Arylacetamides, process for their preparation, compositions containing them and their use as fungicides

The present invention relates to arylacetamides, process for their preparation, compositions containing them and their use as fungicides.

Substituted arylacetamides containing in which an optionally substituted hydroxy group is attached at the ..-position are described as active components in herbicides (JP- 5 8032-853) and as compositions for treating skin diseases (EP-A-98743) . There are also many references to compounds of this type as intermediates and in the chemical literature.

Surprisingly new arylacetamides have been found that show advantageous activity in combating fungi, especially phytopathogenic fungi.

The present invention thus relates to the use for combating fungi, of a compound of formula I, its stereoiso ers as well as mixtures of these, 0

II

A-B-C-N-X-A' (I) ,

in which

A is an optionally substituted aryl group;

A' is an optionally substituted aryl group;

B is a carbonyl group or a methylene group which is substituted by optionally substituted hydroxy and an optional further substituent;

X is an optionally substituted alkylene chain of 2 to 4

carbon atoms, in v/hich two optional substituents on any one carbon can form an oxo or optionally substituted imino group; and R ⁷ is heterocyclyl, aryl, silyl, alkyl, alkenyl, cycloalkyl, alkynyl, cycloalkenyl, amino, hydroxy, mercapto, each of which is optionally substituted or is hydrogen, cyano or acyl and in which when B is substituted by optionally substituted hydroxy, the substituent on the hydroxy can form a ring with either R ⁷ or with the other optional substituent on B.

Many of the compounds of formula I are novel and the invention thus includes all such novel compounds and especially compounds of formula I in which X and R ⁷ are as previously defined;

B is a methylene group which is substituted by optionally substituted hydroxy;

A' is dialkoxyphenyl, in which the phenyl group is optionally further substituted; and A is phenyl, substituted by one or more groups selected from halo, cyano, nitro, optionally substituted amino, optionally substituted alkyl, haloalkoxy, aryl, heterocyclyl, in which the phenyl group is optionally further substituted.

Of these novel compounds A is preferably phenyl, substituted by one or more groups selected from halo, cyano, alkyl, trifluoromethyl and haloalkoxy. It is particularly preferred that there is a substituent in the 4-position.

A' is preferably 3,4-dimethoxyphenyl or 4-ethoxy- 3-methoxyphenyl.

The invention also includes as novel compounds all the compounds in the tables for v/hich a melting point or a physical description, such as oil, gum, wax or foam has been given.

In the above, alkyl groups and the alkyl moiety of alkyl- containing groups are preferably of 1 to 20, eg 1 to 6, carbon atoms. Alkenyl and alkynyl groups are generally of 3 to 6 carbon atoms. Cycloalkyl or cycloalkenyl groups are preferably of 3 to 8 carbon atoms.

Substituents, when present on any alkyl, cycloalkyl, cycloalkenyl, alkenyl, alkynyl, alkoxy or alkylthio group, include halogen, cyano, alkoxy (e.g. of 1 to 4 carbon atoms, and which may be substituted, e.g. by halo) , hydroxy, alkylthio, nitro, optionally substituted amino, carboxy, alkoxycarbonyl, acyl, acyloxy, heterocyclyl and aryl.

Cycloalkyl or cycloalkenyl groups may also be substituted by alkyl.

Aryl groups are phenyl and when optionally substituted, substituents are, e.g. halogen, optionally substituted alkyl or alkoxy, aryl, heterocyclyl, aryloxy, cyano, nitro, optionally substituted amino or acyl or two adjacent groups can form and fused benzo group which is optionally substituted as for aryl. Preferred substituents on any aryl group are halogen, alkyl, trifluoromethyl, alkoxy, haloalkoxy, nitro, dialkylamino, amino or cyano.

Hydroxy and mercapto groups can be substituted by a range of groups including, e.g. optionally substituted alkyl, optionally substituted cycloalkyl, aryl, acyl, cyano and heterocyclyl

Optional further substituents on B, when it is a hydroxy substituted methylene group include those which can be optional substituents on hydroxy.

The term heterocyclyl includes both aromatic and non- aromatic heterocyclyl groups. Heterocyclyl groups are generally 5 or 6-membered rings containing up to 3 hetero atoms from nitrogen, oxygen and sulfur. The heterocyclyl groups may be fused to a benzene ring to form a fused heterocyclyl group. Examples of heterocyclyl groups are thienyl, furyl, pyridyl, pyri idinyl, pyrazolyl, thiazolyl, thiazolinyl, oxazolyl, benzimidazolyl, tetrazolyl, benzoxazolyl, thiadiazolyl, dioxolanyl, imidazopyridinyl, 1, 3-benzoxazinyl, 1, 3-benzothiazinyl, oxazolopyridinyl, triazolyl, triazinyl, imidazolyl, orpholino, benzofuranyl, pyrazolinyl, quinolinyl, quinazolinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, piperidinyl, phthalimido, 2-oxopyrrolidino, 2-oxobenzoxazolin-3-yl and benzofuranyl. Heterocyclyl groups may themselves be substituted for example as for phenyl.

Amino groups may be substituted for example by one or two optionally substituted alkyl or acyl groups, or two substituents can form a ring, preferably a 5 to 7-membered ring, which may be substituted and may contain other hetero atoms, for example morpholine, thiomorpholine, or piperidine.

The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -C0R ^a , -COOR ^a , -CO-Am, -CS-Am, -COSR ^a , -CSSR ^a , -S(0) _q R ^a , -S(0) ₂ OR ^a , -S(0) _q Am, -P(=0) (0R ^a ) (0R ^b ) , -P(=S) (OR ^a ) (0R ^b ) and -CO-COOR", where R ^a and R ^b , which may be the same or different, are hydrogen.

optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, aryl or heterocyclyl, Am is optionally substituted amino and q is 1 or 2.

In a preferred group of compounds

A is a group of formula II or III;

is a group of formula IV or V;

m, n, m' and n' are integers; m = 1 to 5; n = 1 to 7; m' = 0 to 5; n' = 0 to 7;

R ¹ and R ² , which are the same or different and independently of each other, are (C,-C ₁₈ ) -alkyl,

(C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C ₁₂ )-cycloalkyl-(C Cg) -alkyl, (C ₆ -C ₁₈ )-aryl, (C ₆ -Cι ₈ ) -aryl-(C C ₆ ) -alkyl, (C _j -C ₈ ) -heteroaryl, C _[ -C ₈ ) -non-aromatic heterocyclyl, (C _j -C ₈ ) -heteroaryl-(C,-^) -alkyl, (C _j -C ₈ ) -non-aromatic heterocyclyl-(C _j -C ₆ )-alkyl, cyano, nitro, halogen, -COR ³ , -COOR ³ , -CONR-R ⁴ , -OR ³ , -OCOR ³ , -OCOOR ³ , -OCO-NR-R ⁴ , -SR ³ , -SOR ³ , -S0 ₇ R ³ , -S0 ₇ -OR ³ , -S0 ₂ NR ³ R ⁴ ,

-NR ³ R ⁴ , -NR -SO,R ⁴ , -NR -COR ⁴ , -P(0) (OR ³ ) (OR ⁴ ) , -O-

P(0) (OR ³ ) (OR ⁴ ) or -SiR ³ ₃ , and in which in the first ten named groups, optionally at least one of the following conditions is fulfilled:

a) if one, two or three CH-CH-units are present which are not in a ring, each is replaced by one, two or three CH=CH-units,

b) if a CH-i-CH -unit is present which is not in a ring, it is replaced by a C≡C-unit,

c) if a CH-CH-unit is present which is in a ring it is replaced by a C=C-unit,

d) hydrogen atoms present on carbon atoms which are not part of a ring are replaced by up to three of the same or different substituents from the group cyano, nitro, halogen, -COR ³ , -COOR ³ , -CONR-R ⁴ , -OR ³ , -OCOR ³ , -OCOOR ³ , -O-CO-NR-R ⁴ , -SR ³ , -SOR ³ , -S0 ₂ R ³ , -S0 ₂ -OR ³ , -S0 ₂ -NR ³ R ⁴ , -NR ³ R ⁴ , -NR ³ -COR ⁴ , -P(O) (OR ³ ) (OR ⁴ ) , -0-P(0) (OR ³ ) (OR ⁴ ) and -SiR ³ ₃ ,

e) hydrogen atoms remaining on carbon atoms which are not part of a ring, after substitution according to d) , are replaced by partially or fully by the same or different halogen atoms,

f) hydrogen atoms present on carbon atoms which are part of a ring are replaced by up to three of the same or different substituents from the group R ³ (R ³ =hydrogen excepted) and the substituents noted under d) ,

g) hydrogen atoms remaining on carbon atoms which are

part of a ring, after substitution according to f) , are replaced by partially or fully by the same or different halogen atoms,

h) one or two of the CH-,-units present, except those in the coupling position of the groups, are replaced by the same or different groups from the group 0, S, CO and NR ³ ;

R ³ and R ⁴ which are the same or different and independently of each other are hydrogen, (C _j -C ₁₈ ) -alkyl, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C ₁₂ ) -cycloalkyl-(C _| -C ₆ )-alkyl, (C ₆ -C _lg )-aryl, (C ₆ -C ₁₈ ) -aryl-(C _r C ₆ ) -alkyl, (C _j -C ₈ ) -heteroaryl or (C _[ -C ₈ ) -heteroaryl-(C _j -C ₆ ) - alkyl, in which in the first seven named groups, optionally at least one of the following conditions is fulfilled:

a) if one, two or three CH-CH-units are present, which are not in a ring, each is replaced by one, two or three CH=CH-units,

b) if a CH ₂ -CH ₎ -unit is present, which is not in a ring, it is replaced by a C≡C-unit,

c) if a CH-CH-unit is present, which is in a ring, it is replaced by a C=C-unit,

d) hydrogen atoms present on carbon atoms which are not part of a ring, are replaced by up to three of the same or different substituents from the group cyano, nitro, halogen, -COR ^3' , -COOR ^3' , -CONR ^3' ₂ , -OR ^3' , -0C0R ^3' , -OCOOR ^3' , -O-CO-NR ^3' , -SR ^3' , -SOR ^3' , -S0 ₂ R ^3' , -S0 ₂ -0R ^3' , -S0 ₂ -NR ^3' ₂ , -NR ^3' ₂ , -NR ^3' -C0R ^3' , -P(0) (OR ³ ) (OR ⁴ ) , -O-P(O) (OR ³ ) (OR ⁴ ) and -SiR ^3' ₃ ,

e) hydrogen atoms remaining on carbon atoms which are not part of a ring, after substitution according to d) , are replaced by partially or fully by the same or different halogen atoms,

f) hydrogen atoms present on carbon atoms which are part of a ring are replaced by up to three of the same or different substituents from the group R ³ (R ³ =hydrogen excepted and the substituents noted under d) ,

g) hydrogen atoms remaining on carbon atoms which are part of a ring, after substitution according to f) , are replaced by partially or fully by the same or different halogen atoms,

h) one or two of the CH ₂ -units present, except those in the coupling position of the groups, are replaced by the same or different groups from the group O, S, CO and NR ^3' , or

R ³ and R ⁴ together form a (C ₃ -C ₆ ) -alkylene group, in which a CH ₂ -group is optionally replaced by CO, O, S or NR ³ ;

R ^3' is the same or different group from the group hydrogen, (C C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, (C _j -C ₆ ) -haloalkyl, (C ₂ -C ₆ ) -haloalkenyl, (C ₂ -C ₆ ) -haloalkynyl, (C ₃ -C ₆ ) -cycloalkyl, (C ₃ -C ₆ ) -cycloalkyl-(C,-C ₄ ) -alkyl, (C ₆ -C ₁₀ ) -aryl, (C ₇ -C _n ) -aralkyl and (C _| -C ₅ ) -heteroaryl, in which the last three named groups can carry one or two of the same or different substituents in the ring from the group cyano, nitro, halogen, (C _j -C ₄ )-alkyl, (C _j -C ₄ )- haloalkyl, (C _j -C ₄ ) -alkoxy, (C _j -C ₄ ) -haloalkoxy, phenyl.

phenoxy, benzyl and benzyloxy;

B is a group of formula VI or VII;

,.R ⁵ 0

II !

— c— (VI ) — c- ( I I )

- 6

R ⁵ is hydrogen, (C _[ -C ₁₈ ) -alkyl, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C, ₂ ) -cycloalkyl- (C _r C _ύ ) -alkyl, (C ₆ -C ₁₈ ) -aryl, (C ₆ -C ₁₈ ) -aryl-(C,-C ₆ ) -alkyl, (C _j -C ₈ ) -heteroaryl, (C,-C ₈ ) -heteroaryl-(C _[ -C ₆ ) -alkyl, cyano, -COR ³ , -COOR ³ , -CONR-R ⁴ or -SiR ³ ₃ and R ³ and R ⁴ are as defined above, in which in the second to eighth of the named groups optionally at least one of conditions a) to h) specified for groups R ¹ and R ² are fulfilled;

R ⁶ is hydrogen or is as defined for R ¹ , whereby R ⁶ , in the case when R ⁵ =hydrogen, is not connected via an 0-, S- or N-atom, or R ⁵ and R ⁶ together form a (C ₃ -C ₆ ) -alkylene group, in which a CH ₂ - group is optionally replaced by CO, 0, S or NR ³ and/or one of the CH-CH-units present is optionally replaced by a C=C-unit; R ⁷ is hydrogen or, with the exception of nitro and halogen, is defined as for R ¹ , or R ⁵ and R ⁷ together form a (C ₇ -C ₅ ) -alkylene group, in which a CH ₂ -group is optionally replaced by CO, 0, S or NR ³ and/or one of the CH-CH-units present is optionally replaced by a C=C-unit, and R ⁶ is as defined above, R ⁶ and R ⁷ together form a (C ₃ -C ₆ ) -alkylene group, in which a CH ₉ - group is optionally replaced by CO, 0, S or NR ³ and/or one of the CH-CH-units present is optionally

replaced by a C=C-unit, and R ³ is as defined above; X is a group of formula VIII,

-CR ^S R ⁹ -(CR ¹⁰ R ^M ) _p - (VIII)

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , which are the same or different and independently of each other, are as defined for R ⁷ or are halogen or nitro, and where R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ , by forming an oxo group can also together be O, or

R ¹⁰ and R ¹¹ together can form a group =N-OR ³ , or R ⁷ and R ^s together form a (C-,-C ₅ ) -alkylene group, R ⁷ and R ¹⁰ together form a (C,-C ₄ ) -alkylene group or R ⁸ and R ¹⁰ together form a (C ₃ -C ₆ ) -alkylene group in which in each case a CH- _> -group is optionally replaced by CO, 0, S or NR ³ and/or one of the CH-CH-units present is optionally replaced by a C=C-unit, and the groups which are not concerned with this ring connection are as defined above; and p is 1, 2 or 3, as well as their salts, especially acid addition salts.

Preferred compounds of formula I are those in which R ¹ and R ² , which are the same or different and independently of each other, are (C _t -C ₁₂ ) -alkyl, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C ₁₂₎ -cycloalkyl-(C _j -C ₄ ) -alkyl, (C ₆ -C ₁₂ )-aryl, (C ₆ -c ₁₂ ) -aryl-(C _r C ₄ ) -alkyl, (C,-C ₈ ) -heteroaryl, (C,- ₈ ) -heteroaryl-(C _j -C ₄ ) -alkyl, cyano, nitro, halogen, -COR ³ , -C00R ³ , -CONR ³ R ⁴ , -OR ³ , -0C0R ³ , -0C00R ³ , -OCO-NR ³ R ⁴ , -SR ³ , -SOR ³ , -S0 ₂ R ³ , -SO--OR ³ , -S0 ₂ NR ³ R ⁴ , -NR ³ R ⁴ , -NR ³ -SO-R ⁴ , -NR ³ -COR ⁴ or -SiR ³ ₃ , in which in the first seven named groups, optionally at least one of the conditions b) , c) , e) , g) and h) defined for these groups and the

following conditions are fulfilled:

a) if one CH-CH-unit is present which is not in a ring, it is replaced by a CH=CH-unit,

d) hydrogen atoms present on carbon atoms which are not part of a ring are replaced by up to three of the same or different substituents from the group cyano, nitro, halogen, -COR ³ , -COOR ³ , -CONR ³ R ⁴ , -OR ³ , -OCOR ³ , -OCOOR ³ , -0-CO-NRR ⁴ , -SR ³ , -SOR ³ , -S0 ₂ R ³ , -S0 ₂ -OR ³ , -S0 ₂ -NR ³ R ⁴ , -NR ³ R ⁴ , -NR ³ -COR ⁴ , and -SiR ³ ₃

f) hydrogen atoms present on carbon atoms which are part of a ring are replaced by up to three of the same or different substituents from the group R ³ (R ³ =hydrogen excepted) and the substituents noted under d) ,

R ³ and R ⁴ , which are the same or different and independently of each other, are (C,-C ₁₇ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₃ -C ₈ ) -cycloalkyl-(C _j -C ₄ ) -alkyl, (C ₆ -C, ₂ )-aryl, (C ₆ -C, ₂ ) -aryl-(C,-C ₄ ) -alkyl, (C _j -C ₈ ) -heteroaryl or (C ₁ -C ₈ -heteroaryl-(C _j -C ₄ ) -alkyl, in which in the last seven named groups, optionally at least one of the conditions b) , c) , e) , g) and h) defined for these groups and the following conditions are fulfilled:

a) if one CH-CH-unit is present which is not in a ring, it is replaced by a CH=CH-unit,

d) hydrogen atoms present on carbon atoms which are not part of a ring are replaced by up to three of the same or different substituents from the group cyano, nitro, halogen, -COR ^3' , -COOR ^3' , -OR ^3' ,

-OCOR ^3' , -OCOOR ^{3 '} , -O-CO-NR ^{3 '} , -SR ^3' , -SOR ^{3 '} , -S0 ₂ R ^3' , -S0 ₂ -OR ^3' , -SO-.-NRA , -NR ^' ₂ , -NR ^' -COR ^3' and -S i (R ^3' ) ₃ ,

f) hydrogen atoms present on carbon atoms which are part of a ring are replaced by up to three of the same or different substituents from the group R ³ (R ³ =hydrogen excepted) and the substituents noted under d) ,

R ³ ' and B are as defined above;

R ⁵ is hydrogen, (C _| -C,- _> ) -alkyl, (C ₃ -C,-) -cycloalkyl, (C ₃ -C ₁₂ ) -cycloalkyl-(C,-C ₄ ) -alkyl, (C ₆ -C ₁₂ ) -aryl, (C ₆ -C ₁₂ ) -aryl-(C,-C ₄ ) -alkyl, (C,-^) -heteroaryl, (C _j -C ₈ ) -heteroaryl-(C,-C ₄ ) -alkyl, cyano, -COR ³ , -COOR ³ , -CONR ³ R ⁴ or -SiR ³ ₃ and R ³ and R ⁴ are as defined above, in which in the second to eighth of the named groups, optionally at least one of conditions a) to h) specified for groups R ¹ and R ² are fulfilled;

R ⁶ is hydrogen or is as defined for R ¹ , whereby R ⁶ , in the case when R ⁵ =hydrogen, is not connected via an 0-, S- or N-atom, or

R ⁵ and R ⁶ form the above defined ring;

R ⁷ is hydrogen or, with the exception of nitro and halogen, is as defined for R ¹ , or

R ⁵ and R ⁷ form the above defined ring,

R ⁶ and R ⁷ form the above defined ring,

X is as defined above;

R ^s , R ⁹ , R ¹⁰ and R ¹¹ , which are the same or different and independently of each other, are as defined for R ⁷ or are halogen, and where R ^s and R ⁹ , or R ¹⁰ and R ¹¹ , by forming an oxo group can also together be 0, or R ¹⁰ and R ¹¹ together can form a group =N-0R ³ , or

R ⁷ + R ⁸ , R ⁷ + R ¹⁰ or R ^s + R ¹⁰ form the above defined ring

and the groups which are not concerned with this ring connection are as defined above; and

p is as defined above, as well as their salts, especially acid addition salts.

Especially preferred compounds and their salts, are those in which R ¹ and R ² , which are the same or different and independently of each other, are (C _j -C ₁₂ )-alkyl, (C ₂ -C ₁₂ ) -alkenyl, (C ₂ -C ₁₂ )-alkynyl, (C ₆ -C ₁₂ ) -aryl, (C ₇ -C ₁₃ ) -aralkyl, (C _j -C ₁₂ )-alkoxy, (C ₂ -C _I2 )-alkenyloxy, (C,-C ₁₂ ) -alkynyloxy, (C _[ -C ₁₂ )-alkylthio, (C ₆ -C ₁₂ )- aryloxy, (C ₇ -C ₁₃ ) -arylalkoxy, (C ₇ -C ₁₃ ) -arylalkylthio, (C ₆ -C _p ) -arylthio, heteroaryl, heteroaryl-(C _j -C ₄ )- alkyl, heteroaryloxy, heteroaryl-(C _j -C ₄ ) -alkyloxy, heteroaryl- (C _{ -C ₄ ) -alkylthio, heteroaryloxy-(C ₁ -C ₄ ) - alkyl, in which the heterocyclic aryl groups each have up to 8 carbon atoms and up to 4 of the same or different hetero atoms selected from N, S and 0, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C ₁₂ ) -cycloalkoxy, (C ₃ -C ₁₂ ) -cycloalkenyl, (C ₃ -C ₁₂ ) -cycloalkenyloxy, -CN, OH, N0 ₇ , F, Cl, Br, I, -COOR ³ , -COR ³ , -0C0R ³ , -CONR ³ R ⁴ , -R-C0R ⁴ , -NR ³ R ⁴ , -S0 ₇ NR ³ R ⁴ , -NR ³ S0 ₂ R ⁴ , -NR ³ COR ⁴ , -SiR ³ ₃ , -S0 ₂ R ³ or -S0 ₃ R ³ , in which the first 23 groups are optionally substituted as defined above, and

R ³ and R ⁴ have the meanings given above;

R ⁵ and R ⁶ independently of each other are hydrogen,

(Cι-C, ₂ ) -alkyl, (C ₂ -C ₁₂ ) -alkenyl, (C ₂ -C ₁₂ ) -alkynyl, (C ₆ -C ₁₂ ) -aryl, (C ₇ -C, ₂ ) -aralkyl, (C ₇ -C ₁₂ ) -aryloxyalkyl, heteroaryl, heteroaryl- (C _| -C ₄ ) -alkyl, heteroaryloxy- (0,-0 ₄ ) -alkyl, in which the heterocyclic aryl groups each have up to 8 carbon atoms and up to 4 of the same or different hetero atoms selected from N, S and 0, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₃ -C ₁₂ ) -cycloalkenyl, COOR ³ , COR ³ , -CONR ³ R ⁴ or -SiR ³ ₃ , in which the second to twelfth of the named groups are optionally substituted as defined above, or R ⁵ with R ⁶ can form a saturated or unsaturated 5-, 6-, 7- or 8-membered ring and R ³ and R ⁴ have the meaning given above, and when R ⁵ is not hydrogen, R ⁶ can also be

(C _j -C _β ) -alkoxy, (C _| -C ₆ ) -haloalkoxy, phenoxy, CN, -NR ³ R ⁴ . -NR ³ S0 ₂ R ⁴ or -NR ³ COR ⁴ ;

R ⁷ is hydrogen, (C _| -C ₆ ) -alkyl, (C- _> -C ₆ ) -alkenyl,

(C ₂ -C ₆ ) -alkynyl, (C ₆ -c, ₂ ) -aryl, (C ₇ -C ₁₂ ) -alkaryl, (C ₁ -C ₆ ) -alkoxy, (C ₂ -C ₆ ) -alkenyloxy,

(C ₃ -C ₆ ) -alkynyloxy, (C ₆ -C ₁₂ ) -aryloxy, (C ₇ -C ₁₃ ) -alkaryloxy, heteroaryl, heteroaryl- (C^C^ - alkyl, heteroaryloxy, heteroaryl-(C ₁ -C ₄ ) -alkyloxy, in which the heterocyclic aryl groups each have up to 8 carbon atoms and up to 4 of the same or different hetero atoms selected from N, S and O, (C ₃ -C ₃ ) -cycloalkyl, (C ₃ -C ₈ ) -cycloalkoxy, (C ₃ -C ₈ ) -cycloalkenyl, (C ₃ -C ₈ ) -cycloalkenyloxy, -OH, COOR ³ , COR ³ , -0C0R ³ , CONR ³ R ⁴ , NR ³ COR ⁴ , SiR ³ ₃ or NR ³ R ⁴ , in which the second to nineteenth of the named groups are optionally substituted as defined above, and R ³ and R ⁴ have the meanings given above, or R ⁷

with R ⁵ or R ⁶ form part of saturated or unsaturated 5 or 6-membered ring;

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ , which are the same or different and independently of each other, are F, Cl, Br, I, CN or have the same meaning as R ⁷ , or R ⁷ + R ⁸ , R ⁷ + R ^? or R ⁸ + R ¹⁰ form part of a saturated or unsaturated 5 or 6-, 7- or 8-membered ring, and the remaining groups and variables are as defined above.

Particularly preferred are those compounds of formula I, in which,

R ¹ and R ² , which are the same or different and independently of each other, are (C _j -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₇ ) -cycloalkyl, (C ₃ -C ₇ ) -cycloalkenyl, (C ₃ -C ₆ ) -alkoxy, benzyloxy, (C _| -C ₆ ) -alkylthio, phenyl, phenoxy, phenylthio, (C--C ₆ ) -alkenyloxy, (C ₃ -C ₆ )-alkynyloxy, (C ₇ -C ₁₃ ) -phenylalkoxy, (C ₇ -C ₁₃ )-phenylalkylthio, (C _| -C ₆ ) -haloalkyl, (C _[ -C ₆ ) -haloalkoxy, (C ₂ -C ₆ ) -haloalkenyloxy, (C ₃ -C ₆ ) -haloalkynyloxy, especially fluoroalkyl and fluoroalkoxy, (C ₃ -C ₇ ) -cycloalkyloxy, (C ₃ -C ₇ ) -cycloalkenyloxy, (C,-C ₆ ) -haloalkylthio, (C ₂ -C ₆ )-haloalkenylthio, (C ₃ -C ₇ ) -halocycloalkyl, (C ₃ -C ₇ )-halocycloalkenyl, (C ₃ -C ₇ )-halocycloalkoxy, (C ₃ -C ₇ ) -halocycloalkenyloxy,

(C ₃ -C ₇ ) -halocycloalkylthio, especially fluoroalkylthio, CN, OH, N0 ₂ , F, Cl, Br, I, C0 ₂ R ³ , OCOR ³ , COR ³ , NR ³ COR ⁴ , NR R ⁴ , S0 ₃ R ³ , S0-,NR ³ R ⁴ , heteroaryl, heteroaryloxy, in which the heterocyclic aryl groups each have up to 5 carbon atoms and up to 3 of the same or different hetero atoms selected from N, S and 0, and R ³ and R ⁴ have the meanings

given above;

= 1 to 5, n = 1 to 4 m'= 2 to 5 and n'= 2 to 4;

R ⁵ and R ⁶ , which are the same or different and independently of each other, are hydrogen, (C C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, (C ₃ -C ₇ ) -cycloalkyl, (C ₃ -C ₇ ) -cycloalkenyl, phenyl, heteroaryl, in which the heterocyclic aryl groups each have up to 5 carbon atoms and up to 3 of the same or different hetero atoms selected from N, S and O, (C,-C ₆ ) -hydroxyalkyl, (C,-C ₆ ) -haloalkyl, (C ₂ -C ₆ )-haloalkenyl, COOR ³ , COR ³ , CONR ³ R ⁴ or SiR ³ ₃ , and when R ⁵ is not hydrogen, R ⁶ can also be

(C _j -C ₆ ) -alkoxy, phenoxy, (C _j - ₆ ) -haloalkoxy, CN, NR ³ R ⁴ or NR ³ COR ⁴ , or R ⁵ with R ⁶ can form a saturated or unsaturated 5 or 6-membered ring and R ³ and R ⁴ have the meanings given above;

R ⁷ is hydrogen, (C _j -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl,

(C ₂ -C ₆ ) -alkynyl, phenyl, (C,-C ₆ ) -alkoxy, phenoxy,

(C ₂ -C ₆ ) -alkenyloxy, (C ₃ -C _ό ) -alkynyloxy,

(C ₃ -C ₇ ) -cycloalkenyloxy, (C,-C ₆ ) -haloalkyl,

(C,-C ₆ ) -haloalkoxy, -OH, COOR ³ , COR ³ , OCOR ³ , CONR ³ R ⁴ , NR-COR ⁴ , NR ³ R ⁴ or SiR ₃ , or R ⁷ with R ⁵ or R ⁶ can form a saturated or unsaturated 5 or 6-membered ring and R ³ and R ⁴ have the meanings given above;

R ⁸ , R ⁹ , R ^!0 and R ¹¹ , which are the same or different and independently of each other, are F, Cl, Br, I or CN or have the same meaning as R ⁷ , or R ⁷ + R ⁸ or R ⁷ + R ¹⁰

or R ^s + R ¹⁰ can be constituents of a saturated or unsaturated 5 or 6-membered ring and the remaining groups and variables are as defined above, as well as their salts, especially acid addition salts.

Particularly preferred are also compounds of formula I, wherein

R is (C _[ -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₇ ) -cycloalkyl, (C -C ₇ ) -cycloalkenyl, phenyl, (C,-C ₆ ) -haloalkyl, (C-,-C ₆ ) -haloalkenyl, (C ₂ -C ₆ ) -haloalkynyl, (C,-C ₆ ) -haloalkoxy, (C ₂ -C ₆ ) -haloalkenyloxy, (C ₃ -C ₆ ) -haloalkynyloxy, (C ₃ -C ₇ ) -cycloalkyloxy, (C _j -C ₆ ) -haloalkylthio, (C ₂ -C ₆ ) -haloalkenylthio, (C ₃ -C ₇ ) -halocycloalkyl, (C ₃ -C ₇ ) -halocycloalkenyl, (C ₃ -C ₇ ) -halocycloalkoxy, (C ₃ -C ₇ ) -halocycloalkenyloxy,

(C ₃ -C ₇ ) -halocycloalkylthio, CN, OH, N0 ₂ , F, Cl, Br, I, C0 ₂ R ³ , OCOR ³ , COR ³ , NR ³ COR ⁴ , NR ³ R ⁴ , S0 ₃ R ³ , S0 ₂ NR ³ R ⁴ , heteroaryl, in which the heterocyclic aryl groups each have up to 5 carbon atoms and up to 3 of the same or different hetero atoms selected from N, S and O, and R ³ and R ⁴ have the meanings given above, as well as their salts, especially acid addition salts,

and compounds of formula I, wherein

R ² is (C _j -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₇ ) -cycloalkyl, (C ₃ -C ₇ ) -cycloalkenyl, (C _j -C ₆ ) -alkoxy, benzyloxy, (C,-C ₆ ) -alkylthio, phenoxy, phenylthio, (C ₂ -C ₆ ) -alkenyloxy, (C ₃ -C ₆ ) -alkynyloxy, (C ₇ -C ₁₃ ) -phenylalkoxy, (C ₇ -C ₁₃ ) -phenylalkylthio, (C _[ -C ₆ ) -haloalkyl, (C _| -C ₆ ) -haloalkoxy, ( Ci-C _fi ) -haloalkenyloxy, ( C ₂ -C _ύ ) -haloalkynyloxy, (C ₃ -C ₇ ) -cycloalkyloxy, (C ₃ -C ₇ ) -cycloalkenyloxy,

(C,-C ₆ ) -haloalkylthio, (C- _> -C _ό ) -haloalkenylthio, (C ₃ -C ₇ ) -halocycloalkyl, (C ₃ -C ₇ ) -halocycloalkenyl, (C ₃ -C ₇ ) -halocycloalkoxy, (C -C ₇ ) -halocycloalkenyloxy, (C ₃ -C ₇ ) -halocycloalkylthio, C0 ₂ R ³ , OCOR ³ , COR ³ , NR ³ COR ⁴ , NR ³ R ⁴ , heteroaryloxy, in which the heterocyclic aryl groups each have up to 5 carbon atoms and up to 3 of the same or different hetero atoms selected from N, S and 0, and R ³ and R ⁴ have the meanings given above, as well as their salts, especially acid addition salts.

A particularly preferred group of compounds are those where

A is of formula II, in which m is 1 or 2 and R ¹ is halogen,

C _j -C ₄ -alkyl, especially methyl, or halo-C ₁ -C ₄ -alkyl, especially trifluoromethyl and preferably with the R ¹ in the 3 and/or 4 positions; B is -CH(OH)-, -CH(O-acyl)- or -CH(O-alkyl) ; R ⁷ is hydrogen;

X is optionally substituted ethylene; and A' is of formula IV, in which m' is 2 and R ² is

C _j -C ₄ -alkoxy, especially methoxy or ethoxy, and preferably with the R ² in the 3 and 4 positions. It is especially preferred that B is -CH(OH)- and X is ethylene.

In the preceding and following description, by the term "halogen" is to be understood a fluorine, chlorine, bromine or iodine atom; by the term "alkyl" is to be understood a straight chain or branched hydrocarbon group, such as, e.g. methyl, ethyl, propyl, 1-methylethyl, 2-methylpropyl, 1,1- dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl, 1, 1, 3 , 3-tetramethylbutyl, nonyl, isononyl, decyl, undecyl or dodecyl;

by the term "cycloalkyl", v/hich is mono- bi- or tricyclic, preferably onocyclic, is to be understood, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl groups; by the term "cycloalkylalkyl" , is to be understood a hydrocarbon group, v/hich has the meanings given above under the term "alkyl" and v/hich is substituted by a hydrocarbon group, given under the term "cycloalkyl", such as cyclohexylmethyl, 2-cyclohexylethyl or 2-cyclohexyl-2- propyl; by the term "alkoxy", is to be understood a hydrocarbon group, which has the meanings given above under the term

"alkyl; under the term "alkoxyalkyl" is to be understood for example 1-methoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, ethoxymethyl, ethoxy ethyl, 3-methoxypropyl or 4- butoxybutyl; under the term "haloalkyl" is to be understood named alkyl group under the term "alkyl", in which one or more hydrogen atoms are replaced by the halogen atoms, named above, preferably chlorine or fluorine, such as CF ₃ , CF ₂ CHF ₂ , CC1 ₃ , CC1 ₂ F, CF ₂ CF ₂ CF ₃ , CF ₂ CHFCF ₃ , CH ₂ CF ₃ , (CF ₂ ) ₃ CF ₃ , CF ₂ H, CHF ₂ , CH ₂ C1, CHC1-, or CCl ₃ CHτ and correspondingly for haloalkenyl, haloalkynyl and the like; under the term "haloalkoxy" is to be understood a haloalkoxy group, whose halogen-hydrocarbon residue has the meaning given under the term "haloalkyl", such as OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CF ₃ , 0CH ₂ CC1 ₃ , OCH(CF ₃ ) ₂ or OCF ₇ CHFCF ₃ , and correspondingly for haloalkenyloxy, haloalkynyloxy and the like; under the term "aryl" is to be understood for example phenyl, naphthyl or biphenyl, especially phenyl; under the term "aryl-alkyl" is to be understood one of the above named alkyl groups, which is substituted with an aryl group, for example benzyl, 2-phenylethyl, 1-

phenylethyl, 1-methyl-l-phenylethyl , 3-phenylpropyl or 4- phenylbutyl; under the term "heteroaryl" is to be understood an aryl group as previously defined in which at least one CH-group is replaced by N and/or at least two neighbouring CH- groups are replaced by S, NH or O. Examples of such groups are thienyl, furyl, benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl and tetrazolyl; under the term "cycloalkoxy" is to be understood a cycloalkoxy group, whose hydrocarbon group has the meaning given under the term "alkyl"; under the term "alkythio-alkyl" is to be understood for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl or 3-methylthiopropyl; under the term "alkenyl" is to be understood, e.g. allyl, 1-methylallyl, 2-butenyl or 3-methyl-2-butenyl; under the term "alkynyl" is to be understood, e.g. ethynyl, propargyl, 2-butynyl or 2-pentynyl.

For all other groups which have not been specifically mentioned groups, and that can be derived from the above mentioned groups for example by introduction of double or triple bonds, by substituents with one or more of the same or different substituents or by exchange of one or more CH ₂ by e.g. NR ³ , S, 0 or CO, the same applies.

Groups which are commonly substituted, that contain a hydroxy-, mercapto- or optionally monosubstituted amino group on a hydrocarbon, that itself is connected to a further oxygen, sulfur or nitrogen atom (e.g. in hemiacetals and hemiketals) , inasmuch as they are not stabilised by special groups, are as a rule unstable; such

groups are not preferred.

The invention includes all stereoiso ers, that can occur in the compounds of the invention of Formula I, especially individual enantiomers and their mixtures in any ratio, as well as their salts especially acid addition salts.

For the preparation of preferred acid addition salts of the compounds of formula I the following acids can be considered: hydrogen halide acids, such as hydrochloric acid or hydrobromic acid, as well as phosphoric acid, nitric acid, sulfuric acid, mono- or bi-functional carboxylic acids and hydroxycarboxylic such as acetic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, or lactic acid, as well as sulfonic acids such as for example p-toluenesulfonic acid or 1, 5-naphthalene- disulfonic acid. The acid addition salts of the compounds of Formula I can be obtained in a simple manner according to conventional methods for forming salts, e.g. by dissolving in an organic solvent and addition of the acid, and purified in known manner, for example by filtering, isolation and optionally washing with an inert solvent.

Base addition salts can be obtained by treatment with alkali or alkaline earth metal hydroxides or carbonates or with an organic amine.

The novel arylacetamides of formula I can be obtained in known manner, for example a) Arylacetamides of formula I in which B is a group of formula VII, R ⁵ = H and the remaining substituents are as defined in formula I are obtained for example by analogy to the method described in Synthesis (1985,) 12, 1153 by treatment of dioxolanones of

formula IX, in which R ¹ , R ¹³ independently of each other are H, (C,-C ₃ ) -alkyl, (C,-C ₃ ) -haloalkyl or R ¹¹ and R ^1- can be components of a 5-, 6- or 7-membered, saturated or ono-unsaturated, isocyclic ring and the remaining substituents are as defined in formula I with an amine of formula X in which the substituents are as defined in formula I.

R ¹² ' ³

. . 0' 0 X) A ^* (X)

The amines can be obtained in known manner as described for example in Bull. Chem. Soc. Jap. 1990, _6_1, 1252; Angew. Chem. 1989, 101. 202 and 1992, 104, 914; Heterocycles, 1987, _2_6, 1595 and J. Med. Chem.

1988, H, 1282, 1981, _24_, 1063 and 1980, 2 _. 3, 990.

The reaction is carried out at a temperature of 0 up to the boiling point of the mixture, preferably under reflux over 0.5 to 120 hours. The amine of formula X is treated in an amount of 1 to 10, preferably 1 to 2 molar equivalents, per 1 equivalent of dioxolane of formula IX. The reaction is optionally carried out in an inert solvent. Preferred solvents are ethers, aromatic or aliphatic hydrocarbons, halogenated hydrocarbons, ketones, alcohols or a mixture thereof, especially diethyl ether, dioxane, tetrahydrofuran, methyl tert-butyl ether, dimethoxyethane, toluene, xylene, chlorobenzene, hexane, cyclohexane, heptane, petroleum ether, acetone, methyl ethyl ketone, dichloromethane, 1, 2-dichloroethane,

methanol or ethanol.

The dioxolanones of formula IX can be obtained in a similar manner to that described in Organic Synthesis, Coll Vol 3, 536 and J. Org. Chem. Vol. 51 (19), 3747, (1986) .

b) The compounds of formula I can also be obtained by treatment of a carboxylic acid of formula XI,

0

II A - B - C - OH (XI) in which the substituents are defined as in formula I, or by treatment of a reactive derivative of XI, optionally obtained in situ, in which the substituents are defined as in formula I, with an amine of formula X in which the substituents are defined as in formula I.

The process represents the acylation of a compound of formula X with a carboxylic acid of formula XI, whereby the reaction advantageously is carried out in the presence of acid XI activating compound or a dehydrating agent or with a reactive derivative of the carboxylic acid XI or of the educt X.

Examples of derivatives of formula XI that are optionally prepared in the reaction mixture are for example their alkyl, aryl or arylalkyl esters, such as the methyl, ethyl, phenyl or benzyl ester, their imidazolides, their acid halides such as the acid chloride or bromide, their anhydrides, their mixed anhydrides with aliphatic or aromatic carboxylic, sulfonic or carbonic acid esters, for example with acetic acid, propionic acid, p-toluenesulfonic acid or O-ethyl or O-isobutylcarbonic acid or their N-hydroxyimide esters.

Examples of acid activating and/or dehydrating agents are chlorinated carbonic acid esters, such as ethyl chloroformate, isobutyl chlorofor ate, phosphorous pentoxide, N,N'-dicyclohexylcarbodiimide, N,N'-carbonyldiimide, N,N'-carbonyldiimidazole or N,N'-thionyldiimide.

For activating the optionally prepared carboxylic acid ester examples are titanium tetraalkoxides, such as titanium tetraisopropylate, titanium tetraethylate, titanium tetramethylate, titanium tetrapropylate or by the use of increased pressure (Angew Chemie, (1986) , 6, 569).

The reaction is suitably carried out in a solvent or mixture of solvents such methylene chloride, chloroform, carbon tetrachloride, ether, tetrahydrofuran, dioxane, benzene, toluene, acetonitrile, N-methylpyrrolidine or dimethylformamide, optionally in the presence of an inorganic base such as sodium or potassium carbonate or a tertiary organic base such as triethylamine, N-methylmorpholine or pyridine, which can also act at the same time as a solvent, and optionally in the presence of an acid activating agent, at temperatures between -78°C and 120°C, preferably however at temperatures between - 78°C and the boiling point of the reaction mixture. With this it is not necessary to isolate a reactable derivative optionally resulting in the reaction mixture of a compound of general formula X or XI and further the reaction can be carried out also in an excess of the compound of general formula X as solvent.

The preparation of carboxylic acids and of derivatives of carboxylic acids of formula XI optionally obtained in the reaction mixture is known. For example by analogy to methods described in J. Org. Chem. (1978) , 43, (13) , 2702; Org. Synth. (1945) , 25, 33; Org. Synth. Col. Vol. IV,

(1963), 110; Org. Synth. Col. Vol. I, (1941) , 336-SE 7604030-2, Synthesis (1975) , 163, Synth. Commun (1981), 11, 943; Org. Prep. Proced. (1970) , 2, 249, EP 140454.

c) Compounds of formula I in which B is a group of formula VII and R ⁴ and R ⁵ are each H can be converted in known oxidation processes (e.g J. Org. Chem. (1987), 52, (22) , 4978; Heterocyles (1984) 22, (4) , 773, into the corresponding ketone compound of formula I in which B is defined as a group of formula VI.

d) Compounds of formula I in which B is a group of formula C can be reduced in known methods (e.g. J. Chem. Soc. Perkin. Trans. 1(1989) , 1555) to give the corresponding hydroxy compounds of formula I, in which B is a group of formula VII and R ⁴ and R ⁵ are each hydrogen.

e) Compounds of formula I in which B is a group of formula VII and the remaining substituents are as defined in formula I can be obtained by methods analogous to that described in Tetrahedron Letters (1988) , 44, (15), 4805 by reacting a halo compound of formula XII wherein R ¹⁴ = F, Cl, Br or I and the remaining substituents are as defined in formula I, with a hydroxy compound of formula XIII, in which the substituents are as defined in formula I. The compounds of structure XII are known or can be obtained in known manner (e.g. J Org Chem (1955) , 20, 237) .

R ¹⁴ 0

A - C - C - N - X - A' (XII) HO - R ⁴ (XIII) R ⁶ R ⁷ f) Compounds of formula I in which B is a group of formula VII and R ⁵ is not hydrogen can be obtained also b treatment of compounds formula I in which B is a group of

formula VII and R- = H with an alkylating and/or acylating agent of formula Z-R ³ , in which Z is a nucleophilic leaving group, such as Cl, Br, I, alkoxysulfonyl, alkylsulfonyloxy or haloalkylsulfonyloxy and R ⁵ has the meaning given above. The reaction can be carried out in a similar manner to that described in J Org Chem (1978) , 43, 1893; Org Synth Col Vol I, (1941), 12; Tetrahedron Letters (1980), 21, (52) , 4997.

g) Compounds of formula I can also be obtained by ring closure of a compound of formula XIV

A-CH(OH)-CONH ₂ (XIV)

in known manner (eg as described in Chemical Abstracts 3J5 3634) to give a compound of formula XV

which is then reacted with a compound of formula

A'-X-Q

where Q is a leaving groups such as halogen.

The compounds of the invention of formula I are characterised by an excellent fungicidal activity against phytopathogenic fungi. The compounds are especially valuable for their curative activity. This is especially important and advantageous in such fungal diseases that cannot be controlled effectively with conventional fungicides. The activity spectrum of the claimed compounds includes various economically important phytopathogenic

fungi, for example Phytophthora infestans and Plasmopara viticola .

The compounds can be used to treat crop seeds to prevent seed borne diseases.

The compounds of the invention are suitable also for the use in technical areas, for example as wood preservatives, as preservatives in paints, thickeners, in cooling lubricating agents for metal working, or as preservatives in boring and cutting oils.

The compositions of the invention contains generally from 1 to 95 % by weight of the active ingredient.

They can be formulated in various ways according to the biological and/or chemical physical parameters. Formulation possibilities are included, for example, wettable powders (WP) , e ulsifiable concentrates (EC) , aqueous dispersions in oil or water based (SC) , suspoemulsions (SC) , dusting powders (DP) , disinfectants, granules in the form of water-dispersible granules (WG) , ULV-formulations, rr.icrocapsules, waxes or baits.

These individual formulation types are known and are described for example in:

Winnacker-Kuchler, "Chemische Technologie" , Band 7, C-Hauser Verlag Mϋnchen, 4. Aufl. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation additives are also known as inert materials, surfactants, solvents and other additives and are described for example in: Watkins, "Handbook of Insecticide Dust Diluents and

Carrier", 2nd Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, N. Y.; Marschen, "Solvents Guide", 2nd Ed., Interscience, N. Y. 1950; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N. J. ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N. Y. 1964; Schδnfeldt, "Grenzflachenaktive Athylenoxidaddukte" , Wiss. Verlagsgesell. , Stuttgart 1976; Winnacker-Kiichler, "Chemische Technologie" , Band 7, C. Hauser Verlag Mϋnchen, 4. Aufl. 1986.

Based on these formulations combinations with others pesticidally active substances, fertilisers and/or growth regulators can be prepared, for example in the form of a ready formulation or as a tank mix.

Wettable powders are preparations that are evenly dispersible in water which besides the substance also contain a diluent or inert substance including a surfactant, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkyl or alkylphenol sulfonate and dispersing agents for example sodium ligninsulfonates, sodium 2 , 2'-dinaphthyl-methane- 6, 6'-disulfonate, sodium dibutylnapthalenesulfonate or and also sodium salt of oleylmethyltaurine. Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylforma ide, N-octylpyrrolidone, xylene or a high-boiling aromatic or hydrocarbon by addition of one or more emulsifying agents. As emulsifiers there can be used for example, calcium salts of alkylarylsulfonic acids, such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide, ethylene oxide, sorbitan fatty acid esters, polyoxyethylene

sorbitan fatty acid esters or polyoxyethylene sorbitan esters.

Dusting agents can be obtained by milling the active ingredient with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, pyrophyllite, or diatomaceous earths. Granules can be prepared either by distribution of the active ingredients on absorbing granular inert materials or by bringing concentrates of active ingredients by means of sticking agents, for example polyvinyl alcohol, sodium polyacrylates or mineral oils onto the surfaces of carriers such as sand, kaolinite or of granulated inert material. Suitable active ingredients can also be granulated in the usual manner for the preparation of fertiliser granules optionally in mixture with fertiliser.

In wettable powders the active ingredient concentration is for example around 10-9%, the rest of up to 100% comprising conventional formulation parts. In emulsifiable concentrates the active ingredient concentration is around 5-80%. Dusting formulations contain at most 5-20%. In granulates the active ingredient content depends partly on whether the active compound is liquid of solid and which compound is liquid or solid and which granulating materials, fillers and etc are used.

Besides the named active ingredient formulating agents there can be optionally conventional adhesive, surfactant, dispersing, emulsifying, penetration, solvent, filling or carrier substances.

For use, the concentrates in commercially available forms are usually diluted in conventional manner, for example wetting powders, emulsifiable concentrates, dispersions and also micro granules by using water.

Dusts and granule preparations as well as sprayable solutions are generally not diluted before use with further inert substances

With the exceptional condition such as temperature, humidity etc., the necessary rate of use can be varied. It can be limited within wide ranges, for example between 0.005 and 10,0 kg/ha or more active substances, for example by between 0.01 and 5 kg/ha.

The active ingredients of the invention can be used in their commercial formulations, either alone or in combination with other fungicides known in the literature.

The compounds of the invention can be combined with most known fungicides including for example: a compound selected from (i) a conazole steroid demethylation inhibitor, (ii) a steroid reduction inhibitor based on a l-[3-(4-tert-butylphenyl) -2-methylpropyl] group which is attached via the N-atom to piperidine or 2, 6-dimethylmorpholine (iϋ) a dithiocarbamate fungicide

(iv) a phthalimide fungicide in which a chloroalkylthio group is attached via the N-atom to the optionally hydrogenated phthalimide group, (v) an anilide fungicide (vi) an mbc fungicide.

(vii) a carbamate fungicide viii) a copper compound fungicide (ix) a tin compound fungicide (x) a strobilurine type fungicide, and (xi) an anilino pyri idine

(xii) a phosphorus containing compound

(xiii) a fungicide selected from the group consisting of chlorothalonil , dimethomorph, fenpiclonil,

fluazinam, hymexazol, nuarimol, pencycuron, pyrifenox, thicyofen, probenazole, pyroquilon, tricyclazole, quaternary ammonium compounds, fludioxonil, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (and mixtures of these two) , furmecyclox, 3-iodo-2-propynyl butylcarbamate and sulfur. Conazoles are defined in ISO standard 257 as compounds based on i idazole or 1, 2 , 4-triazole and containing a halogenated phenyl group. Examples include prochloraz (and its metal complexes - especially the manganese or copper complex) , propiconazole, flusilazole, hexaconazole, tebuconazole, difenoconazole, bromuconazole, cyproconazole, diniconazole, fenbuconazole, imibenconazole, furconazole, tetraconazole, myclobutanil, penconazole, fluquinconazole, azaconazole, imazalil, triflumizole, epoxiconazole, triticonazole, metconazole and the fungicide having the code No SSF 109. Examples of type (ii) fungicides include fenpropimorph and fenpropidin.

Examples of type (iii) fungicides include ancozeb and thiram.

Examples of type (iv) fungicides include folpet, captafol and captan. Examples of type (v) fungicides include a) 3 ' , 5'-dichloroanilide fungicides in which the anilino nitrogen comprises a ring carrying two oxo substituents, in positions adjacent the nitrogen, e.g. iprodione, vinclozolin or procymidone, or b) acetanilide fungicides, e.g. metalaxyl or ofurace, c) sulfanilide fungicides, e.g. dichlofluanid, d) benzanilide fungicides, e.g. flutolanil, and e) heteroarylanilide fungicides, e.g. thifluzamide. Examples of type (vi) fungicides include carbendazim, benomyl and thiophanate-methyl.

Examples of type (vii) fungicides include diethofencarb

and propamocarb.

Examples of type (viii) fungicides include Bordeaux mixture, oxine-coppe , copper oxychloride and copper naphthenate. Examples of type (ix) fungicides include tributyltin oxide and tributyltin naphthenate.

Strobilurine type fungicides (type (x) fungicides) are methyl esters of arylacetic acid in which the acetic acid also carries a methoxymethylene or methoxyi ino substituent. The aryl group is usually a 2-substituted phenyl group. Examples of such compounds are those disclosed in a wide number of patent applications, including EPS 178326, 203606, 203608, 206523, 229974, 226917, 242070, 242081, 243012, 243014, 251082, 256667, 260794, 260832, 267734, 270252, 273572, 274825, 278595, 291196, 299694, 307101, 307103, 310954, 312221, 312243, 329011 and 336211. Specific compounds are those having the having the code Nos BAS 490F and ICIA 5504. Examples of type (xi) fungicides include pyrimethanil, cyprodinil and mepanipyrim.

Examples of type (xii) fungicides include pyrazophos, fosetyl aluminium and tolclofos-methyl. The names quoted for these compounds are the non- proprietary common names and the chemical structure can be found for example by reference to the "Pesticide Manual", ninth edition, 1991, published by the British Crop Protection Council or in other recent publications.

Besides this, the compounds of the invention in commercial formulations as v/ell as the ready for use forms from these formulations can be mixed with other active ingredients, such as insecticides, desiccating agents, sterilants, acaricide, ne aticides or herbicides. Examples of insecticides include phosphorus acid esters, carbamates, carboxylates, formamidine, tin compounds, compounds prepared from microorganisms, etc..

Preferred mixing partners are:

1. From the group of phosphorus compounds acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, tebupirimifos, bro ophos, bromophos-ethyl, cadusafos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, demeton, demeton-s-methyl , demeton-s-methyl sulfone, dialifos, diazinon, dichlorvos, dicrotophos, chlorethoxyfos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion, fenthion, fonofos, formothion, heptenophos, isazophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthioate, phorate, phosalone, phosfolan, phosmet, phospha idon, phoxim, pirimiphos-ethyl, piri iphos-methyl, profenofos, propaphos, propetamphos, prothiofos, pyraclofos, pyridapenthion, quinalophos, sulprofos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion.

2. From the group of carbamates aldicarb, 2-sec.-butylphenyl methylcarbamate (BPMC) , carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cumenylbutyry1 (methyl) carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox and alanycarb.

3. From the group of pyrethroid carboxylates acrinathrin, allethrin, alpha-cypermethrin, 5-benzyl-3- furylmethyl- (E) -(1R) -cis-2, 2-dimethyl-3- (2-oxothiolan-3- ylidene ethyl)cyclopropane-carboxylate, bioallethrin, bioallethrin( (S) -cyclopentyl isomer) , bioresmethrin, biphenate, cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate,

fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D-isomer) , bifenthrin, permethrin, pheothrin ( (R) -Isomer) , d-pralethrin, pyrethrins (natural products) , res ethrin, tefluthrin, tetramethrin, tralomethrin.

4. Others amitraz, fenbutatin oxide, aba ectin, Bacillus thuringiensis, bensultap, binapacryl, bromopropylate, buprofezin, cartap, chlorobenzilate, chlorfluazuron, clofentezine, chlorfluazuron, cyromazine, dicofol, hexaflumuron, diflubenzuron, N-(2,3-dihydro-3-methyl-l,3- thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, endosulfan, ethofenprox, (4-ethoxyphenyl) (dimethyl) (3-(3- phenoxyphenyl)propyl)silane, silafluofen, fenproximate, fenazaquin, fenoxycarb, fipronil, fluazuron, flufenoxuron, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexathiazox, hexaflumuron, hydramethylnone, imidacloprid, ivermectin, lufenuron, acetamiprid, nithiazine, propargite, py etrozin, pyrolen, pyridaben, triazamate, tebufenozid, tebufenpyrod, teflubenzuron, tetradifon, tetrasul, thiocyclaπ*., triflumuron.

The content of active ingredient in the ready for use forms, prepared from the commercial formulations, can vary over a wide range with the concentration varying from 0.0001 up to 95% by weight of active ingredient, preferably between 0.001 and 1% by weight. The application is carried out in conventional manner adapted to the particular application form.

The following examples illustrate the invention, without being limiting in any way.

A. Formulation examples

a) A dusting composition was obtained by mixing 10 parts by weight active ingredient and 90 parts by weight talc as inert ingredient and micronising in a hammer mill.

b) A wettable powder, easily dispersible in water, was obtained by mixing 25 parts by weight active ingredient 65 parts by weight kaolin containing quartz as inert ingredient, 10 parts by weight potassium lignin sulfonate and 1 part by weight sodium salt of oleylmethyltaurine as wetting and dispersing agents and milled in a pinned disk mill.

c) A dispersible concentrate, easily dispersible in water, was prepared by mixing 40 parts by weight active ingredient with 7 parts by weight of a sulfosuccinate half ester, 2 parts by weight sodium ligninsulfonate and 51 parts by weight water and milling to below 5 microns in grinding ball mill.

d) An emulsifiable concentrate was prepared from 15 parts by weight active ingredient, 75 parts by weight cyclohexanone as solvent and 10 parts by weight nonylphenolethoxylate (10 AeO) as emulsifier.

e) A granulate was prepared from 2 to 15 parts by weight active ingredient and an inert granulate carrier material such as attapulgite, pumice granules and/or quartz sand. Suitably a suspension of the wettable powder from Example b) having a solid material content of 30 % is sprayed on the

surface of a attapulgite granules, dried and mixed intimately. In this way the ready granules comprise an amount by weight of ca. 5 % of the wettable powder and ca. 95 % of the carrier material.

B. Chemical Examples.

Structures of compounds obtained were confirmed by n r and/or other appropriate analyses.

Example 1 N-T2- (3.4-Dimethoxyphenyl. ethyl1-4-chloromandelamide

To a solution of 269.5 g (1.19 mol) 2,2-dimethyl- 4-(4-chlorophenyl)-1,3-dioxolanone in 250 ml acetone was added 323,3 g (1.78 Mol) 2-(3,4-dimethoxyphenyl)- ethylamine. The mixture was stirred for 24 hours at 50°C. The low boiling material was distilled off in vacuo, the residue dissolved in 1500 ml ethyl acetate and the solution washed with 1000 ml each of IN hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated aqueous sodium chloride. After drying the organic phase with sodium sulfate, the organic phase was concentrated, the residue suction filtered and washed 4 times, each time with 500 ml n-pentane. After drying in vacuo , there was obtained 377.8 g (90.5% of theory) of a bright beige solid material having a melting point of 100-101°C.

Example 2

N-(3-Phenylpropyl)-4-trifluoromethylmandela ide

To a solution of 3 g (0.0115 Mol) 2,2-dimethyl- 4-(4-trifluoromethylphenyl)-1,3-dioxolanone in 25 ml ether was added 1.55 g (0.012 Mol) 3-phenylpropylamine. The mixture was stirred for 16 hours at room temperature. The precipitate was suction-filtered off, washed with a small amount of ether and n-pentane and dried in vacuo . There was obtained 30 g (77% of theory) of a white solid material having a melting point of 107°C.

Example 3

N-(l-Phenylcyclopentyl)-methyl-4-chloromandelamide

To a solution of 2.2 g (0.0097 Mol) 2,2-dimethyl- 4-(4-chloro-phenyl)-1,3-dioxolanone in 25 ml ether was added 3.06 g (0.0175 Mol) (1-phenylcyclopentyl)- methylamine. The mixture was stirred for 16 hours at room temperature. It was then taken up in 100 ml ethyl acetate and the organic solution washed with 100 ml each of IN hydrochloric acid, saturated aqueous sodium hydrogen carbonate and sodium chloride and the organic phase dried over sodium sulfate. After removal of the solvent in vacuo there was obtained 2.9 g (87% of theory) of a white solid with a melting point of 84°C.

Example 4 N- ^~ 2-f3,4-Dimethoxyphenyl)ethyll- -propargyl- 4-chloromandelamide

To a solution of 3.97 g (0.015 Mol) 2,2-Dimethyl-4- (4-chlorophenyl)-4-propargyl-l,3-dioxolanone in 5 ml tetrahydrofuran added 4,08 g (0.0225 Mol) 2-(3,4- dimethoxyphenyl)-ethylamine. The mixture was stirred for

16 hours at 60°C and the low boiling solvents distilled in vacuo . The residue was taken up in 100 ml ethyl acetate and washed with each of 100 ml IN hydrochloric acid, saturated aqueous sodium hydrogen carbonate and sodium chloride. After drying the organic phase with sodium sulfate and removal of solvent in vacuo there was obtained 5.0 g (86% of theory) of a colourless oil.

Example 5

N-Methyl-N-f2- (3.4-dimethoxyphenyl. -ethyl]-4- chloromandela ide

To 3.0 g (0,013 Mol) 2,2-dimethyl-4-(4-chlorophenyl)- 1,3-dioxolanone there was added, with stirring, 5.08 g (0.026 Mol) N-[2-(3,4-dimethoxyphenyl)ethyl]methylamine. After stirring for 16 h at room temperature, the reaction mixture was taken up in 100 ml ethyl acetate and washed with each of 100 ml IN hydrochloric acid, saturated aqueous sodium hydrogen carbonate and sodium chloride. After drying, the organic phase with sodium sulfate and separating the low boiling material in vacuo, there was obtained 2.2 g (46% of theory) of a pale yellow oil.

Example 6 N-r2- (3.4-Dimethoxyphenyl)ethyl1-N.O-dimethyl-4-chloro- mandelamide

To a solution of 5.0 g (0.0143 Mol) N-[2-(3,4-dimethoxy- phenyl)ethyl]-4-chloromandelamide in 100 ml dimethylformamide there was added, portionwise, with stirring, at 0-10°C, 1.25 g (0.0313 mol) 60% sodium hydride. After 30 minutes at 10°C, 5.82 g (0.0313 mol) methyl iodide was added dropwise and the mixture stirred for 1 hour at this temperature and then for 2 hours at room temperature. The reaction mixture was poured into ice-water, extracted twice each time with 200 ml ethyl acetate and the combined organic phases dried with sodium sulfate and concentrated in vacuo . The residue was filtered over silica gel (ethyl acetate/petroleum ether 1:1). There was obtained 4.5 g (83% of theory) of a bright yellow oil.

Example 7

5-(4-Chlorophenyl)-3-[2-(3 ,4-dimethoxyphenyl)ethyl-

1.3-oxazolidin-4-one

To a solution of 5 g (0.0143 Mol) N-[2-(3,4- dimethoxyphenyl)-ethyl]-4-chloromandelamide in 100 ml dimethylformamide, there was added with stirring 0-10°C portionwise 1.25 g (0.313 mol) of 60% sodium hydride. After 30 minutes at 0-5°C, 5.832 g (0.313 mol) dibromomethane was added dropwise, the mixture stirred for 1 hour at 0-5°C and then for 2 hours at room temperature. The reaction mixture was added to 800 ml ice- water, extracted twice with ethyl acetate, the combined organic phases dried with sodium sulfate and concentrated in vacuo . After filtration of the residue over silica gel (ethyl acetate/petroleum ether 1:1) there was obtained 3.0 g (58% of theory) of a bright yellow oil.

Example 8

O-Acetyl-N-T2-(3.4-dimethoxyphenyl)ethy11-4- bromomandelamide

To a solution of 1.0 g (0.0025 Mol) N-[2-(3 ,4-dimethoxy- phenyl)ethyl]-4-bromomandelamide (compound 25) in 50 ml methylene chloride there was added dropwise 1.75 g (0.02 mol) acetyl chloride in 10 ml methylene chloride and after 10 minutes at 0-10°C 2.02 g (0.02 mol) triethyla ine was added dropwise and the mixture stirred for 1.5 hours at this temperature. After the addition of 5 ml methanol, the reaction mixture was added to 150 ml saturated aqueous sodium hydrogen carbonate, extracted twice with methylene chloride and the combined organic phases dried with sodium sulfate. After filtration of the residue over silica gel

(ethyl acetate/petroleum ether 1:1) there was obtained 3.7 g (94% of theory) of a beige coloured solid with a melting point of 91°C.

Example 9

N-T2-(3,4-Dimethoxyphenyl. ethyl ^" phenylglvoxylylamide

To a solution of 3.15 g (0.01 Mol) N-[2-(3,4-dimethoxy¬ phenyl)ethyl]mandelamide in 100 ml chloroform was added with stirring and at reflux 5.22 g of (0.06 mol) of activated manganese dioxide portionwise. After 2 hours at reflux the mixture was filtered, the filter cake boiled up 3 times, each time with 150 ml chloroform and washed each time with hot chloroform. Separation of the solvent in vacuo resulted in 3.0 g (96% of theory) of a colourless solid with a melting of 80°C.

Example 10

N-T2-(3.4-Dimethoxyphenyl^ethyllPhenylσlvoxylylamide

At room temperature there was added, dropwise, to a solution of 3.37 g (0.02 Mol) phenylglyoxylyl chloride in 40 ml dry methylene chloride, a mixture of 4.35 g (0.022 Mol) 2-(3,4-dimethoxyphenyl)ethylamine and 2.42 g (0.022 Mol) triethylamine with stirring. The reaction mixture was warmed at 42°C. After 30 minutes the reaction mixture was poured into 40 ml 2N hydrochloric acid, and the organic phase washed with 50 ml each of saturated aqueous sodium hydrogen carbonate and sodium chloride, dried with sodium sulfate and the low boiling materials distilled in vacuo . There was obtained 5.7 g (91% of theory) of colourless solid with a melting point of 80°C.

Example 11

N-f2-(3.4-Dimethoxyphenyl)ethyll-2-fluoro-4-trifluoro- methylmandela ide

2-Fluoro-4-trifluoromethylmandelic acid (1.00 g) and N-hydroxysuccinimide (0.48 g) were dissolved in dry dimethoxyethane (50 ml) under nitrogen at room temperature. Dicyclohexylcarbodiimide (0.87 g) was added in one portion and after 10 minutes a white precipitate (dicyclohexylurea) formed. After stirring for another 15 minutes at room temperature 2-(3,4-dimethoxyphenyl)- ethylamine (0.86 g) was added. The suspension was stirred for 2 hours, dicyclohexylurea filtered off and the residue evaporated. 3.0 g of crude material was obtained which was purified by silica gel chromatography (ethyl acetate) , followed by recrystallisation from diisopropyl ether.

Yield: 1.52 g = 90.5% of theory, mp 108-9

Example 12

N-T2-(3.4-Dimethoxyphenyl)ethyll-4-cvanomandelamide

Tri ethylsilyl chloride (1.1 ml) was added dropwise, with stirring to mixture of 4-cyanomandelic acid (0.7 g, 4.0 mmol) in dry dichloromethane (8 ml) and pyridine (0.67 ml) and a catalytic amount of dimethylaminopyridine. The mixture was stirred for 4 hours at room temperature, cooled to 0°C and 3 drops dimethylformamide added followed by oxalyl chloride (0.36 ml). The mixture was stirred for a further 1 hour at 0°C and 30 minutes at room temperature. It was cooled to 0°C and 2-(3,4-dimethoxy- phenyl)ethylamine (0.8 g) in dry pyridine (1 ml) added. The mixture was stirred for 2 hours at room temperature. Citric acid (0.92 g) in methanol (8 ml) was added and the mixture was stirred for h hour at room temperature. It was

allowed to stand overnight. Ethyl acetate (50 ml) was added and the solution washed with IN hydrochloric acid (40 ml) and the aqueous extract extracted ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate (15 ml) , brine (15 ml) dried and evaporated. The residue was purified by silica gel chromatography to give 0.9 g of product as a brown gum.

Example 13

N-f2-(3.4-Dimethoxyphenyl)-2-hydroxy-l.1-dimethylethyll- 4-chloromandelamide

A mixture of methyl 4-chloromandelate (0.44 g) and 2- amino-2-(3,4-dimethoxyphenyl)-2-methylpropanol (0.86 g) were heated together at 120-130°C for 4 hours. The resulting gum was taken up in ether and the solution evaporated. The residue was purified by silica gel chromatography (ethyl acetate/light petroleum (bp 60-8O°C; 4:1) to give 0.35 g of product as a glass (R _f =0.5)

Example 14 N-Phenylethylmandelamide

A solution of sodium (1.27 g) in methanol (25 ml) was prepared and cooled. A solution of mandelamide (7.6 g) and diethyl carbonate (6.5 g) in methanol (20 ml) was added. The white solid precipitate which formed dissolved on heating to 70°C. The mixture was maintained at this temperature for 1 hour. The methanol was evaporated and the cooled liquid was dissolved in water (75 ml) and acidified to pHl with concentrated hydrochloric acid. The mixture was extracted with ethyl acetate, the extract dried and evaporated to give 5-phenyloxazolidine- 2,4-dione, m.p. 95-8°C.

A mixture of this product (4.4 g) , anhydrous potassium carbonate (3.75 g) and acetone (75 ml) were stirred at room temperature for 1 hour. 2-Bromoethylbenzene (3.5 ml) in acetone (25 ml) was added and the mixture was heated at reflux overnight. The mixture was filtered and the filtrate evaporated and extracted with diisopropyl ether. The extract was evaporated and the residue chilled to give 3-(2-phenylethyl)-5-phenyloxazolidine-2,4-dione, .p. 82-3°C.

This product was added to nitrogen purged dry methanol (50 ml), followed by solid sodium methoxide (0.29 g) . The mixture was agitated for 5 hours, poured into dilute hydrochloric acid, the organic layer, evaporated and extracted with ethyl acetate/water and the organic layer washed with water, dried and evaporated to give 0.48 g of the title product, as an oil.

Example 15

N-f2- (3.4-dimethoxyphenyl)ethyll-O-methyl-3.4- dichloromandelamide

2-(3,4-Dimethoxyphenyl)ethylamine (0.37 g) was added to methyl 0-methyl-3,4-dichloromandelate (0.37 g) and the mixture heated to 103°C for 3 hours. The mixture was extracted with ethyl acetate and the extract washed with 2M hydrochloric acid. The organic fraction was dried over magnesium sulfate, filtered and the solvent evaporated. The residue was purified by silica gel chromatography to give the title product as a yellow oil in 55% yield.

Example 16

N-T2-(3,4-dimethoxyphenyl)-1,1-dimethylethyll-

4-chloromandelamide

Butyllithium (32 ml) was added dropwise via a syringe to diisopropylamine (8.08 g) under nitrogen, dissolved in dry tetrahydrofuran (150 ml) at -60°C. The mixture was warmed to -5°C and then cooled again to -60°C and treated with a solution of isobutyric acid (3.52 g) in tetrahydrofuran (20 ml) . The mixture was allowed to warm to room temperature and 1,3-dimethyl-3,4,5,6-tetrahydro-2(Iff)- pyri idineone (5.12 g) in tetrahydrofuran (15 ml) was added. The mixture was stirred at room temperature for 5 hours. 3,4-Dimethoxybenzyl chloride (7.44 g) in tetrahydrofuran (15 ml) was added via a syringe to the mixture at -5°C. The mixture was stirred for 16 hours at room temperature. Saturated ammonium chloride (10 ml) was added. The mixture was extracted with aqueous sodium hydroxide (7%) . The extracts were extracted with ether. The aqueous layer was acidified with hydrochloric acid. The solid was extracted with dichloromethane and the extract dried and evaporated. The residue was triturated with cold water and filtered. The white solid was extracted with dichloromethane, dried and evaporated to give 3-(3,4-dimethoxyphenyl)-2,2-dimethylpropionic acid, .p. 102-8°C.

A suspension of this product (4.9 g) in toluene (10 ml) was treated with thionyl chloride (2.46 g) and the mixture stirred at 80°C for 2 hours. The mixture was evaporated under reduced pressure and the residual liquid added to dry acetone (10 ml) and the solution added to a stirred solution of sodium azide (2.68 g) in acetone (28 ml) and water (22 ml) at 0°C. Water (30 ml) was added to the solution and the mixture was extracted with toluene. The extracts were dried over magnesium sulfate and heated with

stirring at 80-90°C under nitrogen for 2 hours. The mixture was cooled to room temperature and treated with concentrated hydrochloric acid (3.8 ml) and stirred for 5 minutes at 80-90°C. It was cooled at room temperature and filtered and a flaky solid collected after washing with ether. The filtrate was washed with water, dried and evaporated. The residue was dissolved in tetrahydrofuran and concentrated hydrochloric acid (2 ml) added. This was stirred for 20 minutes and evaporated. The solid residue was dissolved in water and made basic with aqueous sodium carbonate and extracted with dichloromethane. This was combined with the flaky solid which had been dissolved in water, basified and re-extracted with dichloromethane and the two extracts dried and evaporated to give 2-(3,4- dimethoxyphenyl)-1-methylpropylamine, mp 116-8°C.

This was then reacted trimethylsilyl chloride and 4- chloromandelic acid in a similar manner to Example 12 followed by purification by silica gel chromatography (ethyl acetate/light petroleum (bp 60-8O°C; 4:1) to give the title product as a glass (R _f =0.5).

Typical examples of the compounds of the invention which can be prepared as described above are disclosed in Tables 1-7.

Table 1 :

5_?

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00

-43

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00

4>

CO

01

00 σ.

>

<b

Table 2:

Table 3:

Table 4:

Table 5:

Table 6:

Table 7:

Test Example

The compound of the invention was subjected to various tests.

The compound was assessed for activity against Phvtophthora infestans (late tomato blight - PI) and Plasmooara viticola (vine downy mildew - PV) .

Aqueous solutions or dispersions of the compound at the desired concentration, including a wetting agent, were sprayed onto the appropriate plant and then inoculated by spraying with spore suspensions of the fungi. Plants were then kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the leaf surface was visually estimated. The following compounds of the invention gave 100% control at 500 ppm or less against one or both of these diseases.

2, 15, 20, 25, 39, 61, 62, 253, 258, 262, 275, 297, 298, 304, 740, 741, 762, 764, 767, 866, 1008, 1149, 1189, 1190, 1199, 1200, 1405, 2119, 2120, 2134, 2151, 2173, 2174, 2177, 2182, 2183, 2214, 2215, 2216, 2221, 2228, 2229, 2233, 2233, 2237, 2238, 2239