Toluene benzoylation

Using the same toluene-benzoyl peroxide system Nakatsuka (105) measured polymerization rate and molecular weight as functions of temperature (40° and 58°) and of the concentration of.three retarders p-nitrophenol, 2,4-dinitrophenol and picric acid. Results were consistent with a kinetic scheme postulating (among other things) bimolecular initiation involving peroxide and monomer and spontaneous unimolecular termination of growing polymer chains. 

Trimethylsilyl)ethyl 2,3,6-tri-0-benzyl-4-0- Acetal Toluene Benzoyl chloride ... 

Table 4.27 Toluene benzoylation with para-toluoyl chloride over different acid catalysts...

It is prepared by fully chlorinating toluene. When heated with water at 100°C, or with lime, benzoic acid is obtained, benzoyl The group PhC(O)-. 

Figure Bl.16.15. TREPR spectmm after laser flash photolysis of 0.005 M DMPA (5) in toluene, (a) 0.7 ps, 203 K, RE power 10 mW O, lines CH (8), spacing 22.8 G , benzoyl (6), remaining lines due to (7). (b) 2.54 ps, 298 K, RE power 2 mW to avoid nutations, lines of 7 only. Reprinted from [42].

Give benzoyl and toluene-/>-sulphonyl derivatives (Schotten-Baumann reaction) (p. 243) also benzene-sulphonyl derivatives. 

C) Benzoyl and Toluene-sulphonyl Derivatives. Proceed as in (3) above, using benzoyl or toluene p-sulphonyl chlorides benzene"Sul-phonyl chloride can be similarly used (see 3 above). (M.ps., pp. 550 -551.)... 

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 )... 

Benzoyl and Toluene -sulphonyl derivatives. Proceed as in 3 (p 374)- benzene sulphonyl derivatives can be similarly prepared. 

A) Picrates (except diphenylamine). (B) Acetyl Derivatives. (C) Benzoyl, Toluene-p sulphonyl and Benzenesulphonyl Derivatives. (D)... 

Primary and Secondary Amines. Picrates (pp. 374, 376), Acetyl derivatives (pp. 373, 376), Benzoyl derivatives (pp. 374, 376), Toluene-p-sulphonyl and benzene-sulphonyl derivatives (pp. 374, 376), Phenylurea derivatives (pp. 374, 377)-... 

M.p. B.p. Picrate M.p. Acetyl deiiv. M.p. Benzoyl deriv. H.p. Benzene sulph. Onyl deriv. M.p. Toluene p-sulph> onyl deny. M.p. Phenyl urea deriv, M.p. 

Phenyl norhornane is benzoylated faster than isopropylbenzene or toluene despite the bulkiness of the norbomyl group probably because of hyperconjugation (87). Hyperconjugation of the C—C bond is at least as or more important as that of the C—H bond since 1-phenylnorhornane has no a-hydrogen atom. 

Benzoic Acid. Ben2oic acid is manufactured from toluene by oxidation in the liquid phase using air and a cobalt catalyst. Typical conditions are 308—790 kPa (30—100 psi) and 130—160°C. The cmde product is purified by distillation, crystallization, or both. Yields are generally >90 mol%, and product purity is generally >99%. Kalama Chemical Company, the largest producer, converts about half of its production to phenol, but most producers consider the most economic process for phenol to be peroxidation of cumene. Other uses of benzoic acid are for the manufacture of benzoyl chloride, of plasticizers such as butyl benzoate, and of sodium benzoate for use in preservatives. In Italy, Snia Viscosa uses benzoic acid as raw material for the production of caprolactam, and subsequendy nylon-6, by the sequence shown below. 

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. 

Liquid amines can be further purified via their acetyl or benzoyl derivatives (vide supra). Solid amines can be recrystallised from water, alcohol, toluene or toluene-petroleum ether. Care should be taken in handling large quantities of amines because their vapours are harmful (possibly carcinogenic) and they are readily absorbed through the skin. 

Because phenols are weak acids, they can be freed from neutral impurities by dissolution in aqueous N sodium hydroxide and extraction with a solvent such as diethyl ether, or by steam distillation to remove the non-acidic material. The phenol is recovered by acidification of the aqueous phase with 2N sulfuric acid, and either extracted with ether or steam distilled. In the second case the phenol is extracted from the steam distillate after saturating it with sodium chloride (salting out). A solvent is necessary when large quantities of liquid phenols are purified. The phenol is fractionated by distillation under reduced pressure, preferably in an atmosphere of nitrogen to minimise oxidation. Solid phenols can be crystallised from toluene, petroleum ether or a mixture of these solvents, and can be sublimed under vacuum. Purification can also be effected by fractional crystallisation or zone refining. For further purification of phenols via their acetyl or benzoyl derivatives (vide supra). 

Apply sample solution followed by benzoyl chlor- [71] ide solution (5% in toluene), dry and chromatograph. 

Stage A Preparation of 17P-BenzoyloxyEstra-4,9,11-Trien-3-one — 0.400 g of 17/3-benzoyl-oxy-4,5-seco-estra-9,11 -diene-3,5-dione is dissolved in 4 cc of toluene under an inert atmosphere. The solution is cooled to 3°C, then 0.4Bcc is added of the solution of sodium tert-amyl-ate in anhydrous toluene, diluted by the addition of a further 4.8 cc of anhydrous toluene. 

Methyl a-D-mannopyranoside was treated in succession with p-toluene-sulfonyl chloride, carbonyl chloride, and benzoyl chloride, and, without isolating the intermediates, there was obtained in 37% yield methyl 4-0-l enzoyl-2,3-O-carbony 1-6-0-(p-tolylsulfonyl ) -D-mannoside. The tos-yloxyl group of the latter was replaced by iodine, and hydrogenation of the 6-iodo derivative in the presence of a nickel boride catalyst gave methyl 4-0-benzoyl-2,3-0-carbonyl-6-deoxy- -D-mannoside. Treatment of the latter with hydrogen bromide in acetic acid gave crystalline 4-0-benzoyl-2,3-0-carbonyl-6-deoxy-a-D-mannosyl bromide (8) (16). The... 

Finally, it is interesting to note that the similarity between benzenesulphonylation and benzoylation also shows up in the log f0 log fp ratios for toluene which are 0.56184 and 0.54188, respectively, indicating a similar size of electrophile in each case. 

The first significant kinetic study of acylation was that of Steele333, who measured rates of benzoylation of toluene (excess) by benzoyl chloride catalysed... 

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