Synthesis of ethyl chloroformate

Preparation of ethyl chloroformate

Ethyl chloroformate is prepared by passing phosgene in ethyl alcohol:

Preparation of ethyl chloroformate from phosgene and ethyl alcohol

Preparation of ethyl chloroformate from phosgene and ethyl alcohol

In a 3-liter flask fitted with a reflux condenser and a tube through which the phosgene may be passed are placed 736 g (10 mols) of absolute alcohol. This is cooled to and the phosgene passed in until the weight of the alcohol and flask has increased by 1090 g (11 mols). During this operation, the temperature must be kept down below 10° C or else a considerable byproduct of diethyl carbonate results. Moreover, the low temperature causes the hydrochloric acid which is evolved in the reaction to remain in solution in the alcohol so that a fairly accurate weight of the phosgene which has entered can be obtained. The mixture, after the phosgene has been passed in, is allowed to stand for 30 minutes below 10° C in order to be certain that the phosgene has completely reacted and is then allowed to warm up to room temperature. The reaction mixture is now washed twice with an equal volume of ice water in order to remove the slight excess of alcohol, the ethyl chloroformate dried over calcium chloride and distilled. The yield of pure product, boiling 93-96° C, amounts to 1070 g (90% theory). From a large tank of phosgene, the required amount of phosgene may be passed into the alcohol in the course of about 7 hours. It is probable that with a lower temperature, the phosgene could be passed in even more rapidly. If the temperature is kept as low as 10° C during the entrance of the phosgene and then purification of the ethyl chloroformate within a short time is carried out only very small amounts of diethyl carbonate are produced.

Organic Chemical Reagents, A. Rogerby, 42-43, 1919

Slightly modified procedure:

Preparation of ethyl chloroformate from phosgene and ethyl alcohol

Preparation of ethyl chloroformate from phosgene and ethyl alcohol

To 250 g of a 20 % solution of phosgene in ether are added gradually, with cooling, 23 g of absolute alcohol diluted with some ether, followed by 54 g of technical monomethyl aniline in an equal volume of ether. After the reaction is completed the solution is shaken out with dilute acid to remove the methyl aniline hydrochloride, dried, and fractionally distilled collecting fraction passing at 93° C.

Organic medical chemicals, by M. Barrowliff, 37, 1921

IUPAC Name

ethyl carbonochloridate

InChI

InChI=1S/C3H5ClO2/c1-2-6-3(4)5/h2H2,1H3

InChI Key

RIFGWPKJUGCATF-UHFFFAOYSA-N

Canonical SMILES

CCOC(=O)Cl

MeSH Synonyms

ethyl chloroformate, ethyl chloroformate, 14C-labeled, ethylchloroformate

Depositor-Supplied Synonyms

ETHYL CHLOROFORMATE, Ethyl chlorocarbonate, Ethyl carbonochloridate, Cathyl chloride, 541-41-3, Carbonochloridic acid, ethyl ester, Ethoxycarbonyl chloride, ETHYLCHLOROFORMATE, Chloroformic acid ethyl ester, Formic acid, chloro-, ethyl ester, Etil cloroformiato, Ethylchloorformiaat, Etil clorocarbonato, Chlorocarbonic acid ethyl ester, Ethyl chloromethanoate, chloro(ethoxy)methanone, Chlorocarbonate D’ethyle, Ethyle, chloroformiat D’, TL 423, Clhorameisensaeureaethylester, Ethylchloorformiaat [Dutch], Etil cloroformiato [Italian], Etil clorocarbonato [Italian], UNII-09601EZP9R, HSDB 409, Ethylester kyseliny chlormravenci, Cloroformiato de etilo [Spanish], Chlorocarbonate d’ethyle [French], RIFGWPKJUGCATF-UHFFFAOYSA-N, Ethyle, chloroformiat d’ [French], EINECS 208-778-5, UN1182, Chlorameisensaeureaethylester [German], Clhorameisensaeureaethylester [German], BRN 0385653, Ethylester kyseliny chlormravenci [Czech], AI3-19852, ECF, 52803-29-9, ethylcloroformate, ethyl cloroformate, ethvl chloroformate, ethyl chioroformate, ethylchlorocarbanate, ethylchlorocarbonate, carboethoxy chloride, Ethyl chloroforrnate, ethyl chloro-formate, ethyl chloroform ate, ethoxycarbonylchloride, ethyl chloro-carbonate, ethyl-carbonochloridate, Cloroformiato de etilo, ethyl chloroformic acid, chloroformic ethyl ester, Ethoxy carbonyl chloride, ethyl chlorocarbonic acid, Ethyl chloridocarbonate #, DSSTox_CID_7186, SCHEMBL342, Chlorameisensaeureaethylester, chloroformic acid ethylester, AC1L1W8Z, DSSTox_RID_78340, DSSTox_GSID_27186, Chloroformic acid, ethyl ester, 185892_ALDRICH, AC1Q35F8, CHEMBL3183406, Chlorocarbonic acid, ethyl ester, 23131_FLUKA, CTK1H0589, RIFGWPKJUGCATF-UHFFFAOYSA-, MolPort-000-872-022, 09601EZP9R, BB_SC-7081, Tox21_201034, ANW-44937, BBL011487, SBB040861, STL146599, ZINC02034866, AKOS000119319, MCULE-4167904934, RTR-019143, UN 1182, NCGC00248902-01, NCGC00258587-01, AN-21334, BC222115, CAS-541-41-3, CJ-31943, Ethyl chloroformate [UN1182] [Poison], KB-51531, LS-69671, Ethyl chloroformate [UN1182] [Poison], DB-052494, TR-019143, FT-0623663, 11380-EP2269992A1, 11380-EP2275404A1, 11380-EP2275414A1, 11380-EP2281818A1, 11380-EP2286811A1, 11380-EP2289893A1, 11380-EP2289894A2, 11380-EP2289897A1, 11380-EP2292619A1, 11380-EP2298312A1, 11380-EP2298750A1, 11380-EP2298772A1, 11380-EP2301922A1, 11380-EP2305254A1, 11380-EP2305649A1, 11380-EP2305663A1, 11380-EP2305676A1, 11380-EP2305682A1, 11380-EP2308839A1, 11380-EP2308857A1, 11380-EP2308858A1, 11380-EP2308873A1, 11380-EP2308877A1, 11380-EP2308879A1, 11380-EP2311807A1, 11380-EP2311808A1, 11380-EP2311816A1, 11380-EP2311817A1, 11380-EP2311824A1, 11380-EP2311829A1, 11380-EP2311840A1, 11380-EP2314578A1, 11380-EP2314593A1, 11380-EP2316827A1, 11380-EP2371811A2, 11380-EP2371831A1, 93359-EP2269986A1, 93359-EP2272822A1, 93359-EP2277861A1, 93359-EP2280000A1, 93359-EP2289887A2, 93359-EP2289888A2, 93359-EP2292596A2, 93359-EP2305633A1, 93359-EP2374790A1, I14-2766, 3B3-026914, InChI=1/C3H5ClO2/c1-2-6-3(4)5/h2H2,1H3, 503842-49-7

Removed Synonyms

CID10928, c0177, 4-03-00-00023 (Beilstein Handbook Reference)

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