Reactions of gas-phase salts: Substitutions and eliminations in complexes containing a dianion and a tetraalklylammonium cation

被引：22

作者：

Gronert, S ^{[1
]}

Azebu, J ^{[1
]}

机构：

[1] San Francisco State Univ, Dept Chem & Biochem, San Francisco, CA 94132 USA

来源：

ORGANIC LETTERS | 1999年 / 1卷 / 03期

关键词：

D O I：

10.1021/ol990104i

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] Electrospray ionization has been used to generate gas-phase complexes of a dianion (4 carboxy-4'-sulfodiphenylacetylene) with a series of tetraalkylammonium cations. The salt complexes are stable within a quadrupole ion trap but readily react during collision activated dissociation to give substitution and elimination products (alkylation or protonation of the carboxylate with the loss of a trialkylamine). Ab initio calculations at the MP2/6-31 +G(d,p)/MP2/6-31 +G(d) level are presented for the corresponding reactions of a model system, acetate + ethyltrimethylammonium.

引用

页码：503 / 506

页数：4

共 29 条

[1] STERIC EFFECTS IN ELIMINATION REACTIONS .9. THE EFFECT OF THE STERIC REQUIREMENTS OF THE LEAVING GROUP ON THE DIRECTION OF BIMOLECULAR ELIMINATION IN 2-PENTYL DERIVATIVES [J].

BROWN, HC ;

WHEELER, OH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (10) :2199-2202

[2] AMINE OXIDES .3. SELECTIVE FORMATION OF OLEFINS FROM UNSYMMETRICAL AMINE OXIDES AND QUATERNARY AMMONIUM HYDROXIDES [J].

COPE, AC ;

LEBEL, NA ;

LEE, HH ;

MOORE, WR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1957, 79 (17) :4720-4729

[3] ELECTROSPRAY IONIZATION FOR MASS-SPECTROMETRY OF LARGE BIOMOLECULES [J].

FENN, JB ;

MANN, M ;

MENG, CK ;

WONG, SF ;

WHITEHOUSE, CM .

SCIENCE, 1989, 246 (4926) :64-71

[4] The gas-phase reactions of dianions with alkyl bromides:: Direct identification of SN2 and E2 products [J].

Flores, AE ;

Gronert, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (11) :2627-2628

[5]

FRISCH MJ, 1995, GUASSIAN94

[6]

GRONERT S, IN PRESS INT J MASS

[7]

GRONERT S, 1998, MODERN ELECT STRUCTU

[8] On the dissociation and conformation of gas-phase methonium ions [J].

Gross, DS ;

Williams, ER .

INTERNATIONAL JOURNAL OF MASS SPECTROMETRY AND ION PROCESSES, 1996, 157 :305-318

[9] The nature of the alternating effect in carbon chains Part XVIII Mechanism of exhaustive methylation and its relation to anomalous hydrolysis [J].

Hanhart, W ;

Ingold, CK .

JOURNAL OF THE CHEMICAL SOCIETY, 1927, :997-1020

[10]

Hofmann A. W., 1851, LIEBIGS ANN CHEM, V78, P253

← 1 2 3 →