2- Bromoethyl benzene

Ethyl phenylacetate and (2-bromoethyl)benzene as supplied by Eastman Organic Chemicals were used without further purification. 

Bromoethyl)benzene, reaction with ethyl phenylacetate, 47, 72 ic-Bromofluorides from olefins, 46,12 Bromofluorination of olefins, 46, 39... 

Ethyl phenylacetate, reaction with (2-bromoethyl)benzene, 47, 72 Ethyl 2-phenylhexanoate, 47, 74 Ethyl 2-phenylpropionate, 47, 74 Exchange of oxygen by sulfur in preparation of chloromethylphospho-nothioic dichlonde, 46, 21 Extractor, stirred in isolation of 3-hydroxyglutaromtnle, 46, 49... 

Sodium amide, in alkylation, of di-pbenylmetliane, 48, 80 of ethyl phenylacetate with (2-bromoethyl)benzene, 47, 72 in condensation of 2,4-pentanedione and 1-bromobutane to give 2,4-nonanedione, 47, 92 preparation of, 48, 80 Sodium 2-aminobenzenesulfinate, from reduction of 2-nitrobenzenesul-finic acid, 47, 5... 

The use of larger than normal quantities of catalyst leads to some surprising results. The elimination reaction of (2-bromoethyl)benzene in the presence of toluene and aqueous sodium hydroxide is catalysed by the presence of tetrabutylammonium bromide [48]. 

Bromoethyl)benzene can be used Instead of (2-chloroethylJbenzene anhydrous diethyl ether is used as the solvent instead of tetrahydrofuran. 

Bromo-4-ethoxybenzene, AM87 (2-Bromoethyl)benzene, AM83... 

For example, the fermentation of (2-bromoethyl)-benzene with recombinant E. coli furnished excellent yields of the corresponding c/.v-diol. enantiopure 3-(2-bromoethyl)-benzene-l,2-diol. The latter was used as a building block in the total synthesis of (+)-codeine (Fig. 29). Besides a Mitsunobu inversion of one of the stereogenic centers, two successive Heck cyclizations led to the enantiomer of the natural product [173]. Slight modifications of the reaction sequence, generating an epoxide intermediate, also furnished access to the naturally occurring enantiomer (—)-codeine [28]. 

The role of solvent effects in quaternization is one of the first physical organic studies and this is due to Menschutkin (1879LA334). It shows an increase in relative rate from 1 to 742 on going from benzene to benzyl alcohol, which suggests no simple explanation. Typical ranges of solvent-dependent rate ratios are 15,700/1 (nitromethane/cyclohexane) in the alkylation of triethylamine by methyl iodide (68BSF2678), 1660/1 [dimethylsulfoxide (DMSO)/carbon tetrachloride] in the reaction of l,4-diazabicyclo[2,2,2]-octane (DABCO) (5) with (2-bromoethyl)benzene (75JA7433) (Scheme 5),... 

Bromoethyl)benzene was used as supplied by Matheson, Coleman and Boll. 

Fig. 5-12. Correlation between lg k/ko) [65] and the Kirkwood function (cj — l)/(2 j + 1) for the Menschutkin reaction between l,4-diazabicyclo[2.2.2]octane and (2-bromoethyl)benzene in non-FIBD (o) and HBD ( ) solvents at 54.5 °C (rate constants relative to tetrachloromethane as slowest standard solvent).

Extending the media used for the Menschutkin reaction to protic solvents such as alcohols leads to an even worse correlation, as shown in Fig. 5-12 for the quaternization of l,4-diazabicyclo[2.2.2]octane with (2-bromoethyl)benzene studied in a total of thirty-six solvents [65], The group of protic solvents is separated from the assembly of non-HBD solvents, each group showing a very rough but distinct correlation with the function of relative permittivity. Such behaviour has also been observed for several other Menschutkin reactions [60, 61],... 

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