Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
`- 20~077~
The invention relates to new aryloxycarbonyl
compoundc, to a plurality of proce~ses and novel
intermediates for their preparation, and to their use as
herbicides.
It has already been disclosed that phenoxy-
propionic acid derivatives have herbicidal properties
(cf. DE-OS (G~rman Published SpGcification) 2,223,894).
For example, methyl 2-t4-(2,4-dichlorophenoxy)-phenoxy]-
propionate can be employed for combating weeds. However,
the action of this substance is not always sati~factory,
in particular when low amount6 are applied.
New aryloxycarbonyl compounds of the general
formula (I)
xl x2Rl B
Ar-~~(A)n ~ ~CI-~E)m-c-y (I)
R2
in which
m and n represent the number 0 or 1,
Ar represents aryl or heteroaryl,
Q represent~ heteroarylene,
A represents oxygen, ~ulphur or methylene,0 X~ and x2 are identical or different and represent hydro-
gen, halogen, alkyl, halogenoalkyl, alkosy or
halogenoalkoxy,
Rl and R2 are identical or different and repre6ent hydro-
Le A 27 Ç28 - 1 -
20~0~7~
gen, alkyl, halogenoalkyl,
E represents an optionally substituted ethylene or
vinylene group,
and
S Y represents the radical of a carboxylic acid or of a
carboxylic acid derivative,
hsve now been found.
Where appropriate, the compounds of the formula
(I) contain an asymmetric substituted carbon atom and can
in this ca6e occur in various enantiomeric forms. The
invention relates to the individual isomer~ which are
pos~ible as well a8 to mixtures of these isomers.
Furthermore, it has been found that the new
aryloxycarbonyl compounds of the formula (I) are obtained
when
(a) aryl compounds of the general formula (II)
Ar-Q-X3 (II)
in which
Ar and Q have the abovementioned meanings and
X3 represents a nucleofugic group
are reacted with hydroxy- or mercaptoaryloxycarbonyl
compounds of the general formula (III)
xl X2 Rl O
H_~1 ~ -C-(E)m-C-Y (III)
in which
m, ~1, X2, Rl, R2, E nnd Y have the abovementioned
meaning~ and
Al reprssents oxygen or sulphur,
Le A 27 628 - 2 -
2~4~775
if appropriate in the preC;ence of an acid acceptor
and if appropriate in the presence of a diluent, or
when
(b) phenol derivatives of the general formula (IV)
xl x2
Ar-a-(A)n ~ (IV)
in which
n, Ar, Q, A, X1 and ~2 have the abovementioned
~eanings
are reacted with carboxylic acid derivatives of the
general formula (V)
Rl O
11 (V)
X4-C- (E)m-C-Y
R2
in which
m, R1, R2, E and Y have the abovementioned meanings
and
X4 represent6 a nucleofugic group,
if appropriate in the presence of an acid acceptor
and if appropriate in the presence of a diluent.
Finally, it has been found that the new aryloxy-
carbonyl compounds of the general formula (I) have
interesting herbicidal properties.
Surprisingly, the ryloxycarbonyl compounds of
the formula (I) according to the invention have a con-
sider~bly more powerful action again6t certain problem
weeds ~uch a8 ~ in particular, millet ~pecies, than the
Le A 27 628 - 3 -
20~7~
known compound methyl 2-[4-(2,4-dichlorophenoxy)-
phenoxy]-propionate~ which i8 a previously known active
substance of similar structure and the same direction of
action, while being well tolerated by important crop
plants.
Preferred ~ubstituents or ranges of the radicals
mentioned in the formulae above and below are explained
~n the following text:
Alkyl on its own or in composed radical~ repre-
sents straight-chain or branched alkyl having 1 to 6,
preferably 1 to 4, carbon atoms; the following may be
mentioned by way of example as being preferred: methyl,
ethyl, n- and i-propyl and n-, i-, ~- and t-butyl.
Alkoxy in the general formul~e represents
straight-chain or branched alkoxy having 1 to 6, pre-
ferably 1 to 4, carbon atoms; the following may be
mentioned by way of example and as being preferred:
methoxy, ethoxy, n- and i-propoxy and n-, i-, 8- and t-
butoxy.
- 20 Halogenoalkyl and halogenoalkoxy in the general
formulae represent straight-chain or branched halogeno-
alkyl or halogenoalkoxy having 1 to 4, preferably 1 or 2,
carbon atoms and in each case 1 to 9, preferably 1 to 5,
identical or different halogen atoms as defined under
halogen; the following may be mentioned by way of
example: fluoromethyl, chloromethyl, bromomethyl, fluoro-
ethyl, chloroethyl, bromoethyl, fluoro-n-propyl, chloro-
n-propyl, difluoromethyl, trifluoromethyl, dichloro-
methyl, trichloromethyl, difluoroethyl, trifluoroethyl,
trichloroethyl, chlorodifluoro-methyl, trifluorochloro-
Le A 27 628 - 4 _
20~7~
ethyl, chlorobutyl and fluorobutyl, and the halogeno-
alkoxy radical~ corre~ponding to the~e.
Aryl in the general formulae represents
optionally sub~tituted aryl having preferably 6 to 10
S carbon atoms in the aryl moiety. The following may be
mentioned by way of example and as being preferred:
unsubstituted or fiubstituted phenyl or naphthyl, in
particular phenyl.
Heteroaryl in the ganeral formulae repre~ents an
optionally substituted 5- to 6-membered ring which
contains 1 to 3, preferably 1 or 2, identical or dif-
ferent hetero atom~. Hetero atoms which may pref~rably
be mentioned ~re oxygen, ~ulphur and nitrogen; the
following may be mentioned by way of example and a~ being
preferred: pyrimidinyl, pyrrolyl, imidazole, i~o-
thiazolyl, oxazolyl, thienyl, furyl, pyridazinyl, pyra-
zinyl, isoxazolyl, thiazolyl, pyrazolyl and, in par-
ticular, pyridyl.
Heteroarylene in the general formulse represents
a double-linked 5- or 6-membered ring which contains 1 to
4, preferably 1 to 3, identical or different hetero atoms and
which i~ optionally substituted by Cl-C~-alkyl. Hetero
atom~ which may preferably be mentioned are oxygen,
sulphur or nitrogen; the following may be mentionQd by
way of example and as being preferred: pyraz$ne-2,6-diyl,
pyrazine-2,5-diyl, 1,2,4-triazine-3,5-diyl, 1,2,4-tri-
a~ine-3,6-diyl, 1,3-imidazole-2,5-diyl, 1,3-imidazole-
2,4-diyl or 1,2,4-triazole-3,5-diyl (which are in each
ca~e optionally substituted by Cl-C~-alkyl), 1,3-oxazole-
2,5-diyl, 1,3-thiazole-2,5-diyl, 1,3-oxazole-2,4-diyl or
Le A 27 628 - 5 -
20~7~
1,3-thiazole-2,4-diyl and, in particular, 1,3,4-oxa-
diazole-2,5-diyl, 1,3,4-thiadiazole-2,5-diyl, 1,2,4-
oxadiazole-3,5-diyl and 1,2,4-thiadiazole-3,5-diyl.
The radical of a carbo~ylic acid or of a car-
S boxylic acid dexivative in the definition of Y preferably
represents
halogen, hydroxyl, amino, hydrazino, cyano, cyan-
amino, hydroxyamino, isoxazolidinyl, or represents
alkylamino, alkenylamino, alkinylamino, ~rylamino,
aralkylamino, alkoxycarbonylalkylamino, dialkyl-
amino, pyrrolidino, piperidino, morpholino,
dialkenylamino, alkyl~ulphonylamino, ~ryl~ulphonyl-
amino, alkoxyamino, alkylsulphonylhydrazino, ~ryl-
sulphonylhydrazino, alkylthio, arylthio, nralkylthio
and alkoxycarbonylalkylthio each of which is
optionally ~ubstituted, or represents the group -o-R3
where
R3 represents alkyl, alkenyl, alkinyl, alkoxyalkyl,
alkylth$oalkyl,alkylsulphinylalkyl,alkylsulphonyl-
alkyl, aryloxyalkyl, trialkylsilylalkyl, arylthio-
alkyl, aralkoxyalkyl, aralkylthioalkyl, alkoxy-
carbonylalkyl, alkylaminocarbonylalkyl, aralkyl,
azolylalkyl and alkylideneamino, each of which i8
optionally ~ubstituted, or represents ammonium,
alkylammonium, alkali metal or alkaline earth metal
equivalent, or
R3 represents the group 14 1I 5 where
-CH-P~ 6
Le A 27 628 - 6 -
20~077~
R4 represents hydrogen, alkyl, aryl, furyl,
thienyl or pyridyl,
R5 represents alkyl or alkoxy,
R6 represents alkoxy and
Z rQpresents oxygen or sulphur,
or
~3 represents the group -(CH2)p-R7 where
R7 represent~ a heterocyclic radical from the
~eries compri~ing furyl, tetrahydrofuryl,
oxotetrahydrofuryl,thienyl,tetrahydrothienyl,
perhydropyranyl, oxazolyl, isoxazolyl, thi-
azolyl, thiadiazolyl, dioxolanyl, perhydro-
pyrrolyl, oxoperhydropyrrolyl, pyrazolyl,
pyridinyl or pyrimidinyl, each of which is
optionally sub~tituted by halogen and/or alkyl,
and
p represent~ the numbers 0, 1 or 2.
Halogen as a sub~tituent or in the radical
halogenoalkyl generally represents fluorine, chlorine,
bromine and iodine, in particular fluorine and chlorine.
The following may be mentioned as preferred
substituents for the ethylene and vinylene group and for
the hetaryl and aryl radicals:
Halogen; straight-chain or branched alkyl having 1 to 6,
preferably 1 to 4, carbon atoms and particularly prefer-
ably methyl and ethyl (the exemplary enumeration cor-
responds to that siven further above); ~traight-chain or
branched alkoxy and alkylthio having in each case 1 to
6, preferably 1 to 4, carbon atoms and particularly
preferably 1 or 2 carbon atoms (the following may be
Le A 27 28 - 7 -
204~7~
mentioned by way of example: methoxy, ethoxy, n- and i-
propoxy, n-, i-, 8- and t-butoxy, methylthio, ethylthio
and n- and i-propylthio);
straight-chain or branched halogenoalkyl, halogenoalkoxy
and halogenoalkylthio, having prefeably in each case 1 to
4 carbon atoms, particularly preferably in each ca~e 1 or
2 carbon atoms and in each case 1 to 9, preferably 1 to
5, identical or different halogen atom~ as defined under
halogen (the following may be mentioned by way of
examples fluoromethyl, chloromethyl, bromomethyl, fluoro-
ethyl, chloroethyl, bromomethyl, fluoro-n-propyl, chloro-
n-propyl, difluoromethyl, trifluoromethyl, dichloro-
methyl, trichloromethyl, difluoroethyl, trifluoroethyl,
trichloroethyl, chloro-difluoro-methyl, trifluorochloro-
ethyl, chlorobutyl, fluorobutyl, fluoromethoxy, chloro-
methoxy, bromomethoxy, fluoroethoxy, chloroethoxy,
bromoethoxy, fluoropropoxy, chloropropoxy, bromopropoxy,
fluorobutoxy, chlorobutoxy,. fluoro-i-propoxy, chloro-i-
propoxy, difluoromethoxy, trifluoromethoxy, dichloro-
methoxy, trichloromethoxy, difluoroethoxy, trifluoro-
ethoxy, tetrafluoroethoxy, trichloroethoxy, chlorodi-
fluoromethoxy, trifluorochloroethoxy and trifluoromethyl-
thio); straight-chain or branched alkylsulphinyl and
alkylsulphonyl having in each case 1 to 6 and preferably
1 to 4 carbon atoms in the 81kyl moiety, particularly
preferably having 1 or 2 carbon atoms in the alkyl
moiety; hydroxyl, nitro and cyano.
The definitions li~ted here are also true in the
corresponding manner for the preferred combinations of
radicals which are listed below.
Le A 27 628 - 8 -
20~77~
The invention preferably relates to compounds of
the formula (I)
in which
m and n represent the numbers 0 or 1,
Ar represents phenyl or pyridyl, which are in each case
optionally ~ub6tituted by halogen, cyano, nitro
and/or by in each case optionally halogen-sub~ti-
tuted alkyl, alkoxy, alkylthio, alkyl~ulphinyl or
alkyl~ulphonyl having in each case 1 to 6 carbon
atoms in the alkyl moiety,
Q represents a five- or six-membered heterosrylene
radical which contains 2 or 3 nitrogen atoms (of
which one iB optionally alkylated) or 1 or 2 nitro-
gen atoms and sdditionally 1 oxygen atom or sulphur
atom as hetero atoms,
A represents oxygen, ~ulphur or methylene,
Xl and ~2 are identical or different and repre~ent hydro-
gen, halogen, alkyl, alkoxy, halogenoalkyl or
halogenoalkoxy, in each case having 1 to 4 carbon
atoms and where appropriate 1 to 9 identical or
different halogen atoms,
Rl and R2 are identical or different and represent hydro-
gen, alkyl or halogenoalkyl having in each ca~e 1 to
4 carbon atoms and 1 to 9 identical or different
halogen atoms,
OH
E represent~ the groups -CH=CH- or -CH-CH2- and
Y represents halogen in particular chlorine, hydroxyl,
amino, hydrazino, cyano, cyanzmino, hydroxyamino,
Le A 27 628 - 9 -
2Q~77~
isoxazolidinyl, or represents Cl-C6-alkylamino, C3-C4-
alkenylamino, C3-C4-alkinylamino, phenylamino,
benzylamino, C~-C4-alkoxycarbonyl-Cl-C2-alkylamino,
di-(Cl-C4-alkyl)-amino, pyrrolidino, piperidino,
morpholino, di-~C3-C4-alkenyl)-amino, Cl-C4-alkyl-
~ulphonylamino, phenylsulphonylamino, tolyl-
~ulphonylamino, Cl-C6-alkoxyamino, Cl-C~-alkyl-
3ulphonylhydrazino, phenylsulphonylhydrazino,
tolylsulphonylhydrazino,Cl-C4-alkylthio,phenylthio,
benzylthio, Cl-C~-alkoxy-carbonyl-Cl-C2-alkylthio,
each of which is optionally substituted by halogen,
or represents the group -o-R3, where
R3 repre~en~6 C1-C6-alkyl, C3-C4-alkenyl, C3-C4-
~lkinyl, Cl-C4-alkoxy-Cl-C4-alkyl, C1-C4-
alkoxy-Cl-C4-alkoxy-Cl-C4-alkYl, Cl-C4-alkyl-
thio-Cl-C"-alkyl, Cl-C4-alkylsulphinyl-Cl-C4-
alkyl, Cl-C4-alkylsulphonyl-Cl-C~-alkyl, phenoxy-
Cl-C3-alkyl, trimethylsilylmethyl, phenylthio-
Cl-C3-alkyl, benzyloxy-Cl-C3-alkyl, benzylthio-
Cl-C3-alkyl, Cl-C~-alkoxy-carbonyl-Cl-C2-alkyl,
Cl-C4-alkylamino-carbonyl-Cl-C2-alkyl, benzyl,
pyrazolyl-Cl-C4-alkyl, C2-C"-alkylidencamino,
each of which is optionally substituted by
fluorine and/or chlorine, or represents an
ammonium, a Cl-C4-alkylammonium, a sodium,
potassium or calcium equivalent, or
R3 represent~ the group -C ~P~ b where
R4 represents hydroqen, Cl-C~-alkyl, phenyl, furyl,
thienyl or pyridyl,
Le A 27 628 - 10 -
2~4~77~
Rs repre ents Cl-C4-a~ or Cl-C4-alkox~
R6 represent~ C1-C~-alkoxy and
Z represents oxygen or ~ulphur,
or
R3 represents the group -(CH2)p-R7 where
R7 represents a heterocyclic radical from the
series comprising furyl, tetrahydrofuryl,
oxotetrahydrofuryl,thienyl,tetrahydrothienyl,
perhydropyranyl, oxazolyl, isooxazolyl, thia-
zolyl, thi~diazoly, dioxolanyl, perhydro-
pyrrolyl, oxoperhydropyrrolyl, pyridinyl,
pyrazolyl or pyrimidinyl, each of which i~
optionally substituted by iluorine, chlorine,
bromine and/or Cl-C~-alkyl, and
p repre~ents the numbers 0, 1 or 2.
Particularly preferred are compounds of the
formula (I) in which
m and n represent the numbers 0 or 1,
Ar represents phenyl or pyridyl which are in each case
optionally substituted by fluorine, chlorine,
bromine, cyano, nitro and/or by in each case
optionally fluorine- and/or chlorine-~ubstituted
Cl-C~-alkyl, C,-C4-alkoxy, C,-Cj-alkylthio, Cl-C4-
alkylsulphinyl or C~-C~-alkylsulphonyl,
25 Q repre~ents pyr~zine-2,6-diyl, pyrazine-2,5-diyl,
1,2,4-triazine-3,5-diyl, 1,2,4-triazine-3,6-diyl,
1,3-imidazole-2,5-diyl, 1,3-imidazole-2,4-diyl or
1,2,4-triazole-3,5-diyl (which are in each case
opt~onally substituted by Cl-C~-alkyl), or repre~ents
1,3~4-oxadiazole-2,5-diyl, 1,3,4-thiadiazole-2,5-
Le A 27 628 - 11 -
2~77~
diyl, 1,2,4-oxadiazole-3,5-diyl, 1,2,4-thiadiazole-
3,5-diyl, 1,3-oxazole-2,5-diyl, 1,3-thiazole-2,5-
diyl, 1~3-oxazole-2,4-diyl or 1,3-thiazole-2,4-diyl,
A represents oxygen, sulphur or methylene,
xl and x2 are identical or different and represent
~ydrogen, fluorine, chlorina or halogenoalkyl having 1
or 2 carbon ~toms and 1 to 5 identical or different
halo~en atom~,
Rl and R2 ~re identical or different and represent hydro-
gen, Cl-C~-alkyl or halogenoalkyl having 1 to 4
carbon atoms and 1 to 9 identical or different
halogen atoms,
OH
15 E represents the group3 -CH=CH- or -CH-CH2- nnd
Y repre~ents chlorine, hydroxyl, ~mino, hydrazino,
cyano, cyanoamino, hydroxyamino, isoxazolidinyl or
representsCl-C6-alkylamino,C3-C4-alkenylamino, C3-C~-
alkinylamino,phenylamino, benzylamino,Cl-C~-alkoxy-
carbonyl-C~-C2-alkylamino, di-(C,-C~-alkyl)-amino,
pyrrolidino, piperidino, morpholino, di-( C3-C~-
alkenyl)-amino, Cl-C~-alkylsulphonylamino, phenyl-
sulphonylamino, tolylsulphonyl~mino, Cl-C6-alkoxy-
amino, C1-C4-alkylsulphonylhydrazino, phenyl-
~ulphonylhydrazino, tolylsulphonylhydrazino, Cl-C~-
alkylthio, phenylthio, benzylthio, Cl-C4-alkoxy-
carbonyl-Cl-C2-alkylthio, each of which is optionally
substituted by fluorine and/or chlorine, or repre-
sents the group -o-R3 where
R3 repre~ents C1-C6-alkyl, C3-C4-alkenyl, C3-C4-
alkinyl, Cl-C4-alkoxy-Cl-C4-alkyl, C1-C4-
alkoxy-C1-C3-alkoxy-Cl-C3-alkyl, C1-C4-alkyl-
thio-
Le A 2? 628 - ~2 -
~04~77~
Cl-C4-alkyl, Cl-C4-al]q~lsulphinyl-Cl-C4-alkyl,
Cl-C4-alkylsulphonyl-Cl-C"-alkyl, phenoxy-Cl-C3-
alkyl, trimethylsilyl~ethyl, phenylthio-C1-C3-
alkyl, benzyloxy-Cl-C3--alkyl, benzylthio-Cl-C3-
S alkyl, C1-C4-alkoxy-carbonyl-C1-C2-alkyl, Cl-C~-
alkylamino-carbonyl-C~-C2-alkyl, benzyl, pyra-
201yl-C1-C4-alkyl,C2-C~-alkylidene~mino,oachof
which i~ optionally substituted by fluorine
and/or chlorine, or repre~Qnts an ~mmonium, a
Cl-C4-alkylammonium, a sodium, pota~sium or
calcium equivalent, or
R3 represent~ the group 14 Z 5 where
-CH-P~
R4 represent~ hydro~en, Cl-C~-~lkyl, ph~nyl, furyl,
thienyl or pyridyl,
R5 represents C1-C~-alkyl or Cl-C~-alkoxy,
R6 represents Cl-C~-alkoxy and
Z represents oxygen or sulphur,
or
R3 represents the group -(CH2)~-R7 where
R7 represents a heterocyclic radical from the
s~ries comprising furyl, tetrahydrofuryl,
~ oxotetrahydrofuryl,thienyl,tetrahydrothienyl,
perhydropyranyl, oxazolyl, isoxazolyl,
thiazolyl, thiadi~zolyl, dioxol~nyl, perhydro-
pyrrolyl, oxoperhydropyrrolyl, pyridinyl,
pyra201yl or pyrimidinyl, each of which i6
optionally substituted by fluorine, chlorine,
Le A 27 62~ - 13 -
2~40r~75
bromine and/or Cl-C4-alkyl, and
p represents the numbers 0, 1 or 2.
In particular, the invention relate~ to com-
pound~ of the formula (I) in which
m represent~ the number O,
n represents the number~ O or 1,
Ar represents phenyl or pyridyl which ~re option~lly
monosubstituted or di~ubstituted by fluorine and/or
chlorine ~nd/or mono~ub~tituted by m~thyl, tri-
$1uoromethyl, methoxy, difluoromethoxy, trifluoro-
methoxy, methylthio or trifluoromethylthio,
Q represents 1,3,4-oxadiazole-2,5-diyl, 1,3,4-
thiadiazole-2,5-diyl, 1,2,4-oxadiazole-3,5-diyl,
1,2,4-thiadiazole-3,5-diyl, 1,2,4-triazole-3,5-diyl,
1-methyl-1,2,4-triazole-3,5-diyl, 4-methyl-1,2,4-
triazole-3,5-diyl, 1,3-oxazole-2,5-diyl, 1,3-oxa-
zole-2,4-diyl, 1,3-thiazole-2,5-diyl or 1,3-thi-
azole-2,4-diyl,
A repre~ents oxygen,
Xl and x2 represent hydrogen,
Rl represent~ methyl or hydrogen,
R2 represents hydrogen and
Y represents chlorine, hydroxyl, amino, i~oxazoli-
dinyl, or repre~ents in each ca~e optionally F-
and/or Cl-~ubstituted Cl-C~-alkyl~mino, phenylamino,
Cl-C4-alkoxy-carbonyl-Cl-C2-alkylamino, di-(Cl-C3-
~lkyl)amino, Cl-C~-alkyl-~ulphonylamino, phenyl-
~ulphonylamino, Cl-C~-alkoxy~mino, Cl-C~-alkyl-
sulphonylhydrazino, phenylsulphonyl-hydrazinc~Cl-C~-
alkylthioorC1-C4-alkoxy-carbonyl-Cl-C2-alkylthio,or
Le A 27 628 - 14 -
20~077~i
repre~Q~ts th~ group -o-R3 w~ere
R3 repre ent6 in ~ach case optionally Cl- andlor
F-6ubsti~uted Cl-C4-alkYl ~ Cl-C2-alkXY cl C2
alkyl~ C1~C2~alkXY~Cl-C2-alkoxy-methyl, C1-
C2-alkylt.}lio-Cl-C2-alkyl, Cl-C2-alkyl
~ulphinyl-Cl-C2-alkyl, Cl-C2-allylsulphonyl-
Cl-C2-alkyl, b*nzyloxy-Cl-C3-alkyl, benzylthio-
Cl-C3-alkyl, Cl-C"-alkoxy-carbonyl-Cl-C2-alkyl,
1o C1-Cj-alkylamino-carbonyl-C1-C2-alkyl, benzyl,
trimethylsilylmethyl, propargyl or represents
an ammonium, Cl-C3-alkylammonium, ~odium, or
pot~88ium equivalent, or
R3 represents the group -~CH23p-R7 where
R7 represents a heterocyclic r~dical from the series
compri~ing tetrahydrofuryl, i~oxazolyl or pyrazolyl,
and
p represents the numbers 1 or 2.
From the range of the compounds of the formula
(I) which are defined above as being particularly pre-
ferred, those i~omers possible in each case which are
very particularly preferred are those with R-configura-
tion on the carbon atom which ~8 in the ~-position
relative to the carbonyl group.
2s Examples of the compounds of the formula (I) are
listed in Table 1 below.
Xl X2 Rl o
~C I 11
Ar-o-(A)n ~ -I-(E)
L~ A 27 628 - 15 -
20~77~
Table 1: Examples of compounds of the formula (I)
Ar O A n xl x2 R1 R2 m Y
O I H H CH3 H O OH
N___N
CF3 ~ 1 1 O 1 H H CH3 H O OCH3
F
N__-N
~ 1 1 O 1 H H CH3 H O OC2H5
F F
N - N
O 1 H H CH3 H O OH
F Cl
r,c~ N _ N
O 1 H H CH3 H O OCH3
~==~ N N
O 1 H H CH3 H O OC2H5
N N
F ~ ~ O 1 H H CH3 H O OH
N___N
O 1 H H CH3 H O OCH3
Cl
N___N
O 1 H H CH3 H O OC2H5
CF3
Le A 27 62~ - 16 -
20~77~
Table 1 - Continuation
Ar O A n X1 x2 R1 R2 m Y
-
N- N
CF3 ~ ~ ~ O 1 H H CH3 H O OH
r~~~ N N
CF3 ~ I ~ ~ O 1 H H CH3 H 0 OCH3
~=5~ N_----N
O 1 H H CH3 H O OCzH5
~H3
O 1 H H CH3 H O OH
~==~ N - N
N ~ ~ ~ O 1 H H CH3 H O OCH3
N 3 1 1 1 H H CH3 H O OC2H5
r-=~ N N
3 ~ N ~ ~ O 1 H H CH3 H O OH
~ N _ N
Ma ~ 1 1 O 1 H H CH3 H O OCH3
~=-~ N _ N
~ 1 1 O 1 H H CH3 H O OC2H5
OCF3
Le A 27 628 - 17 -
20~077~
Table 1 - Continuation
Ar A n X1 x2 R1 R2 m Y
O~ J~ 1 O 1 H H CH3 H 0 OH
O 1 H H CH3 H 0 OCH3
Cl
N_N
~ J~ O 1 H H CH3 H 0 OCH3
Cl
N
0 1 H H CH3 H 0 OC2H5
N
J~ l~ 1 H H CH3 H O OH
F
N_N
F ~ ~ O 1 H H CH3 H O OC2H5
~--\ N N
F~ J.~ ~1~ o 1 H H CH3 H O OC2H5
N_N
J~ ~ O 1 H H CH3 H O OC2H5
CF3
Le A 27 628 - 18 -
`- 20~077a
Table 1 - Continuation
~r ~ A n x1 x2 Rl R2 m Y
~ ~ 0 1 H H CH3 H O OH
CF3
CF3 ~ ~ 0 1 H H CH3 H O OCH3
N _ N
0 1 H H CH3 H O OCH3
CH3
N _ N
O 1 H H CH3 H O OCzH5
~H3
N N
CH3 ~ ~ 0 1 H H CH3 H O OH
N N
CH3 ~ ~ 0 1 H H CH3 H O OC2H5
~ ~ O 1 H H CH3 H O OC2H5
CH30
O 1 H H CH3 H O OC2H5
SCH3
Le A 27 628 - 19 -
20~77~
Table 1 - Continuation
Ar Q A n ~,~1 x2 Rl R2 m Y
. .
~--''\ N
O 1 H H CH3 H O OCH3
Cl
Cl ~~ O 1 H H CH3 H O OCH3
N 5
O 1 H H CH3 H O OCzH5
CF3
O 1 H H CH3 H O OC3H7
CH3
N S
~~ O 1 H H CH3 H O OH
CH3
3 ~ ~ O 1 H H CH3 H O OCH3
Le A 27 628- 20 -
20~0~7~
Table 1 - Continuation
Ar Q A n Xl x2 Rl R2 m Y
~0
J~ O 1 H H CH3 H O OC2Hs
N
--~hJ~ 1 H H CH3 H O OC2H5
~ N O
CF3~ ~1~ O 1 H H CH3 11 0 OC2H5
f--~ N--O
J~ O 1 H H CH3 H O C2H5
~ N O
CH3~ ~ O 1 H H CH3 H O OH
N
~ ~ O 1 H H CH3 H O OC2H5
Le A 27 628 - 21 -
- 20~077~
Table 1 - Continuation
Ar o A n X 1 x2 R 1 R2 m Y
.
n .~
1`N ~ O 1 H H CH3 H 0 OH
O_N
1~N ~ 1 H H CH3 H O OH
F
O 1 H H CH3 H O OH
r~ O_N
1`N ~ O 1 H H CH3 H O 9CH3
O_N
Cl 1~N ~ 1 H H CH3 H O OCH3
~ 1~N ~ 1 H H CH3 H O OCH3
CF3
~.8~ ~ N
CF3 ~ 1~N ~ I H H CH3 H O OCH3
n ~
Cl ~ ~ ~ O 1 H H CH3 H O OCH3
Le A 27 628 - 22 -
- 20~077~
T~ble_1 - Continuation
Ar o A n ~1 x2 Rl R2 m Y
ICH3
r==~ N----_N
O 1 H H CH3 H O OCH3
.~\ N_----NCH3
O 1 H H CH3 H O OCH3
Cl
O 1 H H CH3 H 0 OCH3
F
N - NCH
~ ~ O 1 H H CH3 H 0 OCH3
r-=~ N NCH3
O 1 H H CH3 H O OCH3
N _ NCH3
O 1 H H CH3 H O OCH3
CF3
~G~ N -NCH3
~ ~ O 1 H H CH3 H O OCH3
CF3
~ N___NCH3
CF3 ~ ~ O 1 H H CH3 H O OCH3
Le A 27 628 - 23 -
` 2~77~
Table 1 - Continuation
Ar t~A n Xl x2 Rl R2 m Y
O 1 H H CH3 H O OCH3
CH3
F ~ O 1 H H CH3 H O OCH3
N__~N
~ ~ O 1 H H CH3 H O OCH3
F CH3
~ ~ O 1 H H CH3 H O OCH3
C1 CH3
Cl ~ ~ O 1 H H CH3 H O OCH3
CH3
3 ~ ~ O 1 H H CH3 H O OCH3
CH3
O 1 H H CH3 H O OCH3
Cl H
Cl ~ N _O 1 H H CH3 H O OCH3
~e A 27 628 - 24 -
20~77~
Table l - Continuation
Ar Q A n Xl x2 Rl R2 m Y
O 1 H H CH3 H O OCH3
F ~ O 1 H H CH3 H 0 OCH3
F ~ O 1 H H CH3 H O OCH3
O 1 H H CH3 H O OCH3
Cl ~ ~ O 1 H H CH3 H O OCH3
~ ~ 1 O 1 H H CH3 H O OCH3
C1
Cl ~ ~ 1 1 H H CH3 H O OCH3
~ ~ 1 O 1 H H CH3 H O OH
CF3 ~ ~ 1 O 1 H H CH3 H O OH
Le A 27 628 - 25 -
2~4~77~
Table 1 - Continuation
Ar O A n X1 x2 R1 R2 m Y
O 1 ~ H CH3 H O OCH3
F ~ ~ o 1 H H CH3 H O OCH3
~ ~T___N
F ~ ~ o 1 H H CH3 H O OCH3
O 1 H H CH3 H 0 OCH3
~--=~ ~ N
O 1 H H CH3 H O OCH3
Cl
N
~ ~ 1 O 1 H H - CH3 H 0 OCH3
Cl
Cl ~ ~ 1 O 1 H H CH3 H O OCH3
O 1 H H CH3 H O OH
CF3
CF3 ~ ~ ~ O 1 H H CH3 H O OH
Le A 27 628 - 26 -
-~ 2~40775
Table 1 - Continuation
Ar ~ A n Xl x2 Rl R2 m Y
~ ~ 1 O 1 H H CH3 H O OCH3
r ~ o 1 H H CH3 H O OCH3
r ~1 1 H H CH3 H O OCH3
O 1 H H CH3 H O OC2H5
Cl ~ ~ O 1 H H CH3 H O OC2H5
Cl ~ ~ O 1 H H CH3 H O OC2H5
Cl ~ ~ 1 O 1 H H CH3 H O OC2H5
~ ~ 1 O 1 H H CH3 H O OC2H5
CF3 ~ ~ 1 1 H H CH3 H O OC2H5
~e A 27 628 - 27 -
~0~077~
Table 1 - Continuation
Ar A n Xl x2 R1 R2 m Y
_
O 1 H H CH3 H O OCH3
N
O 1 H H CH3 H O OCH3
F
N
F ~ ~ 1 H H CH3 H 0 OCH3
O 1 H H CH3 H 0 OC2H5
O 1 H H CH3 H 0 OC2H5
Cl
~ ~ ~ O 1 H H CH3 H 0 OC2H5
Cl
Cl ~ ~ 1 1 H H CH3 H 0 OC2H5
N
O 1 H H CH3 H 0 OC2H5
CF3
N
CF3 ~ ~ ~ 1 H H CH3 H 0 OC2H5
Le A 27 628 - 28 -
204077~
Table 1 - Continuation
Ar A n Xl x2 Rl R2 m Y
N _ N
~ O H H CH3 H 0 OCH3
N--N
_ o H H CH3 H 0 OCH3
N ~
~ ~ S ~ O H H CH3 H 0 OC2H5
Cl
N___N
Cl ~ S ~ H H CH3 H D OC2H5
N _ N
F ~ ~ ~ O H H CH3 H 0 OC2H5
G~ N-- N
F ~ ~ ~ O H H CH3 H C2~5
_ O H H CH3 H 0 OH
r--~ N _ N
~ ~ ~ _ O H H CH3 H 0 9H
CF3
~----~ N___N
CF3~ J~ ~ ~ O H H CH3 H O OH
Le A 27 628 - 29 -
2~Q77~
Table 1 - Continu~tion
Ar a ~ n X1 x2 Rl R2 m Y
N
F ~ ~ - O H H CH3 H O OCH3
--=e\ N M
~ H H CH3 H O OCH3
c~3
N_N
~ H H CH3 H O OC2H5
CH3
~==~ N___N
~ ~ ~ ~ H H CH3 H O OC2H5
CH3
r=-~ N _ N
3 ~ ~ O ~ - O H H CH3 H O OC2H5
~==~ N _ N
~ ~ ~ ~ H H CH3 H O OC2H5
F F
~==~ N N
F ~ ~ ~ - O H H CH3 H O OH
F
r~=~ N___N
CF3 ~ ~ ~ - O H H CH3 H O OH
~.3~
CF3 ~ ~ ~ - O H H CH3 H O OH
Cl
~e A 27 628 - 30 -
20~0775
Table 1 - Continuation
Ar o A n xl x2 Rl R2 m Y
N_N
J~ ~ O 1 H H H H O OC2H5
F
N_N
JJ~ O 1 H H H H O OC2H5
F
N N
O 1 H H H H O OCH3
N N
~ J~ ~ 1 H H H H O OCH3
F F
F~ 1 ,!J~ 1 H H H H O OCH3
CF3~ 1 ~1~ O 1 H H H H O OCH3
O 1 H H H H O OCH3
Cl
N N
O 1 H H H H O OCH3
Cl
N N
C 1~ ~ ~¦~ o 1 H H H H O OCH3
Le A 27 628 - 31 -
204~7~
Table 1 - Continuation
Ar a J~ n Xl x2 Rl R2 m Y
O 1 H H H H O OC2H5
~_~ N~
S~ J'~O~ O 1 H H H H O OC2H5
N_N
J~ ~ O 1 H H H H O OCH3
N U
~ O 1 H H H H O OCH3
F' F
O 1 H H H H O OCH3
N-- N
Q J~ 1 o H H H H O OCH3
Cl
N_N
~ O 1 H H H H O OCH3
Cl
C 1~ J`~ ~1~ O 1 H H H H O OCH3
~e A 27 628 - 32 -
2~077~
Table 1 - Continuation
.
Ar O A n xl x2 Rl R2 m Y
N
F ~ S ~ 1 H H CH3 CH3 0 OH
r~Y~ N- N
~ O 1 H H CH3 H O OH
F S
N _ N
S o 1 H H CH3 H O OH
r--~ N___N
S ~ O 1 H H CH3 H O OC2H5
~----~N___N
F~ S ~ O 1 H H CH3 H O OC2H5
r-=~N _ N
S O 1 H H CH3 H 0 OC2H5
O 1 H H CH3 H O Cl
~ ~ 1 O 1 H H CH3 H O Cl
F
r--e~ N___N
~ ~ S ~ O 1 H H CH3 H O Cl
Le A 27 628 - 33 -
2~77~
Table 1 - Continua~ion
Ar a A n Xl x2 Rl R2 m Y
N - N
~ ~ S ~ O 1 H H CH3 H O OnC3H7
F
~==~ N___N
O 1 H H CH3 H O OnC3H7
F
N~_-N
~ ~ S ~ O 1 H H CH3 H O OnC3H7
N-__N
S ~ O 1 H H CH3 H O OiC3H7
F
~ l 6 ~ I H H CH3 H O OiC3H7
N- N
~ 1 1 O l H H CH3 H O OiC3H7
N - N
F ~ S ~ 1 H H CH3 H O OnC4H9
~==~ N N
30 ~ ~ ~ O 1 H H CH3 H O OnC4H9
N
~ ~ S O 1 H H CH3 H O OnC4H9
Le A 27 628 - 34 -
2~4~775
Table 1 - Con~inuation
Ar Q A n Xl ~2 Rl R2 m Y
. .
N___N
~ 1 1 0 1 H H CH3 H 0 O~C4H9
F
r==~ N___N
0 1 H H CH3 H 0 OsC4H9
F
F ~ 1 1 0 1 H H CH3 H 0 O~C4H9
N--_--N
F ~ ~ 0 1 H H CH3 H 0 OCH2-C--CH
~ 1 ~ 0 1 H H CH3 H 0 OCH2-CECH
N ~ .
~ 1 1 0 1 H H CH3 H 0 OCH2-C-CH
S
~ ~ 0 1 H H CH3 H 0 OCH2C02C2H5
~ 1 ~ 0 1 H H CH3 H 0 OCH2C02C2H5
F
N
~ 1 1 0 1 H H CH3 H 0 OCH2C02C2H5
Le A 27 628 - 35 -
20~77~
Table 1 - Continuation
Ar a A n Xl x2 R~ R2 m Y
-
~ 1 1 o 1 H H CH3 H O CH2c6H5
F 'll ~ O 1 H H CH3 H O OCH2C6H5
N_N
,!J~ 1 H H CH3 H O OCH2C6H5
F 1 ~ O 1 H H CH3 H O OCH20CH2CH20CH3
F 1 ~ O 1 H H CH3 H O OCH20CH2CH20CH3
F~ 1 1 1 H H CH3 H O OCH20CH2CH20CH3
F 1 ~ O 1 H H CH3 H O OCH2CH20CH2CH3
F ~ 1~ 0 1 H H CH3 H O OCH2CH20CH2CH3
F~ 1 JJ~ o 1 H H CH3 H O OCH2CH20CH2CH3
Le A 27 628 - 36 -
-
- 20~07~
Table 1 - Continuation
~r a A n Xl x2 Rl R2 m Y
-
N N
S ~ O 1 H H CH3 H O OCHzCH20CH2C6H4-4C
F
F 1 S ~ o 1 H H CH3 H O ocH2cH2ocH2c6H4-4
F ~ 5 1 O 1 H H CH3 H O OCH2CH20CH2C6H4-2F
~==~ N
S ~ 1 H H CH3 H O OCH2CH20CH2C6H4 2F
r~--~ N
F~ S ~ 1 H H CH3 H O~H2CH25CH2C6H5
F ~ S ~ 1 H H CH3 H CH2cH25cH2c6H5
r----~ N
S O 1 H H CH3 H O OCHtCH3)0CH2C6H5
F
N___N
S ~ 1 H H CH3 H O OCH(CH3)0CH2C6H5
r~.~ N___N
S ~ O 1 H H CH3 H O OCH2CH2CH20CH2C6H5
r----~ N___N
O 1 H H CH3 H O OCH2CH2CH20CH2C6Hs
F
~A 27.628 - 37 -
20~77~
Table 1 - Continuation
Ar /~ n Xl x2 Rl R2 m Y
N N 1=
F ~ ~ O 1 H H CH3 H O OCH2-N~
F~ 1 1 1 H H CH3 H O OCH2-
F ~ ~ O 1 H H CH3 H o OCH2CH2-
F 1 ~ 0 1 H H CH3 H O OCH2CH2-N ~
0 1 H H CH3 H O OCH2 ~ CH3
N ~ ~ CH3
0 1 H H CH3 H O OCH
~O~
o 1 H H CH3 H O N J
F
~O~
r_e~ N N N
~ 1 1 0 1 H H CH3 H O
Le A 27 62B - 38 -
204~77~
Table 1 - Continuation
Ar a ~ n xl x2 Rl R2 m Y
0 1 H H CH3 H O NH2
N_N
O 1 H H CH3 H O NH2
F
O 1 H H CH3 H O NHS02CH3
F
N___N
O 1 H H CH3 H O NH502CH3
N
F ~ ~ O 1 H H CH3 H O OCH25i(CH3)3
N M
F ~ ~ O 1 H H CH3 H O OCH25i(CH3)3
O 1 H H CH3 H O OCH
~ 1 1 O 1 H H CH3 H O OCH
le A 27 628 - 39 -
2 ~ 7 ~
Table 1 - Continuation
Ar O A n xl x2 Rl RZ m Y
O 1 H H CH3 H O NHCHzCOzC2H5
r_ ~N
1 H H CH3 H O NHCH2CO2C2Hs
N M
O 1 H H CH3 H O ONa
F
F~ 1 Jl~ 1 H H CH3 H O ONa
N- N
J~ ~ O 1 H H CH3 H O ONH4
O 1 H H CH3 H O ONH4
Le A 27 628 - 40 -
20~077~
If, for example, 2-chloro-5-(4-fluoro-phenyl)-
1,3,4-oxadiazole and methyl 2-(4-hydroxy-phenoxy)-pro-
pionate are u6ed a6 ~tarting ~ub~tances in proce~ (a)
according to the invention, the cour3e of the reaction
S can be repre~ented by the following equation:
N--N ~
HO~O - Cl I - C - OCH 3
C 1 CH3
N--N
-~C~
O~O-CH-C-OCH3
CH3
If, for example, 3-(4-hydroxy-phenoxy)-5-t4-
trifluoromethyl-phenyl)-1,2,4-thiadiazole and ~thyl 2-
methylsulphonyloxypropionate are used as starting ~ub-
6tance~ in proce~s (b) according to the invention, the
course of the reaction can be represented by the fol-
lowing equation:
~e A 27 628 - 41 -
204~7~
.
O ~ OH O
~==~ N ~ ll
F3C ~ S- N ~ H3C-SO2-O-lH-c-oc2H5
CH3
o
) F3C ~ ~ CH3
-H3C-S03H S--N
Formnla (II) provides a general definition of the
aryl compounds to be u~ed as starting substances in
proce~s (a) according to the invention for the prepara-
tion of compounds of the formula (I).
In formula (II), Ar and Q preferably, or in
particular, have those meanings which have already been
indicated above in connection with the descriptio~ of the
compounds of the formula (I) according to the invention
as being preferred, or particularly preferred, for Ar and
Q-
X3 prefer~bly represents halogen, Cl-C4-alkylthio, Cl-C4-
alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkyl-
sulphonyloxy, phenylffulphonyloxy or tolyl~ulphonyl-
oxy, in particular fluorine, chlorine, bromine or
methylsulphonyl.
~ he starting substances of the formula (II) are
known and/or can be prepared by proces~e~ known per se
(cf. J. Med~ Chem. 31 ~1988), 906-913; US Patent
4,454,147; US Patent 3,959,301; J.Prakt.Chem. 315 (1973),
Le A 27 628 - 42 -
20407~a
185-188; FR-A 1,575,544; J. ~et. Chem. 10 (1973),
611-622, and the preparation example~).
Formula (III) provides a general definition of
the hydroxy- and mercaptoaryloxycarbonyl compound~
S furthermore to be used as ~tarting substances in process
(a) according to the invention for the preparation of
compounds of the formula (I).
In formula (III), m, E, ~1, x2, R1, R2 and Y
preferably, or in particular, h~ve those ms~ning~ wh~ch
have already been indicsted above ~n connection wlth the
description of the compounds of the formul~ (I) nccording
to the invention as being preferred, or particularly
preferred, for m, E, X~, S2, R1, R2 and Y.
Al represents oxygen or sulphur.
The ~tarting substances of the formula (III) are
known and/or can be prepared by processes known per se
(cf. EP-A 82,413; EP 180,126).
Formula ~IV) provide~ a general definition of the
phenol derivatives to be used as starting substances in
process (b) according to the invention for the prepara-
tion of compounds of the formula (I).
In formula (IV), n, Ar, Q, A, Xl and x2 pre-
ferably, or in particular, have those meanings which have
already been indicated above in connection with the
description of the compounds of the formula (I~ according
to the invention as being preferred, or part~cularly
preferred, for n, Ar~ Q, A, X1 and ~Z.
Examplefi of the starting ~ubstances of the
formula (IV~ are the compounds in Table 1 in which the
radical
Le ~ 27 628 - 43 -
~0~-077~
Rl o
11
-O-C-(E)m-C-Y
(according to formula (I)) of the~e compounds i~ replaced
by the hydroxyl group.
The phenol derivatives of the formula (IV) were
hitherto not known from the lit~rature and are a ~ub~ect
of the present Patent Application.
In the event that, in formula (IV), n repre~ents
the number 1 and A represants oxygen or sulphur, the new
phenol derivatives of the formula (IV) ~re obtained when
aryl compounds of the formula (II)
Ar-Q-X3 (II)
in which
Ar, Q and X3 h~ve the abovementioned meanings
are reacted with phenols of the formula (VI)
xl x2
H-Al ~ (VI)
in which
X1 ~nd x2 have the abovementioned meanings and Al repre-
~ ents oxygen or sulphur,in the presence of an acid acceptor, such a8, forexample, potassium hydroxide, and in the pre~ence of a
diluent such as, for example, dimethyl sulphoxide, at
temperatures between O~C and 150-C (cf. the preparation
e A 27 628 - 44 -
~ 204077a
examples).
In the event that, in foxmula (IV), n represents
the number 1 and A represents methylene, or n repre~ents
the number 0, the new phenol derivatives of the formula
S (IV) are obtained when aryl compound6 of the formula
(VII)
Ar Ql (VII)
in which Ar has the abovementioned meaning and Q~ repre-
sents an organic radical having one or two carbon atoms,
for example CN, COOH, COCl, CONH2, CSNH2, CONHNHz, COOCH3,
C ( NH ) NH2 ~ C ( NH ) NHNH2 ~ COCH2Cl or COCH2Br, are reacted with
phenols of the formula (VIII)
xl x2
a2-(cH2)n ~ H (~III)
in which n, X1 and x2 have the abovementioned meanings and
Q2 represents sn organic radical having one or two carbon
atoms, for example CN, COOH, COCl, CONH2, CSNH2, CONHNH2,
COOCH3, C(NH)NH2, C ( NH ) NHNH2 ~ COCH2Cl or COCH2Br.
In this context, Ql in formula (VII) and Q2 in
formula (VIII) are cho3en such that the heterocycle Q can
be constructed with them by processes known per se (cf.
the preparation examples).
Formula ~V) provides a general definition of the
carboxylic acid derivatives furthermore to be used as
starting substances in process (b) according to the
invention for the preparation of compounds of the formula
(I).
~e A 27 628 - 45 -
20~77~
In formula (V), m, E, R1, R2 and Y preferably, or
in particular, have thoGe meaninq~ which have already
bQen indicated above in connection with the description
of the compounds of the formula (I) according to the
invention as being preferred, or particularly preferred,
for m, E, R1, R2 and Y;
X~ prefsrably represents chlorine, bromine, iodine,
optionally fluorine- or chlorine-substituted C~-C~-
alkylsulphonyloxy or optionally fluorine-,
chlorine-, bromine- or methyl-substituted phenyl-
sulphonyloxy, in particular chlorine, bromine,
methyl~ulphonyloxy, phenylsulphonyloxy or 4-methyl-
phenylsulphonyloxy.
Ex~mples of the compounds of the formula (V)
which may be mentioned are:
the methyl, ethyl, propyl, i~opropyl, butyl, isobutyl and
sec-butyl esters of ~-chloro-, ~-bromo- and ~-iodo-
propionic acid, and the methyl, ethyl, propyl, butyl,
isopropyl, i60butyl and sec-butyl esters of ~-methyl-
sulphonyloxy-, ~-ethylsulphonyloxy-, ~-propylsulphonyl-
oxy-, ~-butylsulphonyloxy-, ~-trifluoromethylsulphonyl-
oxy-, ~-phenylsulphonyloxy- and ~-(4-~ethyl-phenyl)-
sulphonyloxy-propionic acid.
In the event that R1 f R2, the abovementioned
compounds of the formula (v) are understood as meaning in
each case the R isomer6, the S isomers and the racemic
mixtures of these isomers.
The starting ~ub~tance~ of the formula (V) sre
known and/or can be prepared by procs~es known per se
(cf. DE-OS (German Published Specification) 2,758,002,
Le A 27 628 - 46 -
--- 204077~
DE-OS (German Published Specification) 2,854,542).
Processes ~a) and (b) according to the invention
for the preparation of the new axyloxycarbonyl compounds
of the formula (I) are preferably carried out using
diluents. Diluent~ which are suitable for thi~ purpose
are virtually all inert organic solvent~. These pre-
ferably include aliphatic and aromatic, optionally
halogenated hydrocarbons ~uch a~ pentane, hexane, hep-
tane, cyclohexane, petroleum sther, benzine, ligroin,
benzene, toluene, ~ylene, methylene chloride, ethylene
chloride, chloroform, carbon tetrachloride, chlorobenz2ne
and o-dichlorobenzene, ethers such a~ diethyl ether,
dibutyl ether, glycol dimethyl ether and diglycol
dimethyl ~ther, tetrahydrofuran and dioxane, ketones such
as ncetone, methyl ethyl ketone, methyl isopropyl ketone
and methyl isobutyl ketone, esters such as methyl acetate
and ethyl acetate, nitriles ~uch as, for ex~mple, aceto-
nitrile and propionitrile, amides such as, for ex~mple,
dimethylformamide, dimethylacetamide and N-methyl-pyrro-
lidone, and dimethyl sulphoxide, tetramethylene ~ulphoneand hexamethylphosphoric triamide.
Acid acceptors which can be employed in processes
(a) and (b) according to the invention are all acid-
binding agents which can customarily be used for reac-
25 - tions of this type. The following are preferably
suitable: alkali metal hydroxides such as, for example,
~odium hydroxide and potassium hydroxide, alkaline earth
metal hydroxides ~uch as, for example, calcium hydroxide,
alkali metal carbonates and alkali metal alcoholates such
as sodium carbonate, potas~ium carbonate, sodium tert-
Le A 27 628 - 47 -
204077~
butylate and potassium tert-butylate, furthermore ali-
phatic, aromatic or heterocyclic amines, for example
triethylamine, trimethylamine, d;Lmethylaniline, dimethyl-
benzylamine~pyridine~l~5-diazabicyclo-[4~3~o]-non-s-ene
(DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and
1,4-diazabicyclo-[2,2,2]-octane (DABC0).
When carrying out processes (a) and (b) according
to the invention, the reaction temperatures can be varied
within a substantial range. In general, the proc~sses are
carried out at temperatures between ODC and 200C,
preferably at temperatures between 20-C and 150C.
Processes (a) and (b) according to the invention
are generAlly carried out under atmospheric pressure.
However, it i~ also possible for the proces~ to be
carried out under increased or reduced pre~sure.
For carrying out processes (a) and (b) according
to the invention, the starting substances required in
each case are generally employed in approximately egui-
molar amounts. However, it i8 also po~sible to u~e a
larger excess of one of the two components employed in
each case. In general, the reactions are ~arried out in
a su$table diluent in the presence of an acid acceptor,
and the reaction mixture i~ stirred for several hours at
the specifically required temperature. Working-up in
process (a) and (b) according to the invention i~ carried
out in each case by customary methods.
The ~ctive compounds accord$ng to the invention
c~n be used as defoliant , desiccants, agents for des-
troying broad-leaved plants and, especially, as weed-
killers. By weeds, in the broadest ~ense, there are to be
Le A 27 628 - 48 -
204~77~
understood all plants which grow in locations where they
are undesired. Whether the substancQs according to the
invention act a~ total or selective herbicide6 depends
essentially on the amount u6ed.
The active compounds according to the invention
can be used, for example, in connection with the fol-
lowing plant6s
Dicotyledon weeds of the genera: Sinapis,
Lepidium, Galium, Stellaria, Matricaria, Anth~mis,
Galinsoga, Chenopodium, Urtica, S~n~cio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,
Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanu~,
~orippa, Rotala, Lindernia, ~amiu~, Veronica, Abutilon,
Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Trifolium, Ranunculus and Taraxacum.
Dicotyledon cultures of the genera: Gossypium,
Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,
Ipomoea, Vicia, Nicotiana, Lycoper~icon, Arachis,
Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledon weeds of the genera: Echinochloa,
Setaria, Panicum, Digitaria, Phleum, Poa, Fe~tuca,
Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperu~,
Sorghum, Agropyron, Cynodon, ~onochoria, ~imbristyl i8,
Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum,
Sphenoclea, Dactyloctenium, Agro~ti~, Alopecurus and
Apera.
Monocotyledon c~ltures of the qenera: Oryza,
Zea, Triticum, Hordeum, Avena, Secal~, Sorghum, Panicum,
Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds accor-
Le A 27 628 _ 49 _
-" 20~077~
ding to the invention i6 in no way re~tricted to these
genera, but ~180 extends in the ~ame manner to other
plants.
The compounds are suitable, depending on the
concentration, for the total combating of weeds, for
example on industrial terrain and rail tracksO ~nd on
paths and square~ with or without tree plantings.
Equally, the compounds can be employed for combating
weed~ in perennial cultures, for example affore~tations,
decorative tree plantings, orchards, vineyards, citrus
groves, nut orchards, banana plantations, coffee planta-
tions, tea plantations, rubber plantations, oil palm
plantations, cocoa plantations, soft fruit plantings and
hopfields, on lawn, turf and pasture-land, and for the
selective combating of weeds in annual cultures.
The compounds of the formula (I) according to the
invention are particularly suitable for selectively
combatin~ monocotyledon weeds in ~onocotyledon and
dicotyledon crops using the pre-emergence and post-
emergence method.
The active compounds can be converted into thecustomary formulations, such as solutions, emulsions,
wettable powders, suspensions, powders, dusting ~gents,
pastes, soluble powders, granules, ~uspension-emulsion
concentrates, natural and synthetic materials impregnated
with active compound, and very fine capsules in polymeric
6ubstances.
The~e formulations are produced in a known
manner, for example by mixing the active compounds with
extender~, that is liquid solvents ~nd/or solid carriers,
Le A 27 628 - 50 -
- 20~0~7~
optionally with the use of ~urface-active agents, that is
emulsifying agents and/or dispersing agent~ and/or foam-
forming agents.
In the case of the use of water as an extender,
organic solvent~ can, for example, also be u~ed as
auxiliary ~olvent~. As liquid solvents, there nre
suitable in the main: aromatics, such as xylene, toluene,
or alkylnaphthalenes, chlorina~ed aromatics and chlorina-
ted aliphatic hydrocarbons, such aB chlorobenzene~,
chloroethylenes or methylene chloride, aliphatic hydro-
carbons, such as cyclohexane or paraffin~, for ex~mple
petroleum fractions, mineral and vegetable oils, alco-
hols, such aa butanol or glycol as wall as their ethers
and e3ter , ketones, such as acetone, methyl ethyl
ketone, methyl i~obutyl ketone or cyclohexanone, ~trongly
polar solvent6, ~uch as dimethylformamide and dimethyl
sulphoxide, as well as water.
A~ solid carriers there are suitables for example
ammonium ~alts and ground natural minerals, such as
kaolins, clays, talc, chalk, quartz, attapulgitei mont-
morillonite or diatomaceous earth, and ground synthetic
minerals, such as highly disperse silica, alu~ina and
~ilicates, as solid carrier6 for granulos there are
~uitable: for example crushed and fractionated natural
rock~ such a~ calcite, marble, pumice, sepiolite and
dolomite, as well as ~ynthetic granules of inorganic and
organic meal~, and granules of organic material such a~
sawdust, coconut shells, maize cobs and tobacco ~talks;
as e~ulsifying and/or foam-forming agents there ~re
suitables for example non-ionic and anionic ~mulqifiers,
Le A 27 628 - 51 -
- 204077~
~uch as polyoxyethylene fatty acid esters, polyoxy-
ethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, ~lkyl~ulphonates, alkyl ~ulphate~,
arylsulphonates as well a8 albumen hydroly~is products;
as dispersing agents there are suitable: for 2xsmple
lignin-sulphite waste liguors and methylcellulose.
Adhesives such as carboxymethylcellulose and
natural and synthetic polymer6 in the form of powders,
qranules or latexes, ~uch as gum arabic, polyvinyl
alcohol and poly~inyl acetate, as well ns natural phos-
pholipid~, such as cephalin~ and lecithins, and synthetic
phospholipids, can be used in the formulation~. Further
additives can be mineral and vegetable oils.
It iB possible to u~e colornnts ~uch as inorganlc
pigments, for example iron oxide, titanium oxide and
Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo dyestuffs and metal phthalocyanine dye-
stuffs, and trace nutrients such as salts of iron,
manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1
and 95 per cent by weight of active compound, preferably
between 0.5 and 90%.
For combating weeds, the active compounds accor-
ding to the invention, as such or in the form of their
formulations, can ~180 be used as mixture6 with known
herbicides, finiched formulations or tank mixes being
possible.
Suitable herbicides for the mixture~ are known
herbicides, ~uch as, for example, 1-~mino-6-ethylthio-3-
(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione
Le A 27 628 - 52 -
- 2040775
(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N~-dimethylurea
(NETABENZTHIAZURON) for combating weeds in cereals; 4-
amino-3-methyl-6-phenyl-l~2~4-triazin-s(4H)-one
(METAMITRON) for combating weeds in sugar beet ~nd 4-
amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-
5(4H)-one (NETRIBUZIN) for combating weeds in ~oya beans;
furthermore al 80 2,4-dichlorophenoxyacetic acid (2,4-D);
4-(2,4-dichlorophenoxy)-butyric acid (2,4-DB); 2,4-
dichlorophenoxypropionic acid (2,4-DP); 5-(2-chloro-4-
trifluoromethyl-phenoxy)-2-nitro-benzoic acid
(ACIFLUORFEN); 2,6-diethyl-N-methoxy-methylchloro-
acetanilide (ALACHLOR); 4-amino-benzenesulphonyl methyl-
carbonate (ASULAM); 2-chloro-4-ethylamino-6-i~opropyl-
amino-l,3,5-triazine (ATRAZINE); methyl 2-1[t[~4,6-
dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino] -8ul-
phonyl~-methyl]-benzoate (BENSULFURON); 3-isopropyl-
2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE);
methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate(BIFENOX);
3,5-dibromo-4-hydroxy-benzonitril; (BROMOXYNIL); N-
(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)-acetamide
(BUTACHLOR); 5-amino-4-chloro-2-phenyl 2,3-dihydro-3-
oxypyridazine (CHLORID~ZON); ethyl 2-~l(4-chloro-6-
methoxy-2-pyrimidinyl)-~minocarbonyl]-aminosulphonyl}-
benzoate (CHLORINURON); N-(3-chlorophenyl)-isopropyl
c~rbamate (CHLORPROPHAN); 2- chloro-N-{[(4-methoxy-6-
methy~ 3~5-triazin-2-yl)-amino]-carbonyl}-benzene
sulphon~mide (CHLORSULFURON); N,N-dimethyl-N~-(3-chloro-
4-methylphenyl)-urea (CHLORTOLURON); 3,6-dichloro-2-
pyridinecarboxylic acid (CLOPYRALID); 2-chloro-4-ethyl-
amino-6-(3-cyanopxopylamino)-1,3,5-triazine (CYANAZINE);
Le A 2? ~
2040775
2-[(2-chlorophPnyl)-methyl]-4,4-dimethylisoxazolidin-3-
one (DINETHAZONE); S-ethyl N,N-di-n-propyl-thiocarbami-
date (EPTA~E); 4-amino-6-t-butyl-3-ethylthio-1,2,4-
triazin-5(4H)-one (ETHIOZIN); N,N-dimethyl-N~-(3-tri-
fluoromethylphenyl)-urea (FLUOMETURON); l-methyl-3-
phenyl-5-(3-trifluoromethylphenyl)-4-pyridone
(FLURIDONE); [(4-hmino-3,5-dichloro-6-fluoro-2-pyri-
dinyl)-oxy]-acetic acid or its l-methylheptyl ester
(F~UROXYPYR).; 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-
methylsulphonyl-2-n$trobenzamide (FONESAFEN); 3-cyclo-
hexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione
(HEXAZINONE);methyl2-14,5-dihydro-4-methyl-4-(l-methyl-
ethyl)-5-oxo-lH-i~idazol-2-yl]-4(5)-methylbenzoate
(IMAZAMETHABENZ); 2-[5-methyl-5-(1-methylethyl)-4-oxo-2-
Lmidazolin-2-yl~-3-quinolinecarboxylic acid (IMAZAQUIN);
2-t4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(lH)-imidazol-
2-yl]-5-ethylpyridine-3-carboxylic acid (I~AZE~HAPYR);
3,5-diiodo-4-hydroxybenzonitril (IOXYNIL); N,N-dimethyl-
N~-(4-isopropylphenyl)-urea (ISOPROTURON); 2-ethoxy-1-
methyl-2-oxo-ethyl 5-[2-chloro-4-(trifluoromethyl)-
phenoxy]-2-nitrobenzoate (LACTOFEN); (2-methyl-4-chloro-
phenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy)-
propionic acid (~CPP?; N-methyl-2-(1,3-benzothiazol-2-
yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethyl-
phenyl)-N-[(lH)-pyrazol-l-yl-methyl]-acetamide
(METAZACHLOR); 2-ethyl-6-methyl-N-(l-methyl-2-methoxy-
ethyl)-chloroacetanilide(METOLACHLOR);2-{tt(t4-methoxy-
6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-
sulphonyl}-benzoic acid or its methyl e~ter
(METSULFURON); S-ethyl N,N-hexamethylenethiolcarbamate
Le A 27 628 _ 54 _
2~Q77~
( MOLINATE ); 1- (3-trifluoromethyl-phenyl)-4-methylamino-
5-chloro-6-pyridazone (NORFLURAZON); 4-(di-n-propyl-
amino)-3,5-dinitrobenzenesulphonamide (ORYZALIN); 2-
chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-phenyl
ether ~O~YFLUORFEN); N-(1-ethylpropyl)-3,4-dimethyl-2,6-
dinitroaniline tPENDIMETHALIN); 3-(ethoxycarbonyl2mino-
phenyl) N-(3'-methylphenyl)-carbamate (PHENMEDIPHAM); 2-
chloro-N-isopropylacetanilide (PROPACHLOR); isopropyl N-
phenyl-cnrba~ate (PROPHAN); 0-(6-chloro-3-phenyl-pyri-
dazin-4-yl) S-octyl thiocarbonate (PYRIDATE); 2-chloro-
4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZINE~; 2,4-bis-
[N-ethylamino]-6-methylthio-1,3,5-triazine (SIMæTRYNE);
4-ethylnmino-2-t-butylamino-6-methylthio-s-trinzine
(TERBUTRYNE); methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-
triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl~-thio-
phene-2-carboxylate (THIAMETURON); S-[(4-chlorophenyl)-
methyl] N,N-diethylthiocarbamate (THIOBENCARB); S-(2,3,3-
trichloroallyl) N,N-diisopropylthiocarbamate (TRIALLATE)
and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline
(TRIFLURALIN). Surprisingly, some mixtures also exhibit
a synerqistic action.
Mixtures with other known active compounds, such
as fungicides, insecticides, acaricides, nematicides,
bird repellants, plant nutrients and agents which improve
80il structure, are also po~sible.
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
solutions, suspensions, emulsions, powders, pastes and
granules. They are used in the custo~ary manner, for
Le A 2? 628 - 55 -
-- 20~077~
example by watering, praying, atomizinq or scattering.
The active compounds according to the invention
can be applied either before or after emergence of the
plants.
They can al~o be inco~porated into the soil
before sowing.
The amount of active compound used can vary
within a substantial range. It depends es~entially on the
nature of the desired effect. In general, the ~mount~
used are between 0.001 and 10 kg of active compound per
hectare of ~oil ~urface, preferably between 0.005 and
5 kg per ha.
The preparation nnd use of the nctive compounds
according to the invention cnn be ~een from the following
examples.
Preparation Example~:
Example 1
N--N
~ S ~ ~ _CIH3
C02CH3
(Proce~s (a~
21.5 g (0.1 mol) of 2-chloro-5-(2-fluorophenyl)-
1,3,4-thiadiazole are dissolved in 1000 ml of aceto-
nitrile. After 30 g of potassium carbonate ~nd 21.6 g
(O.11 mol) of (+)-methyl 2-(4-hydroxyphenoxy)-propionate
have been added, the mixture i~ refluxed for 36 hours.
Le A 27 628 - 56 -
20~77~
After the mixture has cooled, the acetonitrile is removed
$n vacuo, and the residue is partitioned between
dichloromethane and water. The organic phase is separated
off and washed in succes~ion with dilute sodium hydroxide
solution and water, dried and concentrated. The resulting
crude product i~ purified by column chromatography on
silica gel (dichloromethane as the eluent).
This gives 22.6 g (60%) of (~)-~ethyl 2-(4-t5-(2-
fluorophenyl)-1,3,4-thiadiazol-2-yloxy]-phenoxy)-pro-
pionate in form of a yellow solid of melting point 45-C.
~xample 2
Cl
r----~ N----N
¦ (R)
s~ ~_~ *
O~C-CH-COOC2H5
CH3
(Process (b))
A mixture of 15.2 g ~0.05 mol) of 2-(4-hydroxy-
phenoxy)-5-(2-chloro-phenyl)-1,3,4-thiadiazole, 6.9 g of
potassium carbonate and 9S ml of acetonitrile i~ heated
to 60C, and the solution of 13.6 g (0.05 mol) of (S)-
ethyl ~-(4-methyl-phenyl)-sulphonyloxy-propionate in
20 ml of acetonitrile iB added dropwise with stirring.
The reaction mixture i~ then refluxed for 5 hours
and sub6eguently concentrated. The product is extracted
from the residue using chloroform, the organic phsse i~
shaken in uccQssion with 2N sodium hydroxide solution,
wster, 2N hydrochloric acid and again with water, dried
Le A 27 628 - 57 -
2~077~
with sodium ~ulphate and filtered. The solvent i~ care-
fully removed from the filtrate by distillation in a
water pump vacuum.
This gives 14.5 g (72% of theory) of ~R)-ethyl 2-
(4-t5-(2-chloropheny~ 3~4-thiadiazol-2
phenoxy)-propionate of refractive index n20 ~ 1.5974.
For example, the compounds of the formula (I)
listed in Tables 2 below can slso be prepared analogously
to Examples 1 and 2 and following the general description
of the preparation processe~ accordinq to the invention.
xl X2 Rl 11
Ar-0-(A)r, ~ O-l*-(E)m-C-Y ~I)*
Le A 27 628 - 58 -
2~77~
J ~ ~ ~ u
t ~ _ ~ o ~r `D
. .. .;
, E ~ E E E E
:~: N ~ (~ ~ N
El O O O O O O N
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O :~: 2~ X ~: S
O ~ T
- 2
U C _ _ O _ O O
O O O I O I I g
D ~ ~( ~ =( ~ o e
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Le A 27 628 - 59 -
20~07~i
a o~ ~
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u)
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o o o o o
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Le A 27 628 - 61 -
204~7~i
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Le A 27 628 - 63 -
`` 204077~
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--65--
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204077a
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204077~
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204~77~
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2040775
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--76--
Le ~ 27 628
204077~
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3~e A 27 628 77~
204077~
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e A 27 628 -78-
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--79--
Le ~27 628
.. .
204077~
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~e A 27 628 -80-
20~77~
Starting substance6 of the formula (II):
Example (II-l~
F
Cl
StaGe 1:
~--< N--N
~S~
NH2
To a raaction solution which had been prepared by
adding 30.4 g (1/3 mol) of thiosemicarbazide in portions
to 175 g of 70% strength sulphuric acid, are added 40.4 g
(1/3 mol) of 2-fluorobenzonitrile nt a temperature of
50-60C. The rate ~t which the nitrile is added dropwi~e
is chosen in such a way in this procedure that the
internal temperature does not exceed the above~entioned
range. Stirring is continued for 14 hour~ ~t 55-60-C, the
batch is allowed to cool and then poured into 2000 ml of
ice-water, and the mixture i~ rendered neutral by stir-
ring in sodium hydroxide solution. The solid which has
separ~ted is filtered off with suction, washed in succes-
sion with water, petroleum ether and a little ether, and
dried.
This gives 42.8 g (66~) of 2-amino-5-(2-fluoro-
phenyl)-1,3,4-thiadiazole of melting point > 210-C
(decomposition).
Le A 27 628 -81-
-
`- 204~77~
Stage 2s
19.5 g (0.1 ~ol) of 2-amino-5-(2-fluorophenyl)-
1,3,4-thiadiazole together with 3.2 g of copper powder
~nd 0.1 g of coppar(I) chloride are introduced ~t -lO-C
S ~nto 250 ml of concentrated hydrochloric acid. A~ this
temperature, a solution of 13.8 g (O.2 mol) of sodium
nitrite in 40 ml of water i~ added dropwi~e in the cour~e
of 30 minute~. When the addition has ended, stirring iB
continued for 2 hours at O-C ~nd for 2 more hours at
50-C, and the batch i8 then transferred into 3000 ml of
ice-water. The product which precipitate~ i8 filtered off
with suction, washed with water until neutral and dried.
Thi~ gives 18.6 g (87~) of yellow 2-chloro-5-~2-
fluorophenyl)-1,3,4-thiadiazole of melting point 103C.
~xample ~II-2)
Cl
F3C ~ ~
9.3 q (O.05 mol) of perchloromethylmercaptan are
added at 0C in the cour~e of 30 minute~ to 11.2 g
(0.05 mol) of 4-trifluoromethylbenzamidine hydrochloride
in 100 ml of dichloromethane. Stirrinq ~8 continued for
30 minutes at 0C, a solution of 6.0 g (0.15 mol) of
Le A 27 62~ -82-
-- 204077~
~odium hydroxide in 20 ml of water is then added in the
course of 60 minutes, and the mixture i~ gtirred for a
further 90 minutes with ice-cooling. After this, the
organic phase is separated off, washed with water, dried
and concentrated in vacuo.
Thi~ gives 4.5 g (34~) of 3-(4-trifluoromethyl-
phenyl)-5-chloro-1,2,4-thiadiazole as a yellow solid.
lH-NMR (300 MHz, DMSO-d6)s ~ - 7.94 and 8.37
(AA'BB' ~ystem).
Example (II-3)
,CH3
Cl ~ Cl
21 g (0.1 mol) of 2-methyl-5-(4-chlorophenyl)-
1,2,4-triazolin-3-one are refluxed for 7 hours in 150 ml
of phosphorou6 oxychloride with the addition of ~ cata-
lytic amount of triphenylphosphine oxide. The excess
15phosphorous oxychloride is distilled under reduced
pressure, and the liquid residue is stirred into 300 ml
of ice-water. The precipitate is filtered off with
~uction, ~ashed with ice-water and dried in a desiccator.
This gives 15.1 g (66% of theory) of 2-methyl-3-
20chloro-5-(4-chlorophenyl)-1,2,4-triazole as colourless
cry3tsls of melting point 153-155C.
For exa~ple the compounds of the formula (II)
li~ted in Table III below can also be prepared an~lo-
gously to Examples (II-l) to (II-3).
AR-Q-X3 (II)
Le A 27 628 -83-
20~077~
Table 3: Examples of the starting subgtances of the
formula (II)
Example Ar a X3 Physical Data
No. Cl
II-4 ~ 1 5 ~ Cl mp.:82C
II-5 ~ ~ ~ Cl mp.:40C
F ~ ~ 7,1-7,3
II-6 ~ ~ ~ Cl 7 4-7 55,
~ r 7.19,
II-7 ~ 1 Cl 7,46, 7.94,
F ~ N`S 8,04
II-8 ~ ~ 1 Cl ~ ~ 7.16,
N~S 8,25
~T_-_N ~ ~ 7,35-7,50,
II-9 ~ ¦¦ 1 Cl 8,13, 8,25
Cl
`. N ~ s 7,61,
II-10 ~ N~S ~ Cl 7 75, 8,43,
F3~
The ~ values are obtained by ~H-NNR ~easurement a
300 MHz in CDCl3.
Le A 27 ~28 -84-
2~40775
Startina sub~tance~ of the formula (IV):
Example (IV-1~
~S~
A mlxture of 26.4 g (0.24 mol) of hydroquinone,
100 ml of dimethyl sulphoxide and 7.6 g of potas~ium
hydroxide powder (88% ~trength, 0.12 mol of ~OH) i8
stirred for 30 minute6 at 50C. A ~olution of 23.1 g
(0.10 mol) of 2-chloro-5-(2-chlorophenyl~ 3~4-thia-
diazole in 250 ml of dimethyl sulphoxide i8 then added
dropwi~e in the course of 2 hours, and the reaction
mixture i~ stirred for 5 hours at 50C. It i~ then
d~lutsd with water to approximately the four-fold volume
and acidified with 2N hydrochloric acid to a pH of 2, and
the crystalline product is isolated by filtration with
suction. For further purification, the product ~8 suspen-
ded in water, nearly dissolved by adding hot 2N sodium
hydroxide ~olution, and filtered. The filtrate is ad~ust-
ed to pH 1 by adding concentrated hydrochloric acid, and
the product which is obtained in crystalline form in this
process is isolated by filtration with suction.
This gives 18.9 g (62% of theory) of 2-(4-
hydroxy-phenoxy)-5-(2-chloro-phenyl)-1,3,4-thiadiazole.
Le A 27 628 -85-
204077~
xample (IV-2)
Cl
OH
A mixture of 7.8 g (0.05 mol) of 2-chlorobenzoic
acid, 7.6 g of (O.D5 mol) of 4-hydroxybenzhydrazide and
11.5 g (O.075 mol) of phosphorous oxychloride i6 heated
S for 5 hours at 106C. When cold, the reaction product is
pounded in a mortar, washed with water and recrystalli~ed
from isopropanol.
This gives 6.5 g of a colourless solid which,
according to GCMS investigation (m/z = 272, M~, 100% rel.
int.), consists to about 35% of 2-~2-chlorophenyl)-s-~4
hydroxyphenyl)-1,3,4-oxadiazole. This intermediate,
without further purification, i8 further reacted accor-
ding to proces~ (b) to give corresponding compounds of
the formula (I).
For example, the compounds of the formula (IV)
listQd in Table 4 below can al~o be prepared analogously
to Examples (IV-l) and (IV-2).
xl x2
Ar-O~~)n ~ H (IV)
Le A 27 628 -86-
20~0775
Table 4s Example~ of the compounds of the formula (IV)
~x. ~o. Ar Q ~ n xl x2 Nelting
point (-C)
S IV-3 ~ ~N~ O I H H gll--y
I V - 4 ~ 15~ O 1 H H 14 5
I V - 5 ~ lr~l~ o 1 H H 12 0
Le A 27 628 -87-
7~
Use Examples:
In the use examples described below, the fol-
lowing compound was employed as comparison substance:
Cl CH~
C~ C H-COOCH3 (A)
Hethyl 2-[4-(2,4-dichlorophenoxy)-phQnoxy]-
propionate (disclosed $n DE-OS (German Publi~hed Specifi-
cation) 2,223,894)
Le A 27 628 -88-
2040775
~xam~le
Post-~merqence test
Solvent: 5 parts by weight of ~cetone
Emulsifier: 1 part by weight of alkylaryl polyglycol
ether
To produce a suitable preparation of active
compound, 1 part by weight of active compound i~ mlxed
w~th the stated amount of solvent, the ~tated amount of
emulsifier is added and ~he concentrate is diluted with
water to the desired concentration.
Te~t plants which ha~e a he~ght of 5 - 15 cm are
~prayed with the preparation of the active compound ~n
~uch a way as to apply the particular amounts of active
compound desired per unit area. ~he concentration of the
spray liquor i8 80 chosen that the particular amounts of
active compound desired are applied in 1,000 1 of
water/ha. After three weeks, the degree of damage to the
plants is rated in % damage in comparison to the develop-
ment of the untreated control. The figures denote:
0% s no action (like untreated control)
100% = total destruction
In this test, an action against weed which i~ up
to 100% stronger than the known compound (A) i8 BhOWn,
for example, by the compounds according to Preparation
Examples (1), ~13) and (14), while being well tolerated
by crop plant~ such as, for example, wheat, barley, rape
snd ~oya.
Le A 27 628 -89-
2~4~7~5
Example B
Pre-emergence test
Solvent: 5 parts by weight of acetone
kmulsifier: 1 part by weigh~ of alkylaryl polyglycol
ether
To produce a suitable preparation of active
compound, 1 part by weight of active compound i~ mixed
with the stated amount of solvent, the stated smount of
emUlBifier i8 added and the concentrate i~ diluted with
water to the de~ired concentration.
Seeds of the test plants are sown in normal 80il
and, after 24 hours, watered with the prsparation of the
active compound. It i8 expedient to keep con~t~nt the
amount of water per unit area. The concentration of the
active compound in the preparation is of no importance,
only the amount of active compound applied per unit area
being decisive. After three weeks, the degree of damage
to the plants i~ rated in % damage in comparison to the
development of the untreated control. The figures denote:
0~ = no action (like untreated control)
100% = total destruction
In this test, a powerful action against weeds is
shown, for example, by the co~pounds accordiny to Pre-
paration Examples (1) and (20), while being well tolera-
ted by crop plants such as, for example, rice.
Le A 27 628 ~90~
