Note: Descriptions are shown in the official language in which they were submitted.
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Heterocycle-substituted salicylic acid derivatives
The present invention relates to salicylic acid derivatives of
5 the formula I
~ N ~ Z
A ~ X Y R2
o~R3
where the substituents have the following meanings:
A is a 5-membered heteroaromatic ring having one oxygen,
nitrogen or sulfur atom or having one to four nitrogen
atoms or having one to two nitrogen atoms and
additionally one sulfur or oxygen atom in the ring which
has attached to it at least one radical -B-R5 and which
can additionally have attached to it one or more of the
following substituents: nitro, halogen, cyano,
unsubstituted or substituted alkyl, alkylthio,
alkylsulfonyl, alkylsulfinyl, formyl or a radical Rs; a
6-membered heteroaromatic ring having two to three
nitrogen atoms in the ring which has attached to it at
least one radical -B-R5 and which can additionally have
attached to it one or more of the following substituents:
nitro, halogen, cyano, unsubstituted or substituted
alkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, formyl or
a radical R5;
B is oxygen, sulfur, SO, S02;
35 X is oxygen or sulfur;
Y is nitrogen or C-H;
Z is nitrogen or a group C-R4;
Rl is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,
alkylthio, alkylamino and/or dialkylamino;
R2 is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,
alkylthio, alkylamino and/or dialkylamino;
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R3 is hydrogen;
a succinyliminooxy group;
a S-membered heteroaromatic ring containing one to three
nitrogen atoms which can have attached to it one to four
halogen atoms and/or one to two of the following
radicals: alkyl, haloalkyl, alkoxy, haloalkoxy and/or
alkylthio;
a radical oR6;
a radical
(~)m - N
R8
~0
where R7 and R8 can be identical or different and where m
can assume the values 0 or 1;
or a radical
o
Il
- NH - S - R9
O
R4 is hydrogen, alkyl, halogen;
35 R5 is unsubstituted or substituted alkyl, dialkylamino or
unsubstituted or substituted phenyl;
R6 is hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
an alkyl group which can have attached to it one to five
halogen atoms and/or one or two of the following
radicals: alkoxy, alkylthio, cyano, alkylcarbonyl,
alkoxycarbonyl, cycloalkyl, a radical -0-N=CR10Rll,
phenyl, phenoxy, or phenylcarbonyl, it being possible for
the aromatic radicals, in turn, to have attached to them
one to five halogen atoms and/or one to three of the
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following radicals: al:kyl, haloalkyl, alkoxy, haloalkoxy
and/or alkylthio;
an alkyl group which can have attached to it one to five
halogen atoms, and a 5-membered heteroaromatic ring
containing one to three nitrogen atoms, or a 5-membered
heteroaromatic ring containing one to three nitrogen
atoms and additionally one sulfur or oxygen atom in the
ring, it being possible for these to have attached to
them one to four halogen atoms and/or one to two of the
following radicals: alkyl, haloalkyl, alkoxy, haloalkoxy
and/or alkylthio;
an alkyl group which has attached to it in the 2-position
one of the following radicals: alkoxyimino,
alkenyloxyimino, haloalkenyloxyimino or benzyloxyimino;
an alkenyl or an alkynyl group, it being possible for
these groups, in turn, to have attached to them one to
five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted
by nitro, alkyl or alkoxy or mono- to pentasubstituted by
halogen;
a radical -N=CRl0R1l where Rl~ and Rll can be identical or
different;
a 5-membered aromatic heterocycle bonded via a nitrogen
atom and having one to four nitrogen atoms in the ring or
a benzo-fused 5-membered aromatic heterocycle bonded via
a nitrogen atom and having one to three nitrogen atoms in
the ring, it being possible for these to be substituted
by halogen, alkyl, haloalkyl;
R7,R8 are hydrogen;
alkyl, alkenyl, alkynyl, it being possible for each of
these radicals to have attached to it one to five halogen
atoms and/or one to two of the following groups: alkoxy,
alkylthio, cyano, alkylcarbonyl, alkoxycarbonyl,
bis-dialkylamino, cycloalkyl;
phenyl or substituted phenyl;
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together are a cycli2ed alkylene chain or together are a
cyclized alkylene chain having a hetero atom, which can
be oxygen, sulfur or ni.trogen, it being possible for each
of these to haYe attached to it one to three alkyl
substituents;
or a group
CH ~
~--R13
R12
15 R9 is alkyl or phenyl, which can have attached to them one
to four of the following substituents: halogen, nitro,
cyano, alkyl;
R10,Rll are alkyl which can have attached to it a phenyl radical,
an alkoxy and/or an alkylthio group, or are cycloalkyl,
phenyl, or together are an alkylene chain which can have
attached to it one to five alkyl groups and which can be
bridged by an alkylene chain;
25 R12 is hydrogen or alkyl which can be substituted by
hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl,
carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl
or indolyl radicals, or together with R7 is linked via an
alkylene chain to form a ring;
Rl3 is alkyl, alkenyl or a:Lkynyl;
where
35 sub~tituted alkyl, substituted alkoxy, substituted alkylthio,
sub~tituted alkylsulfinyl, substituted alkylsulfonyl, substituted
alkylamino and substituted dialkylamino are to be understood as
meaning in each case that the alkyl groups can be substituted by
one up to the maximum possible number of halogen atoms and/or can
40 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkyl.thio, alkylamino, dialkylamino,
alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is
substituted by one to three hal.oqen atoms or one to three methyl
groups, or phenoxy or phenoxy which is substituted by one to
45 three halogen atoms or one to t.hree methyl groups,
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substituted phenyl, substituted phenoxy, substituted phenylthio
and substituted phenylsulfonyl are to be understood as meaning in
each case that the phenyl ring can have attached to it one to
five halogen atoms, one to three alkyl or alkoxy groups and/or
5 one to three of the following radicals: nitro, cyano, haloalkyl,
haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl,
alkoxycarbonyl, phenyl, phenyl which is substituted by one to
three halogen atoms or one to three methyl groups, or phenoxy or
phenoxy which i8 substituted by one to three halogen atoms or one
10 to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those
where the substituents have the following meanings:
15 A is a 5-membered heteroaromatic ring having one oxygen,
nitrogen or sulfur atom or h~ving one to four nitrogen
atoms or having one to two nitrogen atoms and
additionally one sulfur or oxygen atom in the ring which
has attached to it at ].east one radical -B-R5 and which
can additionally have attached to it one or more of the
following substituents: nitro, halogen, cyano,
unsubstituted or substi.tuted Cl-C6-alkyl, C1-C4-alkylthio,
C1-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a
radical R5; a 6-membered heteroaromatic ring having two
to three nitrogen atoms in the ring which has attached to
it at least one radical -B-R5 and which can additionally
have attached to it one or more of the following
sub~tituents: nitro, halogen, cyano, unsubstituted or
substituted Cl-C6-alkyl, Cl-C4-alkylthio,
Cl-C4-alkylsulfonyl, C1-C4-alkylsulfinyl, formyl or a
radical R5; preferably a 5 -mhered heteroaromatic ring
having one oxygen, nitrogen or sulfur atom or having one
to four nitrogen atoms or having one to two nitrogen
atoms and additionally one sulfur or oxygen atom in the
ring which has attached to it at least one radcial -o-R5
or a 6-membered heteroaromatic ring having two to three
nitrogen atoms in the ring which has attached to it at
least one radical -o-R5;
40 B is oxygen, sulfur, SO or SO2;
X is oxygen or sulfur;
Y is nitrogen or C-H, preferably nitrogen;
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Z is nitrogen or a group C-R4, preferably a group C-H or
nitrogen;
Rl is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,
Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C4-alkylamino and/or
di-Cl-C4-alkylamino; preferably halogen, Cl-C4-alkyl,
Cl-C4 -alkoxy, Cl-C 4- haloalkoxy;
R2 is halogen, Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,
Cl-C4-haloalkoxy, Cl-C4--alkylthio, Cl-C4-alkylamino and/or
di-Cl-C4-alkylamino, preferably halogen, Cl-C4-alkyl,
Cl-C4-alkoxy, Cl-C4-haloalkoxy, especially preferably
Cl-C2-alkoxy and C1-C2-haloalkoxy;
15 R3 is hydrogen;
a succinyliminooxy group;
a 5 s ~ered heteroaromatic ring containing one to three
nitrogen atoms which can have attached to it one to four
halogen atoms and/or one to two of the following
radical~: Cl-C6-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,
Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a radical oR6;
a radical
R7
(~)m - N
R8
where R7 and R8 can be identical or different and where m
can assume the values () or l;
or a radical
o
--NH--S--R9
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preferably hydrogen, a radical oR6, a radical ~(o)m-NR7R8,
especially preferably a radical oR6;
R4 is hydrogen, C1-C4-alkyl, halogen;
R5 is unsubstituted or substituted C1-C6-alkyl,
di-C1-C4-alkylamino or unsubstituted or substituted
phenyl; especially preferably unsubstituted or
substituted C1-C4-alkyl;
R6 i8 hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
a Cl-C8-alkyl group which can have attached to it one to
five halogen atoms and/or one or two of the following
radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano,
Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl,
C3-c6-cYcloalkyl~ a radical -O-N=CR1OR11 where R10 and
can be identical or diiferent, phenyl, phenoxy, or
phenylcarbonyl, it being possible for the aromatic
radicals, in turn, to have attached to them one to five
halogen atoms and/or one to three of the following
radicals: C1-C6-alkyl, Cl-C4-haloalkyl, C1-C4-alkoxy,
Cl-C4-haloalkoxy and/or C1-C4-alkylthio;
a C1-C6-alkyl group which can have attached to it one to
five halogen atoms, and a 5-membered heteroaromatic ring
containing one to three nitrogen atoms, or a 5-membered
heteroaromatic ring containing one to three nitrogen
atoms and additionally one sulfur or oxygen atom in the
ring, it being possible for these to have attached to
them one to four halogen atoms and/or one to two of the
following radicals: Cl-C4-alkyl, C1-C4-haloalkyl,
Cl-C4-alkoxy, C1-C4-haloalkoxy and/or Cl-C4-alkylthio;
a Cl-C6-alkyl group which has attached to it in the
2-position one of the following radicals:
Cl-C4-alkoxyimino, Cl-C4-alkenyloxyimino,
Cl-C4-haloalkenyloxyimino or benzyloxyimino;
a C3-C6-alkenyl or a C3--C6-alkynyl group, it being
possible for these groups, in turn, to have attached to
them one to five halogen atoms;
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phenyl which is unsubstituted or mono- to trisubstituted
by nitro, Cl-Cg-alkyl or Cl-C4-alkoxy or mono- to
pentasubstituted by halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or
different;
a 5-membered aromatic heterocycle bonded via a nitrogen
atom and having one to four nitrogen atoms in the ring or
a benzo-fused 5 ;~ ~ered aromatic heterocycle bonded via
a nitrogen atom and having one to three nitrogen atoms in
the ring, it being possible for these to be substituted
by halogen, Cl-C6-alkyl, Cl-C4-haloalkyl;
15 R7,R8 are hydrogen;
Cl-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, it being
possible for each of these radicals to have attached to
it one to five halogen atoms and/or one to two of the
following groups: Cl-Cg-alkoxy, Cl-C4-alkylthio, cyano,
Cl-C4-alkylcarbonyl, C~-C4-alkoxycarbonyl,
bis-di-Cl-Cg-alkylamino, cyclo-C3-C6-alkyl;
phenyl or substituted phenyl;
together are a cyclized Cl-C6-alkylene chain or together
are a cyclized Cl-C6-alkylene chain having a hetero atom,
which can be oxygen, sulfur or nitrogen, it being
possible for each of these to have attached to it one to
three Cl-C4-alkyl subsl:ituents;
or a group
- CH
\~--R13
R12
40 R9 is Cl-C6-alkyl or phenyl, which can have attached to them
one to four of the following substituents: halogen,
nitro, cyano, Cl-C4-alkyl;
Rl~,Rll are Cl-C6-alkyl which can have attached to it a phenyl
radical, a Cl-C4-alkoxy and/or a Cl-Cg-alkylthio group, or
are C3-C6-cycloalkyl, phenyl, or together are a
Cl-C6-alkylene chain which can have attached to it one to
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five Cl-C4-alkyl groups and which can be bridged by a
Cl-C6-alkylene chain; especially preferably are
Cl-C4-alkyl, and together a Cl-C5-alkylene chain;
5 R12 i9 hydrogen or Cl-C6-alkyl which can be substituted by
hydroxyl, amino, hydrogen sulfide, alkylthio, carboxyl,
carbamoyl, guanidinyl, phenyl, hydroxyphenyl, imidazolyl
or indolyl radicals, or together with R7 is linked via a
Cl-C4-alkylene chain to form a ring;
Rl3 is Cl-C6-alkyl, Cl-C4-a].kenyl or Cl-C4-alkynyl;
where
15 substituted alkyl, substituted alkoxy, substituted alkylthio,
substituted alkylsulfinyl, substituted alkylsulfonyl, substituted
alkylamino and substituted dialkylamino are to be understood as
meaning in each case that the a:Lkyl groups can be substituted by
one up to the ~ possible number of halogen atoms and/or can
20 have attached to them one to three of the following radicals:
nitro, cyano, haloalkoxy, alkylthio, alkylamino, dialkylamino,
alkylcarbonyl, alkoxycarbonyl, phenyl, phenyl which is
substituted by one to three halogen atoms or one to three methyl
groups, or phenoxy or phenoxy which is substituted by one to
25 three halogen atoms or one to three methyl groups, and
substituted phenyl, substituted phenoxy, substituted phenylthio
and substituted phenylsulfonyl are to be understood as meaning in
each case that the phenyl ring ~_an have attached to it one to
30 five halogen atoms, one to three alkyl or alkoxy groups and~or
one to three of the following radicals: nitro, cyano, haloalkyl,
haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylcarbonyl,
alkoxycarbonyl, phenyl, phenyl which is substituted by one to
three halogen atoms or one to three methyl groups, or phenoxy or
35 phenoxy which is substituted by one to three halogen atoms or one
to three methyl groups.
Preferred salicylic acid derivatives of the formula I are those
where the substituent R6 has the following meanings:
R6 is hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to
five halogen atoms and~or one or two of the following
radicals: Cl-C4-alkoxy, Cl-C4-alkylthio, cyano,
Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl,
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C3-C6-cycloalkyl, a radical -0-N=CR10Rll where Rl~ and R
can be identical or different, phenyl, phenoxy, or
phenylcarbonyl, it being possible for the aromatic
radicals, in turn, to have attached to them one to five
halogen atoms and/or one to three of the following
radicals: Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,
Cl-C4-haloalkoxy and~or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2--C4-alkynyl group, it being
possible for these groups, in turn, to have attached to
them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted
by nitro, alkyl or alkoxy or mono- to pentasubstituted by
halogen;
a radical -N=CRl~Rll where R10 and Rll can be identical or
different;
20 and the remaining substituents have the abovementioned meanings.
~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituents R7 and R8 have the following
meanings:
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together
are a cyclized Cl-C6-alkylene chain having a hetero atom,
which can be oxygen, sulfur or nitrogen, it being
possible for each of these to have attached to it one to
three alkyl substituent:s;
and the remaining substituents have the abovementioned meanings.
40 ~urthermore preferred salicylic acid derivatives of the formula I
are those where the substituent R6 has the following meanings:
R6 i5 hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
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1~
a Cl-C2-alkyl group which can have attached to it one to
five halogen atoms and~or one of the following radicals:
alkoxy, alkylthio, phenyl;
5 and the remaining substituents have the abovementioned -Anings
Other preferred salicylic acid derivatives of the formula I are
those where the substituents R6, R7 and R8 have the following
~AningS:
R6 is hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
a Cl-C4-alkyl group which can have attached to it one to
lS five halogen atoms and/or one or two of the following
radicals: C1-C4-alkoxy, Cl-C4-alkylthio, cyano,
Cl-C4-alkylcarbonyl, Cl-C4-alkoxycarbonyl,
C~-C6-cycloalkyl, a radical -O-N=CR10R11 where R10 and R
can be identical or different, phenyl, phenoxy, or
phenylcarbonyl, it being possible for the aromatic
radicals, in turn, to have attached to them one to five
halogen atoms and/or one to three of the following
radicals: C1-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy,
Cl-C4-haloalkoxy and/or Cl-C4-alkylthio;
a C2-C4-alkenyl or a C2-C4-alkynyl group, it being
possible for these groups, in turn, to have attached to
them one to five halogen atoms;
phenyl which is unsubstituted or mono- to trisubstituted
by nitro, alkyl or alkoxy or mono- to pentasubstituted by
halogen;
a radical -N=CRl~Rll where Rl~ and Rll can be identical or
~5 different;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyll Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together
are a cyclized C1-C6-alkylene chain having a hetero atom,
which can be oxygen, slllfur or nitrogen, it being
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12
possible for each of these to have attached to it one to
three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Also preferred salicylic acid derivatives of the formula I are
those where the substituents R6, R7 and R8 have the following
meanings:
10 R6 is hydrogen, an alkali metal cation, the equivalent of an
alkaline earth metal cation or an organic ammonium ion;
a C1-C2-alkyl group which can have attached to it one to
five halogen atoms and/or one of the following radicals:
alkoxy, alkylthio, phenyl;
R7,R8 are hydrogen;
Cl-C4-alkyl, Cl-C4-alkenyl, Cl-C4-alkynyl;
phenyl or substituted phenyl;
together are a cyclized C1-C6-alkylene chain or together
are a cyclized Cl-C6-al.kylene chain having a hetero atom,
which can be oxygen, sulfur or nitrogen, it being
possible for each of these to have attached to it one to
three alkyl substituents;
and the remaining substituents have the abovementioned meanings.
Especially preferred salicylic acid derivatives of the formula I
are those where the substituents Rl, R2 and Y have the following
meanings:
35 Rl,R2 are alkoxy and
Y is nitrogen
and the remaining substituents have the abovementioned -Anings.
Other especially preferred salicylic acid derivatives of the
formula I are those where the substituents Rl, R2, Y and R3 have
the following meanings:
45 Rl,R2 are alkoxy,
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13
Y is nitrogen,
Z is C-H and
5 R3 is hydroxyl
and the remaining substituents have the abovementioned meanings.
Very especially preferred salicylic acid derivatives of the
10 formula I are those where the substituents Rl, R2, Y, R3 and A
have the following meanings:
Rl,R~ are alkoxy,
15 Y is nitrogen,
R3 is hydroxyl and
A is a 5 ~ - 'ered heteroaromatic ring having one oxygen,
nitrogen or sulfur atom or having one to four nitrogen
atoms or having one to two nitrogen atoms and
additionally one sulfur or oxygen atom in the ring which
has attached to it at least one radical -~-R5 and which
can additionally have attached to it one or more of the
following substituents; nitro, halogen, cyano,
unsubstituted or substituted alkyl, alkylthio,
alkylsulfonyl, alkylswlfinyl, formyl or a radical R5,
and the remaining substituents have the abovementioned meanings.
Patent Applications Wo 91/13065 and DE-A 39 19 435 disclose
herbicidally active salicylaldehyde derivatives and salicylic
acid derivatives, respectively, which have a heterocyclic
substituent. The activity of the compounds known from the
35 literature is not always satisfactory with a view to herbicidal
action, crop plant selectivity or bioregulatory action.
It is therefore an object of the present invention to provide
heterocycle-substituted salicylaldehyde and salicylic acid
40 derivatives which have an improved biological activity.
Accordingly, we have found that this object is achieved by the
heterocycle-substituted salicylic acid derivatives I defined at
the outset. The novel compounds I have an outstanding herbicidal
45 action combined with an improved selectivity in crop plants.
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14
We have furthermore found processes for the preparation of the
compounds I and their use as herbicides and growth regulators.
The compounds of the formula I are accessible via a plurality of
5 routes. Particularly advantageous is the route via the
benzo[l,3]-dioxinones IV which can be prepared by known processes
from the heterocyclic tin compounds II and the benzodioxinones
III with palladium catalysis (EP 657 441) and which are first
opened with a nucleophile R3-H in a manner known per se in the
10 presence or absence of a base to give the salicylic acid
derivatives V, which are then reacted with heterocycles of the
type VI in a manner known per se in the presence or absence of a
base:
base
Pd~/pdII ~ R3 - H ~
SnR123 + Rl6 ~ X A ~ X A ~ XH
0 ~ o ~ 0 ~ o ~ ~ ~ R3
II III IV V
~
N ~ Z N ~ Z
A ~ X Y R2 Rl4 ~ Y ~ R2
o R3
I VI
The radicals have the abovement:ioned meanings, Rl2 is Cl-C6-alkyl
and Cl-C6-cycloalkyl, Rl6 is a halogen atom, preferably bromine or
35 iodine, or a trifluoromethylsulfonyloxy group, Rl4 is a
nucleofugic leaving group such as halogenf alkyl- or
arylsulfonyl.
Furthermore, a derivative A-R16 can be reacted with a
40 tin-substituted benzoic acid of the formula VII where Rl5 is
unsubstituted or substituted benzyl, Cl-C4-alkyl, dihydropyranyl,
trialkylsilyl, alkoxyalkyl and dialkoxyalkyl with palladium
catalysis and the resulting benzoic acid VIII can be converted in
a manner known per se into the salicylic acids Va where
45 R3 = hydrogen:
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A - R16 + R123Sn ~ , R15 ~ , R15 ~ OH
OH O OH O OH
VII VIII Va
10 A catalytically active palladium compound i9 employed in each of
the two abovementioned processes. Any palladium salts or
complexes which are at least partially soluble in the reaction
mixture are suitable. The oxidation level of the palladium can be
0 or 2. Suitable counterions for the palladium salts are, inter
15 alia, the following: chloride, bromide, iodide, sulfate, acetate,
trifluoroacetate, acetylacetonate or hexafluoro-2,4-pentadionate.
A large number of different palladium complexes can be used. The
only prerequisite is that the ligands of the palladium can be
displaced by the substrate under the reaction conditions.
20 Especially suitable ligands are phosphine ligands, eg.
aryl-alkylphosphines such as, inter alia,
methyldiphenylphosphine, isopropyldiphenylphosphine,
triarylphosphines such as, inter alia, triphenylphosphine,
tritolylphosphine, trixylylphosphine, trihetarylphosphines, such
25 as trifurylphosphine, or dimer:ic phosphines. Substances which are
also well suited are olefinic ligands, such as, inter alia,
dibenzylideneacetone or its saLts, cycloocta-1,5-diene or amines
such as trialkylamines (eg. triethylamine,
tetramethylethylenediamine, N-methylmorpholine) or pyridine.
The complex used can be employed directly in the reaction. This
procedure can be followed using, for example,
tetrakistriphenylphosphinepalladium(0),
bistriphenylphosphinepalladium dichloride,
35 bistriphenylphosphinepalladium diacetate, a
dibenzylideneacetone/palladium(0) complex, tetrakismethyl-
diphenylphosphinepalladium(0) or
bis(1,2-diphenylphosphinoethane)palladium dichloride. It is also
possible to use a palladium salt and additionally a suitable
40 ligand, and the catalytically active complex is formed in situ
only then. This procedure is suitable, for example, for the
abovementioned salts and phosphine ligands, eg. trifurylphosphine
or tritolylphosphine. Palladium complexes, eg.
tris~dibenzylideneacetone)dipalladium,
45 bis(dibenzylideneacetone)palladium or 1,5-cyclooctadienepalladium
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16
dichloride can also be further activated by the addition of
ligands, eg. trifurylphosphine or tritolylphosphine.
As a rule, 0.001 to 10 mol%, in particular 0.005 to 5 mol%, of
5 the palladium compound (salt or complex) is used, based on the
compounds II or VII. Higher amounts are possible, but tend to be
uneconomical. The amount of II or VII based on the reactants III
and A-R13, respectively, is generally from 0.8 to 3, preferably
0.95 to 1.5, mole equivalents. All solvents which do not react
l0 themselves with the substrates used are suitable for the
reaction. Polar solvents accelerate the reaction. Especially
suitable are ethers such as diethyl ether, methyl tert-butyl
ether, dimethoxyethane, tetrahydrofuran, dioxane, amides such as
dimethylformamide, dimethylacet:amide, N-methylpyrrolidone,
lS dimethylpropyleneurea, or amines such as triethylamine. The use
of mixtures, eg. of ethers with amides, is frequently
advantageous. Other suitable components for mixtures are alkyl
alcohols and water, especially when the radical B contains a
boron atom. The addition of te1:raalkylammonium halides or alkali
20 metal halides, eg. lithium chloride, is frequently useful and
particularly recommended when X is a sulfonyloxy radical. It is
frequently useful to add an organic or inorganic base, such as
potassium carbonate, sodium carbonate, calcium carbonate, calcium
hydroxide, sodium hydroxide, potassium hydroxide, potassium
25 phosphate, sodium phosphate, pyridine or an amine, such as
triethylamine, especially when the radical B contains a boron
atom.
The reaction temperature is from -20 to 200 C, preferably from 50
30 to 160 C. The reaction times are usually from a few minutes to 50
hours, in most cases 0.5 to l0 hours. When using low-boiling
solvents, it is sometimes useful to carry out the reaction in the
autoclave under inherent pressure.
35 The organotin compounds of the formula VII are prepared by
metallating the benzoic acid on which they are based with a
suitable base at low temperatures and subsequently reacting the
product with a trialkyltin compound to give VII:
COOH COOH
R1s~ ~ 1) base R1s~ ~ SnR123
VII
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17
Suitable bases are mainly cycloalkyl- or alkyllithium compounds,
especially suitable being the commercially available butyl- and
hexyllithium isomers. It is frequently expedient to add an
auxiliary to aid metalation. Suitable substances are ethers,
5 alcoholates, eg. potassium tert-butylate, or amines such as
tetramethylethylene~i ~ri ne The metalation can be effected at
from (-130) C to 0 C, preferably from ~-100) to ~-50) C. All
solvents which are normally used for metalation reactions are
also suitable for this reaction, diethyl ether, methyl tert-butyl
10 ether, tetrahydrofuran and simple hydrocarbons being especially
suitable; it may be advantageous to use mixtures of these. The
reaction times for the metalation can be from a few minutes to a
few hours. The trialkyltin compound is subsequently added, R13
being the customary leaving groups, preferably chlorine or
15 bromine. As regards the temperature during the addition and the
subsequent reaction time, what has been described above also
applies here. This may be followed by aqueous or non-aqueous
work-up; it may be useful in the first case to keep constant the
pH of the aqueous phase by means of a buffer. The yield may be
20 increased considerably when a substance which is suitable for
destroying excess base is added at low temperatures prior to
work-up. Suitable substances are, for example, carbon dioxide,
water, alkyl halides or benzyl halides. If required, the
organotin compounds of the formula I can be purified further, for
25 example by chromatography on silica gel. They prove to be stable
during work-up and also to water at various pH values and can be
stored at room temperature.
Another possibility of synthesizing active ingredients of the
30 formula I is to convert a heterocyclic formyl compound IX by
known methods into the corresponding crotonaldehyde X, which is
then reacted in a manner known per se ~EP 402 751) via the
cyclohexenone XI and the salicylic acid derivative XII to give
the active ingredient.
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O O
5 o ~ A H ~ ~ ~ ~ oR6
~B=CH3 or Ph3P=CH)
IX X XI
R
N ~ Z
Rl R14Y ~ R2 OH O
A ~ ~ VI ~ oR6
o OR6
Ib XII
20 Benzoic acid derivatives, ie. compounds I where R3 is an OH group,
can also be synthesized by con~erting a suitable precursor I
where R3 is oR6 into the free acid Ia by means of hydrolysis or
hydrogenation.
Rl R
¦ hydrolysis or
~ N'~z hydrogenation ~ N ~ z
A ~ X Y ~ R2 A ~ X Y ~ R2
30~ ~ R3 0 OH
I Ia
Compounds of the formula I can also be synthesized by starting
from the free acids Ia, ie. substances where R3 is OH, and
35 converting them into an activated form, such as a halide or an
imidazolide, which are then reacted with a nucleophile R3-H in the
presence or absence of a base. Alternatively, it is also possible
first to activate the salicylic acids III and then to react the
resulting derivatives V with heterocycles IV to give the active
40 ingredients I.
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19
A ~ O~ ~ N 1 z
OH O OH
III-OH Ia
1. activation 1. activation
102. R3-H ~2. R3-H
Rl
A ~ OH ~ A ~ X Y R2
o R3
III I
20 In the description, the substituents mentioned preferably have
the following meanings:
Cl-C4-alkyl: methyl, ethyl, l-p:ropyl, 2-propyl, l-butyl, 2-butyl,
2-methyl-propyl, l,l-dimethyl-ethyl;
Cl-C6-alkyl: C1-C4-alkyl and 1-pentyl, 2-pentyl, 3-pentyl,
2-methyl-butyl, 3-methyl-butyl, 2-methyl-2-butyl, 3-methyl-
2-butyl, 1,1-dimethylpropyl, 1,2-dimethyl-propyl,
2,2-dimethylpropyl, l-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl,
30 3-methylpentyl, 4-methylpentyl, 2-methyl-2-pentyl,
3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl,
3-methyl-3-pentyl, 2,2-dimethyl.butyl, 2,3-dimethylbutyl,
3,3-dimethylbutyl, 3,3-dimethyl.-2-butyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, in particular
35 methyl, ethyl, propyl, 2-propy]., butyl, 2-butyl,
l,l-dimethylethyl, pentyl, 2,2-dimethylpropyl, hexyl;
Cl-C4-haloalkyl: chloromethyl, difluoromethyl, dichloromethyl,
trifluoromethyl, trichloromethyl, chlorodifluoromethyl,
40 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
1,1,2,2-tetrafluoroethyl, 2,2,~-trifluoroethyl,
2-chloro-1,1,2-trifluoroethyl and pentafluoroethyl,
decafluorobutyl, l,1-bis-trifluoromethyl-2,2,2-trifluoroethyl,
preferably difluoromethyl, trifluoromethyl, trichloromethyl and
45 chlorodifluoromethyl;
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C3-C8-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, especially preferably
cyclopropyl, cyclopentyl and cyclohexyl;
5 C3-Cl2-cycloalkyl: C3-C8-cycloalkyl and cyclononyl, cyclodecyl,
cycloundecyl and cyclododecyl, especially pre~erably cyclopropyl,
cyclopentyl and cyclohexyl;
Cl-C4-alkylcarbonyl: acetyl, propionyl, l-propylcarbonyl,
10 2-propylcarbonyl, l-butylcarbonyl, 2-butylcarbonyl,
2-methyl-propylcarbonyl, l,1-dimethyl-ethylcarbonyl;
Cl-C4-alkoxycarbonyl: ethoxycarbonyl, propoxycarbonyl,
l-propyloxycarbonyl, 2-propyloxycarbonyl, l-butyloxycarbonyl,
15 2-butyloxycarbonyl, 2-methyl-propyloxycarbonyl,
l,l-dimethyl-ethoxycarbonyl;
C3-C6-alkenyl: propenyl, l-butenyl, 2-butenyl, 2-methylpropenyl,
pentenyl, 2-pentenyl, 2-methy.lbutenyl, 3-methylbutenyl,
20 2-methyl-2-butenyl, hexenyl, 2-hexenyl, 3-hexenyl,
2-methylpentenyl, 3-methylpentenyl, 4-methylpentenyl,
2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,
2,3-dimethylbutenyl, 2-ethylbutenyl, 3,3-dimethylbutenyl,
2,3-dimethyl-2-butenyl;
C3-C6-alkynyl: propynyl, butynyl, 2-butynyl, pentynyl, 2-pentynyl,
3-methylbutynyl, hexynyl, 2-hexynyl, 3-hexynyl,
3-methyl-pentynyl, 4-methyl-pentynyl, 4-methyl-2-pentynyl;
30 Cl-C4-alkoxy: methoxy, ethoxy, propoxy, l-methylethoxy, butoxy,
2-butoxy, l-methylpropoxy, 2-methylpropoxy, l,l-dimethylethoxy,
in particular methoxy, ethoxy, l-methylethoxy;
Cl-C6-alkoxy: Cl-C4-alkoxy and pentoxy, 2-pentoxy, 3-pentoxy,
35 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl-2-
butoxy, 3-methyl-2-butoxy, l,l-dimethylpropoxy,
1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-hexoxy, 2-hexoxy,
3-hexoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy,
2-methyl-2-pentoxy, 3-methyl-2-pentoxy, 4-methyl-2-pentoxy,
40 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethylbutoxy,
2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3-dimethyl-2-butoxy,
3,3-dimethyl-2-butoxy, in particular methoxy, ethoxy,
1-methylethoxy;
45 Cl-C8-alkoxy: Cl-C6-alkoxy and heptoxy, octoxy, 2-ethylhexoxy;
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21
Cl-C4-haloalkoxy: difluoromethoxy, trifluoromethoxy,
chlorodifluoromethoxy, l-fluoroethoxy, 2-fluoroethoxy,
2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy,
2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy and
S pentafluoroethoxy, 1,1,2,3,3,3-hexafluoropropoxy,
heptafluoro-propoxy, decafluorobutoxy,
1,1-bis-trifluoromethyl-2,2,2-trifluoroethoxy, preferably
difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy;
0 Cl-C12-cyc loalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy,
cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy,
cyclodecyloxy, cycloundecyloxy and cyclododecyloxy, especially
preferably cyclopropoxy, cyclopentoxy and cyclohexyloxy;
15 Cl-C4-alkylcarbonyloxy: acetoxy, propionyloxy,
l-propylcarbonyloxy, 2-propylcarbonyloxy, l-butylcarbonyloxy,
2-butylcarbonyloxy, 2-methyl-propylcarbonyloxy,
l,1-dimethyl-ethylcarbonyloxy;
20 Cl-C4-alkylthio: methylthio, ethylthio, propylthio,
l-methylethylthio, butylthio, ~-butylthio, 1-methylpropylthio,
2-methylpropylthio, 1,1-dimethylethylthio, in particular
methylthio, ethylthio, 1-methylethylthio;
25 C1-C4-alkylsulfinyl: methylsulfinyl, ethylsulfinyl,
propylsulfinyl, l-methylethylsulfinyl, butylsulfinyl,
2-butylsulfinyl, l-methylpropylsulfinyl, 2-methylpropylsulfinyl,
l,l-dimethylethylsulfinyl, in particular methylsulfinyl,
ethylsulfinyl, l-methylethylsulfinyl;
Cl-C4-alkylsulfonyl: methylsulfonyl, ethylsulfonyl,
propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl,
2-butylsulfonyl, l-methylpropylsulfonyl, 2-methylpropylsulfonyl,
1,1-dimethylethylsulfonyl, in particular methylsulfonyl,
35 ethylsulfonyl, 1-methylethylsulfonyl;
Cl-C4-alkylamino: methylamino, ethylamino, propylamino,
l-methylethylamino, butylamino r 2-butylamino,
1-methylpropylamino, 2-methylpropylamino, l,l-dimethylethylamino,
40 in particular methylamino, ethylamino, 1-methylethylamino;
di-Cl-C4-alkylamino: dimethylamino, N-methyl-N-ethylamino,
diethylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino,
dipropylamino, diisopropylamino, N-isopropyl-N-methylamino,
45 N-ethyl-N-isopropylamino, N-isopropyl-N-propylamino,
dibutylamino, di-2-methylpropy:Lamino, di-l-methylpropylamino,
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22
N-butyl-N-methylamino and isomers, N-butyl-N-ethylamino and
isomers, N-butyl-N-propylamino and isomers;
C3-C6-alkylene chain: propylene r butylene, pentylene, hexylene;
5-membered heteroaromatics which may be mentioned are mainly the
following heterocycles: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl,
l-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, l-pyrazolyl, 3-pyrazolyl,
4-pyrazolyl, 5-pyrazolyl, l-imidazolyl, 2-imidazolyl,
10 4-imidazolyl, 5-imidazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl,
2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl,
4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl,
5-isothiazolyl, 1,2,3-triazol-1-yl, 1,2,3-triazol-4-yl,
1,2,3-triazol-5-yl, ~lH)1,2,4-triazol-1-yl,
15 (lH)1,2,4-triazol-3-yl, (lH)1,2,4-triazol-5-yl,
(4H)1,2,4-triazol-2(5)-yl, (4H~1,2,4-triazol-4-yl, l-tetrazolyl,
5-tetrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl,
4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl,
5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl,
20 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl,
1,2,4-oxadiazol-5-yl, 3(4)-furazanyl, 1,3,4-oxadiazol-2(5)-yl,
1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl,
1,2,5-thiadiazol-3-yl, 1,3,4-thiadiazol-
2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl.
6 - ~cred heteroaromatics which may be mentioned are mainly the
following heterocycles: 2-pyrimidinyl, 4(6)-pyrimidinyl,
5-pyrimidinyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl,
1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl,
30 1,2,4-triazin-6-yl, 1,2,4,5-tetrazin-3(6)-yl.
The compounds I and their agriculturally useful salts are
suitable - both as isomer mixtures and in the form of the pure
isomers - as herbicides. The herbicidal compositions comprising I
35 are very good at controlling vegetation on non-crop areas,
particularly at high application rates. They act against
broad-leaved weeds and grass weeds in crops such as wheat, rice,
maize, soya beans and cotton without appreciably damaging the
crop plants. This effect is observed mainly at low application
40 rates.
Depending on the particular application method, the compounds I,
or compositions comprising them, can additionally be used in a
further number of crop plants for eliminating undesirable plants.
45 Suitable crops are, for example, the following:
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23
Allium cepa, pnAn~5 comosus, Arachis hypogaea, Asparagus
officinalis, Beta vulgaris ssp~ altissima, Beta vulgaris ssp.
rapa, ~rassica napus var. napus, Brassica napus var.
napobrassica, Brassica rapa var. silvestris, Camellia sinensis,
5 Carth~ s tinctorius, Carya illinoinensis, Citrus limon, Citrus
sinensis, Coffea arabica (Coffea canephora, Coffea liberica),
Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis
guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum,
(Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium),
10 Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus
lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum
usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot
esculenta, Medicago sativa, Musa spp., Nicotiana tabacum
(N.rustica), Olea europaea, Oryza sativa , Phaseolus lunatus,
15 Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum,
Prunus avium, Prunus persica, Pyrus c n;s, Ribes sylvestre,
Ricinus c~ lnis, Saccharum officinarum, Secale cereale, Solanum,
tuberosum, Sorghum bicolor ~s. vulgare), Theobroma cacao,
Trifolium pratense, Triticum aestivum, Triticum durum, Vicia
20 faba, Vitis vinifera, Zea mays.
In addition, the compounds I can also be used in crops which are
tolerant to the action of herbicides as a result of breeding
including genetic engineering methods.
The herbicidal compositions or the active ingredients can be
applied pre- or post-emergence If the active ingredients are
less well tolerated by certain crop plants, application
techniques may be used in which the herbicidal compositions are
30 sprayed, with the aid of the spraying equipment, in such a way
that they come into as little contact as possible with the leaves
of the sensitive crop plants, while the active ingredients reach
the leaves of undesirable plants growing underneath, or the bare
soil surface (post-directed, lay-by).
The compounds I, or the herbicidal compositions comprising them,
can be applied, for example, in the form of directly sprayable
aqueous solutions, powders, suspensions, also highly concentrated
aqueous, oily or other suspensions or dispersions, emulsions, oil
40 dispersions, pastes, dusts, materials for spreading, or granules,
by means of spraying, atomizing, dusting, scattering or pouring.
The use forms depend on the intended purposes; in any case, they
should guarantee the finest possible distribution of the active
ingredients according to the invention.
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Suitable inert additives are essentially as follows: mineral oil
fractions of medium to high boiling point, such as kerosene or
diesel oil, furthermore coal tar oils and oils of vegetable or
animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg.
5 paraffin, tetrahydronaphthalene, alkylated naphthalenes or their
derivatives, alkylated benzenes or their derivatives, alcohols,
such as methanol, ethanol, propanol, butanol, cyclohexanol,
ketones, such as cyclohexanone, or strongly polar solvents, eg.
amines, such as N-methylpyrrolidone or water.
Aqueous use forms can be prepared from emulsion concentrates,
suspensions, pastes, wettable powders or water-dispersible
granules by adding water. To prepare emulsions, pastes or oil
dispersions, the substances, either as such or dissolved in an
15 oil or solvent, can be homogenized in water by means of a wetting
agent, tackifier, dispersant or emulsifier. Alternatively, it is
also possible to prepare concentrates comprising active
ingredient, wetting agent, tackifier, dispersant or emulsifier
and, if desired, solvent or oil, which are suitable for dilution
20 with water.
Suitable surfactants (adjuvants) are the alkali metal salts,
alkaline earth metal salts and ammonium salts of aromatic
sulfonic acids, eg. ligno-, phenol-, naphthalene- and
25 dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and
alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol
sulfates, and salts of sulfated hexa-, hepta- and octadecanols,
and also of fatty alcohol glycol ethers, condensates of
sulfonated naphthalene and its derivatives with formaldehyde,
30 condensates of naphthalene or of the naphthalenesulfonic acids
with phenol and formaldehyde, polyoxyethylene octylphenol ether,
ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl
polyglycol ether, tributylphenyl polyglycol ether, alkylaryl
polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene
35 oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers or polyoxypropylene alkyl ethers, lauryl alcohol
polyglycol ether acetate, sorbitol esters, lignosulfite waste
liquors or methylcellulose.
40 Powders, materials for spreading and dusts can be prepared by
mixing or grinding the active ingredients together with a solid
carrier.
Granules, eg. coated granules, impregnated granules and
45 homogeneous granules, can be prepared by binding the active
ingredients to solid carriers. Solid carriers are mineral earths
such as silicas, silica gels, silicates, talc, kaolin, limestone,
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lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,
calcium sulfate, magnesium sulfate, magnesium oxide, ground
synthetic materials, fertilizers such as ammonium sulfate,
ammonium phosphate, ammonium nitrate, ureas and products of
5 vegetable origin, such as cereal meal, tree bark meal, wood meal
and nutshell meal, cellulose powders or other solid carriers.
The concentrations of the active ingredients I in the
ready-to-use preparations can be varied within wide ranges. In
lO general, the formulations comprise from 0.001 to 98% by weight,
preferably from 0.1 to 95~ by weight, of active ingredient. The
active ingredients are employed in a purity of from 90% to 100%,
preferably 95% to 100% (according to NMR spectrum).
15 The compounds I according to the invention can be formulated, for
example, as follows:
I 20 parts by weight of compound No. 50 are dissolved in a
mixture composed of 80 part~ by weight of alkylated
benzene, 10 parts by weight of the adduct of 8 to 10 mol
of ethylene oxide to 1 mol of oleic acid
N-monoethanolamide, 5 parts by weight of calcium
dodecylbenzenesulfonate and 5 parts by weight of the
adduct of 40 mol of ethylene oxide to 1 mol of castor
oil. Pouring the solution into 100,000 parts by weight of
water and finely distributing it therein gives an aqueou~
dispersion comprising ().02% by weight of the active
ingredient.
30 II 20 parts by weight of compound No. 5 are dissolved in a
mixture composed of 40 parts by weight of cyclohexanone,
30 parts by weight of isobutanol, 20 parts by weight of
the adduct of 7 mol of ethylene oxide to 1 mol of
isooctylphenol and 10 parts by weight of the adduct of
40 mol of ethylene oxide to 1 mol of castor oil. Pouring
the solution into 100,()00 parts by weight of water and
finely distributing it therein gives an aqueous
dispersion comprising 0.02~ by weight of the active
ingredient.
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26
III 20 parts by weight of active ingredient No. 3 are
dissolved in a mixture composed of 25 parts by weight of
cyclohexanone, 65 parts by weight of a mineral oil
fraction of boiling point 210 to 280 C and 10 parts by
weight of the adduct of 40 mol of ethylene oxide to 1 mol
of castor oil. Pouring the solution into 100,000 parts by
weight of water and finely distributing it therein gives
an aqueous dispersion comprising 0.02% by weight of the
active ingredient.
IV 20 parts by weight of active ingredient No. 6 are mixed
thoroughly with 3 parts by weight of sodium
diisobutylnaphthalenesulfonate, 17 parts by weight of the
sodium salt of a lignosulfonic acid from a sulfite waste
liquor and 60 parts by weight of pulverulent silica gel,
and the mixture is ground in a hammer mill. Finely
distributing the mixture in 20,000 parts by weight of
water gives a spray mixture comprising 0.1% by weight of
the active ingredient.
V 3 parts by weight of active ingredient No. S0 are mixed
with 97 parts by weight of finely divided kaolin. This
gives a dust comprising 3% by weight of the active
ingredient.
VI 20 parts by weight of active ingredient No. 5 are mixed
intimately with 2 parts by weight of calcium
dodecylbenzenesulfonate, 8 parts by weight of fatty
alcohol polyglycol ether, 2 parts by weight of the sodium
salt of a phenol/urea/formaldehyde condensate and 68
parts by weight of a paraffinic mineral oil. This gives a
stable oily dispersion.
VII 1 part by weight of compound 3 is dissolved in a mixture
composed of 70 parts by weight of cyclohexanone, 20 parts
by weight of ethoxylated isooctylphenol and 10 parts by
weight of ethoxylated castor oil. This gives a stable
emulsion concentrate.
~0 VIII 1 part by weight of compound 6 is dissolved in a mixture
composed of 80 parts by weight of cyclohexanone and 20
parts by weight of Emulphor EL (ethoxylated castor oil).
This gives a stable emulsion concentrate.
~5 To widen the spectrum of action and to achieve synergistic
effects, the substituted salicylic acid derivatives I can be
mixed with a large number of representatives of other groups of
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27
herbicidal or growth-regulating active ingredients and are then
applied concomitantly. Suitable components for mixtures are
1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric
acid and derivatives thereof, aminotriazoles, anilides,
5 (Het)aryloxyalkanoic acid and derivatives thereof, benzoic acid
and derivatives thereof, benzothiadiazinones,
2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones,
benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates,
quinolinecarboxylic acid and derivatives thereof,
10 chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines,
dichloropropionic acid and derivatives thereof,
dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines,
dinitrophenols, diphenyl ethers, bipyridyls, halocarboxylic acids
and derivatives thereof, ureas, 3-phenyluracils, imidazoles,
15 imidazolinones, N-phenyl-3,4,5,6-tetrahydronaphthalimides,
oxadiazoles, oxiranes, phenols, aryloxy- or
heteroaryloxyphenoxypropionic esters, phenylacetic acid and
derivatives thereof, phenylpropionic acid and derivatives
thereof, pyrazoles, phenylpyrazoles, pyridazines,
20 pyridinecarboxylic acid and derivatives thereof, pyrimidyl
ethers, sulfonamides, sulfonylureas, triazines, triazinones,
triazolinones, triazolecarboxamides and uracils.
It may furthermore be advantageous to apply the compounds I,
25 alone or in combination with other herbicides or growth
regulators, together with further crop protection agents, for
example with pesticides or agents for controlling phytopathogenic
fungi or bacteria. Also of interest is the miscibility with
mineral salt solutions, which are employed for treating nutrient
30 and trace element deficiencies. Nonphytotoxic oils and oil
concentrates may also be added.
Depending on the control aim, the season, the target plants and
the stage of growth, the active ingredient application rates are
~5 from 0.001 to 3.0, preferably 0~01 to 1.0, kg of active
ingredient (a.i.)/ha.
Use Examples
40 The herbicidal action of the substituted salicylic acid
derivatives of the formula I was demonstrated by greenhouse
experiments:
The culture containers used were plastic pots containing loamy
45 sand with approximately 3.0% of humus as the substrate. The seeds
of the test plants were sown separately for each species.
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28
In the case of pre-emergence treatment, the active ingredients,
which were suspended or emulsified in water, were applied
directly after sowing by means of finely distributing nozzles.
The containers were irrigated gently to promote germination and
5 growth and subsequently covered with translucent plastic hoods
until the plants had rooted. This cover resulted in uniform
germination of the test plants, unless germination was adversely
affected by the active ingredients.
10 For the post-emergence treatment, the test plants were first
grown to a plant height of 3 to 15 cm, depending on the plant
habit, and only then treated with the active ingredients which
were suspended or emulsified in water. The test plants were
either sown directly and grown in the same containerR, or first
15 grown separately as seedlings and transplanted to the test
containers a few days prior to treatment. The application rate
for the post-emergence treatment is from 0.0312 to 0.0156 kg of
a.i./ha.
20 The plants were kept at from 10 to 25 C or 20 to 35 C, depending
on the species. The test period extended over 2 to 4 weeks.
During this time, the plants were tended, and their response to
the individual treatments was evaluated.
25 The plants were evaluated using a scale of from 0 to 100. 100
means no emergence of the plants or complete destruction of at
least the aerial parts and 0 means no damage or normal course of
growth.
30 The plants used in the greenhouse experiments belonged to the
following species:
Scientific Name Common Name
35 Amaranthus retrofelux redroot pigweed
Chenopodium album lambsquarters ~goosefoot)
Echinochloa crus-galli barnyardgrass
Oryza sativa rice
40 Sinapis alba white mustard
Solanum nigrum black nightshade
Veronica spp. speedwell
Table 1 - Selective herbicidal activity, post-emergence
treatment in the greenhouse
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29
N ~ S ~ o
O OH
o
\
Ex. No. 50
10Application rate 0.0312 1 0.0156
(kg of a.i./ha~ l
Test plants Damage in %
ORYSA 20 0
AMARE 100 100
15 CHEAL 95 90
Table 2 - Herbicidal activity, post-emergence treatment in the
greenhouse
/ ~ ~ N
N ~ N~o
~ ~ ~ O ~ OH
; N o
o
\
Ex. No. 5
30Application rate 0.0312 ¦ 0.0156
Test plants Damage in %
ECHCG 100 95
AMARE 95 95
35 SINAL 95 95
SOLNI 100 100
VERSS 95 95
40 Synthesis Examples
The protocols given in the Synthesis Examples below were used for
obtaining other compounds I by using different starting
compounds. The resulting compounds are listed in the Table which
45 follows together with physical data. Compounds without these data
can be synthesized from the corresponding educts in a similar
CA 02231493 1998-03-30
0050/46245
manner. The structures given in the Table describe especially
preferred active ingredients of the formula I.
Those 2,2-dimethyl-4H-(1,3)benzodioxin-4-ones, used as starting
5 material, which have not been described in EP 657 441 are
accessible by methods similar to those described in that
publication.
1. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2-methoxythia-
zol-5-yl)benzoic acid (Example No. 50): the starting
material was obtained in the customary manner by coupling
2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-~1,3)benzo-
dioxin-4-one with the tin compound obtained by
metallation and stannylation of 2-methoxythiazole. 1.7 g
(5.8 mmol) of 2,2-dimethyl-5-(2-methoxythiazol-5-yl)-4H-
(l~3)benzodioxin-4-one were refluxed for 4 hours in 80 ml
of water together with 241 mg (5.8 mmol) of 97% pure
sodium hydroxide and 0.2 ml of a 40% strength
tetrabutylammonium hydroxide solution. After filtration,
the mixture was concentrated in vacuo and then extracted
by boiling with toluene 5 times at 70 C under slightly
subatmospheric pressure. The product (1.57 g~ was treated
in 80 ml of dimethyl sulfoxide with a small amount of
molecular sieve (4 Angstrom) and 646 mg (5.8 mmol) of
potassium tert-butylate, and the mixture was stirred for
1 hour at room temperature. 1.26 g (5.8 mmol) of
4,6-dimethoxy-2-methylsulfonylpyrimidine were
subsequently added and the mixture was stirred overnight
at room temperature. The reaction mixture was transferred
to water which had been acidified using phosphoric acid,
and the mixture was extracted repeatedly using ethyl
acetate. The combined organic phases were washed
repeatedly with water, dried over sodium sulfate and
concentrated in vacuo. Yield 2.05 g. Melting point 150 to
153~C.
2. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-
pyrimidin-5-yl)benzoic acid (Example No. 69):
a) 2,4-Dimethoxy-5-tributylstannylpyrimidine: 45 ml of a
1.6 M solution o~ n-butyllithium in hexane were added
dropwise at -70 C to lS.0 g (68.5 mmol) of
2,4-dimethoxy-5-bromopyrimidine in 400 ml of diethyl
ether, and stirring was continued for 1.5 hours at -75 CO
23.2 g (68.5 mmol) of 96% pure tributylstannyl chloride
were then added dropwise to the yellow suspension at this
temperature, the mixture was allowed to come to room
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31
temperature, and stirring was continued for 1 hour. After
concentration in vacuo, there remained 36.6 g of a crude
product which was directly employed further. lH NMR
(CDCl3): ~ = 0.85 (t); 1.05 (t); 1.22 (m); 1.50 (m); 3.95
(s); 4.00 (s); 8.12 (s).
b) 2,2-Dimethyl-5-~2,4-dimethoxy-
pyrimidin-5-yl)-4H-(1,3)benzodioxin-4-one: in an
autoclave, 12.1 g (37 mmol) of
2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-
dioxin-4-one, 20.0 g of the above-described tin compound,
4.72 g (111 mmol) of lithium chloride, 855 mg (0.74 mmol)
of tetrakistriphenylphosphinepalladium(0) and 50 mg of
2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours
at 140 C in 140 ml of dioxane. The mixture was
subsequently concentrated in vacuo, chromatographed on
silica gel using toluene/ethyl acetate mixtures and then
stirred with cyclohexane. Yield 3~5 g. Melting point
194-196 C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-
pyrimidin-5-yl)benzoic acid: 1.5 g (4.8 mmol) of
2,2-dimethyl-5-(2,4-dimethoxypyrimidin-5-yl)-4H-(1,3)-
benzodioxin-4-one were refluxed for 8.5 hours in 60 ml of
water together with 196 mg of 97% pure sodium hydroxide
and 0.16 ml of 40% strength tetrabutylammonium hydroxide
solution. The mixture was filtered, the filtrate was
concentrated in vacuo, and the product was extracted by
boiling 7 times with toluene at 75 C under slightly
subatmospheric pressure and then dried in vacuo. The
product (1.41 g) was transferred into 70 ml of dimethyl
sulfoxide, 532 mg ~4.7'i mmol) of potassium tert-butylate
were added at room temperature, and stirring was
continued for 1 hour. ]..04 g (4.75 mmol) of
4,6-dimethoxy-2-methylsulfonylpyrimidine were then added
and the mixture was stirred overnight at room
temperature. The reaction mixture was transferred into
water which had been acidified with phosphoric acid and
extracted repeatedly using ethyl acetate. The com~ined
organic phases were washed repeatedly with water, dried
over sodium sulfate and concentrated in vacuoO Yield
0.9 g. Melting point 161 to 162 C.
3. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-
pyrimidin-6-yl)benzoic acid (Example No. 68):
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32
a) 2,4-Dimethoxy-6-tributylstannylpyrimidine: 27 ml of a
1.4 M solution of sec-butyllithium in hexane (38 mmol)
were added dropwise at -100~C to 7.55 g (34.5 mmol) of
2,4-dimethoxy-6-bromopyrimidine in 120 ml of diethyl
ether and 120 ml of tetrahydrofuran, and stirring was
continued for 5 minutes at -100 C. At this temperature,
11.7 g (34.5 mmol) of 96% pure tributylstannyl chloride
were then added dropwise, stirring was continued for 30
minutes at -80 C, and the mixture was allowed to come to
room te perature. After concentration in vacuo, there
remained 18.9 g of a crude product which was directly
employed further. lH NMR (CDCl3): ~ = 0.90 (t); 1.07 (t);
1.32 ~m); 1.58 (m); 3.92 (s); 3.97 (s); 6.55 (s).
b) 2,2-Dimethyl-5-(2,4-dimethoxy-
pyrimidin-6-yl)-4H-~1,3)benzodioxin-4-one: in an
autoclave, 7.07 g (21.7 mmol~ of
2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(l,~)benzo
dioxin-4-one, 18.6 g of the above-described tin compound,
2.77 g (65 mmol) of lithium chloride, 502 mg (0.43 mmol)
of tetrakistriphenylphosphinepalladium(0) and 40 mg of
2,6-bis-tert-butyl-4-methylphenol were heated for 3 hours
at 140 C in 200 ml of dioxane. The mixture was
subsequently concentrated in vacuo, chromatographed on
silica gel using toluene/ethyl acetate mixtures and then
stirred with cyclohexane. Yield 2.5 g. Melting point
1~4~C.
c) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(2,4-dimethoxy-
pyrimidin-6-yl)benzoic acid: 1.5 g (4,8 mmol) of
2,2-dimethyl-5-(2,4-dimethoxy-
pyrimidin-6-yl)-4H-(1,3)benzodioxin-4-one were refluxed
for 6 hours in 60 ml of water together with 196 mg of 97%
pure sodium hydroxide and 0.16 ml of 40% strength
tetrabutylammonium hydroxide solution. The mixture was
acidified and extracted, and the extract was dried over
sodium sulfate and concentrated in vacuo. The product
(1.07 g, 3.88 mmol) was transferred into 50 ml of
dimethyl sulfoxide, 870 mg (7.77 mmol) of potassium
tert-butylate were added at room temperature, and
stirring was continued for 0.5 hour. 848 mg (3.89 mmol)
of 4,6-dimethoxy-2-methylsulfonylpyrimidine were then
added and the mixture was stirred overnight at room
temperature. The react:ion mixture was subsequently
transferred into water which had been acidified with
phosphoric acid and extracted repeatedly using ethyl
acetate. The combined organic phases were washed
CA 02231493 1998-03-30
.
OOS0/~6245
33
repeatedly with water, dried over sodium sulfate and
concentrated in vacuo. Yield 0.95 g. Melting point
140-143 C.
5 4. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyra-
zol-5-yl)benzoic acid (Example No. 3):
a) 5-Tributylstannyl-l-methoxy-pyrazole: 15 g (153 mmol) of
l-methoxypyrazole (prepared in accordance with
DE 34 09 317) were dissolved in 280 ml of dry ether and
the solution was cooled to -70 C. 96.8 ml (163 mmol) of a
1.7-molar solution of tert-butyllithium in he~Ane were
added dropwise, stirring was continued for 1.5 hour, and
49.8 g (153 mmol) of tributyltin chloride were then
added. The mixture was allowed to come to room
temperature slowly, and stirring was continued overnight.
Then, the mixture was hydrolyzed using 150 ml of water,
the organic phase was separated off, washed with water
and saturated sodium chloride solution, dried over sodium
sulfate and concentrated. The residue which L- ~ined was
freed from low-boiling substances by distillation. 55 g
of the product remained (GC purity: 93%).
b) 2,2-Dimethyl-5-(1-methoxypyrazol-5-yl)-4H-(1,3)benzo-
dioxin-4-one: in an autoclave, 23.1 g (71 mmol) of
2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-
dioxin-4-one, 26 g of t:he above-described tin compound,
9.45 g (220 mmol) of lithium chloride, 1.7 g of
tetrakistriphenylphosphinepalladium(0) and 90 mg of
2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours
at 140 C in 100 ml of dioxane. The mixture was
subsequently concentrat:ed in vacuo, chromatographed on
silica gel using toluene/ethyl acetate mixtures and then
stirred with hexane. Yi.eld: 5 g of colorless oil.
c) 6-(1-Methoxypyrazol-5-yl)salicylic acid: 3.0 g (11 mmol)
of the above-described compound were dissolved in 40 ml
of acetone, and the solution was added to a solution of
1.77 g (32 mmol) of KO~I and 3 drops of tetrabutylammonium
hydroxide solution in 40 ml of water. The mixture was
stirred for 4 hours at room temperature, concentrated to
half its bulk and extracted using MTBE. The aqueous phase
was acidified using phosphoric acid and extracted three
times by shaking with ~TBE. The combined organic phases
were washed with water and saturated sodium chloride
solution, dried over sodium sulfate and concentrated.
CA 02231493 1998-03-30
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34
There remained 1.9 g of a colorless solid, m.p. 208 to
218 C.
d) 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-methoxypyrazol-5-
yl)benzoic acid: 1.61 ~ (6.9 mmol) of the product of c)
were transferred into 50 ml of dimethyl sulfoxide, 1.55 g
(13.8 mmol) of potassium tert-butylate were added at room
temperature, and stirring was continued for 0.5 hour.
1.5 g (6.9 mmol) of
4,6-dimethoxy-2-methylsulfonylpyrimidine were then added
and the mixture was stirred overnight at room
temperature. The reaction mixture was subsequently poured
into water which had been acidified with phosphoric acid,
and the solid which precipitated was filtered off with
fiuction. The solid was washed with water and dried in a
vacuum drying oven at 50 C. Yield 2.07 g. Melting point
182 to 185VC.
5. 2-(4,6-Dimethoxypyrimidin-2-yloxy)-6-(1-ethoxypyra-
zol-4-yl)benzoic acid (Example No. s):
a) l-Ethoxypyrazole: 104.8 g (0.76 mol) of potassium
carbonate and a solution of 60.1 g (0.385 mol) of ethyl
iodide in 200 ml of acetone are added to a solution of
29.4 g (0.35 mol) of l-hydroxypyrazole (prepared in
accordance with EP 567 827) in 200 ml of acetone, and the
mixture is refluxed for four hours. After cooling, the
precipitate is filtered off with suction and washed using
acetone. The acetone is first distilled off from the
filtrate at atmospheric pressure using a short column,
and the distillation is then continued under reduced
pressure, the product distilling over at 75 C/78 mm in
the form of a colorless liquid. This gives 35.6 g of
product in a purity of 99.8~ (GC).
b) 4-Bromo-l-ethoxy-pyrazole
20.1 g (178 mmol) of l-ethoxypyrazole were dissolved in
120 ml of carbon tetrachloride, and a solution of 28.5 g
(178 mmol) of bromine in 122 ml of glacial acetic acid
was added dropwise at 0 to 5 C while passing through a
gentle stream of nitrogen. Stirring was continued for 30
minutes at this temperature, the reaction mixture was
then allowed to come to room temperature in the course of
one hour and then refluxed for 2.5 hours. After cooling,
the mixture was poured into 500 ml of ice-water, the
organic phase was separated off and the aqueous phase was
CA 02231493 1998-03-30
0050/46245
extracted three more times using dichloromethane. The
combined organic phases were extracted by shaking with
water, 5% strength sodium bicarbonate solution, again
with water and with sat;urated sodium chloride solution
and dried over sodium sulfate, and the methylene chloride
was distilled off on a rotary evaporator. The residue was
distilled over a 15 cm Vigreux column, 33.3 g of the
product distilling over at 52 to 54 C/0.5 mm (GC purity:
97.8%)-
c) 5-Tributylstannyl-l-ethoxypyrazole: 3.81 g (157 mmol) of
magnesium filings were placed in 10 ml of dry THF and the
mixture was activated using grains of iodine. The mixture
was refluxed, the cooling equipment was removed, and a
solution of 27 g (142 mmol) of 4-bromo-1-ethoxypyrazole
in 160 ml of dry THF was added dropwise in such a manner
that the reflux conditions were retained. The mixture was
kept under reflux for a further 3 hours, during which
process most of the magnesium dissolved. The mixture was
allowed to cool to roorn temperature, a solution of 43 g
(132 mmol) of tributyltin chloride in 30 ml of dry THF
was then added dropwise, and the mixture was refluxed for
2 hours. After cooling,, the batch was poured into 500 ml
of 5% strength ammonium chloride solution, and the
aqueous phase was extracted four more times using
methylene chloride. The combined organic phases were
washed with water and saturated sodium chloride solution,
dried over sodium sulfate and concentrated. The residue
which remained was pur:ified on silica gel (deactivated
using hex~ ?thyldisalazane~ using hexane/acetone. This
gives 21.8 g of colorless oil (GC purity: 84%).
d) 5-(1-Ethoxypyrazol-4-yl)-2,2-dimethyl-4H-(1,3)benzodio-
xin-4-one: in an autocLave, 13.3 g (40 mmol) of
2,2-dimethyl-5-trifluoromethylsulfonyloxy-4H-(1,3)benzo-
dioxin-4-one, 20.1 g of the above-described tin compound,
5.23 g (125 mmol) of lithium chloride, 0.94 g of
tetrakistriphenylphosphinepalladium(0) and 39 mg of
2,6-bis-tert-butyl-4-methylphenol were heated for 6 hours
at 140 C in 100 ml of dioxane. The mixture was
subsequently concentrated in vacuo, chromatographed on
silica gel using hexane/acetone and then stirred with
hexane. Yield: 4.6 g of a colorless oil.
e) 6-(1-Ethoxypyrazol-4-yl)salicylic acid: 2.9 g (10 mmol)
of the above-described compound were dissolved in 40 ml
of acetone, and the solution was added to a solution of
CA 02231493 1998-03-30
.
0050/46245
36
1.6 g (29 mmol) of KOH and 3 drops of tetrabutylammonium
hydroxide solution in 40 ml of water. The mixture was
stirred for 2.5 hours at room temperature, concentrated
to half its bulk and extracted using MTBE. The aqueous
phase was acidified using phosphoric acid and extracted
three times by shaking with MTBE. The combined organic
phases were washed with water and saturated sodium
chloride solution, dried over sodium sulfate and
concentrated. 2.27 q of a colorless resin remained.
f) 6-(1-Ethoxypyrazol-4-yl)-2-(4,6-dimethoxypyrimidin-2-yl-
oxy)benzoic acid: using a protocol similar to the one
given above for the l-methoxypyrazol-5-yl derivative,
1.76 g of the product of melting range 57 to 74 C were
obtained from 1.55 g l6 mmol) of
6-(1-ethoxypyrazol-4-yl)salicylic acid, 1.35 g (12 mmol)
of potassium tert-butylate and 1.31 g (6 mmol) of
4,6-dimethoxy-2-methylsulfonylpyrimidine.
CA 02231493 1998-03-30
ooso/46245
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