Method for production of aromatic compounds

• US 6,521,794 B2
• Filed: 02/01/2002
• Issued: 02/18/2003
• Est. Priority Date: 02/02/2001
• Status: Expired due to Fees

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Nippon Shokubai Company Limited
• Inventors: Hirota, Kouichi
• Primary Examiner(s): Barts, Samuel
• Application Number:
  US10/062,007
• Publication Number:
  US 20020156322A1
• Time in Patent Office: 382 Days
• Field of Search: 564/442, 564/441, 564/124, 564/129, 562/456
• US Class Current: 564/442
• CPC Class Codes: C07C 209/68 from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
• CPC Class Codes: C07C 211/52 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups

Abstract

For the production of an aromatic compound by hydrolyzing and decarboxylating a corresponding aromatic cyano compound in the presence of an acidic substance, this invention provides a method for the production of the aromaic compound, characterized by carrying out the reactions of hydrolysis and decarboxylaion in multiple steps. Particularly when the aromatic cyano compound contains a halogen, this method effectively prevents the reaction vessels from being corroded by the by-produced hydrogen halogenide and enables the target compound to be produced in a high yield.

Claims

1. In the production of an aromatic compound represented by the general formula (2) by hydrolyzing and decarboxylating an aromatic cyano compound represented by the general formula (1) in the presence of an acidic substance, a method for the production of the aromatic. compound, characterized by performing the reactions of hydrolysis and decarboylation in multiple steps

(wherein X is a halogen atom, Y is a cyano group, nitro group, or carboxyl group, Z is a nitrogen-containing group represented by —

N(R¹)(R²) (wherein R¹ and R² are identical or not identical substitutes superposed on a nitrogen atom and selected from among hydrogen atom and linear or branched alkyl groups of 1 to 4 carbon atoms), m is 0, 1, or 2, and n is 1, 2, 3, or 4, providing that the sum of m and n falls in the range of 1≦

m+n≦

4)

(wherein the symbols have the same meanings as in the general formula (1).

2. A method according to claim 1, wherein the conversion ratio of the aromatic cyano compound represented by the general formula (1) is fixed at a level of not less than 40 mol % and the molar ratio of the formation of the aromatic compound represented by the general formula (2) to the initial amount of the aromatic cyano compound represented by the formula (1) is fixed at a level of not more than 80 mol % in a former step reaction in said multiple steps respectively, and subsequently the reactions of hydrolysis and decarboxylation are terminated in and after a latter step reactions in said multiple steps.

3. A method according to claim 1, wherein the reactions in the former step and the latter step in said multiple steps are carried out on the conditions of lowering the concentration of said acidic substance and/or increasing the reaction temperature.

4. A method according to claim 3, wherein said acidic substance is an aqueous sulfuric acid solution.

5. A method according to claim 1, wherein said aromatic cyano compound is 4-amino-2,3,5,6-tetrahalogenobenzonitrile and said aromatic compound is 2,3,5,6-tetrahalogenoaniline.

6. A method according to claim 1, wherein said reactions of hydrolysis and decarboxylation are carried out in the presence of sulfuric acid in a reaction vessel made of glass or lined with glass.

7. A method for the production of an aromatic compound, characterized by forming an aromatic compound represented by the general formula (2) by hydrolyzing and decarboxylating an aromatic cyano compound represented by the general formula (1) in the presence of an aqueous medium and subsequently recovering the obtained aromatic compound from the reaction solution by azeotropic distillation with water

(wherein X is a halogen atom, Y is a cyano group, nitro group, or carboxyl group, Z is a nitrogen-containing group represented by —

N(R¹)(R²) (wherein R¹ and R² are identical or not identical substitutes superposed on a nitrogen atom and selected from among hydrogen atom and linear or branched alkyl groups of 1 to 4 carbon atoms), m is 0, 1, or 2, and n is 1, 2, 3, or 4, providing that the sum of m and n falls in the range of 1≦

m+n≦

4)

(wherein the symbols have the same meanings as in the general formula (1).

8. A method according to claim 7, wherein said aqueous medium contains an acidic substance and the concentration of the acidic substance in said aqueous medium is in the range of 80 to 98 weight %.

9. A method according to claim 8, wherein said acidic substance is sulfuric acid.

10. A method according to claim 7, wherein the molar ratio of the formation of the aromatic compound represented by the general formula (2) is not less than 85 mol % to the initial amount of the aromatic cyano compound represented by the general formula (1).

11. A method according to claim 7, wherein said aromatic cyano compound is 4-amino-2,3,5,6-tetrahalogenobenzonitrile and said aromatic compound is 2,3,5,6-tetrahalogenoaniline.

12. A method according to claim 7, wherein said aqueous medium contains an alkaline substance.

13. A method according to claim 7, wherein said aromatic cyano compound is 4-amino-2,3,5,6-tetrafluorobenzonitrile and said aromatic compound is 2,3,5,6-tetrafluoroaniline.

14. In the production of an aromatic compound represented by the general formula (2) by hydrolyzing and decarboxylating an aromatic cyano compound represented by the general formula (1) in the presence of an acidic substance, a method for the production of the aromatic compound, characterized by performing the hydrolysis and decarboxylation in multiple steps and effecting the recovery of the formed aromatic compound from the reaction solution by azeotropic distillation with water

(wherein X is a halogen atom, Y is a cyano group, nitro group, or carboxyl group, Z is a nitrogen-containing group represented by —

N(R¹)(R²) (wherein R¹ and R² are identical or not identical substitutes superposed on a nitrogen atom and selected from among hydrogen atom and linear or branched alkyl groups of 1 to 4 carbon atoms), m is 0, 1, or 2, and n is 1, 2, 3, or 4, providing that the sum of m and n falls in the range of 1≦

m+n≦

4)

(wherein the symbols have the same meanings as in the general formula (1).

15. A method according to claim 14, wherein a former step reactions in said multiple steps are carried out under the condition of an acidic state in a concentration in the range of 80 to 98 weight % to react an aromatic cyano compound represented by the general formula (1) and subsequently a latter step reactions in said multiple steps are carried out under the condition of having the concentration of said acidic substance lowered by a level in the range of 5 to 50 weight % and/or elevating the reaction temperature by a level in the range of 5 to 30°

C.

16. A method according to claim 14, wherein the molar ratio of the formation of the aromatic compound represented by the formula (2) to the aromatic cyano compound represented by the formula (1) in said reaction solution is not less than 85 mol %.

17. A method according to claim 14, wherein said acidic substance is an aqueous sulfuric acid solution.