EP0061835A1 — Triazole compounds, a process for preparing them,…

Claim 1

Independent Claim 134 words

Triazole and imidazole compounds having the general formula (I): wherein R 1 and R 2 , which may be the same or different, are hydrogen, alkyl, optionally substituted cycloalkyl, cycloalkylmethyl, alkenyl, heterocyclyl, aryl or aralkyl optionally substituted with halogen, nitro, alkyl, haloalkyl, haloalkoxy, alkoxy, phenyl, phenoxy, benzyl, benzyloxy, halophenyl or haloalkoxy; R 3 is hydrogen, alkyl, alkenyl, alkynyl, aralkyl or acyl; R 4 and R 5 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; R 6 and R 7 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl: X is oxygen or sulphur or is SO or S0 2 ; and Az is a 1,2,4- or 1,3,4-triazole or imidazole ring; and isomers, acid addition salts and metal complexes thereof.

Claim 2

Dependent Claim 134 words

Triazole and imidazole compounds having the general formula (I): wherein R 1 and R 2 , which may be the same or different, are hydrogen, alkyl, optionally substituted cycloalkyl, cycloalkylmethyl, alkenyl, heterocyclyl, aryl or aralkyl optionally substituted with halogen, nitro, alkyl, haloalkyl, haloalkoxy, alkoxy, phenyl, phenoxy, benzyl, benzyloxy, halophenyl or haloalkoxy; R 3 is hydrogen, alkyl, alkenyl, alkynyl, aralkyl or acyl; R 4 and R 5 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; R 6 and R 7 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl: X is oxygen or sulphur or is SO or S0 2 ; and Az is a 1,2,4- or 1,3,4-triazole or imidazole ring; and isomers, acid addition salts and metal complexes thereof.

Claim 3

Dependent Claim 147 words

Triazole and imidazole compounds having the general formula (I): wherein R 1 is hydrogen, alkyl, optionally substituted cycloalkyl, cycloalkylmethyl, alkenyl, heterocyclyl, aryl or aralkyl optionally substituted with halogen, nitro, alkyl, haloalkyl, haloalkoxy, alkoxy, phenyl, phenoxy, benzyl, benzyloxy, halophenyl or haloalkoxy; R 2 is any of the values for R 1 except optionally substituted phenyl when X is oxygen, and R 3 to R are hydrogen; R 3 is hydrogen alkyl, alkenyl, alkynyl, aralkyl or acyl; R 4 and R 5 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; R 6 and R 7 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; X is oxygen or sulphur or is SO or S0 2 and Az is a 1,2,4- or 1,3,4-triazole or imidazole ring; and isomers acid addition salts and metal complexes thereof.

Claim 4

Dependent Claim 147 words

Triazole and imidazole compounds having the general formula (I): wherein R 1 is hydrogen, alkyl, optionally substituted cycloalkyl, cycloalkylmethyl, alkenyl, heterocyclyl, aryl or aralkyl optionally substituted with halogen, nitro, alkyl, haloalkyl, haloalkoxy, alkoxy, phenyl, phenoxy, benzyl, benzyloxy, halophenyl or haloalkoxy; R 2 is any of the values for R 1 except optionally substituted phenyl when X is oxygen, and R 3 to R are hydrogen; R 3 is hydrogen alkyl, alkenyl, alkynyl, aralkyl or acyl; R 4 and R 5 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; R 6 and R 7 , which may be the same or different, are hydrogen, alkyl, alkenyl or optionally substituted aryl; X is oxygen or sulphur or is SO or S0 2 and Az is a 1,2,4- or 1,3,4-triazole or imidazole ring; and isomers acid addition salts and metal complexes thereof.

Claim 5

Dependent Claim 90 words

Triazole and imidazole compounds having the general formula (I):- wherein R 1 and R 2 , which may be the same or different, are alkyl, cycloalkyl, phenyl or benzyl optionally substituted with halogen, alkyl, alkoxy, phenyl, halophenyl, R 3 is hydrogen, or C 1-6 alkyl; R 4 and R 5 , which may be the same or different, are hydrogen, C 1-6 alkyl or allyl; R 6 and R 7 , are hydrogen; X is oxygen and Az is a 1,2,4-triazole ring; and acid addition salts and metal complexes thereof.

Claim 6

Dependent Claim 90 words

Triazole and imidazole compounds having the general formula (I):- wherein R 1 and R 2 , which may be the same or different, are alkyl, cycloalkyl, phenyl or benzyl optionally substituted with halogen, alkyl, alkoxy, phenyl, halophenyl, R 3 is hydrogen, or C 1-6 alkyl; R 4 and R 5 , which may be the same or different, are hydrogen, C 1-6 alkyl or allyl; R 6 and R 7 , are hydrogen; X is oxygen and Az is a 1,2,4-triazole ring; and acid addition salts and metal complexes thereof.

Claim 7

Dependent Claim 109 words

Triazole and imidazole compounds having the general formula (I):- wherein R 1 and R2, which may be the same or different, are alkyl, cycloalkyl, phenyl or benzyl optionally substituted with halogen, alkyl, alkoxy, phenyl, halophenyl, provided that R 2 is other than optionally substituted phenyl when X is oxygen, R 3 to R 7 are hydrogen; R 3 is hydrogen, or C 1-6 alkyl; R 4 and R 5 , which may be the same or different are hydrogen, C 1-6 alkyl or allyl; R 6 and R 7 are hydrogen; X is oxygen and Az is a 1,2,4- triazole ring; and acid addition salts and metal complexes thereof.

Claim 8

Dependent Claim 109 words

Triazole and imidazole compounds having the general formula (I):- wherein R 1 and R2, which may be the same or different, are alkyl, cycloalkyl, phenyl or benzyl optionally substituted with halogen, alkyl, alkoxy, phenyl, halophenyl, provided that R 2 is other than optionally substituted phenyl when X is oxygen, R 3 to R 7 are hydrogen; R 3 is hydrogen, or C 1-6 alkyl; R 4 and R 5 , which may be the same or different are hydrogen, C 1-6 alkyl or allyl; R 6 and R 7 are hydrogen; X is oxygen and Az is a 1,2,4- triazole ring; and acid addition salts and metal complexes thereof.

Claim 9

Dependent Claim 62 words

Triazole and imidazole derivatives as claimed in any of the preceding claims wherein in formula (I) R 1 is C 1-6 alkyl, phenyl (both optionally substituted with alkyl, alkoxy, phenyl, halogen or halophenyl); R 3 is hydrogen or C 1-6 alkyl: R 4 , R 5 , R 6 and R 7 are hydrogen or C l-6 alkyl; and X is oxygen.

Claim 10

Dependent Claim 59 words

Triazole and imidazole derivatives as claimed in any of the preceding claims provided that R 2 is other than optionally substituted phenyl when R 3 , R 4 , R 5 , R 6 and R 7 are hydrogen, X is oxygen, Az is 1,2,4-triazole or imidazole, and R 1 is alkyl, optionally substituted phenyl or optionally substituted cycloalkyl.

Claim 11

Dependent Claim 102 words

7 . A process for preparing the compounds defined in claims 1 to 6 and wherein R l , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Az in formula I are as defined above which comprises treating the epoxides of general formula (II) with 1,2,4-triazole or imidazole either in the presence of an acid-binding agent or in the form of one of its alkali metal salts in a convenient solvent; and, thereafter, oxidising those compounds wherein X=S to obtain those compounds wherein X is SO or SO 2 .

Claim 12

Dependent Claim 13 words

A process according to claim 7 wherein the oxidising agent is m-chloroperbenzoic acid.

Claim 13

Dependent Claim 77 words

A process according to claim 7 or 8 and wherein a compound of general formula (II) is reacted at 20-100° with sodium or potassium salt of 1,2,4-triazole or imidazole, the salt being prepared by adding either sodium hydride, a sodium alkoxide or potassium t-butoxide to 1,2,4-triazole or imidazole, in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide and thereafter isolating the product by pouring the reaction mixture into water and extracting into a suitable solvent.

Claim 14

Dependent Claim 64 words

A process as claimed in any of claims 7, 8 or 9 wherein the epoxides of general formula (II) wherein R 6 = R 7 = hydrogen are made by reacting a ketone of general formula (III) with dimethyl oxosulphonium methylide (Corey and Chaykovsky, J.Amer.Chem.Soc., 1965, 87, 1353-1364) or dimethyl sulphonium methylide (Corey and Chaykovsky, J.Amer.Chem.Soc., 1962, 84, 3782) by methods known per se.

Claim 15

Dependent Claim 50 words

A process as claimed in any of claims 7, 8, 9 or 10 wherein the epoxides of general formula (II) made by the epoxidation of an olefin of general formula (IV) using a standard oxidising agent such as hypochlorous acid, hydrogen peroxide or a peracid (e.g. peracetic or perbenzoic acid).

Claim 16

Dependent Claim 41 words

A process according to claim 11 wherein the olefin IV is made by treating the ketone of general formula (III) with= a Grignard reagent (V) in a convenient solvent such as ether, tetrahydrofuran or anisole and then dehydrating the intermediate alcohol.

Claim 17

Dependent Claim 50 words

A process for preparing the compounds defined in any of claims 1 to 6 which comprises treating the epoxide of general formula (VI) with an alkali metal salt of an oxygen or sulphur nucleophile (VII) in a convenient solvent such as dimethyl formamide and dimethyl sulphoxide at temperatures of 20-100°C.

Claim 18

Dependent Claim 44 words

A process as claimed in claim 13 wherein.the epoxides of general formula (VI) wherein R 4 = R 5 = H are prepared by reacting a ketone of general formula (VIII) with dimethyl oxosulphonium methylide or dimethyl sulphonium methylide by methods known per se.

Claim 19

Dependent Claim 222 words

A process according to claim 10 wherein the ketones of general formula (III) are made by: (a) Alkylation of the correspondingα-hydroxy ketones themselves made by methods known per se. (b) Grignard reaction of a compound R MgY on the appropriate nitrile R 2 XCR 4 R 5 CN. (c) Grignard reaction of a compound R 1 MgY on the appropriate acid chloride R 2 XCR 4 R 5 COCl. (d) Grignard reaction of a compound R l MgY on the appropriate aldehyde R 2 X CR 4 R 5 CHO to give the secondary alcohol followed by oxidation to give the ketone. (e) Treatment of the epoxide or the halohydrin R 1 CHOHCYR 4 R 5 with an anion R 2 X⊖ followed by oxidation of the alcohol to give the ketone. (f) Reaction of the α-halo ketone with an anion R 2 X 6 . (g) Treatment of the halo-ketal wherein R 8 and R 9 are alkyl or together form a ring with an anion R 2 X⊖ followed by acid hydrolysis to the ketone. (h) For ketones where R 1 = alkyl or aralkyl alkylating the acetylenic alcohol where R 10 is hydrogen, alkyl or aryl, followed by hydrolysis. (i) For ketones where R 1 = aryl by Friedel-Crafts reaction between an appropriately substituted benzene and the acid chloride

Claim 20

Dependent Claim 19 words

A process as claimed in claim 14 wherein the ketones of general formula (VIII) are made by known methods.

Claim 21

Dependent Claim 38 words

A process for preparing salts and metal complexes of the compounds of general formula (I) as defined in any of claims 1 to 6 which comprises reacting the uncomplexed compound with a metal salt in a suitable solvent.

Claim 22

Dependent Claim 37 words

A fungicidal or plant growth regulating composition comprising, as an active ingredient, a compound, or a salt or metal complex thereof, as defined in any of claims 1 to 6 together with a carrier or diluent thereof.

Claim 23

Dependent Claim 64 words

A method of combating fungal diseases in a plant, or of regulating the growth of a plant, which method comprises applying to the plant, to seed of the plant, or to the locus of the plant or seed, a compound or a salt or metal complex thereof as defined in any of claims 1 to 6 or a composition as defined in claim 17.

Claim 24

Dependent Claim 13 words

The compounds defined in any of claims 7 to 15 as novel intermediates.

Claim 25

Dependent Claim 55 words

A method of combating fungal diseases in a plant, which method comprises applying to the plant, to seed of the plant, or to the locus of the plant or seed, a compound as claimed in any of claims 1 to 6 or a salt or complex thereof, or a composition as claimed in claim 17.

Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them

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