Hypervalent iodine chemistry: Mechanistic investigation of the novel haloacetoxylation, halogenation, and acetoxylation reactions of 1,4-dimethoxynaphthalenes

被引:67
作者
Evans, PA
Brandt, TA
机构
[1] Brown Laboratory, Department of Chemistry, University of Delaware, Newark
关键词
D O I
10.1021/jo970525i
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Treatment of 1,4-dimethoxynaphthalenes with iodosobenzene diacetate and trimethylsilyl chloride or bromide furnished the haloacetoxylated, acetoxylated, and halogenated 1,4-dimethoxynaphthalenes in excellent yield. The reaction pathway for each transformation was shown to be a function of reagent stoichiometry. A mechanistic hypothesis is presented that rationalizes the reaction pathways and explains the subtle differences in the halogenation reactions. The acetoxylation, for example, is thought to involve the formation of an iodonium ion that promotes the nucleophilic addition of acetate ion and subsequent 1,2-acetyl migration. Bromination occurs as a direct result of the oxidation of trimethylsilyl bromide to bromine, followed by electrophilic aromatic substitution. Chlorination is thought to proceed via a radical process and not the formation of molecular chlorine from the dissociation of iodosobenzene dichloride. The haloacetoxylation reaction also appears to be fairly specific for 1,4-dimethoxynaphthalenes, since the analogous reaction with a 1,4-dimethoxybenzene derivative was unsuccessful.
引用
收藏
页码:5321 / 5326
页数:6
相关论文
共 38 条
[1]   SYNTHESIS AND REACTIONS OF STABLE ALKOXYARYLTRIFLUOROPERIODINANES - TAMED ANALOG OF IODINE PENTAFLUORIDE FOR USE IN OXIDATIONS OF AMINES, ALCOHOLS, AND OTHER SPECIES [J].
AMEY, RL ;
MARTIN, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (18) :5294-5299
[2]  
ANGELINI G, 1975, GAZZ CHIM ITAL, V105, P961
[3]   RING HALOGENATIONS OF POLYALKYLBENZENES BY IONIC HALIDES AND KOSERS REAGENT [J].
BOVONSOMBAT, P ;
DJUARDI, E ;
MCNELIS, E .
TETRAHEDRON LETTERS, 1994, 35 (18) :2841-2844
[4]  
Evans PA, 1996, TETRAHEDRON LETT, V37, P1367
[5]   Novel haloacetoxylation of 1,4-dimethoxynaphthalenes using hypervalent iodine chemistry [J].
Evans, PA ;
Brandt, TA .
TETRAHEDRON LETTERS, 1996, 37 (36) :6443-6446
[6]  
GALLOS J, 1982, J CHEM RES-S, P150
[7]   MECHANISITIC ASPECTS AND SYNTHETIC APPLICATIONS OF THE ELECTROCHEMICAL AND IODOBENZENE BIS(TRIFLUOROACETATE) OXIDATIVE 1,3-CYCLOADDITIONS OF PHENOLS AND ELECTRON-RICH STYRENE DERIVATIVES [J].
GATES, BD ;
DALIDOWICZ, P ;
TEBBEN, A ;
WANG, SP ;
SWENTON, JS .
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (07) :2135-2143
[8]   REGIOSELECTIVITY IN THE REACTIONS OF METHOXYDEHYDROBENZENES WITH FURANS .2. 2-METHOXYFURAN AND METHOXYDEHYDROBENZENES [J].
GILES, RGF ;
HUGHES, AB ;
SARGENT, MV .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1991, (06) :1581-1587
[9]   RELATION BETWEEN ELECTROCHEMICAL AND SPECTROSCOPIC PROPERTIES OF HALIDE AND PSEUDOHALIDE IONS IN SOLUTION [J].
GUSARSKY, E ;
TREININ, A .
JOURNAL OF PHYSICAL CHEMISTRY, 1965, 69 (09) :3176-&
[10]  
INOUE A, 1961, CHEM ABSTR 13853F, V55