir 《Monatshefte für Chemie / Chemical Monthly》2000,131(10):1067-1072
Summary. The synthesis and characterization of homobimetallic complexes of VO(IV), Cr(II), Co(II), Ni(II), and Cu(II) with the chiral
Schiff base (1S,2S)-N,N-1,2-Diphenylethylene-bis-(5-imino-1-phenyl-1,3-hexa-nedione) is reported. The metal ions occupy both compartments of the ligand; water molecules fill
the coordination spheres to provide an octahedral environment around the central atoms. The antibacterial activity of both
mono- and bimetallic complexes against a number of Gram-positive as well as Gram-negative bacteria has been tested and is discussed.
Received March 28, 2000. Accepted May 26, 2000 相似文献
7.
Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers:
1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol.
Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G* and 6-311G** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds
of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH3, PhC(NOH)–C(O)CH3, and PhC(N–OH)C(O)CH3. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single
bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH3, PhC(N–O)C(OH)CH3, and PhC(NO)C(–OH)CH3. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone:
Ph–CH(NO)C(O)CH3, PhCH(–NO)C(O)CH3, and PhCH(NO)–C(O)CH3. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH2, PhC(N–OH)C(OH)CH2, PhC(NOH)–C(OH)CH2, and Ph-C(NOH)C(–OH)CH2. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH2, PhCH(–NO)C(OH)CH2, PhCH(NO)–C(OH)CH2, and PhCH(NO)C(–OH)CH2. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3
techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone
> 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding
appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated
λmax for the first excited singlet state (S1) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λmax of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental
spectra. 相似文献
8.
Annegret Tillack Harald Trauthwein Christian G. Hartung Martin Eichberger Stephan Pitter Achim Jansen Matthias Beller 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1327-1334
Summary. The oxidative amination of styrene with secondary amines in the presence of cationic rhodium catalysts yields regiospecifically
the corresponding anti-Markovnikov enamines. Styrene as the hydrogen acceptor gave concomitantly ethylbenzene. In the presence of 1,5-cyclooctadiene (cod) preferential reduction to cyclooctene takes place. The addition of cod reduces the rate of the reaction, but also the amount of ethylbenzene produced. Here, for the first time the ratio of enamine:
ethylbenzene is > 1, which is favourable in case of more expensive styrene derivatives. A screening of various ligands for
oxidative amination reveals that hemilabile 2-(ω-phosphino-n-alkyl)-pyridines are superior ligands for this reaction compared to simple alkyl and aryl phosphines.
Received May 30, 2000. Accepted July 11, 2000 相似文献
9.
The interaction of 3-(R-amino)-3-methylthio-1-phenylpropenones and 1-alkyl-5-benzoyl-3-ethoxy-carbonyl-6-methylthio-1,2-dihydropyridin-2-ones
with N,N- and N,C-1,2- and 1,3-dinucleophiles proceeded regioselectively by [3 + 2] and [3 + 3] cyclocondensation with the
formation of derivatives of pyrazole, benzimidazo[1,2-a]-pyridine, benzimidazo[1,2-a]pyrimidine, imidazo[1,2-a]pyrimidine, [1,2,4]triazolo[4,3-b]pyridazine, and 6,7-dihydro-2H-pyrazolo[3,4-b]pyridine. The regioselectivity of the reactions carried out was analyzed. 相似文献
10.
Mokrov G. V. Likhosherstov A. M. Lezina V. P. Gudasheva T. A. Bushmarinov I. S. Antipin M. Yu. 《Russian Chemical Bulletin》2010,59(6):1254-1266
The reactions of methyl α-(2-formyl-1H-pyrrol-1-yl)carboxylates with N-substituted aliphatic 1,2-, 1,3-, and 1,4-diamines afford new pyrrole-containing heterocyclic systems: 1,2,3,10b-tetrahydroimidazo[1,2-a]pyrrolo[2,1-c]pyrazin-5(6H)-ones, 1,3,4,11b-tetrahydro-2H-pyrrolo[2′,1′:3,4]pyrazino[1,2-a]pyrimidin-6(7H)-ones, and 1,2,3,4,5,12b-hexahydro-pyrrolo[2′,1′:3,4]pyrazino[1,2-a][1,3]diazepin-7(8H)-ones. The reduction of these compounds with different reagents was studied. 相似文献
11.
Summary. Reactions of sodium salts of 3-hydroxymethylene-2-alkanones with 2-cyanomethylbenzimidazole afforded benzimidazo[1,2-a]pyridines. Analogues reactions with 2-aminobenzimidazole and 5-aminopyrazoles afforded benzimidazo[1,2-c]pyrimidines and pyrazolo[1,5-a]pyrimidines.
Received December 12, 1999. Accepted (revised) February 12, 2000 相似文献
12.
V. Ya. Sosnovskikh A. Yu. Sizov B. I. Usachev M. I. Kodess V. A. Anufriev 《Russian Chemical Bulletin》2006,55(3):535-542
Reactions of chromones with methyl ketoximes in the presence of lithium diisopropylamide follow the nucleophilic 1,2-addition
mechanism to give spiro[4H-chromene-4,5′-isoxazolines] in good yields. The isoxazoline ring in spiro[4H-chromene-4,5′-isoxazolines] undergoes opening under the action of conc. H2SO4, yielding α,β-unsaturated oximes. Their nitrosation and bromination lead to the corresponding spiroisoxazolines, while the
Beckmann rearrangement, to α,β-unsaturated amides. The latter are also formed directly from spiro[4H-chromene-4,5′-isoxazolines] under the action of PCl5. N-Substituted acetophenone hydrazones in the presence of lithium diisopropylamide react at the C(4) atom of 2-trifluoromethylchromone,
while acetophenone anil under the same conditions, at the C(2) atom.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 516–522, March, 2006. 相似文献
13.
Summary. A new simple, rapid, sensitive, and selective method is proposed for the microdetermination of mercury. Mercury(II) forms
insoluble complexes with 2,3-dichloro-6-(2-hydroxy-3,5-dinitrophenylazo)-quinoxaline (1), 2,3-dichloro-6-(5-amino-3-carboxy-2-hydroxy-phenylazo)-quinoxaline (2), 2,3-dichloro-6-(2,7-dihydroxynaphth-1-ylazo)-quinoxaline (3), and 2,3-dichloro-6-(3-carboxy-2-hydroxy-naphth-1-ylazo)-quinoxaline (4) in aqueous acidic medium; the complexes can be made soluble by the action of an anionic surfactant. The solution of the
pink coloured compounds is stable for at least 24 h. Beer’s law is obeyed over the concentration range from 0.1 to 2.8 μg · cm−3 of mercury. For a more accurate analysis, Ringbom optimum concentration ranges were found to be 0.25–2.5 μg · cm−3. The molar absorpitivity, Sandell sensitivity, and relative standard deviations were also calculated. A slight interference from Pd2+ and Cd2+ is exhibited by the first three ligands, whereas the last one is only negligibly affected by these metal ions. Strong interference
from Ag(I) is evident for all ligands, whereas alkali, alkaline earth, and other transition metals tested posed negligible
interference. 15 μg · cm−3 of Cd2+ and Pd2+ or 10 μg · cm−3 of Ag+ can be tolerated if 1.0 mg of potassium bromide and 2.0 mg of citrate as masking agents are added for the determination of
1.5 μg · cm−3 of mercury(II). The method was applied to the determination of methyl- and ethylmercury chloride and the analysis of environmental
water samples.
Received August 7, 2000. Accepted (revised) October 18, 2000 相似文献
14.
Nabila M. Guindy Zeinab M. Abou-Gamra Michel F. Abdel-Messih 《Monatshefte für Chemie / Chemical Monthly》2000,131(8):857-866
Summary. The kinetics of the formation of the 1:3 complex of chromium(III) with L-glutamic acid and DL-lysine were studied spectrophotometrically at and 550 nm. The reaction was found to be first order in both reactants. Increasing the hydrogen ion concentration from 3.2×10−5 to 1.0×10−3 molċdm−3 retarded the reaction rate which is of the form . Values of 28.8 and 63.6 kJċmol−1 were obtained for the energy of activation and −184 and −116 Jċ K−1ċmol−1 for the entropy of activation for L-glutamic acid and DL-lysine. The logarithms of the formation constants of the two complexes were found to be 5.9 and 5.1.
Received January 7, 2000. Accepted (revised) March 8, 2000 相似文献
15.
Günther Vogg Lex J.-P. Meyer Christian Miesner Martin S. Brandt Martin Stutzmann 《Monatshefte für Chemie / Chemical Monthly》2001,132(10):1125-1135
Summary. Epitaxial thin films of Ca(Si
1 − x
Ge
x
)2 with 0 < x ≤ 1 are found to react with the moisture of ambient atmosphere to form new Ca-Si-Ge-O-H compounds which were studied by X-ray
diffraction, energy dispersive X-ray analysis, infrared absorption, and thermally induced hydrogen desorption measurements.
Pure CaGe2 forms the polygermyne calcium hydroxide intercalation compound Ca(OH)2(GeH)2 upon exposure to humidity, with a trigonal tr6 crystal lattice with a = 4.00(1) and c = 65.3(1)?. In mixed Ca(Si
1 − x
Ge
x
)2 with smaller Ge content, the group-14 layers are subject to intense oxidation leading to decreased crystallinity. The products
exhibit characteristic colours and intense photoluminescence, the peak luminescence varying from 1.35 eV for the reaction
product of Ca(Si0.3Ge0.7)2 to 2.6 eV for that of Ca(Si0.5Ge0.5)2.
Received March 12, 2001. Accepted (revised) May 2, 2001 相似文献
16.
I. P. Romanova G. G. Yusupova O. A. Larionova A. A. Balandina Sh. K. Latypov V. V. Zverev D. G. Yakhvarov G. L. Rusinov O. G. Sinyashin 《Russian Chemical Bulletin》2006,55(3):502-506
The reaction of fullerene C60 with 2-azido-5-nitropyrimidine afforded 1-(5-nitropyrimidin-2-yl)[60]fullereno[1,2-b]aziridine, whose electrochemical reduction proceeds more easily than the reduction of nonmodified C60.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 484–488, March, 2006. 相似文献
17.
Zorica Bugarcěić Slobodan Novokmet Zěeljko Senić Zěivadin Bugarcěić 《Monatshefte für Chemie / Chemical Monthly》2000,131(7):799-802
Summary. Carbonyl compounds of the type XPhCOR (R = H, Me, Ph; X = H, Me, Cl, Br) are prepared in high yields by reaction of the corresponding benzylic alcohols XPhCHOHR with KNa4 [Ag(HIO6)2]×12H2O in alkaline solution. This method allows the selective oxidation of benzylic alcohols in compounds containing other types
of alcoholic functional groups.
Received January 18, 2000. Accepted (revised) February 23, 2000 相似文献
18.
Zusammenfassung. Die Reaktion von racemischem trans-Hexahydrobenzimidazol-2-amin mit drei ausgew?hlten vinylogen Ketonen unter milden Bedingungen wurde untersucht. Nur im Fall
der Umsetzung mit 4-Phenyl-3-buten-2-on konnten Cycloadditionsprodukte isoliert werden. Diese sind laut NMR-Analysen Gemische
von zwei der acht m?glichen Diastereomeren, n?mlich von rac-2β-Methyl-4β-phenyl-trans-5aα- und trans-5aβ-decahydropyrimido[1,2-a]benzimidazol-2α-ol. Bei Umsetzungen des Amins mit Phenylbutenon bei erhoühten Temperatur sowie mit, 2-Methyl-1-phenyl-1-penten-3-on
und 4′-Chlorchalkon bildeten sich Gemische entsprechend substituierter rac-4α-Phenyl-trans-5aβ- und trans-5aα-octahydropyrimido[1,2-a]benzimidazole. Struktur und Stereochemie der Titelverbindungen und ihrer Hydrochloride wurden anhand NMR-spektroskopischer
Untersuchungen aufgekl?rt. Die Ringschlu?reaktionen verlaufen in allen F?llen gleichgerichtet regio-, jedoch nicht diastereoselektiv.
Versuche zur Beeinflussung der Regio- und/oder Diastereoselektivit?t der Cyclisierungsreaktion durch Variation der Reaktionsbedingungen
hatten keinen Erfolg.
Synthesis and Structure Elucidation of Pyrimidobenzimidazoles and Fused Derivatives III [1,2]. Decahydropyrimido[1,2- a ]benzimidazol-2-oles and Octahydropyrimido[1,2- a ]benzimidazoles
Summary. The reaction of racemic trans-hexahydrobenzimidazol-2-amine with three vinylogous ketones under mild conditions was studied. Only in the case of 4-phenyl-3-buten-2-one cycloaddition products could be isolated. According to NMR spectroscopy they consist of mixtures of two of eight possible diastereomers: rac-2β-methyl-4β-phenyl-trans-5aα- and trans-5aβ-decahydropyrimido[1,2-a]benzimidazol-2α-ole. Reaction of the amine with the butenone at higher temperature and with, 2-methyl-1-phenyl-1-penten-3-one, and 4′-chlorochalcone afforded mixtures of two diastereomers each, which turned out as rac-4α-phenyl-trans-5aβ- and trans-5aα-octahydropyrimido[1,2-a]benzimidazoles. Complete structural and stereochemical assignments of the title compounds and their hydrochlorides were established by NMR spectroscopic investigations. The results showed that all investigated cyclization reactions proceeded regioselectively with equal orientation of the components, but not diastereoselectively. Variation of the reaction conditions did influence neither regio- nor diastereoselectivity.
Received October 19, 2000. Accepted October 30, 2000 相似文献
19.
Lixin Zhou 《Theoretical chemistry accounts》2000,105(1):86-92
Results of ab initio self-consistent-field (SCF) and density functional theory (DFT) calculations of the gas-phase structure,
acidity (free energy of deprotonation, ΔGo), and aromaticity of 1,2-diseleno-3,4-dithiosquaric acid (3,4-dithiohydroxy-3-cyclobutene-1,2-diselenone, H2C4Se2S2) are reported. The global minimum found on the potential energy surface of 1,2-diseleno-3,4-dithiosquaric acid presents a
planar conformation. The ZZ isomer was found to have the lowest energy among the three planar conformers and the ZZ and ZE
isomers are very close in energy. The optimized geometric parameters exhibit a bond length equalization relative to reference
compounds, cyclobutanediselenone, and cyclobutenedithiol. The computed aromatic stabilization energy (ASE) by homodesmotic
reaction (Eq 1) is −20.1 kcal/mol (MP2(fu)/6-311+G** //RHF/6-311+G**) and −14.9 kcal/mol (B3LYP//6-311+G**//B3LYP/6-311+G**).
The aromaticity of 1,2-diseleno-3,4-dithiosquaric acid is indicated by the calculated diamagnetic susceptibility exaltation
(Λ) −17.91 (CSGT(IGAIM)-RHF/6-311+G**//RHF/6-311+G**) and −31.01 (CSGT(IGAIM)-B3LYP/6-311+G**//B3LYP/6-311+G**). Thus, 1,2-diseleno-3,4-dithiosquaric
acid fulfils the geometric, energetic and magnetic criteria of aromaticity. The calculated theoretical gas-phase acidity is
ΔGo
1(298K)=302.7 kcal/mol and ΔGo
2(298K)=388.4 kcal/mol. Hence, 1,2-diseleno-3,4-dithiosquaric acid is a stronger acid than squaric acid(3,4-dihydroxy-3-cyclobutene-1,2-dione,
H2C4O4).
Received: 11 April 2000 / Accepted: 7 July 2000 / Published online: 27 September 2000 相似文献
20.
Derek R. Boyd David Clarke Marcel C. Cleij John T. G Hamilton Gary N. Sheldrake 《Monatshefte für Chemie / Chemical Monthly》2000,50(1):673-685
The bacterium Pseudomonas putida ML 2 was used in the oxidative biodegradation of the acyclic dienes isoprene, trans-piperylene, cis-piperylene, and 1,3-butadiene. Regioselective dioxygenase-catalyzed dihydroxylation of alkenes yielded vicinal diols in the preferred sequence monosubstituted > cis-disubstituted > gem-disubstituted > trans-disubstituted. The isolated diol metabolites had an excess of the R configuration (9–97%ee), and further diol oxidation was controlled by addition of propylene glycol as an inhibitor. Stereoselectivity using the ML2 strain resulted from both enzymatic asymmetric alkene dihydroxylation and kinetic resolution of diols. Enantioselective oxidation of the allylic secondary alcohol group of R configuration yielded the corresponding unsaturated ketoalcohol; the residual diol was recovered with a large excess (≥ 93%ee) of the S configuration. In addition to the enzymatic diene oxidation steps yielding unsaturated diols and ketoalcohols, evidence was also found of enzymatic alkene hydrogenation to yield saturated ketoalcohols and diols. 相似文献