CA2062273A1 - Microbicidal compositions - Google Patents

Abstract

Microbicidal compositions Abstract Compositions comprising, as active ingredients, compounds of the formula I

(I) in which:
X1, X2 and X3 independently of one another are hydrogen, methyl, methoxy, methylthio, halogen or nitro;
A is C1-C2alkyl which is substituted by a maximum of 3 X-C1-C4alkyl groups, methyl which is substituted by 2 or 3 halogen atoms, ethyl which is substituted by hydroxyl and/or not more than 4 halogen atoms; vinyl which is unsubstituted or substituted by not more than 3 halogen atoms; furthermore ethynyl, propargyl, formyl, acetyl, acetyl which is substituted by not more than 3 halogen atoms, or one of the groups C(R)=N-N(R2)R3, C(N=N-U1)=N-NH-U1, CH(R)-[N(R1)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(=)nR3, CH(R)-O-N=C(R1)R2, CH(R)-O-N=C(CN)-CONH-R5, C(R6)=N-(O)nR, CH(R)-Y-E-R3, CO-[CtOR)2]nQ, CtQ)=CH-OR or T-Q;
in which furthermore:
n is zero or 1;
X and Y independently of one another are oxygen or sulfur, R and R1 independently of one another are hydrogen or C1-C2alkyl;
R2 is hydrogen, C1-C8alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, benzyl or cyano;
R3 is hydrogen, C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, benzyl or is an aryl radical U;
R4 is hydrogen, C1-C6alkyl, Si(C1-C6alkyl)3 or OCOC1-C3alkyl;

R5 is hydrogen or CONHR1;
R6 is N(R1)R2, hydrazino or Q;
E is CO or SO2;
U and U1 independently of one another are a phenyl radical which is unsubstituted or monosubstituted or polysubstituted by identical or different substituents from the series comprising methyl, methoxy, halogen, trifluoromethyl, nitro or cyano;
T is C1-C2alkylene, methylene which is substituted by amino, hydroxyl or halogen, the substituents being independent of one another, or is ethenylene which is unsubstituted or substituted by halogen or cyano;
Q is COXR or cyano.

The novel compositions have crop-protecting properties and are particularly suitable for protecting plants against infestation by phytopathogenic microorganisms such as fungi, bacteria and viruses.

Description

- . 2a~2~

Microbicidal compositions The present invention relates to novel substituted benzo~ ,3-thiadiazole derivatives of the ~ormula I below. The invention furtherrnore relates to the preparation of these substances and to the compositions comprising, as active ingredients, at least one s)f these compounds. Moreover, the invention relates to the preparation of the abovementioned compositions and to the use of the active ingredients or of the compositions for protecting pl~nts against infestations by harrnful microorganisms, in particular plant-injurious fungi.

The compositions according to the invention comprise, as active ingredients, compounds of the general formula I

~S~ .
X~ N (I) in which:
Xl, X2 and X3 independently of one another are hydrogen, methyl, methoxy, methylthio, halogen or nitro;
A is Cl-C2alkyl which is substituted by a maximum of 3 X-Cl-C4alkyl groups, methyl which is substituted by 2 or 3 halogen atoms, ethyl which is substituted by hydroxyl and/or not more than 4 halogen atoms, vinyl which is unsubstituted or substituted by not more than 3 halogen atoms; furthermore ethynyl, propargyl, formyl, acetyl, ~urtherrnore acetyl which is substituted by not more than 3 halogen atoms7 or one of the groups C(R)=N-N(R2)R3, C(N=N-UI)=N-NH-UI, CH(R)-[N(RI)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(RI)R2, CH(R)-O-I~=C(CN)-CONH-R5, C(R6)=N-(O)nR, CH(R)-Y-E-R3, CO-[C~OR)2]nO, C~Q)=CH-OR or T-Q;
in which furtherrnore:
n is zeroor 1;

.: .... ~

X and Y independently of one another are oxygen or sulfur;
R and Rl independently of one another are hydrogen or Cl-C2alkyl;
R2 is hydrogen, Cl-C8alkyl, C3-C6alkenyl, C3-C6alkynyl, (:13-C7cycloalkyl, benzyl or cyano;
R3 is hydrogen, C~-C6alkyl, C3-C6aLkenyl, C3-C6alkynyl, C3-C7cycloalkyl, benzyl or is an aryl radical U;
R4 is hydrogen, Cl-C6alkyl, Si(CI-C6alkyl)3 or OCOC~-C3alkyl;
Rs is hydrogen or CONHRI;
R6 is hydrazino, N(Rl)R2 or Q;
EisCOorso2;
and ~1 independently of one another are a phenyl radical which is unsubstituted or monosubstituted or polysubstituted by identical or different substituents from the series comprising methyl, methoxy, halogen, trifluoromethyl, nitro or cyano;
T is Cl-C2alkylene, methylene ~,vhich is substituted by amino, hydroxyl or halogen, the substituents being independent of one another, or is ethenylene which is unsubstituted or substituted by halogen or cyano;
Q is CO~R or cyano.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, and then in the sequence chlorine, bromine and iodine. Halogen as substituent in individual radicals can be represented up to 3 times.

Alkyl itself or as a component of another substituent is to be understood as meaning straight-chain and branched alkyl radicals. Depending on the number of carbon atoms indicated, these represent for example the following preferred groups: methyl, ethyl as well as the isomers of propyl, butyl, pentyl or hexyl, for example isopropyl, isobutyl, tert-butyl, sec-butyl or isopentyl.

Akenyl is, for example, prop-1-enyl, allyl, but-1-enyl, but-2-enyl or but-3-enyl, and alkynyl is, for example, prop-2-ynyl, but-1-ynyl or pent-4-ynyl.

Cycloalkyls which may be mentioned are, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane or cycloheptane, preferably cyclopropane, cyclopentane and cyclohexane.

Based on their particular crop-protecting properties, the active ingredients of the forrnula I

, .

, . , ~, ~ :

- ~ ~9 can be divided into the following, preferred groups:

1. Compounds in which:
Xl, X2 and X3 independently of one another are hydrogen or fluorine;
A is Cl-C2alkyl which is substituted by a maximum of 3 X-CI-C4alkyl groups, methyl which is substituted by 2 or 3 halogen atoms, ethyl which is substituted by hydroxyl and/or not more than 4 halogen atoms, vinyl which is unsubstituted or substituted by not more than 3~alogen atoms; furthermore ethynyl, propargyl, formyl, acetyl, or one of the groups CtR)=N-N(R2)R3, C(N=N-UI)=N-NH-U, CH(R)-~N(RI)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(RI)R2, CH(R)-O-N=C(CN)-CONH-Rs, C(R)6=N(O)nR, CH(R)-Y-E-R3, CO-[C(OR)2]nCOxR, C(Q)=CH-OR or T-Q;
in which furthermore:
niszeroorl;
X and Y are oxygen;
R and Rl independently of one another are hydrogen or Cl-C2alkyl;
R2 is hydrogen, Cl-C"alkyl, C3-C4alkenyl, C3-C~alkynyl, C3-C6cycloalkyl or benzyl;
R3 is hy(lrogen, Cl-C4alkyl, C3-C~alkenyl, C3-C~alkynyl, C3-C6cycloalkyl o~ a phenyl radical which is substituted by identical or clifferent substituents from the series comprising methyl, halogen or trifluoromethyl;
R4 is hydrogen, Cl-C3alkyl or Si(CI-C2alkyl)3;
R5 is hydrogen or CONHC~-C3alkyl;
R6 is N(R)RI, hydrazino or Q;
U and Ul independently of one another are a phenyl radical which is substinlted by methyl, halogen, nitro or trifluoromethyl;
E is CO;
T is methylene, methylene which is substituted by amino or ethenylene;
Q is CVOR or cyano.

2. Compounels in which:
Xl, X2 and X3 are hydrogen;
A is methyl which is substituted by a maximum of 2 X-CI-C4alkyl groups, methyl which is substituted by 2 or 3 fluorine or chlorine atoms, ethyl which is substituted by hydroxyl or 1 to 4 halogen atoms, or forrnyl, acetyl, or one of the groups C(R)=N-N(R2)R3, C~(R)~[N(RI)]n~N(R2)R3~ C(R)(CN)OR4, C(~)=N-R3, CH(R)-O-N=C(Rl)R2, CH(R)-O-N=C(CN)-CONHRs, C(R6)=N(O)nR, CH(R)-Y-E-R3, CO[C(OR)2]nCOXR, C(COOR)=CH-OR or T-Q;

2 ~

in which furthermore:
n is 1 ;
X is oxygen;
R ;md Rl independently of one another are hydrogen or methyl;
R2 is hydrogen, C1-C2alkyl, allyl, propargyl, cyclopropyl or benzyl;
R3 is hydrogen, Cl-C2allcyl, allyl, propargyl, cyclQpropyl, or a phenyl radical which is substituted by identical or different substituents from the series comprising methyl, fluorine, chlorine or trifluoromethyl;
R4 is hydrogen, Cl-C2alkyl or Si(CH3)3;
Rs is hydrogen or CONH-CI-C2alkyl;
R6 is amino or Q;
Y is oxygen;
E is CO;
T is methylene or cyano;
Q is COOCH3 or CN

3. Compounds in which:
X~, X~ and X3 are hydrogen;
A is methyl which is substituted by a maximum of 2 X-CI-C2alkyl groups, methyl which is substituted by 2 or 3 fluorine atoms, ethyl which is substituted by hydroxyl or chloline, or formyl, or one of the groups C(R)=N-I`I(R2)R3, CH(R)-[N(R,)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(RI)R2, C(R6)=N-OR, CH(R)-Z-E-R3, CO[C(OR)2]nCOXR or T-Q;
in which furthermore:
n isl;
X is oxygen;
R and Rl independently of one another are hydrogen or methyl;
R2 is hydrogen, methyl, allyl, cyclopropyl or benzyl;
R3 is hydrogen, methyl, allyl, cyclopropyl, or a phenyl radical which is substitu~ed by identical or different substituents from the series comprising methyl, fluorine, chlorine or ~rif luoromethyl;
R4 is hydrogen, methyl or Si(CH3)3;
Rs is hydrogen or CONH-CH2-CH3;
R6 is amino;
Y is oxygen;
EisCO;

. :
;
;

..~

2 ~

T is me~hylene;
Q is cyano or COOCH3.

The following active ingredients of the forrnula I are distingwished by particularly advantageous crop-protecting properties:
7-formyl-1,2,3-benzothiadiazole; (known) 7-acetoxymethyl- 1 ,2,3-benzothiadiazole;
7-[methoxyimino-(2-cyanoacetamidyl)]- 1 ,2,3-benzothiadiazole;
7-(N-methoxyiminomethyl)- 1 ,2,3-benzothiadiazole;
7-(N-methoxyiminohydroxymethyl)- l ,2,3-benzothiadiazole;
7-methoxymethyl- 1 ,2,3-benzothiadiazole;
3-(7-benzo-1 ,2,3-thiadiazolyl)acrylic acid;
7-cyanomethyl- l ,2,3-benzothiadiazole;
7-trichloromethyl- 1 ,2,3-benzothiadiazole;
7-dichloromethyl- 1 ,2,3-benzothiadiazole;
benzo-1 ,2,3-thiadiazole-7-(N-hydroxyc~rboximide-amide);
benzo-1,2,3-thiadiazole-7-(N-methoxyhydroxamic acid);
2-(benzo- 1,2,3-thiadiazolyl)-2-hydroxyimino;lcetonitrile;
S-nuoro-benzo- I ,2,3-thiadiazole-7-c.lrb;lldehy(le;
6-fluoro-benzo- 1 ,2,3-thiadiazole-7-carbaldehyde;

4-fluoro-benzo- l ,2,3-thiadiazole-7-carbaldehyde;
N,N-diphenyl-C-~ benzo- 1 ,2,3-thiadiazol-7'yl~formazane;
7-acetylbenzo- 1 ,2,3-thiadiazole;
7-(bromoacetyl)benzo- 1 ,2,3-thiadiazole.

Compounds which come under the fonnula I are novel with the exception of:
7-fonnyl- 1,2,3-benzothiadiazole;
7-acetyl- 1,2,3-benzothiadiazole;
6-chloro-7-formyl- 1 ,2,3-benzothiadiazole;
6-methylthio-7-forrnyl- 1 ,2,3-benzothiadiazole;
4-bromo-6-chloro-7-formyl- 1 ,2,3-benzothiadiazole;
6-methoxy-7-forrnyl- 1 ,2,3-benzothiadiazole;
7-hydroxyimino- 1 ,2,3-benzothiadiazole;
~-methoxy-7-oximino-1 ,2,3-benzothiadiazole, 7-dibromoacetyl-1,2,3-benzothiadiazole.

-` ` 2~2~

The novel compounds form a special part of the present invention.

The compounds which were designated above as not novel are known from the following literature: J. Chem. Res. 1980, 191 and 2845; J. Chem. Soc. 1971, 3994; British Patent Application 1 176 799; Dutch Patent Specification 67 16077, and German Offenlegungsschrift 1 695 786.

The compounds of the forrnula I are prepared as follows:

I . I Nitration of a compound of the formula II

Al Hal Xl~ (O

with HNO3 with or without an addition of H2SO4 and/or solvents such as CH2CI2, at temperatures from -20 to ~0C, to give a compound of the formula III

,~ Hal X2~ NO2 (III);

1.2 Reaction of a compound of the forrnula III with a compound of the forrnula IIIa MSL (IIIa) in inert solvents with or without a base at temperatures of -5 to 50C to give a compound of the formula IV

~S-L
X1 ~NO~ (IV);

.

C,~ 3 1.3 Reduction of a compound of the formula IV with hydrogen in the presence of ac~talyst or with iron powder in acetic acid in inert solvents at temperatures from 0 to 120C to give a compound of the formula V

(V);

1.4 Diazotisation of a compound of the formula V with NaNO2 in the presence of an acid in water and additionally with inert solvents or without the latter, at temperatures of -3~) to 50C, to give a compound of the formula la X~ ~ N (1~1), where in the above formulae At means the radicals A menlioned under formula I with the exception of those which comprise free hydroxyl, thiol or NH groups, and lhose groups which are unstable in aqueous-acidic medium, for example the acetals or ketals, and Xl, X2 and X3 have the meanings given under formula I;

2.1 Compounds of the formulae Ib, Ic and Id X~X3 2 X3 ~X3 (Ib) (Ic) (Id) are prepared:

,.
~, , 7 ~ ~

2.1. I . by reacting a compound of the formula VI
COOR

2 X3 (Vl) a) with a reducing agent in inert solvents at -20 to 120C, preferably 0 to 80C, for example.

b) with sodium borohydride in inert solvents, for example tetrahydrofuran or dioxane, in the presence of water at -20C to 100C, preferably 0 to 80C, to give a compouncl of the formula Ib; or by reacting the acid chloride of the formula VII' COCI

2 X3 (VII') with hydrogen in a Rosenmund reaction in an inert solvent, for example tetrahydrofuran, in the presence of a base, for example lutidine, by means of a catalyst, for example palladium on barium sulfate, at -20 to 120C, preferably 0 to 120C, furthennore preferably 0 to 80C, to give a compound of the formula Ib, and 2.1.2 by oxidising a compound of the formula Ib with an oxidant, for example manganese dioxide, in an inert solvent, for example chlors~form, or cerium ammonium nitrate in a mixture of acetic acid and water at 0 to 110C? preferably 20 to 100C, to give a compound of the formula Ic.

2.1.3 by reacting a nitrile of the forrnula ~

.;

~$~

CN

2 X3 (V) or a hydroxamic acid derivative of the formula VIII

C1-C4alkyl O=C-N-OC~-C4alkyl (VIII) X ~ ~ N

with a Grignard reagent, CH3Mg-h;llogen, in an inert solvent, for example an open-ch.lin or cyclic ether (for example tetrahydrofuran or dioxane) at -50 to 130~C, preferably -10 or 80C, to give a compound of the formula Id, where the radicals Xl, X2 and X3 which occur in the above-described fonnulae have the meanings given under formula I and R in formula VI is hydrogen or methyl;

3.1 Compounds of the forrnula Ie C~-C2alkylene-Hal Xl ~ N (Ie) are prepared:

by reacting a compound of the formula Ib' .. . . .
:.... .. ... ..

, ~
.,, . ,. :.. :
,; : ~
:

20~ih~7~

Cl-C2alkylene-OH :.

X'x, ~XC3S~,N (Ib ) with a halogenating agent, for example thionyl halide, in inert solvents, such as dichloromethane, in the presence of a base, for example pyridine at -20 to 150C, where Hal is halogen and the radicals Xl, X2 and X3 have the meanings given under formula I;

3.2 Compounds of the formula If HC(Hal)2 Xl ~ N (I

are prepared:

by reacting a compound of the formula Ic CHO

~ S (Ic) with a halogenating agent, for example thionyl halide, in inert solvents, for example dichloromethane, in the presence of a base, for example pyridine, at -20 to 150C, where Hal is halogen and ~he radicals Xl, X2 and X3 have the meanings given under formula I
3.3 Compounds of the formula Ig .
. . .
.
.

- . .': '~' ' : ' .

.' ; : :

C(Hal)3 X2 X3 (Ig) are prepared: ;
3.3.1 by reacting a compound of the forrnula VI' COOH
~ S~
X, ~--N (Vl') with a halogenating agent, for example phosphorus pentahalide, phenylphosphorus oxydichloride or phenyleneoxyphosphorus dichloride, in inert solvents or without the latter, at 20 to 250C, preferably 80 to 200C; or 3.3.2 by reacting a compound of the formula Ig with sulfur tetrafluoride in the presence of hydrofluoric acid in an autoclave at 0 to 250C, where Hal is halogen and R is hydrogen or methyl and the radicals Xl, X2 and X3 have the meanings given under forrnula l;

3.4 Compounds of the formula Ih HO-CH-C(Hal)3 X2 X3 (Ih) are prepared by reacting a compound of ~he formula Ic with 2,2,2-trihaloacetic acid in dipolar aprotic solvents, for example hexamethylphosphoric triamide or dimeLhyl sulfoxide, at 0 to 150C, preferably 20 to 100C; and 3.5 Compounds of the formula li , , ~ ; . ~ : ,.::: : . , 2 ~ ~ 2 2 ~) ~

O=C-C(Hal)3 ¢~ N (li) are pRpared:

3.5.1 by reacting a compound of the formula Id with a halogenating agent, for example elemental halogen or sufonyl halide, with or without an addition of free radicals, or 3.5.2 by oxidising a compound of the forrnula Ih with an oxidant, for example MnO2 or pyridinium chlorochromate, in an iner~ solvent such as chloroform, at 20 to 150C; where in the above formulae E~al is fluorine, chlorine, bromine or iodine;

4. Compounds of the formulae Ikl and Ik2 O=C-CH2Hal o=C-cH(Hal)2 X~ N X~C N

~Ik~ k2) are prepared by reacting in each case one compound of the formula Id with stoichiometrically matched amounts of a halogenating agent, for example elemental halogen or sulfonyl halide, with or without an addition of free radicals, where Hal is halogen and Xl, X2 and X3 have the meanings given under formula I; and 5.1 Compounds of the formula Ill C1 -C2alkylene-CN

Xl ~C "N (Ill) . .

7 ~

are prepared by reacting compounds of the formula le with cyanide compounds of the formula MCN in inert solvents at -10 to 120C, it also being possible for the reaction to be carried out in a 2-phase system, for example in CHC13/H2O, in the presence of a quaternary ammonium salt, for example tetrabutylammonium chloride or tetrabutylammonium iodide; and 5.2 Compounds of the formulae Il2 and Il3 C1-C2alkylene-COOH Cl-C2alkylene-COOR
S ~ S

(Il2) ll13) are preparecl by hydrolysing nitriles of the formula Ill to give the compollnds of the fonnula Il2, and esterification thereof with compounds of the formula ROH, where in the above formulae M is an alkali met~l cation or ammonium cation, R is Cl-C4alkyl and Xl, X2 and X3 have the me.mings given under formula I;

6.1 Compounds of the formulae Iml and Im2 ~ (COXR)a H-C=C ~ (CN)b N
(Iml) ~ , ' ' ' ~; ` ~

? 1~ rl ~3 H3C-C=CH3 COXR/CN

~_ S~

~N

(Inn2) are prepared by condensing compounds of the forrnula Ic or Id H-C=O

X, X~ S~N

(Ic) CH3-C=O

X, ~1--S\N
~--N

(Id) wi~h compounds of the formula H2~ (CXR)a in the presence of catalysts, for example ammonium acetate or lower organic carboxylic acids, as well as bases, for example pyridine or piperidine, with or without an addition of ; .

, :

2 ~ 2 7 ~

solvents, for example toluene, with or without separation of the water formed, for example by azeotropic distillation or by using a molecular sieve, where (a+b) = 2 and a = (2-b) and R, X, Xl, X2 and X3 h~ve the meanings given under formula I.

If ~iesired, decarboxylation (Knoevenagel reaction) can be effected when a suitable malonic acid derivative or cyano acetic acid derivative is used as the active methylene component. This decarboxylation can be effected in one reaction step or in another reaction step by heating to 30 to 300C with or without inert solvents, following hydrolysis of a COXR- or CN- group to give the COOH- group; and 7.1 Compounds of the formula Inl R

I
NC-C-OH

2 X3 (Inl) are prepared by reacting compo~lnds of the forrnulae Ic and Id with alkali metal cyanide or hydrogen cyanide in an inert solvent, for example tetrahydrofuran or methanol, with or without an addition of sodium hydrogen sulfite at -20 to 140C, prefer~bly 0 ~o 90C, or by hydrolysis of silyl esters of the forrnula In2 R
I

NC-C-OSi(C1 -C4alkyl)3 ~ N (In2) with dilute mineral acids, for example HCI, in inert solvent at -20 to 12ûC;

7.2 Compounds of the formula In2 are prepared by reacting aldehydes of the formula Ic or ke~ones of the formula Id with trialkylsilyl cyanide in inert solvents, for example tetrahydrofuran, dioxane, chloroform or dichloromethane, preferably with an addition of , ~ ' -. ; , 2 ~ 1 S3 catalytic amounts of a metal salt, for example ZnI2, at -30 to 130C, preferably -10C to 100C;

7.3 Compounds of the formula In3 R O
l 11 NC-C-O-C-C1 -C4alkyl X2 X3 (In3) are prepared by reacting compounds of the formula Inl with acid chlorides or acid anhydrides in the presence of a base, for example triethylamine, and a catalyst, for example 4-dimethylaminopyridine; and 7.4 Compounds of the formula In4 R
I

NC-C-O-C1 -C~alkyl ~_S~
X1~ ,N (In4) are prepared:

7.4.1 by reacting compounds of the formula Inl with an alkylating agent, for example a Cl-C4alkyl halide, preferably a Cl-C4alkyl iodide, in the presence of a base, for example triethylamine or alkali metal carbonate or alkaline earth metal carbonate, in inert solvents at-20 to 100C; or 7.4.2 by reacting acetals of the formula In~;

, .. .
. .
-. , .

- ~` 2~ 2~3 O-G 1 -C4alkyl R-C/
¦ O-C1-C4alkyl X1 ~N (In~) with tri(CI-C4alkyl)silyl cyanides in the presence of a Lewis acid, for example boron tri~luoride etherate, in inert solvents at -20 to 150C;

8.1 Compounds of the forrnula lo O=C-CN

X1 ~C N (lol) ~re prepared by reacting compounds of the formula IX
O=C-Hal X ~ ~ N (IX) X2 x with rnetal salts of the formula Mm~(CN)m, in which M is a metal cation, for example Nz~, K~3, Ag33 or Pb2~), in inert solvents at -20 to 120C, where m is 1 or 2 and Hal is halo~en;

8.2 Compounds of the formula Io2 o O=C-CXR

S

, - . ~ . , . ~

. ~
.., - . . ;~
.

-2 ~

are prepared:

8.2.1 by oxidising corresponding cc-hydroxy compounds, using an oxidant, for example manganese dioxide or pyridinium chlorochromate; or O.2.2 by acid hydrolysis of compounds of the formula Ii or of compounds of the formula Iol with di}ute bases, for example solutiolls of alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides or alkaline earth metal carbonates, with or without an addition of inert solvents at -10 to 150C, preferably 20 to 100C; or 8.2.3 by reacting compounds of the formula Iq HON=C-COXR

Xl ~ "N (Iq) with excess aqueous formaldehyde or with acetone in the presence of an acid, for example HCl, and with or without an addition of an oxidant, for example dichlorodicyanobenzoquinone, selenium dioxide or pyridinium chlorochromate;

8.2.4 by reacting compounds of the formula Ix2 H
Hal-C-COXR

~X~ (Ix2) with alkali metal azide in inert solvents, for example dimethylformamide, at -20 to 50C, to give compounds of the formula ~;

.,,, : ~ , :
:
:

~a~7~ ~

-HN=C-COXR

Xl ~ N

followed by aqueous hydrolysis with or without an addition of a catalyst, ~or example CuS04; and 8.3 Compounds of the forrnula lo3 O=C[C(OR)2~COOR
X ~S~

are prepared by reacting compounds of the forrnula Vll O=C-Hal Xl ~ N (Vll) with a tetraalkoxyethylene of the formula RO OR
~ .
RO OR

in inert solvents, for example toluene, at 20 to 220C; where Hal is halogen, X is oxygen or sul~ur and R is C2-C4alkyl, and Xl, X2 and X3 have the meanings given under formula I; :

9.1 Compounds of the formula Ip .. ; .. . :.
... .
, .. . . .. .

, ,' ! ;, .:: ', . : ' ~ ' ' ' ', : : ' " ':

~` "' '" ':~

- 2~227~

C1-C2alkylene-X-ER3 X, ~ ,N (Ip) are prepared:

9.1.1 '~y reacting compounds of the fonnula Ib with acid chlorides of the formula R3-E-Hal or acid anhyd;ides of the formula (R3-E)20 in the presence of a base, for example triethylamine, with or without an addition of a catalyst, for example 4-dimethylaminopyridine, in an inert solvent, for example dichloromethane, at -20 to 150C; or 9.1.2 by reacting compounds of the formula Ie with alkali metal salts of the fo;mula R3COXM in a dipolar, aprotic solvent, ~or example N,N-dimethylformamide or dimcthylsulfoxide, at -20 to 150C; where X, E and R3 as well as Xl, X2 and X3 have the meanings given under formula I;

10.1 Compounds of the fomula Iq R6'-C=N-OR3 ~ N (19,) are prepared by reacting compounds of the forrnula Ic, Id, Ii, Ik and Io2 with compounds of the formula NH2OR3 or the hydrochloride thereof in a protic solvent with or without an addition of a base, for example a1kali metal carbonate, alkali metal hydroxide or alkali metal oxide, or with or without an addition of an acid such as acetic acid, at -10 to 120C;
where R6' is hydrogen, methyl, COXR or CN, and X, R and R3 as well as X1, X2 and X3 have the meanings given under formula I; and 10.2 Compounds of the fornula Iq2 ~2'~7~

H2N-C=N-OR3 X~ N (lq2) are prepared by reacting compounds of the formula V with compounds of the forrnula H2N-OR3 in an inert solvent, for example ethanol, at -20 to 1~0(:; and 10.3 Compounds of the forrnula Iq3 R6' ~ :
C=N-OR2 Xl ~ "N (Iq3) are prepared by reacting compounds of the fonnula Ill, 112 and 113 with nitrous acid or with an alkyl ester of nitrous acid, for example iso-amyl nitrite, in the presence of a base, for exarnple an alkali metal hydroxide or alkali metal alcoholate, at -30 to 100C; it being possible for compounds of the forrnula Iq3 in which R2 is hydrogen to be etherified later in the presence of a base, for example sodium hydride, potassium tert-butylate, alkali metal hydroxide or alkali metal carbonate, in an inert solvent at -20 to 100C, using compounds of the folmula R2-Hal, and where R6" is CH3, COXR or CN, R is Cl-C4alkyl and R2, Xl, X2 and X3 have the meanings given under formula I; and 10.4 Compounds of the formula Iq4 R6 " NOH
~C
~S~ ~
X~ N (Iq4) in which R6"' is hydrazino or Nt~(RI) are prepared from the benzohyd;oxamic , 2 ~ ~

chlorides Iq' Cl NOH
\C~

~X3 (Iq~) with an amine of the formula NR(RI) or hydrazine in an inert solvent at -4û to +100C.
Benzohydroxamic chlorides of the formula Iq' are obtained by chlorinating the co.responding aldoximes with a chlorinating agent, for example Cl2, in a suitable solvent such as dilute hydrochloric aeid, at -60 to ~50C.

11.1 Compounds of the formula Ir R-C=N-R3 X~ N (Irl) are prepared by reacting compounds of the formulae Ic or Id with compounds of the formula H2N-R3 in aprotic or protic solvents with or without an addition of an inorganic or organic acid, for example glacial aeetie acid, p-toluenesulfonie aeid or sulfurie aeid, and also with or without earrying out an azeotropie distillation for removing the water of reaetion whieh has formed, or by adsorption of the latter on a moleeular sieve at 0 to 150C; and 11.2 Compounds of the formula Ir2 R-c=N-N(R2)R3 Xl ~N (Ir2) are prepared by reacting compounds of the forrnula Ic or Id with compounds of the ; ~ , ~ :: .
- . :

2 ~ ~

fonnula H2N-N(R2)3 in aprotic or protic solvents with or without an addition of an inorganic or organic acid, for example glacial acetic acid, p-toluenesulfonic acid or sulfuric acid, as well as with or without carrying out an azeotropic distillation for removing the water of reaction which has formed, or by adsorption of the latter on a molecular sieve at 0 to 150C; where R, Rt, R2 and R3 as wel:l as Xl, X2 and X3 have the meanings given under folmula I.
11.3 Compounds of the formula Ir3 Ul-N=N N--NH-U
\C~ ', ~S~
X1 ~_ N (Ir3) arc preparcd by coupling phenyldiazonium salts Ul-N233 to phenyl hydrazones of the (Ir2)' type in aqueous alcoholic solution in a weakly acidic or basic medium at temperatures between -20 and +30C. pl-l values 2 3 during the coupling reaction can be established, for example, by adding inert pyridine bases (pyridine, collidine) or alkali metal hydroxides or alkali metal oxides.

12.1 Compounds of the fo~mulae Isl and Is2 H H
R-C-NH-R3 R-C-NH-N(R2)R3 X1 ~ N Xl ~ N

(Is 1 ) (1S2) are prepared eithcr by reducing the compounds of the forrnulae Irl and Ir2 respectively, for example by catalytic hydrogenation in the presence of a metal catalyst or by means of a complex hydride, and, in a preferred embodiment, by reacting compounds of the formula ~.
, - . ' ' - , ~ ~ .

~ 20~22 a7~

O=C-R

X~

with compounds of the formulae HN(R2)R3 and HN(RI)-N(R2)R3 in the presence of sodium cyanoborohydride in dilute acetic acid at 0 to 120C; where Rl, R2 and R3 as well as X~, X2 and X3 have the meanings given under forrnula I; and 13.1 Compounds of the fonnulae Itl and It2 R1N=GN(R2)R3 R~N=C-N(Rl)-NIR2)R3 X1 ~ N X~ ~ N

(It 1 ) (It2) are prepared:

13.1.1 by reacting compounds of the formula V with compounds of the formula ROH in the presence of an anhyd~ous acid, for example gaseous HCl, at -20 to 90C, to give compounds of the formula IX

HN--C-OR

~S (IX), and subsequently reacting the compounds of the formula IX with compounds of the formulae HN(R2)R3 and HN(R,)-N(R2)R3 in inert solvents at -20 to 12ûC; or 13~1.2 by reacting compounds of the formula X

. .,! ~

~ ~' ' ,. " ' ' ~ ; , . ' 2 ~ 2 r~ f ~

O=CNHR

x~ N (X) with PC15 or CC14 in the presence of P(phenyl)3 and CH3CN in inert solvents, for example toluene or acetonitrile, at -50 to 150C, preferably -20 to 90C, to give compounds of the forrnula XI

Cl-C=N R

~X, (Xl), and subsequently reacting compounds of the forrnula Xl with compounds of the formulae HN(R2)R3 an(l HN(R~)-N(R2,\R3 in inert solvents at -20 to 120C; where R, Rl, R2 ancl R3 as well as Xl, X2 an(l X3 have the rneanings given under formula I;

14.1 Compounds of the formulae Iul, Iu2 and Iu3 Cl -C2alkylene-X-Cl -C4alkyl S (Iul) R-C~X-C1 -C4alkYI)2 X, ~N (Iu2) - , :
:

--` 2~2~

O=C(H)3 mX-(Cl -c4alkyl)m 2 X3 (Iu3) are prepared by reacting compounds of the formulae Ie, If, Ig, Ikl, Ik2 and Ik3 Cl -C2alkylene-Hal X1--~[ "N (Ie) HC(Hal)2 ~S~
X1 ~ N~/N (I~

C-(Hal)3 Xt ~S (Ig) O=C-CH2Hal ~S~
Xl--~ N (Ik~) o=C-CH(Hal)2 c 2 X3 (Ik2) - :` . : :

O=C-C(llal)3 ~--2~C (Ik3) with compounds of the folmula H-X-CI-C4alkyl in inert solvents with or without an addition of a base, for example potassium carbonate, sodium hydride or an alkali metal salt of H-X-CI-C4alkyl, in an inert, preferably dipolar, aprotic solvent, for example dimethylformamide or dimethyl sulfoxide, at -20 to 150C; or 14.2 Compounds of the formula Iu2 are prepared by reacting compounds of the formula Ic and Id with an alcohol of the formula HX-CI-C4alkyl in the presence of an acid catalyst, for example sulfuric acid, p-toluenesulfonic acid or oxalic acid, with or without an addition of a Lewis acid~ for example AICI3 or boron trifluoride etherate, with azeotropic distillation or by means of a molecular sieve in inert solvents, for example toluene, dioxane or tetrahydrofuran, or in an excess of compouncls of the formula HX-CI-C4alkyl at () to 1 80C; or 14.3 Compounds of the formula lu3 in which X is oxygen are prepared by reacting compounds of the formula IX or the hydrohalides thereof with at least 2 equivalents of a compound of the formula HX-C~-C4alkyl with or without an addition of a base, forexample an alkali metal salt of compounds of the folmula HX-CI-C4alkyl, with or without inert solvents at -30 to 80C; where X, Xl, X2 and X3 have the meanings given under formula I; and 15. Compounds of the formulae Ivl and Iv2 C~ -C2alkylene-O-N=C(Fl1)(R2) Xl ~ N (Ivl) X2 x : l .
- : :
.
. '.. . , ~ ~:

2 r7 3 Cl -C2alkylene-O-N=C(CN)-CONH-R5 2 X3 (1V2) are prepared by reacting compounds of the forrnula Ie with compounds of the formulae M-O-N=C(RI)R2 or M-O-N=CICN)CONH-Rs in inert solvents and, in the even~ that M is hydrogen, in the presence of a base, for example al~ali rnetal carbonaEe, sodium hydride or a tert-amine, for example pyridine, at -20 to 140C; where M is hydrogen or an alkali metal atom and Rl, R2 and Rs as well as Xl, X2 and X3 have Ihe meanings given under forrnula I; and 16. Compounds of the forrnula Iw Q-C=CH-OR1 2 X3 (Iw) are prepared:
16.1 by reacting compounds of the forrnula XVI

X~ N (xvI) wi~h Cl-C4alkyl forrnate or Cl-C4alkyl orthoforrnate in the presence of a base, for example sodium alcoholate or sodium hydride, in inert solvents, for example ether, tetrahydrofuran or toluene, at -10 to 120C and 16.2 subsequently allowing the resulting compounds of the formula Iw in which Rl is hydrogen to react with compounds of the formula RlHal where Rl is Cl-C2alkyl, at 0 to ~, , , ",, . , . : . ., -- . . .

-"` 2~273 80C with the addition of a base and a dipolar aprotic solvent, for example dimethylformamide; where Q, Rl, Xl, X2 and X3 have the meanings given under formula 1.

17. Compounds of the forrnula Ixl and Ix2 OH Hal R-C-COXR R-C-COXR

X~X X~ N
(Ix 1~ (Ix~) are prepared by hydrolytic reaction of compounds of the ~onnulae Inl, In2, In3 and In4 with aqueous mineral acids or by basic hydrolysis of compounds of the formula Ih or Ii with alkali metal hydroxide with or without an addition of islert solvents, for example tetrahydrofuran, at -10 to 180C, preferably 0 to 100C; where Hal is halogen and X, R, Xl, X2 and X3 have the meanings given under formula I. This gives the free acids (R =
hydrogen). If desired, these acids can be esterified with an alcohol RXH in the presence of water-eliminating catalysts, for example boron trifluoride etherate, ~t 0 to 160C, with or without solvent; and 18. Compounds of the formula Iy NC-C~NH2 X~ S (Iy) are prepared:

18.1 by reacting compounds of the forrnula Ic or Id with alkali metal cyanide and ammonia in the presence of ammonium halide at -20 to 80C with or without an addition - : :
~ ~

'' ' ,.

j1 ':~

of inert solvents, or 18.2 by reacting compounds of the forrnula Inl, In2, In3 or In4 with ammonia in the presence of ammonium halide at -20 to 80C with or without an addition of inert solvents;
where R, Xl, X2 and X3 have the meanings given under formula I; and 19. Compounds of the formula Iz Xl ~ N (Iz) are prepared by hydrolysing compounds of the forrnula Ig with aqueous mineral acid, for example ~ICl, at -20 to 130C; where R, X, Xl, X2 and X3 have the meanings given under formula I.

Surprisingly, it has now been found that the use of the cornpounds of the forrnula I
according to the inverttion prevents the attack of plants by harmful microorganisms and thus prevents damage to the plants caused by such attacks. It is characteristic of the active ingredients according ~o the invention that protection of the plants can be achieved by direct action on the destructive microorganisms by means of foliar application or application via the soil as well as by activation and stimulation of the plant's defence system (immunisation). The great advantage of the compounds of the formllla I is the fact that maintaining good health of the plants which have been treated with these substances can also be guaranteed on their own account without using further microbicidal substances during the vegetation period. Accordingly, adverse side-effects, as can occur given direct control of parasites using chemical substances, for example on the one hand by inflicting damage on the useful plants (phytotoxicity) and, on the other hand, by causing symptoms of resistance in the harmful microorganisms, can be avoided by using the active ingredients according to the invention, which advantageously entails entirely undisturbed growth of the useful plants.

(~omprehensive protection of the plants against diseases can be achieved because of the I . . .

. . . ~ , :, .:
..

.

r~

-specific mode of action of the compounds of the formula I according to the invention, namely, on the one hand, the possibility of direct control of the plant pathogens and, on the other hand, improvement of the general defence capacity of the plants treated with these active ingredients by immunisation. I'he use of the active ingredients according to the invention is therefore particularly sui~ed to practical conditions. Moreover, the systemic activity of the compounds of the formula I means that the protective effect also extends to newly-growing parts of the treated plants.

The general crop-protecting activity of the active ingredients according to the invention extends, for example, to phytopathogenic fungi of the following classes: Fungi imperfecti (for example Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (for example Hemileia, Rhizocotonia, Puccinia), Ascomycetes (for example Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula).

Moreover, the active ingredients cnn be used particularly advantageously against the following harmful organisms:
fungi, for example Oomycetes (for example Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora, Bremia letucae), Fungi imperfecti (for example Colletotrichum lagen~rium, Pyricularia oryzae, Cercospora nicotinae), Ascomycetes (for example Venturia inaequalis); bacteria, for example Pseudomonas species (pseudomonas lachrymans, Pseudomonas tomato, Pseudomonas tabaci); Xanthomonas species (for example Xanthomonas oryzae, Xanthomonas vesicatoria); Erwinia (for example Erwinia amylovora); and viruses, for example tobacco mosaic virus.

The compounds according to the invention can be used for protecting a variety of useful plants.

Within the scope of the invention, for example the following plant species are suitable for use of the compounds of the forrnula I according to the invention: cereals (wheat, barley, rye, oats, rice, sorghum and related species); beet (sugar and fodder beet); pomaceous fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas, soybeans); oil crops (rape seed oil, mustard, poppies, olives, sunflowers, coconut, castor, cacao, peanuts); cucurbits (pumpkin, cucumbers, melons); fibre plants (cotton, flax, hemp, jute);
citrus fruit (oranges, lemons, grapefruit, tangerines); various vegetables (spinach, lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes, sweet peppers); Lauraceae ' , . .

2 ~

(avocado, Cinnarnonum, camphor~ or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, grape vine, hops, Musaceae and latex plants, as well as ornamentals (flowers, shrubs, deciduous trees and conifers). This list does not imply any limitation.

The following plants can be regarded as particularly suitable target crops ~r the use of the method according to the invention: cucumber, tobacco, grape vine, rice, pepper, potatoes, tomatoes, wheat, barley, pears and apples.

The microbicidal compositions for protecting plants against diseases which are employed within the scope of the invention and comprise the compounds of the formula I as active ingredients are to be considered as part of the invention.

Active ingredients of the fonnula I are customarily used in the form of combinations and can be applied to the plant or its environment simultaneously or in succession with other active ingredients. These other active ingredients can be fertilisers, trace element supplements, or other preparations which have an effect on plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with o~her carriers, surfactants or application-enhancing additives conventionally used in the art of forrnulation.

Suitable carriers and additives can be solid or liquid and correspond to the substances expedient in the art of forrnulation, for exarnple natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilisers.

One method of applying an active ingredient of the forrnula I, or an agrochemical composition comprising at least one of these active ingredients, is application to the plant (foliar application). ~owever, the active ingredients of the forrnula I can also reach the plant *om the soil via the root system (soil application), by soaking the locus of the plant with a liquid preparation or incorporating the substances into the soil in solid forrn, for example in the form of granules. However, the compounds of the forrnula I can also be applied to seed kernels (coating) either by soaking the seeds with a liquid preparation of the active ingredient or by applying a layer of a solid preparation (application by seed-dressing). Moreover, other types of application are possible in specific cases, for example the targeted treatment of the staLIss of the plants, or of the buds.

,. . , - . .

': : , J ~

-The compounds of the formula I are employed in unaltered form, or, preferably, together with the auxiliaries conventionally used in the art of forrnulation. For this purpose, they are processed in a known manner to give, for example, emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, or encapsulations, for example in polymeric substances.
The application methods such as spraying, atomising, dusting, scattering, brushing on or pouring, as well as the type of composition are selected to suit the intended aims and the prevailing circumstances. Favourable rates of applicaLion are generally 50 g to 5 kg of active substances (AS) per ha; preferably 100 g to 2 kg AS/ha, in particular 100 g to 600 g AS/ha.

The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I and, if appropriate, a solid or liquid additive, are prepared by intimately mixing and/or grinding the active ingredients together with extenders, for example with solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).

The following are suitable as solvents: aromatic hydrocarbons, preferably the fractions C8 to Cl2, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols as well as the ethers and esters thereof such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide; and epoxidised or unepoxidised vegetable oils such as epoxidised coconut oil or soya oil; or water.

Solid carriers which are generally used, for example for dusts and dispersible powders, are ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Granular, adsorptive granule carriers which are suitable are porous types, for example pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are, for example, calcite or sand. In addition, a large number of pregranulated materials of inorganic or organic nature such as, in particular, dolomite or comminuted plant residues, can be used.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants , 2~,S~

having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be forrnulated. Surfactants are also to be understood as meaning mixtures of surfactants.

The cationic surfactants are mainly quaternary ammonium salts which comprise at least one alkyl radical having 8 to 22 C atoms as the N substituent ancl have lower, h~logenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.

Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.

Soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C10-~22), for example the soclium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures, for example those which can be obtained from coconut oil or tallow oil.

Synthetie surfactants which ean be used are, in particwlar, fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates. The fatty alcohol sulfonates or fatty alcohol sulfates are generally in the forrn of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts, and have an alkyl radical having 8 to 22 ~ atoms.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkyl phenols.

The cornpositions can also comprise further additives such as stabilisers, defoamers, viscosity regulators, binders and adhesives as well as fertilisers or other active ingredients for achieving specific effects.

The agrochemical preparations generally eomprise 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of active ingredient of the formula I, 99.9 to 1 % by weight, in particular 99.8 to 5 % by weight, of a solid or liquid additive, and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.

' :' :' ' ~ ' 2~ 2~

The examples which follow are intendecl to illustrate the invention in greater detail without implying any limitation of the latter.

1. Preparation examples Example 1.1: Preparation of 7-methylsulfonyloxymethylbenzo-1 ,2.3-thiadiazole (Comp. No. 1.20) ~ \N

To a solution of 3.32 g of 7-hydroxymethylbenzo-1,2,3-thiadiazole, 3.1 ml of triethylamine and 0.~ g of 4-dimethylaminopyridine in 50 ml of methylene chloride there is ad(led dropwise with cooling at -5 to 0C a solution of 2.23 g of methanesulfonyl chloride in 15 ml of (lichloromethane, and the mixture is stirred for 2 hours at room temperature. The reaction mixture is then treated with ice-water and extracted several times using dichloromethane. The combined extracts are washed with water, dried and evaporated. Chromatographic purification on silica gel (CH2Cl2) gives the title compound as a viscous resin.

Example 1.2: Preparation of ben~o-1,2,3-thiadiazole-7-carbaldehYde (Comp. No. 1.4) 1 :

~ N~N

a) 99 g of benzo-1,2,3-thiadiazole-7-carboxylic acid chloride are dissolved in 1.21 of ethyl acetate, the mixture is treated at 0-5C with a solution of 58.7 g of 2,6-lutidine in 200 ml of tetrahydrofuran as well as 33 g of palladium/charcoal catalyst (5 % Pd), and hy~lrogenated under low pressure (104 Pa) with a further addition of a total of 57 g of palladium/charcoal catalyst and 500 ml of te~rahydrofuran in 5 portions. The catalyst is subsequently removed by filtration and washed wi~h tetrahydrofuran, and the filtrate is evaporated. The residue is purified on silica gel (CH2CI2) and gives the title compound of - .- ~ .:

- ,.

:

2 ~

m.p. 134-136C.

b) To a solution of 16.6 g of 7-hydroxymethylbenzo-1,2,3-thiadiazole in 100 ml of chloroforrn there are introduced with stirring at room temperature 35 g of manganese dioxide, during which process the internal temperature rises briefly to 31C. When the temperature has dropped again to 25C, the mixture is heated and refluxed ovemight.
Another S g of manganese dioxide are subsequently added, and heating of the mixture is continued until the reaction is complete. The hot mixture is filtered over Hyflo and the filtrate is then evaporated. The residue is digested in a little hexane and then ~lltered, which gives 15 g (91.4 %) of the title compound of m.p. 134-136C.

Example 1.3: Preparation of 7-trichloromethvlbenzo-1,2.3-thiadiazole (Comp. No. 1.2) ~S\

~ N

26 g of phosphorus pentachloride are introduced in portions to 9.0 g of 7-carboxybenzo-1,2,3-thiadiazole and 10.7 g of benzenephosphonic acid dichloride under a nitrogen atmosphere and with stirring. The mixture (which exists in solid form) is then heated to 160C, during which process melting starts at approx. 100C. After the mixture has been stirred for 16 hours at 160C, it is cooled, carefully poured onto ice, and the mixture is rendered alkaline using solid sodium carbonate. It is then extracted several times using ethyl acetate, the extracts are washed with water and ~lltered over Hyflo, and the filtrate is evaporated. Purification on silica gel (hexane with an increasing addition of ethyl acetate up to a ratio of 8:2) gives white crystals of m.p. 67-69C.

Example 1.4: Preparation of 7-dichloromethvlbenzo-1,2.3-thiadiazole (Comp. No. 1.1) ~ \N

8.7 ml of thionyl chloride are initially introduced, and 0.~ ml of triethylamine are added .

~2~3 with cooling, 6.~ g of benzo-1,2,3-thiadiazole-7-carbaldehyde are then introduced in portions at 15-20C, and the mixture is subse~uently heated for 1 hour at ~5C and then for a further 4 hours at 95C, during which process slight evolution of gas can be observed. The clear solution which has formed is subsequently evaporated, the residue is taken up in meth~lene chloride, and the mixture is washed with ice-water. The organic phase is dried over sodium sulfate and evaporated. The residue is recrystallised from ethyl acetate/hexane, giving the title compound of m.p. 131-133C.
Example 1.5: Preparation of 7-chloromethylbenzo-1~2,3-thiadiazole (intermediate) ~ \N

199.2 g of the compound of Example 1.15 are dissolved in 150 ml of methylene chloride and 150 ml of pyridine at 5C, introduced into ~ reaction vessel, and treated at 5-10C in the course of 3t4 hours with a solution of 12() ml of thionyl chloride in 200 ml of methylene chloride, with cooling. Stirring is then continued at room temperatureovernight, the suspension is poured into ice-water, and the mixture is extracted using methylene chloride. The extracts are washed with ice-water, dried over sodium sulfate and filtered, and the filtrate !S evaporated. The resulting title compound melts at 78-80C.

Example 1.6: Preparation of 7-acetylbenzo-1,2~3-thiadiazole (Comp. No. 1.5) ~ N

0.59 g of magnesium turnings in 3 ml of diethyl ether are activated with 1 drop of bromine, and a solution of 1.5 ml of methyl iodide in 5.5 ml of diethyl ether is added dropwise with stirring. When the exothermic reaction has subsided, the mixture is heated and kept for a further l.S hours at bath temperature 55S~. The resulting solution is added dropwise under a nitrogen atmosphere and with stirring at -10C to ~he initially introduced solution of 4.9 g of N-methyl-N-me~hoxy'oenzo-1 ,2,3-thiadiazole-7-carboxa nide in 2 ~ r7J1 ~7 ~

150 ml of absolute tetrahydrofuran. After stirring has been continued for 1 hour at -10C, the mixture is heated and refluxed at bath temperature 75C for 6 hours. The reaction mixture is then cooled, poured into ice-water, acidified with 2 N hydrochloric acid and extracted several times using ethyl acetate. The extracts are washed with water, dried over sodium sulfate and evaporated. The residue is purified on silica gel (CHCI3), giving the title compound of m.p. 126-127C.

Example 1.7: Preparation of 7-carboxymethylbenzo-1,2,3-thiadiazole (Comp. No. 1.39) - ~ ~N

1.9 g of 7-cyanobenzo- 1,2,3-thiadiazole are heated overnight in ~0 ml of concentrated hydrochloric acid. The mixture is then evaporated and treated with a little cold water, and the solid which has formed is filtered off and washed with water. The residue is dried, resulting in 1.7 g of the title compound of m.p. 148-150C.

Example 1.8: Preparation of 3-~benzo-1~2.3-thiadiazol-7-YllacrYlic acid (Comp. No. 1.98) CH=CH-COOH

~ N~

A mixture of 1.96 g of benzo-1,2,3-thiadiazole-7-carbaldehyde, 1.24 g of malonic acid and 6 ml of pyridine are heated for 26 hours at 120C, with 2 further additions of 0.6 g portions of malonic acid after 4 and 7 hours. The mixture is then cooled, poured into ice-water and acidified with concentrated hydrochloric acid. The precipitate which has formed is filtered of ~ and dissolved in dilute sodium hydroxide solution, the mixture is washed three times with methylene chloride, and the aqueous phase is subsequently acidified once more, using hydrochloric acid. The precipitate obtained is fil$ered off, washed with water and dried in vacuo, resulting in 11 g of the title compound ofm.p. 199-202C.

.

2 ~

Example 1.9: Preparation of 7-cvanomethylbenzo-1~2,3-thiadiazole (Comp. No. 1.38) ~S\N

~N

18.4 g of 7-chloromethylbenzo-1,2,3-thiadiazole are dissolved in 50 ml of chloroform, 0.5 g of tetrabutylammonium iodide are added, the mixture is heated to 50-55C and treated dropwise in the course of 0.5 hours with a solution of 5.6 g of sodium cyanide in 20 ml of water, with stirring. Heating is continued overnight at the same temperature, on the following day the mixture is cooled, ~reated with water and extracted several times using dichloromethane. The extracts are washed with water, dried over sodium sulfate and filtered over Hyflo, and the filtrate is evaporated. The residue is puri~led on silica gel (hexane/ethyl acetate) resulting in the title compound of m.p. 78-80C.

Example 1.1(): Preparatiorl of ethyl _-lbenzo-1,2~3-thiadiazolYII-3-oxo 2~2-diethoxypropionate (Comp No. 1.64) CO-C(OC2H5)2-COOc2Hs ~S\

~ N

71.5 g of benzo-1,2,3-thiadiazole-7-carboxylic acid chloride and 88.1 g of tetraethoxyethylene are refluxed for 17 hours in 180 ml of toluene. The mixture is then cooled, washed with sodium bicarbonate solution and water, dried over sodium sulfate and evaporated. The solid residue is dissolved in hot tetrahydrofuran and precipitated with hexane, with stirring. This results in 61.5 g of the title compound of m.p. 123-125C.

Example 1.11: Preparation of 7-trifluoromethylbenzo-1.2,3-thiadiazole \N

,, ~ :, . .
: ~ : .

;.

2 ~ ~

38.8 g of 3,5-diamino-3-benzylthiobenzotrifluoride in 100 ml of dioxane are added dropwise with vigorous stirring at 0C with cooling to 195 ml of SN hydrochloric acid.
The mixture is subsequently cooled to -15C, and, below the liquid level, treated dropwise with 18.6 g of sodium nitrite in 150 ml of water. The red solution is subsequently stirred for 6 hours at -5C and ~mally poured into hypophosphorous acid (71 ml) which has been cooled to -10C, with stirring. The mixture is allowed to cool to room temperature overnight with continued stirring and on the following day the mixture is extracted several times using methylene chloride, and the extracts are washed with water, dried over sodium sulfate and then evaporated. The oily residue is freed from benzyl chloride by repeated distillation using a bulb tube at 800cr7.8 Pa.

Example 1.12: Preparation of 3,5-diamino-2-benzylthiobenzotrifluoride (intermediate) ~S--CH

3 g of 2-benzylthio-3,5-dinitrobenzotrifluoride in 30 ml of tetrahydrofuran are hydrogenated in a glass hydrogenation apparatus for 22 hours at room temperature, using a total of 3 g of Raney nickel. For working up, the catalyst is removed by filtration and washed with tetrahydrofuran, the filtrate is evaporated, and the residue is directly processed as crude product (brownish liquid).

Example 1.13: P_paration of 2-benzylthio-3,5-dinitrobenzotrifluoride (intermediate) ~S--CH

67.6 g of 2-chloro-3,5-dinitrobenzotrifluoride are dissolved in 150 ml of N,N-dimethylformamide (DMF) and the mixture is treated with 35.9 g of solid potassium carbonate, treated dropwise with 31 g of benzylmercaptan in 200 ml of DMF with stiTring at 0C, and subsequently stirred for a further 16 hours at room temperature, while cooling.

~ :. , . , . , . :

' : . ' ~iJ,~7~

The reaction mixture is then treated with ice-water and extracted several times using methylene chloride. The extracts are washed wilh water, dried and evaporated. The residue is digested with hexane with heating, and the mixture is filtered. This gives yellow crystals of m.p. 93-95C.

Example 1.14: Prepauation of ethvl benzo-1~2,3-thiadiazole-7-carboximidate hydrochloride (intermediate) (+) H2N;~C,Oc2H5 ~ \N

7.2 g of 7-cyanobenzo-1,2,3-thiadiazole are dissolved at 45C in 60 ml of absolute ethanol and 20 ml of îetrahydrofuran, and the solution is cooled to 0C and saturated with gaseous hydrochloric acid in the course of I hour at 0C to 15C, with the exclusion of moisture.
The reaction mixture is then stored for 24 hours in the refrigerator, treated with 70 ml of absolute diethyl ether and allowed to stand for another 4 days in the refrigerator The solid is then filtered off, washed with diethyl ether and dried. This gives 9.4 g of compound 5.2 in the form of beige crystals of m.p. 270-272C.

Example 1.15: Prepara~ion of 7-hydroxymethylbenzo-1,2.3-thiadiazole (intennediate) ~S~

To a suspension of 54 g of carboxybenzo-1,2,3-thiadiazole in 420 ml of tetrahydrofuran there are added dropwise under a nitrogen atmosphere with stirring at room temperature 110 ml of triethyl borate, the mixture is stirred for a further hour and subsequently treated dropwise with 4~.6 ml of boranedimethyl sulfide complex in 60 ml of tetrahydrofuran, with gentle cos)ling, during which process gas is evolved vigorously. The mixture is stirred overnight and allowed to stand at room temperature and then cooled down to S-10C and ~ ' ~

' treated dropwise with 200 ml of methanol with stirring and vigorous cooling, during which process gas is again evolved vigorously. The mixture is subsequently evaporated in vacuo, a further 300 ml of methanol are added, and the mixture is re-evaporated. The residue is purified on silica gel (solvent: ethyl acetate/hexane), and the product obtained is recrystallised from ethyl acetate/hexane. The title compound obtained melts at 79-81C.

Examl?le 1.16: Preparation of 6-chloro-7-hvdroxymethylbenzo-1,~,3-thiadiazole (intermediate) ~ N

To a suspension of 4.5 g of sodium borohydride in 30 ml of water and 70 ml of tetrallydrofuran there are ad(led dropwise with stirring and heating to 40-50C in the course of half an hour a solution of 1.9 g of 6-chloro-7-carbomethoxybenzo-1,2,3-thiadiazole in 30 ml of tetrahydrofuran (dissolved under hot conditions). Heating of the mixture is continued until the reaction is complete, and the mixture is then cooled to -20 to -30C using a CO2 cooling bath and treated dropwise with 15 ml of acetone, during which process gas is evolved vigorously. The reaction mixture is subsequently brought to pH 3 using lS % hydrochloric acid, with further vigorous cooling at -20 to -10C
(evolution of gas), and stirring is continued overnight. Most of the tetrahydrofuran is then evaporated on a rotary evaporator, and the residue is extracted using ethyl acetate. The extracts are washed with water, dried over sodium sulfate and evaporated. The residue gives the title compound of m.p. 138-140C.

Example 1.17: Preparation of 2-(benzo-1,2,3-thiadiazolyl)-2-hydroxviminoacetonitrile ~Comp. No. 1.127) NC-C=N-OH

~ N

A suspension of 0.36 g of potassium tert-butylate in 5 ml of absolute diethyl ether is treated dropwise at -5C in the course of 10 minutes with a solution of 0.5 g of7-cyanomethylbenzo-1,2,3-thiadiazole and 0.43 ml of isoamyl nitrite in 10 ml of absolute tetrahydrofuran, and stirred at room temperature for a total of 48 hours, with three additions of 0.43 ml portions of isoamyl nitrite being added at intervals of 16, a further 16 and 8 hours. The mix~ure is then diluted with ice-water, acidified with lN hydrochloric acid and extracted with ethyl acetate. The extracts are washed with water, dried over sodium sulfate and evaporated. Chromatography of the residue on silica gel (ethyl acetate/hexane 1 :2) gives the title compound of m.p. 249-253C.

Example 1.18: Preparation of 7-(1,1,1-trichloro-2-h~droxv(ethvl)benzo-1.2,3-thiadiazole (Comp. No. 1.108) ~ \N

A mixture of 5.8 g of trichloroacetic acid and 2.6 g of 7-formylbenzo-1,2,3-thiadiazole in 20 ml of hexamethylphosphoric triamide is heated for 4 hours at 70C, during which process the solid dissolves rapidly, with evolution of CO2. The mixture is then cooled, poured into ice-water and extracted wieh ethyl acetate. The extracts are washed with water, dried and evaporated. The residue is recrystallised *om ethyl acetate/hexane, resulting the title compound of m.p. 163-165C.

Example 1.19: Preparation of 7-aminomethylbenzo-1,2.3-thiadiazole (Comp. No. 1.110) ~N

In a hydrogenation vessel, a solution of 14.5 g of 7-cyanobenzo-1,2,3-thiadiazole in 150 ml of methanol is treated with 4.4 g of Raney nickel and with 15 g of liquid nitrogen.
Hydrogen is subsequently injected, the vessel is heated, and the mixture is hydrogenated at 60C and constant hydrogen pressure of 107 Pa until hydrogen is no longer taken up. The ' ~ ' :'- ,`'`

mixture is then cooled, the catalyst is removed by f1ltration, the filtrate is evaporated and chromatographed on silica gel (hexane/elhyl acetate 2:1), resulting in the ti~le compound of m.p. 136-139C).

Example 1.20: Preparation of 7-trichloroacetYlbenzo-1,2.3-thiadia7ole (Comp. No. 1.107) O=C-CC13 ~ N~

A solution of 2.8 g of 7-(1,1,1-trichloro-2-hydroxyeth-2-yl)benzo-1,2,3-thiadiazole in 30 ml of chloroform is treated with 5 g of manganese dioxide and refluxed for 16 hours, with stirring. A further 5 and 3 g of manganese dioxide are added at intervals of 16 hours and 8 hours, respectively. After a total of 40 hours, the mixture is cooled and filtered twice through Hyflo, the filtrate is evaporated and purified using silica gel (hexane/ethyl acetate 7:3), giving the title compound of refractive index n26 = 1.6178.

E mple 1.21: Preparation of 7-acetYlthiomethYIbenzo-1,2.3-thiadiazole (Comp. 1.113) ~S~

A solution of 2.2 g of potassium thioacetate in 20 ml of absolute dimethyl sulfoxide, stirred at 20C, is treated dropwise with stirring with a solution of 2.8 g of 7-chloromethylbenzo-1,2,3-thiadiazole in 10 ml of dimethyl sulfoxide, during which process the internal temperature rises to 37C. The mixture is subsequently stirred overnight at ros)m temperature and, on the following day, poured into ice-water and extracted using ethyl acetate. The extracts are washed five times with water, dried over sodium sulfate and evaporated. The residue which remains is distilled in vacuo, resulting in an oil of refractive index n27 = 1.6478.

~ .
. ~ ~. , - .

, - . . . ~ :

2 ~ ~ ~r~ 2 - 45 ~
-Example 1.22: Preparation of 7-dimethoxvmethyll}enzo-1,2~hiadiazole (Comp. No. 1.12) HC(OcH3)2 ~ N

A solution of 3.3 g of 7-formylbenzo-1,2,3-thiadiazole in 50 ml of methanol and 0.2 g of p-toluenesulfonic acid is refluxed for 6 hours in a Soxhlet apparatus charged with a molecular sieve A4. The mixture is then cooled, rendered basic using solid potassium carbonate, filtered through Hyflo and evaporated. The residue is purified on silica gel using hexane/ethyl acetate (1:1), resulting in the title compound of refractive index nDI =
1.575~).

Fxample 1.23: Preparation of benzo-1,2,3-thiadiazole 7-N-methoxyhvdroxamic acid (Comp. No. 1.112) HO-C=N-OCH3 ~ N

A suspension of 2.4 g of O-methylhydroxylamine hydrochloride, 4.5 g of potassiumcarbonate and 20 ml of dichloromethane, stirred at -5C, is treated dropwise with cooling and stirring with a solution of 4.96 g of benzo-1,2,3-thiadiazole-7-carboxylic acid chloride in 25 ml of dichloromethane. The mixture is stirred overnight at room temperature and filtered, the filtrate is evaporated, and the residue is washed on silica gel (ethyl acetateltetrahydrofuran 1:1). This gives the title compound of m.p. 188-190C.

Example 1.24: Preparation of 7-methoxvmethylbenzo-1l23-thiadiazole (~omp. No. 1.7) f H2-oCH3 ,~`, ~
~ N

,. .
,: ,. ' " . ' .. ~' :~ :.: :: . :
: ~

2 ~

1.4 g of sodium hydride ~S0 % dispersion in oil) in 15 ml of absolute dimethyl sulfoxide are introduced into a reaction vessel, and a solution of 4.15 g of 7-hydroxymethylbenzo-1,2,3-thiadiazole in 15 ml of tetrahydrofuran is added dropwise at 0-5C under a nitrogen atmosphere and with stirring, during which process hydrogen is evolved. After 20 minutes of stirring at 10C, the mixture is cooled down to 0-5C, and a solution of 4 g of methyl iodide in 15 ml of tetrahydrofuran is added dropwise. Stirring is continued for another hour at room temperature, and the mixture is cooled, treated with ice-water, neutralised with dilute hydrochloric acid and extracted with ethyl acetate. The extracts are washed with water, dried over sodium sulfate and evaporated, and the residue is dried in a high vacuum, resulting in the title compound in the form of a yellow oil, n2D7 = 1.5912.

Exam~e 1.25: Preparation of 7-oximinobenzo-1.2,3-thiadiazole (Comp. No. 1.65) HC=N-OH
~5~

A solution of 4.9 g of 7-formylbenzo-1,2,3-thiadiazole in 70 ml of absolute methanol is treated with 2.1 g of hydroxylamine hydrochloride and 2.4 g of sodium acetate, and the mixture is maintained at 70C for 6 hours. Most of the solvent is then evaporated in vacuo, the residue is treated with ice-water, and the precipitate is filtered off, washed with water and dried, resulting in the title compound of m.p. 230-231C ~decomp.).

Example 1.26: Preparation of 7-rnethox~iminobenzo ,2.3-thiadiazole (Comp. No. 1.66) HC=N-OCH3 ~S~
~ // .

A suspension of 0.92 g of sodium hydride (~0 % dispersion in oil) in 10 ml of dimethyl sulfoxide and 10 ml of tetrahydro~uran is treated dropwise under a nitrogen atrnosphere 1 .

~3~2'~

and with stirring at 0-10C with a solution of 3.0 g of 7-oximinobenzo-1,2,3-thiadiazole in 10 ml of tetrahydrofuran and, after stirring for 0.5 hours at 15-20C, treated with 2.7 g of methyl iodide in 10 ml of ~etrahydrofuran. After stirring for S hours at room temperature, the mixture is treated with ice-water and extracted with methylene chloride, and the extracts are washed with water and dried. The residue which remains after evaporation is digested with hexane, resulting in pale yellow crystals of m.p. 121-123C.

Example 1.27: Preparation of 7-(3-trifluoromethvlphenYlimino)benzo-1,2,3-thiadiazole (Comp. No. 1.79) H-C=N~

(~ N~N

A solution of 2.46 g of 7-forrnylbenzo-1,2,3-thiadiazole and 2.41 g of 3-aminobenzotrifluoride is stirred for 16 hours at room temperature with a spatula-tipful of p-toluenesulfonic acid and approx. S g of molecular sieve A4 in 50 ml of toluene. The mixture is then fill~ered and the filtrate is evaporated, and the residue is washed with hexane and dried, resulting in the title compound of m.p. 120-122C.

Example 1.28: Preparation of the 2,4,6-trichlorophen~lhydrazone of benzo-1,2,3-thiadiazole-7-carbaldeh~/de (Comp. No. 1.89) HC=N--NH~CI

~ N~

2.11 g of 2,4,6-trichlorophenylhydrazine is dissolved under hot conditions in 3û ml of methanol and 20 ml of tetrahydrofuran, the mixture is cooled to 40C and, together with a solution of 2.46 g of benzo-1,2,3-thiadiazole-7-carbaldehyde, poured into lû ml of , 2 ~ 3 methanol, with stirring. After stirring for 4 hours at room temperature, ~ ml of glacial acetic acid are added, and stir;ing is continued at 40C until the reaction is complete. The mixture is then filtered, washed with methanol and dried, resulting in the title compound as beige solid (m.p. >250C).

Example 1.29: Benzo-1,2~3-thiadiazole-7-(N-hydroxycarboximid(amide) (Compound 1 .106) H

~ S

A solution of 5.0 g of 7-cyanobenzo-1,2,3-thiadiazole, introduced into the reaction vessel, and 2.5 g of hydroxylamine hydrochloride in 34 ml of ethanol and 16 ml of water are treated with 6.4 g of potassium carbonate in portions, during which process the internal temperature rises from 24 to 36C, with gentle evolution of CO2. A-fter stirring for 1 1/2 hours at room temperature, the mixture is refluxed for a further 3 hours, and the suspension which has forrned is treated with ice-water, and the solid is filtered off and washed with water and a little diethyl ether. The precipitate corresponds to the title compownd of m.p. 209-211C.

Example 1.30: Preparation of 7-bromoacetYlbenzo-1.2.3-thiadiazole (Compound 1.125) 0.9 g of 7-acetylbenzo-1,2,3-thiadiazole is dissolved in 20 ml of chloroform, and 0.~8 g of bromine is added dropwise at room temperature. StilTing is then continued for 2 hours at the same temperature, during which process a yellow precipitate forms. This precipitate is filtered off, washed with hexane and dried. The title compound which is thus obtained melts at 15~-157C.

Example 1.31: Preparation of N,N'-diphenyl-C-~benzo-1 ,2,3-thiadiazol-7'-yllfonnazan Compound No. 4.1) 1.65 g of aniline are diazotised at 0C using a solution of 1.25 g of soelium nitrite in 2.2 ml of water, in the presence of 4 ml of hydrochloric acid ~30 %) and 1.8 g of ice. A solution of 4.6 g of benzo-1,2,3-thiadiazole-7-carbaldehydephenylhydrazone in 60 ml of pyridine and 90 ml of ethanol is introduced into the reaction vessel, the solution of the diazonium ~.
' t;~6~

salt is added dropwise with stirring and cooling at -5 to 0C, and the reaction mixture is stirred at room temperature for a further 18 hours. The mixture is subsequently concentrated in vacuo and extracted with ethyl acetate. The extracts are washed with water, dried and evaporated. The residue is purified on silica gel (ethyl acetate/hexane 9:1), resulting in the title compound of m.p. 185-187C.

.

, - so -T~ble 1 ~ N

Comp. No. A Physical data 1.] CHCl2 m.p. 131-133CC
1.2 CC13 m.p. 67-69C
1.3 CH(CI)CH
1.4 CBr3 I.S H3C-C(OC~I3)2 1.6 CH20COCH3 m.p. 52-54C
1.7 CH20CH3 n2D7= 1.~912 1.8 CH20-CO-cyclopropyl 1.9 CH(OH)CH3 1. 10 c(oc~I3)3 1.11 C(OC2Hs)3 2 1.12 CH(OCH3)2 nD~750 1. 13 CH((:)C2Hs) 1. 14 CH[OCH(C~3)2]2 1. l S CH(OC4Hs-n)2 1.16 CH~SCH3)CH3 1.17 CF3 m.p. 800cr7.8 Pa 1.18 CH2SC~3 nD7 = 1.6311 1. 19 CH(S-isoC3H7)2 1.20 CH20-SO2CH3 resin 1.21 CH2O-S02-C2Hs 1.22 CH20-SO2-cyclohexyl 1.23 CH20-CO-cyclopropyl 1.24 CH(CH3)0-COCH3 1.25 CH2OCO-CH2CH=cH2 ,~
.
,. :

3 $ D~

Comp. No. A Physicaldata _ 1.26 CH~OCO-CH2-C_CH
1.27 CH2OCO-CH2CH=CH-CH3 1.28 CH2OCO-CH2-CH=CH-C2Hs 1.29 CH2OCO-C6Hl3-n 1.30 CH(CH3)OCO-cyclohexyl 1.31 CH2OCO-penyl m.p.73-74~C
1.32 CH2OCO-2-hydroxyphenyl 1.33 CH2OCO-C(CI)=C(cl)2 m.p.123-124C
1.34 CH2O-tosyl 1.35 CH2O-SO2-4-bromophenyl 1.36 CH(CH3)O-SO2CH3 1.37 CH2O-SO2C6HI3-n 1.38 CH2CN m.p.78-80C
I.39 CH2COOH m.p.148-150C
1.40 CH2CON~I2 1.41 CH2COOCH3 1.42 CH2COOC4H9-~e~.
1.43 CH2CO-SCH3 1.44 CH2CO-S-phenyl 1.45 CH2COO-phenyl 1.46 CH2COO-2-hyc~oxyphenyl 1.47 CH(CH3)-COOCH3 1.48 CH(OH)COOH
1.49 CH(OH)-COOCH3 1.50 CH2J
1 .S 1 CH(CH3)Br 1.52 CH(OH)CN
1.53 C(CH3)(0H)CN
1.54 CH(OCH3)CN
1.55 CH[OSi(CH3)3]CN
1.56 CH(NH2)CN
1.57 CH(NH2)COOCH3 1.58 CH(MnH2)COOH

- : :

~ ~$~p~s~

~ - 52 -Comp. No. A Physical data _ l.S9 COCOOH
1.60 COCOOCH3 1.61 COCOC)C2Hs 1.62 COCOOCsHll-n 1.63 COC~OCH3)2COOCH3 1.64 COC(OC2H5)2COOC2Hs m.p. 123-125~C
1.65 C--CH
1.66 CH=NOCH3 m.p. 121-123C
1.67 CH=NOC2H5 1.68 CH=NOC4Hg-i 1.69 C(CH3)=NOH
1.70 C(CH3)=NOCH3 1.71 CH=NH
1.72 CH=NCH3 1.73 CH=N-phenyl 1.74 CH=N-cyclohexyl 1.75 CH=N-cyclopropyl 1.76 CH=N-allyl 1.77 C(CH3)=N(3,5-diCl-phenyl) 1.78 CH=N(3-NO2-phenyl) 1.79 CH=N(3-CF3-phenyl) m.p. 120-122C
1.80 CH2-O-N=C(CM3)2 1.81 CH2-O-N=C(CH3)C2Hs 1.82 CH2ON=C(CN)CH3 1.83 CH2ON=c(cN)cONH2 m.p. 157-159C
1.84 CH2ON=C(CN)CONHCONHC2Hs 1.85 CH=N-NH2 m.y. 156-158C
1.86 CH=N-NH-C2H5 1.87 CH=N-N(CH3)2 1.88 CH=N-NH-phenyl m.p. 167-168C
1.89 CH=N-NH-2,4,6-TriCl-phenyl m.p. >250C
1.90 CH-N-NH-2,6-Di-CI-phenyl 1.91 CH=N-NH-cyclohexyl `
- . , , : :`
:

., ., ~ .
.

?~

Comp. No. A Physical data 1.92 CH=N-benzyl 1.93 C(CH3)=N-NH-3-NO2-phenyl 1.94 COCN
1.95 CH(OCH3)COOCH3 1.96 CH(CI)COOCH3 1.97 CH(Cl)COOC2Hs 1.98 CH=CHCOOH m.p. 199-202C
1.99 CH=C(CN)COOH
1.100 CH=CHCN
1.101 CH=C(CN)COOCH3 m.p. 15û-153C
1.102 CH=C(cOOc2Hs)2 I .103 CH2-CH2COOH
1.104 C~12-C~12-COOCH3 1.105 C~l(Br)CH(Br)COOCl^I3 1.1()6 C(NH2)=NOH m.p. 209-211C
1.107 COCCl3 n2D6 = 1.6178 1.108 CH(OH)CCl3 m.p. 163-165C
1.109 CH=CH-COOCH3 1.110 CH2NH2 m.p. 136-139C
1.111 CH=CH-CONH2 1.112 ~(OH)=NOCH3 m.p. 188-190C
1.113 CH2SCOCH3 n27 1.6478 1.114 Cl~12SCO-C6~-~s 1.115 CH2NHCH3 1.116 CH2N(~H3)2 1.117 CH2NH-C6Hs 1.11 O CH2N(CH3)C6H4-(4-CH3) 1.119 CH2NH(3,5-di-CI-C6H3) 1.120 CH(CH3)NHC6Hs 1.121 CH2NH-NH-C6Hs 1.122 CH2NH-NH2 1.123 CH2NH-N(CH3)2 ~. . . 1 . , , . ,~...... , . . ; . ~

,; . '" ~

Comp. No. A Physicaldata 1.124 CH(Br)COOC6Hs 1.125 COCH2Br m.p. 155-157C
1.126 C(NH2)=NH HCI
1.127 C(CN)=NOH m.p. 249-253C
1.128 C~CN)=NOCH3 1.129 C(OH)-CF3 1.130 CO-CF3 1.131 C(=NH)-N(CH3)2 (hydrogenoxalate) 1 132 C(=NH)NH(3,5-di-CI-C6H3)HCI
1.133 CH(CI)COOH
1.134 CH(Cl)COOCH3 1.135 CH(Br)COOC2Hs I .136 C(CI)=C(CI)COOCH3 1.137 C(CI)=C(Cl)2 1.138 C(NH2)(CH3)CN
1.139 C(CH3)(NH2)-cS~OcH3 1.140 C(COOCH3)(=CH-OH) 1.141 C(COOCH3)(=CH-OCH3) 1.142 C(CN)(=CH-OCH3) 1.143 C(=NH)(NEI-NH2) 1.144 C(CH3)-C)N=C(CH3)2 1.145 CH=CH2 I .146 CH--CH-CH3 1.147 CH=CCI2 1.148 C(CI)-CCI3 1.149 CHBr-CH2Br '. :

T.lble 2 A

X1 ~ \N

Comp. No. Xl, X2, X3 A Physical data 2. 1 6-Cl CCI3 2.2 6-F CF3 2.3 5-F CF3 2.4 6-Br CHO
2.5 6-F CHO
2,6 6-F CH2O(CO)-phenyl 2.7 5-F CH2QCOCH3 2. 8 4-F COCH3 2.9 6-F COCH3 2.10 4,5-di-F CHO
2.11 S-F CE~2OSO2CH3 2.12 6-F c(OC~I3)3 2.13 5,6-di-F CH2COOH
2.14 4-F CH2COS-phenyl 2.15 5-Br CH(OH)COOH
2.16 6-CI CH~OSi(CH3)3]CN
2.17 4-CI C~-l=NOH
2.18 s-No2 COCOOCH3 2.19 4-CH3 CH2ON=c(cN)cONH2 2.20 5-F CH=N-2'-CI-benzyl 2.21 5-P CH=CH-COOH
2.22 6-F C(NH2)=NOCH3 2.23 6-F CH2NH-cyclopropyl 2.24 6-F CH2NH-~(C2Hs)2 2.25 6-Br CH(Br)COO-benzyl , :. ............ ... . .

~; :: ,, . . : :
, .

- ~6 -~ . . i Comp. No. Xl, X2, X3 A Physical data 2.26 6-F CH2OCO-(2'-OH)-C6H4 2.27 6-F CH(OH)CH3 2.28 6-CH3 CHO
2.29 4,6-di-CH3 CHO
2.30 5-C~I3 CH2O~H3 2.31 S-CH3 CH2OCOCH3 2.32 5-F CHO m.p.129-131C
2.33 6-SCH3 COCH3 2.34 5-SCH3 CHO
2.35 5-F CI-I(OH)CCI3 m.p. l48-150~C
2.36 5-F CH2O(CO)-cyclopropyl m.p. 74-76C
2.37 4,6-di-F CHO
2.38 6-P CH2CN
2.39 6-F CHtNH2)CN
2.40 6-F C(N(CH3)2)=NH
2.41 5-F C(COOCH3)=CH-OH
2.42 5-F C(COOCH3=CH-OMe 2.43 S-F C(=NOH)NH2 2.44 4-F CHO
2.45 5-F C(=NOH)CN
2.46 5-F C-CH
2.47 5-F CH(CI)CCI3 2.48 6-F CH=CH2 2.49 4-F CH=CCI2 .. .
: 1 - : ~ . .

~ , 20$~27~' Table 3 ,.
X;~ N--N--C = N--NH~

X9 1~ N \~

Comp. No. Xl, X2, X3 X1', X2', X3 Xl'', X2', X3 Physical data 3.2 4-CI 4-Cl 3.3 - 4-NO2 3 4 - 3,5-di-CI
3.5 - - 2,4,6-triCI
3.6 - 3-C~3 3.7 - 3,5-di-CF3 2F
3.8 - - 3CF3 2,4-di-NO2 3.10 - 2-Me 2 Br 3.11 - - 2,6-di-Br 3.12 - 2-Cl 4-Me 3.13 4-F - -3.14 5-F
3.15 6-F
3.16 6-F - 2,4,6-tri-CI
3. 17 4,6-di-F
3. 18 5, 6-di-F
3.19 4,5-diF
3.20 4,5,6-triF
3.21 5-Br 4-NO2 2-CI
3.22 5-NO2 3.23 6-OMe 3-CF3 3,5-di-Br 3.24 6-SMe - 6-NO2 . . , ~ ", : ..

. .

2 ~

Table 4 Compounds known frorn the literature whose use as fun~icides is novel X2 ~ N~

Comp. No. Xl, X2, X3 A Physical data 4.1 - CHO m.p. 134-138C
4.2 - COCH3 m.p. 126-127C
4.3 6-Cl CHO m.p. 148-150C
4.4 6-SMe CHO m.p. 157-158C
4.5 4-Br-6CI CHO m.p. 131-133C
4.6 6-OMe CHO m.p. 174-176C
4.7 - CH=NOH m.p. 230C
4.8 6-OMe CH=NOH m.p. 217-218C
4.9 - COCHBr2 m.p. 119-120C

Formulation examples of active in~redients from the tables ~% = per cent bY wei~ht~
2.1 Wettablepowder a) b) c) Active ingredient from the tables 25 % 50 %75 %
Sodium lignin sulfonate 5 % 5 %
Sodium lauryl sulfate 3 % - 5 %
So(lium diisobutylnaphthalene sulfonate - 6 % 10 %
Octylphenol polyethylene glycol ether - 2 %
(7-8 mol of ethylene oxide) Highly-disperse silica 5 % 10 %10 %
Kaolin 62 % 27 %

The active ingredient is mixed with the additives and ground in a suitable mill until homogeneous. This gives wettable powders which can be diluted with water to givesuspensions of any desired concentration.

. . , , -.

, ~ .

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2 2 Emulsion concentrate Active ingredient from the tables10 %
Octylphenol polyethylene glycol ether 3 %
(4-5 mol of ethylene oxide) Calcium dodecylbenzene sulfonate3 %
Castor oil polyglycol ether 4 %
(35 mol of ethylene oxide) Cyclohexanone 30 %
Xylene mixture 50 %

Emulsions of any desired concen~ration can be prepared from this concentrate by dilu~ion with water.

2.3 Dllsts .1) b) _ Ac~ive ingredient from the tables5 % 8 %
'I~;llc 95 %
Kaolin - 92 %

Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture on a suitable mill.

2.4 Extmder ~ranules Active ingredient from the tables10 %
Sodium lignin sulfonate 2 %
Carboxymethyl cellulose 1 %
Kaolin 87 %

The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.

2.5 Coated granules Active ingredient from the tables3 %
Polyethylene glycol (MW 200) 3 %
Kaolin 94 %
(MW = molecular weight) .. " ; ; ~ .
... . .
..~, .

The kaolin is moistened with polyethylene glycol and, in a mixer, coated uniformly with the ~lnely ground active ingredient. In this manner, dust-free coated ~ranules are obtained.

2.6 Suspension concentrate Active ingredient from the tables 4~) %
Ethylene glycol 10 %
Nonylphenol polyethylene glycol ether 6 %
(15 mol ethylene oxide) Sodium lignin sulfonate 10 %
Carboxymethylcellulose 1 %
37 % aqueousformaldehyde solution 0.2 %
Silicone oil in the folm of a 75 %
aq~leous emwlsion 0.8 %
Water 32 %

Thc finely ground active ingredient is mixed intimately with the additives. 'I'his gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

3. Biological examples Example 3.1: ActivitY a~ainst Colletotrichum la~enarium on Cucumis sativus L.
a) Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture prepared with a wettable powder of the active ingredient (concentration: 200 ppm). After 48 hours, the plants are infected with a spore suspension (1.5 x 105 spores/ml) of the fungus and incubated for 36 hours at high atmospheric humidity and a temperature of 23C. The incubation is then continued at normal atmospheric humidity and 22C to 23C.

The protective action is assessed 7-8 days after the infection, using the fungus infestation as parameter.

b) Cucumber plants are grown for 2 weeks and then treated with a spray mixtllre prepared with a wettable powder of the active ingredient by soil application (concentration: ~0 or 2û ppm, relative to the soil volume). After 48 hours9 the plants are infected with a spore suspension (1.5 x 105 spores/ml) of the fungus and incubated for 36 hours at high .

atmospheric humidity and a temperature of 23C. The incubation is then continued at normal atmospheric humidity and 22C.

The protective action is assessed 7-8 days after the infection, using the fungus infestation as parameter.

c) Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture prepared with a wettable powder of the active ingredient (concentration: 200 ppm).

After 3 weeks, the plants are infected with a spore suspension (1.5 x 10~ spores/ml) of the fungus and incubated for 36 hours at high atmospheric humidity and a temperature of 23C. The incubation is then continued at normal atmospheric humidity and 22C to 23C.

Thé protective action is assessed 7-8 days after the infection, using the fungus infestation as parameter.

In tests (a) and (b), good activity is shown by compounds from Tables 1 to 4. For example, compounds 1.2, 1.6, 1.7, 1.12, 1.33, 1.38, 1.64, 1.79, 1.83, 1.85, 1.89, 1.91, 1.106, 1 108, 1.110, 1.113, 1.125, 1.127. 3.1,4.1 and4.2reducefungusinfestationtoOto20%. In contrast, untreated, but infected control plants show Colletotrichum infestation of lU0 %.

F,xample 3.2: Activitv a~ainst Phytophthora infestans on tomato plants a) Tomato plants are grown for 3 weeks and then sprayed with a spray mixture prepared with a wettable powder of the active ingredient (0.02 % active substance). After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is assessed after incubation of the infected plants for S days at 90-100 %
relative atmospheric humidity and 20C.

b) Tomato plants are grown for 3 weeks, and a spray mixture prepared with a wettable powder of the active ingredient is then poured near them (0.006 % active substance relative to the soil volume). Care is taken that the spray mixture does not come into contact with the above ground parts of the plants. After 48 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungus infestation is assessed after incubation of the infected plants for 5 days at 90-lûO % relative atmospheric humidi~y and 20C.

.

: ' , . '' '"""`' ,,, ~

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Compounds from Tables 1 to 4 show good protective action against the Phytophthora fungus. For example, fungus infestation is reduced to 0 to 20 % in test a) by compounds 1.6, 1.31, 1.38~ 1.83, 1.127 and 4.1 and in test b) by 1.1, 1.6, 1.12, 1.31, 1.38, 1.83, 1.85, 1.101 and 1.1()6. In contrast, untreated, but infected control plants show Phytophthora infestation of 100 %.

Example 3.3-. ActivitY a~ainst Pvricularia orvzae on rice plants a) Rice plants are grown for 2 weeks and then sprayed with a spray rr~ixture prepared with a wettable powder of the active ingredient (0.02 % active substance). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. Fungus infestation is assessed after incubation for 5 days at 95-100 % relative atmospheric humidity and 24C.

b) A spray mixture prepared with a wettable powder of the active ingredient (0.006 %
active substance relative to the soil volume) is poured near rice plants aged 2 weeks. The pots are then filled with water to such an extent that the lower portions of the stems of the rice plants are immersed in the water. After 96 hours, the treated rice plants are in~ected with a conidia susyension of the fungus. Fungus infestation is assessed after incubation of the infected plants for 5 days at 95-100 % relative atmospheric humidity and approx.
24C.

Compared with untreated control plants (100 % infestation) Tice plants which have been treated with a spray mixture comprising, as active substance, a compound from Tables 1 to 4, only show a low level of fungus infestation. For example, the infestation is reduced to 0 to 20 ~o in test (a) by compounds 1.6, 1.98, 1.101 und 4.1 and in test (b) by compounds 1.6, 1.64, 1.66, 1.101, 4.1 and 4.7.

Example 3.4: ActivitY against Peronospora tabacina on tobacco plants A) Foliar application Tobacco plants (8 weeks old) are sprayed with a formulated solution of the active ingredient (concentration: 0.02 % active substance). Four days after the treatment, the plants are inoculated with a sporangia suspension of Peronospora tabacina (104 sporangia/ml), kept for 20 hours in the dark at 25C and high atmospheric humidity, and then incubated further with normal day/night rythm.

,: ::
' ~ ;
. ~ .

B) Soil application Tobacco plants (8 weeks old) are treated with a forrnulated solutîon of the active ingredient by soil application (concentration: ~).006 % active substance relative to the soil volume). After 4 days, the plants are inoculated with a sporangia suspension of Peronospora tabacina (1~4 sporangia/ml), kept for 20 hours in the dark at 25C and high atmospheric humidity, and then incubated further with normal day/night rythm.

The symptoms in tests A and B are assessed using the fungus-in1Fested leaf area as parameter.

The control plants show infestation of 90 to 100 %. Plants which have been treated with compound 1.6 or 4.1 in test A, show infestation of 0-30 %.

Example 3.5: Activitv a~ainst Bremia lactucae in lettuce A formlllated solution of the active ingredient (0.002 % active substance relative to the soil volume) is poured near lettuce plants aged two weeks. After 5 days, the treated plants are inoculated with a spore suspension of îhe fungus (5 x 104 s/ml). The plants are incubated at 18C, first under a cover (relative atmospheric hurnidity 90-100 %) for 2 days, then without cover for 7 days. To induce sporulation of the fungus, the plants are again placed under a cover for 3 days.

Fungus infestation is assessed 12 days after inoculation, using the fungus-infested leaf area as parameter.

Compounds from Tables 1 to 4 show good activity against Bremia. ror example, plants which have been treated with compounds 1.1, 1.2, 1.6, 1.98 or 4.1, remain largely free from infestation (damage 0-30 %). In contrast, untreated, but infected plants (control) show a Bremia infestation of 100 %.

Example 3.6: Activity a~ainst Erysiphe ~raminis in wheat Protective action: Wheat plants, 17 days old, are sprayed with a forrnulated solution of the active ingredient (0.02 % active substance). Immediately after the treatment, the plants are incubated under cylindrical covers. After 24 hours, the plants are uncovered. After a further 3 days, the treated plants are cut above the primary leaf. The primary leaves are positioned horizontally and, in an ins)culation tower, inoculated with spores of Erysiphe ~1 . :! .

', ' , : ' , ,, ,' : : : . ~

2 ~

- 6q graminis (spore density: 0.2 mg per m~-). I'he test is carried out in a controlled-environment cabinet with 12h light (18 KLux), 20C and 12h darkness, 18C.
The infestation is assessed 9 and 13 days after inoculation.

In this test, compounds from Tables 1 to 4 used as active ingredient show a good activity against Erysiphe grarninis. ~or example, plants which have been ~reated with compound 1.1, 1.2, 1.6, 1.7, 1.12, 1.31, 1.33, 1.38, 1.66, 1.83, 1.98, 1.1û8, 4.1 or 4.2 remain largely free from Erysiphe infestation (damage 0 to 20 %). In contrast, un~reated, but infected plants (control) show Erysiphe infestation of 100 %.

Example 3.7: Activitv a~ainst Cercospora arachidicola on peanut plants Peanut plants, 10-15 cm in height, are sprayed with a spray mixture prepared with a wettable powder of the active ingredient (O.Q2 % active substance) and, after 48 hours, infected with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at approx. 21C and high atmospheric humidity, and subsequently placed in a greenhouse until the typical lesions on the leaves appear. The fungicidal activity is assesse~l 12 days after infection, using number and size of the lesions as parameter.

Compared with untreated, but infected control plan.s (number and size of lesions =
100 %), peanut plants which have been treated with active ingredients fTom Tables 1 to 4 show substantially reduced Cercospora infestation. For example, in the above experiments, compounds ~os. 1.83, 1.85, 1.108, 1.125, 1.127, 3.1 and 4.7 largely prevent the occurrence of lesions (0-20 %).

Example 3.8: Activity a~ainst Puccinia ~raminis in wheat a) Residual-protective action 6 days after sowing, wheat plants are sprayed with a spray mixture prepared with a wettable powder of the active ingredient (0.02 % active substance). 24 hours later, the treated plants are infected with a ureido spore suspension of the fungus. After incubat;on for 48 hours at 95-100 % relative atmospheric humidity and approx. 20C, the infected plants are placed in a greenhouse at approx. 22C. The development of rust pus~ules is assessed 12 days after infection.

b) Systemic ac~ion 5 days after sowing, a spray mi7~ture prepared with a wettable powder of the active . .

.
, ingredient (0.006 % active substance relative to the soil volume) is poured near wheat plants. After 48 hours, the treated plants are infected with a ureido spore suspension of the fungus. ~rter incubation for 48 hours at 9~-100 % relative atmospheric homidity and -approx. 20C, the infected plants are placed in a greenhouse at approx. 22C. The development of rust pustules is assessed 12 days a-fter infection.

Untreated, but infected control plants show Puccinia infestation of 100 %. Compounds from Tables 1 to 4 show good action against Puccinia fungi.

For example, fungus infestation was reduced to less than 20 % in test a) by compounds Nos. 1.7, 1.8, 1.31, 1.64, 1.79, 1.83, 1.98, 1.113, 1.125, 1.127 and in test b) by No. 1.113.

Example 3.9: Action a ainst Pseudomonas lachrvmans on Cucumis sativus L.
A) Foliar application Cucumber plants are grown for 2 weeks and then sprayed with a spray mixture prepared with a wettable powder of the active ingredient (concentration: 0.02 G/o active substance).

After I week, the plants are infecte(l with a b.tcteria suspension (108 bacteria/rnl) and incubated for 7 days at high atmospheric humidity and a temperature of 23C.

The protective action is assessed 7-8 days after infection, using bacterial infestation as parameter.

Compounds from Tables 1 to 4 provide good protection against Pseudomonas lachryrnans.
For example, plants which have been treated with compound 1.31, 1.38, 1.108 or 4.2 remain largely free from Pseudomonas (infestation 20 to 0 %).

B) Soil application Cucumber plants are grown for 2 weeks and then treated by soil application with a spray mixture prepared with a wettable powder vf the active ingredient (concentration: 0.002 %
active substance relative to the soil volume).

After 1 week, the plants are infected with a bacteria suspension (108 bacteria/ml) and incubated for 7 days at high atmospheric humidity and a temperature of 23C.

The protective action is assessed 7-8 days after infection, using bacterial infestation as the :
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parameter.

Compounds from Tables 1 to 4 effect good immunisation against Pseudomonas lachrymans. For example, plants which have been treated for example with compound 1.31, 1.33, 1.38 or 1.108 remain virtually completely free from Pseudomonas (infestation 20 t~ 0 %).

In tests A and B, untreated, but infected control plants show a disease level of 100 %.

Example 3.10: Activity a~ainst Plasm~ara viticola on ~rape vine Grape vine seedlings in the 4-5 leaf stage are sprayed with a spray mixture prepared with a wettable powder of the active ingredient (0.02 % active substance). After 1 week, the treated plants are infected with a sporangia suspension (S x 104 sporangia/ml) of the fungus. The protective action is assessed after incubation for 6 days at 95-100 % relative atmospherlc humidity and 20C.

In this test, untreated, but infected control pl~mts show an infestation of 100 %.

Compounds from Tables 1 to 4 effect good immunisation against Plasmopara viticola. For e~sample, grape vines which have been treated for example with compound 1.83 or 1.125 remain largely free from Plasmopara viticola (infestation 20 to 0 %).

Example 3.11: Activitv a~ainst Cercospora nicotianae on tobacco plants Foliar application Tobacco plants (8 weeks old) are sprayed with a formulated solution of the active ingredient ~concentration: 200 ppm). Four days after the treatment, the plants are inoculated with a spore suspension of Cercospora nicotianae (105 spores/ml) and incubated for S days at high atmospheric humidity and a temperature of 22-25~. The incubation is then continued at norrnal atmospheric humidity and 20-22C

The symptoms in the test are assessed 12-14 days after infection, using fungus infestation as parameter.

The control plants show in~estation of 100 %. Plants which have been treated with compounds 1.83, 1.85, 1.108, 1.125, 1.127, 3.1 or 4.7 show infestation of 0-20 %.

.;

~3227~

Example 3.12: Activity a~ainst Pvthium ultimum on Zea maize (maize, cv. Sweet Corn) l'est principle: Soil fwngus: protective-local soil application.

Test method: Mycelium of PYthium ultimum mixed with soil (500 ml mycelium suspension per 10 litres of soil), and 250 ml plastic dishes are filled with the fungu.s/soil mixture. After incubation for 4 days at 10C, 10 kernels of the test plant (maize) are placed into each dish. On the following day, the dishes which have been prepared in this way are each irrigated with 5û ml of spray solutions prepared with 25 % wettable powder and water comprising 20; 6; 2; 0.6; 0.2; 0.06 and 0.02 ppm of active substance. After an incubation phase of 7 days a~ 10C and a subsequent incubation phase of 4 days at 22C, the effect of the test substances is assessed by numeric determination of the emergence of the test plants.
Compounds from Tables 1-4 show good activity against Pythium ultimum. For example, compound 1.125 shows an activity of above 80 %.

.

Claims (20)

1. A composition for controlling or preventing infestation by harmful microorganisms, which comprises, as active component, at least one compound of the formula I

(I) in which:
X1, X2 and X3 independently of one another are hydrogen, methyl, methoxy, methylthio, halogen or nitro;
A is C1-C2alkyl which is substituted by a maximum of 3 X-C1-C4alkyl groups, methyl which is substituted by 2 or 3 halogen atoms, ethyl which is substituted by hydroxyl and/or not more than 4 halogen atoms, vinyl which is unsubstituted or substituted by not more than 3 halogen atoms; furthermore ethynyl, propargyl, formyl, acetyl, acetyl which is substituted by not more than 3 halogen atoms, or one of the groups C(R)=N-N(R2)R3, C(N=N-U1)=N-NH-U1, CH(R)-[N(R1)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(R1)R2, CH(R)-O-N=C(CN)-CONH-R5, C(R6)=N-(O)nR, CH(R)-Y-E-R3, CO-[C(OR)2]nQ, C(Q)=CH-OR or T-Q;
in which furthermore:
n is zero or 1;
X and Y independently of one another are oxygen or sulfur;
R and R1 independently of one another are hydrogen or C1-C2alkyl;
R2 is hydrogen, C1-C8alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, benzyl or cyano;
R3 is hydrogen, C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, benzyl or is an aryl radical U;
R4 is hydrogen, C1-C6alkyl, Si(C1-C6alkyl)3 or OCOC1-C3alkyl;
R5 is hydrogen or CONHR1;
R6 is N(R1)R2, hydrazino or Q;
E is CO or SO2;
U and U1 independently of one another are a phenyl radical which is unsubstituted or monosubstituted or polysubstituted by identical or different substituents from the series comprising methyl, methoxy, halogen, trifluoromethyl, nitro or cyano;

T is C1-C2alkylene, methylene which is substituted by amino, hydroxyl or halogen, the substituents being independent of one another, or is ethenylene which is unsubstituted or substituted by halogen or cyano;
Q is COXR or cyano, together with a suitable carrier material.

2. A composition according to claim 1, which comprises, as active component, at least one compound of the formula I in which:
X1, X2 and X3 independently of one another are hydrogen or fluorine;
A is C1-C2alkyl which is substituted by a maximum of 3 X-C1-C4alkyl groups, methyl which is substituted by 2 or 3 halogen atoms, ethyl which is substituted by hydroxyl and/or not more than 4 halogen atoms, or formyl, acetyl, or one of the groups C(R)=N-N(R2)R3, CH(R)-[N(R1)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(R1)R2, CH(R)-O-N=C(CN)-CONH-R5, C(R6)=N-(O)nR, CH(R)-Y-E-R3, CO-[C(OR)2]nCOXR, C(Q)=CH-OR or T-Q;
in which furthermore:
n is zero or 1;
X and Y are oxygen;
R and R1 independently of one another are hydrogen or C1-C2alkyl;
R2 is hydrogen, C1-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, C3-C6cyeloalkyl or benzyl;
R3 is hydrogen, C1-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, C3-C6cycloalkyl or a phenyl radical which is substituted by identical or different substituents from the series comprising methyl, halogen or trifluoromethyl;
R4 is hydrogen, C1-C3alkyl or Si(C1-C2alkyl)3;
R5 is hydrogen or CONHC1-C3alkyl;
R6 is amino or cyano;
E is CO;
T is methylene, methylene which is substituted by amino or ethenylene;
Q is COOR or cyano.

3. A composition according to claim 1, which comprises, as active component, at least one compound of the formula I, in which:
X1, X2 and X3 are hydrogen;
A is methyl which is substituted by a maximum of 2 X-C1-C4alkyl groups, methyl which is substituted by 2 or 3 fluorine or chlorine atoms, ethyl which is substituted by hydroxyl or chlorine, or formyl, acetyl, or one of the groups C(R)=N-N(R2)R3, CH(R)-[N(R1)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N(O)nR3, CH(R)-O-N=C(R1)R2, CH(R)-O-N=C(CN)-CONHR5, C(R6)=N-OR, CH(R)-Y-E-R3, CO[C(OR)2]nCOXR, C(COOR)=CH-OR or T-Q;
in which furthermore:
n is 1;
X is oxygen;
R and R1 independently of one another are hydrogen or methyl;
R2 is hydrogen, C1-C2alkyl, allyl, propargyl, cyclopropyl or benzyl;
R3 is hydrogen, C1-C2alkyl, allyl, propargyl, cyclopropyl, or a phenyl radical which is substituted by identical or different substituents from the series comprising methyl, fluorine, chlorine or trifluoromethyl;
R4 is hydrogen, C1-C2alkyl or Si(CH3)3;
R5 is hydrogen or CONH-C1-C2alkyl;
R6 is amino;
Y is oxygen;
E is CO;
T is methylene or cyano.

4. A composition according to claim 1, which comprises, as active component, at least one compound of the formula I, in which:
X1, X2 and X3 are hydrogen;
A is methyl which is substituted by a maximum of 2 X-C1-C2alkyl groups, methyl which is substituted by 2 or 3 fluorine atoms, ethyl which is substituted by hydroxyl or chlorine, or formyl, or one of the groups C(R)=N-N(R2)R3, CH(R)-[N(R1)]n-N(R2)R3, C(R)(CN)OR4, C(R)=N-R3, CH(R)-O-N=C(R1)R2, C(R6)=N-OR, CH(R)-Z-E-R3, CO[C(OR)2]nCOXR or T-Q;
in which furthermore:
n is 1;
X is oxygen;
R and R1 independently of one another are hydrogen or methyl;
R2 is hydrogen, methyl, allyl, cyclopropyl or benzyl;
R3 is hydrogen, methyl, allyl, cyclopropyl, or a phenyl radical which is substituted by identical or different substituents from the series comprising methyl, fluorine, chlorine or trifluoromethyl;
R4 is hydrogen, methyl or Si(CH3)3;
R5 is hydrogen or CONH-CH2-CH3;

R6 is amino;
Y is oxygen;
E is CO;
T is methylene;
Q is COOCH3 or cyano.

5. A composition according to claim 1, which comprises, as active component, at least one compound from the group:
7-formyl- 1,2,3-benzothiadiazole;
7-acetoxymethyl- 1,2,3-benzothiadiazole;
7-[methoxyimino-(2-cyanoacetamyl)]- 1,2,3-benzothiadiazole;
7-(N-methoxyiminomethyl)- 1,2,3-benzothiadiazole;
7-(N-methoxyiminohydroxymethyl)- 1,2,3-benzothiadiazole;
7-methoxymethyl-1,2,3-benzothiadiazole;
3-(7-benzo-1,2,3-thiadiazolyl)acrylic acid;
7-cyanomethyl-1,2,3-benzothiadiazole;
7-trichloromethyl- 1,2,3-benzothiadiazole;
7-dichloromethyl- 1,2,3-benzothiadiazole;
benzo-1,2,3-thiadiazole-7-(N-hydroxycarboximidamide);
benzo- 1,2,3-thiadiazole-7-(N-methoxyhydroxamic acid);
2-(benzo-1,2,3-thiadiazolyl)-2-hydroxyiminoacetonitrile;
5-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;

6-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;
4-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;
N,N-diphenyl-C-[benzo-1,2,3-thiadiazol-7'yl]formazan;

7-acetylbenzo-1,2,3-thiadiazole;
7-(bromoacetyl)benzo-1,2,3-thiadiazole.

6. A compound of the formula I according to claim 1, with the exception of the following compounds:
7-formyl-1,2,3-benzothiadiazole;
7-acetyl-1,2,3-benzothiadiazole;
6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methylthio-7-formyl-1,2,3-benzothiadiazole;
4-bromo-6-chloro-7-formyl-1,2,3 benzothiadiazole;
6-methoxy-7-formyl-1,2,3-benzothiadiazole;

7-hydroxyimino-1,2,3-benzothiadiazole;
6-methoxy-7-oximino-1,2,3-benzothiadiazole, 7-dibromoacetyl-1,2,3-benzothiadiazole.

7. A compound of the formula I according to claim 2, with the exception of the following compounds:
7-formyl-1,2,3-benzothiadiazole;
7-acetyl-1,2,3-benzothiadiazole;
6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methylthio-7-formyl-1,2,3-benzothiadiazole;
4-bromo-6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methoxy-7-formyl-1,2,3-benzothiadiazole;
7-hydroxyimino-1,2,3-benzothiadiazole;
6-methoxy-7-oximino-1,2,3-benzothiadiazole, 7-dibromoacetyl-1,2,3-benzothiadiazole.

8. A compound of the formula I according to claim 3, with the exception of the following compounds:
7-formyl-1,2,3-benzothiadiazole;
7-acetyl-1,2,3-benzothiadiazole;
6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methylthio-7-formyl-1,2,3-benzothiadiazole;
4-bromo-6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methoxy-7-formyl-1,2,3-benzothiadiazole;
7-hydroxyimino-1,2,3-benzothiadiazole;
6-methoxy-7-oximino-1,2,3-benzothiadiazole, 7-dibromoacetyl-1,2,3-benzothiadiazole.

9. A compound of the formula I according to claim 4, with the exception of the following compounds:
7-formyl-1,2,3-benzothiadiazole;
7-acetyl-1,2,3-benzothiadiazole;
6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methylthio-7-formyl-1,2,3-benzothiadiazole;
4-bromo-6-chloro-7-formyl-1,2,3-benzothiadiazole;
6-methoxy-7-formyl-1,2,3-benzothiadiazole;

7-hydroxyimino-1,2,3-benzothiadiazole;
6-methoxy-7-oximino-1,2,3-benzothiadiazole, 7-dibromoacetyl-1,2,3-benzothiadiazole.

10. A compound of the formula I, selected from the group:
7-acetoxymethyl-1,2,3-benzothiadiazole;
7-[methoxyimino-(2-cyanoacetamidyl)]-1,2,3-benzothiadiazole;
7-(N-methoxyiminomethyl)-1,2,3-benzothiadiazole;
7-(N-methoxyiminohydroxymethyl)-1,2,3-benzothiadiazole;
7-methoxymethyl-1,2,3-benzothiadiazole;
3-(7-benzo-1,2,3-thiadiazolyl)acrylic acid;
7-cyanomethyl-1,2,3-benzothiadiazole;
7-trichloromethyl-1,2,3-benzothiadiazole;
7-dichloromethyl-1,2,3-benzothiadiazole;
benzo-1,2,3-thiadiazole-7-(N-hydroxycarboximide-amide);
benzo-1,2,3-thiadiazole-7-(N-methoxyhydroxamic acid);
2-(benzo-1,2,3-thiadiazolyl)-2-hydroxyiminoacetonitrile;
5-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;
6-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;
4-fluoro-benzo-1,2,3-thiadiazole-7-carbaldehyde;
N,N-diphenyl-C-[benzo-1,2,3-thiadiazol-7'yl]formazan;
7-acetylbenzo-1,2,3-thiadiazole;
7-(bromoacetyl)benzo-1,2,3-thiadiazole.

11. A method of controlling or preventing infestation of crop plants by phytopathogenic microorganisms, which comprises applying to the plant, parts of the plant or the locus of the plant, a compound of the formula I according to claim 1 as active ingredient.

12. A method according to claim 11, wherein a compound according to claim 2 is applied as active ingredient.

13. A method according to claim 11, wherein a compound according to claim 3 is applied as active ingredient.

14. A method according to claim 11, wherein a compound according to claim 4 is applied as active ingredient.

15. A method according to claim 11, wherein a compound according to claim 5 is applied as active ingredient.

16. A method according to claim 11, wherein phytopathogenic fungi and bacteria are controlled.

17. A method according to claim 11, wherein useful plants are immunised against diseases.

18. A process for the preparation of an agrochemical composition according to claim 1, wherein at least one compound of the formula I is mixed intimately with suitable solid and/or liquid carriers.

19. The use of a compound of the formula I according to claim 1 for protecting plants against diseases.

20. The use according to claim 19 of a compound according to one of claims 2 to 5.

FD 4.5/PK/lb