AU716093B2 - Substituted 1-(3-pyrazolyl)-pyrazoles having herbicidal activity and intermediates for their preparation - Google Patents
Substituted 1-(3-pyrazolyl)-pyrazoles having herbicidal activity and intermediates for their preparation Download PDFInfo
- Publication number
- AU716093B2 AU716093B2 AU39412/97A AU3941297A AU716093B2 AU 716093 B2 AU716093 B2 AU 716093B2 AU 39412/97 A AU39412/97 A AU 39412/97A AU 3941297 A AU3941297 A AU 3941297A AU 716093 B2 AU716093 B2 AU 716093B2
- Authority
- AU
- Australia
- Prior art keywords
- cyano
- halogen
- alkoxy
- carbon atoms
- ochf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
WO 98/06702 PCT/EP97/04083 -1- SUBSTITUTED 1-(3-PYRAZOLYL)-PYRAZOLES HAVING HERBICIDAL ACTIVITY AND INTERMEDIATES FOR THEIR PREPARATION The invention relates to novel substituted 1-( 3 -pyrazolyl)pyrazoles, to processes for their preparation and to their use as herbicides.
Substituted pyrazolyl pyrazoles, such as, for example, the compound 4 1-(4-chloro-5-difluoromethoxy- -methyl-pyrazol-3 -yl)pyrazol alias difluoromethoxy-l',5'-dimethyl-1,3'-bi-1H-pyrazole)-4-carbonitrile, are already known as potential herbicides (cf. EP 542388, WO 94/08999). However, these compounds have not attained any particular importance.
This invention, accordingly, provides the novel substituted 1-( 3 -pyrazolyl)-pyrazoles of the general formula (I)
R
2
R
3
N-
N-N
(I)
N-N
R6 R4
R
in which R' represents optionally hydroxyl-, cyano-, carboxyl-, halogen-, C 1
-C
4 -alkoxy-, C,-
C
4 -alkyl-carbonyl- or Ci-C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms,
R
2 represents hydrogen, hydroxyl, halogen, cyano, nitro, N(R"R 1 2 or represents alkyl, aralkyl, alkoxy or alkylthio having in each case 1 to 6 carbon atoms in the alkyl moiety and being in each case optionally substituted by cyano, halogen or Cl-C 4 -alkoxy, -2-
R
3 represents hydroxyl, cyano, nitro, or represents a radical from the series alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or C 1
-C
4 -alkoxy,
R
3 represents a radical from the series alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by halogen,
R
4 represents hydrogen, halogen or optionally cyano, halogen- or C,-C 4 alkoxy-substituted alkyl having 1 to 6 carbon atoms,
R
5 represents hydrogen, cyano, nitro, amino or halogen, represents optionally cyano-, hydroxyl-, halogen- or C-C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms, represents the grouping -(CH 2 )m-O-R 7 the grouping
-(CH
2 )m-S(O)n-R 8 the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m-CO- O-RO, the grouping -(CH 2 R 2
R
6 represents hydrogen, cyano, amino, halogen, represents alkyl having 1 to 6 carbon atoms and being in each case optionally substituted by cyano, hydroxyl, carboxyl, halogen, C,-C 4 -alkoxy or C 1
-C
4 -alkoxy-carbonyl,
R
6 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents alkoxymethylene amino having 1 to 4 carbon atoms in the alkoxy group,
R
6 furthermore represents optionally nitro-, cyano-, halogen-, C-C 4 -alkyl-, C 1
C
4 -halogenoalkyl-, C 1
-C
4 -alkoxy- or C -C 4 -halogenoalkoxy-substituted phenyl,
R
6 furthermore represents pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl, -3each of which is optionally substituted by Ci-C 4 -alkyl, represents the grouping -(CH 2 )m-R 1 2 represents the grouping -(CH2)-O-R 7 the grouping
-(CH
2 8 the grouping -(CH2)m-CO-R 9 the grouping -(CH 2 )m-CO-
O-R'
0 the grouping -(CH 2 2 or the grouping -(CH 2 )m-CQ- N(R",R1 2 or the grouping -(CH 2 )mN=CH-R 2
R
6 furthermore represents one of the groupings below O O O O N N N N each of which is optionally substituted by halogen or C 1
-C
4 -alkyl,
R
7 represents hydrogen, represents optionally cyano-, carboxyl-, nitro-, hydroxyl-, halogen-, C 1
-C
4 -alkoxy- or C 1
-C
4 -alkoxycarbonyl-substituted alkyl having 1 to 6 carbon atoms,
R
7 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen,
R
7 furthermore represents alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case up to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or
C-C
4 -alkoxy, or
R
7 furthermore represents cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups and being in each case optionally substituted by cyano, carboxyl, halogen or
C
1
-C
4 -alkyI, -4-
R
8 represents optionally cyano-, carboxyl-, halogen-, CI-C 4 -alkoxyor C 1
-C
4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen,
R
9 represents hydrogen, represents optionally cyano-, carboxyl-, halogen-, C 1
-C
4 -alkoxy- or C -C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen,
R'
1 represents hydrogen, represents optionally cyano-, carboxyl-, halogen-, CI-C 4 -alkoxy- or C 1
-C
4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen, R" represents hydrogen or formyl, represents optionally cyano-, carboxyl-, halogen-, C-C 4 -alkoxy- or C 1
-C
4 -alkoxy-carbonylsubstituted alkyl having 1 to 6 carbon atoms, R furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents a radical from the series alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulphonyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulphonyl having in each case up to 6 carbon atoms in the alkyl or cycloalkyl groups and being in each case optionally substituted by cyano, halogen or Ci-C4-alkoxy, R" furthermore represents hetarylcarbonyl or arylcarbonyl,
R
12 represents hydrogen, carbamoyl, represents optionally cyano-, carboxyl-, halogen-, Ci-C 4 -alkoxy- or Cl-C 4 -alkoxy-carbonylsubstituted alkyl or haloalkyl having 1 to 6 carbon atoms,
R
12 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents a radical from the series alkoxy, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylamino, alkylaminocarbonyl, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, alkylsulphonyl, cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulphonyl having in each case up to 6 carbon atoms in the alkyl or cycloalkyl groups and being in each case optionally substituted by cyano, halogen or C 1
-C
4 -alkoxy, or represents phenyl-C l-C 2 -alkyl, phenyl-C, -C 2 -alkylcarbonyl, phenoxy, benzoyl or furoyl, each of which is optionally substituted by fluorine or chlorine,
R
1 2 furthermore represents hetarylcarbonyl or arylcarbonyl, Q represents O or S, m represents the numbers 0, 1, 2 or 3 and n represents the numbers 0, 1 or 2.
The novel substituted 1-(3-pyrazolyl)-pyrazoles of the general formula are obtained when hydrazinopyrazoles of the general formula (II) -6-
R
2 RN R 3
(II)
NH N
NH,
in which
R
2 and R 3 are each as defined above are reacted with cyanoalkenyl ethers of the general formula (III)
OR
NCR
4
(III)
in which
R
4 and RS are each as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent and, if appropriate, further conversions within the scope of the above definition of substituents are carried out by customary methods on the resulting compounds of the formula The compounds of the general formula can be converted by customary methods into other compounds of the general formula in accordance with the above definition of substituents, for example by customary alkylation, acylation or sulphonylation reactions (for example R 5 CN COOH, CONH 2
CSNH
2
R
6
NH
2
NHC
2
NHCOCH
3
NHSO
2
CH
3 cf. also the Preparation Examples.
-7- The novel substituted 1-(3-pyrazolyl-pyrazoles of the general formula exhibit strong herbicidal activity. Moreover, they are tolerated well by important crop plants, such as, for example, wheat, barley, soya and sugar beet.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl are in each case straight-chain or branched i.e. also in combination with heteroatoms, such as in alkoxy or alkylthio.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula in which R' represents methyl, ethyl, n- or i-propyl, s- or t-butyl cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, each of which is optionally substituted by hydroxyl, cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl.
R
2 represents hydrogen, hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro,
N(R"R'
2 or represents methyl, ethyl, n-propyl, i-propyl, s- or t-butyl, methoxy or ethoxy, n- or i-propoxy, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, s- or t-butylthio or phenyl-Cl-C 4 -alkyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R
3 represents hydroxyl, cyano, nitro, represents methyl, ethyl, n- or i-propyl, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or ipropylthio, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or represents a radical from the series ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by fluorine, chlorine or bromine, -8-
R
4 represents hydrogen, fluorine, chlorine, bromine or represents a radical from the series methyl, ethyl, n- or i-propyl, s- or t-butyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R
5 represents hydrogen, cyano, nitro, amino, fluorine, chlorine, bromine, represents a radical from the series methyl, ethyl, n- or i-propyl, s- or t-butyl, each of which is optionally substituted by cyano, hydroxyl, fluorine, chlorine, methoxy or ethoxy, represents the grouping -(CH 2 )m-O-R 7 the grouping
-(CH
2 )m-S(O)nR 8 the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m-CO-O-R 0 the grouping -(CH 2 R1 2
R
6 represents hydrogen, cyano, amino, fluorine, chlorine, bromine, represents a radical from the series methyl, ethyl, n- or i-propyl, s- or t-butyl, each of which is optionally substituted by cyano, hydroxyl, carboxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or ipropoxycarbonyl,
R
6 furthermore represents a radical from the series ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, represents methoxymethylene amino or ethoxymethylene amino,
R
6 furthermore represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, s- or t-butoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl, represents pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl, each of which is optionally substituted by methyl and/or ethyl, represents the grouping -(CH 2 )m-R 1 2 represents the grouping -(CH 2 )m-O-R 7 the grouping -(CH 2 )m-S(O)nR 8 the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m- CO-O-R'O, the grouping -(CH 2 )m-N(R 1
R'
2 the grouping -(CH 2 )m-CQ-
N(R'
2
,R
1 2 or the grouping -(CH 2 )m-N=CHR 2 -9-
R
6 furthermore represents one of the groupings below 0 0 0 0 0 0 0 0 which are in each case optionally substituted by fluorine, chlorine, bromine, methyl or ethyl,
R
7 represents hydrogen, represents methyl, ethyl, n- or i-propyl, n- or s- or t-butyl, each of which is optionally substituted by cyano, carboxyl, nitro, hydroxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl.
R
7 furthermore represents ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R
7 furthermore represents acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, s- or t-butylsulphonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or
R
7 furthermore represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methyl or ethyl,
R
8 represents methyl, ethyl, n- or i-propyl, s- or t-butyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or ipropoxycarbonyl, or
R
8 furthermore represents ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R
9 represents hydrogen, represents optionally cyano-, carboxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted methyl, ethyl, n- or ipropyl, s- or t-butyl, or
R
9 furthermore represents ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R'
0 represents hydrogen, represents methyl, ethyl, n- or i-propyl, s- or tbutyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or
R'
1 furthermore represents ethenyl, propenyl, butenyl, ethinyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, R" represents hydrogen or formyl, represents optionally cyano-, carboxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted methyl, ethyl, n- or ipropyl, s- or t-butyl, R" furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or 11 R" furthermore represents acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarboyl, methylsuiphonyl, ethylsuiphonyl, n- or i-propylsulphonyl, s- or t-butylsulphonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl, cyclohexylaminocarbonyl, cyclopropylsuiphonyl, cyclobutylsuiphonyl, cyclopentylsuiphonyl, cyclohexylsuiphonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or represents thiophenylcarbonyl,
R'
2 represents hydrogen, carbamoyl, represents methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, R1 2 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or
R'
2 furthermore represents optionally methyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
R'
2 furthermore represents methoxy, ethoxy, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylamino, dimethylamino, methylaminocarbonyl, ethylaminocarbonyl, n- or ipropylaminocarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylchloroethyl, dimethylaminocarbonyl, methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, s- or t-butylsulphonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl,cyclohexylainocarbonyl, cyclopropylsuiphonyl, cyclobutylsulphonyl, cyclopentylsulphonyl, cyclohexylsulphonyl, benzoyl, 12furoyl, phenoxy, thiophenylcarbonyl, p-chlorobenzylcarbonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, or represents p-chlorobenzyl, Q represents O or S, m represents the numbers 0, 1, 2 or 3 and n represents the numbers 0, 1 or 2.
The invention in particular relates to compounds of the formula in which R' represents methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R
2 represents hydrogen, hydroxyl, fluorine, chlorine, bromine, cyano, nitro,
N(R"R'
2 or represents methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methyl, ethyl, n- or i-propyl, s- or t-butyl, benzyl, phenylethyl, phenyl-l-prop-2-yl, phenyl-l-prop-3-yl, phenyl-l-but-2-yl, phenyl- 1-but-3-yl, phenyl-l-but-4-yl, phenyl-l-(1-methyl)-prop-3-yl, phenyl-l-(2methyl)-prop-3-yl, phenyl-l-(3-methyl)-prop-3-yl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R
3 represents methoxy, cyano, nitro or represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R
4 represents hydrogen, fluorine, chlorine, bromine or represents methyl, ethyl, nor i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, 13
R
5 represents hydrogen, cyano, fluorine, chlorine, bromine, represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, represents the grouping -(CH 2 )m-O-R 7 the grouping -(CH 2 the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m-
CO-O-R'
1 the grouping -(CH 2 )m-CQ-N(R 1
,R'
2
R
6 represents hydrogen, cyano, amino, fluorine, chlorine, bromine, represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl or ethoxycarbonyl,
R
6 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R
6 furthermore represents methoxymethyleneamino or ethoxymethyleneamino,
R
6 furthermore represents optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, trifluoromethyl-, methoxy-, ethoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl,
R
6 furthermore represents pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl, each of which is optionally substituted by methyl and/or ethyl, represents the grouping -(CH,)m-R 2 the grouping -(CH 2 )m-O-R 7 the grouping -(CH 2 )m-S(O)n-
R
8 the grouping -(CH2)m-CO-R 9 the grouping -(CH 2 )m-CO-O-RO, the grouping
(CH
2 2 the grouping -(CH2)m-CQ-N(R",R 2 or the grouping -(CH 2 )m-
N=CHR
1 2
R
7 represents hydrogen, represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, carboxyl, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, represents propenyl, butenyl, propinyl or butinyl, each of which is. optionally substituted by cyano, fluorine, chlorine or bromine, represents acetyl, propionyl, 14methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or ethylsulphonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or
R
7 furthermore represents cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl or cyclohexylmethyl, each of which is optionally substituted by cyano, fluorine, chlorine, methyl or ethyl,
R
8 represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl or
R
8 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R
9 represents hydrogen, represents optionally cyano- fluorine-, chlorine-, methoxy-, ethoxy-, methoxycarbonyl- or ethoxycarbonyl-substituted methyl, ethyl, n- or i-propyl, or
R
9 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine,
R
1 0 represents hydrogen, represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl, or
R'
0 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, R" represents hydrogen or formyl, represents optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, methoxycarbonyl- or ethoxycarbonylsubstituted methyl, ethyl, n- or i-propyl, 15 R" furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or R" furthermore represents acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, methylsulphonyl, ethylsulphonyl, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl,cyclohexylaminocarbonyl,cyclopropylsulphonyl, cyclopentylsulphonyl, cyclohexylsulphonyl or thiophenylcarbonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R'
2 represents hydrogen, represents methyl, ethyl, n- or i-propyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl,
R'
2 furthermore represents propenyl, butenyl, propinyl or butinyl, each of which is optionally substituted by cyano, fluorine, chlorine or bromine, or
R'
2 furthermore represents methylcyclopropyl, cyclopropyl, cyclobutyl or cyclohexyl,
R
2 furthermore represents methoxy, ethoxy, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylamino, dimethylamino, methylaminocarbonyl, ethylaminocarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylchloroethyl, dimethylaminocarbonyl, methylsulphonyl, ethylsulphonyl, cyclopropylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclopentylaminocarbonyl, cyclohexylaminocarbonyl, cyclopropylsulphonyl, cyclophenylsulphonyl, cyclohexylsulphonyl, benzoyl, furoyl, phenoxy, thiophenylcarbonyl, each of which is optionally substituted by cyano, fluorine, chlorine, methoxy or 16ethoxy, or represents p-chlorobenzylcarbonyl, Q represents O or S, m represents the numbers 0, 1, 2 or 3 and n represents the numbers 0, 1 or 2.
The abovementioed general or preferred radical definitions apply both to the end products of the formula and, correspondingly, to the starting materials or -intermediates required in each case for the preparations. These radical definitions can be combined with each other at will, i.e. combinations between the stated preferred ranges are also possible.
Examples of the compounds of the formula according to the invention are listed in the groups below: Group 1
R
2 R3 R N
R
N
N-N
CH CH3
CN
(IA-1)
R
2 and R 3 have, for example, the meanings given in the list below:
R
1 R R 3
CH
3 OCHF 2 CH 3
CH
3
OCHF
2
CH
2 Br
CH
3
OCHF
2
CH
2 C1 -17 Group 1 (continued) ~R2
CH
3 OCHF 2 CHC1 2
CH
3 OCHF 2 CC1 3
CH
3
OCHF
2
CH
2
F
CH
3 OCHF 2 CHF 2
CH
3 OCHF 2 CCIF 2
CH
3
OCHF
2 CC1 2
F
CH
3 OCHF 2 CF 3
CH
3
OCHF
2 CH 2
CF
3
CH
3
OCHF
2 CF 2
CF
3
CH
3
OCHF
2
CH
2
CH
2
CH
2
F
CH
3 SCHF 2 CH 3
CH
3 SCHF., CH 2 Br
CH
3 SCHF 2 CH 2 C1
CH
3 SCHF 2 CHC1 2
CH
3 SCHF 2 CCd 3
CH
3
SCHF
2
CH
2
F
CH
3 SCHF 2 CHF 2
CH
3 SCHF 2 CC1F 2
CH
3
SCHF
2 CC1 2
F
-18 Group 1 (continued)
CH
3
SCHF
2 CF 3
CH
3
SCHF
2 CH 2
CF
3
CH
3 SCHFI,
CF
2
CF
3
CH
3
SCIIF
2
CH
2
CH
2
CH
2
F
CH
3
OCH
3 CH 3
CH
3
OCH
3
CH
2 Br
CH
3
OCH
3 CH 2 C1
CH
3
OCH
3 CHC1 2
CH
3
OCH
3 CCd 3
CH
3
OCH
3 CHF
CH
3
OCH
3 CHF 2
CH
3
OCH
3 CC1F 2
CH
3
OCH
3 CC1 2
F
CH
3
OCH
3 CF 3
CH
3 Gd 3 CH 2
CF
3
CH
3
OCH
3 CF 2
CF
3
CH
3 0C 2
H
5 CH 3
CH
3 0C 2
H
5 CF 3
CH
3 0C 2
H
5
CH
2 Br 19 Grout) 1 (continued)
CH
3 0C 2
H
5
CH
2 C1 CAH OCHF 2
CH
3 CAH OCHF 2
CH
2 Br CAH OCHF 2
CH
2 C1 CAH OCHF2 CH 2
F
CAH OCHF 2
CHF
2 2
CF
3 (CHA)CH OCHF 2
CH
3 (CHA)CH OCHF 2
CH
2 Br (CHA)CH OCHF 2
CH
2 C1 (CHA)CH OCHF 2
CH
2
F
(CHA)CH OCHF2
CHF
2 (CHA)CH OCHF 2
CF
3
CH
3
OCH
2 F CH 3
CH
3
OCH
2 F CH 2 Br
CH
3
OCH
2 F CH 2 C1
CH
3
OCH
2 F CH 2
F
CH
3
OCH
2 F CHF 2
CH
3
OCH
2 F CF 3 Group 1 (continued) [H SCR2C2 JR3
CH
3
SCH
2
CH
2 F CH2B
CH
3
SCH
2
CH
2 F CH 2 Br
CH
3
SCH
2
CH
2 F CHC12
CH
3
SCH
2
CH
2 F CC1
CH
3 SCH2CH 2 F CHY
CH
3
SCH
2 CH2F
CH
2
CH
3
SCH
2
CH
2 F CHIF 2
CH
3
SCH
2
CH
2 F CC12F
CH
3
SCH
2
CH
2 F CF
CH
3
SCI{,CH
2 F CH2F 3
CH
3
SCH
2
CH
2 F CH 2
CF
3
CH
3
SCH
2
CH
2 F CF 2 CH2H2
CH
3
OCF
3 CH 3
CH
3
OCHF
2 CAH
CH
3
OCHF
2
(CH
3 2
CH
CH
3
OCH(CH
3 2
CH
3
CH
3
OCH(CH
3 2
CF
3
CH
3
OCH(CH
3 2
CH
2 Br
CH
3
OCH(CH
3 2
CH
2 C1
CH-
3
OCH
2
CH
2 F CH 3
CH
3
OCH
2
CH
2 F CH 2 Br -21 GrouD 1 (continued) I l j2 R 3]
CH
3
OCH
2
CH
2 F CH 2 C1
CHF
2 Gd-IF 2 CC1 3
CLIF
2
OCHF
2
CH
2
F
CHF
2
OCHF
2
CHF
2
CHF
2
OCHF
2 CC1F-,
CHF
2
OCHF
2 CC1 2
F
CHF
2
OCHF
2
CF
3
CHF
2
OCHF
2
CH
2
CF
3
CHF
2
OCHF
2
CF
2
CF
3
CHF
2
OCHF
2
CH
2
CH
2
CH
2
F
CHF2 SCHF 2
CH
3
CHF
2
SCHF
2
CH
2 Br
CHF
2
SCHF
2
CH
2 C1 CHF., SCHF 2 CHC1 2
CHF
2
SCHF
2 CC1 3
CHF
2
SCHF
2
CH
2
F
CHF
2
SCHF
2
CHF
2
CHF
2
SCHF
2 CC1F 2
CHF
2
SCHF
2 CC1 2
F
CIIF
2
SCHF
2 CF 3
CHF
2
SCHF
2
CH
2
CF
3
CHF
2
SCHF
2 CF 2
CF
3
CHF
2
SCHF
2
CH
2
CH
2
CH
2
F
CHF
2
OCH
3 CH 3
CHF
2
OCH
3
CH
2 Br -22 Group 1 (continued) jR2 R 3
CHF
2 OCH 3 CH 2 C1
CHF
2 0C11 3 CHC1 2
CHF
2
OCH
3 CCd 3
CHF
2
OCH
3 CH 2
F
CHF
2
OCH
3 CHF 2
CHF
2
OCH
3 CC1F 2
CHF
2
OCH
3 CC1 2
F
CHF
2
OCH
3 CF 3
CHF
2
OCH
3 CH 2
CF
3
CHF
2
OCH
3 CF 2
CF
3
CHF
2 0C 2
H
5 CH 3
CHF
2 0C 2
H
5 CF 3 CHF., 0C 2
H
5
CH
2 Br
CHF
2 0C 2
H
5 CH 2 C1 CH 2
CF
3
OCHF
2 CH 3
CH
2
CF
3
OCHF
2
CH
2 Br
CH
2
CF
3
OCHF
2 CH 2 C1 CH2CF 3
OCHF
2 CHC1 2
CH
2
CF
3
OCIJF
2 Cd1 3
CH
2
CF
3
OCIIF
2 CI-{ 2
CH
2
CF
3
OCHF
2 CHF 2
CH
2
CF
3
OCHF
2 CC1F 2
CH
2
CF
3
OCHF
2 CC1 2
F
CH
2
CF
3
OCHF
2 CF 3
CH
2
CF
3
OCHF
2 CH 2
CF
3 -23 Group 1 (continued) R' 1R2
JR'
CH
2
CF
3
OCHF
2 CF 2
CF
3
CH
2
CF
3
OCHF
2 CH2CH 2
CH
2
F
CH
2
CF
3
SCHF
2 CH 3
CH
2
CF
3
SCHF
2
CH
2 Br CH2CF 3
SCHF
2 CH 2 C1
CH
2
CF
3
SCHF
2 CHC1 2
CH
2
CF
3
SCIIF
2 CC1 3
CH
2
CF
3
SCHF
2
CH
2
F
CH
2
CF
3
SCHF
2 CHF 2
CH
2
CF
3 SCHF., CC1F 2
CH
2
CF
3
SCHF
2 CC1 2
F
CH
2
CF
3
SCHF
2 CF 3 CH2CF 3
SCHF
2 CH 2
CF
3
CH
2
CF
3
SCHF
2
CF
2
CF
3
CH
2
CF
3
SCHF
2
CH
2
CH
2
CH
2
F
CH2CF 3
OCH
3 CH 3
CH
2
CF
3
OCH
3
CH
2 Br
CH
2
CF
3
OCH
3 CH 2 C1
CH
2
CF
3
OCH
3 CHC1 2
CH
2
CF
3
OCH
3 CC1 3
CH
2
CF
3
OCH
3 CH 2
F
CH
2
CF
3
OCH
3 CHF 2
CH
2
CF
3
OCH
3 CC1F 2
CIJ
2
CF
3
OCH
3 CC1 2
F
CH
2
CF
3
OCH
3 CF 3 24 Group 1 (continued) R' 1R' 1R'
CH
2
CF
3
OCH
3
CH
2
CF
3
CH
2
CF
3
OCH
3
CF
2
CF
3
CH
2
CF
3 OC2H 5
CH
3
CH
2
CF
3 0C 2
H
5
CF
3
CH
2
CF
3 0C 2
H
5
CH
2 Br
CH
2
CF
3 0C 2
H
5
CH
2 C1
CH
3 OCHF2 CN
CH
3
OCHF
2
OCH
3
CH
3
OCHF
2 0C 2
H
CH
3 OCHF-,
OCHE.,
CH
3 OCHF-,
SCH
3
CH
3
OCHF
2
SCHF
2 CHF2 OCHF 2
OCHF,
CHF
2 OCHF.,
OCH
3
CHF
2
OCHF
2
SC
3
CHF
2
OCHF
2
CN
CH
3
OCHF
2
SCF
3
CH
3
OCHF
2
SOCF
3
CH
3
OCHF
2
SO
2
CF
3 cyclo-prop. OCHF 2
CH
3 cyclo-prop. OCHF 2
CF
3
CH
3 Cl
CU
3
CH
3 Cl
CF
3
CU
3 Cl CHCd 2
CU
3 dl
CCIF
2 25 Group 1 (continued) lR' JR 3
CH
3 Cl
NO
2
CH
3 CN
CH
3
CH
3 CN
CF
3
CH
3 CN CHC1 2
CH
3 CN
NO
2
CH
3
OCHF
2
NO
2
CH
3
OCHF
2
CN
CH
3 CN CN
CH
3
NO
2
CN
CH
3
NO
2 CH 3
CH
3
NO
2 CHF 2
CH
3 CN
CHF
2
CH
3 H
CH
3
CH
3 H
CF
3
CH
3 H CHC1 2
CH
3 H
CCIF
2
CH
3 H
NO
2
CH
3 OH
CH
3
CH
3 OH
CF
3
CH
3
N(CH
3 2
CH
3
CH
3
N(CH
3 2 CF 3
CH
3
N(CH
3 2 CHCl 2
CH
3
N(CH
3 2 CCIF 2
CH
3
N(CH
3 2 NO 2
CH
3
N(CH
3 2
CN
26 Group 1 (continued) JRI 1R2 R 3]
CH
3 CH- 3 CH 3
CU
3 CH 3 CF 3
CH
3 CH3
CHCI
2
CU
3 CH 3 CCIF 2
CH
3 CH 3 NO 2
CH
3
CH
3 CN
CH
3 CU 3 OCHF 2
CH
3 CH 3 SCH 3
CH
3 CU 3 OCU 3
CU
3 CN
OCHF
2
CU
3 N(CH 3 2 SCH 3
CU
3 NO 2 OCH 3
CU
3 CN
SCHF
2
CU
3 N(CH 3 2 OCU 3
CU
3 NO 2 SCH 3
CU
3 CN
OCU
2 Ph
CU
3 CF 3 CU 3
CU
3 CF 3 CHC1 2
CU
3 CF 3 CCIF 2
CU
3 CF 3 NO 2
CU
3
CF
3 CN
CU
3 CF 3 OCHF 2
CU
3 CF 3 SCH 3
CU
3 CF 3 OCH 3
CU
3
NO
2 OCU 2 Ph -27 Group 1 (continued) R' jR2 R 3
CH
3
CF
3 OCH 2 Ph
CH
3
N(CH
3 2
OCH
2 Ph
CH
3 CN
OCH
2 Ph cycl.-hexyl
OCHF
2 CH 3 cycl.-hexyl
OCHF
2 CF 3
CH
2
CF
3
N(CH
3 2 NO 2
CH
2
CF
3
N(CH
3
CN
CH
2
CF
3 CN
CN
CH9F 2 Cl
NO
2
CHF
2 Cl
NO
2
CHF
2 CN
CH
3
CHF
2
N(CH
3 2 NO 2 CHF., N(CH 3 2
CN
CH
3 0C 2
H
5
OCH
2 Ph
CH
3 0C 2
H
5 CH 3
CH
3 OC 2
H
5 CHC1 2
CH
3 OC 2
H
5 CCIF 2
CH
3 OC 2
H
5 NO 2
CH
3
OC
2
H
5
CN
CH
3 OC 2
H
5 OCHF 2
CH
3 OC 2
H
5 SCH 3
CH
3 OC 2
H
5 OCH 3
CH
2
CF
3
OC
2 H5 OCH 2 Ph
CH
2
CF
3
OC
2
H
5 CH 3
CH
2
CF
3
OC
2
H
5 CHCI 2 28 Group I (continued)
CH
2
CF
3 0C 2
H
5
CCIF
2
CH
2
CF
3 0C 2
H
5
NO
2
CH
2
CF
3 0C 2
H
5
CN
CH
2
CF
3 0C 2
H
5
OCHF
2
CH
2
CF
3
OC
2
H
5
SCH
3
CH
2
CF
3 0C 2
H
5
OCH
3
CH
3
OCH
3
NO
2
CH
3
OCH
3
CN
CH
3
OCH
3 CHC1 2
CH
3 0C14 3
CCIF
2
CH
3
OCH
3
SCK
3 Group 2 (IA-2) CH 3 Here, R 2 and R 3 have, for example, the meanings given above in Group 1.
-29- Group 3 (IA-3) Here, R 2 and R 3 have, for example, the meanings given above in Group 1.
Group 4
R
2
R(-R
3 N .(IA-4)
CH
3
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 R-N R 3
N-N
CH! Y" C I
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
30 Group 6
'N-
NN
CF
3
CN
(IA-6) R' and R 3 have, for example, the meanings given above in Group 1.
Group 7 N (IA-7)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 8
N-N
N-
CH
3 y COOCH 3 (IA-8)
W
2 and R 3 have, for example, the meanings given above in Group 1.
31 Growp 9 R 3 R R3
NN
N
CH
3
CI
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group R I N R R 3 -NN (IA- 1)
N
C F 3
Y
COOCH 3 R' and R3~ have, for example, the meanings given above in Group 1.
Group I11 R1N R 3 N- (IA-i11)
CF
3 32
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 12
R
2 R R 3 -N (IA-12) -N
CF
3
CONHCH
3
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 13 (IA-13)
NO
2
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 14 R 2
R
'N 'N
N-
'N
CH
3
COCH
3 (IA-14) -33
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 R-N1 R 3 N
N-N
C
2
H
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 16
R
2 R~N R 3
N
^N-y^ (IA-16)
N-N
CH3-NH
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 17
R
2 RN R 3
N-
(IA-17) CH-N -N C2HN CN
CN
-34-
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 18
R
2 1 R3 R'NxR 3
N
N-N (IA-18)
NH
-C2H CN CA 0
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 19
R
2 1 R 3 R N R O N-N (IA-19) CH, N
CN
CH
3 0
R
2 and R 3 have, for example, the meanings given above in Group 1.
35 Group
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 21
R
2 R- R
N=
Q 1,1 (IA-21)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 22 R-N R
R^
3
N=-
-N
CN
(IA-22) -36-
R
2 and R have, for example, the meanings given above in Group 1.
Group 23 1 R 3 N N -N (IA-23)
SN
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 24
R
2 R1 R 3 R' N
R
-N (IA-24)
-N
N
|Y
CSNH
2
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 R.N R
N-
O -N
CH
3
N
CH O CSNH2
R
2 and R 3 have, for example, the meanings given above in Group 1.
R2 and R 3 have, for example, the meanings given above in Group 1.
37 Group 26 R~N R 3 N-N (IA-26)
N
0 -j COOC
H
R
2 and R' have, for example, the meanings given above in Group 1.
Group 27 R N R 3 N-N (IA-27)
NCY"
COOc 2
H
R
2 and R' have, for example, the meanings given above in Group 1.
Group 28 R~N R 3
N-N
NC
CN
(IA-28) R(2 and R(3 have, for example, the meanings given above in Group 1.
38 Group 29
N-N
H 2 NSC6 CSNH 2 (JA-29) R 2 and R' have, for example, the meanings given above in Group 1.
Group N H7>
R
2 and R' have, for example, the meanings given above in Group 1.
Group 3 1
NH-
CN
(IA-3 1)
R
2 and R 3 have, for example, the meanings given above in Group 1.
-39- Group 32 (IA-32)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 33
R
2 CH3 N, H3 (IA-33)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 34 (IA-34)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
.OCH
3
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 36 (IA-36)
,OC
2
H,
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 37 1 Rl
N
(IA-37)
R
2 and R 3 have, for example, the meanings given above in Group 1.
-41 Group 38 (IA-38)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 39
R
2 1 3 R(N R 3 (IA-39)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
COOC
2 Hs
R
2 and R 3 have, for example, the meanings given above in Group 1.
-42 Group 41 NCOOC (IA-41) COOC2
H
COOC2,H
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 42
R
2 N R 3 N COO 2 H (IA-42)
OCH(CH
3 2
R
1
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 43 N OC H (IA-43)
CSNH,
R
2 and R 3 have, for example, the meanings given above in Group 1.
43 Group 44 R Nx R 3 N- NHSO 2c2HS (IA-44) CSNH 2
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group R N R 3 N- NHSO 22H5
CN
R(2 and R 3 have, for example, the meanings given above in Group 1.
Group 46 N ~NHS02 C 2H 5(IA-46)
COOCH
3 R(1, W( and W( have, for example, the meanings given above in Group 1.
-44- Group 47 (IA-47)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 48
R
2 I4 3 R'N R (IA-48)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 49 (IA-49)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 51
R
2 RN R 3 N (IA-51)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 52
CH,
1 3 (IA-52)
R
2 and R 3 have, for example, the meanings given above in Group 1.
-46 Group 53 (IA-54)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 R
R
3 N
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 56 (IA-56)
NO
2
R
2 and R 3 have, for example, the meanings given above in Group 1.
-47- Group 57 (IA-57)
,OCH(CH
3
)CO
2
CH
3
NO
2
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 58 (IA-58)
NHCOCH,
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 59 (IA-59)
NHCONH
2
R
2 and R 3 have, for example, the meanings given above in Group 1.
-48 Group
CH
2 COCH
CHOCOCH,
R
2 and R' have, for example, the meanings given above in Group 1.
Group 61
R
2 R R 3 R N R N .(IA-61)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 62 (IA-62)
R
2 and R 3 have, for example, the meanings given above in Group 1.
-49- Group 63 (IA-63)
CH
2 NHC 2H
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 64 (IA-64)
,CH
2 0CH 2
CI
CN
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 66 (IA-66) CH OCH(CH3)C=CH
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 67
R
2 R R(I N- (IA-67)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 68 1 R-
N
(IA-68)
R
2 and R 3 have, for example, the meanings given above in Group 1.
-51 Group 69
R
2
RNR
3 N- N
-N
H 2
N
(IA-69)
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group
R
2 RLN R 3
N-
N ci S F Cl
R
2 and R 3 have, for example, the meanings given above in Group 1.
Group 71 (IA-71) T cI soI
CI
R
2 and R 3 have, for example, the meanings given above in Group 1.
52 Using, for example, 5-difluoromethylthio-1,4-dimethyl-3-hydrazino-pyrazole and ethoxymethylene-malononitrile as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following scheme:
SCHF
2
S.,CHF,
H3C CH 3 NC H CSN CH 3 NH
N-N
NH2 H2
N
CN
The formula (II) provides a general definition of the hydrazinopyrazoles to be used as starting materials in the process according to the invention for preparing compounds of the formula In the formula R 2 and R 3 each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula according to the invention, as being preferred or as being particularly preferred for R 2 and R 3 The hydrazinopyrazoles of the general formula (II) have hitherto not been disclosed in the literature; as novel compounds, they also form part of the subject-matter of the present application.
The novel hydrazinopyrazoles of the general formula (II) are obtained when pyrazoles of the general formula (IV)
R
2 R N
(IV)
R
4 in which
R
2 and R 3 are each as defined above 53 are reacted with an alkali metal nitrite, such as, for example, sodium nitrite or potassium nitrite, in the presence of an acid, such as, for example, hydrochloric acid, and in the presence of a diluent, such as, for example, water, at temperatures between and +20°C, the reaction mixture is subsequently reacted with tin (II) chloride (dihydrate), if appropriate in the presence of an acid, such as, for example, hydrochloric acid, at temperatures between -20°C and +20°C and finally reacted with aqueous sodium hydroxide solution at temperatures between -20°C and +20°C (cf. the Preparation Examples).
Only some of the pyrazoles of the general formula (IV) required as precursors are known, and/or they can be prepared by known processes (cf. WO 94/08999, Preparation Examples). They can be prepared, for example, according to the scheme below: -54-
Q
R N R
N
COOC
,H
R
2 ^N
R
3 R N R
N=
SNH
3
R
2 RN R3
N
CONH
2 NaOH Br 2
R
2 RN
R
3
N-
NH2
H
2 0 OH.
SOCI
2
NH
3 The formula (III) provides a general definition of the cyanoalkenyl ethers further to be used as starting materials in the process according to the invention for preparing compounds of the formula In the formula (III), R 4 and R 5 each preferably or in particular have those meanings which have already been mentioned above, in connection with the description of the compounds of the formula according to the invention, as being preferred or as being particularly preferred for R 4 and R 5
R
preferably represents alkyl having 1 to 4 carbon atoms, in particular represents methyl L or ethyl.
'TL
55 The starting materials of formula (III) are known and/or can be prepared by known processes.
Suitable diluents for carrying out the process according to the invention are in particular inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chloro-benzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,Ndimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
Suitable reaction auxiliaries for the process according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide or potassium methoxide, sodium ethoxide or potassium ethoxide, sodium n- or i-propoxide or potassium n- or ipropoxide, sodium s- or t-butoxide or potassium s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N,N- -56 dimethyl-aniline, N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and 3,5-dimethyl-pyridine, 5-ethyl-2-methylpyridine, 4-dimethylamino-pyridine,N-methyl-piperidine, 1,4-diazabicyclo[2,2,2]-octane (DABCO), 1,5-diazabicyclo[4,30]-non-5-ene (DBN), or 1,8 diazabicyclo[5,4,0]-undec-7ene (DBU).
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between o0C and 150 0 C, preferably between 10 0 C and 120 0
C.
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure generally between 0.1 bar and 10 bar.
For carrying out the process according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to employ a relatively large excess of one of the components. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for a number of hours at the temperature required. Work-up is carried out by customary methods (cf. the Preparation Examples).
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 depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants: Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, 57- Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and railway tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for the control of weeds in perennial crops for example forests, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre-emergence and post-emergence.
58 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 formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifying agents and/or dispersing agents and/or foamforming agents.
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially the following: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
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, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as protein hydrolysates; suitable dispersing agents, are: for example lignin-sulphite waste liquors and methylcellulose.
43 -59- Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium 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, 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 For the control of 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, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochioridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl), hexazinone, imazamethabenz(methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachior, methabenzthiazuron, metobenzuron, metobromuron, metolachior, metosulam, metoxuron, metsulfuron- (-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norfiurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachior, primisulfuron(-methyl), prometryn, propachior, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchiorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenyichior, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active 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 -61 essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.
62 Preation Examples Example 1
OCHF
2
H
3 N
CH
3
N-N
H
2 N
-Y
CN
7.8 g (40 mmol) of 5-difluoromethoxy-3-hydrazino-1,4-dimethyl-pyrazole in 100 ml of ethanol are admixed with 5,1 g (42 mmol) of ethoxymethylenemalononitrile, stirred at reflux temperature for 12 hours and cooled to 15'C, and the precipitated product is isolated by filtration.
This gives 5.7 g of (53% of theory) of 5 -amino- 1-(5 -difluoromethoxy- 1,4-dimethyl-3pyrazolyl)-4-pyrazolecarbonitrile of melting point 1 ExaMle 2
OCHF
2
H
3 C N C H 3
N-N
H
2
N-
COOC
2
H
g (18 mmol) of 5-difluoromethoxy-3-hydrazino-1,4-dimethyl-pyrazole in 100 ml of ethanol are stirred with 3.38 g (20 mmol) of ethyl-2-(ethoxymethylene)-2-cyanoacetate and 1.08 g (0.02 mmol) of sodium methoxide at reflux temperature for 3 hours. The mixture is cooled and concentrated, the residue is stirred with water and the A- 1 63 precipitated product is isolated by filtration.
This gives 2.5 g (44% of theory) of ethyl 5-amino-1-(5-difluoromethoxy-1,4-dimethyl- 3-pyrazolyl)-4-pyrazolecarboxylate of melting point 72 0
C.
Example 3
OCHF
2
H
3 CN CH,
N-N
H
3
C
CONH-<
1.7 g (5,6 mmol) of 5-methyl-i -(5-difluoromethoxy- 1 ,4-dimethyl-3-pyrazolyl)-4-pyrazolecarbonyl chloride in 30 ml of acetonitrile are admixed with 0.64 g (11.2 mmol) of cyclopropylamine, and the mixture is stirred at approximately 25 0 C for about 2 hours.
The mixture is then concentrated, the residue is stirred with water and acidified with conc. hydrochloric acid and the product, which slowly precipitates, is isolated after hours by filtration.
This gives 0.9 g (50% of theory) of N-cyclopropyl-5-methyl-1-(5-difluoroethoxy-1,4dimethyl-3-pyrazolyl)-4-pyrazolecarboxamide of melting point 155 0
C.
Example 4
OCHF
2
H
3 CH 3
N-
N-N
NHY
0- CH3 -64g (3.7 mmol) of 5-amino-1-(5-difluoromethoxy-1,4-dimethyl-3-pyrazolyl)-4-pyrazolecarbonitrile in 30 ml of acetonitrile is admixed with 0.37 g (3.7 mmol) of triethylamine and subsequently admixed with 0.29 g (3.7 mol) of acetyl chloride, and the mixture is stirred at 25 0 C for 12 hours. The mixture is subsequently concentrated, stirred into water and extracted with methylene chloride, and the organic phase is dried over sodium sulphate and concentrated again. The crude product is purified over silica gel using cyclohexane/ethylacetate 7:1.
This gives 0.58 g (50.5% of theory) of 5-acetylamino-l-(5-difluoromethoxy-l,4dimethyl-3-pyrazolyl)-4-pyrazolecarbonitrile of melting point 133 0
C.
Example
OCHF
2
H
3 C,
CH
3
N-N
N-N
H
3
C
S
NH
2 0.6 g (2.2 mmol) of 5-methyl-l-(5-difluoromethoxy-l,4-dimethyl-3-pyrazolyl)-4pyrazolecarbonitrile in 10 ml of thioacetic acid are stirred at reflux temperature for 2 hours, concentrated, stirred with water and extracted with methylene chloride, dried over sodium sulphate, subsequently dissolved in diethyl ether and the product is precipitated with petroleum ether and isolated by filtration.
This gives 0.4 g (60.4% of theory) of 5-methyl-l-(5-difluoromethoxy-1,4-dimethyl-3pyrazolyl)-4-thiocarbamoyl-pyrazole of melting point 151 C.
Similarly to Examples 1 5, and in accordance with the general description of the preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula listed in Table 1 below.
/O?L 65 R 6 R 4 R Table 1: Examples of compounds of the formula (1) Ex R' R' R' R 5 R6physical No. data 6 CH 3
OCHF
2 Gir 3 H CN Br 71 OC 7 CH 3
OCHF
2
CH
3 CN NH 2 186'C
IH
CN
8 GH, OCHF., GB 3 H COOG 2
H
5
CH
3 'H NMR (GDGI 3 1.95; 2.55; 4.30- 4.38 ppm 9 GB 3
OGHF
2
CH
3 H GOOH GB 3 177'C
GB
3
OGHF
2
GH
3 H GONH 2
GB
3 96'C I1 GBC 3
OGHF
2
GH
3 H CN CH 3 81'C 12 GB 3
OGHF
2
GCH
3 H CN 1- Hm.p.:>250'G 0 NHCH 3 66 Ex R' R 3 R6 physical- No. data 13 CH 3
OCHF
2
GH
3 H CN -N(C 2
H
5 )2 log P 2.83 (acidic) 14 CH 3
OCHF
2 Gil 3 H CN -NHCOCF 3 173'C Gil 3
OGHF
2
CH
3 H 0GirlC 3 152'C
NHC
4
H.-S
16 Gil 3
OCHF
2 Gil 3 H CN 82'C 17 Gil 3
OCHF
2 Gil 3 H COOC 2 H, -NHCOCF, I110 0
G
18 Gil 3
OCHF
2 Gil 3 H GN OGH 3 250'C 19 Gil 3
OCHF
2 Gil 3 H COOC 2
H
5 'I (amorphous) 0C 2 H Gil 3
OGHF
2
GH
3 H GOOG 2
H
5
GF
3 (amorphous) 21 Gil 3
OGHF
2 Gil 3 H -fNH< GE 3 (amorphous) 0 22 Gil 3
OGHF
2 Gil 3 H -C-NH, GE 3 146'G 23 Gil 3
OCHF
2 Gil 3 H GN GF 3 76'G 67 Ex R' R' R' R 4 R' R physical No. data 24 CH 3
OCHF
2
CH
3 H CN -H C 6 H5 193 0
C
11 0
CH
3
O)CHF
2
CH
3 H CN -NHCH 3 148'C 26 CH 3
OCHF
2
CH
3 H CN -NH-C-C(CH 3 3 146 0
C
0 27 CH 3
OCHF
2
CH
3 H CN -HC0 201'C 11 0 0 28 CH 3
OCHF
2 Gil 3 H CN 109,C 29 CH 3
OCHF
2
CIA
3 H CN S 83'C
CH
3
CHF
2
CIA
3 H CN -NHCH(CH 3 2 72*C 31 CH 3 OC"iF 2 CH, H CN -NH-COCHBR 148-149-C 32 CIA 3
OGRE
2
GH
3 H GN 109-1 10 0
G
33 Gil 3
OCHF
2 Gil 3 H CN S 125-126 0
C
E34 G 3 O GR 2
G
3 H CN -NH-O-iC3
H
7 79-80'C GiH 3
IOGRE
2 Gil 3 H CN -NH-CO-CH-G 3
H
7 80-81 0
C
68 Ex R' R 2 R 3 R 4 R5 R6 physical No. data 36 CH 3
OCHF
2
CH
3 H CN 71-72 0
C
H
3 c 37 CH 3 OCH4F 2
CH
3 H CN 82-83 0
C
-NH-CO0 38 CH 3
OCHF
2
CH
3 H CN -NH-CO-0C 6 H, 102-1031C 39 CH 3
OCHF
2
CH
3 H CN -NH-SO 2
CH
3 11 7-1181C
CH
3
OCHF
2
CH
3 H CN -NH-COOC 3
H
7 83-841C 41 CH 3 OCHf 2
CH
3 H CN -NC3-o< Wax 42 CH 3
OCHF
2
CH
3 H CN s 4-41 43 CH 3 OCHF, CH 3 H CN -NHC 2
H
5 90-91,C 44 Cf! 3
OCHF
2
CH,
3 H CN -N(CH 3 2 116-117'C Cf! 3
OCHF
2
CH
3 H CN -NH-CH-(CH 3 CAH Oil 46 Cf! 3
OCHF
2
CH
3 H CN -N(CH 2
-CHF)
2 Oil 47 CH 3
OCHF
2
CH
3 H CN -NH-CH 2
-C
3
H
7 Wax 48 Cf! 3
OCHF
2 Cf! 3 H CN -N(CH C=C) i 49 Cf! 3
OCHF
2
CH
3 H CN -NHCON(C! 3 2 Oil Cf! 3
OCHF
2
CH
3 H CN -Nf!C00C 2 H, 84-85 0
C
51 Cf! 3
OCHF
2 Cf! 3 H CN -NHCSN(CH 3 2 Oil 52 Cf! 3
OCHF
2
CH
3 H CN -NSo2C,-K 141-142 0
C
53 Cf! 3
OCHF
2
CH
3 H CN -HO2-& C 114-115'C 54 Cf! 3
OCHIF
2
ICH
3 IH CN -NH-SO 2
C
2 H, 133-134 0
C
69 Ex R' R 2 R( 14 R 5 R(6 physical No. data Gil 3
OCHF
2
CH
3 H GN Cj1 Oil -CH
-C-COOCH
3
UCH
3 56 Gil 3
OCHF
2
CH
3 H GN -N=CH-N(CH 3 2 1 14'C 57 Gil 3
OCHF
2
CH
3 H CN -NHCOCH 2 Cl 153'C 58 Gil 3
OCHF
2
CH
3 H CN jm.p.: 83'C 59 Gil 3 OGRE, GH 3 H CN -N=GHOG 2
H
5 101 0
G
GH
3
N(GH
3 CN H GN -NH 2 223-224'G 2 61CH 3
OHF
2
GH
3 H CN -C 3 Oil 62 Gil 3
OGHIF
2 Gil 3 H CN I-*CH 3 Oil 63 Gil 3
OGHF
2 Gil 3 H CN CH 3 Oil 64 Gil 3
OGHF
2
CH
3 H GN -NI-CH 3 Oil Starting materials of the formula (II): Example (II-1)
OCHF
2 H3C"N
CH
3
N
NH-NH
2 10.5 g (59 mmol) of 5-difluoro-methoxy-3-amino-l,4-dimethyl-pyrazole are dissolved in 68 ml of water and 135 ml of conc. hydrochloric acid, a solution of 5.52 g mmol) of sodium nitrite in 24 ml of water is added dropwise at -10 0 C and the mixture is stirred for an hour at -10 0 C. 38 g (0.17 mol) of tin(II) chloride dihydrate dissolved in 49 ml of conc. hydrochloric acid are then added dropwise at the same temperature.
The mixture is stirred for a further 1.5 hours and 250 ml of 32% strength aqueous sodium hydroxide solution are subsequently added dropwise at -10 0 C. The mixture is extracted repeatedly with methylene chloride and ethyl acetate, the organic phase is dried over sodium sulphate and concentrated under water pump vacuum.
This gives 9.9 g (87% of theory) of 5-difluoromethoxy-3-hydrazino-1,4-dimethylpyrazole as an amorphousous product.
'H NMR (CDC1 3 2.00; 3.70; 6.45; 7.25 ppm -71 Starting materials of the formula (IV): Example (IV-1)
OCHF
2 H3 C N
CH
3
NH
2 Step 1
OCHF
2 H N CH 3 (IV-
N
COOC
2
H
168 g (0.92 mol) of 5-hydroxy-3-ethoxycarbonyl-l,4-dimethyl-pyrazole with 317 g (2.3 mol) of potassium carbonate in 700 ml of dimethylformamide are initially stirred at 80 0 C for 1 hour. At 110 0 C, chlorodifluoromethane is subsequently introduced for approximately 2 hours. After cooling to 25 0 C, the mixture is filtered off with suction, the filtrate is concentrated on a rotary evaporator, the residue is stirred with water, acidified with cone. hydrochloric acid and stirred at 25 0 C for 12 hours and the precipitated product is isolated by filtration.
This gives 185 g (86% of theory) of 5-difluoromethoxy-3-ethoxycarbonyl- 1,4-dimethylpyrazolyl of melting point 59 0
C.
-72- Step 2
OCHF
2 H3C N CH 3 (IV-2)
N
COOH
92.5 g (0.39 mol) of 5-difluoromethoxy-3-ethoxycarbonyl-1,4-dimethyl-pyrazole are stirred into 500 ml of 20% strength aqueous sodium hydroxide solution, the mixture is stirred at 80 0 C for one hour, stirred into ice-water and acidified with conc. hydrochloric acid, and the precipitated product is isolated by filtration.
This gives 58 g (72 of theory) of 5-difluoromethoxy-3-carboxy-1,4-dimethyl-pyrazole of melting point 175 0
C.
Step 3
OCHF
2 HC Nx CH 3 (IV-3)
N
COCI
58 g (0.28 mol) of 5-difluoromethoxy-3-carboxy-l,4-dimethyl-pyrazole in 400 ml of toluene are admixed with 5 drops of dimethylformamide, 42 g (0.35 mol) of thionyl chloride are added dropwise at 80 0 C over a period of 30 minutes and the mixture is subsequently stirred at reflux temperature until the evolution of gas has ceased, cooled to 25 0 C and concentrated on a rotary evaporator under water pump vacuum.
This gives 62,0 g (98 of theory) of 5-difluoromethoxy-3-chlorocarbonyl-1,4dimethyl-pyrazole as an oil.
'H NMR(CDCl3): 2.20; 3.90; 6.58 ppm.
73 Step 4
OCHF
2 HC
CH
3 (IV-4)
N_
CONH
2 36.9 g (0.16 mol) of 5-difluoromethoxy-3-chlorocarbonyl-l,4-dimethyl-pyrazole are initially charged in 250 ml of acetonitrile and, at at most 40 0 C (ice-bath cooling), ammonia gas is introduced rapidly over a period of 30 minutes. The mixture is stirred for another 30 minutes and filtered off with suction at 20 0 C, and the residue is rinsed thoroughly with water. The filtrate is concentrated under water pump vacuum and the residue is stirred with water, filtered off with suction and washed with water. Both filter residues are combined.
This gives 31.8 g (97 of theory) of 5-difluoromethoxy-3-carbamoyl-l,4-dimethylpyrazole of melting point 128 0
C.
Step
OCHF
2
H
3 C" N^ CH, H3 CH
N-
NH
2 At 5 0 C, 50 g (0.31 mol) of bromine are added dropwise to 63 g (1.6 mol) of sodium hydroxide in 300 ml of water and then, at the same temperature, 57 g (0.28 mol) of 5-difluoromethoxy-3-carbamoyl-1,4-dimethyl-pyrazole are introduced. The cooling bath is removed and the mixture is then stirred until a clear solution has formed. The mixture is subsequently heated to 80 0 C, stirred at this temperature for approximately 2 hours, then cooled to 25 0 C and extracted repeatedly with methylene chloride and ethyl acetate, and the organic phase is dried over sodium sulphate and concentrated under water pump vacuum.
74 This gives 41 g (82.7 of theory) of 5-difluoromethoxy-3 -amino- 1,4-dimethylpyrazole as an oil.
'H NMR(CDC1 3 1.85; 3.55; 6.45 ppm.
75 Further examples of intermediates of the formula (IV):
N-.
Table 2 CH, OCHF 2 0C 2
H
5 COOH 108 0
C
(WV-6) CH 3 OH 0C 2
H
5
COOC
2
H
5 'H NMR*): 3.7; 4.00-4.09; 4.3 1 4.40 ppm (WV-7) CH 3 OH OCH 3
COOC
2
H
5 82 0
C
(IV-8) CH 3 OH SCH 3
COOC
2
H
5 'H NMR*): 2.26; 3.79 ppm (WV-9) CH 3
OCHF
2 OH CN 60 0
C
(IV- 10) CH 3
OCHF
2 OH CONH 2 70 0
C
(IV- 11) CH 3
OCHF
2
OC
2
H
5 COOc 2
H
5 'H NMR*): 3.80; 4.10-4.18; 6.78 ppm (IV- 12) CHF 2
OCHF
2 H COOC 2
H
5 55 0
C
(IV- 13) CH-F 2
OCHF
2 H CONH 2 87 0
C
(IV- 14) CHF 2
OCHF
2
CH
3
COOC
2
H
5 72 0
C
CHF
2
OGRE
2
CH
3
COONH
2 67 0
C
(IV- 16) CH 3
OCHF
2
OC
2
H
4
OCHF
2
COOC
2
H
5 'H NMR*): 2.90- 2.96; 4.38- 4.45 ppm (IV-17) CH 3
OCH
2
C
6
H
5 H COOC 2
H
5 'H NMR*): 3.75; 10; 7.3 8 ppm 76 No. R1 R M.P.
(IV-18) Gil 3 OCH2C 6
H
5 H COOH 120 0
C
(IV-19) CH 3
OGH
2
G
6
H
5 H CONH 2 135 0
C
CH
3
OGHF
2
CH
3 NH2 'H NMR*): 1.85; 3.55; 6.45 ppm (IV-21) CH 3
OGHF
2
GH
2 Br COOG 2
H
5 'H NMR*): 3.85; 4.67; 6.76 ppm (IV-22) CH 2
GF
3
OCHF
2 Gil 3
GOOGH
5 58 0
C
(IV-23) CH 2
CF
3
OGHF
2
GH
3 GOOH 134 0
C
(IV-24) Gil 3 GN CN NH-, 123 0
C
Gil 3
N(CH
3 2 GN NH 2 1 04 0
C
(IV-26) Gil 3 H CN Nil 2 (IV-27) Gil 3 Gil 3 CN Nil 2 143 0
C
(IV-28) GH 3
SGH
3 GN NH 2 11 0 0
G
(IV-29) Gil 3
SCH(CH
3 2 CN NH 2 73 0
C
Gil 3 SCPH GN Nil, 82 0
C
(IV-3 1) GH 2
GF
3 OH H GOOG 2
H
5 135 0
C
(IV-32) Gil 3 0GH 3
OC
2 il 5
GOOG
2 H 'H NMR 4 3.70; 4.12; 4.35- 4.40 ppm (IV-33) Gil 3
OGH
3 0G 2
H
5 GOOH 1 16 0
C
The 1H NMR spectra were recorded in deuterochioroform (GDG1 3 using tetramethylsilane (TMS) as internal standard. Stated is the chemical shift as 8 value in ppm.
77 Use Examples: In the use examples, the following compound is used as comparative substance: OCHF 2
H
3 C' N '~CI
(A)
N-N
H 3
CY
CN
1 -(4-chloro-5-difluoromethoxy- 1 -methyl-pyrazol-3-yl)-pyrazole alias 4' -chloro-5 '-difluoromethoxy-1' ,5-dimethyl-( 1,3'-hi-i H-pyrazole)-4-carbonitrile (known from EP 542388, WO 94/08999).
-78- Example A Pre-emergence-Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound 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 sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is chosen so that the particular 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 in comparison with the development of the untreated control.
The figures denote: 0 no effect (like untreated control) 100 total destruction In this test, at application rates of 30, 60 and 125 g/ha, for example the compounds of Preparation Example 6 and 7 exhibit very strong activity against weeds such as Amaranthus Solanum Chenopodium Veronica (100%), Sorghum Stellaria Viola Echinocloa and Digitaria (100%), and were tolerated well by crop plants, such as, for example, wheat barley soya (0 and cotton (0 79 Table Al: Pre-emergence Test/Greenhouse Active compound Application rate (g of ai./ha) Wheat Soya Amaran- Cheno- Solanum thus podium
OCHF
2 H3C -N K CI
N-N
H
3 C
CN
95 100 100 100
OCHF
2 HGCN
H
3 NK CH
N-N
Br__
CN
0 0 100 REPLACEMENT SHEET (RULE 26) 80 Table A2: Pre-emergence Test/Greenhouse Active compound Application rate Barley Wheat Amaran- Sola- Vero- (g of ai./ha) thus num nica
OCHF
2
H
3 C_ N CI
N-N
H
3
C
CN
125 70 95 100 100 100 70 90 100 100 100
OCHF
2
H
3 C. N
CH
3
N-N
H
3 C
CN
125 0 0 100 100 100 0 0 100 100 100 REPLACEMENT SIHEET (RULE 26) 81 Table A3: Pre-emergence Test/Greenhouse Active compound Application rate Barley Cotton Digi- Echino- Sola- Vero- (g of ai./ha) taria chloa num nica
OCHF
2 H3C -N CH3
N-N
Br
N
CN
0 0 100 80 100 100 Active compound Appli- Maize Echino- Setaria cation rate chloa (g of ai./ha) Sorghum Chenopodium Stel- Viola laria
OCHF
2
H
3 CN -N
CH
3
N-N
H
3 C
N_
CN
(11) 95 90 100 95 99 REPLACEMENT SHEET (RULE 26) -82- Example B Post-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound 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.
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 desired per unit area. The concentration of the spray liquor is chosen so that the particular 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 in comparison with the development of the untreated control.
The figures denote: 0 no effect (like untreated control) 100 total destruction In this test, at application rates of 60 or 125 g/ha, for example the compounds of Preparation Example 6 and 11 exhibit very strong activity against weeds such as Amaranthus Datura Ipomoea Polygonum Solanum Abutilon (95-100%), Chenopodium (95-100%), Stellaria (95-100%) and Viola and were better tolerated by crop plants, such as, for example, wheat (10 barley (20 and maize (20 than 40%, REPLACEMENT SHEET (RULE 26) 83 Table Bi: Post-emergence Test/Greenhouse Active compound Appli- Barley Wheat Maize Ama- Datura Ipo- Poly- Solacation ranthus moea gonum num rate (g of ai./ha) OCHF 2
H
3 CN N~CI
N-N
H
3
CY
ON
90 40 90 100 100 100 100 100 OCHF 2 HOC- CH3
N
N-N
Br
K_
ON
20 10 20 100 100 100 100 100 OCHF 2 3 N K
N-N
H
3 0
ON
10 10 100 100 100 100 100 REPLACEMENT SHEET (RULE 26) 84 Table B2: Post-emergence Test/Greenhouse Active compound Application rate (g of ai./ha) Abuti- Ion Chenopodium Stellaria Veronica Viola
OCHF
2 H3C -N CH3 3 N N
N-N
Br 'Ny
CN
95
OCHF
2
H
3 CN
N~CH
3
N-N
H
3 C Nj
CN
100 100 100 REPLACEMENT SHEET (RULE 26)
Claims (4)
1. 1-(3-Pyrazolyl)-pyrazoles of the general formula (I) R 2 RN R 3 N (I) N-N R6 R 4 R characterized in that R' represents optionally hydroxyl-, cyano-, carboxyl-, halogen-, C 1 -C 4 -alkoxy-, Cl-C 4 -alkyl-carbonyl- or C 1 -C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, R 2 represents hydrogen, hydroxyl, halogen, cyano, nitro, N(R"R' 2 or represents alkyl, aralkyl, alkoxy or alkylthio having in each case 1 to 6 carbon atoms in the alkyl moiety and being in each case optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy, R 3 represents hydroxyl, cyano, nitro, or represents a radical from the series alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or C-C 4 -alkoxy, R 3 represents a radical from the series alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by halogen, REPLACEMENT SHEET (RULE 26)
86- R 4 represents hydrogen, halogen or optionally cyano-, halogen- or C,-C 4 alkoxy-substituted alkyl having 1 to 6 carbon atoms, R 5 represents hydrogen, cyano, nitro, amino or halogen, represents optionally cyano-, hydroxyl-, halogen- or C-C 4 -alkoxy-substituted alkyl having 1 to 6 carbon atoms, represents the grouping -(CH 2 )m-O-R 7 the grouping -(CH 2 )m-S(O)n-R 8 the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m-CO- O-R' 1 the grouping -(CH 2 R1 2 R 6 represents hydrogen, cyano, amino, halogen, represents alkyl having 1 to 6 carbon atoms and being in each case optionally substituted by cyano, hydroxyl, carboxyl, halogen, C 1 -C 4 -alkoxy or C-C 4 -alkoxy-carbonyl, R 6 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents alkoxymethylene amino having 1 to 4 carbon atoms in the alkoxy group, R 6 furthermore represents optionally nitro-, cyano-, halogen-, C 1 -C 4 -alkyl-, C l C 4 -halogenoalkyl-, C 1 -C 4 -alkoxy- or Cl-C 4 -halogenoalkoxy-substituted phenyl, R 6 furthermore represents pyrrolyl, pyrrolidinyl, piperidinyl or morpholinyl, each of which is optionally substituted by C 1 -C 4 -alkyl, represents the grouping -(CH 2 )m)-R 2 represents the grouping -(CH 2 )m-O-R 7 the grouping -(CH2)m-S(O)n-R, the grouping -(CH 2 )m-CO-R 9 the grouping -(CH 2 )m-CO- O-R'O, the grouping -(CH 2 )m-N(R",R 2 the grouping -(CH 2 )m-CQ- N(R",R 1 2 or the grouping -(CH 2 )mN=CHR 2 R 6 furthermore represents one of the groupings below REPLACEMENT SHEET (RULE 26)
87- 0 U 0 O 0 0 0 0 each of which is optionally substituted by halogen or C,-C 4 -alkyl, R 7 represents hydrogen, represents optionally cyano-, carboxyl-, nitro-, hydroxyl-, halogen-, C,-C 4 -alkoxy- or Cl-C 4 -alkoxy- carbonyl-substituted alkyl having 1 to 6 carbon atoms, R 7 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen, R 7 furthermore represents alkylcarbonyl, alkoxycarbonyl or alkylsulphonyl having in each case up to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or Cl-C 4 -alkoxy, or R 7 furthermore represents cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups and being in each case optionally substituted by cyano, carboxyl, halogen or C-C 4 -alkyl, R 8 represents optionally cyano-, carboxyl-, halogen-, C 1 -C 4 -alkoxy- or C-C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 REPLACEMENT SHEET (RULE 26) 88 carbon atoms and being in each case optionally substituted by cyano or halogen, R 9 represents hydrogen, represents optionally cyano-, carboxyl-, halogen-, C-C 4 -alkoxy- or C -C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen, R 1 0 represents hydrogen, represents optionally cyano-, carboxyl-, halogen-, Cl-C 4 -alkoxy- or C 1 -C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms or represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen, R" represents hydrogen or formyl, represents optionally cyano-, carboxyl-, halogen-, C 1 -C 4 -alkoxy- or C-C 4 -alkoxy-carbonyl- substituted alkyl having 1 to 6 carbon atoms, R" furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents a radical from the series alkylcarbonyl, alkoxycarbonyl, alkylaminocarbonyl, alkylsulphonyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulphonyl having in each case up to 6 carbon atoms in the alkyl or cycloalkyl groups and being in each case optionally substituted by cyano, halogen or Cl-C 4 -alkoxy, R" furthermore represents hetarylcarbonyl or arylcarbonyl, REPLACEMENT SHEET (RULE 26)
89- R 1 2 represents hydrogen, carbamoyl, represents optionally cyano-, carboxyl-, halogen-, C-C 4 -alkoxy- or C -C 4 -alkoxy-carbonyl- substituted alkyl or haloalkyl having 1 to 6 carbon atoms, R 12 furthermore represents alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by cyano or halogen or represents a radical from the series alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylamino, dialkylamino, dialkylaminocarbonyl, alkylaminothiocarbonyl, dialkylaminothiocarbonyl, alkylaminocarbonyl, alkylsulphonyl, cycloalkyl, cycloalkylcarbonyl, cycloalkyloxycarbonyl, cycloalkylaminocarbonyl or cycloalkylsulphonyl having in each case up to 6 carbon atoms in the alkyl or cycloalkyl groups and being in each case optionally substituted by cyano, halogen or C-C 4 -alkoxy, or represents phenyl-Cl-C 2 -alkyl, phenyl-C-C 2 alkylcarbonyl, phenoxy, benzoyl or furoyl, each of which is optionally substituted by fluorine or chlorine, R 12 furthermore represents hetarylcarbonyl or arylcarbonyl, Q represents O or S, m represents the numbers 0, 1, 2 or 3 and n represents the numbers 0, 1 or 2. 2. Process for preparing the l-(3-pyrazolyl)-pyrazoles of the general formula (I) REPLACEMENT SHEET (RULE 26) R 2 RN- R 3 (I) N-N R 6 R 4 R in which R 2 R 3 R 4 R 5 and R 6 are each as defined in Claim 1, characterized in that hydrazinopyrazoles of the general formula (II) R 2 RI R 3 NH N- NH NH, in which, R 2 and R 3 are each as defined above are reacted with cyanoalkenyl ethers of the general formula (III) OR NC R 4 (111) R in which R 4 and R 5 are each as defined above, REPLACEMENT SHEET (RULE 26) -91 if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent. 3. Herbicidal compositions, characterized in that they contain at least one 1-3- pyrazolyl)-pyrazole of the formula according to Claim 1. 4. Method for controlling undesirable plants, characterized in that 1-(3-pyrazolyl)- pyrazoles of the formula according to Claim 1 are allowed to act on undesirable plants and/or their habitat. Use of 1-(3-pyrazolyl)-pyrazoles of the formula according to Claim 1 for controlling undesirable plants. 6. Process for preparing herbicidal compositions, characterized in that 1-(3- pyrazolyl)-pyrazoles of the formula according to Claim 1 are mixed with extenders and/or surfactants. 7. Hydrazinopyrazoles of the general formula (II) R 2 R~N R 3 /(II) N= NH NH 2 characterized in that R' represents optionally hydroxyl-, cyano-, carboxyl-, halogen-, C 1 -C 4 -alkoxy-, CI-C 4 -alkyl-carbonyl- or C-C 4 -alkoxy-carbonyl-substituted alkyl having 1 to 6 carbon atoms, REPLACEMENT SHEET (RULE 26) 92 R 2 represents alkoxy or alkylthio having in each case 1 to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or C,-C4- alkoxy, R 3 represents hydroxyl, cyano, or represents a radical from the series alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and being in each case optionally substituted by cyano, halogen or Cl-C 4 -alkoxy, or R 3 represents a radical from the series alkenyl or alkinyl having in each case 2 to 6 carbon atoms and being in each case optionally substituted by halogen. 8. Pyrazoles of the general formula (IV) (IV) characterized in that the substituents in the formula (IV) are designated as follows R' R 2 R 3 R 4 CH 3 OCHF 2 OC 2 H 5 COOH CH 3 OH OCzH 5 COOC2H CH 3 OH OCH 3 COOC 2 H, CH 3 OH SCH 3 COOCH, CH 3 .OCHF 2 OH CN CH 3 OCHF 2 OH CONH 2 CH 3 OCHF 2 OC 2 H, COOC 2 H, REPLACEMENT SHEET (RULE 26) 93 )R2 R3 JR 4 CHF 2 OCHF 2 CH 3 COOCAH CHF 2 OCHF 2 CH 3 COONH 2 CH 3 OCHF 2 OC2H 4 OCHF 2 COOC2H CH 3 OCH 2 C 6 H. H COOC2H CH 3 OCH 2 C 6 H 5 H COOH CH 3 OCH 2 C 6 H. H CONH 2 CH 3 OCHF 2 CH 3 COO IH CH 3 OCHF 2 CH 3 COOCAH CH 3 OCHF 2 CH 3 CONH 2 CH 3 OCHF 2 CH 3 NH 2 CH 3 OCHF 2 CH 2 Br COOCAH CH 2 CF 3 OCHF 2 CH 3 COOCAH CH 2 CF3 OCHF 2 CH 3 COOH CH 3 OCH 3 0CAH COOC 2 H CH 3 OCR 3 0C 2 H, COOH CH 3 OCHF 2 CH 3 COdI REPLACEMENT SHEET (RULE 26)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19631865 | 1996-08-08 | ||
| DE1996131865 DE19631865A1 (en) | 1996-08-08 | 1996-08-08 | Substituted 1- (3-pyrazolyl) pyrazoles |
| PCT/EP1997/004083 WO1998006702A1 (en) | 1996-08-08 | 1997-07-28 | Substituted 1-(3-pyrazolyl)-pyrazoles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3941297A AU3941297A (en) | 1998-03-06 |
| AU716093B2 true AU716093B2 (en) | 2000-02-17 |
Family
ID=7802022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU39412/97A Ceased AU716093B2 (en) | 1996-08-08 | 1997-07-28 | Substituted 1-(3-pyrazolyl)-pyrazoles having herbicidal activity and intermediates for their preparation |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0923558A1 (en) |
| JP (1) | JP2000516926A (en) |
| CN (1) | CN1227546A (en) |
| AU (1) | AU716093B2 (en) |
| BR (1) | BR9711120A (en) |
| CA (1) | CA2262606A1 (en) |
| DE (1) | DE19631865A1 (en) |
| WO (1) | WO1998006702A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030032610A1 (en) | 1996-06-03 | 2003-02-13 | Gilchrest Barbara A. | Method to inhibit cell growth using oligonucleotides |
| US7183285B2 (en) | 2004-04-29 | 2007-02-27 | Pharmix Corp. | Compositions and treatments for inhibiting kinase and/or HMG-CoA reductase |
| US7163945B2 (en) | 2004-04-29 | 2007-01-16 | Pharmix Corp. | Compositions and treatments for inhibiting kinase and/or HMG-CoA reductase |
| US7199126B2 (en) | 2004-04-29 | 2007-04-03 | Pharmix Corporation | Compositions and treatments for inhibiting kinase and/or HMG-CoA reductase |
| WO2019196731A1 (en) * | 2018-04-08 | 2019-10-17 | 海利尔药业集团股份有限公司 | Substituted pyrazolyl pyrazole sulfonylurea compound or pesticide acceptable salt or composition thereof and use thereof |
| WO2019233372A1 (en) * | 2018-06-04 | 2019-12-12 | 海利尔药业集团股份有限公司 | Substituted pyrazolyl pyrazole sulfonamide compound or pesticidally acceptable salt thereof, composition and use thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2219484A1 (en) * | 1972-04-21 | 1973-10-31 | Bayer Ag | 0-PYRAZOLO (THIONO) -PHOSPHORUS (PHOSPHONE) ACID ESTER, METHOD FOR THEIR PRODUCTION AND USE AS INSECTICIDES AND ACARICIDES |
| IL103678A (en) * | 1991-11-13 | 1996-09-12 | Schering Ag | Pyrazolylpyrazole derivatives processes for the preparation thereof and herbicidal compositions containing the same |
| SK281874B6 (en) * | 1992-10-12 | 2001-08-06 | Hoechst Schering Agrevo Gmbh | New substituted pyrazole derivatives, processes for their preparation and their use as herbicides |
| DE4435373A1 (en) * | 1994-09-22 | 1996-03-28 | Hoechst Schering Agrevo Gmbh | Substituted pyrazolyl-pyrazole derivatives, process for their preparation and their use as agents with herbicidal activity |
| DE19532347A1 (en) * | 1995-09-04 | 1997-03-06 | Bayer Ag | 4-thiocarbamoyl-1- (3-pyrazolyl) pyrazole |
-
1996
- 1996-08-08 DE DE1996131865 patent/DE19631865A1/en not_active Withdrawn
-
1997
- 1997-07-28 EP EP97936663A patent/EP0923558A1/en not_active Withdrawn
- 1997-07-28 JP JP10509336A patent/JP2000516926A/en active Pending
- 1997-07-28 CN CN 97197114 patent/CN1227546A/en active Pending
- 1997-07-28 BR BR9711120-1A patent/BR9711120A/en not_active Application Discontinuation
- 1997-07-28 CA CA002262606A patent/CA2262606A1/en not_active Abandoned
- 1997-07-28 AU AU39412/97A patent/AU716093B2/en not_active Ceased
- 1997-07-28 WO PCT/EP1997/004083 patent/WO1998006702A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| BR9711120A (en) | 2000-08-08 |
| CA2262606A1 (en) | 1998-02-19 |
| CN1227546A (en) | 1999-09-01 |
| EP0923558A1 (en) | 1999-06-23 |
| AU3941297A (en) | 1998-03-06 |
| JP2000516926A (en) | 2000-12-19 |
| WO1998006702A1 (en) | 1998-02-19 |
| DE19631865A1 (en) | 1998-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE19641691A1 (en) | Substituted 2-amino-4-alkylamino-1,3,5-triazines | |
| US6348435B1 (en) | Substituted 2,4-diamino-1,3,5-triazine and their use as herbicides | |
| US6175010B1 (en) | 3-amino-1-cyanophenyl-uracils | |
| AU731129B2 (en) | Heterocycle-substituted aromatic amino compounds with herbicidal action | |
| AU723259B2 (en) | Substituted 2,4-diamino-1,3,5-triazines as herbicides | |
| AU716093B2 (en) | Substituted 1-(3-pyrazolyl)-pyrazoles having herbicidal activity and intermediates for their preparation | |
| AU761661B2 (en) | Substituted 3-aryl-pyrazoles | |
| CA2381009C (en) | Substituted thienyl(amino)sulfonylureas | |
| CA2256508A1 (en) | 3-cyanoaryl pyrazoles and use thereof as herbicides | |
| JP2000514805A (en) | Substituted aromatic carbonyl compounds and their derivatives | |
| AU6831000A (en) | Substituted heterocyclyl-2h-chromenes | |
| US6544931B1 (en) | Substituted heteroaryloxyacetanilides and their use as herbicides | |
| CA2275248A1 (en) | Heterocyclyluracil | |
| CA2251783A1 (en) | 3-cyanoaryl pyrazoles and their use as herbicides | |
| CA2274079C (en) | Substituted thienyl(amino)sulphonyl(thio)ureas as herbicides | |
| AU765922B2 (en) | Substituted N-cyano amidines | |
| MXPA03003426A (en) | Substituted phenyluracils. | |
| AU723070B2 (en) | Arylalkyltriazole derivatives and their use as herbicides | |
| AU743810B2 (en) | Thienylalkylamino-1,3,5-triazines and the use thereof as herbicides | |
| CA2319053A1 (en) | Substituted heteroarylmethyl compounds used as herbicides | |
| MXPA99000958A (en) | Substituted 1-(3-pyrazolyl)-pyrazoles | |
| CA2332443A1 (en) | Substituted 1,3-diaza-2-(thi)oxo-cycloalkanes | |
| MXPA99004750A (en) | Phenyl-uracil derivatives with herbicide effect | |
| MXPA00003381A (en) | Substituted 2,4-diamino-1,3,5-triazine and their use as herbicides | |
| MXPA00008639A (en) | Optically active substituted 2,4-diamino-1,3,5-triazines as herbicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) | ||
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |