AN ABNORMAL ALLYLIC DISPLACEMENT IN REACTION OF 2-HALO-3-METHYLBENZO[BETA]THIOPHENE 1,1-DIOXIDES WITH PIPERIDINE

被引：16

作者：

BORDWELL, FG

HEMWALL, RW

SCHEXNAY.DA

机构：

[1] Chemistry Department, Northwestern University, Evanston

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1968年 / 33卷 / 08期

关键词：

D O I：

10.1021/jo01272a042

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A kinetic study has shown that the reaction of 2-halo-3-methylbenzo [b] thiophene 1,1-dioxides (1) with piperidine in methanol to give 3-(1-piperidylmethylene)-2,3-dihydrobenzo [b] thiophene 1,1-dioxide (5) occurs in the following steps: (1) rapid tautomeric equilibration to form the allylic halide 2, (2) Sn2′ displacement, (3) loss of a proton to give 4, and (4) tautomerism to 5 (rate controlling). In the presence of added methoxide ion step 2 becomes rate controlling. The Br:Cl rate ratio for Sn2′ displacement is estimated to be ca. 1.4:1.0. © 1968, American Chemical Society. All rights reserved.

引用

页码：3233 / &

共 7 条

[1] EFFECT OF THE LEAVING GROUP ON THE RATES OF SN2 AND SN2' REACTIONS IN ALLYLIC SYSTEMS [J].

BORDWELL, FG ;

SOKOL, PE ;

SPAINHOUR, JD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (11) :2881-2888

[2] AN ABNORMAL ALLYLIC SUBSTITUTION FOLLOWED BY A NOVEL ALLYLIC REARRANGEMENT [J].

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HEMWALL, RW ;

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JOURNAL OF ORGANIC CHEMISTRY, 1968, 33 (08) :3226-&

[3] SN2 AND SN2' REACTIONS OF 2-CHLOROMETHYLBENZOTHIOPHENE AND 3-CHLOROMETHYLBENZOTHIOPHENE 1,1-DIOXIDES [J].

BORDWELL, FG ;

ROSS, F ;

WEINSTOCK, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (11) :2878-2881

[4]

CROMWELL NH, UNPUBLISHED RESULTS

[5] EFFECT OF METHYLMERCAPTO METHYLSUFINYL + METHYLSULFONYL GROUPS ON EQUILIBRIUM IN 3-CARBON PROTOTROPIC SYSTEMS [J].

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LYNESS, WI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (18) :3840-&

[6]

SCHEXNAYDER DA, 1968, THESIS NORTHWESTERN

[7]

STREITWIESER A, 1962, SOLVOLYTIC DISPLACEM, P29

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