CA1132573A - N-(1,2-azolyl)alkyl-halogenoacetanilides, processes for their preparation and their use as herbicides - Google Patents

Abstract

A B S T R A C T
The invention relates to the new N-(1,2-azoyl)-alkyl-halogeno-acetanilides of the general formula

Description

11;325t73 The present invention relates to certain new N-(1,2-azolyl)alkyl-halogenoacetanilides, to a process for their preparation and to their use as herbicides.
It has already been disclosed that 2,6-diethyl-N-methoxymethyl-chloroacetanilide can be used for selectively combating weeds (see R. Wegler, Chemie der Pflanzenschutz- und Schadlingsbe]campfungsmittel (Chemistry of Plant Protection Agents and Agents for Combating Pests), Volume 5, page 225, Springer-Verlag (1977)). However, this compound is not always sufficiently active and its selectivity is not always quite satisfactory.
The present invention now provides, as new compounds, the N-(1,2-azolyl)alkyl-ha1ogenoacetanilides of the general formula R`~ ~ ~ ~ ~ X
R O
in which A represents oxygen, sulphur or the grouping ~ NR, wherein R represents hydrogen or alkyl, Rl represents hydrogen, alkyl or alkoxy, R represents hydrogen, alkyl, alkoxy or halogen, R3 represents hydrogen, alkyl, alkoxy or halogen, R4 represents hydrogen or alkyl, xl represents hydrogen, alkyl, halogen, alkoxy, alkylthio, halogenoalkyl, alkoxycarbonyl, dialkyl-amino, cyano, phenyl, phenylthio, 1~32573 x2 represents hydrogen, alkyl, halogen, alkoxy, alkylthio, halogeno-alkyl, alkoxycarbonyl, dialkylamino, cyano, phenoxy or phenylthio and Z represents halogen, and the azolyl radical is bonded via a carbon atom, and acid addition salts and metal salt complexes thereof.
The N-~1,2-azolyl)alkyl-halcgenoacetanilides of the formula (I) and acid addition salts and metal salt complexes thereof have powerful herbicidal properties, in particular selective herbicidal properties.
Preferably, in formula (I), A represents oxygen, sulphur of the grouping ~ NR, R represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, Rl represents hydrogen or straight-chain or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms, R2 and R3, which may be identical or different, each represent hydrogen, straight-chain or branched alkyl or alkoxy with in either case 1 to 4 carbon atoms, fluorine, chlorine or bromine, R4 represents hydrogen or alkyl with 1 to 4 carbon atoms, xl and X2, which may be identical or different, each represent hydrogen, straight-chain or branched alkyl with 1 to 4 carbon atoms, straight-chain or kranched alkoxy with 1 to 4 carbon atoms, straight-chain or branched alkylthio with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, fluorine, chlorine, bromine, halogenoalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms (preferred halogens being fluorine, chlorine and bromine), dialkylamino with 1 to 4 carbon atoms in each alkyl part, cyano, phenyl, phenoxy or phenylthio, and .

~13Z573 Z represents chlorine, bromine or iodine.
The invention also provides a process for the prepara-tion of an N-(1,2-azolyl)alkyl-halogenoacetanilide of the formula (I), or an acid addition salt or metal salt complex thereof, in which (a) an N-(1,2-azolyl)alkyl-aniline of the general formula R3 R~ 7~ N A X~
~ \ ~ X2 (II), in which A, R , R2, R3, R4, Xl and x2 have the meaning stated above, is reacted with a halogenoacetic acid chloride or bromide or anhydride of the general formula Z-CH2-C0-Cl(Br) (IIIa) or (Z CH2 C)2 (IIIb), in which Z has the meaning stated above, in the presence of a diluent and if appropriate in the presence of an acid-binding agent, or (b) a halogenoacetanilide of the general formula R3 R~

\ C - CH2 - Z (IV), Le A 19 121 ~13ZS~3 in which Rl, R2, R3 and Z have the meaning stated above, is reacted with an azolyl-alkyl derivative of the general formula R N - A
~X' (V), in which A, R4, Xl and x2 have the meaning stated above and Y represents halogen or the mesylate or tosylate radical, in the presence of an acid-binding agent and if appropriate in the presence of an organic solvent, and, in either variant, an acid or a metal salt is then optionally added on.
Surprisingly, the possibilities of using the N-(1,2-azolyl)alkyl-halogenoacetanilide5 according to the invention, which have a very good herbicidal action, as agents for selectively combatingweeds in important crop - plants are better than those of the abovementioned, already known compound, which is a substance of great activity and the same type of action. The substances according to the invention thus represent a valuable enrichment of the herbicidal agents for selectively combating weeds.
Those N~ 2-azolyl)alkyl-halogenoacetanilides of the formula ~I) are particularly preferred in which A represents oxygen, sulphur or the grouping > NR, R representing methyl, ethyl, propyl or butyl; Rl represents hydrogen, methyl, ethyl, isopropyl, sec.-butyl, tert.-butyl, methoxy, ethoxy or isopropoxy; R2 and R3 are identical or different a~d represent hydrogen, methyl, ethyl, isopropyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, isopropoxy, chlorine or bromine; R4 represents hydrogen or methyl; Xl and x2 Le A 19 121 ~Llt~ 73 are identical or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, isopropoxy, methylthio, ethylthio, isopropylthio, methoxy-carbonyl, ethoxycarbonyl, chlorine, bromine, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, trifluoromethyl, dimethylamino, ethylmethylamino, cyano, phenyl, phenoxy or phenylthio; and Z represents chlorine or bromine.
In addition to the compounds mentioned in the preparative examples given later in this text, the following compounds of the general form~la (I) may be mentioned specifically:

1 x2 R3 Rl R4 (Ia) N / N

IC - CH2 - C1(Br) o ~132573 R' R2 R3 R4 X' X2

2 H5 CH3 H H H H
2 H5 C2 Hs H H H H
C(CH3 )3 H H H H H

C(CH3 )3 H H CH3 H H

CH3 H s-CH3 H H H - -CH3 Cl H H H H
C(CH3 )3 Cl H H H H

C2 Hs C2 H5 H H H CH3 C(CH3 )3 H H H H CH3 Cz Hg CH3 H CH3 H CH3 C2H5 . C2 Hs H CH3 H CH3 C(CH3 )3 H H CH3 H CH3 CH3 Cl H H H CH3 C(CH3 )3 Cl H H H CH3 CH3 CH3 H H H C2 Hs C2H5 CH3 H H H C2 Hs C2 H5 C2 H5 H H H C2 Hs Le A 19 l21 _ CH3 CH3 H. H H Cl C2 H5 CH3 H H H Cl C2 H5 C2 H5 H H H Cl CH3 CH3 H H H Br C2 H5 CH3 H H H Br C~ H5 C2 H3 H H H Br CH3 CH3 H H Cl CH3 C2 ~5 CH3 H H Cl CH3 C2 H5 C2 H5 H H Cl CH3 CH3 CH3 H H Cl H
C2H5 CH3 H H Cl H
~2 H5 C2 H5 H H Cl H
CH3 CH3 H H H ~9 C2 H5 C~3 H H H
C2 H5 C~ H5 H H H ~
CH3 CH3 H H Br CH3 C2 H5 CH3 H H Br CH3 C2 ~5 C2 H5 H H Br CH3 CH3 CH3 H H Br H
C2H5 CH3 H H Br H
C ~ H5 ~ C2 H5 H H Br H

Cz Hg c~3 H H CH3 H
C2 H5 C2 ~rI5 H H CH3 H

Cz H5 CH3 H H CH3 CH3 C2 ~5 C2 H5 H H CH3 CH3 CH3 CH3 H H H C(CH3 )3 C2H5 CH3 H H H C(CH3 )3 C~:-I5 C2H5 H H H C(CH3 )3 C~ H5 CH3 H H H C3 H7 C~ H C2H5 H H H C3H7 Le A 19 121 1~32573 R4 X' X2 - N ~ (I b) R2IC - CH2 - Cl(Br) o R'_ R2 R3R4 X _ _ X2 CHI C2 H, H H H H
C2 H5 C2 H~ H H H H

C2 H, C2 H5 H H H CH3 CH3 Cz H5 H H H i-C3 H7 C2 H5 C2 H5 H H H i-C3 H7 CH3 C2 H~ . H H H C(CH3 )3 C2 H5 C2 H5 H H H C(CH3 )3 X' R4 ~ N
R3 ,R' I l I
CH - ~ 0 (I c) R2 Cl - CH2 - Cl(Br) o R' R2 R3R4 X~ X2 CH~ C2 H5 H H H H

Le A 19 121 -l~ZS73 R

CH - ~ N ~
N \ (I d) \ R2 ICI - CH2 - Cl(Br) o R1 R2 R3 R4 X' X2 CzH5 C2H5 H H H H

C(CH3)3 H H H H H

CH3 H s-CH3 H H H
CH3 Cl H H H H
C(CH3)3 Cl H H H H
OCH3 c~.3 H H H H
C2H5 ,C2H5 H H H CH3 C2H5 C2H5 H H H Cl CH3 C2H5 H H H Cl CH3 C~3 H H H Cl C2;~5 C2H5 H H H Br CH3 C2H5 H H H Br CH3 CH3 H H H Br C~I5 C2H5 H H Br H
C'~3 C2H5 H H Br H
C~3 CH3 H H Br H
C(CH3 )3 H H H Br H
'~2 H5 C2H5 H H Cl H
C'T3 C2H5 H H Cl H
CH3 CH3 H H Cl H
Le A 19 121 11~}2573 Rl R2 R3 R4 X' .XZ
C2 H5 C2H5 H H c~3 H

C(CH3 )3 H H H CH3 H

C2 Hs C2 H5 H H CN H

CH3 C2 Hs H H H CH2 Br C2 H5 C2H5 H H H CH2 Br CH3 CH3 H H H CH2 Br CH3 Cz H5 H H -CO-OCH

R~ ~ X' XZ

\ C - CH2 - Cl(Br) O
R1 R2 R3 R4 _ X' _ X2 CH3 CH3 H H Br CH3 C2 H~ CH3 H H Br CH3 C2 H5 C2 H5 H H Br CH3 C2 H5 CH~ H H H CH3 R~ X' I \~======N
R3 ~ ~, CH ¦ ~ S

C - CH2 - Cl(Br) lo Le A 19 121 "~

~13Z57~3 R1 R2 R3 R~ X1 X2 CH3 C~H5 H H CH3 H

X~ X2 ~ - N / ~ ~

R R2 R3 _ _R~ X~ _ 2_ _ _R _ C2H5 CzHg H H H H CH3 C2H~ CpH~ H CH3 H H CH3 CH3 Cl H H H H CH3 C(CH3)3 Cl H H H H CH3 CH3 CH3 H H H CH3 ~H3 C(CH3)3 H H H H CH3 CH3 CH3 Cl H H H CH3 CH3 Le A 19 121 R' R2 R3 ~ X1 X2 R
CH3 C2H5 H H H H Cz H5 2H, C2 H5 H H H H C2 H5 CH3 C2 H, H H H H C3 H?
CH3 CH3 H H H H C~Hg 2 H5 C2H5 H H H H C~H9 C2H5 CH3 H H H H C~Hg CH3 C~, H H H CH3 C2 H5 CH3 C2 H~ H H H CH3 C2 Hs C2 H5 C2 H, H H H CH3 C2 H5 CH3 C~3 H H CH3 CH3 CH3 s C2H~ H H CH3 H CH3 CH3 C2H~ H H CH3 H CH3 CH3 CH3 H H H Cl CH3 C2 H5 C2 H5 H H H Cl CH3 CH3 C2H5 H H H Cl CH3 C(CH3 ~3 H H H H Cl CH3 CH3 CH3 H H Cl CH3 CH3 C2 H, C2 H5 H H Cl CH3 CH3 CH3 C2 H5 H H Cl CH3 C~3 CH3 CH3 H H Cl H CH3 C2 H5 C2 H5 H H Cl H CH3 CH3 C2 H, H H Cl H CH3 CH3 CH3 H H Br H CH3 C2 H, C2 H5 H H Br H CH3 CH3 C2 H, H H Br H CH3 113~573 R~ X' x2 R3 R~
~v~~~~ CH _ ~ N
-N / ~ INR ~ (I h) RZ R CH2 -- Cl(Br) o R' R2 - R3 R~ X' X2 R

C2Hg C2 H, H H H CH3 CH3 CH3 CH3 H H Cl CH3 CH3 CH~ C2 H~ H H Cl CH3 CH3 C2 H5 C2 H5 H H Cl CH3 CH3 R~ ~ N
R R' / CH _ ~ / N - R
> - N l2 (I i) ~ R2 C - CH2 - Cl(Br) R' R2 R3 - R~ X' x2 R
CH3C2 H~ H H CH3 CH3 CH~

Le A 19 121 1~32573 Further preferred compounds according to the invention are addition products of acids and those N-(1,2-azolyl)-alkyl-halogenoacetanilides of the formula (I) in which A, R, Rl, R2, R3, R4, Xl, X2, and Z have the meanings which have already been mentioned as preferred therefor.
The acids which can be added on include, as preferences, hydrogen halide acids (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid, maleic acid, succinic acid, fu~aric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid), and sulphonic acids (for example p-toluenesulphonic acid and 1,5-naphthalenedisul-phonic acid).
Further preferred compounds according to the inventionare addition products of salts of metals of main groups II
to IV and of sub-groups I and II and IV to VII and those N-(1,2-azolyl)alkyl-halogenoacetanilides of the formula (I) in which A, R, Rl, R2, R3, R4, Xl, x2 and Z have the meanings which have already been mentioned as preferred therefor. Salts of copper, zinc, manganese, magnesium, tin, iron, and nickel are particularly preferred here.
Possible anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. In this connection, particularly preferred acids of this type are the hydrogen halide acids (for example hydrochloric acid and hydrobromic acid), phosphoric acid, nitric acid and sulphuric acid.
If 2-ethyl-6-methyl-N-(3'-tert.-butyl-isoxazol-5'-yl-methyl)-aniline and chloroacetyl chloride are used as starting substances in process variant (a), the course of the reaction can be represented by the following equation:

N~ ~o~N
CzHs Le A 19 121 11~2573 (CH3 )3C

CH
C2 H, CO-CH2 -Cl If 2-ethyl-6-methyl-chloroacetanilide and 5-bromo-methyl-3-methyl-isoxazole are used as starting substances in process variant (b), the course of the reaction can be represented by the following equation:

CzH CO-CHzCl BrCH& ~ HBr -~~

CH~

3 / CH

C2H5 \ CO-CH2Cl The formula (II) provides a general definition of the N-azolylslkyl-anilines required as starting substances in carrying our process variant (a) according to the invention. In this formula, A, R, Rl, R2, R3, R4, X
and X2preferably represent those radicals which have already been mentioned as preferred therefor in connection with the description of the substances of the formula (I).
lS The following compounds may be mentioned as specific examples of compounds of the formula (II):
Le A 19 121-~L~L3Z57;~

R~ ~~ X2 R3 R' l \ ~ ( II a ) R' _ _P. _ R3 . _ R _ _ X~ ~,2 ... .
CH3 CH3 H . H H H
C2 ~5 CH3 H H H H
C~H5 C2H, H H H H
C(CH3)3 H H H H H

C2 H, CH, H CH3 H H
C~ Hs C2 H, H CH3 H H
C(CH3 )3 CH3 H CH3 .H H-C~3 H 3-CH3 H H H
CH3 H s-CH3 H H H
CH3 Cl H H H H
C(CH3 )3 Cl H H H H

CCH~, c2 H5 H H H H
CH3 CH~ H H H CH~;
C2 H5 CH3 H H H CE~.3 C2 E~sC2 H5 H H H CH3 C(CH3 )3 H H H H CH3 CH~ CH3 H CH3 H CH3 C2 Hs CH3 H CH3 H CH3 C2 H~ C2 H5 H CH3 H CH3 C(CH3 )3 H H CH3 H CH3 C.~3 H 3-CH3 H H CH3 CH3 H 5-CH~ H H CH3 CH3 Cl H H H CH3 C(CrI3 )3 Cl H H H CH3 Le A 19 121 ,, ;

CH3 C.i3 3-CH3 H H CH3 CH3 CH3 H H H C2 H~
C2 Hs CH3 ~ H H C2 Hs C2H5 C2Hs H H H C2H~
CH3 CH3 H H H Cl C2 H5 CH3 H H H Cl C.~H5 C2~s H H H Cl C~ CH3 H H H Br C2H~ CH3 H H H Br C2 H, C2 H5 H H H Br CH3 CH3 H H Cl c~3 C2 H, CH3 H H Cl CH3 C2 H, C2 H, H H . Cl CH3 CY.3 Cu3 ~ H Cl H
C2~.~5 CH3 H H Cl H
C2H5 C2H, H H Cl H
CH3 CH3 H H H ~3 C2 H~ C2 H, H . H H OE~
CH3 CH~ H H Br CH3 C2H~ CH3 H H Br CH3 C2 H5 C2 H, H H Br CH3 CH3 CH ~ H H Br H
C Hs C~.3 H H Br H
C2 ~5 C2 H~ H H Br H
C~.3 CH3 H H CH3 H
C2 ~5 CH3 H H CH3 H
C2 H5 C2 H, H H CH3 H
C~3 CH3 H H C~3 CH3 Le A 19 121 ;?~1 F~2 , ~ 3 R~ Xl X
C2 H~ CH3 H H CH3 CH3 C2 Hs C2H5 H H CH3 CH3 CH3 CH~ H H H C(CY3 )3 C2H5 CH3 H H H C(CH3 )3 C~jU5 C2H, H H H C(CH3 )3 C2 H5 C2 H, H H H C~ H7 R~ X~ x2 R3~ 0 ~ ( I Ib ) R' R2 R3 R~ X' X2 . . ; . , . --CH~ C2 H~ H H H H
C2 ~ C2H, H . H H H
CH3 C2 H~ H H H CYy Ca H~ C2 Hs H H H CH~
CH3 C2 H5 H H H l-C~ H7 C2H5 C2Hs H H i H i-C3~17 CH3 C2H5 H H H C(CH3 )3 C2H, H H H C(CH3 )5 X' R3 ~ =N
CH - ~0 ( IIc ) Le A 19 121 ~13257~3 R' R2 R~ R'~ X' x2 C2 H5C2 Hs H H H H
CH3 C2 H, H H CH3 H
Cz H3C2 H~ H H CH3 H
CH3 C2 Hs H . H CH3 CH3 C2 H~C2 H~ H H CH3 CH3 CY.3 CH, H H CH3 CH3 X~ x2 R3 R' R~ \~
~ CH_ ~ ~S

RZ H

R' R2 - R3 R4 X x2 .

C2 ~3 CH3 H H H H
C2 X5 C2 ~5 H H H H
C~3 c~3 H CH3 H H
C2 H, CY3 H CH3 H H
C2 H,C2 Hs H CH.~ H H
C(CH~)3 H H H H H
CH3 H 3-CH, H H H

CH3 Cl H H H . H
C(CH3 ).~ Cl H H H H

C2 H, C2 H, H H H CH3 C~3 C2 Hs H H H CH3 CH3 CH3 H H H . CH., Le A 1~ 121 ..

R' _ RZ R3 R~ X' _ X2 C2 H~ Cz H~ H H H Cl CH3 C2 H5 H H H Cl CH3 CH3 H H H Cl C~ H~ C2 H,; H H H Br C~3 C2~ rI H H Br C~3 c.~3 H H H Br C2 H5 C2 H, H H Br H
CH3 C2 H5 H H Br H
CH3 CH3 H H Br H
C(CH3 )3 H H H Br H
C2 H, C2 H~ H H Cl H
CH5 C2 H5 H H Cl H
CH3 CH3 H H Cl H
C2 H, C2 H5 H H CH3 H
CH3 C2 H, H H CH3 H

C(CH~ )3 H H H CH3 H
CH3 C2 H, H H CN H
C2 H, C2 H, H H CN H

CH3 C2 H5 H H H CH2 Br C2 H3 C2 H, H H H CHz Br ~H3 c~3 H H H CH2 Br R~ X~ x2 R~_< R1 ~ ~
~ N ~ S~ (IIe) Le A 19 121 1~3Z573 CH3 CH3 H H Br CH3 C2 H, CH3 H H 8r CH3 C2 H~ C2 H, H H Br CY3 C2Hs CH3 H H H CH3 . . 'I . C2 ~5 X H H CH~

R~ X' R3~ I J~N

CH3 ~ H~ H H C~3 H
C2 H.~ C2 Hg H H CH3 H
CH3 C2 H~ H H CH3 CH3 CH3 C2 H, H H CH3 ~X~ x2 R~ R1 R~
~R2 ~ (IIg) Le A 19 121 .. ..

11~2573 Rl R2 _ _ R3 _ R~_ X1 X2 R

C2 H, CH3 H H H H CH~
C2 Hs C2 H, H H H H CH3 CH3 CH3 H C~H,H H CH3 C2 Hs CH3 H CH3 H H CH3 C2 H~ C2 H~ H CH3 H H CH3 CH3 H 3-CH~ H H H CH3 CH3 Cl H H H H CH3 OCH~ CH3 H H H H ~H3 C(CH3 )3 Cl H H H H c~3 OC~.5 OCH3 H H H H C~3 CH3 CH3 H H H C~3 ~H3 CH3 C2 H5 H H H CH~ CH3 C2 H~ C2H~ H H H CH3 CH3 C(CH3 )3 H H H H CH3 CH3 CH3 H 3-CH~ H H CH3 CH3 CH3 H 5-CH~ H H C~ CH3 OCH~ CH~ H H H CH3 CH3 CH~ Cl H H H CH~ . CH3 CU3 C2 H5 H H H H C2 H, c~3 CH~ H H H H C2 Hs C2 H~ C2H5 H H H H C2 H5 C.Y.3 CH~ H H H H c3 ~7 C2 H, C2 H, H H H H C~ H7 C.~3 C2 H, H H H H C3 H7 CH3 CH3 H H H , H C~ Hg C2H~ C2 H5 H K H H C~ Hg C2 H5 CH3 H H H H C~ H~
C~ CH~ H H H ~-H3 Cz ~5 CH3 C2 HS ~ H H CH3 C~ y5 .3'~573 C2 H, C2 H, H~ H H CH, C2 H~
CH~ CH, H H CH~ CH3 CY.
CH, C2 H, H H CH~ CH3 CH~
CH3 CH, H H CH~ H CH~
C2 H, C2 H, H H CH~ H CH3 CH~ C2 H, H H CH5 H CH, CH~ CH~ H H H Cl CH, C2 H, C2 H, H H H Cl CH, CH, C2 H, H H H Cl CH, C(CH~ )~ H H H H Cl C~3 CH~ CH~ H H Cl CH~ CH3 C2 H, C2 H~ H H Cl CH3 CH, C~.3 C2 Hy H H Cl CH3 CH, CHy CH, H H Cl H CH3 C2 H5 C2 H, . H H Cl H CU~3 CH3 C~ H~ H H Cl H CH~
CH3 CH3 H H Br H CY., C2 ~ C2 H, ` H H - Br }~ CH3 CH~ C2 H, H . H Br H C~I5 R~ X' x2 R2 El Le A 19 121 ~132~7;3 R1 R2-- -- R3 R~ X' X2 _ R
CH, Cl13 H H H CH3Cr~3 CI~3 C2 H, H H H CH~CH3 C2 H, C2 H~ H X H C~3CH3 CH3 c~3 H H H H CH3 C~I3 c2 H5 H H H H. CH3 C2 H~ C2 H~ H H H H CH3 CH3 CH3 H H Cl CH3CH3 CH, c2 H, H H Cl CH3CH3 C2 H, C2 ~ H H Cl CH3CX3 R~ - .
R~, ~ R1 ~CH_ ~I~ - R
C~-- N~ 12 ~IIi) . R2 H

CH3 C2 H.l H H CH3 CH3CH3 ~2 H~ C2 H.~ H H CH3 CH3CH3 CH3 C2 H, H H H H CH3 C2 H~ C2 H~ H H H H CH3 The N-(1,2-azolyl)alkyl-anilines of the formula (II) have not hi~herto been described in the literature. They are obtained when anilines of the general formula R3 R' ~ NH2 (VI), Le A 19 121 in which Rl, R2 and R3 have the meanings stated above, (~) are reacted with azolylalkyl derivatives of the general formula Y-CH~ X 1 ( V ), in which A, R4, Xl and x2 and Y have the meanings stated above, in the presence of an acid-binding agent and if appropriate in the presence of a diluent, or (~) are reacted with azole-aldehydes of the general formula ~ C ~ X2 (VII), in which A, Xl and x2 have the meanings stated above, in the presenceof an inert organic solvent and if appropriate in the presence of a catalyst, and the imines formed, of the general formula Rs R~
~ N - CH ~ (VIII), in which A, Rl, R2, R3, Xl and x2 have the meanings stated above, are reduced, if appropriate in the presence of a polar diluent. In process variant C~), only those compounds (II) in which R4 denotes hydrogen are formed.
Le A 19 121 1~3Z573 The anilines of the formula (VI) required as starting substances in the preparation of the N-(1,2-azolyl)alkyl-anilines of the formula (II) are generally known compounds of organic chemistry. Examples are: aniline; 2-methyl-aniline; 2-ethylaniline; 2-isopropylaniline; 2-sec.-butyl-aniline; 2-tert.-butylaniline; 2,6-dimethylaniline; 2,3-dimethylaniline; 2,5-dimethylaniline; 3,5-dimethylaniline;
2,6-diethylaniline; 2-ethyl-6-methyl-aniline; 2,3,4-tri-methylaniline; 2,4,6-trimethylaniline; 2,4,5-trimethyl-aniline; 2-ethyl-4,6-dimethylaniline; 2,6-diethyl-4-methylaniline; 2,6-diisopropyl-4-methylaniline; 2,3,5-tri-methylaniline; 2,3,6-trimethylaniline; 2-methyl-6-chloro-aniline; 2-tert.-butyl-6-chloroaniline; 2-methoxy-6-methyl-aniline; 2,6-dimethoxyaniline; 2-methoxy-6-ethylaniline and 2,6-diethoxyaniline.
The azole-aldehydes of the formula (VII) also required as starting substances in the preparation of the N-(1,2-azolyl)alkyl-anilines of the formula (II) are known (see, for example, Arch. Pharm. 264 (1926); and J. Chem.
Soc. 1957, 3314 and 1964, 3114), or they can be obtained by processes described in the literature.
Acid-binding agents which can be used in the pre-paration of the N-(1,2-azolyl)alkyl-anilines of the formula (II) according to process (~) are any of the customary acid acceptors. An alkali metal carbonate, such as potassium carbonate or sodium carbonate, is preferably used.
Possible diluents which can be employed in process (~) are any of the customary inert organic solvents.
Dimethylforma~Qde or toluene is preferably used.
The reaction temperatures can be varied within a substantial range in process (~). In general, the reaction is carried out between 0C and 180C, preferably between 20C and 160C.
The anilines of the formula (VI) and the azolyl-alkyl derivatives of the formula (V) are in general employed in equimolar amounts in the reaction according to Le A 19 121 1~325~3 process (~). However, it is also possible to employ one of the components, preferably the aniline of the formula (VI), in excess. Working up and isolation of the reaction products are carried out by customary methods.
Inert organic solvents which can beused in the first stage in the preparation of the N-(1,2-azolyl)alkyl-anilines of the formula (II) according to process (~) are any of the customary solvents of this type. An aromatic solvent, such as toluene, is preferably used.
Catalysts which can be used in the first stage in reaction (~) are any of the reaction accelerators customary for addition reactions of this type. A strong organic acid, such as ~-toluenesulphonic acid, is preferably used.
Solvents which can be used in the second stage of process (~) are any of the inert polar organic solvents.
An alcohol, such as methanol, is preferably used.
The reducing agent which can be used in carrying out the second stage of process (~) is preferably a complex hydride, for example sodium borohydride.
The reaction temperatures can be varied within a substantial range both in the first and in the second stage in carrying our process (~). In the first stage, the reaction is in general carried out at temperatures between 40C and 140C, preferably between 60C and 120C.
In the second stage, the reaction is in general carried out at temperatures between -10C and 1100C, preferably between 0C and 80C.
The anilines of the formula (VI) and the azole-aldehydes of the formula (VII) are in general employed in equimolar amounts in carrying out process (~). However, it is also possible to employ one of the components, preferably the aniline of the formula (VI), in excess.
The reducing agent required in the second stage is 3~ appropriately employed in excess. Working up and isclation of the reaction products are in each case carried out by customary methods.

113Z5'73 The formulae (IIIa) and (IIIb) provide general definitions of the halogenoacetic acid chlorides and bromides and anhydrides also to be used as starting substances for process variant (a) according to the invention. In these formulae, Z preferably represents chlorine, bromine or iodine.
The halogenoacetic acid chlorides and bromides and anhydrides of the formulae (IIIa) and (IIIb) are generally known compounds of organic chemistry. Examples which may lD be mentioned are: chloroacetyl chloride, bromoacetyl chloride, iodoacetyl chloride and the corresponding bromides and anhydrides.
The formula (IV) provides a general definition of the halogenoacetanilides required as starting substances in carrying out process variant (b) according to the invention.
In this formula, Rl, R2, R3 and Z preferably have those meanings which have already been mentioned as preferred therefor in connection with the description of the compounds of the formula (I).
The halogenoacetanilides of the formula (IV) are generally known, or they can be obtained in a manner which is generally known, by reacting corresponding anilines with a halogenoacetic acid chloride or bromide or anhydride, of the formula (IIIa) or (IIIb), in the presence ofan inert organic solvent, for example toluene or dimethylformarnide, if appropriate in the presence of an acid-binding agent, for example potassium carbonate or triethylamine, at temperatures between 0 and 100C (see also the preparative - examples given later in this text). The chloroacetanilides and bromoacetanilides of the abovementioned anilines of the formula (VI) may be mentioned as examples.
The formula (V) provides a general definition of the azolylalkyl derivatives also to be used as starting sub-stances for process (b) according to the invention. In this formula, A, R4, Xl and x2 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the 1~3Z~73 -2~-formula (I). Y preferably represents chlorine, bromine, or the mesylate or tosylate radical.
The azolyl-alkyl derivatives of the formula (V) are known (see, inter ali-a, J. Chem. Soc. 1965, 7274 and 1978, 994; DE-OS (German Published Specification) 2,549,962 and C.A.50, 3402i); or they can be obtained in a manner which is generally known, for example by halogenating the corresponding methyl derivatives by customary methods. The following compounds may be mentioned as specific examples of compounds of the formula (V):
R4 X ~ X2 Y - CH ~ ~ ~0 (Va) N

H H H Cl(Br) H H ~ Cl(Br) H H CH3 Cl(Br) H Br CH3 Cl(Br) H H C2H5 Cl(Br) H Br H Cl(Br) H H Cl Cl(Br) H CH3 CH3 Cl(Br) H H Br Cl(Br) H H C(CH3)3Cl(Br) H Cl CH3 Cl(Br) H H C3H7 Cl(Br) H Cl H Cl(Br) Xl ~X2 (Vb) ~4 X1 X2 Y R4 X~ X2 v H H H Cl(Br) H H i-C3 7 Cl(Br) H H CH3 Cl(Br) H H C(CH3 )3Cl(Br) Le A 19 121 X~
R~ N
Y - ~H - ~ o (Vc), x2 t~4 Xl ;~2 y H H H Cl(Br) H CH3 H Cl(Br) H CH3 CH~ Cl(3r) X~ x2 R~
l I I (Vd), Y CH~N~S

l~ X' XZ y I R~ X9 x2 y . ~ _ H H C;~Br) ¦ H CN H Cl(Br) H H CH3 Cl(Br) ¦ H H CH2Br CltBr) H H Cl Cl(Br) 8CH ~ Cl(Br) H H Br Cl(Br) 3 H Br H Cl(Br) H Cl H Cl(Br) R~ X~ X2 Y - CH_ ~ (Ve) S~

H Br CH3 Cl(Br) H H CH3 Cl(Br) Le A 12 191 ~13Z573 X1 ~

¦= I ( V f ) Y - CH_~f R~ X~ X _ Y
H CH3 H Cl(Br) H CH3 CH3 Cl ( Br ) H CH3 ~ Cl(Br) X~ x2 R~ ( Vg ) Y - CH~ ~ - R

CH3 H H H Cl ( Br ) CH3 H H CH3 Cl (Br ) C2H~ H H H Cl(Br) C3 H7 H H H Cl ( Br ) C4 Hg H H H Cl ( Br ) C2H5 H H CH3 Cl(Br) CH3 H CH3 CH3 Cl ( Br ) CH3 H CH3 H Cl ( Br ) CH3 H H Cl Cl(Br) CH3 H Cl CH3 Cl(Br) CH3 H Cl H Cl (Br ) CHy H Br H Cl (Br ) X~ X2 Y - CH--~ (Vh) R
Le A 19 121 ~1~2S73 R R" X~ X2 Y
CH~ H H CH~ Cl ( Br ) ~H3 H H H Cl (Br) CH,~ H Cl CH3 Cl ( Br ) R~ X~

Y - CH~N - R ( Vi ) x2 R R~ X' x2 y CH3 H CH~ CH3 Cl (Br ) CH3 H H H Cl ( Br ) Preferred diluents for the reaction, according to the invention, in process variant (a) are inert organic solvents.
These include, as preferences, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone;
nitriles, such as propionitrile, and in particular acetonitrile;
ethers, such as tetrahydrofuran or dioxan; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, such as methyl-ene chloride, carbon tetrachloride, chloroform or chloro-benzene; and esters, such as ethyl acetate.
If appropriate, process variant (a) according to the invention can be carried out in the presence of an acid-binding agent (hydrogen chloride acceptor). Any of the customary acid-binding agents can be used here. These include, as preferences, organic bases, such as tertiary amines, for example triethylamine, or such as pyridine, and furthermore inorganic bases, for example alkali metal hydroxides and alkali metal carbonates.
The reaction temperatures can be varied within a substantial range in carrying out process variant (a) according to the invention. In general, the reaction is Le A 19 121 .
. , 113'2573 carried out at from 0 to 120C, preferably from 20C to 100C.
In carrying out process variant (a) according to the invention, 1 to 1.5 moles of halogenoacetylating agent and, if appropriate, 1 to 1.5 moles of acid-binding agent are preferably employed per mole of the compound of the formula (II). Isolation of the compounds of the formula (I) is effected in the customary manner.
Possible diluents for the reaction, according to the invention, in process variant (b) are any of the inert water-immiscible organic solvents. These include, as preferences, ethers, such as diethyl ether; aromatic hydrocarbons, such as benzene, toluene or xylene;
halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.
The reaction, according to the invention, in process variant ~b) is carried out in the presence of an acid-binding agent. Any of the customary acid-binding agents can be used here. These include, as preferences, inorganic bases, for example alkali metal hydroxides and alkali metal carbonates, for example sodium or potassium hydroxide and sodium or potassium carbonate.
The reaction temperatures can be varied within a substantial range in carrying out process variant (b) according to the invention. In general, the reaction i5 carried out at from -70C to +100C, preferably at from -20C to +80~.
In carrying out process variant (b) according to the invention, 1 to 1.5 moles of azolyl-alkyl derivative of the formula (V) are preferably employed per mole of halogeno-acetanilide of the formula (IV). Isolation of the com-pounds of the formula ~I) is effected in the customary manner.
In a preferred embodiment, the reaction, according to the invention, in process variant (b) is carried out in a two-phase system, for example aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methy-Le A 19 121 1~3Z573 lene chloride, if appropriate with the addition of 0.1 to 1 mole of a phase transfer catalyst, for example an ammonium or phosphonium compound; benzyl-dodecyl-dimethyl-ammonium chloride (Zephirol) and triethyl-benzyl-ammonium chloride may be mentioned as examples (see also the preparative examples).
The compounds of the formula (I) according to the invention, whether prepared by process variant (a) or by process variant (b), can be converted into acid addition salts or metal salt complexes.
The following acids are preferably used for the preparation of physiologically acceptable acid addition salts of the compounds of the formula (I): the hydrogen halide acids (for example hydrobromic acid and, in particular, hydrochloric acid), phosphoric acid, nitric acid, sulphuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetlc acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid), and sulphonic acids (for example p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid).
The acid addition salts of the compounds of the for-mula (I) can be obtained in a simple manner by customary salt formation methods, for example by dissolving a compound of the formula (I) in a suitable inert solvent and adding the acid, for example hydrochloric acid, and can be isolated in a known manner, for example by filtration, and if appropriate purified by washing with an inert organic solvent.
Salts of metals of main groups II to IV and of sub-groups I and II and IV to VIII are preferably used for the preparation of metal salt complexes of the compounds of the formula (I), examples of metals which may be mentioned being copper, zinc, manganese, magnesium, tin, iron and nickel. The anions of the salts are preferably derived from the following acids: hydrogen halide acids (for example hydrochloric acid and hydrobromic acid), phosphoric Le A 19 121 1~32573 acid, nitric acid and sulphuric acid.
The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt in alcohol, for example ethanol, and adding the solution to the compound of the formula (I). The metal salt complexes can be isolated in a known manner, for example by filtra-. tion, and if appropriate purified by recrystallisation.
The active compounds according to the inventîon influence plant growth and can there~ore be used as de~oliants,desiccants, agents for destroying grasses and broad-leaved plants, germination inhibitors and, especially, as weed~
killers. By "weeds~' in the broadest sense there are meant plants growing in places where they are not desired.
Whether the compounds according to the invention act as total herbicides or selective herbicides depends essentially on the amount used.
The active compounds according to the present in-vention may be used, for example, to combat the following plants:
dicotyledon weeds of the genera Sinapis, Lepidium, Galium5 Stellaria,' Mat~icaria,''Anthemis, Galinsoga, --Chenopodium, Urtica, Senecio, Amaranthus,' Portulaca, Xanthium, Convolvulus, ~pomoea,- Polygonum, Sesbania, Ambrosia,-Cirsium, Carduus, Sonchus, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, ~atura, Viola, Galeopsis,-Papaver, Centaurea and Solanum, and monocotyledon weeds of the genera Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, SPhenoclea~ DactYloctenium~ A~rostis, Alopecurus and Apera.

Le A 19 121 ~13Z5'73 The active compounds according to the present in-vention may be used, for example, as selective herbicides in the following cultures:
dicotyledon cultures of the genera Cossypium, Glyci-ne, Beta, ~aucus, Ph:aseoIus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon,' Arachis, - Brassica, Lactuca, Cucumis and Cucurbita; and monocotyledon cultures of the genera Oryza, Zea, Triticum, ~ordeum, Avena,' Secale,'-Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera but also embraces other plants, in the same way.
~ epending on the concentrations, the compounds can be used for the total combating of weeds, for example on industrial terrain and railway tracks and on paths and squares with or without trees. Equally, the compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cacao plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.
In addition to a good action against graminaceous weeds, the active compounds according to the invention also exhibit, in particular, a good herbicidal action in the case of broad-leaved weeds. It is possible to employ the active compounds according to the invention selectively, 3 especially in maize, groundnut, beet, soya bean, cotton and rice and other varieties of cereal.
The active compounds can be converted into the custom-ary formulations~ such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, Le A 19 121 ~13'~5'7 natural and synthetic materials impregnated with active com-pound, and very fine capsules in polymeric substances.
These formulations may be produced in known manner, for example by mixing the active compounds with extenders, that is to say liquid or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, especially solvents, there are suitable in the main, aromatic hydrocarbonsj such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such as dimethylformamide and dimethyl-sulphoxide, as well as water.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk~ quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. As solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such Le A 19 121 ~13Z5'73 as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organlc dyestuffs, such as alizarin - dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the inmention, as such or in the form of their formulations, can also be used, for combating weeds, as mixtures with other herbicides, finished formulations or tank mixing being possible.
Mixtures with other active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, growth factors, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution~ such as ready-to-use solu-tions, suspensions, emulsions, powders, pastes and granules.
They may be used in the customary manner, for example by watering, spraying, atomising or scattering.
The active compounds according to khe invention can be applied either before or after emergence of the plants.

Le A 19 121 113;~573 They are preferably applied before emergence of the plants, that is to say by the pre-emergence method. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are from 0.1 to 10 kg of active compound per ha, preferably from 0.1 to 5 kg/ha.
The present invention also provides a herbicidal composition containing as active ingredient a compound of the present invention in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
- The present invention also provides a method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by weeds by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
The herbicidal activity of the compounds of this invention is illustrated by the following biotest Example.
In this Example, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
The known comparison compound is identified as follows:

Le A 19 121 ^~ :
' (A) = ~ C2H~ CH2 - OCH3 c2~ CH2C1 (2,6-Diethyl)-N-methoxymethyl-chloroacetanilide.
Example~ A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether - To produce a suitable preparation of active compound, O 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
Seeds of the test plants were sown in normal soil and, after 24 hours, watered with the preparation of the active compound. It was expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation was of no im-portance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants was determined in % damage in comparison to the development of the untreated control.
The figures denoted:
0% = no action (like untreated control) 100% = total destruction In this test, the active compounds (5) and (2) exhibited a better selective activity than substance (A) known from the prior art.

Le A 19 121 .

. .

1~3Z5~7~3 Prep'arati'v'e EXa~ples Example 1 CH2 ~ C(CH3)3 C2H5 C0 - CH2Cl Process variant (a) 13.6 g (0.05 mol) of 2-ethyl-6-methyl-N-(3'-tert.-butyl-isoxazol-5'-yl-methyl)-aniline and 5.2 g (0.071 mol) of pyridine were initially introduced into 50 ml of toluene, and 6.2 g (0.055 mol) of chloroacetyl chloride were added at 0 - 5C, whilst stirring and cooling. The mixture was subsequently stirred at room temperature for two hours and the precipitate which had formed was filtered off. The filtrate was washed with water, dried over sodium sulphate and concentrated by distilling off the solvent in vacuo.
The residue was recrystallised from petroleum ether.
8.1 g (49% of theory) of 2-ethyl-6-methyl-N-(3t-tert.-butyl-isoxazol-5'-yl-methyl)-chloroacetanilide of melting point 78 - 79C were obtained.
Preparat'ion of the start'ing material (II - 1) ~ C(CH3)3 ~ - N / ~ ~

Process (a) 65.1 g (C.48 mol) of 2-ethyl-6-methylaniline, 33 g (0.19 mol) of 5-chloromethyl-3-tert.-butyl-isoxazole and 26.2 g (0.19 mol) of powdered potassium carbonate were heated to 100C in 48 ml of dimethylformamide for 5 hours, whilst stirring. Thereafter, the reaction mixture was Le A 19 121 1~3Z573 poured onto 150 ml of water and extracted with methylene chloride. The organic phase was dried over sodium sulphate and conoentrated by distilling off the solvent in vacuo.
The residue was distilled'in''v'a'cuo. 35.2 g (68% of theory) of 2-ethyl-6-methyl-N-(3 t -tert.-butyl-isoxazol-5'-yl-methyl)-aniline of boiling point 140-141C/0.1 mm Hg were obtained, with a purity of 95% (determined by gas chromato-graphy) and a refractive index of nD = 1.52'77.
Example 2 ~ / 2 ~N~ (2) CH3 C0 - CH2Cl Process variant (a) 6.48 g (0.03 mol) of 2,6-dimethyl-N-(5'-methyl-isoxazol-3'-yl-methyl)-aniline and 2.4 g (0.033 mol) of pyridine were heated to the boil in 100 ml of tetrahydro-furan, and 3.8 g (0.033 mol) of chloroacetyl chloride were added dropwise, whilst stirring. After 15 minutes, the reaction mixture was concentrated in vacuo and the residue was taken up in water. The crystalline precipitate which formed was filtered off and dried. 8.2 g (93% of theory) of 2,6-dimethyl-N-(5'-methyl-isoxazol-3'-yl-methyl)-chloro-acetanilide of melting point 73-76C were obtained.
Preparation of the starting mat'erial (II-2) CH

Le A 19 121 ` 113'~573 ~ 43 -Process varlant (~) 6 g (0.16 mol) of sodium borohydride were added in portions of 13.7 g (0.064 mol) of 1-(5'-methyl-isoxazol-3'-yl-methyleneimino)-2,6-dimethylbenzene in 150 ml of methanol 5 until no further starting material could be detected by thin layer chromatography. The methanol was then stripped off, the residue was partitioned between water and methylene chloride and the organic phase was separated off, dried over sodium sulphate and concentratea 'in''v'ac'uo. 11.6 g (84%
10 f theory) of 2,6-dimethyl-N-(5~-methyl-isoxazol-3'-yl-methyl)-aniline of melting point 49-51C were obtained.
(VIII-l) _CH~

10.9 g (0.09 mol) of 2,6-dimethylaniline and 10.6 g 15 (0-09 mol) of 5-methyl-isoxazole-~-carboxaldehyde were heated in 100 ml of toluene, after adding 0.1 g of p-toluene-sulphonic acid, for 2 hours using a water separator. The reaction mixture was then concentrated and the residue was distilled. 15.1 g (78% of theory) of 1-(5'-methyl-20 isoxazol-3l-yl-methyleneimino)-2~6-dimethylbenzene of boiling point 118-125C/0.4 mm Hg were obtained.
E'xa'mp'l'e' 3 CH3 CH2~ c~3 N / ~
\--~C2H~ CO - CH2 Cl Process variant (b) 2.4 g (OoOll mol) of 2-ethyl-6-methyl-chloroacet-anilide were dissolved in a two-phase mixture of 20 ml of Le A 19 121 1~3'~57 toluene and 10 ml of 50% strength sodium hydroxide solution, after adding 0.1 g of triethyl-benzyl-ammonium chloride, and 2 g (0.011 mol) of 5-bromomethyl-3-methyl-isoxazole were added dropwise, whilst stirring vigorously. ~he mixture was subsequently stirred at room temperature for 3 hours.
m e toluene phase was then separated off, washed several times with water and dried over sodium sulphate. After distilling off the solvent in vacuo, 1.9 g (56% of theory) of 2-ethyl-6-methyl-N-(3'-methyl-isoxazol-5'-yl-methyl)-chloroacetanilide of melting point 78-79C were obtained.
Preparation of the starting material (IV-l) ~c2H, 8 - CHZCl 152 g (1.1 mol) of potassium carbonate were added to 135.2 g (1 mol) of 2-ethyl-6-methyl-aniline in 1,000 ml of toluene. 113 g (1 mol) of chloroacetic acid chloride were added dropwise to the mixture, whilst stirring.
When the exothermic reaction had subsided, the mixture was subsequently stirred under reflux for 2 hours. m e reaction mixture was then filtered and the filtrate was con-centrated to 500 ml _ vacuo. The crystals thereby formed were filtered off and washed with petroleum ether.
189.6 g (98% of theory) of 2-ethyl-6-methyl-chloroacet-anilide were obtained in the form of white crystals of melting point 120C.
Those compounds listed by means of their formulae in Table 1 were obtained in a corresponding manner.

Le A 19 121 ~3'~573 ~ ~o ~ ~r, ~ .~.
- -- x x ~
x I ~ \~ ~ \ L~
c~ ~ ~ v = ~ ' ~

~ r )~ = O 1~1 C C X X
E-~ \ /
a ~ X~

C;

z a) X

Le A 19 121 ~ ' 113;~573 C I ; ~D

~X ~

~ . ''C~ C.) ~, ,~
.

~P;
~ U~
~ . ~ ~ U~ ~
a) ~
~ æ 0 o~
~3 Le A l9 121 ~1;3;2573 .,1 ao ~D
~D ~ 0 0 ~
~ ~ ~ ~D CD
bo r~
;t ~ ~ ~D ~ O
o ~ a :~:

~X ~X ~
~ ~ ~V~ ~ ~ r~
X X
, ~ ~ ~ ~ ~
V V V V

X

V~ V~

~_ V V ~ ~ V V
V

~o ~ ~ ~ ~ ~ ~
~ :~ ~ ~ ~ ~ ~ ~

Le A 19 121 The starting materials o~ the formula (II) listed by way of their formulae in Table 2 below were obtained by one or more of the processes described in this specification, and in a manner corresponding to Examples 1 and 2.

Le A 19 121 ; ' . ~ , ' ,, .
:;
' 1~3Z57 ..~ .. ..
o ~ U~
~o ~ ~ o ~o ~
O O o Ir~ L~ O 0 3 0~ 0 p,~ Ll~
~q ~ ~ O ~D
V ~ O
C~ ~ ~ I ~10 ~1 1 1 ~ ~ O rl O O ~ ~ O
H ~ 0 3 0 3 ~J ~ O ~ ~`J
H~1~ m ~I m ~ ~ m ~
~X ~q ~:

Le A 19 121 :

.. ~ .. ~ - - ~

.~ o o o oo o o ~ ,~, "~, " ~"
'~ o o C~
C~ ~ ~ ~ o ~ o rl ~ O r~ ~ rl ~r~ ~ rl L~
Cq rl <X rl O ~ 1 0 O rl O ~ O ~O ~ O
c~ ~ ~q ~ m :

~ K ~ Z ~Z ~a ::: X

u~

. U~
.
.
a) : ~ -- -- o O H H H H H
X _ _ _ _ Le A 19 121 , 1~L3'~'~573 .. .. .. .. o~ ..
+, ~ C~J
rl O ~ 1 0 o o o~ o o o U~ ~ ~ P~V ~ ~ ~V
b~V ~OV ~ DO ~00 bD~
C~ ~ ~ ~o ~Q tQ ~ ~ ~ 0 ~ ~ ~0 ~0 ~ I
~ ~ ~ I ~ I ~ 1 0 ~1 0 ~1 ,~ o ~ a~o o~ o~ O~D OU~
~ t) ~ ~ Q~

~ r~ ~ e~ C~ ~e ~z ~C ~
X ~ ~ X
~C~
X :C ~ X

~ x ~v v~ v~ ~ ~

r~
~: v v~ ~ v~ v ~
v a~
~ c~
~ ~
tl) Z~ H H H H H H
H H H H H H

Le A 19 121 ~13~573 The starting materials of the formula (:IV) listedby way of their formulae in Table 3 below are obtained by known processes, in a manner corresponding to Example 3.
T a b l e 3 R3 R~ .

C - CH2 - Z ( IV ) R2 ¦1 Example R' R2 R3 zpoint (C) ( IV-2 ) CH3 CH3 H Cl148 ( IV-3 ) C2 H~ C2 H5 H Cl133 ( IV-4 ) i-C3 H7 H H Cl 79 ( IV-5 ) tert . -C4 Hg H H Cl 96 ( IV-6 ) Cz H!s H H Cl .103 ( IV-7 ) CH3 H H Cl109 ( IV-8 ) CH3 H 3-CH3 Cl135 ( IV-g ) CH3 H 5-CH3 Cl154 ( IV-10) CH3 CH3 4-CH3 Cl177 ( IV-ll ) C2 H, CH3 4-CH3 Cl134 ( IV-12 ) sec-. -C~, Hg H H ClOi 1 ( IV-13 ) H H H Cl132 Le A 19 121

Claims (32)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. N-(1,2-Azolyl)alkyl-haloacetanilide compounds of the formula (I) wherein A is oxygen, sulfur or the grouping > NR, wherein R is hydrogen or alkyl;
R1 is hydrogen, alkyl or alkoxy;
R3 is hydrogen, alkyl, alkoxy or halogen;
R3 is hydrogen, alkyl, alkoxy or halogen;
R4 is hydrogen or alkyl;
X1 is hydrogen, alkyl, halogen, alkoxy, alkylthio, haloalkyl, alkoxy-carbonyl, dialkylamino, cyano, phenyl. phenoxy or phenylthio;
X2 is hydrogen, alkyl, halogen, alkoxy, alkylthio, haloalkyl, alkoxycarbonyl, dialkylamino, cyano, phenyl, phenoxy or phenylthio; and Z is halogen, and the azolyl radical is bonded via a carbon atom, and acid addition salts thereof.

2. N-(1,2,-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein A is oxygen.

3. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein A is sulfur.

4. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein A is the grouping ?NR.

5. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 4 wherein R is hydrogen or alkyl of up to 4 carbon atoms.

6. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein R1 is hydrogen.

7. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein R1 is alkyl or alkoxy of up to 4 carbon atoms.

8. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein R2 and R3 are individually selected from hydrogen, alkyl or alkoxy of up to 4 carbon atoms, fluorine, chlorine or bromine.

9. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein R4 is hydrogen.

10. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein R4 is alkyl of up to 4 carbon atoms.

11. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein X1 and x2 are individually selected from hydrogen, alkyl with up to 4 carbon atoms, alkoxy with up to 4 carbon atoms, alkylthio with up to 4 carbon atoms, alkoxycarbonyl with from 1 to 4 carbon atoms in the alkoxy group, fluorine, chlorine, bromine, haloalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms, dialkylamino with up to 4 carbon atoms in each alkyl moiety, cyano, phenyl, phenoxy and phenylthio.

12. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein Z is chlorine, bromine or iodine.

13. N-(1,2-Azolyl)alkyl-haloacetanilide compounds as claimed in claim 1 wherein A is oxygen, sulfur or the grouping >NR
in which R is hydrogen or alkyl with 1 to 4 carbon atoms;
R1 is hydrogen, alkyl or alkoxy with up to 4 carbon atoms;
R2 and R3 are individually selected from hydrogen, alkyl or alkoxy with up to 4 carbon atoms, fluorine, chlorine or bromine;
R4 is hydrogen or alkyl with up to 4 carbon atoms;
X1 and X2 are individually selected from hydrogen, alkyl with up to 4 carbon atoms, alkoxy with up to 4 carbon atoms, alkylthio with up to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, fluorine, chlorine, bromine, haloalkyl with up to 2 carbon atoms and up to 5 identical or different halogen atoms, dialkylamino with up to 4 carbon atoms, in each alkyl part, cyano, phenyl, phenoxy and phenylthio; and Z is chlorine, bromine or iodine.

14. N-(1,2-Azolyl)alkyl haloacetanilide compound as claimed in claim 1 in the form of an acid addition salt wherein the acid is selected from hydrogen halide, phosphoric acid, nitric acid, sulfuric acid, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids.

15. 2-Ethyl-6-methyl-N-(3'-methyl-isoxazol-5'-yl-methyl)-chloroacetanilide.

16. 2,6-Diethyl-N-(isothiazol-3'-yl-methyl)-chloroacetanilide.

17. 2-Ethyl-6-methyl-N-(1',5'-dimethylpyrazole-3'-yl-methyl)-chloro-acetanilide.

18. 2-Ethyl-6-methyl-N-(isoxazol-3'-yl-methyl)-chloroacetanilide.

19. 2,6-Diethyl-N-isoxazol-3'-yl-methyl)-chloroacetanilide.

20. 2,6-Dimethyl-N-(isoxazol-3'-yl-methyl)-chloroacetanilide.

21. Method of combating weeds which method comprises applying to the weeds, or their habitat, a herbicidally effective amount of an N-(1,2-azolyl) alkyl-haloacetanilide compound as claimed in claim 1.

22. Method as claimed in claim 21 wherein said N-(1,2-azolyl)alkyl haloacetanilide compound is applied in the form of a composition containing said compound as active ingredient in admixture with a suitable diluent or carrier.

23. Method as claimed in claim 21 or 22 wherein said compound is applied at a dosage of 0.1 to 10 kg per hectare.

24. Method as claimed in claim 21 or 22 wherein said compound is applied at a dosage of 0.1 to 5 kg per hectare.

25. Method as claimed in claim 21 or 22 wherein said compound is a compound according to claim 11.

26. Method as claimed in claim 21 or 22 wherein said compound is a compound according to claim 13.

27. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 16.

28. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 17.

29. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 18.

30. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 19.

31. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 20.

32. Method as claimed in claim 21 or 22 wherein said compound is the compound of claim 15.