Imidazole and triazole carboxylates, and processes for preparing

Details Imidazole and triazole carboxylates, and processes for preparing Imidazole and triazole carboxylates, and processes for preparing

1995-05-09

1996-09-03

Wilson, D. R.

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

5482668, 5483341, C07D26344, C07D23360, C07D24908

Patent

active

055525547

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

This invention pertains to a process for the preparation of one class of fungicidal oxazolidinone, the 2,4-oxazolidinediones, and intermediate triazole or imidazole carboxylates.
Fungicides that effectively control plant diseases are in constant demand by growers. Plant diseases are highly destructive, difficult to control and quickly develop resistance to commercial fungicides. U.S. Pat. No. 4,957,933 and Synthesis 1981, 38-40 disclose the preparation of 2,4-oxazolidinedione fungicides by treatment of N-hydroxy-2-hydroxyhydroxamic acids with 1,1'-carbonyldiimidazole to form dioxazinediones, and subsequent treatment of the dioxazinediones with phenylhydrazine. WO 90/12791 discloses the preparation of 2,4-oxazolidinediones from 2-thioxooxazolidin-4-ones by desulfurization. However, there is a need for a more efficient process. The present invention provides a new efficient process for the preparation of 2,4-oxazolidinediones.


SUMMARY OF THE INVENTION

This invention comprises a process for the preparation of 2,4-oxazolidinediones of Formula I ##STR2## wherein: R.sup.1 is phenyl substituted with 1-2 halogen: or 4-phenoxy, 4-(1-phenethyloxy) or 4-benzyloxy each optionally substituted with R.sup.2 on the phenyl ring (i.e., R.sup.1 is phenyl substituted with 1.2 halogen, 4-phenoxy, 4-(1-phenethyloxy) or 4-benzyloxy with each 4-phenoxy, 4-(1-phenethyloxy) or 4-benzyloxy optionally substituted with R.sup.2 on the phenyl ring): and ##STR3## wherein R.sup.1 and R.sup.2 are as defined above in Formula I; and ##STR4## wherein: Y is 1-imidazolyl or 1,2,4-triazolyl; provided that Y is 1,2,4-triazolyl when R.sup.1 in Formula II is phenyl substituted with 4-(1-phenethyloxy) or 4-benzyloxy (with each 4-(1-phenethyloxy) or 4-benzyloxy optionally substituted with R.sup.2 on the phenyl ring as noted above); ##STR5## wherein R.sup.l, R.sup.2, R.sup.3 and Y are as defined above: above with phenylhydrazine in the presence of an acid to yield a compound of Formula I.
Scheme 1 depicts the process of the present invention. ##STR6##
This invention further comprises a compound of Formula IV: ##STR7## wherein R.sup.1 is phenyl substituted with 1-2 halogen, 4-phenoxy, 4-(1-phenethyloxy) or 4-benzyloxy with each 4-phenoxy, 4-(1-phenethyloxy) or 4-benzyloxy optionally substituted with R.sup.2 on the phenyl ring; when R.sup.1 is phenyl substituted with 4-(1-phenethyloxy) or 4-benzyloxy (with each 4-(1-phenethyloxy) or 4-benzyloxy optionally substituted with R.sup.2 on the phenyl ring as noted above).


DETAILED DESCRIPTION OF THE INVENTION

Preferred processes of the present invention for the preparation of 2,4-oxazolidinediones are processes A to H as follows:
Preferred Process A is the process defined above in Scheme 1 wherein R.sup.1 of Formula II is 4-phenoxyphenyl and Y of Formula III is 1-imidazolyl. Preferred Process B is the process defined above in Scheme 1 wherein Y of Formula III is 1,2,4-triazolyl. Preferred Process C is the process of Preferred Process B wherein R.sup.1 of Formula II is 4-phenoxyphenyl. Preferred Process D is the process of Preferred Process B wherein R.sup.1 is 2,4-difluorophenyl. Preferred Process E is the process defined above in Scheme 1 wherein the compound of Formula III is prepared in situ in the presence of the ester of Formula II. Preferred Process F is the process of Preferred Process E wherein the compound of Formula III is prepared from the alkali metal salt of triazole and phosgene. Preferred Process G is the process defined above in Scheme 1 wherein compounds of Formula IV are not isolated but treated in situ with phenylhydrazine and acid. Preferred Process H is the process of Preferred Process G wherein the compound of Formula IV is prepared using a picoline or mixture of picolines as the organic base, and further comprising filtering the crude reaction mixture containing the compound of Formula IV resulting from step 1) prior to reacting the filtrate with phenylhydrazine in the presence of acetic acid in step 2).
Preferred compounds of Formula IV of the present

REFERENCES:
patent: H1401 (1995-01-01), Campbell
patent: 3954992 (1976-05-01), Davidson
patent: 4507310 (1985-03-01), Devoise-Lambert et al.
patent: 4957933 (1990-09-01), Geffken et al.
patent: 5356908 (1994-10-01), Geffken et al.
Geffken, D., Synthesis, pp. 38-40 (1981).
Abstract 100:6469q re Geffken, D., Z. Naturforsch. 38B(8), 1008-1014 (1983).
Abstract 97:182374h re Geffken, D., Arch. Pharm. (Weinheim, Ger.), 315(9), 802-810 (1982).

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