CA1144560A - Substituted sulfonic acid anilides, their preparation and their use - Google Patents
Substituted sulfonic acid anilides, their preparation and their useInfo
- Publication number
- CA1144560A CA1144560A CA000342977A CA342977A CA1144560A CA 1144560 A CA1144560 A CA 1144560A CA 000342977 A CA000342977 A CA 000342977A CA 342977 A CA342977 A CA 342977A CA 1144560 A CA1144560 A CA 1144560A
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- Prior art keywords
- alkyl
- anilide
- substituted
- halogen
- dimethyl
- 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.)
- Expired
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/06—Sulfonic acid amides
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- 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
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- 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
- A01N47/02—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 no bond to a nitrogen atom
- A01N47/04—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 no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups
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- 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
- A01N47/02—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 no bond to a nitrogen atom
- A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
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- 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<
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- A—HUMAN NECESSITIES
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- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
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- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
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- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- A—HUMAN NECESSITIES
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- 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
- A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/48—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —S—C≡N groups
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/12—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines
- C07C259/18—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. N-hydroxyamidines having carbon atoms of hydroxamidine groups bound to carbon atoms of six-membered aromatic rings
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- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/52—Y being a hetero atom
- C07C311/64—X and Y being nitrogen atoms, e.g. N-sulfonylguanidine
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- C07C335/04—Derivatives of thiourea
- C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
- C07C335/10—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C335/12—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
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Abstract
ABSTRACT OF THE DISCLOSURE:
Novel substituted sulfonic acid anilides of the formula:
Novel substituted sulfonic acid anilides of the formula:
Description
- l - O.Z. 0050/033601 Substituted sulfonic acid anilides, their preparation and their use The present invention relates to novel sulfonic acid anilides, processes for the preparation of these compounds, the use of the compounds as growth regulators, and herbicide~, agents and mixtures which contain these acti~e in OE edients, as well as processes for the prepara-tion of these agents and of mixtures, and their use ln agriculture.
The use of fluorinated alkanesulfonic acid anilides as growth regulators and herbicides has been - 10 disc~-osed (U.S. Patent 3,639,474); compounds proposed lncllde, in particular, trifluoromethanesulfonic acld 5-acetamido-2-methyl-anilide and trifluoromethanesulfonic acid 5-acetamido-2-chloro-anilide (U.S. Patent 3,639,474), and trifluoromethanesulfonic acid 5-acetamido-
The use of fluorinated alkanesulfonic acid anilides as growth regulators and herbicides has been - 10 disc~-osed (U.S. Patent 3,639,474); compounds proposed lncllde, in particular, trifluoromethanesulfonic acld 5-acetamido-2-methyl-anilide and trifluoromethanesulfonic acid 5-acetamido-2-chloro-anilide (U.S. Patent 3,639,474), and trifluoromethanesulfonic acid 5-acetamido-
2,4-dlmethyl-anilide (U.S. Patents 3,894,078 and 4,013,444, German Laid-Open Applications DOS 2,406,475 and DOS 2,412,578, and J Agr. Food Chem. 22 (1974), 1111). Further, it has been disclosed that N-carbonyl-fluoroalkanesulfonic acid anilides substituted at the sulfonamide nitrogen (German Laid-Open Application DOS
1,917,821), fluoroalkanesulfonamido-diaryl ethers and thioethers (Belgian Patent 765,558) and N-cyano-halo-alkanesul~onic acid anilides (U,S. Patent 3,793,372) are effective growth regulators and herbicides. However, the activity and in particular the selectivity of these compounds is no~ satisfactory.
The present ipve~tio~ relates to substituted sulfonic acid a~ilides of the formula (I):
R3 ~
N-SO2CF3 (I) where R is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl (each of up to 12 çarbon atoms) or arylalkyl (of 7 to 14 carbon atoms), each of which may be unsubstituted or substituted by halogen, cyano, thiocyanato, azido, nitro, Cl_4-alkoxy, C6_10-aryloxy, Cl_4-alkylthio, C6 8-arylthio, Cl 4-alkylsulfinyl, Cl 4-alkylsulfonyl, arylsulfinyl, arylsulfonyl, Cl 5-alkanoyl, Cl 5-alkoxycarbonyl, Cl 5-alkylcarbamyl, di-~Cl 5-alkyl)-carbamyl, Cl 4-alkanoylamino, Cl 4-haloalkanoylamino, C1 6-alkanoyloxy, Cl 4-alkanoylthio, Cl 4-alkoxycarbonylamino, C7 13-aroyloxy, Cl 6-alkylamino, 1 6 ~ 6-12 arylamino, Cl 6-alkylcarbamylamino di-(Cl 6-alkyl)-carbamylamino, Cl 6-alkylcarbamyloxy, di-(Cl 6-alkyl)-carbamyloxy, Cl 4-alkylaminosulfonyloxy or di-(Cl 4-alkyl)-aminosulfonyloxy or combinations of these groups, or ls cyano, thiocyanato, unsubstltuted or Cl 4-alkyl-substituted amino, aminosulfonyl, guanyl, N -hydroxyguanyl, hydroxymoyl or Cl 5-alkoxyimidoyl, or is unsubstituted or halogen-substituted Cl 4-alkylsulfenyl or Cl 4-alkylsulfinyl, or is unsubstituted or halogen- and/or Cl 4-alkyl-substituted arylsulfinyl or arylsulfonyl, where aryl is of up to 10 carbon atoms, R and R are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1 4-alkyl, Cl 4-alkoxy, Cl 4-;
alkylthio, Cl 4-alkylsulfinyl, Cl 4-alkylsulfonyl ox Cl 4-alkanoyl.
R may be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, lsobutyl, tert.-butyl, cyclob.utyl, n-pentyl, pent-2-yl, pent-3-yl, tert.-amyl, neopentyl, 2-methyl-butyl, 3-methyl-butyl, 3-methyl-but-2-yl, cyclo-pentyl, n-hexyl, 4-methyl-pent-2-yl, 2,3-dimethylbutyl, 2-methyl-pent-2-yl, hex-2-yl, hex-3-yl, 3-methyl-pent-2-yl,
1,917,821), fluoroalkanesulfonamido-diaryl ethers and thioethers (Belgian Patent 765,558) and N-cyano-halo-alkanesul~onic acid anilides (U,S. Patent 3,793,372) are effective growth regulators and herbicides. However, the activity and in particular the selectivity of these compounds is no~ satisfactory.
The present ipve~tio~ relates to substituted sulfonic acid a~ilides of the formula (I):
R3 ~
N-SO2CF3 (I) where R is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl (each of up to 12 çarbon atoms) or arylalkyl (of 7 to 14 carbon atoms), each of which may be unsubstituted or substituted by halogen, cyano, thiocyanato, azido, nitro, Cl_4-alkoxy, C6_10-aryloxy, Cl_4-alkylthio, C6 8-arylthio, Cl 4-alkylsulfinyl, Cl 4-alkylsulfonyl, arylsulfinyl, arylsulfonyl, Cl 5-alkanoyl, Cl 5-alkoxycarbonyl, Cl 5-alkylcarbamyl, di-~Cl 5-alkyl)-carbamyl, Cl 4-alkanoylamino, Cl 4-haloalkanoylamino, C1 6-alkanoyloxy, Cl 4-alkanoylthio, Cl 4-alkoxycarbonylamino, C7 13-aroyloxy, Cl 6-alkylamino, 1 6 ~ 6-12 arylamino, Cl 6-alkylcarbamylamino di-(Cl 6-alkyl)-carbamylamino, Cl 6-alkylcarbamyloxy, di-(Cl 6-alkyl)-carbamyloxy, Cl 4-alkylaminosulfonyloxy or di-(Cl 4-alkyl)-aminosulfonyloxy or combinations of these groups, or ls cyano, thiocyanato, unsubstltuted or Cl 4-alkyl-substituted amino, aminosulfonyl, guanyl, N -hydroxyguanyl, hydroxymoyl or Cl 5-alkoxyimidoyl, or is unsubstituted or halogen-substituted Cl 4-alkylsulfenyl or Cl 4-alkylsulfinyl, or is unsubstituted or halogen- and/or Cl 4-alkyl-substituted arylsulfinyl or arylsulfonyl, where aryl is of up to 10 carbon atoms, R and R are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1 4-alkyl, Cl 4-alkoxy, Cl 4-;
alkylthio, Cl 4-alkylsulfinyl, Cl 4-alkylsulfonyl ox Cl 4-alkanoyl.
R may be methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, lsobutyl, tert.-butyl, cyclob.utyl, n-pentyl, pent-2-yl, pent-3-yl, tert.-amyl, neopentyl, 2-methyl-butyl, 3-methyl-butyl, 3-methyl-but-2-yl, cyclo-pentyl, n-hexyl, 4-methyl-pent-2-yl, 2,3-dimethylbutyl, 2-methyl-pent-2-yl, hex-2-yl, hex-3-yl, 3-methyl-pent-2-yl,
3-me~hylpentyl, 3-methyl-pent-3-yl, 4,4-dimethylbutyl, cyclohexyl, heptyl, hept-2-yl, hept-3-yl, hept-4-yl, cycloheptyl, oct-l-yl, oct-2-yl, oct-3-yl, oct-4-yl, oct-6-yl, 5-ethyl-hept-2-yl, 2,6-dimethyl-hept-4-yl, 7-ethyl-2-methyl-non-4-yl, 2,4-dlmethyl-pent-3-yl, 3-methyl-hept-2-yl, 5-ethyl-non-2-yl, nonyl, decyl, undecyl, dodecyl, 6-ethyl-dec-3-yl, 6-ethyl-oct-3-yl, 2-methyl-pent-2-yl, 2,3-dimethyl-but-2-yl, 2-methyl-hex-2-yl, 3-ethyl-pent-3-yl, 3-methyl-hex-3-yl, 2,3-dimethyl-pent-3-yl, 2,4-_~_ , . ...
` 1144560 - - 4 - o.Z. OoS0/033601 dimethyl-pent-2-yl, 2,2,3-trimethyl-but-3-yl, 2-methyl-hept-2-yl, 4-methyl-hept-4-yl, 2,4-dimethyl-hex-2-yl, 2-methyl-oct-2-yl, l-methyl-cyclopent-l-yl, l-methyl-cyclohex-l-yl, l-ethyl-cyclohex-l-yl, chloro-tert.-butyl, 1,1-d~chloro-2-methyl-prop-2-yl', 1,3-dichloro-2-methyl-prop-2-yl, l-cyclohexyl-eth-l-yl, l-chloroethyl, 2-chloro-ethyl, l-chloropropyl, 2-chloropropyl, 3-chloropropyl, l-chloro-prop-2-yl, 2-chlorobutyl, 2-chloro-2-methyl-prop-3-yl, l-fluoroethyl, 2-fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 1-fluoro-prop-2-yl, 2-fluorobutyl, 2-fluoro-2-methyl-prop-3-yl, 2-bromoethyl, 3-bromopropyl,
` 1144560 - - 4 - o.Z. OoS0/033601 dimethyl-pent-2-yl, 2,2,3-trimethyl-but-3-yl, 2-methyl-hept-2-yl, 4-methyl-hept-4-yl, 2,4-dimethyl-hex-2-yl, 2-methyl-oct-2-yl, l-methyl-cyclopent-l-yl, l-methyl-cyclohex-l-yl, l-ethyl-cyclohex-l-yl, chloro-tert.-butyl, 1,1-d~chloro-2-methyl-prop-2-yl', 1,3-dichloro-2-methyl-prop-2-yl, l-cyclohexyl-eth-l-yl, l-chloroethyl, 2-chloro-ethyl, l-chloropropyl, 2-chloropropyl, 3-chloropropyl, l-chloro-prop-2-yl, 2-chlorobutyl, 2-chloro-2-methyl-prop-3-yl, l-fluoroethyl, 2-fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 1-fluoro-prop-2-yl, 2-fluorobutyl, 2-fluoro-2-methyl-prop-3-yl, 2-bromoethyl, 3-bromopropyl,
4-chlorobutyl, 2-chlorocyclohexyl, 1,1,l-trifluoroiso-propyl, hexafluoro-2-methyl-isopropyl, hexafluoroiso-propyl, hexachloroisopropyl, 1,2-dibromo-allyl, 2,2,2-trifluoroethyl, l-chlorobut-2-yn-4-yl, 3-chlorobut-1-yn-4-yl, 1-chlorobut-2-en-4-yl, 2,3-dibromo-prop-1-yl, 2,2,2-trichloroethyl, 1-chloropent-2-yn-4-yl, 2,2,2-tri-bromoethyl, 3,4,4-trichlorobut-3-en-2-yl, l-bromo-prop-2-yl, 1,3-dibromo-prop-2-yl, 3-chlorobut-1-en-4-yl, allyl, methallyl, crotyl, 2-ethylhex-2-en-1-yl, hex-5-en-l-yl, undec-10-en-1-yl,2-methyl-but-2-en-1-yl, 2-methyl-but-l-en-3-yl, but-1-yn-3-yl, but-2-yn-1-yl, but-1-en-3-yl, propargyl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-,4-yl, 3-methylbut-1-en-3-yl, l-ethynylcyclohexyl, methoxy-ethyl, ethoxyethyl, 3-methoxypropyl, methoxyisopropyl, 3-methoxybutyl, 1-methoxybut-2-yl, ethoxy-tert.-butyl, methoxy-tert.-butyl, cyclohexoxy-tert,-butyl, 2-methoxy-butyl, 4-methoxy-butylS methyl-mercapto-ethyl, ethyl-mercapto-ethyl, 3-methylmercapto-propyl, 3-methyl-4S6(~
- 5 - o.z. oO50/033601 mercaptobutyl, l-methylmercapto-but-2-yl, methylmercapto-tert.-butyl, 2-methylmercaptobutyl, 4-methylmercaptobutyl, 3-n-butoxyethyl, 2-ethoxypropyl, 3-ethoxy-prop-2-yl, 2-methylbutan-3-on-1-yl, 2-methylpentan-4-on-2-yl, butan-3-on-1-yl, butan-3-on-2-yl, propan-2-on-1-yl, pentan-2-on-l-yl, methylacetate-2, ethylacetate-2, methylpropionate-2, methylpropionate-3, 2-ethoxy-ethylacetate-2, 2-methoxy-methylpropionate-2, methyl-(2-vinyl-propionate-2), methylcarbamyl_methyl, dimethyl-lo carbamyl-methyl, cyano, thiocyanato, guanyl, N2-methyl-guanyl, Nl-methylguanyl, Nl-isopropylguanyl, Nl,Nl-dimethylguanyl, Nl,Nl,N2-trimethylguanyl, N2-hy~roxy-guanyl, N2-methoxyguanyl, methoxy-imidoyl, iso~ropoxy-imidoyl, methanecarbohydroximoyl, ben~ohyd.oximoyl, 0-methyl-benzo-hydroximoyl, aminocarbonylmethyl, amino-carbonylethyl, amino, dimethylamino, N-isopropyl-N-methyl-amino, methylamino~ isopropylamino, ethylsulfenyl, 2,4-dinitrophenylsulfenyl, dichlorofluoromethylsulfenyl, tri-chloromethylsulfenyl, N-methylsulfamyl, N-isopropyl-N-2~ methylsulfamyl, a-cyanoethyl, ~-cyanoethyl, cyanomethyl, thiocyanatomethyl, methylsulfinyl-methyl, benzylsulfinyl-methyl, 4-methylsulfinyl-butyl, 1-methylsulfonyl-but-2-yl, ethylsul~onylethyl, methylsulfonylmethyl, p-chloro-benzylsulfonylmethyl, phenylsulfonylmethyl, azidomethyl, ~-azidoethyl, acetylaminomethyl, p-chlorobenzoylamino-methyl, propionyloxymethyl, acetoxymethyl, N-(2,6-dimethylphenyl)-N-methoxycarbonyl-aminomethyl, N-(2-ethylphenyl)-N-ethoxycarbonyl-ami~omethyl, N-12-methyl-6-ethyl-phenyl)-N-chloroacetyl-aminomethyl, ~-N,N-dimethylamino-ethyl, ~-N,N-diisopropylaminoethyl, ~-N-phenylaminoethyl, piperidinomethyl, dimethylaminomethyl, morpholinomethyl, methylsulfonyloxymethyl and N-methylamlnosulfonyloxymethyl.
In a particularly preferred category of sulfonic acld anilides of the general formula (I), R is Cl 4-alkyl which is unsubstituted or is substituted in the a-or ~-position (relative to the sulfonamide nitrogen) by halogen, cyano, thiocyanato or azido, or is Cl 3-alkyl which may be substituted at the a- or ~-carbon by Cl 4-alkoxy, Cl 3-alkylsulfinyl, Cl 2-alkylsulfonyl, N-chloroacetyl-N-arylamino, di-(Cl 4-alkyl)-carbamylamlno, Cl 4-alkoxycarbamyl, Cl_6-alkanoyloxy or C7_13-aroyloxy, or is unsubstituted or halogen-substituted alkenyl or alkynyl of 3 or 4 carbon atoms, or is cyano or thiocyanato, R and R3 independently of one another are each hydrogen, methyl, halogen, methoxy, methylthio or methylsulfonyl.
For the purposes of the invention, halogen is preferably fluorine, chlorine or bromine and cycloalkyl ls preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
The lnventlon further relates to a process for the preparation of a substituted sulfonic acid anilide of the general formula (I), wherein:
a) a compound of the formula (II):
~-SO2CF3 (II) R2 Rl ~ 4560 where R2 and R3 have the above meanings, is reacted with a compound of the formula (III):
Rl _ L (III) where Rl has the above meanings and L is a nucleophilically displaceable leaving group æelected from the group consisting of halogen, bisulfate, halosulfonate, unsubstituted or substi-tuted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, oxonium, sulfonium and ammonium, in the presence or absence of a diluent, in the presence or absence of an acid acceptor and in the presence or absence of a reaction accelerator at from 0 to 170C, or b) a compound of the formula (IV):
~H-CO-CH3 ~ N-R
R2 H (IV) where Rl, R2 and R3 have the above meanings, is reacted with a sulfonating agent of the formula (V):
CF3 - SO2 - Z (V) where Z is a leaving group, selected among halogen and anhydride radical CF3-SO2O-! in the presence or absence of a diluent and in the preæence or absence of an organic or inorganlc base, at from -60 to +120C.
Instead of the free hydrogen-containing compounds of the formulae (II) or (IV), it is possible to use the corresponding salts, for example alkali metal salts, alkaline earth metal salts or unsubstituted or alkyl-substituted ammonium salts, which may be prepared by conventional methods in a preliminary reaction, or which may, if desired, be prepared in situ by adding the equi-valent amount of an organic or inorganic base.
A derivative obtained by the above methods, where .~ - 7 -11~4560 Rl is alkylthioalkyl ox arylthioalkyl, may, if desired, be oxidized to the corresponding sulfinyl or sulfonyl compound.
A derivative where Rl is cyano may be reacted with an amine, alcohol or hydroxylamine to qive the cor-responding guanyl or alkoxyimldoyl compound.
If trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anllide and methyl bromide are used as starting materials, the course of the reaction in variant a) of the process according to the invention may be represented by the followinq equation~
-' 1144S60 :
_ 9 _ O.z. 00~0/033601 n O
Nl HC-CH3 NHC-CH3 3C`[~3~ + CH3Br ~ ~L
N-S02CF3 ~N-S02C~3 3 C~ CH3 If the sodium salt of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anilide and chloroaceto-nitrile are used as starting materials and sodium iodide as the reaction accelerator, the course of the reaction in variant a) of the process according to the invention can be represented by the following equa-tion: ' O O
NHC-CX3 N~C-CH3 N SO CF H2CN -NaCl~ ~ 2C~3 CH3 Na CH
If 5-acetamido-2-methyl-phenyl-cyanamide and trifluoromethanesulfonic acid chloride are used as starting materials, the course of the reaction in ~ariant - b) of the process according to the invention can be rep-resented by the following equation:
ClS02CF3 HCl) ~
N-SO CF
- 10 - o.z. 0050/033601 The following are examples of solvents or dilu-ents which can be used for either variant of the process:
water; formamides, eg. dimethylformamide, formamide;
dimethylacetamide; nitriles, eg. acetonitrile, benzonitrile and butyronitrile; sulfoxides, eg. dimethylsulfGxide;
phosphoric acid amides, eg. hexamethylphosphorotriamide;
ketones, eg. acetone, ethyl methyl ketone, cyclohexanone and acetophenone; ethers, eg. tetrahydrofuran, anisole, dimethoxyethane, n-butyl ethyl ether and dioxane; nitro-alkanes, eg. nitromethane; nitrobenzene; alcohols, eg.methanol, ethanol, isopropanol, n-butanol and 3-methyl-butanol; ureas, eg. tetramethylurea; ether-alcohols, eg. ethylene glycol monomethyl ether; sulfones, eg.
sulfolan; esters, eg. ethyl acetate, methyl propionate and methyl formate; halohydrocarbons, especially chloro-hydrocarbons, eg. methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2- or 1,1,1,2-tetrachloroethane, dichloropropane, trichloroethylene, chlorobenzene, o-, m-and p-dichlorobenzene, fluorobenzene, o-, m- and p-chloro-toluene; dichloronaphthalene and carbon tetrachloride;aliphatic and cycloaliphatic hydrocarbons, eg heptane, pinane, o-, m- and p-cymene, gasoline fractions boiling within the range from 70 to 190C, cyclohexane, methyl-cyclohexane, decalin, petroleum ether, naphtha, 2,2,4-trimethylpentane and octane; aromatic hydrocarbons, eg.
benzene, toluene, o-, m- and p-xylene and tetralin; and mixtures of the above. AdYant2geously the amount of ``" ~144S60 ~ O.Z. 0050~033601 solvent used is from 100 to 2,000% by weight, preferably from 100 to 1,000% by weight, based on the starting com-pound (II) or (IV).
Processes a) and b) according to the invention are preferably carried out in the presence of an organic or inorganic base. In particular, basic hydroxy com-pounds, basic oxides, tertiary amines, alcoholates, carbonates or hydrides are used', eg. potassium hydroxide, sodium hydroxide, potassium carbonate, calcium oxide, barium oxide, magnesium hydroxide, magnesium oxide, barium hydroxide, calcium carbonate, magnesium carbonate, magnesium bicarbonate, zinc hydroxidé, zinc oxide, zinc carbonàt'e, zinc bicarbonate, sodium methylate, magnesium ethylate, potassium ethylate, sodium propylate, aluminum isopropylate,'sodium butylate, lithium methylate, calcium cyclohexanolate, sodium isopropylate, potassium tert.-butylate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec.-butylaminé, tri-tert -butylamine, tribe~zylamine, tricyclohexylamine, triamylamine', trihexylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-diisopropyl-aniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dipropyltoluidine, N,N-dimethyl-p-aminopyridine, N,N-dlethyl-p-aminopyridine, N-methylpiperidine, N-ethyl-piperidine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpyrrole, N-methylmorpholine, N-ethylmorphollne, N-methylhexamethyleneimine, pyridine, quinoline, ~ - and ~-picoline, N,N,N',N'-tetramethylethylenediamine, N-ethyldiisoprcpylamine, N,N-dimethylcyclohexylamine, sodium i14~560 - 12 - o.Z. 0050/033601 hydride, lithium hydride and calcium hydride. How-ever, other basic compounds conventionally employed may also be used. Preferred reaction accelerators are metal iodides and bromides, eg. sodium iodide, potassium bromide and calcium iodide, crown ethers, quaternary ammonium compounds, eg. tetrabutylammonium iodide or tetrabutylammonium bromide, and combinations of these compounds Process a) is in general carried out continuously lo or batchwise at from 0 to 170C, preferably from 0 to 140C, for from 30 minutes to 100 hours, preferably from 1 hour t~ 24 hours, under atmospheric or superatmospheric pressure.
In general, in process a), from 0.5 to 2 moles, preferably from 0.9 to I 5 moles, of compound (III), with or without from 0.5 to 2 moles of base and from 0.01 to 0.1 mole of reaction accelerator, are employed per mole of compound (II) or of a corresponding salt. Where a water-miscible solvent or diluent has been used, the end product of the formula (I) is isolated by introducing the reaction solution, or the residue which remains after remo~al of the solvent or diluent, into dilute aqueous alkali solution. If an oil separates out, it is extracted or the supernatant solution is decanted; if a precipitate is formed, it is filtered off. Where a water-immiscible diluent has been used, the organic phase is in general extracted with a dilute, aqueous alkali solution, dried and concentrated. If the desired product prec pitates directly during the reaction, it can `" 11~4560 - 13 - O.Z. 0050/033601 be isolated by simple suction filtration. Where necessary, the end products can be purified further in a con~entional manner, for example by recrystallization or chromatography.
Process b) is in general carried out continuously or batchwise, at from -60 to +120C, prefer-ably from -40 to +80C, in from 1 to 100 hours, under atmospheric or superatmospheric pressure. In general, from 0.8 to 1.3 moles, preferably from 0.9 to 1.1 moles, lo of the sulfonating agent, and from 0.8 to 2 moles of the base, are employed per mole of the compound of the for-mula (IV). The end product of the formula (I) is isolated by the methods described for process a).
A solution of 5.9 parts of sodium cyanide in 40 parts of water is added dropwise in the course of about 10 minutes to a suspension of 19.2 parts of bromine in 80 parts of water at from 0 to 10C, whilst stirring.
After the mixture has become colorless, a solution of 4 parts of sodium hydroxide and 31 parts of trifluoro-methanesulfonic acid 5-acetamido-2,4-dimethyl-anilide in 50 parts of water is run in and stirring is continued for 5 hours at 50C. When the batch has cooled, it is rendered alkaline with a small amount of aqueous alkali metal hydroxide solution and the precipitate is filtered off. After drying, 29.5 parts (88% of theory) of trifluoromethanesulfonic acid 5-acetamido-Nl-cyano-2,4-dimethyl-anilide, of melting point 110 - 111C, are obtained.
- 14 - o.~. o~o/033601 15.5 parts of chloromethyl methyl sulfide are added in one shot to a solution of 49.8 parts of the Na salt of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anilide in 150 parts of dimethylformamide.
The reaction mixture is then stirred for about 8 hours at room temperature, poured into water and extracted with ether, and the organic phase is washed with water and 1 N
aqueous sodium hydroxide solution. After drying and concentrating the organic phase and stirr ng the residue with diisopropyl ether, 48.1 parts (86.7% of theory) of tri nuoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylthiomethyl-anilide, of melting point 106 - 107C, are obtained 17 parts of trifluoromethanesulfonic acid chlor-ide and 10.~ parts of triethylamine are added dropwise, ; simultaneously but separately, to 17.3 parts of 5-acet-amido-2,4-dimethyl-N-methylaniline in 100 parts of chloroform at 0C. The mixture is then stirred o~er-night at room temperature,after which the precipitate is filtered off and thoroughly washed with chloroform, and the organic phase is extracted with water and 2 N aqueous hydrochloric acid. After drying and concentrating the organic phase, 24 parts (82% of theory) of trifluoro-methanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methyl-anilide, of melting point 128-130C, are obtained.
7.2 parts of sodium carbonate are added to a - 15 - o.Z. oOSo/033601 suspension of lO parts of O-methylhydroxylamine hydro-chloride in lOO parts of ethanol and the mixture is then stirred for l hour at room temperature. After adding 37 parts of tr~fluoromethanesulfonic acid 5-acetamido-Nl-cyano-2,4-dimethyl-anilide, the batch is stirred for lO hours at room temperature and 5 hours at 50C, the sol~ent is stripped off under reduced pressure and the residue is poured into water. The oil which separates out is extracted with ethyl acetate and the organic phase is washed-twice with water, dried and concentrated.
On treating the residue with diisopropyl ether/toluene, 25 parts of trifluoromethanesulfonic acid 5-acetamido-2,4-dlmethyl-Nl-(N2 -methoxy)-guanyl)-anilide, of melting point 105 - 107C, are obtained, A solution of 10 parts of 85% pure m-chloroper-benzoic acid in 120 parts of chloroform is added to 18.6 parts of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylthiomethyl-anilide (Example 2) in 200 parts of chloroform at -10C. After the mixture has stood o~ernight, it is poured into excess saturated aqueous bicarbonate solution and the organic phase is separated off, again washed with bicar-bonate solution, dried and concentrated. On thor-i oughly stirring the residue with diisopropyl ether, 16.5 parts (82% of theory) of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylsulfonylmethyl-anilide, of melting point 161 - 163C, are obtained.
- 16 - o.z. 0050/0336~1 The following further compounds of the general formula (I) were prepared by the processes described above.
11~456~1 - 17 - O.Z. 0050~033601 .
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~1~4560 - 28 - O.Z. OOSOJ033601 The novel active ingredients have a strong bio-logical action on plants, ie. they influence plant growth either by retarding upward ~rowth, by changing the con-centration of plant materials or by destroying undesirable ; plants whilst sparing the crop plants.
The agents according to the invention may be applied, for instance, in the form of directly sprayable solutions,powders,suspensions or dispersions,emulsions,oil dispersions,pastes, dusts, broadcasting agents or granules, by spraying, atomizing, dusting, broadcasting or water-ing The forms of application depend entirely on the purpose for which the agents are being used.
For the preparation of directly sprayable solu-tlons, emulsions, pastes and oil dispersions,mineral oil - fractions of medium to high boiling point, such as kero-sene or diesel oil, coal tar oils and the like,andoils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene, xylene, paraffin, tetrahydronaphthalene and alkylated naphthalenes, and their deri~ati~es, eg. methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene or isophorone, and strongly polar solvents, eg dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and water, are suitable.
A~ueous formulations may be prepared from emul-sion concentrates, pastes, wettable powd~rs or oil dis-persions by adding water. To prepare emulsions, pastes or oil dispersions, the ingredients as such, or 1144~60 - 29 - o.Z. oOSo/033601 dissolved in an oil or solvent, may be homogenized in water by means of wetting agents, adherents, dispersants or emulsifiers. However, concentrates which are suit-able for dilution with water may also be prepared from the active ingredient', wetting agent', adherent, dispers-ant or emulsifier, with or without a solvent or oil.
Examples of suitable surfactants are: alkali metal salts, alkaline earth metal salts and ammonium ' 'salts o~ lignin-sulfonic acid, naphthalenesulfonic acids and phenolsulfonic acids, alkylarylsulfonates, alkyl-sulfates, alkylsulfonates, alkali metal salts and alka-line earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether-sulfate, fatty alcohol-sulfates, alkali metal salts and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols', heptadecan-ols and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonsted naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalene-20 sulfonic acids with phenol and formaldehyde, polyoxy-ethylene octylphenol ethers, oxyethylated isooctylphenol, oxyethylated octylphenol and oxyethylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether-alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, oxyethylated castor oil, polyoxyethylene alkyl ethers, oxyethylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin~ sulfite waste liquors and methyl-cellulose.
_ 30 _ o.z. oO50/033601 Powders, broadcasting agents and dusts may be prepared by mixing or conjointly grinding the active ingredients with a solid carrier.
Granules, eg. coated, impregnated or homogeneous granules, may-be prepared by bonding the active ingredi-ents to solid carriers. Examples of solid carriers are mineral earths, such as silica gel, silicic acids, silicic acid gels, silicates, talc, kaolin~ Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground plastics, fertilizers, eg.
ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, vegetable products, such as grain flours, bark meal, wood meal and nutshell meal, cellulosic powders and other solid carriers.
The formulations contain from 0.1 to 95% by weight of active ingredient, preferably from 0.5 to 90%
by weight.
In various cases, it may prove advantageous to combine or mix the compounds according to the invention with other active ingredients which regulate plant growth, for example with ethylene-forming compounds of various .
chemical structures (eg. phosphonic acid derivatives, silanes and ethylhydrazines) or onium compounds (eg.
trimethylammonium, hydrazonium and sulfonium salts, and derivatives of morpholinium, piperidinium and pyridazinium compounds). Combinations with other growth-regulating compounds are also of interest, for example with compounds 4~60 - 31 - O.Z. OOS0/033601 from the group comprising maleicacid hydrazides, abscisic acid derivatives, chlorinated phenoxy-fatty acids having an auxin-like action, and polyhydric alcohols and fatty acid esters possessing a specific action on meristematic tissue.
The amount in which an agent according to the invention is employed can vary and depends in the main on the nature of the effect desired. In general, the amount employed per hectare is from 0.1 to 15 kg or more, preferably from 0.2 to 6 kg.
The agents according to the invention influence the growth of visible and underground parts of the plants ln various ways, and, at the con~entional use concen-trations, possess only a low toxicity to warm-blooded animals.
The novel agents affect the physiological pro-cesses of plant development and can be employed for various purposes. The diverse effects of ~he acti~e ingredients essentially depend on the stage of develop-ment of the ~eed or plant at which the agentsare applied,and on the concentration used.
The novel agents influence both vegetative and generative plant growth and, at appropriate concentra-tions, also influence the germinating capacity.
The influence on vegetative development is parti-cularly evident in a reduction in height~ as a result of which numerous plants, in particular cereals, are firmer and more capable of resisting the tendency to lodging.
At the same time, tillering is improved, resulting in a 11~4S60 - 32 o.z. 0050/033601 larger number of ear-bearing stems per unit area.
In the case of grass, the reduction in height of growth results in a denser, more resistant sward and in particular means that less mowing is necessary. The latter factor is of great advantage'_ because it saves lab~r _ where lawns are concerned, but also in the case of grass verges of roads', and in the case of parks.
In addition to the reduction in height, the chlorophyll content is increased, as a result of which treated areas of grass and other stands of plants assume a distinctly darker green color.
The effect on vegetative growth results, in the case of many plants, eg. cotton and'soybean, in a great increase in blossoming and setting of fruit.
An aspect to be mentioned particularly is that treatment with the compounds according to the invention promotes root growth. This leads to more efficient utilization of water and nutrients by the treated plants;
not only drought resistance but also frost resistance is improved There are also diverse and extensive potential uses in fruit-growing and growing of ornamentals, in landscaping, including proper control of vegetation on fallow ground, and in airport areas and training grounds The compounds can also be employed successfully in the control of blossoming and ripening, and in special propagation processes Last but not least, the novel agents can also have an advantageous effect on the concentration of 11~4560 - 33 _ o.z. 0050/033601 important plant materials, eg. s~gars and proteins.
The extent and nature of the effect depend on various factors, especially on the time of application relative to the stage of development of the plant, and on the concentration used. These factors, in turn, vary with the species of plant and with the effect desired For example, lawns are treated over the entire growth period; ornamentals, where the intensity of blossoming, and number of blossoms, are to be increased, are treated before budding; plants whose fruit is to be utilized are treated long enough before harvesting.
Various derivatlves of the category of compounds described in the present text pocsess herbicidal proper-ties. They can therefore be used for eliminating and repressing the growth of undesirable plants.
The following are examples of formulations:
I 20 parts by weight of the compound of Example 1 are thoroughly mixed with 3 parts by weight of sodium dlisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 60 parts by weight of silica gel powder, and the mixture is milled in a hammer mill.
On fine dispersion of the mixturé in 20,000 parts by weight of water, a spray liquor containing 0.1% by weight of the active ingredient is o~tained.
II 3-parts by weight of the compound of Example 2 are intimately mixed with 97 parts by weight of finely 11~4S60 34 o.z. ooso/03360 divided kaolin. This gives a dust which contains 3%
by weight of the active ingredient.
III 30 parts by weight of the compound of Example 3 are intimately mixed with a mixture of 92 parts by weight of silica gel powder and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. A well-adhering formulation of the active ingredient is obtained.
IV ~ 40 parts by weight of the compound of Example 4 are intimately mixed with lO parts of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion con-taining 0.04% by weight of active ingredient.
V 20 parts of the compound of Example are intimately mixed with 2 parts of calcium dodecyl-benzenesulfonate, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acld/urea/formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
Vl 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-a-pyrroli-done, and a solution suitable for use in the form of minute droplets is obtained VII 20 parts by weight of the compound of Example 2 are dissolved in a mixture comprising 80 parts by weight of xylene, 10 parts by weight of an adduct of 8-10 moles - 35 - O.z. oOSO/033601 of ethylene oxide with 1 mole of oleic acid N-mono-ethanolamide, 5 parts by weight of calcium dodecyl-benzenesulfonate and 5 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
On pouring this solution into 100,000 parts by weight of water and finely dispersing it therein, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.
VIII 20 parts by weight of the compound of Example 3 are dissolved in a mixture which comprises 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. - On pouring this solution into 100,000 parts by weight of water and finely dispersirg it therein, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.
IX 20 parts by weight of the compound of Example 3 are dissolved in a mixture which comprises 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 - 280C and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. On pouring this solution into 100,000 parts by weight of water and finely dispersing it therein, an aqueous dispersion containing 0.0~/0 by weight of the active ingredient is obtained.
The use forms described above may contain the agents according to the invention together with other 11~4560 - 36 - O.Z. 0050/033601 active ingredients, eg. herbicides, insecticides, other growth regulators and fungicides, and may also be mixed with fertilizers. In the case of mixtures with fungicides, a broadening of the spectrum of action, and an increase in performance (ie. a synergistic effect) i8 achieved in many cases.
Examples of fungicides which may be combined with the compounds according to the invention are dithio-carbamates and their derivatives, eg ferric dimethyldi-thiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-thiocarbamate, manganese/zinc ethylene-diamine-bis-dithiocarbamate, zinc ethylene-bis-thio-carbamate, tetram_thylthiuram disulfides, the ammonia complex pf zinc-(N,N-ethylene-bis-dithiocarbamate) and N,N'-polyethylene-bis-(thiocarbamyl)-disulfide, zinc-(N,N'-propylene-bis-dithiocarbamate), and the ammonia complex of tin-(N,N'-propylene-bis-dithiocarbamate) and N,N'-polypropylene-bis-(thiocarbamyl)-disulfide; nitro-phenol derivati~es', eg. dinitro-(l-methylheptyl)-phenyl -crotonate, 2-sec.-butyl-4,6-dinitrophenyl-3',3-dimethyl-acrylate,and 2-sec.-butyl-4',6-dinitrophenyl isopropyl-'carbonate; heterocyclic compounds, eg N-trichloromethyl-thio-tetrahydrophthalimide', N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazole-acetate', 2',4-di-chloro-6-(o-chloroanilino)-s-triazine', 0,0-diethyl-phthalimidophosphonothionate', 5-amino-1-(bis-(dimethyl-amino)-phosphiny~)-3-phenyl-1,2',4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2',3-dicyano-1,4-di-_ 37 _ o.z. 0050/033601 thiaanthraquinone, 2-thio-1,3-dithio-(4',5-b)-quinoxaline, l-butylcarbamyl-2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2-thio-cyanatomethylthio-benzthiazole', 4-(2-chlorophenyl-hydrazono)-3-methyl-5-isoxazolone', pyridine-2-thiol 1-oxide, 8-hydroquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1',4-oxathiine 4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2-(fur-2-yl)-benzimidazole, piperazine-1,4-diyl-bis-1-(2,2,2-trichloroethyl)-formamide, 2-thiazol-4-yl-benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(~-chlorophenyl)-~-pyridine-methanol, 1,2-.,,.. _. __ bi's-(3-ethoxycarbonyl-2-thioureido)-benzene'and 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, as well as miscellaneous fungicides such as dodecylguanidine acetate, 3-(2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl)-glutarimide, hexachlorobenzene, N-dichlorofluoromethyl-thio-N,N'-dimethyl-N-phenyl-sulfuric acid diamide, D, L-~nethyl-N-~ 2, 6-dimethyl-phenyl )-N-fur-2-yl-alanate, D,L-methyl N-(2,6-dimethyl-phenyl)-N-(2'-methoxyacetyl) alanate', diisopropyl 5-nitro-iso-phalate', 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide, 1-(~,4-dichloroanilino)-l-formylamino-2,2,2-trichloroethane', 2,6-dimethyl-N-tridecyl-morpholine and its salts, 2,6-dimethyl-N-cyclo-dodecyl-morpholine and its salts, 2,3-dichloro-1',4-naphthoquinone, 1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene-diazine-(sodium sulfonate), 1-~` li44S60 - 38 - O.Z. 0050/033601 chloro-2-nitro-propane, polychloronitrobenzenes, eg.
pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics, eg. griseoful~in or kasugamycin, tetra-fluorodichloroacetone, l-phenylthiosemicarbazide, Bordeaux mixture, nickel-containing compounds and sulfur.
Examples A and B, which follow, show the bio-~og~cal action of the novel compounds. The compara-ti~e compounds used were trifluoromethanesulfonic acid 5-acetamido-2-methyl-anilide (~luoridamide, U.S. Patent 3,639,474) and trifluoromethanesulfonic acid 5-acet-amido-2,4-dimethyl-anilide (Mefluidide, U.S. Patent 3,894,078).
EXAMPLE A
Action on cereals - The cereals wheat (Colibri) and barley (Union) were sown, in a greenhouse, in plastic pots of 11.5 cm diameter containing a peat culture substrate provided with an adequate supply of nutrients. The act$ue ingre-dientæ were applied to the leaves in varying amounts.
Application was by spraying in the conventional manner when the plants had grown to a height of 10 cm.
During the growth period of 18 days, the treated plants showed substantially less upward growth than the untreated control, and this was confirmed by final length measurements, in which loO plants of each series were measured.
-` 1144560 _ 39 _ o.z. oOSo/033601 Results:
S~rin~ wheat (Colibri) Active ingredient Amount applied Plant height from Example kg/ha cm relative .~
- - 26.8 100 Fluoridamide 1.5 17.0 63.4
In a particularly preferred category of sulfonic acld anilides of the general formula (I), R is Cl 4-alkyl which is unsubstituted or is substituted in the a-or ~-position (relative to the sulfonamide nitrogen) by halogen, cyano, thiocyanato or azido, or is Cl 3-alkyl which may be substituted at the a- or ~-carbon by Cl 4-alkoxy, Cl 3-alkylsulfinyl, Cl 2-alkylsulfonyl, N-chloroacetyl-N-arylamino, di-(Cl 4-alkyl)-carbamylamlno, Cl 4-alkoxycarbamyl, Cl_6-alkanoyloxy or C7_13-aroyloxy, or is unsubstituted or halogen-substituted alkenyl or alkynyl of 3 or 4 carbon atoms, or is cyano or thiocyanato, R and R3 independently of one another are each hydrogen, methyl, halogen, methoxy, methylthio or methylsulfonyl.
For the purposes of the invention, halogen is preferably fluorine, chlorine or bromine and cycloalkyl ls preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
The lnventlon further relates to a process for the preparation of a substituted sulfonic acid anilide of the general formula (I), wherein:
a) a compound of the formula (II):
~-SO2CF3 (II) R2 Rl ~ 4560 where R2 and R3 have the above meanings, is reacted with a compound of the formula (III):
Rl _ L (III) where Rl has the above meanings and L is a nucleophilically displaceable leaving group æelected from the group consisting of halogen, bisulfate, halosulfonate, unsubstituted or substi-tuted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, oxonium, sulfonium and ammonium, in the presence or absence of a diluent, in the presence or absence of an acid acceptor and in the presence or absence of a reaction accelerator at from 0 to 170C, or b) a compound of the formula (IV):
~H-CO-CH3 ~ N-R
R2 H (IV) where Rl, R2 and R3 have the above meanings, is reacted with a sulfonating agent of the formula (V):
CF3 - SO2 - Z (V) where Z is a leaving group, selected among halogen and anhydride radical CF3-SO2O-! in the presence or absence of a diluent and in the preæence or absence of an organic or inorganlc base, at from -60 to +120C.
Instead of the free hydrogen-containing compounds of the formulae (II) or (IV), it is possible to use the corresponding salts, for example alkali metal salts, alkaline earth metal salts or unsubstituted or alkyl-substituted ammonium salts, which may be prepared by conventional methods in a preliminary reaction, or which may, if desired, be prepared in situ by adding the equi-valent amount of an organic or inorganic base.
A derivative obtained by the above methods, where .~ - 7 -11~4560 Rl is alkylthioalkyl ox arylthioalkyl, may, if desired, be oxidized to the corresponding sulfinyl or sulfonyl compound.
A derivative where Rl is cyano may be reacted with an amine, alcohol or hydroxylamine to qive the cor-responding guanyl or alkoxyimldoyl compound.
If trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anllide and methyl bromide are used as starting materials, the course of the reaction in variant a) of the process according to the invention may be represented by the followinq equation~
-' 1144S60 :
_ 9 _ O.z. 00~0/033601 n O
Nl HC-CH3 NHC-CH3 3C`[~3~ + CH3Br ~ ~L
N-S02CF3 ~N-S02C~3 3 C~ CH3 If the sodium salt of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anilide and chloroaceto-nitrile are used as starting materials and sodium iodide as the reaction accelerator, the course of the reaction in variant a) of the process according to the invention can be represented by the following equa-tion: ' O O
NHC-CX3 N~C-CH3 N SO CF H2CN -NaCl~ ~ 2C~3 CH3 Na CH
If 5-acetamido-2-methyl-phenyl-cyanamide and trifluoromethanesulfonic acid chloride are used as starting materials, the course of the reaction in ~ariant - b) of the process according to the invention can be rep-resented by the following equation:
ClS02CF3 HCl) ~
N-SO CF
- 10 - o.z. 0050/033601 The following are examples of solvents or dilu-ents which can be used for either variant of the process:
water; formamides, eg. dimethylformamide, formamide;
dimethylacetamide; nitriles, eg. acetonitrile, benzonitrile and butyronitrile; sulfoxides, eg. dimethylsulfGxide;
phosphoric acid amides, eg. hexamethylphosphorotriamide;
ketones, eg. acetone, ethyl methyl ketone, cyclohexanone and acetophenone; ethers, eg. tetrahydrofuran, anisole, dimethoxyethane, n-butyl ethyl ether and dioxane; nitro-alkanes, eg. nitromethane; nitrobenzene; alcohols, eg.methanol, ethanol, isopropanol, n-butanol and 3-methyl-butanol; ureas, eg. tetramethylurea; ether-alcohols, eg. ethylene glycol monomethyl ether; sulfones, eg.
sulfolan; esters, eg. ethyl acetate, methyl propionate and methyl formate; halohydrocarbons, especially chloro-hydrocarbons, eg. methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2- or 1,1,1,2-tetrachloroethane, dichloropropane, trichloroethylene, chlorobenzene, o-, m-and p-dichlorobenzene, fluorobenzene, o-, m- and p-chloro-toluene; dichloronaphthalene and carbon tetrachloride;aliphatic and cycloaliphatic hydrocarbons, eg heptane, pinane, o-, m- and p-cymene, gasoline fractions boiling within the range from 70 to 190C, cyclohexane, methyl-cyclohexane, decalin, petroleum ether, naphtha, 2,2,4-trimethylpentane and octane; aromatic hydrocarbons, eg.
benzene, toluene, o-, m- and p-xylene and tetralin; and mixtures of the above. AdYant2geously the amount of ``" ~144S60 ~ O.Z. 0050~033601 solvent used is from 100 to 2,000% by weight, preferably from 100 to 1,000% by weight, based on the starting com-pound (II) or (IV).
Processes a) and b) according to the invention are preferably carried out in the presence of an organic or inorganic base. In particular, basic hydroxy com-pounds, basic oxides, tertiary amines, alcoholates, carbonates or hydrides are used', eg. potassium hydroxide, sodium hydroxide, potassium carbonate, calcium oxide, barium oxide, magnesium hydroxide, magnesium oxide, barium hydroxide, calcium carbonate, magnesium carbonate, magnesium bicarbonate, zinc hydroxidé, zinc oxide, zinc carbonàt'e, zinc bicarbonate, sodium methylate, magnesium ethylate, potassium ethylate, sodium propylate, aluminum isopropylate,'sodium butylate, lithium methylate, calcium cyclohexanolate, sodium isopropylate, potassium tert.-butylate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, tri-sec.-butylaminé, tri-tert -butylamine, tribe~zylamine, tricyclohexylamine, triamylamine', trihexylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-diisopropyl-aniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dipropyltoluidine, N,N-dimethyl-p-aminopyridine, N,N-dlethyl-p-aminopyridine, N-methylpiperidine, N-ethyl-piperidine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpyrrole, N-methylmorpholine, N-ethylmorphollne, N-methylhexamethyleneimine, pyridine, quinoline, ~ - and ~-picoline, N,N,N',N'-tetramethylethylenediamine, N-ethyldiisoprcpylamine, N,N-dimethylcyclohexylamine, sodium i14~560 - 12 - o.Z. 0050/033601 hydride, lithium hydride and calcium hydride. How-ever, other basic compounds conventionally employed may also be used. Preferred reaction accelerators are metal iodides and bromides, eg. sodium iodide, potassium bromide and calcium iodide, crown ethers, quaternary ammonium compounds, eg. tetrabutylammonium iodide or tetrabutylammonium bromide, and combinations of these compounds Process a) is in general carried out continuously lo or batchwise at from 0 to 170C, preferably from 0 to 140C, for from 30 minutes to 100 hours, preferably from 1 hour t~ 24 hours, under atmospheric or superatmospheric pressure.
In general, in process a), from 0.5 to 2 moles, preferably from 0.9 to I 5 moles, of compound (III), with or without from 0.5 to 2 moles of base and from 0.01 to 0.1 mole of reaction accelerator, are employed per mole of compound (II) or of a corresponding salt. Where a water-miscible solvent or diluent has been used, the end product of the formula (I) is isolated by introducing the reaction solution, or the residue which remains after remo~al of the solvent or diluent, into dilute aqueous alkali solution. If an oil separates out, it is extracted or the supernatant solution is decanted; if a precipitate is formed, it is filtered off. Where a water-immiscible diluent has been used, the organic phase is in general extracted with a dilute, aqueous alkali solution, dried and concentrated. If the desired product prec pitates directly during the reaction, it can `" 11~4560 - 13 - O.Z. 0050/033601 be isolated by simple suction filtration. Where necessary, the end products can be purified further in a con~entional manner, for example by recrystallization or chromatography.
Process b) is in general carried out continuously or batchwise, at from -60 to +120C, prefer-ably from -40 to +80C, in from 1 to 100 hours, under atmospheric or superatmospheric pressure. In general, from 0.8 to 1.3 moles, preferably from 0.9 to 1.1 moles, lo of the sulfonating agent, and from 0.8 to 2 moles of the base, are employed per mole of the compound of the for-mula (IV). The end product of the formula (I) is isolated by the methods described for process a).
A solution of 5.9 parts of sodium cyanide in 40 parts of water is added dropwise in the course of about 10 minutes to a suspension of 19.2 parts of bromine in 80 parts of water at from 0 to 10C, whilst stirring.
After the mixture has become colorless, a solution of 4 parts of sodium hydroxide and 31 parts of trifluoro-methanesulfonic acid 5-acetamido-2,4-dimethyl-anilide in 50 parts of water is run in and stirring is continued for 5 hours at 50C. When the batch has cooled, it is rendered alkaline with a small amount of aqueous alkali metal hydroxide solution and the precipitate is filtered off. After drying, 29.5 parts (88% of theory) of trifluoromethanesulfonic acid 5-acetamido-Nl-cyano-2,4-dimethyl-anilide, of melting point 110 - 111C, are obtained.
- 14 - o.~. o~o/033601 15.5 parts of chloromethyl methyl sulfide are added in one shot to a solution of 49.8 parts of the Na salt of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-anilide in 150 parts of dimethylformamide.
The reaction mixture is then stirred for about 8 hours at room temperature, poured into water and extracted with ether, and the organic phase is washed with water and 1 N
aqueous sodium hydroxide solution. After drying and concentrating the organic phase and stirr ng the residue with diisopropyl ether, 48.1 parts (86.7% of theory) of tri nuoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylthiomethyl-anilide, of melting point 106 - 107C, are obtained 17 parts of trifluoromethanesulfonic acid chlor-ide and 10.~ parts of triethylamine are added dropwise, ; simultaneously but separately, to 17.3 parts of 5-acet-amido-2,4-dimethyl-N-methylaniline in 100 parts of chloroform at 0C. The mixture is then stirred o~er-night at room temperature,after which the precipitate is filtered off and thoroughly washed with chloroform, and the organic phase is extracted with water and 2 N aqueous hydrochloric acid. After drying and concentrating the organic phase, 24 parts (82% of theory) of trifluoro-methanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methyl-anilide, of melting point 128-130C, are obtained.
7.2 parts of sodium carbonate are added to a - 15 - o.Z. oOSo/033601 suspension of lO parts of O-methylhydroxylamine hydro-chloride in lOO parts of ethanol and the mixture is then stirred for l hour at room temperature. After adding 37 parts of tr~fluoromethanesulfonic acid 5-acetamido-Nl-cyano-2,4-dimethyl-anilide, the batch is stirred for lO hours at room temperature and 5 hours at 50C, the sol~ent is stripped off under reduced pressure and the residue is poured into water. The oil which separates out is extracted with ethyl acetate and the organic phase is washed-twice with water, dried and concentrated.
On treating the residue with diisopropyl ether/toluene, 25 parts of trifluoromethanesulfonic acid 5-acetamido-2,4-dlmethyl-Nl-(N2 -methoxy)-guanyl)-anilide, of melting point 105 - 107C, are obtained, A solution of 10 parts of 85% pure m-chloroper-benzoic acid in 120 parts of chloroform is added to 18.6 parts of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylthiomethyl-anilide (Example 2) in 200 parts of chloroform at -10C. After the mixture has stood o~ernight, it is poured into excess saturated aqueous bicarbonate solution and the organic phase is separated off, again washed with bicar-bonate solution, dried and concentrated. On thor-i oughly stirring the residue with diisopropyl ether, 16.5 parts (82% of theory) of trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-Nl-methylsulfonylmethyl-anilide, of melting point 161 - 163C, are obtained.
- 16 - o.z. 0050/0336~1 The following further compounds of the general formula (I) were prepared by the processes described above.
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~1~4560 - 28 - O.Z. OOSOJ033601 The novel active ingredients have a strong bio-logical action on plants, ie. they influence plant growth either by retarding upward ~rowth, by changing the con-centration of plant materials or by destroying undesirable ; plants whilst sparing the crop plants.
The agents according to the invention may be applied, for instance, in the form of directly sprayable solutions,powders,suspensions or dispersions,emulsions,oil dispersions,pastes, dusts, broadcasting agents or granules, by spraying, atomizing, dusting, broadcasting or water-ing The forms of application depend entirely on the purpose for which the agents are being used.
For the preparation of directly sprayable solu-tlons, emulsions, pastes and oil dispersions,mineral oil - fractions of medium to high boiling point, such as kero-sene or diesel oil, coal tar oils and the like,andoils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene, xylene, paraffin, tetrahydronaphthalene and alkylated naphthalenes, and their deri~ati~es, eg. methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene or isophorone, and strongly polar solvents, eg dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and water, are suitable.
A~ueous formulations may be prepared from emul-sion concentrates, pastes, wettable powd~rs or oil dis-persions by adding water. To prepare emulsions, pastes or oil dispersions, the ingredients as such, or 1144~60 - 29 - o.Z. oOSo/033601 dissolved in an oil or solvent, may be homogenized in water by means of wetting agents, adherents, dispersants or emulsifiers. However, concentrates which are suit-able for dilution with water may also be prepared from the active ingredient', wetting agent', adherent, dispers-ant or emulsifier, with or without a solvent or oil.
Examples of suitable surfactants are: alkali metal salts, alkaline earth metal salts and ammonium ' 'salts o~ lignin-sulfonic acid, naphthalenesulfonic acids and phenolsulfonic acids, alkylarylsulfonates, alkyl-sulfates, alkylsulfonates, alkali metal salts and alka-line earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether-sulfate, fatty alcohol-sulfates, alkali metal salts and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols', heptadecan-ols and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonsted naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalene-20 sulfonic acids with phenol and formaldehyde, polyoxy-ethylene octylphenol ethers, oxyethylated isooctylphenol, oxyethylated octylphenol and oxyethylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether-alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, oxyethylated castor oil, polyoxyethylene alkyl ethers, oxyethylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin~ sulfite waste liquors and methyl-cellulose.
_ 30 _ o.z. oO50/033601 Powders, broadcasting agents and dusts may be prepared by mixing or conjointly grinding the active ingredients with a solid carrier.
Granules, eg. coated, impregnated or homogeneous granules, may-be prepared by bonding the active ingredi-ents to solid carriers. Examples of solid carriers are mineral earths, such as silica gel, silicic acids, silicic acid gels, silicates, talc, kaolin~ Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate and magnesium oxide, ground plastics, fertilizers, eg.
ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, vegetable products, such as grain flours, bark meal, wood meal and nutshell meal, cellulosic powders and other solid carriers.
The formulations contain from 0.1 to 95% by weight of active ingredient, preferably from 0.5 to 90%
by weight.
In various cases, it may prove advantageous to combine or mix the compounds according to the invention with other active ingredients which regulate plant growth, for example with ethylene-forming compounds of various .
chemical structures (eg. phosphonic acid derivatives, silanes and ethylhydrazines) or onium compounds (eg.
trimethylammonium, hydrazonium and sulfonium salts, and derivatives of morpholinium, piperidinium and pyridazinium compounds). Combinations with other growth-regulating compounds are also of interest, for example with compounds 4~60 - 31 - O.Z. OOS0/033601 from the group comprising maleicacid hydrazides, abscisic acid derivatives, chlorinated phenoxy-fatty acids having an auxin-like action, and polyhydric alcohols and fatty acid esters possessing a specific action on meristematic tissue.
The amount in which an agent according to the invention is employed can vary and depends in the main on the nature of the effect desired. In general, the amount employed per hectare is from 0.1 to 15 kg or more, preferably from 0.2 to 6 kg.
The agents according to the invention influence the growth of visible and underground parts of the plants ln various ways, and, at the con~entional use concen-trations, possess only a low toxicity to warm-blooded animals.
The novel agents affect the physiological pro-cesses of plant development and can be employed for various purposes. The diverse effects of ~he acti~e ingredients essentially depend on the stage of develop-ment of the ~eed or plant at which the agentsare applied,and on the concentration used.
The novel agents influence both vegetative and generative plant growth and, at appropriate concentra-tions, also influence the germinating capacity.
The influence on vegetative development is parti-cularly evident in a reduction in height~ as a result of which numerous plants, in particular cereals, are firmer and more capable of resisting the tendency to lodging.
At the same time, tillering is improved, resulting in a 11~4S60 - 32 o.z. 0050/033601 larger number of ear-bearing stems per unit area.
In the case of grass, the reduction in height of growth results in a denser, more resistant sward and in particular means that less mowing is necessary. The latter factor is of great advantage'_ because it saves lab~r _ where lawns are concerned, but also in the case of grass verges of roads', and in the case of parks.
In addition to the reduction in height, the chlorophyll content is increased, as a result of which treated areas of grass and other stands of plants assume a distinctly darker green color.
The effect on vegetative growth results, in the case of many plants, eg. cotton and'soybean, in a great increase in blossoming and setting of fruit.
An aspect to be mentioned particularly is that treatment with the compounds according to the invention promotes root growth. This leads to more efficient utilization of water and nutrients by the treated plants;
not only drought resistance but also frost resistance is improved There are also diverse and extensive potential uses in fruit-growing and growing of ornamentals, in landscaping, including proper control of vegetation on fallow ground, and in airport areas and training grounds The compounds can also be employed successfully in the control of blossoming and ripening, and in special propagation processes Last but not least, the novel agents can also have an advantageous effect on the concentration of 11~4560 - 33 _ o.z. 0050/033601 important plant materials, eg. s~gars and proteins.
The extent and nature of the effect depend on various factors, especially on the time of application relative to the stage of development of the plant, and on the concentration used. These factors, in turn, vary with the species of plant and with the effect desired For example, lawns are treated over the entire growth period; ornamentals, where the intensity of blossoming, and number of blossoms, are to be increased, are treated before budding; plants whose fruit is to be utilized are treated long enough before harvesting.
Various derivatlves of the category of compounds described in the present text pocsess herbicidal proper-ties. They can therefore be used for eliminating and repressing the growth of undesirable plants.
The following are examples of formulations:
I 20 parts by weight of the compound of Example 1 are thoroughly mixed with 3 parts by weight of sodium dlisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 60 parts by weight of silica gel powder, and the mixture is milled in a hammer mill.
On fine dispersion of the mixturé in 20,000 parts by weight of water, a spray liquor containing 0.1% by weight of the active ingredient is o~tained.
II 3-parts by weight of the compound of Example 2 are intimately mixed with 97 parts by weight of finely 11~4S60 34 o.z. ooso/03360 divided kaolin. This gives a dust which contains 3%
by weight of the active ingredient.
III 30 parts by weight of the compound of Example 3 are intimately mixed with a mixture of 92 parts by weight of silica gel powder and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. A well-adhering formulation of the active ingredient is obtained.
IV ~ 40 parts by weight of the compound of Example 4 are intimately mixed with lO parts of the sodium salt of a phenolsulfonic acid/urea/formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion con-taining 0.04% by weight of active ingredient.
V 20 parts of the compound of Example are intimately mixed with 2 parts of calcium dodecyl-benzenesulfonate, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acld/urea/formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
Vl 90 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-a-pyrroli-done, and a solution suitable for use in the form of minute droplets is obtained VII 20 parts by weight of the compound of Example 2 are dissolved in a mixture comprising 80 parts by weight of xylene, 10 parts by weight of an adduct of 8-10 moles - 35 - O.z. oOSO/033601 of ethylene oxide with 1 mole of oleic acid N-mono-ethanolamide, 5 parts by weight of calcium dodecyl-benzenesulfonate and 5 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
On pouring this solution into 100,000 parts by weight of water and finely dispersing it therein, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.
VIII 20 parts by weight of the compound of Example 3 are dissolved in a mixture which comprises 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. - On pouring this solution into 100,000 parts by weight of water and finely dispersirg it therein, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.
IX 20 parts by weight of the compound of Example 3 are dissolved in a mixture which comprises 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction of boiling point 210 - 280C and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. On pouring this solution into 100,000 parts by weight of water and finely dispersing it therein, an aqueous dispersion containing 0.0~/0 by weight of the active ingredient is obtained.
The use forms described above may contain the agents according to the invention together with other 11~4560 - 36 - O.Z. 0050/033601 active ingredients, eg. herbicides, insecticides, other growth regulators and fungicides, and may also be mixed with fertilizers. In the case of mixtures with fungicides, a broadening of the spectrum of action, and an increase in performance (ie. a synergistic effect) i8 achieved in many cases.
Examples of fungicides which may be combined with the compounds according to the invention are dithio-carbamates and their derivatives, eg ferric dimethyldi-thiocarbamate, zinc dimethyldithiocarbamate, manganese ethylene-bis-thiocarbamate, manganese/zinc ethylene-diamine-bis-dithiocarbamate, zinc ethylene-bis-thio-carbamate, tetram_thylthiuram disulfides, the ammonia complex pf zinc-(N,N-ethylene-bis-dithiocarbamate) and N,N'-polyethylene-bis-(thiocarbamyl)-disulfide, zinc-(N,N'-propylene-bis-dithiocarbamate), and the ammonia complex of tin-(N,N'-propylene-bis-dithiocarbamate) and N,N'-polypropylene-bis-(thiocarbamyl)-disulfide; nitro-phenol derivati~es', eg. dinitro-(l-methylheptyl)-phenyl -crotonate, 2-sec.-butyl-4,6-dinitrophenyl-3',3-dimethyl-acrylate,and 2-sec.-butyl-4',6-dinitrophenyl isopropyl-'carbonate; heterocyclic compounds, eg N-trichloromethyl-thio-tetrahydrophthalimide', N-trichloromethylthio-phthalimide, 2-heptadecyl-2-imidazole-acetate', 2',4-di-chloro-6-(o-chloroanilino)-s-triazine', 0,0-diethyl-phthalimidophosphonothionate', 5-amino-1-(bis-(dimethyl-amino)-phosphiny~)-3-phenyl-1,2',4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole, 2',3-dicyano-1,4-di-_ 37 _ o.z. 0050/033601 thiaanthraquinone, 2-thio-1,3-dithio-(4',5-b)-quinoxaline, l-butylcarbamyl-2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2-thio-cyanatomethylthio-benzthiazole', 4-(2-chlorophenyl-hydrazono)-3-methyl-5-isoxazolone', pyridine-2-thiol 1-oxide, 8-hydroquinoline and its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1',4-oxathiine 4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine, 2-(fur-2-yl)-benzimidazole, piperazine-1,4-diyl-bis-1-(2,2,2-trichloroethyl)-formamide, 2-thiazol-4-yl-benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(~-chlorophenyl)-~-pyridine-methanol, 1,2-.,,.. _. __ bi's-(3-ethoxycarbonyl-2-thioureido)-benzene'and 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, as well as miscellaneous fungicides such as dodecylguanidine acetate, 3-(2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl)-glutarimide, hexachlorobenzene, N-dichlorofluoromethyl-thio-N,N'-dimethyl-N-phenyl-sulfuric acid diamide, D, L-~nethyl-N-~ 2, 6-dimethyl-phenyl )-N-fur-2-yl-alanate, D,L-methyl N-(2,6-dimethyl-phenyl)-N-(2'-methoxyacetyl) alanate', diisopropyl 5-nitro-iso-phalate', 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide, 2-methyl-benzoic acid anilide, 1-(~,4-dichloroanilino)-l-formylamino-2,2,2-trichloroethane', 2,6-dimethyl-N-tridecyl-morpholine and its salts, 2,6-dimethyl-N-cyclo-dodecyl-morpholine and its salts, 2,3-dichloro-1',4-naphthoquinone, 1,4-dichloro-2,5-dimethoxybenzene, p-dimethylaminobenzene-diazine-(sodium sulfonate), 1-~` li44S60 - 38 - O.Z. 0050/033601 chloro-2-nitro-propane, polychloronitrobenzenes, eg.
pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics, eg. griseoful~in or kasugamycin, tetra-fluorodichloroacetone, l-phenylthiosemicarbazide, Bordeaux mixture, nickel-containing compounds and sulfur.
Examples A and B, which follow, show the bio-~og~cal action of the novel compounds. The compara-ti~e compounds used were trifluoromethanesulfonic acid 5-acetamido-2-methyl-anilide (~luoridamide, U.S. Patent 3,639,474) and trifluoromethanesulfonic acid 5-acet-amido-2,4-dimethyl-anilide (Mefluidide, U.S. Patent 3,894,078).
EXAMPLE A
Action on cereals - The cereals wheat (Colibri) and barley (Union) were sown, in a greenhouse, in plastic pots of 11.5 cm diameter containing a peat culture substrate provided with an adequate supply of nutrients. The act$ue ingre-dientæ were applied to the leaves in varying amounts.
Application was by spraying in the conventional manner when the plants had grown to a height of 10 cm.
During the growth period of 18 days, the treated plants showed substantially less upward growth than the untreated control, and this was confirmed by final length measurements, in which loO plants of each series were measured.
-` 1144560 _ 39 _ o.z. oOSo/033601 Results:
S~rin~ wheat (Colibri) Active ingredient Amount applied Plant height from Example kg/ha cm relative .~
- - 26.8 100 Fluoridamide 1.5 17.0 63.4
6.0 15.0 56.0 67 1.5 13.5 50.4 - 6.o 12.0 44.8 1 . 1.5 13.0 48.5 6.0 12.6 46.6 .
Spr~ barley (Union~
a) .
Active ingredient Amount app~ed Plant height from Example kg/ha cm relative - --- _ _ _ - 26.0 100 Fluoridamide 1.5 20.0 76.9 6,o 16.0 61.5 67 1.5 13.0 50.G
6,o 13,0 50.0 1 1.5 13.0 50.0 6.o 13.0 50.0 - 40 - o.z. oo50/033601 b) Active ingredient Amount applied Plant height . from Example kg/ha cm relative , . _ - 28,0 lO0 Mefluidide 0, 25 27, 0 96, 4 0,75 18.0 64.3 1,50 17.5 62.5 3.00 16.0 57.1 0,25 26.5 94.6 0,75 16.0 57.1 111 1, 50 16, 0 57, 1 3,00 15,0 53,6 EXAMELE B
Effect on grass and lawns In a vegetation experiment carried out in Mitscherlich vessels, a standard lawn mixture of the following composition was sown on a loamy sandy soil:
Agrostis tenuis 10%, Cynosurus cristatus lO~o, Festuca rubra 15%, Lolium perenne 3596 and Poa pratensis 30%, The soil was fertilized with 1.5 g of N, in the form of ammonium nitrate (z l.S kg/ha), and 1 g of P205, in the form of secondary potassium phosphate (= l ~g/ha). After the . 10 grass had been cut twice, various amounts of the active ingredients were applied by spraying in the conventional manner, with the grass having grown to a height of 4 cm, 20 days after the treatment, ~he height of the grass was - 41 - o.z. 0050/033601 determined; it was then cut-, its re-growth over 4 weeks, up to the time of the 2nd cut, was observed and length measurements were again carried out in order to examine the longer-term effect, Compared to the control, the treated plants show very pronounced shortening. The longer-term effect is better than in the case of the conventional substance employed for comparison, as is shown by the Table which follows.
_ . . _ .
Active Amount 1st cut 2nd cut ingredient ~pplied, plant height plant height of Example kg/ha cm relative l cm relative _ _ 14,3 100 11.0 100 Fluoridamide 0.5 13.5 94.4 ll 0 100 0.75 12.5 87.4 lO.0 90.9 67 0.5 14.0 97.4 11.0 100 0.75 12.5 87.4 9.0 81.8 1 0.5 5.5 38 5 8 0 72.7 0.75 4 5 31 5 7,0 63.6
Spr~ barley (Union~
a) .
Active ingredient Amount app~ed Plant height from Example kg/ha cm relative - --- _ _ _ - 26.0 100 Fluoridamide 1.5 20.0 76.9 6,o 16.0 61.5 67 1.5 13.0 50.G
6,o 13,0 50.0 1 1.5 13.0 50.0 6.o 13.0 50.0 - 40 - o.z. oo50/033601 b) Active ingredient Amount applied Plant height . from Example kg/ha cm relative , . _ - 28,0 lO0 Mefluidide 0, 25 27, 0 96, 4 0,75 18.0 64.3 1,50 17.5 62.5 3.00 16.0 57.1 0,25 26.5 94.6 0,75 16.0 57.1 111 1, 50 16, 0 57, 1 3,00 15,0 53,6 EXAMELE B
Effect on grass and lawns In a vegetation experiment carried out in Mitscherlich vessels, a standard lawn mixture of the following composition was sown on a loamy sandy soil:
Agrostis tenuis 10%, Cynosurus cristatus lO~o, Festuca rubra 15%, Lolium perenne 3596 and Poa pratensis 30%, The soil was fertilized with 1.5 g of N, in the form of ammonium nitrate (z l.S kg/ha), and 1 g of P205, in the form of secondary potassium phosphate (= l ~g/ha). After the . 10 grass had been cut twice, various amounts of the active ingredients were applied by spraying in the conventional manner, with the grass having grown to a height of 4 cm, 20 days after the treatment, ~he height of the grass was - 41 - o.z. 0050/033601 determined; it was then cut-, its re-growth over 4 weeks, up to the time of the 2nd cut, was observed and length measurements were again carried out in order to examine the longer-term effect, Compared to the control, the treated plants show very pronounced shortening. The longer-term effect is better than in the case of the conventional substance employed for comparison, as is shown by the Table which follows.
_ . . _ .
Active Amount 1st cut 2nd cut ingredient ~pplied, plant height plant height of Example kg/ha cm relative l cm relative _ _ 14,3 100 11.0 100 Fluoridamide 0.5 13.5 94.4 ll 0 100 0.75 12.5 87.4 lO.0 90.9 67 0.5 14.0 97.4 11.0 100 0.75 12.5 87.4 9.0 81.8 1 0.5 5.5 38 5 8 0 72.7 0.75 4 5 31 5 7,0 63.6
Claims (4)
1. A substituted sulfonic acid anilide of the formula (I):
(I) where R1 is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl (each of up to 12 carbon atoms) or arylalkyl (of 7 to 14 carbon atoms), each of which may be unsubstituted or substituted by halogen, cyano, thiocyanato, azido, nitro, C1-4-alkoxy, C6-10-aryloxy, C1-4-alkylthio, C6-8-arylthio, C1-4-alkylsulfinyl, C1-4-alkylsulfonyl, arylsulfinyl, aryl-sulfonyl, C1-5-alkanoyl, C1-5-alkoxycarbonyl, C1-5-alkyl-carbamyl, di-(C1-5-alkyl)-carbamyl, C1-4-alkanoylamino, C1-4-haloalkanoylamino, C1-6-alkanoyloxy, C1-4-alkanoylthlo, C1-4-alkoxycarbonylamlno, C7-13-aroyloxy, C1-6-alkylamino, di-(C1-6-alkyl)-amino, C6-12-arylamino, C1-6-alkylcarbamino, di-(C1-6-alkyl)-carbamylamino, C1-6-alkylcarbamyloxy, di-(C1-6-alkyl)-carbamyloxy, C1-4-alkylaminosulfonyloxy or di-(C1-4-alkyl)-aminosulfonyloxy or combinations of these groups, or is cyano, thiocyanato, unsubstituted or C1-4-alkyl-substituted amino, aminosulfonyl, guanyl, N2-hydroxy-guanyl, hydroxymoyl or C1-5-alkoxyimidoyl, or is unsubstituted or halogen-substituted C1-4-alkylsulfenyl or C1-4-alkylsulflnyl, or is unsubstituted or halogen- and/or C1-4-alkyl-substituted arylsulfinyl or arylsulfonyl, where aryl is of up to 10 carbon atoms, R2 and R3 are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1-4-alkyl, C1-4-alkoxy, C1-4-alkylthio, C1-4-alkylsulfinyl, C1-4-alkylsulfonyl or C1-4-alkanoyl.
(I) where R1 is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl (each of up to 12 carbon atoms) or arylalkyl (of 7 to 14 carbon atoms), each of which may be unsubstituted or substituted by halogen, cyano, thiocyanato, azido, nitro, C1-4-alkoxy, C6-10-aryloxy, C1-4-alkylthio, C6-8-arylthio, C1-4-alkylsulfinyl, C1-4-alkylsulfonyl, arylsulfinyl, aryl-sulfonyl, C1-5-alkanoyl, C1-5-alkoxycarbonyl, C1-5-alkyl-carbamyl, di-(C1-5-alkyl)-carbamyl, C1-4-alkanoylamino, C1-4-haloalkanoylamino, C1-6-alkanoyloxy, C1-4-alkanoylthlo, C1-4-alkoxycarbonylamlno, C7-13-aroyloxy, C1-6-alkylamino, di-(C1-6-alkyl)-amino, C6-12-arylamino, C1-6-alkylcarbamino, di-(C1-6-alkyl)-carbamylamino, C1-6-alkylcarbamyloxy, di-(C1-6-alkyl)-carbamyloxy, C1-4-alkylaminosulfonyloxy or di-(C1-4-alkyl)-aminosulfonyloxy or combinations of these groups, or is cyano, thiocyanato, unsubstituted or C1-4-alkyl-substituted amino, aminosulfonyl, guanyl, N2-hydroxy-guanyl, hydroxymoyl or C1-5-alkoxyimidoyl, or is unsubstituted or halogen-substituted C1-4-alkylsulfenyl or C1-4-alkylsulflnyl, or is unsubstituted or halogen- and/or C1-4-alkyl-substituted arylsulfinyl or arylsulfonyl, where aryl is of up to 10 carbon atoms, R2 and R3 are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1-4-alkyl, C1-4-alkoxy, C1-4-alkylthio, C1-4-alkylsulfinyl, C1-4-alkylsulfonyl or C1-4-alkanoyl.
2. A process for the preparation of a substituted sulfonic acid anilide of the general formula (I) as claimed in claim 1, wherein:
a) a compound of the formula (II):
(II) where R2 and R3 are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1-4-alkyl, C1-4-alkoxy, C1-4-alkylthio, C1-4-alkyl-sulfinyl, C1-4-alkylsulfonyl or C1-4-alkanoyl, is reacted with a compound of the general formula (III):
R1 - L (III) where R1 has the definition given in claim 1 and L is a nucleo-philically displaceable leaving group selected from the group consisting of halogen, bisulfate, halosulfonate, unsubstituted or substituted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, oxonium, sulfonium and ammonium, in the presence or absence of a diluent, in the presence or absence of an acid acceptor and in the presence or absence of a reaction accelerator at from 0 to 170°C, or b) a compound of the formula (IV):
(IV) where R1, R2 and R3 have the above meanings, is reacted with a sulfonating agent of the general formula (V):
CF3 - SO2 - Z (V) where Z is a leaving group selected among halogen and anhydride radical CF3-SO2O- in the presence or absence of a diluent and in the presence or absence of an organic or inorganic base, at from -60 to +120°C.
a) a compound of the formula (II):
(II) where R2 and R3 are identical or different and each is hydrogen, halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1-4-alkyl, C1-4-alkoxy, C1-4-alkylthio, C1-4-alkyl-sulfinyl, C1-4-alkylsulfonyl or C1-4-alkanoyl, is reacted with a compound of the general formula (III):
R1 - L (III) where R1 has the definition given in claim 1 and L is a nucleo-philically displaceable leaving group selected from the group consisting of halogen, bisulfate, halosulfonate, unsubstituted or substituted alkylsulfonyloxy, arylsulfonyloxy, alkylsulfate, oxonium, sulfonium and ammonium, in the presence or absence of a diluent, in the presence or absence of an acid acceptor and in the presence or absence of a reaction accelerator at from 0 to 170°C, or b) a compound of the formula (IV):
(IV) where R1, R2 and R3 have the above meanings, is reacted with a sulfonating agent of the general formula (V):
CF3 - SO2 - Z (V) where Z is a leaving group selected among halogen and anhydride radical CF3-SO2O- in the presence or absence of a diluent and in the presence or absence of an organic or inorganic base, at from -60 to +120°C.
3. A compound selected from the group comprising trifluoromethanesulfonic acid 5-acetamido-N1-cyano-2,4-dimethyl-anilide, trifluoromethanesulfonic acid 5-acetamido-N1-cyano-2-methyl-anilide, trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-N1-methoxymethyl-anilide, trifluoromethanesulfonic acid 5-acetamido-2,4-dimethyl-N1-propargyl-anilide, trifluoromethane-sulfonic acid 5-acetamido-N1-acetyloxymethyl-2,4-dimethyl-anilide, trifluoromethanesulfonic acid 5-acetamido-N1-propionyloxymethyl-2,4-dimethyl-anilide and trifluoromethanesulfonic acid 5-acetami-do-N1-(4'-chlorophenyl)-methyl-2,4-dimethyl-anilide.
4. Process for regulating plant growth, wherein use is made of an amount of from 0.2 to 6 kg per hectare of a growth-regulating agent containing as active ingredient a substituted sulfonic acid anilide of the formula (I) as defined in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2900685.7 | 1979-01-10 | ||
| DE19792900685 DE2900685A1 (en) | 1979-01-10 | 1979-01-10 | SUBSTITUTED SULPHONIC ACID ANILIDES, THEIR PRODUCTION AND USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144560A true CA1144560A (en) | 1983-04-12 |
Family
ID=6060263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342977A Expired CA1144560A (en) | 1979-01-10 | 1980-01-03 | Substituted sulfonic acid anilides, their preparation and their use |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0013742B1 (en) |
| JP (1) | JPS5594355A (en) |
| AT (1) | ATE2067T1 (en) |
| BR (1) | BR8000095A (en) |
| CA (1) | CA1144560A (en) |
| CS (1) | CS212334B2 (en) |
| DD (1) | DD148581A1 (en) |
| DE (2) | DE2900685A1 (en) |
| DK (1) | DK9680A (en) |
| FI (1) | FI800013A (en) |
| IL (1) | IL59051A0 (en) |
| PL (1) | PL119195B2 (en) |
| SU (1) | SU932965A3 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4312663A (en) * | 1980-09-18 | 1982-01-26 | Minnesota Mining And Manufacturing Company | Cyclicacylaminoperfluoroalkanesulfonanilides and derivatives thereof |
| EP0049042B1 (en) * | 1980-09-18 | 1984-03-21 | Minnesota Mining And Manufacturing Company | Acyclicacylaminoperfluoroalkanesulfonanilides and derivatives thereof |
| US4405359A (en) * | 1980-09-18 | 1983-09-20 | Minnesota Mining And Manufacturing Company | Acyclicacylaminoperfluoroalkanesulfonanilides and derivatives thereof |
| EP0048551B1 (en) * | 1980-09-18 | 1985-04-10 | Minnesota Mining And Manufacturing Company | N,n-diacylaminoperfluoroalkanesulfonanilides and derivatives thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3639474A (en) * | 1969-06-12 | 1972-02-01 | Minnesota Mining & Mfg | N-substituted perfluoroalkane-sulfonamides |
| NL174644C (en) * | 1970-04-13 | 1984-07-16 | Minnesota Mining & Mfg | METHOD FOR PREPARING A HERBICIDE COMPOUND; ALSO METHOD FOR PREPARING A PREPARATION WITH HERBICIDE ACTION. |
| US3725451A (en) * | 1970-04-13 | 1973-04-03 | Riker Laboratories Inc | Substituted benzoylhaloalkanesulfonanilides |
| US3793372A (en) * | 1971-07-28 | 1974-02-19 | Minnesota Mining & Mfg | N-cyanohaloalkanesulfonanilides |
| US3981914A (en) * | 1971-08-03 | 1976-09-21 | Minnesota Mining And Manufacturing Company | N-alkylsulfonylperfluoroalkanesulfonanilides |
| US3894078A (en) * | 1973-02-12 | 1975-07-08 | Minnesota Mining & Mfg | 5-Acetamido-2,4-dimethyltrifluoromethanesulfonanilide |
| IT1049273B (en) * | 1973-03-16 | 1981-01-20 | Minnesota Mining & Mfg | PROCEDURE FOR THE PRODUCTION OF AROMATIC SULPHONES REPLACED USEFUL IN PARTICULAR AS WEEDERS AND OR REGULATORS OF PLANT GROWTH |
-
1979
- 1979-01-10 DE DE19792900685 patent/DE2900685A1/en not_active Withdrawn
- 1979-12-17 AT AT79105218T patent/ATE2067T1/en not_active IP Right Cessation
- 1979-12-17 DE DE7979105218T patent/DE2964393D1/en not_active Expired
- 1979-12-17 EP EP79105218A patent/EP0013742B1/en not_active Expired
- 1979-12-28 IL IL59051A patent/IL59051A0/en unknown
-
1980
- 1980-01-02 FI FI800013A patent/FI800013A/en not_active Application Discontinuation
- 1980-01-03 CA CA000342977A patent/CA1144560A/en not_active Expired
- 1980-01-04 SU SU802863202A patent/SU932965A3/en active
- 1980-01-08 BR BR8000095A patent/BR8000095A/en unknown
- 1980-01-08 PL PL1980221261A patent/PL119195B2/en unknown
- 1980-01-08 DD DD80218352A patent/DD148581A1/en unknown
- 1980-01-09 DK DK9680A patent/DK9680A/en not_active Application Discontinuation
- 1980-01-09 CS CS80214A patent/CS212334B2/en unknown
- 1980-01-10 JP JP96680A patent/JPS5594355A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE2067T1 (en) | 1983-01-15 |
| DE2900685A1 (en) | 1980-07-24 |
| EP0013742B1 (en) | 1982-12-22 |
| DE2964393D1 (en) | 1983-01-27 |
| SU932965A3 (en) | 1982-05-30 |
| FI800013A (en) | 1980-07-11 |
| JPS5594355A (en) | 1980-07-17 |
| DK9680A (en) | 1980-07-11 |
| IL59051A0 (en) | 1980-03-31 |
| DD148581A1 (en) | 1981-06-03 |
| CS212334B2 (en) | 1982-03-26 |
| BR8000095A (en) | 1980-10-07 |
| PL221261A2 (en) | 1980-12-15 |
| PL119195B2 (en) | 1981-12-31 |
| EP0013742A1 (en) | 1980-08-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |