REARRANGEMENT OF RIGID CYCLOPROPYLCARBINYL RADICALS - INVESTIGATION OF A REPORTER SYSTEM FOR THE DETECTION OF VERY SHORT-LIVED RADICALS

被引：22

作者：

LEMIEUX, RP ^{[1
]}

BEAK, P ^{[1
]}

机构：

[1] UNIV ILLINOIS,ROGER ADAMS LAB,DEPT CHEM,URBANA,IL 61801

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 20期

关键词：

D O I：

10.1021/jo00307a015

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The ring-opening rearrangements of the spiro[cyclopropane-1,r-indan]-2-yl radicals 1 and 2, the dispiro-[cyclopropane-1,T-indan-3',l“-cyclopropane]-2’-yl radical 3, and the 3,4-dihydrospiroIcyclopropane-1jT-(27f)-naphthalen]-2-yl radicals 4 and 5 were investigated by the tin hydride method. At 75 °C, the following unimolecular rate constants (kr) were obtained: 2.1 × 109 s-1(1), 8.6 × 109 s_1 (2), 5.3 × 108 s-1 (3), 3.0 × 109 s_1 (4), and 3.6 × 109 s_1 (5). The rate of ring opening of the 3,3-dimethylspirofcyclopropane-1,1-indan]-2yl radical 2 is comparable to that of the bicyclo[2.1.0]pent-2-yl radical and is one of the fastest cyclopropylcarbinyl radical rearrangements currently known. © 1990, American Chemical Society. All rights reserved.

引用

页码：5454 / 5460

页数：7

共 46 条

[1] RATE CONSTANTS FOR THE CYCLIZATION OF SOME ARYL RADICALS BEARING UNSATURATED ORTHO-SUBSTITUENTS [J].

ABEYWICKREMA, AN ;

BECKWITH, ALJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (06) :464-465

[2] OUTER-SPHERE AND INNER-SPHERE PROCESSES IN ORGANIC-CHEMISTRY - REACTION OF TRIFLUOROMETHYL BROMIDE WITH ELECTROCHEMICALLY GENERATED AROMATIC ANION RADICALS AND SULFUR-DIOXIDE ANION RADICALS [J].

ANDRIEUX, CP ;

GELIS, L ;

SAVEANT, JM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (02) :786-791

[3] COMPETING NUCLEOPHILIC DISPLACEMENT AND RADICAL CHAIN REDUCTION IN REACTIONS OF TRANSITION-METAL HYDRIDE ANIONS WITH ALKYL BROMIDES [J].

ASH, CE ;

HURD, PW ;

DARENSBOURG, MY ;

NEWCOMB, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (11) :3313-3317

[4] SINGLE-ELECTRON TRANSFER, A MAJOR REACTION PATHWAY IN ORGANIC-CHEMISTRY - AN ANSWER TO RECENT CRITICISMS [J].

ASHBY, EC .

ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (11) :414-421

[5] USE OF THE CYCLOPROPYLCARBINYL TEST TO DETECT A RADICAL-LIKE INTERMEDIATE IN PENICILLIN BIOSYNTHESIS [J].

BALDWIN, JE ;

ADLINGTON, RM ;

DOMAYNEHAYMAN, BP ;

KNIGHT, G ;

TING, HH .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (21) :1661-1663

[6] NEW METHOD FOR DEOXYGENATION OF SECONDARY ALCOHOLS [J].

BARTON, DHR ;

MCCOMBIE, SW .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1975, (16) :1574-1585

[7] ENDOCYCLIC RESTRICTION TEST - EVALUATION OF TRANSITION-STRUCTURE GEOMETRY FOR AN ARYL BROMIDE ALKYLLITHIUM EXCHANGE-REACTION [J].

BEAK, P ;

ALLEN, DJ ;

LEE, WK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (04) :1629-1630

[8] KINETICS AND MECHANISM OF SOME VINYL RADICAL CYCLIZATIONS [J].

BECKWITH, ALJ ;

OSHEA, DM .

TETRAHEDRON LETTERS, 1986, 27 (38) :4525-4528

[9] KINETICS AND REGIOSELECTIVITY OF RING-OPENING OF SUBSTITUTED CYCLOPROPYLMETHYL RADICALS [J].

BECKWITH, ALJ ;

BOWRY, VW .

JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (11) :2681-2688

[10] INTRAMOLECULAR RADICAL ADDITIONS TO THE AZO GROUP - FAST AND INDISCRIMINATE 5-EXO AND 6-ENDO CYCLIZATIONS [J].

BECKWITH, ALJ ;

WANG, SF ;

WARKENTIN, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (17) :5289-5291

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