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The linear hydrazone form is represented by (E,E')- and (E,Z')-conformational isomers, differing in the disposition relative to the amide C–N bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the ES steric constants of the alkyl substituents. In the series of the aromatic aldehydes 2- mercaptobenzoylhydrazones the linear tautomer prevails, and the logarithms of the tautomeric equilibrium constants KT correlate with the σ-constants of the substituents in the aromatic nucleus. Andrei Yu Ershov, Igor V. Lagoda, Marina Yu Vasileva, Stanislav I. Yakimovich, Boris V. Chernitsa, Lyudmila Yu Kuleshova, Lyudmila V. Pavlova, Aleksandr V. Yakimansky Adobe PDF Library 11.0 Hammett and Taft Equations, Ring-Chain Tautomerism 2-Mercaptobenzoylhydrazones, Benzo-1,3,4-Thiadiazepines D:20170512054813 It has been shown by 1H and 13C NMR spectroscopy that 2-mercaptobenzoyl- hydrazones of aliphatic and aromatic aldehydes exist in solution as tautomeric mixtures of linear and cyclic benzo-1,3,4-thiadiazepine forms. The linear hydrazone form is represented by (E,E')- and (E,Z')-conformational isomers, differing in the disposition relative to the amide Câ•fiN bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the ES steric constants of the alkyl substituents. In the series of the aromatic aldehydes 2- mercaptobenzoylhydrazones the linear tautomer prevails, and the logarithms of the tautomeric equilibrium constants KT correlate with the Ï…-constants of the substituents in the aromatic nucleus. endstream endobj 50 0 obj <>stream h225R0Pw/+Q04L)625 )I 14P`"g 3bC* RS  endstream endobj 51 0 obj <>stream hޔVn6%<[ I`l_hHU~p$e- X\̜ x{>11Աغ,[|h,toģE S\BvV.K>9œREI0V=J;y T0u12%0ON %`SLh`e em{={qe Y,3l;v.-ޞ~bUs-gcc׸Y&H?/9w-Q(JC{IT~VH,Ib4)b+^D^k:m?$JJȅٹ5uUwy$ѶߨIٹ7$p\ɸ=;= `L<8df؜LDTd$(rIb#Wh3=RU9lxl6!#!P{]]%H<#iNєm ;f7_CB7GwuiuUy{N>?w9N_iWy˘5Nϗ:^+а;C6;ʧK̹O$K]P\bɟO "nZ0%,{'zRG2S#_0 ,b endstream endobj 52 0 obj <>/Filter/FlateDecode/ID[<1519EBBAA56399409A14A7B7D9B51084>]/Info 253 0 R/Length 244/Root 255 0 R/Size 254/Type/XRef/W[1 3 1]>>stream hbb&Fi L@F4"]HF? h,k"6 R'X|6XDMqHEF?09DxeH)`93a( 6,"ނuu1*ԁE~f;HC7ncDJ׀դ?/}4z5X\M0&KU{|8xC}3?N ~)2 endstream endobj startxref 116 %%EOF 1 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 8 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 11 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 14 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 17 0 obj <>/ExtGState<>/Font<>/XObject<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 28 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 31 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 34 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 37 0 obj <>/ExtGState<>/Font<>>>/Rotate 0/Tabs/S/Type/Page>> endobj 49 0 obj <>stream 2017-05-12T13:50:26+08:00 2017-05-12T13:48:27+08:00 2017-05-12T13:50:26+08:00 Acrobat PDFMaker 11 Word 版 uuid:73117a50-f3f1-422a-80a9-fcf3761b18ca uuid:199d34a6-e809-48bc-9259-212851ba6a37 468 application/pdf Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors It has been shown by 1H and 13C NMR spectroscopy that 2-mercaptobenzoyl- hydrazones of aliphatic and aromatic aldehydes exist in solution as tautomeric mixtures of linear and cyclic benzo-1,3,4-thiadiazepine forms. The linear hydrazone form is represented by (E,E')- and (E,Z')-conformational isomers, differing in the disposition relative to the amide C–N bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the ES steric constants of the alkyl substituents. In the series of the aromatic aldehydes 2- mercaptobenzoylhydrazones the linear tautomer prevails, and the logarithms of the tautomeric equilibrium constants KT correlate with the σ-constants of the substituents in the aromatic nucleus. Andrei Yu Ershov, Igor V. Lagoda, Marina Yu Vasileva, Stanislav I. Yakimovich, Boris V. Chernitsa, Lyudmila Yu Kuleshova, Lyudmila V. Pavlova, Aleksandr V. Yakimansky Adobe PDF Library 11.0 Hammett and Taft Equations, Ring-Chain Tautomerism 2-Mercaptobenzoylhydrazones, Benzo-1,3,4-Thiadiazepines D:20170512054813 It has been shown by 1H and 13C NMR spectroscopy that 2-mercaptobenzoyl- hydrazones of aliphatic and aromatic aldehydes exist in solution as tautomeric mixtures of linear and cyclic benzo-1,3,4-thiadiazepine forms. The linear hydrazone form is represented by (E,E')- and (E,Z')-conformational isomers, differing in the disposition relative to the amide Câ•fiN bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the ES steric constants of the alkyl substituents. 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