Benzyl chloride benzaldehyde from

Derivation (a) By hydrolysis of benzyl chloride (b) from benzaldehyde by catalytic reduction or Cannizzaro reaction. 

In the past benzal and benzyl chlorides were co-produced for the manufacture of benzaldehyde and benzyl alcohol, but today the vast majority of the benzaldehyde produced from benzal chloride is that which is made from recovered (by-product) material. For an historical article regarding the chlorination of toluene and the subsequent production of benzaldehyde, benzyl alcohol, and benzoic acid, see reference 4. 

Benzyl chloride readily forms a Grignard compound by reaction with magnesium in ether with the concomitant formation of substantial coupling product, 1,2-diphenylethane [103-29-7]. Benzyl chloride is oxidized first to benzaldehyde [100-52-7] and then to benzoic acid. Nitric acid oxidizes directly to benzoic acid [65-85-0]. Reaction with ethylene oxide produces the benzyl chlorohydrin ether, CgH CH20CH2CH2Cl (18). Benzylphosphonic acid [10542-07-1] is formed from the reaction of benzyl chloride and triethyl phosphite followed by hydrolysis (19). 

Phenol (508) is found to be produced continuously from benzene (507) by aerial oxidation in aqueous sulfuric acid when a Cu(I)/Cu(II) redox couple is used as a mediator (Scheme 176) [581]. The Cu(I)-mediated electroreduction of oxygen in the presence of chloride is found to be effective for toluene oxidation, leading to benzaldehyde and benzyl chloride [582]. Recently, benzene has also been oxidized... 

Chemical/Physical. Anticipated products from the reaction of benzyl chloride with ozone or OH radicals in the atmosphere are chloromethyl phenols, benzaldehyde and chlorine radicals (Cupitt, 1980). 

Kennedy and Stock reported the first use of Oxone for many common oxidation reactions such as formation of benzoic acid from toluene and of benzaldehyde, of ben-zophenone from diphenyhnethane, of frawi-cyclohexanediol Ifom cyclohexene, of acetone from 2-propanol, of hydroquinone from phenol, of e-caprolactone from cyclohexanone, of pyrocatechol from salicylaldehyde, of p-dinitrosobenzene from p-phenylenediamine, of phenylacetic acid from 2-phenethylamine, of dodecylsulfonic acid from dodecyl mercaptan, of diphenyl sulfone from diphenyl sulfide, of triphenylphosphine oxide from triphenylphosphine, of iodoxy benzene from iodobenzene, of benzyl chloride from toluene using NaCl and Oxone and bromination of 2-octene using KBr and Oxone . Thus, they... 

The oxidation of benzaldoxime with perchloryl fluoride (FClOj) has been reported [29 a) to give a complex mixture in which benzaldoxime benzoate and diphenyl oxadiazole are the main products. Sodium nitrohydroxamate [Na2(02NN0)] has been reported [99b) to oxidize benzyl chloride to a mixture of compounds from which benzyl alcohol, benzaldehyde, benzoic acid, 3,4,5-triphenylisoxazole, benzyl-ethyl-ether, phenylnitromethane and diphenyloxadiazole have been isolated. 

R = CH2C6Hs, C14H12O2, Mr 212.25, 6p2.okPa 170-171 °C, df 1.1121, ng 1.5680, is the main component of Peru balsam oil. It occurs in fairly large amounts in a number of blossom concretes and absolutes (e.g., tuberose and hyacinth). It forms either a viscous liquid or solid flakes mp 21 22°C) and has a weak, sweet-balsamic odor. It is prepared either by transesterification of technical methyl benzoate with benzyl alcohol, or from benzyl chloride and sodium benzoate. A third process starts with benzaldehyde which is converted in high yield into benzyl benzoate in the presence of sodium or aluminum benzylate (Tishchenko reaction). 

No studies were available on the disposition of benzotrichloride, benzal chloride or benzoyl chloride. Benzyl chloride is rapidly absorbed and distributed from the gastrointestinal tract. Excretion is mainly in urine as S -benzyl-A-acetylcysteine, benzyl alcohol and benzaldehyde. 

Benzyl alcohol, on the other hand, is produced industrially from benzaldehyde or benzyl chloride, which are available economically in large amounts. 

Benzoic acid also can be obtained as a by-product of the manufacture of benzaldehyde from benzal chloride or benzyl chloride. 

Benzal chloride, used for the preparation of benzaldehyde, should be free from benzyl chloride. It should be fractionated carefully, therefore, removing the portion boiling below 180°. 

Tri-3-amino-tri-p-tolylarsine, formed from the nitro-oxide by reduction wth tin and hydrochloric acid, crystallises in prisms, M.pt. 198° C. It yields a hydrochloride, crystallising in fine, colourless needles, and a crystalline acid stdphate. The triacetyl derivative melts at 228° C., and a ibenzyl derivative (CH3.C8H3.NH.CH2.CgH5)3A,s is formed by heating the amino-arsine with benzyl chloride (3 mols.), but has only been isolated in the form of its hydrochloride. The amino-arsine also condenses with benzaldehyde and with diazobenzene cliloride. 

Lithiated DBU (40), prepared from DBU and -butyllithium, was reacted with benzophenone, acetophenone, benzaldehyde, phenylacetyl chloride, benzyl chloride, 1-bromopentadecane and phenyl isocyanate to give the respective 6-substituted pyrimido-[l,2-a]azepines (562-564) (86JHC885). When heated at 150 or 180°C, the hydroxy derivatives 562 decomposed and the starting ketones and DBU were recovered. 

Mercury ethyl benzyl is prepared from ethyl magnesium bromide and benzyimercuric chloride. It is an oil, decomposing on long keeping into mercury diethyl and mercury dibenzyl. When treated with thallic chloride it yields thallous chloride, ethylmercuric chloride, benzyl-mercuric chloride, and benzaldehyde. ... 

Manufacture of Benzaldehyde from Benzyl Chloride using Hexamine... 

Derivation (a) By a Cannizzaro reaction from benzaldehyde, (b) by esterifying benzyl alcohol with benzoic acid, (c) by treating sodium benzoate with benzyl chloride. 

It is true that, for instance, one does not find under the keyword aldehyde the preparation of benzaldehyde (a) from toluene by way of benzyl chloride or benzaldehyde dichloride, (b) from benzene and hydrogen cyanide-hydrogen chloride (Gattermann-Koch) or from bromobenzene by way of phenyl-magnesium bromide and formic ester (Grignard), and (c) from stilbene and ozone or from 1,2-diphenyl-1,2-ethanediol and lead tetraacetate but such a collection of syntheses is to be found in the systematic textbooks and reference works of organic chemistry, and the compass of the large reactions remains nevertheless substantially intact in our treatment. 

Selectivity of multiphase reactions catalysed by phase transfer catalysts can be greatly improved by the use of the so called capsule membrane - PTC (CM-PTC) technique. We report here the theoretical and experimental analysis of the CM-PTC and Inverse CM-PTC for exclusively selective formation of benzyl alcohol and benzaldehyde from the alkaline hydrolysis and oxidation of benzyl chloride, respectively. The theoretical analysis shows that it is possible to simultaneously measure rate constant and equilibrium constant under certain conditions. The effects of speed of agitation, catalyst concentration, substrate concentration, nature of catalyst cation, membrane structure, nucleophile concentration, surface area for mass transfer and temperature on the rate of reaction are discussed. 

Benzoic Acid, CeHs.COOH, occurs in gum-benzoin, in many resins, in the balsams of Peru and Tolu, in cranberries, in coal-tar, and in combination with glycine as hippuric acid in the urine of herbivorous animals. It may be made by the general synthetic methods which have been described. It is prepared for use in pharmacy bysublimination from gum-benzoin. It is manufactured on the large scale from toluene, and is a by-product in the preparation of benzaldehyde. Toluene is converted by direct oxidation into benzoic acid. As benzyl chloride, C6H5.CH2CI, is more readily oxidized than toluene, the latter is first treated with chlorine, and then heated with dilute nitric acid. It has been shown recently that if a mixture of air and the vapor of toluene is passed over vanadium oxide at about 400° the hydrocarbon is oxidized to benzoic acid. 

Benzaldehyde is a liquid with an agreeable odor, which boils at 179°, and has the specific gravity 1.0504 at 15°. It can be formed by oxidizing benzyl alcohol, or distilling calcium benzoate with calcium formate. It is manufactured by heating benzal chloride with milk of lime, or by oxidizing benzyl chloride with a solution of lead nitrate. It has been prepared from toluene directly by electrolytic oxidation or by oxidation with air in the presence of a catalyst. 

Figure 5 LC separation of benzyl chloride during BAK synthesis. Peaks 1= benzyl alcohol, 2 = benzaldehyde, 3 = benzyl chloride, 4 = unidentified impurity, 5 = Ci2 homolog, 6 = Cu homolog, 7 = Ci6 homolog. (Reproduced from Prieto-Bianco MC, Lopez-Mahia P, and Prada-Rodriguez D (1999) Journal of Chromatographic Science 37 295-299 by permission of Preston Publications, A Division of Preston Industries, Inc.)...

Benzyl alcohol is the second most important product from benzyl chloride. Stanislao Cannizzaro deduced its structure in 1853 from the reaction of benzaldehyde with potassium hydroxide. 

---