Pyrolysis reactions of 4-phenyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether and 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether:: remarkable rearrangement reactions of intramolecular Diels-Alder products.: Mechanistic implications of a new thermal retro-Diels-Alder reaction to cyclohexa-2,4-dienylmethyl fluoroketenes and recyclisations by π4s+π2s and/or π2s+π2a routes

被引：5

作者：

Allen, DM ^{[1
]}

Batsanov, AS ^{[1
]}

Brooke, GM ^{[1
]}

Lockett, SJ ^{[1
]}

机构：

[1] Univ Durham, Dept Chem, Sci Labs, Durham DH1 2LE, England

来源：

JOURNAL OF FLUORINE CHEMISTRY | 2001年 / 108卷 / 01期

关键词：

Diels-Alder adducts; retro-Diels-Alder products; (pi)4(s) + (pi)2(s) and/or (pi)2(s) + (pi)2(a) cyclisations; 2,4,5-trifluoro-3-(substituent)-2,4-cyclohexadienylmethyl fluoroketenes;

D O I：

10.1016/S0022-1139(00)00405-X

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The pyrolyses of 4-phenyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether (26) under flash vapour phase (FVP) conditions at 350 degreesC and of 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl prop-2-enyl ether (27) on heating in vacuo at 169 degreesC give mixtures of products which include 3-phenyl-2,4,5,7-tetrafluorotricyclo[3.3.1.0(2.7)]non-3-ene-6-one (28), and 3-trifluoromethyl-2,4,5,7-tetrafluorotricyclo[3.3.1.0(2.7)]non-3-ene-6-one (31), respectively, the products of one of the two possible intramolecular Diels-Alder reactions of the Claisen rearrangement intermediates 2. FVP of 26 at 430 degreesC and 27 at 450 degreesC give the bicyclic compounds 7-phenyl-2,5 beta ,6,7a beta -tetrafluoro-3a beta ,4,5,7a-tetrahydroinden-1-one (34) and 7-trifluoromethyl-2,5 beta ,6,7a beta -tetrafluoro-3a beta ,4,5,7a-tetrahydroinden-1-one (37). respectively. It is proposed that these latter two compounds are formed via two possible intermediates produced by recyclisations of the tethered 2,4,5-trifluoro-3-(substituent)-2,4-cyclohexadienylmethyl fluoroketene (23), itself formed via new retro-cyclisation reactions of 28 and 31, respectively. Also formed from 27 via 31 is 1,2,4 beta ,5,7-tetrafluoro-3-(trifluoromethyl)bicyclo[3.3.1]nona-2,6-dien-8-one (39). (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：57 / 67

页数：11

共 19 条

[1] Pyrolysis reactions of nonafluorobiphenyl-4-yl prop-2-enyl ether: a remarkable rearrangement reaction of an intramolecular Diels-Alder product [J].

Batsanov, AS ;

Brooke, GM ;

Holling, D ;

Kenwright, AM .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2000, (11) :1731-1734

[2] POLYFLUOROARENES .18. SOME REACTIONS OF 2,3,4,5,6-PENTAFLUOROBIPHENYL AND RELATED COMPOUNDS [J].

BIRCHALL, JM ;

HASZELDI.RN ;

WOODFINE, H .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1973, (10) :1121-1125

[3] PYROLYSES OF PENTAFLUOROPHENYL PROP-2-ENYL AND [2,3,3-H-2(3)]PROP-2-ENYL ETHERS - FORMATION OF 1-FLUOROVINYL 2,3,4-TRIFLUOROPHENYL KETONES VIA INTERNAL DIELS-ALDER REACTIONS [J].

BROOKE, GM ;

HALL, DH .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1976, (13) :1463-1465

[4]

BROOKE GM, 1971, TETRAHEDRON LETT, P2377

[5]

BROOKE GM, 1978, J CHEM SOC PERK T 1, P780, DOI 10.1039/p19780000780

[6]

BROOKE GM, 1974, J CHEM SOC PERK T 1, P233, DOI 10.1039/p19740000233

[7]

BROOKE GM, 1983, J FLUORINE CHEM, V22, P283

[8]

BROOKE GM, 1982, F FLUORINE CHEM, V20, P163

[9]

CHAUDHRY MT, 1963, J CHEM SOC, P4281

[10]

Hyatt J., 1994, ORG REACTIONS, V45, P159

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