Synthesis of 4-chlorobenzyl chloride

Preparation of 4-chlorobenzyl chloride

The chlorination is best carried out in a three-necked flask with a mercury immersion lamp, a gas inlet tube, and a highly efficient reflux condenser.

A glass apparatus for the photochlorination

A glass apparatus for the photochlorination

If no mercury immersion lamp is available, the mixture can be irradiated from outside with a 500-watt photolamp or the chlorination can be carried out in direct sunlight. However, the reaction then takes place somewhat more slowly and the yields are generally lower. The gaseous chlorine is dried in a wash-bottle with concentrated sulfuric acid. An empty wash-bottle must be connected on either side of this washing bottle as safety vessels. The 4-chlorotoluene is heated to the boiling point, using a heating bath, and a vigorous stream of gaseous chlorine is passed in. During the chlorination reaction no gaseous chlorine should pass through the condenser (color). Chlorination is continued until the calculated increase in weight has been obtained. On cooling, the solidified 4-chlorobenzyl chloride can be purified directly by filtering off with suction and recrystallization. Furthermore, in order to obtain the pure product, the reaction product is fractionated through a 20-cm Vigreux column in the vacuum after the addition of a spatula-tip of sodium hydrogen carbonate. The yield is 85%, m.p. 28 °C, b.p. 216-222 °C; 92°C/10 mm; n25/D 1.5651 (on supercooled melt).

Organicum. Practical Handbook of Organic Chemistry, by Heinz Becker, Werner Berger and Günter Domschke, Addison-Wesley Pub. Co, 168-169,  (1973)

To prepare the 4-chlorobenzyl chloride a molar ratio of 4-chlorotoluene to sulfuryl chloride of 1.2:1 is used. After the addition of 0.002 mole of benzoyl peroxide or, still better, azo-bis-isobutyronitrile (referred to 1 mole of sulfuryl chloride) the 4-chlorotoluene and the sulfuryl chloride are heated to the boil in a round-bottomed flask with a very efficient reflux condenser and a calcium chloride tube. At intervals of 1 hr, the same amount of chain initiator is added. The reaction is complete in 8-10 hours and  when no further evolution of gas can be observed. The mixture is allowed to cool and is washed with water and it is then dried with magnesium sulfate and fractionated through a 20-cm Vigreux column yielding 70% of 4-chlorobenzyl chloride, m.p. 31 °C; b.p. 92°C/10mm; n20/D 1.5671.

Organicum. Practical Handbook of Organic Chemistry, by Heinz Becker, Werner Berger and Günter Domschke, Addison-Wesley Pub. Co, 170, (1973)

IUPAC Name

1-chloro-4-(chloromethyl)benzene

InChI

InChI=1S/C7H6Cl2/c8-5-6-1-3-7(9)4-2-6/h1-4H,5H2

InChI Key

JQZAEUFPPSRDOP-UHFFFAOYSA-N

Canonical SMILES

C1=CC(=CC=C1CCl)Cl

MeSH Synonyms

1-chloro-4-(chloromethyl)benzene

Depositor-Supplied Synonyms

4-Chlorobenzyl chloride, 104-83-6, 1-Chloro-4-(chloromethyl)benzene, alpha,4-Dichlorotoluene, p-Chlorobenzyl chloride, 4-chlorobenzylchloride, Benzene, 1-chloro-4-(chloromethyl)-, 1-Chloro-4-chloromethyl-benzene, (4-Chlorophenyl)methyl chloride, p-Chlorophenylmethyl chloride, alpha,p-Dichlorotoluene, NSC 34032, 1-CHLORO-4-CHLOROMETHYLBENZENE, Toluene, p,alpha-dichloro-, Toluene, p,.alpha.-dichloro-, CCRIS 5106, HSDB 2731, JQZAEUFPPSRDOP-UHFFFAOYSA-N, 1-chloro-4-(chloromethyl)-benzene, EINECS 203-242-7, MFCD00000914, BRN 0471558, p-Chlorobenzyl chloride, liquid or solid, AI3-14884, p-chlorobenzylchloride, 4-chlorobenzylchlorine, 4chlorobenzyl chloride, PubChem5797, p-chloro benzylchloride, p-chloro-benzylchloride, 4-chloro-benzylchloride, parachlorobenzyl chloride, p-chloro-benzyl-chloride, 4-chloro-benzyl chloride, 4-chlorobenzyl- chloride, AC1L1PEL, .alpha.4-Dichlorotoluene, .alpha.,p-Dichlorotoluene, .alpha.-p-Dichlorotoluene, p,.alpha.-Dichlorotoluene, p-.alpha.-Dichlorotoluene, .alpha.,4-Dichlorotoluene, ACMC-2098dd, UN 2235 (Related), UNII-Q9HS4N7D3M, AC1Q3U1H, Q9HS4N7D3M, 4-chlorophenylmethyl chloride, KSC174Q7J, SCHEMBL120896, 111961_ALDRICH, CTK0H4874, JQZAEUFPPSRDOP-UHFFFAOYSA-, (4-chlorophenyl) methyl chloride, MolPort-000-871-731, BB_SC-7002, ZINC559400, NSC34032, STR00186, ANW-15119, BBL012559, NSC-34032, SBB058606, STL163634, ZINC00559400, AKOS000118783, AM90499, CS19806, LS11418, MCULE-3948857908, RP22380, RTX-012031, TRA0064461, AC-11570, AJ-23483, AK-53438, BC678529, BR-53438, CJ-04343, KB-11934, OR025154, OR145438, SC-00198, ZB014423, AB1002978, DB-000220, KB-190981, LS-154058, ST2408749, D0421, FT-0618195, ST50214096, M-6006, 82822-EP2272517A1, 82822-EP2272817A1, 82822-EP2295409A1, 82822-EP2298758A1, 82822-EP2298759A1, 82822-EP2305664A1, I01-0782, W-108806, 3B3-035863, InChI=1/C7H6Cl2/c8-5-6-1-3-7(9)4-2-6/h1-4H,5H2

Removed Synonyms

|A,4-Dichlorotoluene, 4-Chlorobenzal chloride, Para-chlorobenzyl Chloride, Toluene,.alpha.-dichloro-, CID7723, 4-05-00-00816 (Beilstein Handbook Reference)

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