Alcohols benzoylations

Naphtha Coal Tar Benzyl Alcohol Benzoyl Chloride Benzoic Acid... 

On the other hand, in the case of benzoyl fluoride, the reaction is very slow and does not lead to the ultimate formation of a tertiary alcohol, but of the product 24 of the esterification of benzoic acid by the tertiary alcohol.Benzoyl chlorides react with perfluoroalkyl iodides in the presence of tris(diethylamino)phosphane in a nonpolar solvent to give the corresponding polyfluoroalkyl aryl ketones 25 via substitution of the chlorine. 

SAFETY PROFILE Stable in dry air at room temperature. It decomposes above 125° forming Al, H2, and lithium hydride. Very powerful reducer. Can ignite if pulverized even in a dry box. Reacts violendy with air, acids, alcohols, benzoyl peroxide, boron trifluoride etherate, (2-chloromethyl furan + ethyl acetate), diethylene glycol dimethyl ether, diethyl ether, 1,2-dimethoxyethane, dimethyl ether, methyl ethyl ether, (nitriles + H2O), perfiuorosuccinamide,... 

Oxidative Methods.—Oxidation of Alcohols. Benzoyl peroxide catalysed by nickel(ii) bromide gives high yields of aldehydes and ketones from the corresponding alcohols. Similar yields are obtained with t-butyl hydroperoxide catalysed by diaryl diselenides, a method particularly recommended for benzylic or allylic alcohols. Ketones are obtained from secondary alcohols using hydrogen peroxide catalysed by molybdenum or tungsten peroxo-complexes/ and nickel peroxide has been employed to prepare a-allenic aldehydes and ketones from allenic alcohols. ... 

CfiHi 05 0 C6H4 CH20H. Colourless, bitter crystals, m.p. 20 PC soluble in water and alcohol, insoluble in chloroform. It occurs in the leaves, bark and twigs of species of willow and poplar. On oxidation with dilute nitric acid it is converted into helicin, the glucoside of salicylaldehyde, which has been made the starting point of further syntheses. Gives populin with benzoyl chloride. 

A crystalline derivative of benzyl alcohol cannot be obtained by using benzoyl chloride, because the benzyl benzoate, C HiCOOCHiCaHj, so obtained has m.p. 18°, and is thus usually liquid the present preparation illustrates therefore the use of a substituted benzoyl chloride (p-nitrobenzoyl chloride, m.p. 75°) in order to obtain a crystalline derivative of suitably high m.p. 

Note. PRIMARY ALIPHATIC AMINES. The lower amines are gases or low-boiling liquids (b.ps. CHjNH, 7 CiHjNH, 17 CH,(CH2,>,NH 49 (CHg)jCHNHa, 34 ) but may be encountered in aqueous or alcoholic solution, or as their crystalline salts. They are best identified as their benzoyl, or toluene-/>-sulphonyl derivatives (c/. (C) above), and as their picrates when these are not too soluble. This applies also to benzylamine, CjHsCHjNH, b.p. 185 also to ethylenediamine, usually encountered as the hydrate, NHj (CHj)j NH2,HjO, b.p. 116 , for which a moderate excess of the reagent should be used to obtain the di-acyl derivative. (M.ps., pp. 55 55 )... 

Benzoates. Alcohols react with benzoyl chloride in the presence of pyridine or of sodium hydroxide solution to produce esters of benzoic acid ... 

Benzoates. Dissolve 0-5 g. of the amino acid in 10 ml. of 10 per cent, sodium bicarbonate solution and add 1 g. of benzoyl chloride. Shake the mixture vigorously in a stoppered test-tube remove the stopper from time to time since carbon dioxide is evolved. When the odour of benzoyl chloride has disappeared, acidify with dilute hydrochloric acid to Congo red and filter. Extract the solid with a little cold ether to remove any benzoic acid which may be present. RecrystaUise the benzoyl derivative which remains from hot water or from dilute alcohol. 

In a 50-100 ml. conical flask place a solution of 0 -5 g. of glucose in 5 ml. of water, 12-15 ml. of 10 per cent, sodium hydroxide solution and 1 ml. of benzoyl chloride, cork tightly, and shake until the odour of benzoyl chloride has disappeared and a crystalline (frequently sticky) soUd has separated. Filter oflF the solid, wash it with a Uttle water, and recrystaUise it from ethyl or n-butyl alcohol. (If the product is sticky, it should be removed, and spread on a porous tile before recrystaUisation.) Glucose pentabenzoate has m.p. 179°. Fructose pentabenzoate, m.p. 78-79°, may be similarly prepared. 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Of the crystalline derivatives of thiols, those formed with 3 5-dinitro-benzoyl chloride are not very satisfactory since they have, in general lower melting points than those of the corresponding alcohols (compare Section 111,27,7) and do not diflfer widely from ethyl to n-heptyl. The best results are obtained with 2 4-dinitrochlorobenzene. 

The benzoyl compounds frequently occlude traces of unchanged benzoyl chloride, which thus escape hydrolysis by the caustic alkali it is therefore advisable, wherever possible, to recrystaUise the benzoyl derivatives from methyl, or ethyl alcohol or methylated spirit, since these solvents will esterify the unchanged chloride and so remove the latter from the recrystalKsed material. Sometimes the benzoyl compound does not crystallise well this difficulty may frequently be overcome by the use of p-nitrobenzoyl chloride or 3 5-dinitro-benzoyl chloride, which usually give highly crystalline derivatives of high melting point (see Section IV,114j. 

Suspend 1 g. (or 1 ml.) of the substance in 20 ml. of 5 per cent, sodium hydroxide solution in a well-corked boiling tube or small conical flask, and add 2 ml. of redistilled benzoyl chloride, ca. 0-5 ml. at a time, with constant shaking, and cooling in water (if necessary). Shake vigorously for 5-10 minutes until the odour of the benzoyl chloride has disappeared. Make sure that the mixture has an alkaline reaction. Filter oflF the solid benzoyl derivative, wash it with a little cold water, and recrystalHse it from alcohol or dilute alcohol. 

It is essential to use freshly recrystallised benzoyl peroxide. The commercial material usually gives poor results. Commercial benzoyl peroxide may bo recrystal, lised from a small amount of hot chloroform, or by dissolving in chloroform and precipitating with absolute methyl alcohol. 

Heat 20 g. of styrene (Section IX,6) with 0 -2 g. of benzoyl peroxide (Section IV,196) on a water bath for 60-90 minutes. A glass-bke polymer (polystyrene) is produced. The polymer is soluble in benzene and in dioxan and can be precipitated from its solution by alcohol. 

Neutrahse about one third of the filtrate with 5N sodium hydroxide and add a further 2 ml. of the alkah solution. Add 1 ml. of benzoyl chloride and stir until the odour of the acid chloride disappears. Collect the solid by suction filtration, wash it with water until free from alkah, and then recrystalhse it from dilute alcohol. The product is the dibenzoyl derivative of hexamethylenediamine and melts at 159°. 

Bemoyl chloride may replace acetyl chloride as a class reagent it possesses the advantage that it is only very slowly decomposed by cold water and consequently may be employed for detecting alcohols even in aqueous solution. The reaction is usually carried out in aqueous solution containing sufficient caustic alkali to decompose any excess of benzoyl chloride into the water-soluble alkali benzoate (Schotten - Baumann reaction compare Section IV,52). The benzoyl esters formed are insoluble in water ... 

Benzoyl peroxide Direct sunlight, sparks and open flames, shock and friction, acids, alcohols, amines, ethers, reducing agents, polymerization catalysts, metallic naph-thenates... 

Benzyl Chloride. Benzyl chloride is manufactured by high temperature free-radical chlorination of toluene. The yield of benzyl chloride is maximized by use of excess toluene in the feed. More than half of the benzyl chloride produced is converted by butyl benzyl phthalate by reaction with monosodium butyl phthalate. The remainder is hydrolyzed to benzyl alcohol, which is converted to ahphatic esters for use in soaps, perfume, and davors. Benzyl salicylate is used as a sunscreen in lotions and creams. By-product benzal chloride can be converted to benzaldehyde, which is also produced directiy by oxidation of toluene and as a by-product during formation of benzoic acid. By-product ben zotrichl oride is not hydrolyzed to make benzoic acid but is allowed to react with benzoic acid to yield benzoyl chloride. 

The only industrially important processes for the manufacturing of synthetic benzaldehyde involve the hydrolysis of benzal chloride [98-87-3] and the air oxidation of toluene. The hydrolysis of benzal chloride, which is produced by the side-chain chlorination of toluene, is the older of the two processes. It is no longer utilized ia the United States. Other processes, including the oxidation of benzyl alcohol, the reduction of benzoyl chloride, and the reaction of carbon monoxide and benzene, have been utilized ia the past, but they no longer have any iadustrial appHcation. 

Benzoyl chloride is an important benzoylating agent. In this use the benzoyl radical is introduced into alcohols, phenols, amines, and other compounds through the Friedel-Crafts reaction and the Schotten-Baumaim reaction. Other significant uses are in the production of benzoyl peroxide [94-56-0], benzophenone [119-61-9], and in derivatives employed in the fields of dyes, resins, perfumes, pharmaceuticals, and as polymerization catalysts. 

Nearly all of the benzyl chloride [100-44-7], henzal chloride [98-87-3], and hen zotrichl oride /P< -(97-i manufactured is converted to other chemical intermediates or products by reactions involving the chlorine substituents of the side chain. Each of the compounds has a single primary use that consumes a large portion of the compound produced. Benzyl chloride is utilized in the manufacture of benzyl butyl phthalate, a vinyl resin plasticizer benzal chloride is hydrolyzed to benzaldehyde hen zotrichl oride is converted to benzoyl chloride. Benzyl chloride is also hydrolyzed to benzyl alcohol, which is used in the photographic industry, in perfumes (as esters), and in peptide synthesis by conversion to benzyl chloroformate [501-53-1] (see Benzyl ALCOHOL AND p-PHENETHYL ALCOHOL CARBONIC AND CARBONOCm ORIDIC ESTERS). 

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