Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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~, ~ b
Subsliluled arvlsulphonvlamino(thio)carbonvllr;~olin(e-thi)ones
The invention relates to novel substituted arylsulphonylamino(thio)carbonyltriazolin(e-
thi)ones, to a plurality of processes for their prep~alion and to their use as herbicides.
It is a].ready known that certain sulphonylaminocarbonyltriazolinones have herbicidal
properties (cf. EP-A 341489, EP-A 422469, EP-A 425948, EP-A 431291, EP-A
507171). However, the activity ofthese compounds is not satisfactory in every respect.
This invention, accordingly, provides the novel substituted arylsulphonylamino(thio)-
- carbonyltriazolin(e-thi)ones of the general formula (I)
Q' ~ (I)
l O in which
Ar represents respectively optionally substituted arylene or heteroarylene,
Q' represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
R' represents hydrogen, hydroxyl, amino, alkylideneamino or represents a
respectively optionally substituted radical from the group consisting of alkyl,
alkenyl, alkinyl, alkoxy, alkenyloxy, alkylamino, dialkylamino, alkanoylamino,
cycloalkyl, cycloalkylalkyl, aryl, arylalkyl,
R2 represents hydrogen, hydroxyl, mercapto, amino, halogen or represents a
respectively optionally substituted radical from the group consisting of alkyl,
alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinyl-
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thio, alkylamino, alkenylamino, alkinylarnino, dialkylarnino, alkanoylarnino,
aziridino, pyrrolidino, piperidino, morpholino, cycloalkyl, cycloalkenyl, cyclo-alkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl, cycloalkylalkoxy,
cycloalkylalkylthio, cycloalkylalkylamino, aryl, aryloxy, arylthio, arylarnino,
S arylalkyl, arylalkoxy, arylalkylthio, arylalkylarnino, heterocyclyloxy, hetero-
cyclylthio, or
R' and R2 together represent optionally branched ~lk~ne~liyl, and
R3 l~,es~ optionally sub~liluled heterocyclyl,
and salts of the compounds of the formula (I).
] 0 The novel substituted arylsulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the
general forrnula (I) are obtained when
(a) triazolin(e-thi)ones of the general formula (II)
H--N~N--R' (Il)
N =(R2
in which
IS Q', R' and R2 are each as defined above
are reaicted with substituted arylsulphonyliso(thio)cyanates of the general formula (III)
R3-O-CO-Ar-SO2-N=C=Q2 (III)
in which
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Ar, Q2 and R3 are each as defined above,
if a~ l;ate in the presence of a reaction auxiliary and if a~ropliate in the presence
of a diluent,
or
5 (b) triazolin(e-thi)one derivatives of the general forrnula (IV)
z J~--N )~ N--R1 (IV)
in which
Ql, Q2, R~ and R2 are each as defined above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy
] 0 are reacted with sulphonarnides of the general forrnula (V)
R3-o-co-Ar-so2-NH2 (V)
in which
Ar ancl R3 are each as defined above,
if app~opl;ate in the presence of an acid acceptor and if applu~l;ate in the presence of
] 5 a diluent,
or
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(c) triazolin(e-thi)ones of the general forrnula (II)
H--N N--R (Il)
N =~
R2
in which
Q', R' and R2 are each as defined above
S are reacted with substituted arylsulphonarnide derivatives of the general formula (VI)
R3-O-CO-Ar-SO2-NH-CQ2-Z (VI)
in which
Ar, Q2 and R3 are each as defined above and
Z represents represents halogen, alkoxy, aryloxy or arylalkoxy,
10 if a~,pluyliate in the presence of an acid acceptor and if apl)lo~l;ate in the presence of
a diluent,
or
(d) triazolin(e-thi)ones of the general forrnula (II)
H_NJ~N_R' (Il)
~N =(R2
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in which
Q', R' and R2 are each as defined above
are reacted with substituted arylsulphonyl halides of the general formula (VII)
R3-O-CO-Ar-SO2-X (VII)
5 in which
Ar and R3 are each as defined above and
X represents halogen
and metal (thio)cyanates of the general formula (VIII)
MQ2CN (VIII)
10 in whic:h
Q2 is as defined above and
M represents an alkali metal or an ~Ik~line earth metal equivalent,
if applop,iate in the presence of a reaction auxiliary and if approl,l;ate in the presence
of a di]uent,
15 and, if approp~;ate, the compounds of the formula (I) obtained by the processes (a), (b),
(c) or (d) are converted into salts by customary methods.
The novel sulphonylamino(thio)carbonyl-triazolin(e-thi)ones of the general formula (I)
have strong herbicidal activity.
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The invention preferably provides compounds of the formula (I) in which
Ar represents phenylene or naphthylene, each of which is optionally substituted by
halogen, cyano, nitro, by C,-C4-alkyl, C1-C4-alkoxy, C,-C4-alkylthio, C,-C4-
alkylsulphinyl, C,-C4-alkylsulphonyl, di-(CI-C4-alkyl)-arnino-sulphonyl orN-C~-
C4-alkoxy-N-C,-C4-alkyl-amino-sulphonyl (each of which is optionally
substituted by fluorine and/or chlorine), or represents heteroarylene of 5 or 6
ring members, at least one of which is oxygen, sulphur or nitrogen and one or
two more are optionally nitrogen, which is optionally substituted by halogen,
cyano, nitro, by C,-C4-alkyl or C,-C4-alkoxy (each of which is optionally
11~ substituted by fluorine andlor chlorine),
Ql represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
Rl :represents hydrogen, hydroxyl, amino, represents C2-C10-alkylideneamino,
:represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-alkoxy-, Cl-
C4-alkyl-carbonyl- or Cl-C4-alkoxy-carbonyl-substituted C~-C6-alkyl, represents
:respectively optionally fluorine-, chlorine- and/or bromine-substituted C2-C6-
.alkenyl or C2-C6-alkinyl, represents respectively optionally fluorine-, chlorine-,
cyano-, C,-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C,-C6-alkoxy, Cl-C6-
,alkylamino or C,-C6-alkanoylamino, represents C3-C6-alkenyloxy, represents di-
I(C,-C4-alkyl)-amino, represents respectively optionally fluorine-, chlorine-,
bromine-, cyano- andlor C,-C4-alkyl-substituted C3-C6-cycloalkyl or C3-C6-
cycloalkyl-C~-C4-alkyl, or represents respectively optionally fluorine-, chlorine-,
bromine-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- andlor C~-C4-alkoxy-
.substituted phenyl or phenyl-C,-C4-alkyl,
25 R2 :represents hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine,
:iodine, represents optionally fluorine-, chlorine-, bromine-, cyano-, C,-C4-
,alkoxy-, C~-C4-alkyl-carbonyl- or C~-C4-alkoxy-carbonyl-substituted C~-C6-alkyl,
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represents respectively optionally fluorine-, chlorine- and/or bromine-substituted
C2-C6-alkenyl or C2-C6-alkinyl, le~rese~ respectively optionally fluorine-,
chlorine-, cyano-, Cl-C4-alkoxy- or C,-C4-alkoxy-carbonyl-substituted Cl-C6-
alkoxy, C,-C6-alkylthio, C,-C6-alkylamino or C,-C6-alkanoylamino, represents
C2-C6-alkenyloxy, C2-C6-alkinyloxy, C2-C6-alkenylthio, C2-C6-alkinylthio, C2-C6-alkenylamino or C2-C6-alkinylamino, represents di-(C,-C4-alkyl)-amino,
represents respectively optionally methyl- and/or ethyl-substituted aziridino,
pyrrolidino, piperidino or morpholino, represents respectively optionally
fluorine-, chlorine-, bromine-, cyano- and/or C,-C4-alkyl-substituted C3-C6-
cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-
C6-cycloalkylamino, C3-C6-cycloalkyl-C,-C4-alkyl,- C3-C6-cycloalkyl-C,-C4-
alkoxy, C3-C6-cycloalkyl-CI-C4-alkylthio or C3-C6-cycloalkyl-C~-C4-alkylamino,
or represents respectively optionally fluorine-, chlorine-, bromine-, cyano-,
nitro-, C,-C4-alkyl-, trifluoromethyl- and/or C,-C4-alkoxy-substituted substituted
phenyl, phenyl-C,-C4-alkyl, phenoxy, phenyl-C,-C4-alkoxy, phenylthio, phenyl-
C,-C4-alkylthio, phenylamino or phenyl-C,-C4-alkylamino, or represents
respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-, C,-C4-alkyl-
, trifluoromethyl- and/or C,-C4-alkoxy-substituted heterocyclyloxy or
heterocyclylthio, the heterocyclyl component being in each case selected from
the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, thietanyl,
thienyl, tetrahydrothienyl, or
R~ and R2 together represent optionally branched alkanediyl having 3 to 11 carbon
atoms, and
R3 represents respectively optionally halogen- or C,-C4-alkyl-substituted oxetanyl,
thietanyl, furyl, tetrahydrofi~ryl, thienyl or tetrahydrothienyl.
Furthelmore, the invention preferably provides the sodium, potassium, magnesium,calcium, ammonium, Cl-C4-alkyl-ammonium, di-(C~-C4-alkyl)-ammonium, tri-(C~-C4-
alkyl)-ammonium, tetra-(C,-C4-alkyl)-ammonium, tri-(C,-C4-alkyl)-sulphonium, C5- or
C6-cycloalkyl-ammonium and di-(C,-C2-alkyl)-benzyl-ammonium salts of compounds
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of the ~formula (I) in which Ar, Ql, Q2, Rl, R2 and R3 are each as defined above by way
of preference.
The invention in particular provides compounds of the formula (I) in which
Ar leplesenl~ respectively optionally fluorine-, chlorine-, bromine-, cyano-, nitro-,
S methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoro-
methoxy-, trifluoromethoxy-, methylthio- or ethylthio-substituted 1,2-phenylene
(ortho-phenylene), pyridine-2,3-diyl, thiophene-2,3-diyl or pyrazol-4,5-diyl,
Ql represents oxygen or sulphur,
Q2 represents oxygen or sulphur,
10 Rl represents hydrogen, hydroxyl, amino, represents C3-C8-alkylideneamino,
represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents
respectively optionally fluorine-, chlorine- or bromine-substituted propenyl,
butenyl, propinyl or butinyl, represents respectively optionally fluorine-,
chlorine-, cyano-, methoxy- or ethoxy- substituted methoxy, ethoxy, n- or i-
propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino,
n-, i-, s- or t-butylamino, represents propenyloxy or butenyloxy, represents
dimethylamino or diethylamino, represents respectively optionally fluorine-,
chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclo-
hexylmethyl, or repl~sent~ respectively optionally fluorine-, chlorine-, methyl-,
trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,
R2 le~leselll~ hydrogen, hydroxyl, mercapto, amino, fluorine, chlorine, bromine,
represents respectively optionally fluorine-, chlorine-, cyano-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents
respectively optionally fluorine-, chlorine- or bromine-substituted propenyl,
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butenyl, propinyl or butinyl, represents respectively optionally fluorine-,
chlorine-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-
propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s-
or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-
butylamino, represents propenyloxy, butenyloxy, propinyloxy, butinyloxy,
propenylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenyl-
amino, propinylamino, or butinylamino, represents dimethylamino, diethylamino
or dipropylamino, represents respectively optionally fluorine-, chlorine-, methyl-
and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino,
cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexyl-
methoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio,
cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclo-
pentylmethylamino or cyclohexylmethylamino, or represents respectively
optionally fluorine-, chlorine-, methyl-, trifluoromethyl- and/or methoxy-
substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio,
phenylamino or benzylamino, or represellt~ respectively optionally fluorine-,
chlorine-, methyl-, trifluoromethyl- and/or methoxy-substituted oxetanyloxy,
furyloxy, tetrahydrofuryloxy, thienyloxy or tetrahydrothienyloxy, or
R' and R2 together represent optionally branched alkanediyl having 3 to 11 carbon
atoms, and
R3 represents respectively optionally fluorine-, chlorine-, methyl- or ethyl-
substituted oxetanyl, thietanyl, furyl, tetrahydrofuryl, thienyl or tetrahydro-
thienyl.
A very particularly preferred group of compounds of the formula (I) are the compounds
of the i~ormula (Ia)
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~ 2'NJ~--N N - R (la)
in whirch
Ql, Q2, R~, R2 and R3 each have the me~nine~ given above as being particularly pre-
ferred.
5 The general or preferred radical definitions listed above are valid both for the end
products of the formula (I) and also, in a corresponding manner, for the starting
materials or intennetli~tes which are required in each case for the p~ ~dlion. These
radical definitions can be combined with each other at will, i.e. including combinations
between the given ranges of plef~ d compo~imds.
l O Using, for example, 2-(oxetan-3-yl-oxy-carbonyl)-phenylsulfonylisocyanate and 5-ethyl-
4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of the
reaction in the process (a) according to the invention can be illustrated by the following
scheme:
~ H--N N--OCH3 [~1~ so2 )~--N )~ N--OCH3
o o C2Hs 0~0 C2Hs
~0 ~0
15 Using, for example, 2-(thietan-3-yl-oxy-carbonyl)-benzenesulphonamide and 2-chloro-
carbonyl-4-dimethylamino-5-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-thione as starting
materials, the course of the reaction in the process (b) according to the invention can
be illu,trated by the following scheme:
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O~s ~cS
[~ ~ S ~Z--N )~--N N _ N(CH,)2
Using, for example, N-methoxycarbonyl-2-(2-tetrahydrofuryl-methoxy-carbonyl)-
benzenesulphonamide and 5-ethoxy-4-methyl-2,4-dihydro-3H- 1 ,2,4-triazol-3-one as
starting materials, the course of the reaction in the process (c) according to the
5 invention can be illustrated by the following scheme:
1~ 1
0 ~,0
0' o"
J"'~O + ~ ~ '' ~O o ~
"' - '''' SO N, N HOCH ~ ~-' " SO ~ N ~ N - CH3
~ N ~, OCH3 OC2H5 OC2H5
Using, for exarnple, 4-ethyl-5-ethylthio-2,4-dihydro-3H-1,2,4-triazol-3-one and 2-(3-
thietanyl-oxy-carbonyl)-benzenesulphonyl chloride and potassium cyanate as starting
materia,ls, the course of the reaction in the process (d) according to the invention can
10 be illustrated by the following scheme:
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~S ~c~S
[~o H_NJ~N_C2Hs ~ KOCN ~2 NH \ =~
SC2Hs
The fo~mula (II) provides a general definition of the triazolin(e-thi)ones to be used as
starting materials in the processes (a), (c) and (d) according to the invention for
preparing compounds of the formula (I). In the formula (II), Ql, R' and R2 each
S preferably or in particular have those me~ning.C which have already been given above,
in connection with the description of the compounds of the formula (I) according to the
invention as being preferred or as being particularly plefe.,cd for Q~, R' and R2.
The tri,azolin(e-thi)ones of the general formula (II) are known and/or can be prepared
by processes known per se (cf. Arch. Pharm. 301 (1968), 827; loc. cit. 307 (1974), 889;
Bull. Soc. Chim. France 1962, 1365; loc. cit. 1975, 1191; Chem. Ber. 90 (1957), 909-
921; loc. cit. 98 (1965), 3025-3099; loc. cit. 102 (1969), 755; J. Heterocycl. Chem. 15
(1978), 237-240; J. Indian Chem. Soc. 6 (1929), 565; Liebigs Ann. Chem. 637 (1960),
135; M~onatshefte Chemie 123 (1992), 257; Tetrahedron 32 (1976), 2347-2352; Helv.
Chim. .Acta 63 (1980), 841-859; J. Chem. Soc. C 1967, 746-751; loc. cit. 1970, 26-34;
J. Chern. Soc. Perkin I 1973, 2644; Fen Fak. Derg., Seri A (Ege Univ.) 7 (1984), 1-6 -
cited in Chem. Abstracts 101:90846m; EP-A 283876; EP-A 294666; EP-A 298371;
EP-A 301946; EP-A 305844; EP-A 341489; EP-A 362633; EP-A 370293; EP-A
391187; EP-A 398096; EP-A 398097; EP-A 399294; EP-A 415196; EP-A 422469;
EP-A 425948; EP-A 431291; EP-A 477646; EP-A 502307; EP-A 503437; EP-A
505815'; EP-A 511569; EP-A 513621; DE-A 2336827; DE-A 3839206; DE-A 3916208;
DE-A :3916930; DD-P 64970; WO-A 93/04050; P.cparalion Examples).
The formula (III) provides a general definition of the substituted arylsulphonyl iso-
(thio)cyanates fi~rther to be used as starting materials in the process (a) according to the
invention for p.cpa hlg compounds of the formula (I). In the formula (III) Ar, Q2 and
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R3 each preferably or in particular have that me~ning which has already been given
above, in connection with the description of the compounds of the formula (I)
according to the invention, as being ple~llcd or as being particularly preferred for Ar,
Q2 ancl R3.
S The slarting materials of the formula (III) are known and/or can be prepared by
processes known per se (cf. EP-A 496701, EP-A 558445).
The formula (IV) provides a general definition of the triazolin(e-thi)one derivatives to
be used as starting materials in the process (b) according to the invention for ~,lep~illg
the compounds of the general formula (I). In the formula (IV), Ql, Q2, Rl and R2 each
10 preferably or in particular have those meanings which have already been indicated
above, in connection with the description of the compounds of the formula (I), as being
preferred or as being particularly prefe.l~,d for Q~, Q2, R~ and R2; Z preferably repre-
sents fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or
nitro-phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
15 Some of the starting materials of the formula (IV) have not been disclosed in the
literature and form part of the subject matter of commonly ~sign~d earlier patent
applications.
The compounds of the general formula (IV) are obtained when triazolin(e-thi)ones of
the general forrnula (II)
H_N~N_R' (Il)
N ~(R2
in which
Q', R' and R2 are each as defined above
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are reacted with carbonic acid derivatives of the general formula (IX)
z-co-zl (IX)
in which
Z is as defined above and
5 Z1 represents halogen, alkoxy, aralkoxy or aryloxy (and has the same preferred m-o~nings as Z),
if apl)lol fiate in the presence of an acid acceptor such as, for example, sodium
hydroxide or potassium hydroxide, sodium t-butoxide or potassium t-butoxide, and if
applol,,;ate in the presence of a diluent such as, for example, methylene chloride,
10 tetrahydrofuran or dimethoxyethane and/or water, at te~l~pc.~lu,es between 0~C and
1 OO~C.
The formula (V) provides a general definition of the sulphonamides further to be used
as starting materials in the process (b) according to the invention for ~ al;llg the
compolmds of the general formula (I). In the formula (V), Ar and R3 each preferably
15 or in particular have that meaning which has already been given above, in connection
with the description of the compounds of the formula (I), as being plefelled or as being
particularly preferred for Ar and R3.
The starting materials of the formula (V) are known and/or can be prepared by pro-
cesses known per se (cf. EP-A 496701, EP-A 558445).
20 The formula (VI) provides a general definition of the substituted arylsulphonamide
derivatives to be used as starting materials in the process (c) according to the invention
for plepal;llg the compounds of the formula (I). In the formula (VI), Ar, Q2 and R3
each preferably or in particular have that meaning which has already been given above,
in connection with the description of the compounds of the formula (I), as being
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- 15 -
pler~.l, d or as being particularly p~c~-~cd for Ar, Q2 and R3; Z preferably represents
fluorine, chlorine, bromine, methoxy, ethoxy, benzyloxy, phenoxy, halogeno- or nitro-
phenoxy, in particular methoxy, phenoxy or 4-nitro-phenoxy.
The st~rting materials of the formula (VI) are known ancl/or can be prepared by
5 processes known per se.
The folmula (VII) provides a general definition of the substituted arylsulphonyl halides
to be used as starting materials in the process (d) according to the invention for pre-
paring the compounds of the formula (I). In the formula (VII), Ar and R3 each pre-
ferably or in particular have that me~ning which has already been given above, in
10 connection with the description of the compounds of the formula (I), as being preferred
or as being particularly preferred for Ar and R3; X preferably represents fluorine,
chlorine or bromine, in particular chlorine.
The starting m~tt~ri~l~ of the formula (VII) are known and/or can be prepaled byprocesses known per se (cf. EP-A 496701, EP-A 558445).
The processes (a), (b), (c) and (d) according to the-invention for the prep~lion of the
novel compounds of the formula (I) are preferably carried out using diluents. Suitable
diluents in this context are virtually all inert organic solvents. These include,
preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as
pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene,
toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane,
chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether,
glycol ,dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones
such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl
ketone, esters such as methyl acetate and ethyl acetate; nitriles, for example acetonitrile
and propionitrile; amides, for example dimethylformamide, dimethylacetamide and
N-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and
hexam~ thylphosphoric triamide.
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- - 16 -
As reaction auxiliaries and/or as acid acceptors in the processes (a), (b), (c) and (d)
according to the invention it is possible to employ all acid-binding agents which can
customarily be used for such reactions. Preference is given to alkali metal hydroxides,
for example sodium hydroxide and potassium hydroxide, ~Ik~lin~ earth metal
5 hydroxides, for example calcium hydroxide, alkali metal carbonates and alkoxides, such
as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-
butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine,
tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropyl-
amine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline,
pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-
-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-
diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1 ,4-diazabicyclo-[2,2,2]-octane (DABCO).
The reaction te~ dlules in the processes (a), (b), (c) and (d) according to the
invention can be varied within a relatively wide range. The reactions are in general
carried out at telll~ res of between -20~C and +150~C, preferably at temperatures
bet~,veen 0~C and +100~C.
The processes (a), (b), (c) and (d) according to the invention are generally carried out
under atmospheric pressure. However, it is also possible to operate under elevated or
reduced pressure.
20 For calrying out processes (a), (b), (c) and (d) according to the invention, the starting
materials required in each case are in general employed in approximately equimolar
quantities. However, it is also possible to use one of the components employed in each
case in a relatively large excess. The reactions are in general carried out in a suitable
diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a
25 number of hours at the particular telllpeldlur~ required. Work-up in the processes (a),
(b), (c) and (d) according to the invention is in each case carried out by customary
methods (cf. the Plel)~dlion Examples).
Salts of the compounds of the general formula (I) according to the invention can be
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,lepaled if desired. Such salts are obtained in a simple manner by customary methods
of fornning salts, for example by dissolving or dispersing a compound of the formula
(I) in an applopl;ate solvent, for example methylene chloride, acetone, tert-butyl methyl
ether or toluene, and adding an applop~iate base. The salts can then - if desired after
5 prolonged stirring - be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants,
haulm killers and, especially, as weed-killers. By weeds, in the broadest sense, there
are to be understood all plants which grow in locations where they are not wanted.
Whether the substances according to the invention act as total or selective herbicides
] 0 depencls essentially on the amount used.
The active compounds according to the invention can be used, for example, in
connec:tion with the following plants:
Dicotvledonous weeds of the ~enera: Sinapis, Lepidium, Galium, Stellaria, Matricaria,
Anthemi~, Galinsoga, Chenopodium, Urtica, Senecio, Alll;~lllhus, Portulaca,
15 Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsiurn, Carduus,
Sonchus, Solanum, Rorippa, Rotala, Lin~eTni~ Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the ~enera: Gossypiurn, Glycine, Beta, Daucus, Phaseolus,
Pisum. Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica,
20 Lactuca, Cucumis and Cucurbita.
Monocot~ledonous weeds of the ~enera: Echinochloa, Setaria, Panicum, Digitaria,
Phleurn, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and
25 Apera.
Monocotvledonous crops of the ~enera: Oryza, Zea, Triticum, Hordeum, Avena,
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Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no wayrestricted to these genera, but also extends in the same manner to other plants.
The co:mpounds are suitable, depending on the concentration, for the total control of
5 weeds, for example on industrial terrain and rail tracks, and on paths and squares with
or without tree pl~nting~. Equally, the compounds can be employed for controlling
weeds in perennial crops, for example forests, decorative tree pl~ntings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea
plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit
10 pl~nting~ and hopfields, in lawns, turf and pasture-land, and for the selective control of
weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable
for the selective control of monocotyledonous and dicotyledonous weeds in mono-
cotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
15 The active compounds can be converted into the customary formulations, such as
solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes,
soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials
impregnated with active compound, and very fine capsules in polymeric substances.
These i'ormulations are produced in a known manner, for example by mixing the active
20 compol,mds with extenders, that is liquid solvents and/or solid carriers, optionally with
the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If water is used as extender, it is also possible to use for example organic solvents as
auxiliary solvents. Essentially, suitable liquid solvents are the following: aromatics,
such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated
25 aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride,
aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum
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fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their
ethers ;md esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone
or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl
sulphoxide, and water.
5 Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc,
chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for
granules are: for example crushed and fractionated natural rocks such as calcite,
10 - marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic
meals, and granules of organic material such as sawdust, coconut shells, maize cobs
and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example non-ionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene
fatty a]cohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl
15 sulphates, arylsulphonates as well as protein hydrolysates; suitable di~e,sa~ are: for
example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the
form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and
20 synthetic phospholipids, can be used in the formulations. Further additives can be
mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide,
titaniurn oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and
metal phthalocyanine dyes, and trace nutrients such as salts of iron, m~ne~nese, boron,
25 copper. cobalt, molybdenum and zinc.
The fo]mulations in general comprise between 0.1 and 95 per cent by weight of active
compolmd, preferably between 0.5 and 90%.
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For controlling weeds, the active compounds according to the invention, as such or in
the form of their formulations, can also be used as mixtures with known herbicides,
ready-l:o-use formulations or tank mixes being possible.
Possibile components for the mixtures are known herbicides, for example anilides, such
5 as diflufenican and propanil; arylcarboxylic acids, such as dichiloropicolinic acid,
dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D,2,4-DB,2,4-DP, fluroxy-
pyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-
methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl;
azinones, such as chloridazon and norflurazon; carb~m~tes, such as chlol~lol)ha~10 desmedipham, phenme-liph~m and plol)halll; chloroacet~nili-les, such as alachlor,
acetochlor, butachlor, metazachlor, metolachlor, pretilachilor and propachlor; dinitro-
anilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as
acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen;
ureas, such as chilorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz-
] S thiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imi-l~7.nlinones, such as imazethapyr, im~7~methabenz, imazapyr and
imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such
as mc fenacet; sulphonyl-ureas, such as amidosulphuron, bensulphuron-methyl,
chilorin;luron-ethyl, chlorsulphuron, cinosulphuron, metsulphuron-methyl, nicosulphuron,
20 primisulphuron, pyrazosulphuron-ethyl, thifensulphuron-methyl, triasulphuron and
kibenuron-methyl; thiocarb~m~tes, such as butylate, cycloate, .~ tc~ EPTC,
esprocarb, molinate, prosulphocarb, thiobencarb and triallate; triazines, such as atrazine,
cyanaz;ine, ~im~7ine, simetryne, terbukyne and terbutylazine; triazinones, such as
hexazi:none, metamikon and metribuzin; others, such as aminotriazole, benfuresate,
25 bentazone, cinmethylin, clomazone, clopyralid, defenzoquat, dithiopyr, ethofumesate,
fluoroc,hiloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,
sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides,
acaricides, nematicides, bird repellents, plant nukients and agents which improve soil
30 structure, are also possible.
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The acl:ive compounds can be used as such, in the form of their formulations or in the
use folms prepal~,d thelcrlom by further dilution, such as ready-to-use solutions,
suspensions, emulsions, powders, pastes and granules. They are used in the customary
manner, for example by watering, spraying, atomizing or scattering.
5 The acl:ive compounds according to the invention can be applied either before or after
emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends
essçnti.~lly on the nature of the desired effect. In general, the amounts used are between
10 g and 10 kg of active compound per hectare of soil surface, preferably between
10 50 g and 5 kg per ha.
The pll~p~dlion and use of the active compounds according to the invention can be
seen from the examples that follow.
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Preparation Examples:
Example 1
~O
O~J .
[~SO~_ N )~--N N ~ CH3
S-CH3
(Process (d))
A mixlure of 2.3 g (8 mmol) of tetrahydrofur-3-yl 2-chlorosulphonylbenzoate, 1.2 g
(8 mmol) of 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.0 g (8 mmol)
of sodium cyanate and 100 ml of acetonitrile is heated under reflux with stirring for
about 15 hours. The mixture is then concentrated using water pump vacuum, the
residue is shaken with methylene chloride and aqueous hydrochloric acid (pH 1), and
the organic phase is separated off, dried with sodium sulphate and filtered. The filtrate
is concentrated using water pump vacuum, the residue is digested with diethyl ether
and the crystalline product is isolated by filtration with suction.
0.7 g (20% of theory) of 4-methyl-5-methylthio-2-[2-(tetrahydro-fur-3-yl-oxycarbonyl)-
phenyl sulphonyl-aminocarbonyl]-2,4-dihydro-3H- 1 ,2,4-triazol-3-one of melting point
1 60~C is obtained.
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Example 2
r~
o~
SO~--N ~--N N_CH3
C2Hs
(Process (d))
A mixture of 2.8 g (10 mmol) of oxetan-3-yl 2-chlorosulphonyl-benzoate, 1.3 g
(10 mnnol) of 5-ethyl-4-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 1.3 g (20 mmol) of
sodiurn cyanate and 50 ml of acetonitrile is heated under reflux for 90 mimltes The
mixture is subsequently concentrated using water pump vacuum and the residue is
stirred with methylene chloride and IN hydrochloric acid. The organic phase is then
dried ~vith sodium sulphate and filtered. The filkate is concenkated~ the residue is
digested ~vith isoplopal1ol and the resulting crystalline product is isolated by filtration
with suction.
1.7 g l~41% of theory) of 5-ethyl-4-methyl-2-[2-(oxetan-3-yl-oxycarbonyl)-phenyl-
sulphonyl-aminocarbonyl]-2,4-dihydro-3H-1,2,4-triazol-3-one of melting point 137~C
are obtained.
By the methods of Examples 1 and 2 and according to the general description of the
p~ lion processes according to the invention, it is also possible to prepare, for
example, the compounds of the formula (I) and the compounds of the formula (Ia)
listed in Table I below.
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~,SO2 ~ N )~ N--R (la)
Table :i: Examples of compounds of the formula (Ia)
Ex Q Q2 R' R2 R3 Melting
No point (~C)
3 O O CH3 ~C2Hs ~ 127
4 O O CH3 n-c3H7 ~1~
O O CH3 i-C3H, ~G~
6 O ~ CH3 OCH3 ~G~
7 O O CH3 ~C2Hs ~GO 148
8 O ~ CH3 OC3H7-n ~G~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
9 0 0 CH3 OC3H,~ o
0 ~ CH3 OC4Hg-n ~co
11 0 ~ CH3 OC4H9-i ~o
12 O ~ CH3 OC4Hg-s ~cO
13 O ~ CH3 OC6Hs ~~
14 O ~ CH3 O-cH2-cH=cH2 ~~
O ~ CH3 SCH3 ~JO 123
16 O ~ CH3 SC2Hs ~1~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Q~ Q2 Rl R2 R3 Melting
No. point
(~C)
17 0 ~ CH3 SC3H~-n ~CI~
18 0 ~ CH3 SC3H7-i ~G~
19 0 ~ CH3 S-CH2-CH=CH2 ~C1~
O ~ CH3 S ~ ~~
21 0 ~ CH3 SCH2CH2F ~G~
22 0 ~ CH3 SCH2CHF2 ~1~
23 0 ~ CH3 SCH2CF3 ~C~~
24 0 ~ CH3 N(CH3)2 ~0
O O CH, SCH2F ~ o
REPLACEMENT SHEET (RULE 26)
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Table l:(continued)
Ex Q' Q2 R~ R2 R3 point (~C)
26 0 ~ CH3 SCH2Cl ~G~
27 0 ~ CH3 SCH2CH2Cl ~G~
28 0 ~ CH3 Cl ~G~
29 0 ~ CH3 Br ~G~
0 0 CH3 CH3 ~0
31 0 ~ CH3 C4Hg-n ~CI~
32 0 0 CH3 ~ ~G~
33 0 0 CH3 CH=CH-CH3 ~G~
34 0 0 CH3 CH2OC2Hs ~J~
REPLACEMENT SHEET (RULE 26)
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Table :I: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. (poocn)t
O O CH3 CH2-CH=CH2 ~G~
36 O ~ CH3 CH20CH3 ~1~
37 O O CH3 OCH2CF3 ~1~
38 O ~ CH3 OcH2cHF2 ~CI~
39 O O CH3 OcH2cF2cHF2 ~C~~
O O CH3 ~ ~o
41 O ~ CH3 OCH2CH2OCH3 ~C1~
42 S ~ CH3 OC2H5 CI~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Ql Q2 Rl R2 R3 Melting
No. point (~C)
43 O S CH3 OC2H5 ~cO
44 S S CH3 OC2H5 ~O
O O C2Hs OC2H5
46 O ~ C2Hs C2H5 ~O
47 O O C2Hs n-c3H7 ~G~
48 O ~ C2H5 i-C3H7 ~G~
49 O O C2Hs OCH3 ~CI~
O O C2H5 OC2H5 ~Jo
51 O ~ C2H5 OC3H7-n ~1~
REPLACEMENT SHEET (RULE 26)
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Table :1: (continued)
Ex. Q' Q2 Rl R2 R3 Melting
No. point ( C)
52 O ~ C2H5 OC3H7-i ~C~~
53 O O C2Hs OC4H9-n ~C~
54 O O C2Hs OC4H9-i ~o
O O C2Hs OC4H9-s ~LI~
56 O ~ C2H5 OC6H5 ~O
57 O O C2Hs O-cH2-cH=cH2 ~C~~
58 O ~ C2H5 SCH3 ~O
59 O O C2Hs SC2Hs ~GO
O ~ C2H5 SC3H,-n ~O
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
61 O ~ C2H5 SC3H7-i ~o
62 O ~ C2H5 S-cH2-cH=cH2 ~C1~
63 O ~ C2H5 S ~ ~G~
64 O ~ C2H5 SCH2CH2F ~CI~
O ~ C2H5 SCH2CHF2 ~~
66 O ~ C2H5 SCH2CF3 ~CI~
67 O ~ C2H5 N(CH3)2 ~Jo
68 O ~ C2H5 SCH2F ~G~
69 O ~ C2H5 SCH2Cl ~G~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex Q' Q2 R' R2 R3 Melting
No point (~C)
O O C2H5 SCH2CH2CI ~G~
71 O ~ C2H5 Cl ~cO
72 O ~ C2H5 Br ~G~
73 O O C2Hs CH3 ~G~
74 O O C2Hs C4Hg-n ~Go
O O C2H5 f ~ ~G~
76 O ~ C2H5 CH=CH-CH3 ~C1~
77 O O C2Hs CH2OC2Hs ~G~
78 O O C2H, CHz-cH=cH2 ~C~~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex Q' Q2 R' R2 R3 Melting
No point (~C)
79 O O C2Hs CH20CH3 ~Go
O ~ C2H5 OCH2CF3 ~G~
81 O ~ C2H5 OCH2CHF2 ~~
82 O ~ C2H5 OcH2cF2cHF2 ~G~
83 O o C2H5 ~ ~G~
84 O ~ C2H5 OCH2CH20CH3 ~G~
S ~ C2H5 OC2H5 ~CJ~
86 O S C2H5 OC2H5 ~O
87 O O ~ ~ OC2H5 ~O
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Exo Ql Q2 Rl R2 R3 pomt (~C)
88 O O ~ C2Hs ~L~
89 O O ~ n-C3H7 ~c~o
0 0 ~ i-C3H7 ~CI~
91 0 0 ~ OCH3 ~G~
92 O O ~ OC2H5 ~cO
93 O O ~, OC3H7-n ~C~~
94 O O ~ 0~3H7-i ~1~
O O ~,~ OC4Hg-n ~C~~
96 O O ~ OC4H9-i ~o
REPLACEMENT SHEET (RULE 26)
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Table ]: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
97 O O OC4H9-s o
98 O O OC6H5 O
99 o O O-cH2-cH=cH2 ~
100 O O SCH3 O
~ ,G .
101 0 o SC2H5 0
102 O O SC3H7-n O
~ )~
103 O O SC3H7-i O
~ ,G
104 O O ~ S-CH2-CH=CH2 ~C1~
105 O O ~ ~ ~ ~ o
REPLACEMENT SHEET (RULE 26)
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Ex. Q' Q2 R' R2 R3 Melting
No. point
(~C)
106 O O ~ SCH2CH2F ~O
107 O O ~ SCH2CHF2 ~O
108 O O ~ SCH2CF3 ~Jo
109 0 0 ~ N(CH3)2 ~~
11 0 0 0 ~ SCH2F ~G~
111 0 0 ~ SCH2C1 ~G~
112 O O ~ SCH2CH2C1 ~o
113 O O ~ Cl ~C1~
1 14 O O ~ Br ~C~o
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point
(~C)
1 15 O O ~ CH3 ~Co
1 16 O O ~ C4Hg-n ~o
117 O O ~ ~ ~C~o
1 18 O O ~ ~ CH=CH-CH3~Co
119 0 0 ~ CH2OC2Hs ~G~
120 O ~ ~ CH2-cH=cH2 ~G~
121 O O ~ CH20CH3 ~G~
122 O O OCH2CF3 r~
REPLACEMENT SHEET (RULE 26)
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Table 1: (contim~ed)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
123 O O ~ OcH2cHF2 ~CI~
124 O O ~ OcH2cF2cHF2 ~C~~
125 ~ ~ ~ O~
126 O O ~ OCH2CH2OCH3 ~O
127 S O ~ ~C2Hs ~GO
128 O S ~ OC2H5 ~c~O
129 O O OCH3 OC2H5 ~
130 O O OCH3 C2Hs ~G~
131 O O OCH3 n-C3H7 ~O
REPLACEMENT SHEET (RULE 26)
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Table 1: (col-tinllec~)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
132 O O OCH3 i-C3H, ~C~
133 O O OCH3 OCH3 ~c~o
134 O O OCH3 OC2H5 ~cO
135 O O OCH3 OC3H7-n ~C~~
136 O O OCH3 OC3H7-i ~C~~
137 O O OCH3 OC4Hg-n ~c~o
138 O O OCH3 OC4H9-i ~G~
139 O ~ OCH3 OC4Hg-s ~G~
140 O O OCH3 OC6H5 ~O
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Ql Q2 R' R2 R3 Melting
No. point (~C)
141 O O OCH3 O-cH2-cH=cH2 ~G~
142 O O OCH3 SCH3 ~G~
143 O O OCH3 S~2H5 ~O
144 O O OCH3 SC3H7-n ~O
145 O O OCH3 SC3H7-i ~O
146 O ~ OCH3 S-cH2-cH=cH2 ~G~
147 O O OCH3 ~ S ~ ~1
148 O O OCH3 SCH2CH2F ~o
REPLACEMENT SHEET (RULE 26)
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Table:l:(continued)
Ex Q' Q2 R' R2 R3 pomt (~C)
149 O ~ OCH2 SCH2CHF2 p ~
150 O O OCH3 SCH2CF3 ~O
151 0 0 OCH3 N(CH3)2 ~C~
152 O ~ OCH3 SCH2F ~o
153 O O OCH3 SCH2CI ~c~o
154 O O OCH3 SCH2CH2CI ~o
155 O O OCH3 Cl po
156 O O OCH3 Br po
157 O O OCH3 CH3 ~CI~
REPLACEMENT SHEET (RULE 26)
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3
No.
158 O O OCH3 C4H9-n ~c~o
159 O O OCH3 ~,~ ~CI~
160 O O OCH3 CH=CH-CH3 ~G~
161 O O OCH3 CH2OC2Hs ~C~~
162 O O OCH3 CH2-cH=cH2 ~G~
163 O O OCH3 CH2OCH3 ~O
164 O O OCH3 OCH2CF3 ~C~~
165 O ~ OCH3 OCH2CHF2 ~~
166 O O OCH3 OCH2CF2CHF2 ~c~
REPLACEMENT SHEET (RULE 26)
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Table l: (continued)
Ex. Q' Q2 R' R2 R3
No.
167 O O OCH3 ~, ~O
168 O ~ OCH3 OCH2CH2- O
OCH3 ~C
169 S O OCH3 OC2H5 ~CI~
170 O S OCH3 OC2Hs ~C1~
171 O ~ OC2H5 OC2H5 ~
J'
172 O ~ OC2H5 C2H5 CI~
173 O ~ OC2H5 n-C3H, ~O
174 O ~ OC2H5 i-C3H, ~cO
175 O ~ OC2H5 OCH3 ~c~o
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3
No.
176 O ~ OC2H5 OC2H5 ~CJ~
177 O ~ OC2H5 OC3H,-n ~cO
178 O ~ OC2H5 OC3H,-i ~CI~
179 O ~ OC2H5 SCH3 ~c~O
180 O ~ OC2H5 SC2Hs ~C~~
181 O ~ OC2H5 N(CH3)2 ~G~
182 O ~ OC2H5 SCH2F ~o
183 O ~ OC2H5 SCH2CI ~CI~
184 O ~ OC2H5 SCH2CH2CI ~G~
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point (~C)
185 O O OC2E~5 Cl ~G~
186 0 ~ OC2H5 Br ~0
187 0 ~ OC2H5 CH3 ~CJ~
188 0 ~ OC2H5 f ~ ~CI~
189 0 ~ OC2H5 CH=CH-CH3 ~o
190 0 ~ OC2H5 CH2OC2Hs ~~
191 0 ~ OC2H5 CH2-CH=CH2 ~G~
192 0 ~ OC2H5 CH20CH3 ~C~
193 0 0 N(CH3)2 C2Hs ~GO
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Table 1: (continued)
Ex. Q' Q2 R' R2 R3 Melting
No. point ( C)
194 O O N(CH3)2 n-C3H, ~C~~
195 O O N(CH3)2 CH3 ~CI~
196 O O N(CH3)2 OCH3 ~C~
197 O O N(cH3)2 OC2Hs ~Cl~
198 O O N(CH3)2 OC3H,-n ~CI~
199 0 0 N(CH3)2 SCH3 ~O
200 O ~ CH3 C2H5 ~CI~ 159
By the methods of Examples 1 and 2, it was also possible to prepare the following
compolmds:
REPLACEMENT SHEET (RULE 26)
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Examlple 201
~0
OJ~
_~H~N~N_cH,
OC2H5
Melting point: 146~C
Example 202
~0
[~2--NH~ N J'' N--CH3
CH3 N =(
SCH3
MeltinlJ point: 1 58~C
REPLACEMENT SHEET (RULE 26)
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Startinp materials of the formula (VII):
Example (VII-1)
~bo
SO2-CI
At -lO"C, a solution of 3.4 g of pyridine in 20 ml of methylene chloride is added
dropwi ,e with stirring to a mixture of 9.46 g (39 mmol) of 2-chlorosulphonyl-benzoyl
chloride, 3.5 g (39 mmol) of 3-hydroxymethyl-tetrahydrofuran and 100 ml of
methylene chloride, and the reaction mixture is then stirred at 20~C for about 6 hours.
The mixture is subsequently concentrated using water pump vacuum, the residue isshaken with methylene chloride and aqueous hydrochloric acid (pH 1), and the organic
phase is separated off, dried with sodium sulphate and filtered. The solvent is carefully
distillecl off from the filtrate using water pump vacuum.
8.2 g (72.5% of theory) of tetrahydrofur-3-yl 2-chlorosulphonyl-benzoate are obtained
as an oily residue which can be used directly as such for further reactions.
Example (VII-2)
o~lo
SO2-CI
Step 1
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A mixl[ure of 68.3 g (0.20 mol) of bis-(2-chlorocarbonyl-phenyl) disulphide, 29.6 g
(0.40 mol) of 3-hydroxy-oxetane, 42.5 g (0.42 mol) of triethylamine and 500 ml of
methyllene chloride is stirred at 20~C for 15 hours. 200 ml of lN hydrochloric acid are
then added and the organic phase is separated off, washed with water, dried with5 sodiwn sulphate and filtered. The filtrate is concentrated using water pump vacuum, the
residue is digested with diethyl ether and the resulting crystalline product is isolated by
filtration with suction.
48.6 g (58% of theory) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl] ~ phide of
meltin~ point 143~C are obtained.
10 Step 2
At -5~C to 0~C, 11.2 g of chlorine are introduced over a period of about 15 minutes
into a mixture of 10.5 g (25 mmol) of bis-[2-(oxetan-3-yl-oxycarbonyl)-phenyl]
disulphide, 12.9 g of sodium acetate and 100 ml of 50% strength aqueous acetic acid.
The reaction IllixLule is stirred at 0~C for a further 15 minutes and then admixed with
15 150 ml of methylene chloride. The methylene chloride phase is then separated off,
washed with ice-water, dried with sodium sulphate and filtered. The filtrate is concen-
trated using water pump vacuum and the residue is purified twice by silica gel column
chromatography (first run with methylene chloride, second run with ethyl acetate).
10.4 g (75% of theory) of oxetan-3-yl 2-chlorosulphonyl-benzoate are obtained as a
20 yellowish oil.
'H NMR (CDCl3, TMS, ~): 4.9 (m, 2H), 5.0 (m, 2H), 5.8 (m, lH), 7.8 (m, 3H), 8.2 (m,
lH) ppm.
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Use examples:
Example A
Pre-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable active compound plcpa~dtion, 1 part by weight of active com-
pound is mixed with the stated amount of solvent, the stated amount of emulsifier is
added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is
10 watered with the p,cpaldlion of active compound. It is advantageous to keep the
amount of water per unit area constant. The concentration of the active compound in
the ~lcl,~dlion is immaterial, only the amount of active compound applied per unit
area matters.
After tllree weeks, the degree of damage to the plants is rated in % damage by com-
15 parison with the development of the untreated control.
The fi~ures denote:
0% = no effect (like untreated control)
100% = total destruction
In this test, the compounds of the formula (I) according to the invention show strong
20 activity against weeds (cf. Table A).
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Example B
Post-ernergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
5 To produce a suitable active compound plep~lion, 1 part by weight of active com-
pound is mixed with the stated amount of solvent, the stated amount of emlllcifier is
added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the
active compound in such a way as to apply the particular amounts of active compound
10 desired per unit area. The concentration of the spray liquor is chosen so that the
particu]ar amounts of active compound desired are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage by com-
parison with the development of the untreated control.
The figures denote:
0% = no effect (like untreated control)
100% = total destruction
In this test, the compounds of the formula (I) according to the invention show strong
activity against weeds (cf. Table B).
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Table A: Pre-emergence test/greenhouse
Active com- Applic- Maize Alope- Cype- Seta- Amaran- Sina-
pound ation rate curus rus ria thuspis
(according to (g/ha)
Preparation
Ex.)
(7) 250 10 80 - 70 100
(201) 250 - 80 95 80 70 100
(202) 250 0 80 1 00 70 - 70
10 Table :B: Post-emergence test/greenhouse
Active com- Application Maize Alopecurus Avena fatua Sinapis
pound rate
(according to (glha)
Plep~lion Ex.)
(201) 250 10 80 80 100
