RU96100845A

RU96100845A - METHOD OF ADDING PHYTOPATHOGENIC MUSHROOMS AND THE FIGHT AGAINST PLANT DISEASES, BENZOPHENON DERIVATIVES, METHODS OF THEIR PRODUCTION AND COMPOSITION ON THEIR BASIS

Info

Publication number: RU96100845A
Application number: RU96100845/04A
Authority: RU
Inventors: Куртце Юрген; Хелене Гертруд Рудольф Кристине; Шредер Людвиг; Альберт Гвидо; Эдит Элизе Рениг Аннерозе; Герхард Зивердинг Эвальд
Original assignee: Американ Цианамид Компани
Priority date: 1995-01-20
Filing date: 1996-01-19
Publication date: 1998-03-27

Claims

1. A method for suppressing phytopathogenic fungi or diseases caused by them, characterized in that said fungi are brought into contact with a fungicide-effective amount of a compound of formula I

where R ¹ represents a halogen atom, an optionally substituted alkyl or alkoxy group, a cyano or nitro group;
m is 0 or integers 1, 2, 3 or 4;
R ² independently represents a halogen atom, an optionally substituted alkyl or alkoxy group, a nitro group or, when R ¹ and R ^{2 are} attached to adjacent carbon atoms, R ¹ and R ² can together form an optionally substituted chain —CH = C - CH = CH, alkylene or oxyalkylene;
R ³ represents a hydrogen or halogen atom, cyano, carboxy, hydroxy or nitro, optionally substituted alkyl, alkoxy, alkenyl, alkylthio, alkylsulfinyl, alkylsulfonyl, or amino;
R ⁴ represents hydrogen or an optionally substituted alkyl or acyl group;
R ⁵ represents a hydrogen atom or a halogen atom, a nitro group, an optionally substituted alkyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, cycloalkyl, cycloalkyloxy, hydroxy, arylcosi, trialkylsilyoxy, -ONa, -OK, -OC (O) R ⁷ -, OCHR ⁸ C (O) R ⁷ , -OC (O) NR ⁸ R ⁹ , -S (O) ₂ R ⁸ , -OS (O) ₂ NR ⁸ R ⁹ -, OP (X ') (OR ⁸ ) OR ⁹ , -OP (X ¹ ) (R ⁸ ) R ⁹ , -S (O) R ⁸ , -S (O) ₂ R ⁸ , or R ⁴ and R ⁵ may together form an optionally substituted alkylene or alkyleneoxy chain;
n is 0 or an integer 1 or 2;
R independently represents a halogen atom or an optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkoxy, hydroxy, —OC (O) R ¹ ⁰ group, or when R ⁵ and R ^{6 are} attached to adjacent carbon atoms , R ⁵ and R ⁶ together can form an optionally substituted chain —CH═CH — CH = CH— or oxyalkyleneoxy chain;
R ⁷ represents a hydrogen atom or an optionally substituted alkyl or alkoxy group;
R ⁸ , R ⁹ and R ¹ ⁰ independently of one another represent a hydrogen atom, alkyl, aryl or aralkyl or R ⁸ and R ⁹ together can form an alkylene chain, optionally interrupted by an oxygen or nitrogen atom,
X represents an oxygen or sulfur atom or a NOR group;
X ¹ represents an oxygen or sulfur atom;
Y represents an oxygen or sulfur atom or a sulfonyl or sulfinyl group;
R represents a hydrogen atom or an optionally substituted alkyl, aralkyl, aryl or acyl group.

2. A method according to claim 1, wherein the compound of formula I is selected from the group including:
2,3,5,6-tetramethyl-4 ', 5', 6'-trimethoxy-2'-methylbenzophenone;
2,6-dichloro-4 ', 5'-dimethoxy-2'-methylbenzophenone-0-methyloxime;
2,6-dichloro-5'-tert-butoxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5 ', 6'-di-n-butoxy-4'-methoxy-2'-methylbenzophenone;
2'-benzoylmethoxy-2,6-dichloro-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2'-allyloxy-2,6-dichloro-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2'-benzyloxy-2,6-dichloro-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2'-butoxy-2,6-dichloro-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2'-cyclohexylmethoxy-2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-benzophenone;
2'-cyclopentyloxy-2,6-dichloro 3 ', 4'-dimethoxy-6'-methylbenzophenone;
2,6-dichloro-2 ', 3', 4'-trimethoxy-6'-methylbenzophenone;
2,6-dichloro-2'-ethoxy-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2,6-dichloro-2'-heptyloxy-3 ', 4'-dimethoxy-6'-methylbenzophenone;
2,6-dichloro-2'-hexyloxy-3'4'-dimethoxy-6'-methylbenzophenone;
2,6-dichloro-3 ', 4'-dimethoxy-2' - (2-methoxyethoxy) -6'-methylbenzophenone;
2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-2' - (3-methylbutoxy) benzophenone;
2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-2' - (prop-2-ynyloxy) benzophenone;
2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-2'-pentyloxybenzophenone;
2,6-dichloro-3 ', 4'-dimethoxy-6'-methyl-2'-propoxybenzophenone;
2,6-dichloro-4 ', 5'-dimethoxy-2'-methylbenzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5 '- (3-methylbutoxy) benzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5 '- (prop-2-yloxy) benzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5 '- (octyloxy) benzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5 '- (pentyloxy) benzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5'-propoxybenzophenone;
2,6-dichloro-4'-methoxy-2'-methyl-5'-trimethylsilanylmethoxybenzophenone;
2,6-dichloro-5'- (1-ethylpropoxy) -4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5'-difluoromethoxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5'-ethoxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5'-heptyloxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5'-hexyloxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-4 ', 5'-dimethoxy-2'-methylbenzophenone-O-n-propyloxime;
2,6-dichloro-5'-isobutoxy-4'-methoxy-2'-methylbenzophenone;
2,6-dichloro-5'-isopropoxy-4'-methoxy-2'-methylbenzophenone;
5'-butoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;
5'-cyclohexylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;
5'-cyclohexyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;
5'-cyclopentyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone;
5'-cyclopropylmethoxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone or
5'-decyloxy-2,6-dichloro-4'-methoxy-2'-methylbenzophenone.

3. The compound of formula Ia

where R ¹ represents a halogen atom, an optionally substituted alkyl group or a cyano group;
m takes integer values 1, 2, 3, or 4;
R ² independently represents a halogen atom, an optionally substituted alkyl or alkoxy group, or when R ¹ and R ^{2 are} attached to adjacent carbon atoms, R ¹ and R ² can together form an optionally substituted chain —CH = C – CH = CH or alkylene or oxyalkylene group;
R ³ represents a hydrogen or halogen atom, an optionally substituted alkyl, alkoxy, alkenyl, alkylthio, alkylsulfinyl, alkylsulfonyl, cyano, carboxyl, hydroxy and nitro, or an optionally substituted amino group;
R ⁴ is an optionally substituted alkyl or acyl group;
R ⁵ is a halogen atom, an optionally substituted alkoxy, alkenyloxy, alkynyloxy, alkylthio group, cycloalkyl, cycloalkyloxy, trialkylsilyoxy, -ONa, -OK, -OC (O) R ⁷ , -OCHR ⁸ C (O) R ⁷ , -OC (O) NR ⁸ R ⁹ , -OS (O) ₂ R ⁸ , -OS (O) ₂ NR ⁸ R ⁹ , -OP (X ¹ ) (OR ⁸ ) OR ⁹ , -OP (X ¹ ) ( R ⁸ ) R ⁹ ,
—S (O) R ⁸ , —S (O) ₂ R ⁸ , or R ⁴ and R ⁵ may together form an optionally substituted alkylene or alkyleneoxy chain;
n is 0 or takes integer values 1, 2;
R ⁶ independently represents an optionally substituted alkoxy, hydroxyl or —OC (O) R ¹ ⁰ group or, when R ⁵ and R ^{6 are} attached to adjacent carbon atoms, R ⁵ and R ⁶ together can form the chain —CH = CH- CH = CH- or optionally substituted oxyalkylene chain;
R ⁷ represents a hydrogen atom or an optionally substituted alkyl or alkoxy group;
R ⁸ , R ⁹ and R ¹ ⁰ independently of one another represent a hydrogen atom or an alkyl group, or R ⁸ and R ⁹ together can form an alkylene chain, optionally including an oxygen or nitrogen atom;
X represents an oxygen or sulfur atom or a NOR group;
X ¹ represents an oxygen or sulfur atom;
Y represents an oxygen or sulfur atom or a sulfonyl or sulfinyl group;
R represents a hydrogen atom or an optionally substituted alkyl, aralkyl, aryl or acyl group, provided that when X is an oxygen or sulfur atom and
i) when R ¹ is a halogen atom, then R ² must be different from the halogen atom or must represent no more than one alkyl or alkoxy group;
(ii) when R ¹ is an alkyl group, then R ² must be different from alkyl;
(iii) when m is 1, then R ² should not be an alkoxy group;
(iv) when R ³ is a substituted alkenyl group, then R ³ as a substituent must contain a group other than alkoxy or acyl.

(v) when R ³ is a haloalkyl group, then R ¹ and R ² must not be a haloalkyl group and
(vi) when Y represents an oxygen atom, then R ³ and R ⁵ both must not be hydrogen and n must be 1 or 2.

4. The compound according to claim 3 of formula Ib

where Q represents a hydrogen or chlorine atom, R represents a hydrogen atom, a C ₃ -C ₈ cycloalkoxy group or a C ₁ -C ₈ alkoxy group, optionally substituted by one or more fluorine atoms, or one substituent from the group comprising: phenyl, phenoxy, a phenylthio or benzyloxy group, where the phenyl moiety may contain a substituent from the group including halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, trifluoromethyl and / or trifluoromethoxy, and R 'is hydrogen or C ₁ -C ₄ -alkyl, optionally containing one or more substituents from the group, inc sistent halo C ₁ - C ₄ alkoxy, phenyl, phenoxy or phenylthio, wherein the phenyl moiety may have a substituent from the group consisting of halogen, C ₁ - C ₄ alkyl, C ₁ - C ₄ alkoxy, trifluoromethyl or trifluoromethoxy , provided that when Q and R are hydrogen, R 'should not be methyl.

5. The compound according to claim 3 of formula Ic

where Q and Q 'independently represent a hydrogen atom or a methyl group; R represents a hydrogen atom, a C ₃ -C ₈ cycloalkyl group or a C ₁ -C ₈ alkoxy group, optionally substituted by one or more fluorine atoms, phenyl, phenoxy, phenylthio or benzyloxy, where the phenyl moiety may contain one or more substituents from the group consisting of halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy-, trifluoromethyl or trifluoromethoxy; R 'represents hydrogen or C ₁ - C ₁ ₀ -alkyl, optionally containing one or more substituents from the group comprising halogen, C ₁ - C ₄ -alkoxy, phenyl, phenoxy or fininylthio groups, where the phenyl moiety may contain one or more substituents from the group including halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, trifluoromethyl or trifluoromethoxy groups.

6. The method according to claim 1 of protecting a plant from damage caused by a phytopathogenic fungus, or from a disease that it causes, characterized in that it includes application to the plant, its seeds, or tubers, or to the place where it grows or where it will be planted seeds or tubers, a fungicidal effective amount of a compound of formula I

7. A fungicidal composition that includes an agriculturally acceptable carrier and a fungicidal acceptable amount of the compound of formula I

where X, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n have the meanings indicated in item 1.

8. The composition according to claim 7, where X represents an oxygen atom or a group of NOR; Y is an oxygen atom; R ¹ , R ² , R ³ and R ⁴ each independently represents a halogen atom or C ₁ - C ₆ -alkyl; R ⁵ and R ⁶ independently represent an optionally substituted C ₁ -C ₆ alkoxy group; m takes integer values 1 or 3 and n is 0 or 1.

9. The method of obtaining the compounds of formula I

where X represents an oxygen atom and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y, m and n have the meanings defined in claim 1, which includes the interaction of the compounds of formula II

with a compound of formula III

where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Y, m and n have the meanings given for formula I, and one of the substituents Z ¹ and Z ² is a hydrogen atom, and the other is the COCl group, or one is the magnesium halide MgHal, where Hal is a bromine or iodine atom, and the other is a COCl group.

10. The method of obtaining the compounds of formula Ib

where X is a group of NOH; m is 0 or an integer 1, 2, or 3; Y represents an oxygen atom; R ⁴ is methyl; R ⁵ - methoxy and R ³ , R ⁶ and n have the meanings defined in claim 1, which includes the interaction of the compounds of formula VI

with at least one molar equivalent of the compound of formula VII

in the presence of at least one molar equivalent of aluminum chloride and a non-polar solvent for the formation of an intermediate product and hydrolysis of the indicated intermediate compound in the presence of acid and water to obtain the product - a compound of formula Ib