Electron-withdrawing substituents decrease the electrophilicity of the carbonyl carbon.: An investigation with the aid of 13C NMR chemical shifts, v(C=O) frequency values, charge densities, and isodesmic reactions to interprete substituent effects on reactivity

被引:98
作者
Neuvonen, H [1 ]
Neuvonen, K
Koch, A
Kleinpeter, E
Pasanen, P
机构
[1] Turku Univ, Dept Chem, FIN-20014 Turku, Finland
[2] Univ Potsdam, D-14415 Potsdam, Germany
关键词
D O I
10.1021/jo020121c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
C-13 NMR chemical shifts and nu(C = O) frequencies have been measured for several series of phenyl-or acyl-substituted phenyl acetates and for acyl-substituted methyl acetates to investigate the substituent-induced changes in the electrophilic character of the carbonyl carbon. Charge density, bond order, and energy calculations have also been performed. The spectroscopic and charge density results indicate that opposite to the conventional thinking, electron-withdrawing substituents do not increase the electrophilicity of the carbonyl carbon but instead decrease it. On the other hand, reaction energies of the isodesmic reactions designed show that electron-withdrawing substituents destabilize the carbonyl derivatives investigated. So, a significant ground-state destabilization of carboxylic acid esters, and carbonyl compounds in general, due to the decreased resonance stabilization, is proposed as a novel concept to explain both the increase in their reactivity and the changes in the chemical shifts and carbonyl frequencies induced by electron-withdrawing substituents.
引用
收藏
页码:6995 / 7003
页数:9
相关论文
共 65 条
[1]   An analysis of substituent effects on 1H and 13C NMR parameters of substituted furans.: Linear free energy relationships and PM3 semiempirical calculations [J].
Alvarez-Ibarra, C ;
Quiroga-Feijoo, ML ;
Toledano, E .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1998, (03) :679-689
[2]  
Asao N, 2001, ANGEW CHEM INT EDIT, V40, P3206, DOI 10.1002/1521-3773(20010903)40:17<3206::AID-ANIE3206>3.0.CO
[3]  
2-5
[4]  
AVRAM M, 1972, INFRARED SPECTROSCOP, P416
[5]  
AVRAM M, 1972, INFRARED SPECTROSCOP, P341
[6]   O-17 NMR-SPECTROSCOPY - EFFECT OF SUBSTITUENTS ON CHEMICAL-SHIFTS FOR PARA-SUBSTITUTED BENZOIC-ACIDS, METHYL BENZOATES, CINNAMIC-ACIDS AND METHYL CINNAMATES [J].
BALAKRISHNAN, P ;
BAUMSTARK, AL ;
BOYKIN, DW .
ORGANIC MAGNETIC RESONANCE, 1984, 22 (12) :753-756
[7]   CONCERTEDNESS IN ACYL GROUP TRANSFER IN SOLUTION - A SINGLE TRANSITION-STATE IN ACETYL GROUP TRANSFER BETWEEN PHENOLATE ION NUCLEOPHILES [J].
BASAIF, S ;
LUTHRA, AK ;
WILLIAMS, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (21) :6362-6368
[8]   CONCERTED ACETYL GROUP TRANSFER BETWEEN SUBSTITUTED PHENOLATE ION NUCLEOPHILES - VARIATION OF TRANSITION-STATE STRUCTURE AS A FUNCTION OF SUBSTITUENT [J].
BASAIF, S ;
LUTHRA, AK ;
WILLIAMS, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2647-2652
[9]   ACYLATING FRIEDEL-CRAFTS COMPLEXES - MULTINUCLEAR NMR DATA AND CHEMICAL-REACTIVITY [J].
BIGI, F ;
CASNATI, G ;
SARTORI, G ;
PREDIERI, G .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1991, (08) :1319-1321
[10]   C-13 SUBSTITUENT CHEMICAL-SHIFTS IN THE SIDE-CHAIN CARBONS OF AROMATIC SYSTEMS - THE IMPORTANCE OF PI-POLARIZATION IN DETERMINING CHEMICAL-SHIFTS [J].
BROMILOW, J ;
BROWNLEE, RTC ;
CRAIK, DJ ;
FISKE, PR ;
ROWE, JE ;
SADEK, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1981, (05) :753-759