Method for converting carboxylic acid groups to trichloromethyl groups

• US 4,419,514 A
• Filed: 05/18/1981
• Issued: 12/06/1983
• Est. Priority Date: 08/21/1980
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Rogers, Richard B., McKendry, Lennon H., Ricks, Michael J.
• Primary Examiner(s): Raymond, Richard
• Assistant Examiner(s): Whittenbaugh, Robert C.
• Application Number:
  US06/264,491
• Time in Patent Office: 932 Days
• Field of Search: 546/346, 546/345, 546/304, 546/297, 546/315, 546/286, 546/303, 546/312, 570/194, 570/195, 544/334, 260/465 G, 568/936, 568/588
• US Class Current: 544/334
• CPC Class Codes: C07C 17/093 by replacement by halogens
• CPC Class Codes: C07C 201/12 by reactions not involving the formation of nitro groups
• CPC Class Codes: C07C 205/11 having nitro groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 205/37 the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
• CPC Class Codes: C07C 22/04 containing six-membered aromatic rings
• CPC Class Codes: C07C 22/06 Trichloromethylbenzene
• CPC Class Codes: C07C 25/02 Monocyclic aromatic halogenated hydrocarbons
• CPC Class Codes: C07C 25/13 containing fluorine
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/50 to carbon atoms of non-condensed six-membered aromatic rings
• CPC Class Codes: C07D 213/61 Halogen atoms or nitro radicals
• CPC Class Codes: C07D 215/18 Halogen atoms or nitro radicals

Abstract

Method for converting carboxylic acid groups to trichloromethyl groups which comprises contacting a compound containing a carboxylic acid group with a phenylphosphonic dichloride and phosphorus pentachloride and recovering the thus produced product.

Claims

1. A method for converting a carboxylic acid group on the ring of an aryl or nitrogen heteroaromatic compound to a trichloromethyl group which comprises contacting said aryl or nitrogen heteroaromatic compound with a phenylphosphonic dichloride and phosphorus pentachloride in a ratio of from about 0.01:

1 to about 10;

1 for a time and at a temperature sufficient to carry out the conversion of the carboxylic acid group to a trichloromethyl group.

2. The method as defined in claim 1 wherein the conversion is carried out at a temperature of from about 100°

C. to about 250°

C.

3. The method as defined in claim 1 wherein the phenylphosphonic dichloride is present in an amount of from about 0.1 to about 20 molar equivalents of the phenylphosphonic dichloride per carboxylic acid group to be converted.

4. The method as defined in claim 3 wherein the amount is from about 1 to about 10 molar equivalents of the phenylphosphonic dichloride per carboxylic acid group.

5. The method as defined in claim 1 wherein the phosphorus pentachloride is present in an amount of from about 2 to about 10 molar equivalents of the phosphorus pentachloride per carboxylic acid group to be converted.

6. The method as defined in claim 1 wherein a carboxylic acid group on an aryl compound is converted.

7. The method as defined in claim 1 wherein a carboxylic acid group on a nitrogen heteroaromatic compound is converted.

8. The method of claim 6 wherein the aryl compound contains one carboxylic acid group.

9. The method of claim 6 wherein the aryl compound contains two carboxylic acid groups in non-sterically hindered ring positions.

10. The method of claim 7 wherein the nitrogen heteroaromatic compound contains one carboxylic acid group.

11. The method of claim 7 wherein the nitrogen heteroaromatic compound contains two carboxylic acid groups in non-sterically hindered ring positions.

12. The method of claim 1 wherein the aryl compound is ring substituted with at least one sterically compatible group from the group consisting of chloro, fluoro, bromo, nitro, cyano, alkyl, alkoxy, alkylthio, hydroxy, aryl, alkyl substituted aryl, alkoxy substituted aryl, aryloxy or trifluoromethyl, with the proviso that when the substituent is alkyl, alkylthio or alkoxy, that a strong electron withdrawing group is also on the ring.

13. The method of claim 1 wherein the nitrogen heteroaromatic compound is ring substituted with at least one sterically compatible group from the group consisting of chloro, fluoro, bromo, nitro, cyano, alkyl, alkoxy, alkylthio, hydroxyl, aryl, alkyl substituted aryl, alkoxy substituted aryl, aryloxy or trifluoromethyl.