Phenyl 2-chloroacetate

As a real reaction, the basic hydrolysis of phenyl chloroacetate was investigated in a kind of quench-flow analysis experiment [6]. 

Also obtained (poor yield) by heating a mixture of 2,4,6-trimethylphenyl acetate and 4-methyl-phenyl chloroacetate with aluminium chloride (10%) [2535]. 

Preparation by Fries rearrangement of 2-chloro-4-fluoro-phenyl chloroacetate with aluminium chloride without solvent at 130-140° (63%) [4539],... 

Also obtained by Fries rearrangement of phenyl chloroacetate,... 

This reaction involves the condensation of an aldehyde or ketone with an a-halo ester in the presence of a basic condensing agent (sodium ethoxlde, sodamide, finely divided sodium or potassium iert.-butoxide) to give a glycldio (or ap-epoxy) ester. Thus acetophenone and ethyl chloroacetate yield phenyl-methylglycidic ester (I) ... 

The glycidic esters are of interest primarily because upon hydrolysis aud decarboxylation they aflFord aldehydes (if ClCHjCOOEt is used) or ketones (if substituted chloroacetic esters- ClCHRCOOEt are employed) having a higher carbon content than the original aldehyde or ketone. Thus (I) gives o-phenyl-propionaldehyde or hydratropaldehyde (II) ... 

Phenylglycine-o-carboxylic acid. In a 750 ml. round-bottomed flask, fitted with a reflux condenser, place 14 g. of anthranilic acid (Section IV,170), 10 g. of chloroacetic acid, 20 g. of anhydrous sodium carbonate and 200 ml. of water. Reflux the mixture for. 3 hours, then pour into a beaker, cool, render shghtly acid with concentrated hy dro-chloric acid, and allow to stand overnight. Filter off the crude acid and wash it with water. Recrystalhse from hot water with the aid of a little decolourising carbon, and dry the acid at 100°. The yield of phenyl-glycine-o-carboxyhc acid, m.p. 208°, is 12 g. 

V-Phenyl glycine [103-01 -5] the key intermediate for indigo, may be manufactured by alkylation of aniline with chloroacetic acid, but it is much more economical, even though three in situ stages are required, to use formaldehyde as the alkylating agent. 

Butyl alcohol in synthesis of phenyl 1-butyl ether, 46, 89 1-Butyl azidoacetate, 46, 47 hydrogenation of, 46, 47 1-Butyl chloroacetate, reaction with sodium azide, 46, 47 lre l-4-i-BUTYLCYCLOHEXANOL, 47,16 4-(-Butylcyclohexanonc, reduction with lithium aluminum hydride and aluminum chloride, 47, 17 1-Butyl hypochlorite, reaction with cy-clohexylamine, 46,17 l-Butylthiourea, 46, 72... 

Phenylmercunc chlonde, conversion to phenyltnchloromethylmercury by reaction with sodium tn-chloroacetate 46, 98 2 Phenyl 2 oxazolin-5 one, 47,... 

The only 5//-1,3,6-triazonine system which has been reported and is fully supported by spectral data and elemental analysis is obtained by reaction of the imine 1 with chloroacetic acid and polyphosphoric acid.22 From a mixture of products, 2-chloro-6-(chloromethyl)-13-phenyl-dibenzo[e/, h [, 3,6]triazonine (2) was separated by silica-gel flash chromatography in poor yield. 

Early work on the asymmetric Darzens reaction involved the condensation of aromatic aldehydes with phenacyl halides in the presence of a catalytic amount of bovine serum albumin. The reaction gave the corresponding epoxyketone with up to 62% ee.67 Ohkata et al.68 reported the asymmetric Darzens reaction of symmetric and dissymmetric ketones with (-)-8-phenylmenthyl a-chloroacetate as examples of a reagent-controlled asymmetric reaction (Scheme 8-29). When this (-)-8-phenyl menthol derivative was employed as a chiral auxiliary, Darzens reactions of acetone, pentan-3-one, cyclopentanone, cyclohexanone, or benzophenone with 86 in the presence of t-BuOK provided dia-stereomers of (2J ,3J )-glycidic ester 87 with diastereoselectivity ranging from 77% to 96%. 

A" 0-Butenolide, 46, 22 /-Butyl alcohol, in synthesis of phenyl /-butyl ether, 45, 89 reaction with sodium cyanate and trifluoroacetic acid, 48, 32 /-Butyl azidoacctatc, 46, 47 hydrogenation of, 45, 47 /-Butyl carbamate, 48,32 /-Butyl chloroacetate, reaction with sodium azide, 45, 47 /ra S-4-/-BuTYI,CYCLOHEXANOL, 47,16... 

Synthetic approaches to representatives of this ring system have been discussed in CHEC-II(1996) <1996CHEC-II(8)496>. Research activity in this area has been considerably extended during the past years. Thus, the basic starting material is a 6,6-disubstituted tetrahydro[l,2,4,5]tetrazin-3-thione 52, which has been converted in three different ways reaction with phenacyl bromides led to 3,3-disubstituted 3,4-dihydro-6-phenyl-2//-thiazolo[3,2-4]-[l,2,4,5]tetrazines 53, reaction of 52 with 1,2-dibromoethane gave 3,4,6,7-tetrahydro-2//-thiazolo[3,2-7][l,2,4,5]tetra-zines 54, whereas transformation of 52 with chloroacetic acid in the presence of sodium acetate yields substituted 3,4-di hydro-1-2//-thiazolo[3,2- 1 [ 1,2,4,5]tctrazin-6(7//)-oncs 55 <2001IJB584> (Scheme 17). Details are shown in Table 2. 

Ethyl fluoroacetate 2-Chloroethyl fluoroacetate 2-Fluoroethyl acetate 2-Fluoroethyl chloroacetate 2-Fluoroethyl fluoroacetate Phenyl fluorothiolacetate 2-Chloroethyl fluorothiolacetate... 

The formation of cyclopropanes from 7C-deficient alkenes via an initial Michael-type reaction followed by nucleophilic ring closure of the intermediate anion (Scheme 6.26, see also Section 7.3), is catalysed by the addition of quaternary ammonium phase-transfer catalysts [46,47] which affect the stereochemistry of the ring closure (see Chapter 12). For example, equal amounts of (4) and (5) (X1, X2 = CN) are produced in the presence of benzyltriethylammonium chloride, whereas compound (4) predominates in the absence of the catalyst. In contrast, a,p-unsatu-rated ketones or esters and a-chloroacetic esters [e.g. 48] produce the cyclopropanes (6) (Scheme 6.27) stereoselectively under phase-transfer catalysed conditions and in the absence of the catalyst. Phenyl vinyl sulphone reacts with a-chloroacetonitriles to give the non-cyclized Michael adducts (80%) to the almost complete exclusion of the cyclopropanes. 

Darzens reaction of (-)-8-phenylmethyl a-chloroacetate (and a-bromoacetate) with various ketones (Scheme 2) yields ctT-glycidic esters (28) with high geometric and diastereofacial selectivity which can be explained in terms of both open-chain or non-chelated antiperiplanar transition state models for the initial aldol-type reaction the ketone approaches the Si-f ce of the Z-enolate such that the phenyl ring of the chiral auxiliary and the enolate portion are face-to-face. Aza-Darzens condensation reaction of iV-benzylideneaniline has also been studied. Kinetically controlled base-promoted lithiation of 3,3-diphenylpropiomesitylene results in Z enolate ratios in the range 94 6 (lithium diisopropylamide) to 50 50 (BuLi), depending on the choice of solvent and temperature. ... 

Lipase Catalyzed Kinetic Resolution of Alcohols via Chloroacetate Esters (-)-(lR,2S)-trans-2-Phenylcyclohexano1 and (+)-(lS,2R)-trans-2-Phenyl cyclohexanol... 

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