Dimethyldioxirane converts benzene oxide/oxepin into (Z,Z)-muconaldehyde and sym-oxepin oxide: Modeling the metabolism of benzene and its photooxidative degradation

被引：14

作者：

Bleasdale, C ^{[1
]}

Cameron, R ^{[1
]}

Edwards, C ^{[1
]}

Golding, BT ^{[1
]}

机构：

[1] Univ Newcastle Upon Tyne, Dept Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England

来源：

CHEMICAL RESEARCH IN TOXICOLOGY | 1997年 / 10卷 / 12期

关键词：

D O I：

10.1021/tx970122d

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

Oxidation of 7-oxabicyclo[4.1.0]hepta-2,4-diene (benzene oxide)/oxepin with dimethyldioxirane (DMDO) gave mainly (Z,Z)-muconaldehyde, with complete diastereoselectivity. Similarly, 2-methyl-7-oxabicyclo[4.1.0]hepta-2,4-diene (toluene 1,2-epoxide)/2-methyloxepin gave (Z,Z)-1,6-dioxohepta-2,4-diene, while 2,6-dimethyl-7-oxabicyclo[4.1.0]hepta-2,4-diene (1,2-dimethylbenzene 1,2-epoxide)/2,7-dimethyloxepin gave (Z,Z)-2,7-dioxo-3,5-octadiene. By monitoring the DMDO oxidation of benzene oxide/oxepin by H-1 NMR spectroscopy, a significant byproduct was identified as 4,8-dioxabicyclo[5,1.0]octa-2,5-diene (sym-oxepin oxide). This observation supports the hypothesis that the route to (Z,Z)-muconaldehyde proceeds from oxepin via 6,8-dioxabicyclo[5.1.0]octa-2,4-diene (oxepin 2,3-oxide), with a minor pathway leading to sym-oxepin oxide. The DMDO oxidations described provide model systems for the cytochrome P450-dependent metabolism of benzene and for the atmospheric photooxidation of benzenoid hydrocarbons.

引用

页码：1314 / 1318

页数：5

共 33 条

[1] SPECTRAL AND CHEMICAL-PROPERTIES OF DIMETHYLDIOXIRANE AS DETERMINED BY EXPERIMENT AND ABINITIO CALCULATIONS [J].

ADAM, W ;

CHAN, YY ;

CREMER, D ;

GAUSS, J ;

SCHEUTZOW, D ;

SCHINDLER, M .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (13) :2800-2803

[2] OXIDATION OF FURANS WITH DIMETHYLDIOXIRANE [J].

ADGER, BM ;

BARRETT, C ;

BRENNAN, J ;

MCKERVEY, MA ;

MURRAY, RW .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1991, (21) :1553-1554

[3] PREPARATION OF THE 8,9-EPOXIDE OF THE MYCOTOXIN AFLATOXIN-B1 - THE ULTIMATE CARCINOGENIC SPECIES [J].

BAERTSCHI, SW ;

RANEY, KD ;

STONE, MP ;

HARRIS, TM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (23) :7929-7931

[4] REACTIONS OF MUCONALDEHYDE ISOMERS WITH NUCLEOPHILES INCLUDING TRI-O-ACETYLGUANOSINE - FORMATION OF 1,2-DISUBSTITUTED PYRROLES FROM REACTIONS OF THE (Z,Z)-ISOMER WITH PRIMARY AMINES [J].

BLEASDALE, C ;

GOLDING, BT ;

KENNEDY, G ;

MACGREGOR, JO ;

WATSON, WP .

CHEMICAL RESEARCH IN TOXICOLOGY, 1993, 6 (04) :407-412

[5] PREPARATION OF ETHENYL AND OXIRANOL CARBAMATE AND THEIR (2-H-2(2))-DERIVATIVES USING SELENIUM CHEMISTRY - THERMOLYSIS OF OXIRANOL CARBAMATE AND REACTION WITH ADENOSINE [J].

BLEASDALE, C ;

GOLDING, BT ;

KITSON, SL .

BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 1994, 4 (02) :291-296

[6] IDENTIFICATION OF CIS-2-BUTENE-1,4-DIAL AS A MICROSOMAL METABOLITE OF FURAN [J].

CHEN, LJ ;

HECHT, SS ;

PETERSON, LA .

CHEMICAL RESEARCH IN TOXICOLOGY, 1995, 8 (07) :903-906

[7] DETECTION OF CYCLIC 1,N-2-PROPANODEOXYGUANOSINE ADDUCTS IN DNA OF RATS TREATED WITH N-NITROSOPYRROLIDINE AND MICE TREATED WITH CROTONALDEHYDE [J].

CHUNG, FL ;

YOUNG, R ;

HECHT, SS .

CARCINOGENESIS, 1989, 10 (07) :1291-1297

[8] BENZENE OXIDE OXEPIN - OXIDATION TO MUCONALDEHYDE [J].

DAVIES, SG ;

WHITHAM, GH .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1977, (11) :1346-1347

[9] TOLUENE DEGRADATION PRODUCTS IN SIMULATED ATMOSPHERIC CONDITIONS [J].

DUMDEI, BE ;

OBRIEN, RJ .

NATURE, 1984, 311 (5983) :248-250

[10] Fission of the epoxide ring in 6,8-dioxabicyclo[5.1.0]octa-2,4-diene (epoxyoxepin) and in 8-oxabicyclo[5.1.0]octa-2,4-diene: An ab initio molecular orbital study [J].

George, P ;

Bock, CW ;

Glusker, JP .

JOURNAL OF MOLECULAR STRUCTURE, 1996, 376 :425-435

← 1 2 3 4 →