Phenylacetyl chlorides

Monoprotection of a symmetrical diol can be effected by reaction with a polymer-supported phenylacetyl chloride. The free hydroxyl group is then converted to an ether and the phenylacetate cleaved by aqueous ammonia-dioxane, 48 h. ... 

Benzyl chloromethyl ketone has been prepared by the reaction of diazomethane with phenylacetyl chloride. The method of Clibbens and Nierenstein, in which one equivalent of diazomethane is added to the acyl chloride and the chloromethyl ketone obtained directly, could not be duplicated by Bradley and Schwarzenbach or by the submitters. 

The activity of acylureas as hypnotic and anticonvulsant agents is dealt with in some detail later. This is again one of the cases in which the functionality rather than structure determines pharmacologic activity. Thus, acylation of urea with phenylacetyl chloride gives the anticonvulsant agent, phenacemide... 

Schiff s base (j ) derived by reaction of p-chloro-anil ine and borohydride followed by acylation with phenylacetyl chloride produces amide 22,. Selective hydrolysis with HBr followed by alkylation with isopropyl bromide completes the synthesis of lorcainide (20). ... 

Diblock copolymers PEO-fo-PS have been prepared using PEO macroinitiator and ATRP techniques [125]. The macroinitiator was synthesized by the reaction of monohydroxy-functionalized PEO with 2-chloro-2-phenylacetyl-chloride. MALDI-TOF revealed the successful synthesis of the macroinitiators. The ATRP of styrene was conducted in bulk at 130 °C with CuCl as the catalyst and 2,2 bipyridine, bipy, as the ligand. Yields higher than 80% and rather narrow molecular weight distributions (Mw/Mn < 1.3) were obtained. The surface morphology of these samples was investigated by atomic force microscopy, AFM. 

R)-( I )-a-Mcthoxy-a-(trinuoromethyl)phenylacetyl chloride (MTPA chloride) or the (,S)-enantiomer, 5 mg, 0.02 mmol... 

In a NMR tube, to a solution of the epoxy alcohol (2.5 mg) in CDCI3 (0.5 mL) was added 4-dimethylaminopyridine (5 mg) and (R)-(+)-a-methoxy-a-(trifluor-omethyl)phenylacetyl chloride (5 mg). The mixture was allowed to stand overnight at room temperature. The reaction was monitored by TLC to ensure complete consumption of the starting material. H and 19F NMR spectra were carried out on the crude reaction mixture. In the 19F NMR spectrum, each enantiomer gave a signal an additional signal at —71.8 ppm was ascribed to residual MTPA. (19F NMR (250 MHz, CDCI3) 8 - 70.7 (s, (2R,3R)-enantio-mer) —72.0 (s, (25 ,3.S)-enantiomer)). 

Eastman Kodak Company white label grade of phenylacetyl chloride was used, but equally good results are obtained with the crude acid chloride obtained by treating phenylacetic acid with an excess of thionyl chloride and removing the latter under reduced pressure. 

This is a general method for converting 2a-thiohomophthaIim-ides to homophthalic acids. Since 2a-thiohomophthalimides are readily obtained from phenylacetyl chlorides,2 this is a convenient method for preparing homophthalic acids. 

A. Phenylacetyl isothiocyanate. Twenty-five grams (0.16 mole) of phenylacetyl chloride (Note 1), 100 ml. of benzene, and 53 g. (0.16 mole) of lead thiocyanate (Note 2) are placed in a 1-1., three-necked, round-bottomed flask equipped with a mechanical stirrer and a reflux condenser. The stirrer is started and the mixture is refluxed for 5 hours. A small amount of activated charcoal is added, and refluxing is continued for 5 minutes. The warm mixture is filtered through a Buchner funnel under suction (Note 3), and the solid on the filter is washed with two 50-ml. portions of benzene. The solvent is removed from the filtrate under reduced pressure, and the residue is distilled at once to yield 17.5— 22.7 g. (61-79%) of phenylacetyl isothiocyanate, b.p. 83-91° at about 0.3 mm. It is a colorless liquid that rapidly darkens on standing (Notes 4 and 5). 

Phenylacetyl chloride and hydrocin-namoyl chloride are reduced at mercury to form both acyl radicals and acyl anions as intermediates [76]. From electrolyses of phenylacetyl chloride, the products include 1,4-diphenyl-2-butene-2,3-diol diphenylac-etate, phenylacetaldehyde, toluene, 1,3-diphenylacetone, and l,4-diphenyl-2,3-butanediol, and analogous species arise from the reduction of hydrocinnamoyl chloride. Reduction of phthaloyl dichloride is a more complicated system [77] the electrolysis products are phthalide, biph-thalyl, and 3-chlorophthalide, but the latter compound undergoes further reduction to give phthalide, biphthalyl, and dihydrobi-phthalide. 

Lozano and Barba [82] electrolyzed 2-chloro-2-phenylacetyl chloride at mercury in methylene chloride and obtained derivatives of pyran-2-one and pyran-4-one, where R is H and C6H5CH2CO, respectively, at high and low current density (Scheme 6). In later work [83], the same workers reduced 2-bromo-2,2-diphenylacetyl bromide in methylene dichloride saturated with hydrogen sulfide gas three sulfur-containing... 

Scheme 6 Cathodic reduction of 2-chloro-2-phenylacetyl chloride to pyran-2-one and pyran-4-one derivatives [82].

Alternatively, phosphine imines 266 were treated with various phenylacetyl chlorides 270 (method B). Surprisingly, phosphonium salts 271 were isolated with 25 to 97% yield, which could be deprotonated by means of a base to build up the corresponding phosphoranes 272 (66-89% yield). Upon heating to... 

A kinetic smdy of the acylation of ethylenediamine with benzoyl chloride (110) in water-dioxane mixtures at pH 5-7 showed that the reaction involves mainly benzoylation of the monoprotonated form of ethylenediamine. Stopped-flow FT-IR spectroscopy has been used to study the amine-catalysed reactions of benzoyl chloride (110) with either butanol or phenol in dichloromethane at 0 °C. A large isotope effect was observed for butanol versus butanol-O-d, which is consistent with a general-base-catalysed mechanism. An overall reaction order of three and a negligible isotope effect for phenol versus phenol- /6 were observed and are consistent with either a base- or nucleophilic-catalysed mechanism. Mechanistic studies of the aminolysis of substituted phenylacetyl chlorides (111) in acetonitrile at —15 °C have revealed that reactions with anilines point to an associative iSN2 pathway. ... 

A 100% molar excess of aluminum chloride is necessary to obtain an acceptable yield in a short time. The reaction of phenylacetyl chloride with ethylene requires only 1 mole of aluminum chloride per mole of acid chloride. 

Mesoionic 1,3-thiazole -ones of type 34 are known as thioisomiinchnones. As one of the mesomeric structures demonstrates, these species contain the structural fragment characteristic of thiocarbonyl ylides (61). A convenient access to thioisomiinclinones involves the reaction of A(-arylthiobenzamides with a-bromo-phenylacetyl chloride (62). 

Cyclocondensation of 3-(2-fluorophenyl)-4-aminopyridazine-5-carbaldehyde 284 with phenylacetyl chloride gave the tetrahydropyridopyridazine derivative 285, which upon dehydration with /i-toluenesulfonic acid gave 286 (Scheme 7) <2006TL2257>. 

Acylation of the theophylline diamine intermediate (26-6) with phenylacetyl chloride affords the corresponding amide (28-2). Base catalyzed cyclization then leads to the purine (28-3) that now includes a quite lipophilic benzyl group on the fused imidazole ring. The molecule is then provided with a side chain that incorporates basic nitrogen, arguably to improve water solubility. The anion from (28-3) is thus first alkylated with bromochloroethane to afford the chloroethyl product (28-4). The displacement of chlorine with ethanolamine affords the bronchodilator bamifylline (28-5) [28]. 

S)-(+)-a-Methoxy-a-(trifluoromethyl)phenylacetyl chloride Hydratropoyl chloride, P,p,p-trifluoro-a-methoxy-, (+)- (8,9) (20445-33-4)... 

---