Benzyl chloride reaction with

Benzyl chloride reacts with alkenes bearing an EWG[8], The reaction with acrylate proceeds smoothly to give 7-phenylcrotonate (76) in the presence of BujN without a ligand. No reaction takes place with Pd(Ph,P)4[77]. 

The Pd-catalyzed coupling of an acyl chloride with benzyl chloride to form the benzyl ketone 854 proceeds in the presence of an excess of Zn. In this reaction, benzyl chloride reacts with Zn to form benzylzinc, which undergoes transmetallation with acylpaliadium complex[729]. The reaction has been applied to the synthesis of riccardin B (855)[730]. 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

The stereospecific conversion of menthyl arenesulphinates into chiral aryl methyl sulphoxides may also be achieved by means of methyllithium . The reaction of methyllithium with diastereoisomerically or enantiomerically pure arenesulph-inamides 283 was found to give optically active aryl methyl sulphoxides 284 (equation 156). The preparation of optically active sulphoxides 285 and 286, which are chiral by virtue of isotopic substitution (H - D and - respectively), involves the reaction of the appropriate non-labelled menthyl sulphinates with fully deuteriated methyl magnesium iodide (equation 157) and with benzylmagnesium chloride prepared from benzyl chloride labelled with carbon (equation 158). 

A propoxyphene-like analgesic which obeys the empirical morphine rule is pyrroliphene (101). A Mannich reaction involving pyrrolidine, formaldehyde and propiophenone gave amino ketone 99, which was converted to tertiary carbinol 100 by reaction with benzyl magnesium chloride reaction with acetyl... 

The reactions of 6-indazolylaminomethylenemalonate (1470) with benzyl chloride and with trityl chloride in a mixture of DMF and ethanol and... 

Lund and coworkers [131] pioneered the use of aromatic anion radicals as mediators in a study of the catalytic reduction of bromobenzene by the electrogenerated anion radical of chrysene. Other early investigations involved the catalytic reduction of 1-bromo- and 1-chlorobutane by the anion radicals of trans-stilhene and anthracene [132], of 1-chlorohexane and 6-chloro-l-hexene by the naphthalene anion radical [133], and of 1-chlorooctane by the phenanthrene anion radical [134]. Simonet and coworkers [135] pointed out that a catalytically formed alkyl radical can react with an aromatic anion radical to form an alkylated aromatic hydrocarbon. Additional, comparatively recent work has centered on electron transfer between aromatic anion radicals and l,2-dichloro-l,2-diphenylethane [136], on reductive coupling of tert-butyl bromide with azobenzene, quinoxaline, and anthracene [137], and on the reactions of aromatic anion radicals with substituted benzyl chlorides [138], with... 

Benzophenone, 46, 36 N-(2-Benzothiazolyl)urea, 46, 72 Benzoyl chloride, reaction with hydrogen fluoride, 46, 4 Benzoyl fluoride, 46, 3 Benzoylhydrazine, 46, 8S Benzoyl peroxide, reaction with diethyl ethylmalonate, 45, 37 2-Benzyl-2-carbomethoxycyclopenta-none, 45, 7... 

Fig. 1. Change in butyl (or benzyl) chloride yield with reaction time in a halide exchange between butyl (or benzyl) bromide and the hydrotalcite-1ike material containing interlayer Cl anions.

The equivalence of sulfur and oxygen in this ring system carries over to NSAIDs as well. Preparation of the sulfur analogue of isoxepac (6-4) starts with the alkylation of thiophenol (27-1) with benzyl chloride (26-1). Cyclization of the intermediate thioether (27-2) then affords the homothioxanthone (27-3). The carboxyl side chain is then extended by means of the Amdt-Eistert homologation reaction. The acid is thus hrst converted to its acid chloride by means of thionyl chloride. Reaction with excess diazomethane leads to the diazoketone (27-4). Treatment of that intermediate with silver benzoate and triethylamine leads the ketone to rearrange to an acetic acid. There is thus obtained tiopinac (27-5) [28]. 

With phenols either the phenolic nr nuclear hydrogens can react lo give benzylaryl ether or benzylated phenols. Reaction with NaCN gives benzyl cyanide (phenylacelonitrile) with aliphatic primary amines the product is (he N-alkylbenzylamine. and with aromatic primary amines N-benzylaniline is formed. Benzyl chloride is converted 10 butyl benzyl phlhalatc plasticizer and other chemicals. 

He suggested that CH2=SnX2 was an intermediate product in the process and that MeSnX3 was formed by addition of HX to the intermediate, which, in turn, was the insertion product of Sn into CH2X2. The reaction of CH2I2 with Sn at 170-180°C led only to carbon and SnLt. It is noteworthy that benzyl chloride acted with tin powder in water or in alcohol under mild conditions to give (PhC SnCl634 in 85% yield. 

Final purification by use of metal complexes was also applied in the syntheses of the ligands XS4—H4. These ligands exclusively contain thiolate donors and were prepared by Hahn et al. (23) using 2,3-dimercaptobenzoic acid as starting material (Scheme 8). Isopropyl or benzyl protection of the thiol functions, conversion into the acyl chlorides, reaction with a,oo-diamines, and deprotection of the sulfur atoms enabled the connection of two 1,2-benzene-dithiol units via carboxylic acid amide bonds. 

A novel method for the palladium-catalyzed tandem allylative dearomatization is also reported by us [82], The reaction of benzylic chlorides 126 with... 

The mechanism of this reaction has been investigated in some detail. RX must be an activated halide, such as a benzyl halide, a-halo ether, or a 1,1-dihalocarbon where at least one of the halides is Br or L Simple halocarbons do not react, nor does methylene chloride. Reaction with chloroform is slow, while reaction with carbon tetrachloride is instantaneous at room temperature. The (pseudo) first-order rate constant is linearly correlated to the polarographic reduction potential of the halide thus electron transfer from (38) to RX (equation 57) is the rate-determining step, followed by rapid cleavage of the RX radical anion into R and X . 

In 1973, Sagdeev et al. [16] reported MFEs on thermal reactions of substituted benzyl chlorides (ACl) with n-butyl lithium (BLi) in hot hexane and cyclohexane. Although there were many serious misprints in this paper, this was the first report for MFEs on chemical reactions through radical pairs. The reactions occur through the following scheme ... 

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