Nazarov, I. N.; Semenovskii, A. V. published the artcile< Orientation of chloromethylation reaction>, Reference of 112-63-0, the main research area is .
The isomers formed in chloromethylation of aromatic compounds show o-p-isomer formation which parallels the data on nitration of halobenzenes and chlorination of halobenzenes with FeCl3 (cf. Kovacic and Brace, C.A. 49, 13133g). Passage of HCl 0.5 hr. into 100 ml. CCl4, 6 g. paraformaldehyde, and 6 g. ZnCl2, followed by 32.8 g. PhCH2CO2Et, 2 g. ZnCl2, and stirring 7 hrs. at 50æ?gave, after washing with H2O, 31% mixed ClCH2C6H4CH2CO2Et, b8 148-51æ? [n]D20 1.5240, d20 1.1623; this (3.81 g.) oxidized with 60 ml. 20% HNO3 under 30 atm. N 1.5 hrs. in an autoclave at 200æ?gave benzenedicarboxylic acids, 60.4% p-, 27% o- and 12.6% m-isomer, separated through the Ba salts. Similar reaction with C6H6 gave a mixture of xylylene dichlorides, b9 118.5-20æ? which on oxidation was shown to contain 69% p-, 16% o- and 15% m-isomers. A considerable part of the p-xylylene chloride may be frozen out and this product, m. 99-100.5æ? on oxidation with CrO3 in AcOH gave 98.3% terephthalic acid, while hydrolysis of the dichloride with chalk-H2O gave 78.3% p-C6H4 (CH2OH)2, m. 111-12æ? PhCH2Cl (63.3 g.), 15 g. paraformaldehyde, and 20 g. ZnCl2 in a stream of HCl gave 20 g. p-xylylene dichloride, m. 99-100æ? along with 9.7 g. liquid mixture of the o-, m-, and p-xylylene dichlorides. Passage of HCl 45 min. into 150 ml. CCl4, 17 g. paraformaldehyde, and 10 g. ZnCl2 followed by dropwise addition of 53 g. EtPh at 50æ?and stirring 20 min. longer gave 44.5% mixed EtC6H4CH2Cl, b12 95-101æ? and 12 g. (EtC6H4)2CH2, b12 150æ? Oxidation of the chloromethyl derivatives with CrO3-AcOH gave 70% p- and 30% o-isomers. Similar chloromethylation of cumene gave 45% mixed isomers of iso-PrC6H4CH2Cl, b15 100-10æ? which oxidized to 85% p- and 15% o-acids. Similarly, chloromethylation of Me3CPh gave 58% p-Me3CC6H4CH2Cl, b7 101-5æ? with much unreacted hydrocarbon, which oxidized with HNO3 as above gave only terephthatic acid. Passage of HCl 5 hrs. into 90 ml. concentrated HCl, 30 g. paraformaldehyde, and 80 g. EtPh, followed by stirring 20 hrs. at 50-5æ?gave 60% isomeric EtC6H4CH2Cl, 77% p- and 23% o-isomers as shown by oxidation with 20% HNO3, as above; similarly iso-PrPh gave 50% mixed iso-PrC6H4CH2Cl isomers, b11 98-102æ? which on oxidation contained 85% p- and 15% o-isomer. Passage of HCl 1.5 hrs. into 100 ml. CCl4, 30 g. paraformaldehyde, and 20 g. ZnCl2 followed by addition of 48 g. PhF and stirring 5.5 hrs. at 50æ?with addition of 1.5 g. ZnCl2 gave 78% mixed FC6H4CH2Cl, b17 69-74æ? which on freezing gave 20% p-isomer; the residue gave 3.35 g. diarylated product, b14 125-35æ? oxidation with CrO3-AcOH gave 80-9.6% p-isomer and about 11% o-isomer. Similar reaction with PhCl gave 62% mixed isomers of ClC6H4CH2Cl, b34 113-16æ? which on freezing gave 30% p-isomer, m. 27-8æ? the latter oxidized completely to p-ClC6H4CO2H, and oxidation of the total mixture indicated the formation of 62.6% p-isomer. Similarly, PhBr gave 76.2% mixed BrC6H4CH2Cl, b3 83-7æ? which gave 35% p-isomer, m. 37-8æ? oxidation with CrO3 showed the total formation of 58% p-isomer and residual 42-3% o-isomer. PhI similarly gave 76% chloromethylation product, b5 113-17æ? which gave 30% p-IC6H4CH2Cl, m. 52-3æ? while oxidation of the products with CrO3 showed 52.4% p- and 47% o-isomer. Oxidation of chloromethylated halobenzenes with HNO3 gave similar results for Cl and Br derivatives, but the iodine-derivative failed to give a product containing iodine.
Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya published new progress about Chloromethylation. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Reference of 112-63-0.
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