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91.
92.
Shtamburg V. G. Klots E. A. Pleshkova A. P. Avramenko V. I. Ivonin S. P. Tsygankov A. V. Kostyanovsky R. G. 《Russian Chemical Bulletin》2003,52(10):2251-2260
Procedures were developed for the synthesis of N-acyloxy-N-alkoxy derivatives of ureas, carbamates, and benzamides by the reactions of the corresponding N-alkoxy-N-chloro derivatives with sodium carboxylates in MeCN. N-Chloro-N-ethoxy-p-toluenesulfonamide was inert in this reaction. Alcoholysis of N-acyloxy-N-alkoxy derivatives of ureas, carbamates, and tert-alkylamines afforded the corresponding N,N-dialkoxy derivatives, whereas alcoholysis of N-acetoxy-N-ethoxybenzamide gave rise to alkyl benzoates. 相似文献
93.
The factors determining the kinetic and thermodynamic stabilities of N-chlorohydrazines are discussed. Acyclic N-chlorohydrazines exist only as trialkyldiazenium chlorides 3a,b. Chlorination of 2-acyl-1, 1-dimethylhydrazines 6a,b gave 1,4-diacyl-2,3-dimethylhexahydro-1,2,4,5-tetrazines 7a,b via hydrazyl radical intermediates, and chlorination of a 1-phenylpyrazolidin-5-one 8 gave phenylazoisovaleric esters 9a,b. Stable N-chlorohydrazines were obtained from bicyclic hydrazines; viz. the 2-chloro-1,2-diazabicyclo [2.2.2]octan-3-one 12 and 7-chloro-1,7-diazabicyclo[2.2.1]heptane 16. The restricted inversion of N(7) in 16 and its 1-methyl quaternary salt 21 were observed in the 13C-NMR spectra. The acyclic N-chloro-hydrazinium salt 25 was isolated. 相似文献
94.
By means of the reaction of O-tosyloxime 1a with propargyl amine, esters of glycine and (S)-α-alanine, β-acetoxyethyl amine and β-dimethylaminoethyl amine functionally substituted 3,3-bis(trifluoromethyl)diaziridines 2a–g have been obtained. In the reactions with more bulky amines, (S)-phenylalanine Et ester, (R, S)-α-phenylethyl amine and t-butyl amine, 1a acts as a tosylating reagent. The ester group in diaziridine 2e is readily saponified by alcoholic alkali, whereas diaziridine 2c is rearranged in these conditions with ring-expansion. Complete asymmetric transformation has been found to take place on the formation of the solid phase of diastereomers 2d and 2j, and a closed cycle of diastereomeric transformations has been accomplished. Diaziridine 2g with chiral centres only at the nitrogen atoms has been obtained with the optical purity of 85.5% by resolution via salt 5c with d-(+)-camphor-3-carboxylic acid. The absolute configuration of (+)-2g and its quaternary salt, (+)-2h, has been determined from CD spectra. Optically active (?)-2h salt (optical purity 2.0%) has been also obtained by asymmetric synthesis on the basis of 1–10-camphorsulphonyl oxime 1b. From the kinetics of 2g, h racemization and 2d, e, i, j, k epimerization the energy parameters of the inversion of N atoms in 3,3-bis (trifluoromethyl)diaziridines have been determined. 相似文献
95.
96.
R. G. Kostyanovsky E. E. Mikhlina E. I. Levkoeva L. N. Yakhontov 《Journal of mass spectrometry : JMS》1970,3(8):1023-1029
The mass spectra of the quinuclidine-2 (and -3)-ones and other functional derivatives of quinuclidine as well as 2-azaquinuclidine and benzoquinuclidine have been investigated. The fragmentation through the open form of the molecular ion and the applicability of Bredt's rule to amine fragmentation of the bridgehead nitrogen bicyclic systems are discussed. 相似文献
97.
98.