Kinetics of reaction of copper with substituted benzyl chlorides in dipolar aprotic solvents

被引：12

作者：

Egorov, Anatoly M.

Matyukhova, Svetlana A.

机构：

[1] Tula State Univ, Dept Nat Sci, R-300600 Tula, Russia

[2] Orels Acad Publ Adm, R-300600 Tula, Russia

来源：

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS | 2007年 / 39卷 / 10期

关键词：

D O I：

10.1002/kin.20266

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reaction of copper with benzyl chlorides in dipolar aprotic solvents has been investigated. The kinetic and thermodynamic parameters of the reaction of copper with benzyl chloride in dimethyl sulfoxide, dimethylacetamide, and hexamethylphosphoramicle have been obtained. Hammett plots of log (k/k degrees) versus the substituent constant a gave good correlation. The structure of the organic group has little effect on the rate of reaction of benzyl chloride with copper, The kinetic and thermodynamic parameters were correlated with donor number of solvent (DNSbCl5). The ratio k(RBr)/k(RCl) and Hammett p values provide evidence in favor of the halogen atom transfer mechanism. (C) 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 547-555, 2007

引用

页码：547 / 555

页数：9

共 23 条

[1] KINETICS AND MECHANISM OF THE ALKYLNICKEL FORMATION IN ONE-ELECTRON REDUCTIONS OF ALKYL-HALIDES AND HYDROPEROXIDES BY A MACROCYCLIC NICKEL(I) COMPLEX [J].

BAKAC, A ;

ESPENSON, JH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (04) :713-719

[2] Mimicking aspects of heterogeneous catalysis: Generating, isolating, and reacting proposed surface intermediates on single crystals in vacuum [J].

Bent, BE .

CHEMICAL REVIEWS, 1996, 96 (04) :1361-1390

[3] POLAR RADICALS .14. MECHANISM OF TRIALKYLSTANNANE REDUCTIONS - POSITIVE-RHO VALUES FOR THE TRI-NORMAL-BUTYLSTANNANE REDUCTION OF BENZYL HALIDES - CORRELATION WITH SIGMA [J].

BLACKBURN, EV ;

TANNER, DD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (02) :692-697

[4] Kinetics and mechanism of the reaction of substituted benzyl chlorides with copper in dimethylformamide [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2005, 18 (10) :1023-1031

[5] The kinetics of reaction of copper with substituted benzyl bromides in dipolar aprotic solvents [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2005, 37 (08) :496-501

[6] Kinetics and mechanism of reaction of benzyl bromide with copper in dimethylacetamide [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2005, 18 (05) :456-461

[7] Kinetics and mechanism of the reaction of substituted benzyl bromides with copper in dimethylformamide [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

APPLIED ORGANOMETALLIC CHEMISTRY, 2005, 19 (05) :605-613

[8] Kinetics and mechanism of the reaction of benzyl bromide with copper in hexamethylphosphoramide [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2005, 37 (05) :296-305

[9] Kinetics and mechanism of the reaction of carbon tetrachloride with copper in dimethylacetamide [J].

Egorov, AM ;

Matyukhova, SA ;

Anisimov, AV .

KINETICS AND CATALYSIS, 2003, 44 (04) :471-475

[10] DETECTION OF INTERMEDIATES IN GRIGNARD REACTION ON THE MAGNESIUM SURFACE [J].

EGOROV, AM ;

ANISIMOV, AV .

APPLIED ORGANOMETALLIC CHEMISTRY, 1995, 9 (03) :285-289

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