Phosgenation under pressure of alcohol's for producing chloroformates

• US 6,479,690 B1
• Filed: 03/06/2000
• Issued: 11/12/2002
• Est. Priority Date: 09/04/1997
• Status: Expired due to Fees

• Current Assignee: Isochem Company
• Original Assignee: Societe Nationale Des Poudres Et Explosifs
• Inventors: Metz, François, Garel, Laurent
• Primary Examiner(s): Killos, Paul J.
• Application Number:
  US09/486,892
• Time in Patent Office: 981 Days
• Field of Search: 558/280, 558/281, 558/282, 558/283
• US Class Current: 558/280
• CPC Class Codes: C07C 68/02 from phosgene or haloformates
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids

Abstract

The invention concerns a method for phosgenation of monohydroxy alcohol'"'"'s and/or polyols characterised in that it consists of treating alcohol and or polyol, whether in the presence of solvent or not, with a molar excess of phosgene, preferably 2 to 30 times more phosgene than the hydroxyl groups, at temperatures ranging between 0 and 200° C. and at pressure levels ranging between 2 and 60 bar, preferably in the absence of any catalyst. The method is further characterised in that pressure is further used to facilitate the separation of hydrochloric acid from phosgene, in a column external to the reactor.

Claims

1. Process for phosgenating monohydroxy alcohols and/or polyols to obtain the corresponding chloroformates, which comprises reacting the alcohol and/or polyol in the presence or absence of solvent with a molar amount of phosgene of at least 3.4 per hydroxyl group, at a temperatures of between 0 and 200°

C. and at a pressure of between 2 and 60 bar without a catalyst.

2. Process according to claim 1 wherein the reaction is carried out with up to 30 times more phosgene relative to each hydroxyl group.

3. Process according to claim 1 or 2, wherein the reaction is carried out in an open system with partial degassing.

4. Process according to claim 1 or 2 wherein the reaction temperature is between 20 and 150°

C.

5. Process according to claim 1 wherein the pressure is between 6 and 40 bar.

6. Process according to claim 1 wherein an alcohol and/or polyol of formula R(OH)_n is converted to a chloroformate R(OCOCl)_n, n being an integer from 1 to 6 and R being defined as follows:

- a saturated or unsaturated, linear or branched aliphatic radical having 1 to 22 carbon atoms which is optionally substituted a) by one or more identical or different halogen atoms, b) by one or more nitro groups, or c) by at least one alkyloxy, aryl, aryloxy or arylthio group, each of these groups being unsubstituted or substituted;

- a saturated or unsaturated, linear or branched polyoxyalkylene radical which is optionally substituted by the substituents indicated above and has a molecular mass of between 200 and 6000 (with the proviso that the alcohols are liquid or can be dissolved under the reaction conditions);

- a cycloaliphatic radical having 3 to 8 carbon atoms which bears or does not bear one or more substituents selected from a) halogen atoms, b) alkyl or haloalkyl radicals, c) nitro groups and d) aryl, aryloxy or arylthio radicals, it being possible for these radicals themselves to be unsubstituted or substituted;

- an aromatic carbocylic radical which is unsubstituted or substituted by one or ore substituents selected from the group consisting of halogen atoms, alkyl or haloalkyl radicals having 1 to 12 carbon atoms, C₂-C₆ alkenyl, C₃-C₈ cycloalkyl, C₄-C₁₀ cycloalkylalkyl, C₇-C₁₀ aralkyl and C₇-C₁₀ aralkoxy radicals, alkylthio or haloalkylthio radicals having 1 to 6 carbon atoms, alkylsulphinyl or haloalkylsulphinyl radicals having 1 to 6 carbon atoms, alkylsulphonyl or haloalkylsulphonyl radicals having 1 to 6 carbon atoms, alkyloxy or haloalkyloxy radicals having 1 to 6 carbon atoms, aryl, arylthio or aryloxy radicals, and the nitro group;

- a 5- or 6-membered aromatic or nonaromatic heterocyclic radical having one or more identical or different heretoatoms selected from oxygen, sulphur and nitrogen atoms and being unsubstituted or substituted by one or more substituents selected from halogen atoms, nitro groups, alkyl, haloalkyl, alkyloxy, haloalkyloxy, aryl, arylthio and aryloxy radicals and/or being optionally condensed with an aromatic carbocycle which itself is unsubstituted or substituted.

7. Process according to claim 1 or 2 wherein a mixture of monohydroxy alcohols is converted to chloroformates.

8. Process according to claim 1 or 2 wherein a mixture of monohydroxy alcohols and polyols is converted to chloroformates.