Selective chlorination of a 1-(2-fluorophenyl)-1,2,4-triazole

• US 5,965,742 A
• Filed: 06/25/1998
• Issued: 10/12/1999
• Est. Priority Date: 12/29/1995
• Status: Expired due to Fees

• Current Assignee: FMC Corporation
• Original Assignee: FMC Corporation
• Inventors: Goudar, Jaidev S.
• Primary Examiner(s): Morris, Patricia L.
• Application Number:
  US09/091,867
• Time in Patent Office: 474 Days
• Field of Search: 548/263.2
• US Class Current: 548/263.2
• CPC Class Codes: C07D 249/12 Oxygen or sulfur atoms

Abstract

A process is disclosed in which the 4-position of the 1-(2-fluorophenyl) group attached to a 4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole, an intermediate in the route to prepare the herbicide ethyl α-2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate, is chlorinated in good yield. The process involves adding chlorine gas in three separate steps, with by-product hydrogen chloride being removed at the end of each chlorine addition step.

Claims

1. A process for the chlorination of 1-(2-fluorophenyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole (the "2-fluorophenyl compound") in the 4-position of the phenyl ring which comprises

a) adding 0.8 to 1.6 molar equivalents of chlorine to a stirred slurry of 1-(2-fluorophenyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole in a solvent selected from acetonitrile, N,N-dimethylformamide, nitromethane, and nitrobenzene, at a temperature in the range of ambient to 50°

C., at a rate such that the temperature does not exceed 50°

C., and continuing the stirring at 30 to 50°

C. for from one to ten hours;

b) for a period of from one to six hours, while maintaining the temperature at 30 to 50°

C., reducing the pressure in the reaction vessel so that the solvent refluxes and most of the hydrogen chloride by-product is driven off;

c) optionally, purging the reaction vessel with nitrogen to reduce the hydrogen chloride concentration in the reaction mixture to below 1%;

d) repeating steps a, b, and c two times;

e) recovering 1-(4-chloro-2-fluorophenyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole.

2. A process of claim 1 which comprises

a) adding 0.9 to 1.5 molar equivalents of chlorine to a stirred slurry of the 2-fluorophenyl compound in acetonitrile, the weight percent of the 2-fluorophenyl compound per volume of acetonitrile being in the range of 5 to 70%, at a temperature in the range of 30°

C. to 40°

C., at a rate such that the temperature is between 35 and 40°

C., and continuing the stirring at 30 and 40°

C. for from three to six hours;

b) for a period of from two to four hours, while maintaining the temperature at 35 and 40°

C., reducing the pressure in the reaction vessel so that the solvent refluxes and most of the hydrogen chloride by-product is driven off.

3. A process of claim 2 in which steps a through d are carried out at reduced pressure.

4. A process of claim 3 in which the reduced pressure is in the range of 300 to 500 mm of mercury.

5. A process for chlorination of 1-(2-fluorophenyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole at the 4-position of the phenyl ring which comprises the steps of:

(a) adding chlorine to a mixture of 1-(2-fluorophenyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole and a solvent, wherein said addition forms hydrogen chloride as a by-product; and

(b) reducing the concentration of the hydrogen chloride by-product after said addition.

6. The process of claim 5, wherein steps (a) and (b) are each performed three times in sequential order.

7. The process of claim 5, wherein said chlorine is added in step (a) in an amount of about 0.8 to about 1.6 molar equivalents.

8. The process of claim 6, wherein said chlorine is added in each step (a) in an amount of about 0.8 to about 1.6 molar equivalents.

9. The process of claim 5, wherein said solvent is selected from the group consisting of acetonitrile, N,N-dimethylformamide, nitromethane and nitrobenzene.

10. The process of claim 5, wherein said chlorine is added in step (a) at a temperature in the range of about ambient to about 50 C and at a rate such that the temperature does not exceed about 50 C.

11. The process of claim 9, wherein said solvent is acetonitrile.

12. The process of claim 6, wherein said solvent is selected from the group consisting of acetonitrile, N,N-dimethylformamide, nitromethane and nitrobenzene.

13. The process of claim 12, wherein said chlorine is added in step (a) at a temperature in the range of about ambient to about 50 C and at a rate such that the temperature does not exceed about 50C.