WO1998031672B1

WO1998031672B1 - Method of producing n,n'-diazole compounds

Info

Publication number: WO1998031672B1
Application number: PCT/US1998/000592
Authority: WO
Filing date: 1998-01-09
Publication date: 1998-09-03
Anticipated expiration: 1999-07-17

Abstract

Describes a method of producing N,N'-diazole compounds, e.g. N,N'-carbonyldiimidazole, by reacting in an inert solvent, e.g., toluene, a 1-unsubstituted 1H-azole compound, e.g., 1H-imidazole, and a dihalide compound, e.g., phosgene, in the presence of an organic base, e.g., a tertiary amine such as tri(n-butyl)amine. The molar ratio of the 1-unsubstituted 1H-azole compound to the dihalide compound may range from 1.7:1 to 2.3:1. The organic base: 1-unsubstituted 1H-azole compound molar ratio is 1:1 when the molar ratio of the 1-unsubstituted 1H-azole compound to the dihalide compound is less than 2:1. The organic base has a basicity greater than that of the 1-unsubstituted 1H-azole compound, and along with its hydrohalide salt is soluble in the inert solvent.

Claims

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AMENDED CLAIMS

[received by the International Bureau on 22 July 1998 (22.07.98); original claims 1, 11, 16, 18 and 19 amended; original claim 10 cancelled, remaining claims unchanged (5 pages)]

1. A method of producing N,N'-diazole compound selected from the group consisting of N,N' -carbonyldiazole, N,N' -carbonothioicdiazole and N,N' -thionyldiazole compounds, comprising reacting in an inert solvent:

(a) 1-unsubstituted IH-azole compound represented by the following general formula,

wherein X¹, X² and X are independently CR¹ or nitrogen, provided that at least one of X , X and X is nitrogen; R and R² are independently hydrogen, halogen, C_x - C₆ alkyl, phenyl, substituted phenyl, or when X is CR , R¹ and R² together form a fused ring having 4 to 6 carbon atoms inclusive of the two carbon atoms in the 1-unsubstituted IH-azole ring through which R¹ and R are connected; and

(b) a dihalide compound selected from a member of the group consisting of

wherein Z is oxygen or sulfur, and Y is independently fluorine, chlorine or bromine, the molar ratio of said 1- unsubstituted IH-azole compound to said dihalide compound being from 1.7:1 to 2.3:1, in the presence of a tertiary amine selected from the group consisting of tri (alkyl) amines, wherein each alkyl group contains from 3 to 12 carbon atoms, and tribenzylamine, said tertiary amine being soluble in said inert solvent and having a basicity greater than that of said 1-unsubstituted IH-azole compound, the molar ratio of said - 26 - tertiary amine to said 1-unsubstituted IH-azole compound being 1:1 when the molar ratio of said 1-unsubstituted IH-azole compound to said dihalide compound is less than 2:1, thereby producing said N,N'-diazole compound and a hydrohalide salt of said tertiary amine, said hydrohalide salt being soluble in said inert solvent.

2. The method of claim 1 wherein when X³ is CR¹ and R¹

2 . . . and R together form a fused ring, said fused ring is a benzene ring.

The method of claim 1 wherein X and X are CR¹ and

X is nitrogen.

4. The method of claim 3 wherein R and R are each hydrogen.

5. The method of claim 1 wherein Y is chlorine or bromine .

6. The method of claim 5 wherein Y is chlorine.

7. The method of claim 6 wherein said dihalide compound is phosgene.

8. The method of claim 1 wherein the molar ratio of said 1-unsubstituted IH-azole compound to said dihalide compound is from 1.8:1 to 2:1.

9. The method of claim 8 wherein the molar ratio of said 1-unsubstituted IH-azole compound to said dihalide compound is from 1.9:1 to 2:1. 27

11. The method of claim 1 wherein said tertiary amine is selected from at least one of the group consisting of N,N- dimethylethyl amine, tri (n-propyl) amine, tri (isopropyl) amine and tri (n-butyl) amine .

12. The method of claim 11 wherein said organic base is tri (n-butyl) amine .

13. The method of claim 1 wherein said inert solvent is selected from the group consisting of aromatic solvents and halogenated solvents.

14. The method of claim 13 wherein said inert solvent is an aromatic solvent.

15. The method of claim 14 wherein said inert solvent is toluene.

16. A method of producing N,N' -carbonyldiazole compounds, comprising reacting in an inert solvent:

wherein X¹, X and X are independently CR¹ or nitrogen provided that at least one of X , X and X³ is nitrogen; R¹ and R² are independently hydrogen, halogen, C - C₆ alkyl, phenyl, substituted phenyl, or when X³ is CR¹, R¹ and R² together form a fused ring having 4 to 6 carbon atoms inclusive of the two ¹ - 28 - carbon atoms in the 1-unsubstituted IH-azole ring through which R and R² are connected; and

(b) a dihalide compound represented by the following general formula,

wherein Y is independently fluorine, chlorine or bromine, the molar ratio of said 1-unsubstituted IH-azole compound to said dihalide compound being from 1.7:1 to 2.3:1, in the presence of a tertiary amine selected from the group consisting of tri (alkyl) amines, wherein each alkyl group contains from 3 to 12 carbon atoms, and tribenzylamine, said tertiary amine being soluble in said inert solvent and having a basicity greater than that of said 1-unsubstituted IH-azole compound, the molar ratio of said tertiary amine to said 1-unsubstituted IH-azole compound being 1:1 when the molar ratio of said 1- unsubstituted IH-azole compound to said dihalide compound is less than 2:1, thereby producing said N,N' -carbonyldiazole compound and a hydrohalide salt of said tertiary amine, said hydrohalide salt being soluble in said inert solvent.

17. The method of claim 16 wherein when X³ is CR¹ and R¹ and R together form a fused ring, said fused ring is a benzene ring.

18. The method of claim 16 wherein X¹ and X³ are CR¹, X² is nitrogen, Y is chlorine and said inert solvent is selected from the group consisting of aromatic solvents and halogenated solvents . - 29 -

19. The method of claim 18 wherein R and R are each hydrogen, said tertiary amine is tri (n-butyl) amine, said inert solvent is an aromatic solvent, and the molar ratio of said 1- unsubstituted IH-azole compound to said dihalide compound is from 1.8:1 to 2:1.

20. The method of claim 19 wherein said inert solvent is toluene, and the molar ratio of said 1-unsubstituted IH-azole compound to said dihalide compound is from 1.9:1 to 2:1.

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STATEMENT UNDER ARTICLE 19

Enclosed herewith are replacements for pages 20-24 of the subject application in which amendments to the claims are made. The difference between the claims as filed and the claims as amended are as follows: a) Claims 1, 11, 16, 18 and 19 have been amended; b) Claim 10 has been cancelled; and c) Claim 2-9, 12-15, 17 and 20 remain unchanged.

Claims 1 and 16 have been amended to include omitted language when R¹ and R² together form a fused ring, which disclosure can be found on page 5, lines 6-11, and to amend the definition OF the organic base to be a tertiary amine selected from the group consisting of tri (alkyl) amines wherein each alkyl group contains from 3 to 12 carbon atoms and tribenzylamine. Basis for the later amendment may be found on page 12, lines 4-13 of the specification. Amendments to claims 11, 18 and 19 change the reference to the organic base to that of a tertiary amine in accordance with the amendments to claims 1 and 16.

The amendments to the claims which amend the definition of the organic base to certain tertiary amines has been made for the reason that the lower tertiary amines such as triethyl amine are not appropriate for the claimed invention because they result in the formation of a precipitated hydrohalide salt - the claims requiring the hydrohalide salt to be soluble in the inert solvent. An amendment to the description to place the disclosure in accord with the amended claims will be made under Article 34 when appropriate.