Note: Descriptions are shown in the official language in which they were submitted.
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-
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
--3--
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),
R2 11
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),
X2
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
CH3 CH3 H H H H
2 H5 CH3 H H H H
2 H5 C2 Hs H H H H
C(CH3 )3 H H H H H
CH3 CH3 H CH3 H H
2 H5 CH3 H CH3 H H
2 H5 C2 H5 H CH3 H H
C(CH3 )3 H H CH3 H H
CH3 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
CH3 CH3 3-CH3 H H H
OCH3 CH3 H H H H
OCH3 OCH3 H H H H
OCH3 C2 H5 H H H H
CH3 CH3 H H H CH3
C2H5 CH3 H H H CH3
C2 Hs C2 H5 H H H CH3
C(CH3 )3 H H H H CH3
CH3 CH3 H CH3 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 H 3-CH3 H H CH3
CH3 H 5-CH3 H H CH3
CH3 Cl H H H CH3
C(CH3 )3 Cl H H H CH3
CH3 CH3 3-CH3 H H CH3
OCH3 CH3 H H H CH3
OCH3 OCH3 H H H CH3
OCH3 C2 H5 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
_
113Z573
--7--
R1 R2 R3 R4 X1 X2
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
CX3 CH3 H H CH3 H
Cz Hg c~3 H H CH3 H
C2 H5 C2 ~rI5 H H CH3 H
CH3 CH3 H H CH3 CH3
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
CH3 CH3 H H H C3 H7
C~ H5 CH3 H H H C3 H7
C~ H C2H5 H H H C3H7
Le A 19 121
1~32573
--8--
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
CH3 C2 H5 H H H CH3
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
C2 H5 C2 H5 H H H H
CH3 C2 H5 H H CH3 H
C2H5 C2 H5 H H CH3 H
CH3 C2H5 H H CH3 CH3
C2 H5 C2H5 H H CH3 CH3
CH3 CH3 H H CH3 CH3
Le A 19 121
-
l~ZS73
X1 X2
R
R3 R
CH - ~ N ~
N \ (I d)
\ R2 ICI - CH2 - Cl(Br)
o
R1 R2 R3 R4 X' X2
CH3 CH3 H H H H
C2H5 CH3 H H H H
CzH5 C2H5 H H H H
CH3 CH3 H CH3 H H
C2H5 CH3 H CH3 H H
C2H5 C2H5 H CH3 H H
C(CH3)3 H H H H H
CH3 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
OCH3 c~.3 H H H H
C2H5 ,C2H5 H H H CH3
CH3 C2H5 H H H CH3
CH3 CH3 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
--10--
Rl R2 R3 R4 X' .XZ
C2 H5 C2H5 H H c~3 H
CH3 C2 H5 H H CH3 H
CH3 CH3 H H CH3 H
C(CH3 )3 H H H CH3 H
CH3 C2 H5 H H CN H
C2 Hs C2 H5 H H CN H
CH3 CH3 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)
R2 11
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
CH3 CH3 H H H CH3
C2 H5 CH~ H H H CH3
C2 H5 C2 H5 H H H CH3
R~ X'
I \~======N
R3 ~ ~, CH ¦ ~ S
C - CH2 - Cl(Br)
lo
Le A 19 121
"~
~13Z57~3
--11--
R1 R2 R3 R~ X1 X2
CH3 C~H5 H H CH3 H
C2H5 C2H5 H H CH3 H
CH3 C2H5 H H GH3 CH3
CH3 C2H5 H H
X~ X2
~ - N / ~ ~
R R2 R3 _ _R~ X~ _ 2_ _ _R _
CH3 CH3 H H H H CH3
C2H5 CH3 H H H H CH3
C2H5 CzHg H H H H CH3
CH3 CH3 H CH3 H H CH3
C2H5 CH3 H CH3 H H CH3
C2H~ CpH~ H CH3 H H CH3
CH3 H 3-CH3 H H H CH3
CH3 H 5-CH3 H H H CH3
CH3 Cl H H H H CH3
OCH3 CH3 H H H H CH3
C(CH3)3 Cl H H H H CH3
OCH3 OCH3 H H H H CH3
CH3 CH3 H H H CH3 ~H3
CH3 C2H5 H H H CH3 CH3
C2H5 C2H5 H H H CH3 CH3
C(CH3)3 H H H H CH3 CH3
CH3 H 3-CH3 H H CH3 CH3
CH3 H 5-CH3 H H CH3 CH3
OCH3 CH3 H H H CH3 CH3
CH3 Cl H H H CH3 CH3
Le A 19 121
113Z573
-12-
R' R2 R3 ~ X1 X2 R
CH3 C2H5 H H H H Cz H5
CH3 CH3 H H H H C2H5
2H, C2 H5 H H H H C2 H5
CH3 CH3 H H H H C3 H7
2 H5 C2 H5 H H H H C3 H7
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
CH3 C2 H5 H H CH3 CH3 CH3
CH3 CH3 H H CH3 H 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
A 19 121
113~573
-13-
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
CH3 CH3 H H H CH3 CH3
CH3 C2 H5 H H H CH3 CH3
C2Hg C2 H, H H H CH3 CH3
CH3 CH3 H H H H CH3
CH3 C2 H5 H H H H CH3
C2 H5 C2 H5 H H H H 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~
C2 H5C2 H5 H H CH3 CH3 CH3
CH3C2 H5 H H H H CH3
C2H5 C2H5 H H H H CH3
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
--15--
(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 )
R2
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
CH3 CH3 H CH3 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
CH3 CH3 3-CH3 H H H
OCH3 CH3 H H H H
OCH3 OCH3 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
,, ;
Z573
CH3 C.i3 3-CH3 H H CH3
OCH3 CH3 H H H CH3
OCH3 OCH3 H H H CH3
OCH3 C2 H5 H 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
C2H5 CH3 H H H
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
113Z573
--18--
;?~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
CH3 CH3 H H H C3 H7
C2 H5 CH3 H H H C3 H7
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 )
R2 H
Le A 19 121
~13257~3
--19--
R' R2 R~ R'~ X' x2
CH3 C2H5 H H H H
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
.
CH CH3 H H H H
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 H 5-CH3 H H H
CH3 Cl H H H . H
C(CH3 ).~ Cl H H H H
OCH3 CH3 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
..
113Z573
--20--
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
CH3 CH3 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 CH3 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
CH3 C2 H5 H H -C0-OCH
R~ X~ x2
R~_< R1 ~ ~
~ N ~ S~ (IIe)
R2
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
CH3 CH3 H H H CH3
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
-22-
Rl R2 _ _ R3 _ R~_ X1 X2 R
CH3 CH3 H H H H CH3
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 H 5-CH3 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
A 19 121
.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
-24
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),
R2
Le A 19 121
1132573
-25-
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
0 N A X1
~ 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
-27-
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
-28-
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
R4 X X2 -Y - R4 X1 X2 Y
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
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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
--31--
X1 ~
¦= I ( V f )
Y - CH_~f
X2
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
--32--
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
-34-
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
- 36 --
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,
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- 37 -
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
- 38 -
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
- 39 -
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
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'
113257
-- 40 --
(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
- 41 -
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 / ~ ~
C2H5
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
- 42 -
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
I - CH3
~ / 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
CH3 H
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~
CH3
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
- 44 -
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
- 45 -
~ ~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
- 46 -
C I ; ~D
~X ~
~ . ''C~ C.) ~,
,~
.
~P;
~ U~
~ . ~ ~ U~ ~
a) ~
~ æ 0 o~
~3
Le A l9 121
~1;3;2573
- 47 -
.,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
113ZS73
-- 48 --
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
- 49
..~ .. ..
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
:
113ZS73
- 50 --
.. ~ .. ~ - - ~
.~ 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
51
.. .. .. .. 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
-- 52 -
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
