Hydrogenation of ethyl esters of 4-phenyl-and (2-furyl)-substituted 2,4-dioxobutyric acids at palladium black

The hydrogenation of ethyl 4-R-2,4-dioxobutyrates (R = phenyl, 2-furyl) at 5% Pt/Al₂O₃ catalyst, modified with cinchonidine, and at palladium black was investigated. The former had low activity under the conditions we tested. The main products during the hydrogenation of these compounds at palladium black are ethyl 4-R-2-hydroxy-4-oxobutyrates. The yield of the phenyl derivative amounts to 68.5%, while the yield of the corresponding 2-furyl derivative amounts to 97%. In the last case ethyl 2-hydroxy-4-oxo-4-(2-tetrahydrofuryl)butyrate was detected as impurity. The optimum conditions for the formation of ethyl 2-hydroxy-4-phenylbutyrate (yield 88.2%) were determined. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 655–659, May, 2006.     

Tandem cleavage of 2,3,5-trimethyl 7-trifluoroacetyl-1,2,3,4-tetrahydro-pyrrolo[1,2-<Emphasis Type="Italic">c</Emphasis>]pyrimidine by activated alkynes,caused by Michael addition of a tertiary nitrogen atom to a triple bond

The interaction of 7-trifluoroacetyltetrahydropyrrolo[1,2-c]pyrimidine with acetylenedicarboxylic ester (DMAD) and ethyl propiolate in acetonitrile and alcohols has been studied. It was established that DMAD splits pyrrolopyrimidine at the aminal fragment in acetonitrile and methanol with the formation of 1-H-and 2-(N-dimethoxycarbonylvinyl-N-methyl)aminoethyl-1-methoxymethyl-3-methyl-5-trifluoroacetylpyrroles. In acetonitrile ethyl propiolate splits pyrrolopyrimidine both at the aminal fragment and at the C₍₃₎-N₍₂₎ bond (Hofmann reaction), but in ethanol only at the C₍₃₎-N₍₂₎ bond with the formation of 2-propenylpyrroles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1082–1087, July, 2007.     

十八烷基（2—亚硫酸）乙基二甲基铵的合成

由Ｎ,Ｎ－二甲基十八烷基胺和乙撑亚硫酸酯反应合成十八烷基（２－亚硫酸）乙基二甲基铵是一种新型的亚硫酸内酯型两性表面活性剂,经红外光谱和核磁共振谱分析,确定了该化合物的结构,该两性表面活性剂合成方法简单,原料易得,用途广泛,有发展前途。     

固体杂多酸催化合成乳酸乙酯的研究

研究了硅鸽酸催化合成乳酸乙酯的方法;考察了催化剂、酸醇比、带水剂和反应时间等因素对产率的影响。     

氯代吲哚丁酸乙酯的合成研究

以Ｆｅ粉为催化剂,用直接通入Ｃｌ２的方法对吲哚丁酸乙酯进行氯化,其氯代产物经确证为一未见文献报道的新化合物,对其合成方法进行了详细的讨论。     

Bifunctional pyridyl alcohols with the bicyclo[3.3.0]octane scaffold in the asymmetric addition of diethylzinc to aldehydes

Some new pyridyl alcohols with the cis-bicyclo[3.3.0]octane scaffold were synthesized and used as chiral ligands for the enantioselective addition of diethylzinc to aldehydes. Ligands 4 were found to be far superior to the C₂-symmetric ligands 2 in terms of enantioselectivities. Quantitative yields and enantiomeric excesses of up to 92% were obtained when the ligand 4 was used. The carbonyl function in 4 proved to be beneficial for the high enantioselectivities in the addition of diethylzinc to aldehydes. Conversion of the carbonyl group into oxime or oxime ether group led to a sort of more active ligands, which catalyzed the same reaction with rate acceleration.     

Interaction of (1-phenylethyl)indole-2-carbonitrile with C-nucleophiles

Methods of obtaining ketones and enamino esters have been developed on the basis of reactions of 1-(1-phenylethyl)indole-2-carbonitrile with organomagnesium and organozinc compounds. Removal of a benzyl group from the indole nitrogen atom by the Grignard reagent has been discovered. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1179–1183, August, 2006.     

Functionalized naphthol[2,3-h] quinoline-7,12-diones

The addition of secondary and primary amines to ethyl (1-amino-9,10-anthraquinon-2-yl)propynoate affords an easily separable mixture of the corresponding ethyl 3-dialkylaminoor 3-alkylamino-3-(1-amino-9,10-anthraquinon-2-yl)acrylate and 3-dialkylamino- or 3-alkylaminonaphthol[2,3-h]quinoline-2(1H), 7,12-trione (in ∼4: 1 ratio). Intramolecular cyclization of the resulting substituted ethyl acrylates results in the formation of 4-dialkylaminoor 4-alkylamino-2-chlorinated pyridine rings. Subsequent nucleophilic substitution of the chlorine atom gives 2-functionalized 4-dialkylamino- or 4-alkylaminonaphtho[2,3-h]quinoline-7,12-diones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2327–2332, November, 1998.     

过氧化氢与N—甲基苯胺盐酸盐引发体系的研究

在水介质中,研究了新型的过氧化氢/N-甲基苯胺盐酸盐引发体系对 AM 与 PVA 的接枝共聚。产物经紫外光谱、红外光谱和 ~1H-核磁共振进行表征,并提出了引发机理。     

MP2 study of substituent effects of 2-substituted alkyl ethyl methylcarbamates in homogeneous, unimolecular gas phase elimination reaction

Møller-Plesset MP2/6-31G method was used to examine the gas-phase elimination of 2-substituted alkyl ethyl N,N-dimethylcarbamates. The results of these calculations support a concerted non-synchronous six-membered cyclic transition state mechanism for carbamates containing a C_β–H bond at the alkyl side of the ester. These substrates produce the N,N-dimethylcarbamic acid and the corresponding olefin. The unstable intermediate, N,N-dimethylcarbamic acid, rapidly decomposes through a four-membered cyclic transition state to dimethylamine and CO₂ gas. Correlation of the logarithm of theoretical rate coefficients against original Taft's σ* values gave an approximate straight line (ρ*=−1.39, r=0.9558 at 360 °C). In addition to this fact, when log k_rel is plotted against the theoretical log k_rel for 2-substituted ethyl N,N-dimethylcarbamates a reasonable straight line (r=0.9919 at 360 °C) is obtained, suggesting similar mechanism.