WO1997025319A1 - Substituted 1,2,4,6-thiatriazines useful as herbicides - Google Patents

Substituted 1,2,4,6-thiatriazines useful as herbicides Download PDF

Info

Publication number
WO1997025319A1
WO1997025319A1 PCT/EP1996/005727 EP9605727W WO9725319A1 WO 1997025319 A1 WO1997025319 A1 WO 1997025319A1 EP 9605727 W EP9605727 W EP 9605727W WO 9725319 A1 WO9725319 A1 WO 9725319A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
crc
phenyl
substituted
halogen
Prior art date
Application number
PCT/EP1996/005727
Other languages
French (fr)
Inventor
André Stoller
Walter Kunz
Original Assignee
Novartis Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Novartis Ag filed Critical Novartis Ag
Priority to AU13757/97A priority Critical patent/AU1375797A/en
Priority to BR9612409A priority patent/BR9612409A/en
Priority to EP96944022A priority patent/EP0873328A1/en
Priority to JP9512986A priority patent/JP2000505052A/en
Publication of WO1997025319A1 publication Critical patent/WO1997025319A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/15—Six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si

Definitions

  • the present invention relates to novel herbicidally active thiatriazine derivatives, to processes for their preparation, to compositions comprising these compounds, and to their use for controlling weeds, mainly in crops of useful plants, or for inhibiting plant growth.
  • Thiatriazine compounds are described, for example, in Chem. Ber. 121 , 383-386 (1988), Z. Naturforsch. 43, 763-768 (1988), Chem. Ber. 126, 2601-2607 (1993), J. Am. Chem. Soc. 1989, 11 1 , 1 180-1185 and DD 113 006.
  • novel thiatriazine derivatives having herbicidal and growth-inhibitory properties.
  • the present invention thus relates to compounds of the formula I
  • R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 3 alkyl which is substituted by S(O) n R6, halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C ⁇ -C 4 alkylammonium, -COOH, -COOR 20 , -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C- 3 -C 8 cycloalkyl, d-C 3 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C ⁇ alkylamino, d-C 3 alkoxycarbonyl, C 2 - C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phen
  • R 2 and R 3 independently of one another are C 2 -Cealkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C ⁇ -C alkylammonium, -COOH, -COOR 2 0, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C 3 -C ⁇ cycloalkyl, CrCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cealkylamino, C 2 -C 5 alkoxycarbonyl, C 2 -Ci2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it
  • R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, d-C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C ⁇ -C alkylammonium, -COOH, -COOR ⁇ , -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C 3 -C 8 cycloalkyl, d-C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkylamino, d-C 5 alkoxycarbonyl, C 2 -C ⁇ 2 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio
  • R 2 and R 3 independently of one another are formyl, d-dsalkylcarbonyl,
  • -COOR20 -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrC 8 alkoxycarbonyl, C -C ⁇ 0 cycloalkoxycarbonyl, Ci-C ⁇ alkylaminocarbonyl or
  • R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C -Csalkyl, d-C 5 alkoxy, C ⁇ -C 5 alkylcarbonyl, d-C 5 alkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, Ci-C ⁇ alkylaminocarbonyl or
  • C 2 -C ⁇ dialkylaminocarbonyl or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, C ⁇ -C 5 alkyl, d-C 5 alkoxy, d-C 3 alkylcarbonyl, C T C ⁇ alkoxycarbonyl, aminocarbonyl, d-C ⁇ alkylamino or d-C 3 alkylcarbonyloxy, or
  • R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-d-C 6 alkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-
  • R 2 and R 3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, Ci-Csalkyl, Ci-Csalkoxy,
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 5 alkyl, C ⁇ -C 3 alkoxy, halogen, cyano or nitro, or
  • R 2 and R 3 independently of one another are amino, CrC 6 alkylamino, C 2 -C ⁇ dialkylamino, phenylamino, naphthylamino, C ⁇ -C 6 alkylcarbonylamino, C ⁇ -C ⁇ oalkoxycarbonylamino, hydroxyl, d-C 6 alkoxy, d-C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy,
  • X is O or S(O) Xl in which x is 0, 1 or 2, and R 4 is d-C 8 alkyl, C 2 -C 8 alkenyl, d-C ⁇ alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl, C 3 -
  • R 4 is phenyl, biphenyl, naphthyl, heterocyclyl, d-C 4 alkylphenyl, d-C alkylnaphthyl, phenyl-
  • Cioalkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, C ⁇ -C alkyl, d-C 4 alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R 4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, O, C C ⁇ oalkyl, d-Cioalkoxy, C ⁇ -C ⁇ oalkylthio, d-
  • Ciohaloalkyl hydroxyl, C 3 -C 10 alkoxy-carbonylalkoxy, d-C 6 alkylsulfinyl, C ⁇ -C 6 alkylsulfonyl,
  • R 5 is hydrogen, Ci-C ⁇ alkyI, d-C ⁇ haloalkyl, C 2 -C 5 alkoxyalkyl, d-C 6 cyanoalkyl, phenyl, phenyl-C ⁇ -C alkyl, formyl, C 2 -dalkylcarbonyl, CrC ⁇ alkoxycarbonyl, d-C 6 alkyl- aminocarbonyl, C 2 -C 8 dialkylaminocarbonyl, benzoyl, halobenzoyl, C ⁇ -C 6 alkylamino,
  • R 6 is hydrogen or cyano when n is 0 or
  • Re is d-Csalkyl, C 2 -C 5 alkenyl, d-dalkynyl, d-Cealkoxyalkyl, d-C 5 haloalkyl, d-C 5 hydroxyalkyl, phenyl, phenyl-d-C 4 alkyl, heterocyclyl, heterocyclyl-C -C alkyl or
  • R 7 is hydrogen, C ⁇ -C 12 alkyl, d-C 12 haloalkyl, d-C 6 nitroalkyl, C C 6 cyanoalkyl, phenyl,
  • R ⁇ and R 9 independently of one another are hydrogen, phenyl, d-C 8 alkyl, C C 8 haloalkyl,
  • R ⁇ and R 9 together with the nitrogen atom to which they are bonded form a three- to seven- membered heterocycle which can contain one or two further hetero atoms and, in turn can be substituted by ⁇ alkyl groups or halogen,
  • R 10 and Rn independently of one another are hydrogen, phenyl, d-C 8 alkyl, C ⁇ -C 8 haloalkyl, d-C 8 alkoxy, phenoxy, C 2 -C ⁇ cyanoalkyl, Crdalkenyl, C 3 -dalkynyl, C 2 -C 8 alkoxyalkyl,
  • R 10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which can contain one or two further hetero atoms and, in turn, can be substituted by C h alky! groups or halogen,
  • R 12 is C ⁇ -C 8 alkyl, d-dalkoxy, d-C ⁇ alkenyloxy, d-C B alkynyloxy, d-C 8 haloalkyl, phenyl, phenyloxy,
  • R 13 and R independently of one another are hydrogen, d-C 6 alkyl, C 2 -C ⁇ alkylcarbonyl or phenyl, and
  • Ri5, R 1 6, Ru, i ⁇ and R 19 independently of one another are d-C ⁇ 0 alkyl, C 3 -C 6 cycloalkyl,
  • R 15 , Ri ⁇ . i7, Ri ⁇ and Rig independently of one another are halogen, cyano, azido, nitro,
  • alkyl groups in the definitions of the substituents can be straight-chain or branched and mono- or polysubstituted; they are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and their branched isomers.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the abovementioned alkyl radicals.
  • the alkenyl and alkynyl groups can be mono- or polyu ⁇ saturated.
  • Suitable cycloalkyl substituents contain 3 to 8 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Corresponding cycloalkenyl substituents can be mono- or polysubstituted and mono- or else polyunsaturated, for example cyclopentadienyl or cyclooctatetraenyl.
  • alkyl, alkenyl or alkynyl are substituents on a cycloalkyl, cycloalkenyl, phenyl, biphenyl, naphthyl or heterocyclyl, these ring systems may also be mono- or polysubstituted by alkyl, alkenyl or alkynyl.
  • halogen is fluorine, chlorine, bromine or iodine.
  • halogen in conjunction with other meanings such as haloalkyl or halophenyi.
  • Phenyl may be unsubstituted or mono- or polysubstituted by halogen, cyano, nitro, -OR 5 , -NR10R11, d-C 4 alkyl, formyl, d-C 4 alkylcarbonyl, -COOR 7 , d-C 4 alkylthio, d-C alkylsulfonyl or -CONR 8 R 9 .
  • Heterocyclyl radicals are to be understood as meaning ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Such ring systems preferably contain 3 to 8 ring atoms. This also applies to those heterocycles which are formed by 2 substituents bonded to a nitrogen atom, as is the case in groups such as -NR 10 Rn.
  • Heterocyclyl ring systems within the scope of the present invention may also be mono- or polysubstituted.
  • suitable substituents are C C alkyl, d-C 4 haloalkyl, C ⁇ -C alkoxy, cyano, nitro or C 3 -C ⁇ cycloalkyl.
  • Heterocyclyl as a substituent of a group Ri can be, for example, epoxidyl, dioxolanyl, pyrrolidyl, piperidinyl, morpholinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, thiazolyl, oxazolinyl (for
  • Preferred heterocycles R 6 are, inter alia, pyridyl, pyrimidinyl and triazinyl.
  • Preferred heterocycles R 7 are, for example, oxetanyl, pyridyl, thiophenyl and furyl.
  • R 8 and R 9 preferably form rings such as piperidinyl, morpholinyl and pyrrolidinyl.
  • heterocycles formed by R 1 0 and R , or R 2 and R 3 , with the nitrogen atom to which these radicals are bonded are piperidinyl, morpholinyl, pyrrolidyl, triazolyl, tetrazolyl and imidazolyl.
  • Preferred heterocycles R 9 are thiophenyl, furyl, pyridyl and oxetanyl.
  • Phenyl and naphthyl rings R 4 can be substituted by carbo- or heterocyclic radicals which are formed on these phenyl or naphthyl rings by 2 adjacent substituents.
  • the carbocycles preferably contain 4 to 6 carbon atoms, such as cyclobutyl, cyclopentyl and cyclohexyl.
  • heterocyclic groups are dioxolanyl and tetrahydrofuryl.
  • Heterocycles R 4 such as succinimidyl, pyridyl, thiophenyl or furyl, may contain fused carbocycles, such as phenyl or cyclohexenyl.
  • Preferred heterocycles R 2 and R 3 are pyridyl, pyrrolidyl and pyrimidinyl.
  • Heterocycles formed by -NR 2 R 3 include, for example, succinimidyl, imidazolyl and triazolyl, it being possible for such groups to contain fused carbocycles, such as phenyl or cyclohexenyl.
  • Heterocyclylcarbonyl R 2 or R 3 is, for example, pyridyl, pyrrolidyl, triazolyl, thiophenyl, furyl or isoxazolyl.
  • C 2 -C 7 alkylcarbonyl within the scope of the present invention is, for example, methylcarbonyl, ethylcarbonyl, propylcarbonyl, i-propylcarbonyl, butylcarbonyl, pentylcarbonyl and hexylcarbonyl and also the branched isomers of these.
  • alkali metals and alkaline earth metals are lithium, sodium, potassium, magnesium, calcium or barium.
  • the invention equally includes the salts which the compounds of the formula I can form, in particular with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • Salt formers which must be emphasized among the alkali metal and alkaline earth metal hydroxides are the hydroxides of lithium, sodium, potassium, magnesium or calcium, but in particular those of sodium or potassium.
  • amides which are suitable for ammonium salt formation are not only ammonia, but also primary, secondary and tertiary d-C ⁇ 8 alkylamines, d-C 4 hydroxy- alkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, h ⁇ ptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyl nonylamine, methylpe ⁇ tadecylamine, methyloctadec
  • the compounds of the formula I have an asymmetric centre in the sulfur atom of the thiatriazine ring. This is why, upon preparation of these compounds, racemates are obtained which can be separated into the corresponding enantiomers by customary separation methods. If further asymmetric centres exist in the substituents of the thiatriazine ring, the corresponding diastereoisomers may also be separated in the customary manner.
  • the present invention also includes such diastereoisomers and enantiomers.
  • R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 aikyl which is substituted by S(O) n R 6 ⁇ halogen, cyano, nitro, d-C ⁇ alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C ⁇ -C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -C 8 cycloalkyl, d-C 5 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkylamino, d-dalkoxycarbonyl, C 2 -C 12 dia!kylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphen
  • R 2 and R 3 independently of one another are C 2 -C ⁇ alkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, C ⁇ -C 8 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-d- dalkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 8 cycloalkyl, Crdalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C ⁇ alkylamino, C 2 -C 3 alkoxycarbonyl, C 2 -C ⁇ 2 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementi
  • R 2 and R 3 independently of one another are C 3 -C 6 alkynyl, d-dalkynyl which is substituted by halogen, cyano, nitro, C ⁇ -C 8 alkoxy, d-C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-C ⁇ - C 4 alkyiammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -C 8 cycloalkyl, d-C 3 alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C 6 alkyiamino, d-C 5 alkoxycarbonyl, C 2 -C 12 dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the above
  • R 2 and R 3 independently of one another are formyl, C ⁇ -C 15 alkylcarbonyl, d-d 5 alkenyl- carbonyl, C -C 9 cycloalkylcarbonyl, C 6 -C 9 cycloalkenylcarbonyl or C 3 -C 8 cycloalkyl- C ⁇ -C 6 alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Ci-C ⁇ alkylamino, C 2 -C 12 dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 8 alkoxy- carbonyl, C -C ⁇ ocycloalkoxycarbonyl, d-C 8 alkylaminocarbonyl or C 2 -C ⁇ ;>dialkyl- aminocarbonyl, or
  • R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, C ⁇ -C 5 alkoxy, d-Csalkylcarbonyl, C ⁇ -C 3 alkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, d-C 6 alkylaminocarbonyl or C 2 -C 1 dialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, d-dalkoxy, d-C 5 alkylcarbonyl, d-C 6 alkoxycarbonyl, aminocarbonyl, d-C 6 alkylamino or d-C 5 alkylcarbonyloxy, or R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl,
  • R 2 and R 3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C 5 alkyl, C ⁇ -C 5 alkoxy, C ⁇ -C 3 alkylthio, -COOH, -CONH 2 , d-C 6 alkylaminocarbonyl, C 2 -C ⁇ odialkylaminocarbonyl, C C s alkylcarbonyl or d-C 5 alkoxycarbonyl, or
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 5 alkyl, d-C 5 alkoxy, halogen, cyano or nitro, or R 2 and R 3 independently of one another are amino, d-C 6 alkylamino, d-C 8 dialkylamino, phenylamino, naphthylamino, C ⁇ -C 6 alkylcarbo ⁇ ylamino, d-doalkoxycarbonylamino, hydroxyl, Ci-C ⁇ alkoxy, d-C 6 alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, and i 5 , Ri 6 , Ri7, ⁇ and R ⁇ 9 independently of one another are C ⁇ -C oalkyl, d-C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C ⁇ -C alkyl, d-C 6 al
  • Especially preferred compounds of the formula I are distinguished by the fact that R 15 , R ⁇ .
  • R 1 l Ri ⁇ and R 19 independently of one another are C ⁇ -C ⁇ oalkyl, C 3 -C 6 cycloalkyl,
  • R17, Ri ⁇ and R 19 independently of one another are halogen, cyano, -OR s , -S(O)nR ⁇ ,
  • R 5 is hydrogen, d-C 8 alkyl, d-C 6 haloalkyl, C 2 -C 3 alkoxyalkyl, phenyl, phenyl-C ⁇ -C 4 alkyl,
  • R 8 is hydrogen when n is 0, or
  • R 6 is C ⁇ -C 5 alkyl, phenyl, phenyl-C ⁇ -C 4 alkyl or heterocyclyl,
  • R 7 is hydrogen, C ⁇ -C 6 alkyl, d-C e haloalkyl, C C 6 cyanoalkyl, C 2 -C 10 alkoxycarbonylalkyl, heterocyclyl, C 3 -C 6 cycloalkyl or C 2 -C 6 dialkylamino,
  • R 8 and R 9 independently of one another are hydrogen or d-C 8 alkyl, or R 8 and R 9 together with the nitrogen atom to which they are bonded form a three to seven- membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C h alky! groups,
  • R 10 and Rn independently of one another are hydrogen, phenyl, C ⁇ -C 8 alkyl, Ordalkenyl, (d-CealkylaminoJcarbonyl, (C 2 -C 6 dialkylamino)carbonyl, (C ⁇ -C 7 alkyl)carbonyl, (C ⁇ -C 6 alkoxy)carbonyl or heterocyclylcarbonyl, or
  • R 10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C,. 6 alkyl groups.
  • R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, d-C 6 alkyl which is substituted by halogen, cyano, nitro, d-C 4 alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-Ci- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 3 -C ⁇ cycloalkyl, Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C ⁇ alkylamino, C ⁇ -C 5 alkoxycarbonyl, C 2 -C ⁇ dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 ,
  • R 2 and R 3 independently of one another are C ⁇ Cealkenyl, C 2 -C 6 alkenyl which is substituted by halogen, cyano, nitro, C ⁇ -C 4 alkoxy, C 3 -C 6 -trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or ah alkali metal or alkaline earth metal atom, or by C ⁇ -C e alkylamino, C 2 -dalkoxycarbonyl, C 2 -C 6 dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 Rn, C ⁇ -C alkyl, formyl, C ⁇ -C 4 alkylcarbonyl, -COOR 7 , d-C alkylthio, d-
  • R 2 and R 3 independently of one another are C 3 -C ⁇ alkynyl, C 3 -C 6 alkynyl which is substituted by halogen, cyano, nitro, Ci-C ⁇ alkoxy, C 3 -C 6 trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C 6 alkylamino, C 2 -C 5 alkoxycarbonyl, Crdsdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR 5 , -NR 10 R 11 , d-C alkyl, formyl, d-C 4 alkylcarbonyl, COOR 7 , C ⁇ -C 4 alkylthio, d-C 4 alkyl
  • C 6 alkylcarbonyl it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, C ⁇ -C 8 alkylamino, C 2 -C ⁇ dialky!amino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C 2 -C B alkoxycarbonyl,
  • R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Ci-Csalkyl, CrC 5 alkoxy, Ci-Csalkylcarbonyl, d-Csalkylcarbonyloxy, d-C 6 alkoxycarbonyl, aminocarbonyl, d-Cealkylaminocarbonyl or
  • R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Ci-Cealkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-d-
  • R 2 and R 3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C alkyl,
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C 4 alkyl, d-C alkoxy, halogen, cyano or nitro, or
  • R 2 and R 3 independently of one another are amino, C ⁇ -C 4 alkylamino, C 2 -C ⁇ dialkylamino, phenylamino, d-Csalkylcarbonylamino, C ⁇ -C 5 alkoxycarbonylamino, hydroxyl, d-C 4 alkoxy,
  • R 5 is hydrogen, C -C ⁇ alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, C ⁇ -C 6 cyanoalkyl, phenyl, haiophenyl, Ci-C 4 alkoxyphenyl, phenyl-d-C 4 alkyl, C ⁇ -C 4 alkylcarbonyl, benzoyl, halobenzoyl, d-C alkylamino, C 2 -C6dialkylamino, C 3 -C 6 trialkylsilyl, C 3 -C ⁇ cycloalkyl, C 2 -
  • R 7 is hydrogen, d-C alkyl, C ⁇ -C 4 haloalkyl r d-C 4 cyanoalkyl, phenyl, haiophenyl,
  • R ⁇ and R 9 independently of one another are hydrogen, phenyl, haiophenyl, C ⁇ -C 4 alkyl, d-C 4 haloalkyl, d-C 4 cyanoalkyl, d-dalkenyl, C 3 -C 4 alkynyl or C 2 -C 4 alkoxyalkyl, or
  • R 8 and R 9 together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by C ⁇ -C alkyl
  • R10 and R independently of one another are hydrogen, phenyl, haiophenyl, d-dalkyl, d-C 4 haloalkyl, C ⁇ -C cyanoalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 2 -C 4 alkoxyalkyl, formyl, d-C alkylcarbonyl or phenylcarbonyl, it being possible for the phenyl moiety therein to be substituted by C ⁇ -C 4 alkyl, halogen, C ⁇ -C alkoxy, hydroxyl, cyano, nitro or C ⁇ -C alkoxy- carbonyl, or
  • R10 and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by d-C 4 alkyl.
  • R 2 and R 3 independently of one another are hydrogen, d-C 6 alkyl, C ⁇ -C 6 alkyl which is substituted by halogen, hydroxyl, amino, ammonium, tri-C ⁇ -C 4 alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, d-C 6 alkylamino, C ⁇ -C 5 alkoxycarbonyl or C 2 -C 6 dialkylamino, or R 2 and R 3 independently of one another are formyl, C ⁇ -C 8 alkylcarbonyl, d-dalkenyl- carbonyl, C 4 -C 9 cycloalkylcarbonyl, Ce-Cgcycloalkenylcarbonyl or C 3 -dcycloalkyl-C ⁇ - C 6
  • R 2 and R 3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C 5 alkyl, d-C 5 alkoxy or d-C ⁇ alkoxy- carbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CrC 4 alkyl, d-C alkoxy or CrC 4 alkoxycarbonyl, or
  • R 2 and R 3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-C ⁇ -C 6 alkylcarbonyl, biphenyl-d-C 6 alkylcarbonyl, naphthyl-C ⁇ - C 6 alkylcarbonyl, phenyl-C 2 -C 6 alkenylcarbonyl, biphenyl-C 2 -C 6 alkenylcarbonyl or naphthyl- C 2 -C 6 alkenylcarbonyl, it being possible for these substituents to be substituted by d- dalkyl, d-C alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkylcarbonyl, halogen, cyano, amino, nitro, -COOH, Ci-Csalkoxycarbonyl, hydroxyl or C ⁇ -C 4 alkylsulfon
  • R 2 and R 3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by C ⁇ -C 4 alkyl, C ⁇ -C alkoxy, halogen or cyano.
  • R 3 are hydrogen, or
  • R 2 and R 3 independently of one another are formyl, d-C 8 alkylcarbonyl, C 2 -
  • R 2 and R 3 are phenylcarbonyl, it being possible for the phenyl ring to be substituted by C dalkyl, C ⁇ -C 4 alkoxy, C C 4 alkylthio, d-C 4 haloalkyl, halogen, cyano, nitro, -COOH, C ⁇ -
  • a further preferred group of compounds of the formula I is the group in which X is O or
  • R is methyl which is substituted by halogen, cyano, nitro or OR 5 , or
  • R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 5 -C 8 cycloalkenyl,
  • R 4 is phenyl which is substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl,
  • R 4 is biphenyl, naphthyl, heterocyclyl, C ⁇ -C 4 alkylphenyl, C C 4 alkylnaphthyl, phenyl-d-
  • C 4 alkyl or naphthyl-C ⁇ -C alkyl it being possible for the substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, C ⁇ -C alkyl, C ⁇ -C 4 alkyloxy, d-C alkylthio, d-C 4 haloalkyl, C ⁇ -C 4 haloalkoxy, d-C haloalkylthio, C 2 -C 6 alkoxycarbonylalkoxy, d-C 4 alkyl- sulfinyl, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C 6 alkyloxycarbonyl, d-C 6 alkylcarbonyl, -CONH 2 , formyl, C
  • R 5 is hydrogen, d-C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C e alkoxyalkyl, d-Cecyanoalkyl, phenyl, haiophenyl, C ⁇ -C 4 alkoxyphenyl, phenyl-d-C alkyl, C ⁇ -C alkylcarbonyl, benzoyl, halobenzoyl, d-C 4 alkylamino, C 2 -C 6 dialkylamino, C 3 -C e trialkylsilyl, C 3 -C 6 cycloalkyl, C 2 -
  • R is methyl which is substituted by halogen or cyano, or
  • R 4 is C 2 -C 8 alkyl, C 2 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C ⁇ cycloalkyl, Cs-C ⁇ cycloalkenyl, C 3 -C ⁇ - cycloalkyl-C ⁇ -C 4 alkyl or Ci-dalkyl-drC ⁇ cycloalkyI, it being possible for the substituents herein to be substituted by halogen or cyano, or
  • RJ 4 is phenyl which is substituted by halogen, cyano, nitro, amino, C ⁇ -C 4 alkyl, C ⁇ -C 4 alkyloxy, d-C alkylthio, C 1 -C 4 haloalkyl, C ⁇ -C haloalkoxy, C 2 -C 6 alkoxycarbonylalkoxy, C ⁇ -C 4 alkyl- sulfonyl, C ⁇ -C ⁇ alkyloxycarbonyl, d-C 6 alkylcarbonyl, formyl, C ⁇ -C alkyiamino,
  • R 4 is biphenyl, naphthyl, heterocyclyl, d-dalkylphenyl, C ⁇ -C 4 alkylnaphthyl, phenyl-d-
  • C 4 alkyl or naphthyl-d-C 4 alkyl it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, d-dalkyl, C ⁇ -C 4 alkyloxy, d-C alkylthio, d-C haloalkyl, d-C 4 haloalkoxy, C 2 -C ⁇ alkoxycarbonylalkoxy, C ⁇ -C 4 alkylsulfonyl, d-C 8 alkyloxycarbonyl, d-C 6 alkylcarbonyl, C 3 -C 6 trialkylsilyl or C ⁇ -C 6 alkylcarbonyloxy, very preferably X being O and R being phenyl which is substituted by halogen, cyano, nitro, amino, C ⁇ -C 4 alkyl, d-C 4 alkyloxy, C ⁇ -C 4 alkylthio, C ⁇ -C haloalkyl, hal
  • R 1S , R ⁇ 6 , R 17 , Ri ⁇ and R ⁇ 9 independently of one another are C ⁇ -C alkyl, C 2 -C 4 alkenyl, C ⁇ -C 4 alkoxy, fluorine, chlorine, bromine, phenyl, d-C alkoxy-C ⁇ -C alkoxy, trimethylsilyl, di-C ⁇ -C 4 alkyl- amino, di-Ci-dalkylamino-d-dalkyl, morpholinyl-d-C 4 alkyl, d-C 4 alkylthio, d-C 4 - alkylsulfinyl, C ⁇ -C 4 alkyl.sulfonyl, d-C 4 alkylcarbonyl, d-C 4 alkoxy-C,-C 4 alkyl, 1 -(C ⁇ -C 4 alkyl)- dioxolanyl, 1-phenyldioxo
  • cyclohexyl, thienyl or the group or is phenyl, naphthyl, pyridyl or thienyl, each of which is substituted by d-C 4 alkyl, C ⁇ -C alkoxy, fluorine, chlorine, nitro, cyano, C 3 - C 6 cycloalkyloxycarbonyl, d-C 6 alkylthio, C ⁇ -C 4 hydroxycarbonyl, alkylsulfonyl, di-d-C alkylamino, d-C alkylsulfonyl or trifluormethyl.
  • R is the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , C2, C3, C4, C5, C6, D1 , D2 or D3, but preferably the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1, C2, C3, C4, C5 or C6.
  • R ⁇ 5 , R 16 , R 17 , R 18 and R ⁇ 9 independently of one another are halogen, d-C ⁇ alkyl or d-Cealkoxy, preferably fluorine, chlorine, d-C 4 alkyl or d-C 4 alkoxy.
  • R ⁇ 5 is fluorine when R, is A1 , B1 , B2, B3, C1 , C2 or C6.
  • the compounds of the formula I can be prepared in various ways via process steps known per se using known starting materials.
  • compounds of the formula I can be prepared by reacting an S,S- diorganosulfodiimide with an O.O'-diaryl N-cyanoimidocarbonate and subsequently subjecting the product to cyclization under acidic conditions:
  • Ri has the abovementioned meaning
  • R is R or another group which is suitable for the reaction, for example methyl or benzyl
  • Ar is an aryl group, for example phenyl.
  • Hal radicals independently of one another are fluorine, bromine or, in particular, chlorine, and reacting this trihalogenated thiatriazine with the corresponding organometallic compound of the formula III
  • Ri has the abovementioned meanings and M is a mono- or polyvalent metal atom, which, depending on the valence, can have attached to it an appropriate number of Ri groups, in order to introduce the phenyl ring.
  • suitable metals are, in particular, lithium, magnesium, zinc, aluminium, silicon, tin, and furthermore also manganese and titanium.
  • the polyvalent metal atoms can also have attached to them further substituents such as halogen, cyano, d-C 4 alkyl, tetrafluoroborate or halogenated or unhalogenated alkanesulfonates.
  • the organometallic compound of the formula III can furthermore be used in combination with salts such as aluminium chloride, zinc chloride, tin chloride, cerium chloride, aluminium bromide and/or copper bromide, aluminium chloride, aluminium bromide and zinc chloride being preferred.
  • the compounds of the formula III can be prepared by customary methods, for example
  • halogen/metal exchange reaction of the corresponding halide Rrhalogen, halogen preferably being bromine or iodine, with a reactive organometallic compound, such as an alkyllithium compound, for example n-butyl-, s-butyl- or t-butyllithium,
  • Aromatics of the formula Ri-H which are especially suitable for this reaction are those which carry a function which facilitates deprotonation and/or which influence orientation (see, for example, Snieckus V. Chem. Rev. (1990) 90, 879-933),
  • organometallic compound is not isolated but is reacted directly with the thiatriazine halide, in the presence or absence of a metal salt.
  • the group R may be introduced in an aprotic solvent such as a hydrocarbon, for example hexane, heptane or toluene, or an ether such as dioxane, diethyl ether or, in particular, tetrahydrofuran, at temperatures from -100 C C to 150°C, in particular -80°C to 50°C (depending on the solvent).
  • aprotic solvent such as a hydrocarbon, for example hexane, heptane or toluene
  • an ether such as dioxane, diethyl ether or, in particular, tetrahydrofuran
  • the group Ri may be introduced by means of a Friedel-Crafts reaction between the aromatic R H and a compound of the formula It in the presence or absence of a catalyst such as a Lewis acid (for example AICI 3 , SnCI 4 and the like) or activated clay (for example montmorillonite).
  • a catalyst such as a Lewis acid (for example AICI 3 , SnCI 4 and the like) or activated clay (for example montmorillonite).
  • This reaction can be carried out in an aprotic solvent such as a hydrocarbon, for example nitrobezene, benzene, carbon tetrachloride and the like, or an ether, such as diethyl ether or tetrahydrofuran at temperatures from -50°C to 120°C, in particular -10°C to 60°C (depending on the solvent).
  • RT has the abovementioned meaning and Hal radicals independently of one another are fluorine, chlorine or bromine, with the exception of the compounds 1-(4- methylphenyl)-3,5-dichlorothiatriazine, 1 -(4-hydroxyphenyl)-3,5-dichlorothiatriazine, 1 -(4- methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(4-chlorophenyl)-3,5-dichlorothiatriazine, 1 -(2- hydroxy-5-tert-butylphenyl)-3,5-dichlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3,5- dichlorothiatriazine and 1 -(4-hydroxy-3-methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3,5-d
  • the compounds of the formula V are pretreated with a base such as metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts.
  • a base such as metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts.
  • a base such as metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts.
  • the reaction mixture of the compounds of the formulae IV and V may also be treated with the abovementioned bases.
  • Solvents which are suitable for this step are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene, ethers such as tetrahydrofuran, dioxane or diethyl ether, and also tertiary amides such as dimethylformamide. It is also possible to employ a mixture of these solvents with water, in which case it is advantageous to use a phase transfer catalyst. As a rule, the reaction temperatures are between -50°C and 100°C, preferably between 0°C and 40°C.
  • the compounds of the formula V are known and can be prepared in a manner known to those skilled in the art.
  • R 2 and R 3 have the abovementioned meanings and M is hydrogen or a metal atom such as lithium, sodium, potassium or calcium, the process advantageously being carried out in the presence of a base.
  • M 1 is preferably hydrogen.
  • R 2 or R 3 is an acyl group, Mi is preferably lithium, sodium or potassium.
  • Solvents which are suitable for this reaction are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene or dichloromethane, ethers such as diethyl ether, dioxane or tetrahydrofuran, alcohols such as ethanol or isopropanol, esters such as ethyl acetate, nitriles such as acetonitrile, or water.
  • the reaction temperatures are in the range of from -70°C to 100°C, in particular 0°C to 40°C.
  • an acid binder is preferably used in order to scavenge the Hal acid.
  • This may be, for example, a second equivalent of the compound of the formula VII, or a tert-amine such as triethylamine, pyridine, or an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate.
  • a tert-amine such as triethylamine, pyridine
  • an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate.
  • R 2 , R 3 and Mi are hydrogen
  • an excess of base may be used. If required, the process may be carried out under pressure.
  • R ⁇ R 2 and R 3 have the abovementioned meanings and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1-(4-methylphenyl)-3-amino-5-chloro- thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-chlorothiatriazine, 1 -(4-methoxyphenyl)-3-amino- 5-chlorothiatriazine, 1 -(4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(2-hydroxy-5-tert- butylphenyl)-3-amino-5-chlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3-amino-5- chlorothiatriazine, 1 -(4-hydroxy-3-methoxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5-
  • the end products of the formula I can be isolated in the customary manner by concentrating and/or evaporating the solvent and purified by recrystaiiization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatographic methods.
  • All application methods conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and a variety of methods and techniques, for example controlled release of active ingredient, are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them.
  • a solution of the active ingredient is applied to mineral carriers for granules or to polymerized granules (urea/formaldehyde), and these are dried. If required, an additional coating may be applied (coated granules) which allows the active ingredient to be released in a controlled manner over a specific period.
  • the compounds of the formula I can be employed as pure active ingredients, i.e.
  • auxiliaries conventionally used in the art of formulation to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the application methods such as spraying, atomizing, dusting, wetting, scattering or pouring, and the type of composition, are selected to suit the intended aims and the prevailing circumstances.
  • compositions i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I, or at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries
  • formulation auxiliaries for example solvents or solid carriers.
  • Surface-active compounds surfactants may furthermore additionally be used in the preparation of the formulations.
  • aromatic hydrocarbons preferably the fractions C 8 to d 2 , for example xylene mixtures or substituted naphthalenes, phthalate esters such as di butyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethyiformamide, or epoxidized and unepoxidized vegetable oils such as epoxidized coconut oil or soya oil; or water.
  • aromatic hydrocarbons preferably the fractions C 8 to d 2
  • phthalate esters such as di butyl phthalate or dioctyl phthalate
  • Solid carriers which are used for example for dust and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silica or highly disperse absorptive polymers Suitable paniculate, absorptive carriers for granules are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and non-sorptive carrier materials, for example, calcite or sand.
  • a large number of pregranulat ⁇ d materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are non-ionic, cation ic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated.
  • Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
  • Soaps which are suitable are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (do-da), for example the sodium or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tallow oil. Furthermore mention must also be made of the fatty acid methyltaurine salts.
  • the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.
  • This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives have preferably 2 sulfonyl groups and a fatty acid radical of 8 to 22 C atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfuric acid, of dibutylnaphthalenesuffonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.
  • Non-ionic surfactants which are suitable are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of alkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkyl phenols.
  • non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups.
  • the abovementioned compounds normally have 1 to 5 ethylene glycol units per polypropylene glycol unit.
  • non-ionic surfactants examples include nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are mainly quaternary ammonium salts which have, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts are preferably in the form of haiides, methylsulfates or ethylsulfates, examples being stearyltrimethylammonium chloride or benzyldi(2- chloroethyl)ethylammonium bromide.
  • the herbicidal formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.
  • compositions may also comprise further additives such as stabilizers, for example free or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients.
  • stabilizers for example free or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil)
  • antifoams for example silicone oil
  • preservatives for example silicone oil
  • viscosity regulators binders
  • adhesives adhesives and fertilizers or other active ingredients.
  • Emulsifiable concentrates Active ingredient: 1 to 90%, preferably 5 to 50% Surfactant: 5 to 30%, preferably 10 to 20% Solvent 15 to 94%, preferably 70 to 85%
  • Active ingredient 0.1 to 50%, preferably 0.1 to 1%
  • Solid carrier 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates Active ingredient: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30%
  • Wettable powders Active ingredient: 0.5 to 90%, preferably 1 to 80%
  • Surfactant 0.5 to 20%, preferably 1 to 15%
  • Solid carrier 5 to 95%, preferably 15 to 90%
  • Active ingredient 0.1 to 30%, preferably 0.1 to 15%
  • Solid carrier 99.5 to 70%, preferably 97 to 85%
  • the active ingredients of the formula I are successfully applied to the plant or its environment at rates of application of from 0.001 to 5 kg, in particular between 0.005 and 2 kg.
  • the dosage required for the desired activity can be determined by experiments. It depends on the type of activity, the development stage of the crop plant and of the weed, and on the application (location, timing, method) and can, due to these parameters, vary within wide ranges.
  • the compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties, which allow them to be used in crops of useful plants, in particular in cereals, cotton, soya beans, sugar beet, sugar cane, plantations, oil seed rape, maize and rice.
  • Crops are also to be understood as meaning those which have been made tolerant to herbicides, or classes of herbicides, by conventional breeding or genetic engineering methods.
  • the weeds to be controlled can be both mono- and dicotyledon weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Example H1 Preparation of 3.5-dichloro-1- 2-methylphenyl)thiatriazine: A 2 M solution of o-tolylmagnesium bromide in tetrahydrofuran (150 ml) is added dropwise with intensive stirring and cooling at a temperature of -20°C to a solution of 40.9 g of ZnCI 2 (0.3 mol) in 500 ml of absolute tetrahydrofuran. The resulting mixture is stirred for 45 minutes at a temperature of -20°C and subsequently cooled to a temperature of -70°C.
  • Example H2 Preparation of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro- 1 -(2-methylphenyl)thiatriazine (39.0 g, 0.150 mol) in 700 ml of tetrahydrofuran at a temperature of 0°C. When passing-in is complete, the reaction mixture is concentrated by half in vacuo, diluted with water to 1 I and stirred. The resulting suspension is filtered with suction, until the filter residue is washed with water and dried. This gives 3-amino-5-chloro- 1 -(2-methylphenyl)thiatriazine in the form of white crystals of melting point 196°C (decomposition).
  • Example H3 Preparation of 3-amino-1-(2-methylphenyl)-5-(4-(3-oxobutvD- phenoxy)thiatriazine:: A mixture of 2.4 g of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine (0.010 mol), 1.8 g of 4-hydroxyphenyl)-2-butanone (0.011 mol) and 70 ml of dichloromethane is treated with 6.0 ml of 2 N sodium hydroxide solution (0.012 mol) and 1.5 g of trimethylamine solution (40% in water). The reaction mixture is subsequently stirred for 2 days at a temperature of 20°C.
  • Example H4 Preparation of 3.5-dichloro-1- 2.5-dichlorophenyl)thiatriazine: A solution of 43.7 g of 1 ,4-dichloro-2-iodobenzene (0.16 mol) in 200 ml of absolute tetrahydrofuran is treated at a temperature of from -70°C to -65°C with a solution of 0.16 mol of n-butyllithium in 100 ml of hexane. Then, a solution of 21.8 g of ZnCI 2 in 150 ml of absolute tetrahydrofuran is added dropwise.
  • Example H5 Preparation of 3-amino-5-chloro-1-(2.5-dichlorophenvDthiatriazine: Ammonia is passed into a vigorously stirred solution of 2.2 g of 3,5-dichloro-1 -(2,5- dichlorophenyl)thiatriazine (0.007 mol) in 80 ml of tetrahydrofuran at a temperature of 0 C C. When the starting material has reacted completely, the reaction mixture is treated with ethyl acetate and water. The organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. When the liquid is reduced, crystals precipitate.
  • Example H6 Preparation of 3-amino-5-(3.5-bistrifluoromethylphenoxy)-1 -(3.5- dimethylphenvDthiatriazine.
  • Example H7 Preparation of 3.5-dichloro-1-(2.4.6-trimethylphenylUhiatriazine: A 1 M solution of 2-mesitylmagnesium bromide in diethyl ether (100 ml) is added dropwise with vigorous stirring and cooling at a temperature of 20°C to a solution of 13.6 g of ZnCI 2 (0.1 mol) in 200 ml of absolute tetrahydrofuran. The mixture obtained is subsequently stirred for 45 minutes at a temperature of 20°C and then cooled to a temperature of -70°C.
  • Trituration of the residue with pentane results in the formation of yellow crystals of 3,5-dichloro-1 -(2,4,6-trimethyiphenyl)thiatriazine which, after washing with pentane and subsequent drying, have a melting point of 98-100°C.
  • Example H8 Preparation of 3-amino-5-chloro-1-(2.4.6-trimethylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro-1 -(2,4,6-trimethyl- phenyl)thiatriazine (10.1 g, 0.035 mol) in 200 ml of tetrahydrofuran at a temperature of 0°C. When the addition is complete, the reaction mixture is treated with ethyl acetate and water. After extraction, the organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. The solution is then concentrated until a viscous suspension is formed which is filtered with suction.
  • Example H10 Preparation of 3.5-dichloro-1-(2.3.5.6-tetramethylphenylUhiatriazine: A solution of 13.6 g of ZnCI 2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,5,6-tetramethylphenylmagnesium bromide (prepared with 21.3 g of 1-bromo-2,3,5,6-tetramethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 100 ml of absolute tetrahydrofuran) at a temperature of -20°C.
  • the mixture is subsequently stirred for 1 hour at a temperature of 20°C and then cooled to a temperature of -70°C.
  • a solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is subsequently added dropwise to the mixture at a temperature of from -70°C to -65°C.
  • the reaction mixture is subsequently allowed to come to room temperature and then transferred into 1 litre of water.
  • the suspension is placed on a suction filter, and the residue obtained is washed with water, dried with suction and then washed with pentane and dried. This gives 3,5-dichloro-1-(2,3,5,6-tetramethylphenyl)thiatriazine in the form of yellow crystals of melting point 138-140°C.
  • Example H11 Preparation of 3-amino-5-chloro-1-(2.3.5.6-tetramethylphenylHhiatriazine.
  • Ammonia is passed into a vigorously stirred solution of 15.2 g of 3,5-dichloro- 1-(2,3,5,6-tetramethylphenyl)thiatriazine (0.0503 mol) in 300 ml of tetrahydrofuran at a temperature of 0°C.
  • the reaction mixture is treated with water.
  • the suspension is placed on a suction filter, and the residue is washed with water, dried with suction, washed with diethyl ether and dried.
  • Example H13 Preparation of 3.5-dichloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine: A solution of 13.6 g of ZnCI 2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,4,5,6-pentamethylphenylmagnesium bromide (prepared with 22.7 g of 1-bromo-2,3,4,5,6-pentamethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 130 ml of absolute tetrahydrofuran) at a temperature of -20°C.
  • 2,3,4,5,6-pentamethylphenylmagnesium bromide prepared with 22.7 g of 1-bromo-2,3,4,5,6-pentamethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 130 ml of absolute tetrahydrofuran
  • the mixture is stirred for 30 minutes at a temperature of 20°C and subsequently cooled to a temperature of -70°C.
  • a solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is then added dropwise to the mixture at a temperature of from -70°C to -65 C C.
  • the reaction mixture is allowed to come to room temperature, with stirring, and is subsequently transferred into 1 litre of water.
  • the suspension is then placed on a suction filter and the residue obtained is washed with water, dried with suction, washed with pentane and dried.
  • Example H14 Preparation of 3-amino-5-chloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 14.0 g of 3,5-dichloro- 1-(2,3,4,5,6-pentamethylphenyl)thiatriazine (0.0443 mol) in 300 ml of tetrahydrofuran at a temperature of 0°C. After the starting material has reacted completely, the reaction mixture is evaporated and the residue obtained is treated with water.
  • Example H16 Preparation of methyl 2-ri-(3.5-difluoroph ⁇ nyl)-5-chloro-1 ⁇ 4 -(1.2.4.6)- thiatriazin-3-ylamino1-3-methyl-pentanoate (Example B5.052): A cooled suspension of 1.27 g of L-isoleucine methyl ester hydrochloride in 15 ml of tetrahydrofuran is treated with 14 ml of propylene oxide and 2.1 g of 3,5-dichloro- 1-(3,5-difluorophenyl)1 4 -(1 ,2,4,6)thiatriazine in 3 ml of tetrahydrofuran and 0.68 ml of 1 ,8-diazabicyclo[5.4.0]undec-7-ene(1 ,5-5) (DBU).
  • Example H17 Preparation of methyl 2-ri-(3.5-difluorophenyl)-5-pentafluorophenoxy-1 ⁇ 4 - (1.2.4.6)thiatriazin-3-ylamino1-3-methylpentanoate (Compound B6.009): 1.6 g of the product obtained in Example H16 are dissolved in 35 ml of dichloromethane, and the solution is treated with 0.65 ml of trimethylamine solution (45%, aqueous) and 27.3 ml of a 0.145 molar solution of pentafluorophenol in dichloromethane.
  • Example H20 Preparation of 2.6-dichloro-N-f1-(3-chloro-4-methvtphenyl)- pentafluorophenoxy-1 ⁇ 4 -(1.2.4.6)thiatriazin-3-y ⁇ isonicotinamide (Compound B6.033): A solution of 1.5 g 2,6-dichloroisonicotinoyl chloride in 6 ml of acetonitrile is added dropwise to a stirred solution of 2.5 g of 1-(3-chloro-4-methylphenyl)-5-pentafluorophenoxy-3-amino- 1 ⁇ 4 -(1 ,2,4,6)thiatriazine in 16 ml of pyridine under a nitrogen atmosphere at a temperature of from -5 to 0°C , and the resulting solution is stirred for 30 hours at a temperature of 0°C.
  • reaction mixture is then diluted with ethyl acetate, transferred into ice-water and is extracted rapidly with ethyl acetate while adding saturated sodium chloride solution.
  • the extracts are dried over sodium sulfate and evaporated, and the residue is purified on silica gel (hexane/ethyl acetate 7:3). This gives 2,6,-dichloro-N-[1-(3-chloro-4-methylphenyl)- pentafluorophenoxy-1 ⁇ 4 -(1,2,4,6)-thiatriazin-3-yl]isonicotinamide of melting point 196- 198°C.

Abstract

Compounds of formula (I) in which R1 is a substituted phenyl group and X is O, S, SO or SO2, are well suited for use as herbicides.

Description

SUBSTITUTED 1 ,2, 4, 6-THIATRIAZINES USEFUL AS HERBICIDES.
Novel herbicides
The present invention relates to novel herbicidally active thiatriazine derivatives, to processes for their preparation, to compositions comprising these compounds, and to their use for controlling weeds, mainly in crops of useful plants, or for inhibiting plant growth.
Thiatriazine compounds are described, for example, in Chem. Ber. 121 , 383-386 (1988), Z. Naturforsch. 43, 763-768 (1988), Chem. Ber. 126, 2601-2607 (1993), J. Am. Chem. Soc. 1989, 11 1 , 1 180-1185 and DD 113 006. There have now been found novel thiatriazine derivatives having herbicidal and growth-inhibitory properties.
The present invention thus relates to compounds of the formula I
Figure imgf000003_0001
in which Ri is a group
A2 or A3 ,
Figure imgf000003_0003
Figure imgf000003_0002
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000004_0003
Figure imgf000004_0004
Figure imgf000005_0001
R2 and R3 independently of one another are hydrogen, d-C6alkyl, d-C3alkyl which is substituted by S(O)nR6, halogen, cyano, nitro, d-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C4alkylammonium, -COOH, -COOR20, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C-3-C8cycloalkyl, d-C3alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, d-C3alkoxycarbonyl, C2- C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NR10Rn, C C alkyl, formyl, d-C alkylcarbonyl, COOR7, d-C4alkylthio, Cι-C4alkylsulfonyl or -CONRβR9) or
R2 and R3 independently of one another are C2-Cealkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, d-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C alkylammonium, -COOH, -COOR20, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C3-Cβcycloalkyl, CrCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cealkylamino, C2-C5alkoxycarbonyl, C2-Ci2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NRι0Rn, Cι-C4alkyl, formyl, Cι-C4alkylcarbonyl, -COOR7, Cι-C4alkylthio, Cι-C alkylsulfonyl or -CONR8R9l or
R2 and R3 independently of one another are C3-C6alkynyl, C3-C6alkynyl which is substituted by halogen, cyano, nitro, d-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C alkylammonium, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C3-C8cycloalkyl, d-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C6alkylamino, d-C5alkoxycarbonyl, C2-Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NR10Rn, d-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR7,
C,-C4alkylthio, d-C4alkylsulfonyl or -CONR8R9, or
R2 and R3 independently of one another are formyl, d-dsalkylcarbonyl,
C2-C15alkenylcarbonyl, d-Cgcycloalkylcarbonyl, C8-C9cycloalkenylcarbonyl or
C3-Cβcycloalkyl-Cι-Cealkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, d-Cealkylamino, C2-C12dialkylamino, -COOH,
-COOR20, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrC8alkoxycarbonyl, C -Cι0cycloalkoxycarbonyl, Ci-Cβalkylaminocarbonyl or
C2-Ci2dialkylaminocarbonyl, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, C -Csalkyl, d-C5alkoxy, Cι-C5alkylcarbonyl, d-C5alkylcarbonyloxy, d-C6alkoxycarbonyl, aminocarbonyl, Ci-Cβalkylaminocarbonyl or
C2-Cιιdialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, Cι-C5alkyl, d-C5alkoxy, d-C3alkylcarbonyl, CTCβalkoxycarbonyl, aminocarbonyl, d-Cβalkylamino or d-C3alkylcarbonyloxy, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-d-C6alkylcarbonyl, biphenyl-d-C6alkylcarbonyl, naphthyl-
CrCβalkylcarbonyl, phenyl-C2-Ceaikenylcarbonyl, biphenyl-C2-Cealkenylcarbonyl, naphthyl-
C2-C6alkenylcarbonyl, phenyl-d-Cealkynylcarbonyl, biphenyl-C3-Cβalkynylcarbonyl or naphthyl-C3-Cβalkynylcarbonyl, it being possible for these substituents to be substituted by d-C5alkyl, d-C5alkoxy, d-C5alkylthio, C C5haloalkyl, Ci-Csalkylcarbonyl, halogen, cyano, amino, nitro, -COOR7, d-C8alkoxycarbonyl, hydroxyl, Cι-C5alkylsulfinyl, d-C5alkylsulfonyl,
CrCβalkylaminocarbonyl or C2-C12dialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, Ci-Csalkyl, Ci-Csalkoxy,
Cι-C5alkylthio, -COOH, -CONH2, d-C6alkylaminocarbonyl, C2-Cιodialkylaminocarbonyl, d-Csalkylcarbonyl or Ci-Csalkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C5alkyl, Cι-C3alkoxy, halogen, cyano or nitro, or
R2 and R3 independently of one another are amino, CrC6alkylamino, C2-Cβdialkylamino, phenylamino, naphthylamino, Cι-C6alkylcarbonylamino, Cι-Cιoalkoxycarbonylamino, hydroxyl, d-C6alkoxy, d-C6alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy,
X is O or S(O)Xl in which x is 0, 1 or 2, and R4 is d-C8alkyl, C2-C8alkenyl, d-Cβalkynyl, C3-C8cycloalkyl, C5-C8cycloalkenyl, C3-
CBcycloalkyl-CrC alkyl or Cι-C4alkyl-C3-Cβcycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or -OR5, or
R4 is phenyl, biphenyl, naphthyl, heterocyclyl, d-C4alkylphenyl, d-C alkylnaphthyl, phenyl-
Cι-C alkyl or naphthyl-Cι-C alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, Cι-d0alkyl, d-C10alkyloxy, d-
C6alkylamino, di-C2-C8alkylamino, d-Cioalkylthio, Cι-Cιohaloalkyl, Ci-dohaloalkoxy, d- dohaloalkylthio, C2-Cιoalkoxycarbonylalkoxy, Cι-C6alkylsulfinyl, d-Cealkylsulfonyl, d-
C6alkyloxycarbonyl, d-C6alkylcarbonyl, -CONH2, formyl, d-dalkylaminocarbonyl, C2-
Cndialkylaminocarbonyl, d-Cβtrialkylsilyl, d-doalkylcarbonylamino, d-
Cioalkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cι-C alkyl, d-C4alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, =O, C Cιoalkyl, d-Cioalkoxy, Cι-Cιoalkylthio, d-
Ciohaloalkyl, hydroxyl, C3-C10alkoxy-carbonylalkoxy, d-C6alkylsulfinyl, Cι-C6alkylsulfonyl,
C2-C6alkyloxycarbonyl, C2-C6alkyl-carbonyl, -CONH2, formyl, C2-C7alkylaminocarbonyl, d-
Cndialkylaminocarbonyl, d-C6trialkylsilyl, d-Cioalkylcarbonylamino, C2-
C10alkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cι- dalkyl, d-C alkoxy, cyano, nitro or amino,
R5 is hydrogen, Ci-CβalkyI, d-Cβhaloalkyl, C2-C5alkoxyalkyl, d-C6cyanoalkyl, phenyl, phenyl-Cι-C alkyl, formyl, C2-dalkylcarbonyl, CrCτalkoxycarbonyl, d-C6alkyl- aminocarbonyl, C2-C8dialkylaminocarbonyl, benzoyl, halobenzoyl, Cι-C6alkylamino,
C2-C8dialkylamino, -N=CH2, -N^H-d-dalkyl, -N=C(d-C4alkyl)2, tri(Cι-C4alkyl)silyl,
C3-Cτcycloalkyl, C2-C7alkenyl or C3-Cτalkynyl, heterocyclyl, n is 0, 1 or 2,
R6 is hydrogen or cyano when n is 0 or
Re is d-Csalkyl, C2-C5alkenyl, d-dalkynyl, d-Cealkoxyalkyl, d-C5haloalkyl, d-C5hydroxyalkyl, phenyl, phenyl-d-C4alkyl, heterocyclyl, heterocyclyl-C -C alkyl or
C3-Cτcycloalkyl,
R7 is hydrogen, Cι-C12alkyl, d-C12haloalkyl, d-C6nitroalkyl, C C6cyanoalkyl, phenyl,
C2-Cιoalkoxyalkyl, C2-doalkylcarbonylalkyl, C2-C10alkoxycarbonylalkyl, heterocyclyl,
C3-Cτcycloalkyl, C3-C7haiocycloalkyl, -N=CH2, -N=CH-Cι-C4alkyl, -N=C(Cι-C4alkyl)2 or
C2-C6dialkylamino, Rθ and R9 independently of one another are hydrogen, phenyl, d-C8alkyl, C C8haloalkyl,
Cι-Cβalkoxy, phenoxy, C2-Cτcyanoalkyl, C3-Cτalkenyl, d-C7alkynyl, C2-Cβalkoxyalkyl, d-C6alkylamino or C2-C6dialkylamino, or
Rβ and R9 together with the nitrogen atom to which they are bonded form a three- to seven- membered heterocycle which can contain one or two further hetero atoms and, in turn can be substituted by ^alkyl groups or halogen,
R10 and Rn independently of one another are hydrogen, phenyl, d-C8alkyl, Cι-C8haloalkyl, d-C8alkoxy, phenoxy, C2-Cτcyanoalkyl, Crdalkenyl, C3-dalkynyl, C2-C8alkoxyalkyl,
Cι-C6alkylamino, (d-C6alkylamino)carbonyl, d-Cedialkylamino, (C2-
C6dialkylamino)carbonyl, formyl, (d-C7alkyl)carbonyl, (d-C6alkoxy)carbonyl, phenylcarbonyl, phenoxycarbonyl, benzyloxycarbonyl, heterocyclylcarbonyl, heterocyclyloxycarbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which can contain one or two further hetero atoms and, in turn, can be substituted by Chalky! groups or halogen,
R12 is Cι-C8alkyl, d-dalkoxy, d-Cβalkenyloxy, d-CBalkynyloxy, d-C8haloalkyl, phenyl, phenyloxy,
Figure imgf000008_0001
R13 and R independently of one another are hydrogen, d-C6alkyl, C2-Cβalkylcarbonyl or phenyl, and
Ri5, R16, Ru, iβ and R19 independently of one another are d-Cι0alkyl, C3-C6cycloalkyl,
C3-C6cycloalkyl-Cι-C alkyl, d-Cβalkyl-d-dcycloalkyl, C2-C10alkenyl, C3-C6cycloalkyl-
C2-C alkenyl, C2-C6alkenyl-C3-C6cycloalkyl, d-C10alkynyl, C3-Cβcycloalkyl-C2-C4alkynyl,
Figure imgf000008_0002
C5-C6cycloalkenyl, C3-C6cycloalkenyl-Cι-C4alkyl, d-Cβalkyl-
C5-C6cycloalkenyl, C5-C6cycloalkenyl-C2-C4alkenyl, C2-C8alkenyl-C5-C6cycloalkenyl,
C5-C6cycloalkenyl-C2-C4alkynyl, C2-C6alkynyl-C5-C6cycloalkenyl, C3-C6cycloalkyl-
C3-C6cycloalkyl, C5-C6cycloalkenyl-C5-Cecycloalkenyl, C3-C6cycloalkyl-C5-Cβcycloalkenyl,
Cs-Cβcycloalkenyl-Cs-Cβcycloalkyl, C2-C8alkynyl-C2-C8alkenyl or C2-C8alkenyl-C2-C8alkynyl, phenyl, phenyl-Cι-C alkyl, phenyl-C2-C alkenyl, phenyl-C2-C4alkynyl, heterocyclyl, heterocyclyl-d-C4alkyl, heterocyclyl-C2-C4alkenyl or heterocyclyl-d-C4alkynyl, it being possible for the substituents R15, R16, R17, R1β and R19 independently of one another to be substituted by halogen, cyano, azido, nitro, -ORs, =O, -S(O)„R6, -COOR7, -CONR8R9,
-NR10Rn, =NR12 or =N-NR13R14) or
R15, Riβ. i7, Riβ and Rig independently of one another are halogen, cyano, azido, nitro,
-ORs, -S(O)nR6, -COOR7, -CONR8R9, -NR10Rn, tri(d-C4alkyl)silyl, di(C,-C4alkyl)- (d-C4alkoxy)silyl, -B(OH)2 , -B(C,-C4alkoxy)2 , tri(d-C4alkyl)silyl, tri(d-C4alkyl)silyl- Cι-C3alkyl, ^(d-C^lky silyl-CrCealkenyl, tri(d-C4alkyl)silyl-C2-C6alkynyl, tri(d-C4alkyl)stannyl,
Figure imgf000009_0001
tri(Cι-C4alkyl)stannyl-C2-C6alkenyl, tri(d-C4alkyl)stannyl-d-C6alkynyl, and
R20 is d-Ci2alkyl, C Cι2haloalkyl, d-C6nitroalkyl, d-C6cyanoalkyl, phenyl, C2-Cιoalkoxyalkyl, C2-Cιoalkylcarbonylalkyl, d-Cioalkoxycarbonylalkyl, heterocyclyl, C3-C7cycloalkyl, C3-C7halocycloalkyl, -N=CH2, -N=CH-C C4alkyl, -N=C(d-C4alkyl)2 or C -C6dialkylamino, and to the salts of the compounds of the formula I, with the exception of the compounds 1 -(4-hydroxyphenyl)-3-amino-5-(2,5-difluorophenoxy)thiatriazine, 1 -(4-methylphenyl)-3- amino-5-phenoxythiatriazine, 1-(4-methoxyphenyl)-3-amino-5-(2,3,4,5,6-pentafluoro- phenoxy)thiatriazine, 1-(4-methoxypheπyl)-3-amino-5-(2,3,4-trichlorophenoxy)thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-(2,3,4,5,6-pentafluorophenoxy)thiatriazine, 1 -(4-chlorophenyl)- 3-amino-5-(2,3-dichlorophenoxy)thiatriazine, 1-(2-hydroxy-5-tert-butylphenyl)-3-amino-5- (2,5-difluorophenoxy)thiatriazine, 1-(4-hydroxy-3-methylphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(4-hydroxy-3-methoxyphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethyl-2-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1 -(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-(2,5- difluorophenyloxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,3,4,5,6- pentafluorophenoxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,4,6- trichlorophenoxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,5- difluorophenoxy)thiatriazine, 3-amino-5-(2,5-difluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine and 3-amino-5-(2,3,4,5,6-pentafluorophenoxy)- 1 -(2,3,4,5,6-pentafluorophenyl)thiatriazine.
The alkyl groups in the definitions of the substituents can be straight-chain or branched and mono- or polysubstituted; they are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the abovementioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or polyuπsaturated. Suitable cycloalkyl substituents contain 3 to 8 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Corresponding cycloalkenyl substituents can be mono- or polysubstituted and mono- or else polyunsaturated, for example cyclopentadienyl or cyclooctatetraenyl.
When alkyl, alkenyl or alkynyl are substituents on a cycloalkyl, cycloalkenyl, phenyl, biphenyl, naphthyl or heterocyclyl, these ring systems may also be mono- or polysubstituted by alkyl, alkenyl or alkynyl.
As a rule, halogen is fluorine, chlorine, bromine or iodine. The same applies analogously to halogen in conjunction with other meanings such as haloalkyl or halophenyi.
Phenyl may be unsubstituted or mono- or polysubstituted by halogen, cyano, nitro, -OR5, -NR10R11, d-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR7, d-C4alkylthio, d-C alkylsulfonyl or -CONR8R9.
Heterocyclyl radicals are to be understood as meaning ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Such ring systems preferably contain 3 to 8 ring atoms. This also applies to those heterocycles which are formed by 2 substituents bonded to a nitrogen atom, as is the case in groups such as -NR10Rn.
Heterocyclyl ring systems within the scope of the present invention may also be mono- or polysubstituted. Examples of suitable substituents are C C alkyl, d-C4haloalkyl, Cι-C alkoxy, cyano, nitro or C3-Cβcycloalkyl.
Heterocyclyl as a substituent of a group Ri can be, for example, epoxidyl, dioxolanyl, pyrrolidyl, piperidinyl, morpholinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, thiazolyl, oxazolinyl (for
example: ), oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl or
Figure imgf000010_0001
phthalimidyl. Preferred heterocycles R6 are, inter alia, pyridyl, pyrimidinyl and triazinyl.
Preferred heterocycles R7 are, for example, oxetanyl, pyridyl, thiophenyl and furyl.
R8 and R9 preferably form rings such as piperidinyl, morpholinyl and pyrrolidinyl.
Preferred examples of heterocycles formed by R10 and R , or R2and R3, with the nitrogen atom to which these radicals are bonded are piperidinyl, morpholinyl, pyrrolidyl, triazolyl, tetrazolyl and imidazolyl.
Preferred heterocycles R9 are thiophenyl, furyl, pyridyl and oxetanyl.
Phenyl and naphthyl rings R4 can be substituted by carbo- or heterocyclic radicals which are formed on these phenyl or naphthyl rings by 2 adjacent substituents. The carbocycles preferably contain 4 to 6 carbon atoms, such as cyclobutyl, cyclopentyl and cyclohexyl. Especially suitable as heterocyclic groups are dioxolanyl and tetrahydrofuryl.
Heterocycles R4, such as succinimidyl, pyridyl, thiophenyl or furyl, may contain fused carbocycles, such as phenyl or cyclohexenyl.
Preferred heterocycles R2 and R3 are pyridyl, pyrrolidyl and pyrimidinyl.
Heterocycles formed by -NR2R3 include, for example, succinimidyl, imidazolyl and triazolyl, it being possible for such groups to contain fused carbocycles, such as phenyl or cyclohexenyl.
Heterocyclylcarbonyl R2 or R3 is, for example, pyridyl, pyrrolidyl, triazolyl, thiophenyl, furyl or isoxazolyl.
The alkyl radicals in substituents such as -N=C(Cι-C alkyl)2 can be identical or different. They preferably have the same meaning. The same applies analogously to the alkyl radicals in dialkylamino, dialkylaminocarbonyl, trialkylammonium and trialkylsilyl substituents. C2-C7alkylcarbonyl within the scope of the present invention is, for example, methylcarbonyl, ethylcarbonyl, propylcarbonyl, i-propylcarbonyl, butylcarbonyl, pentylcarbonyl and hexylcarbonyl and also the branched isomers of these.
Suitable examples of alkali metals and alkaline earth metals are lithium, sodium, potassium, magnesium, calcium or barium.
The invention equally includes the salts which the compounds of the formula I can form, in particular with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
Salt formers which must be emphasized among the alkali metal and alkaline earth metal hydroxides are the hydroxides of lithium, sodium, potassium, magnesium or calcium, but in particular those of sodium or potassium.
Possible examples of amides which are suitable for ammonium salt formation are not only ammonia, but also primary, secondary and tertiary d-Cι8alkylamines, d-C4hydroxy- alkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, hβptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methyl nonylamine, methylpeπtadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihβxylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2- amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2- amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example aniline, methoxyaniline, ethoxyaniline, o,m,p- toluidine, phenylenediamine, benzidine, naphthylamine and o,m,p-chloroaniline; but, in particular, triethylamine, isopropylamine and diisopropylamine.
The compounds of the formula I have an asymmetric centre in the sulfur atom of the thiatriazine ring. This is why, upon preparation of these compounds, racemates are obtained which can be separated into the corresponding enantiomers by customary separation methods. If further asymmetric centres exist in the substituents of the thiatriazine ring, the corresponding diastereoisomers may also be separated in the customary manner. The present invention also includes such diastereoisomers and enantiomers.
Preferred amongst the compounds of the formula I are those in which R2 and R3 independently of one another are hydrogen, d-C6alkyl, d-C6aikyl which is substituted by S(O)nR6ι halogen, cyano, nitro, d-Cθalkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3-C8cycloalkyl, d-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C6alkylamino, d-dalkoxycarbonyl, C2-C12dia!kylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR10R11, d-C alkyl, formyl, d-C alkylcarbonyl, -COOR7, C C4alkylthio, d- dalkyisulfonyl or -CONRβR9, or
R2 and R3 independently of one another are C2-Cβalkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, Cι-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d- dalkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C8cycloalkyl, Crdalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, C2-C3alkoxycarbonyl, C2-Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR10Rn, d-C alkyl, formyl, Cι-C alkylcarbonyl, -COOR7, d-C4alkylthio, d- C4alkylsulfonyl or -CONR8R9, or
R2 and R3 independently of one another are C3-C6alkynyl, d-dalkynyl which is substituted by halogen, cyano, nitro, Cι-C8alkoxy, d-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι- C4alkyiammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3-C8cycloalkyl, d-C3alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C6alkyiamino, d-C5alkoxycarbonyl, C2-C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NR10Rιι, C,-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR7, C,-C4alkylthio, Ci- dalkylsulfonyl or -CONR8R9, or
R2 and R3 independently of one another are formyl, Cι-C15alkylcarbonyl, d-d5alkenyl- carbonyl, C -C9cycloalkylcarbonyl, C6-C9cycloalkenylcarbonyl or C3-C8cycloalkyl- Cι-C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Ci-Cβalkylamino, C2-C12dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C8alkoxy- carbonyl, C -Cιocycloalkoxycarbonyl, d-C8alkylaminocarbonyl or C2-Cι;>dialkyl- aminocarbonyl, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C5alkyl, Cι-C5alkoxy, d-Csalkylcarbonyl, Cι-C3alkylcarbonyloxy, d-C6alkoxycarbonyl, aminocarbonyl, d-C6alkylaminocarbonyl or C2-C 1dialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C5alkyl, d-dalkoxy, d-C5alkylcarbonyl, d-C6alkoxycarbonyl, aminocarbonyl, d-C6alkylamino or d-C5alkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-CrC6alkylcarbonyl, biphenyl-d-C6alkylcarbonyl, naphthyl-Cι- C6alkylcarbonyl, phenyl-C2-Cβalkenylcarbonyl, biphenyl-C2-C6alkenylcarbonyl, naphthyl-C2- C6alkenylcarbonyl, phenyl-C3-C6alkynylcarbonyl, biphenyl-C3-C6alkynylcarbonyl or naphthyl- C3-Cβalkynylcarbonyl, it being possible for these substituents to be substituted by Ci- Csalkyl, d-dalkoxy, Cι-C5alkylthio, Cι-C5haloalkyl, Cι-C3alkylcarbonyl, halogen, cyano, amino, nitro, -COOR , Ci-Cβalkoxycarbonyl, hydroxyl, Ci-Csalkylsulfinyl, Cι-C5alkylsulfonyl, Cι-C6alkyl-aminocarbonyl or C2-C12dialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C5alkyl, Cι-C5alkoxy, Cι-C3alkylthio, -COOH, -CONH2, d-C6alkylaminocarbonyl, C2-Cιodialkylaminocarbonyl, C Csalkylcarbonyl or d-C5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C5alkyl, d-C5alkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, d-C6alkylamino, d-C8dialkylamino, phenylamino, naphthylamino, Cι-C6alkylcarboπylamino, d-doalkoxycarbonylamino, hydroxyl, Ci-Cβalkoxy, d-C6alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, and i5, Ri6, Ri7, ιβ and Rι9 independently of one another are Cι-C oalkyl, d-C6cycloalkyl, C3-C6cycloalkyl-Cι-C alkyl, d-C6alkyl-C3-C6cycloalkyl, d-Cioalkenyl, C3-C6cycloalkyl- C2-C alkenyl, C2-C6alkenyl-C3-C6cycloalkyl, d-Cι0alkynyl, C3-C6cycloalkyl-C2-C4alkynyl, C2-C6alkynyl-C3-C6cycloalkyl, Cs-Cecycloalkenyl, C5-C6cycloalkenyl-CrC4alkyl, d -Cealkyl-Cs-Cβcycloalkenyl, C5-C6cycloalkenyl-C2-C alkenyl , d-Cealkenyl-Cs-Cβcydo- alkenyl, C5-C6cycloalkenyl-C2-C alkynyl, C2-Cealkynyl-C5-C6cycloalkenyl, C3-Cecycloalkyl- C3-C6cycloalkyl, C3-Cβcycloalkenyl-C5-C6cycloalkenyl, C3-C6cycloalkyl-C5-C6cycloalkenyl, C5-C6cycioalkenyl-C3-C6cycloalkyl, C2-C8alkynyl-C2-C8alkenyi or C2-C8alkenyl-C2-Cβalkynyl, phenyl, phenyl-Cι-C alkyl, phenyl-C2-C alkenyl, phenyl-C2-C4alkynyl, heterocyclyl, heterocyclyl-C C alkyl, heterocyclyl-C2-C4alkenyl or heterocyclyl-d-C4alkynyl, it being possible for the substituents R15, R16, R17, Riβ and R19 to be substituted by halogen, cyano, azido, nitro, -OR5, =O, -S(O)nR6, -COOR7, -CONR8R9, -NR10Rn, =NR12 or =N-NRι3Rι4, or Ri5> Rιe, R17, Riβ and Rι9 independently of one another are halogen, cyano, azido, nitro, -OR5, -S(O)nR6, -COOR7, -CONRβRg, -NR10R11, tri(Cι-C4alkyl)silyl, di(Cι-C4alkyl)-(Cι- C4alkoxy)silyl, -B(OH)2 or -B(Cι-C4alkoxy)2.
Especially preferred compounds of the formula I are distinguished by the fact that R15, R β.
R1 l Riβ and R19 independently of one another are Cι-Cιoalkyl, C3-C6cycloalkyl,
C2-C10alkenyl, C2-Cιoalkynyl, Cs-Cβcycloalkenyl, C2-C8alkynyl-C2-C8alkenyl or C2-Cβalkenyl-
C2-C8alkynyl, phenyl, pheπyl-Cι-C alkyl, phenyl-C2-C alkenyl, heterocyclyl, heterocyclyl-
Cι-C alkyl or heterocyclyl-QrC4alkenyl, it being possible for Rι5, Rι6, R17. iβ and Rι9 independently of one another to be substituted by halogen, cyano, -OR5, =O, -S(O)nRe,
-COOR7, -CONRβRg or -NR10Rn, or
R15 R16. R17, Riβ and R19 independently of one another are halogen, cyano, -ORs, -S(O)nRβ,
-COOR7, -CONR8R9 or -NR10Rn,
R5 is hydrogen, d-C8alkyl, d-C6haloalkyl, C2-C3alkoxyalkyl, phenyl, phenyl-Cι-C4alkyl,
C2-Cτalkylcarbonyl, d-C6alkylaminocarbonyl, d-C8dialkylaminocarbonyl, tri(Cι-C alkyl)silyl,
C2-C7alkenyl or d-dalkynyl or heterocyclyl,
R8 is hydrogen when n is 0, or
R6 is Cι-C5alkyl, phenyl, phenyl-Cι-C4alkyl or heterocyclyl,
R7 is hydrogen, Cι-C6alkyl, d-Cehaloalkyl, C C6cyanoalkyl, C2-C10alkoxycarbonylalkyl, heterocyclyl, C3-C6cycloalkyl or C2-C6dialkylamino,
R8 and R9 independently of one another are hydrogen or d-C8alkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a three to seven- membered heterocycle which may contain one or two further hetero atoms and which may be substituted by Chalky! groups,
R10 and Rn independently of one another are hydrogen, phenyl, Cι-C8alkyl, Ordalkenyl, (d-CealkylaminoJcarbonyl, (C2-C6dialkylamino)carbonyl, (Cι-C7alkyl)carbonyl, (Cι-C6alkoxy)carbonyl or heterocyclylcarbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C,.6 alkyl groups.
Very specially preferred are those compounds of the formula I in which R2 and R3 independently of one another are hydrogen, d-C6alkyl, d-C6alkyl which is substituted by halogen, cyano, nitro, d-C4alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Ci- C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3-Cβcycloalkyl, Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-Cβalkylamino, Cι-C5alkoxycarbonyl, C2-Cβdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NR10R11, Cι-C4alkyl, formyl, C -C4alkylcarbonyl, -COOR7, d-C alkylthio, d-C4alkylsulfonyl or -CONRβRg , or
R2 and R3 independently of one another are C^Cealkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, Cι-C4alkoxy, C3-C6-trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C4alkylammonium, -COOH, -COOM, in which M is ammonium or ah alkali metal or alkaline earth metal atom, or by Cι-Cealkylamino, C2-dalkoxycarbonyl, C2-C6dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NR10Rn, Cι-C alkyl, formyl, Cι-C4alkylcarbonyl, -COOR7, d-C alkylthio, d-C4alkylsulfonyl or -CONRβRg, or
R2 and R3 independently of one another are C3-Cβalkynyl, C3-C6alkynyl which is substituted by halogen, cyano, nitro, Ci-Cβalkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C6alkylamino, C2-C5alkoxycarbonyl, Crdsdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NR10R11, d-C alkyl, formyl, d-C4alkylcarbonyl, COOR7, Cι-C4alkylthio, d-C4alkylsulfonyl or -CONRβRg, or R2 and R3 independently of one another are formyl, d-C8alkylcarbonyl, C2-C8alkenyl- carbonyl, C4-C9cycloalkylcarbonyl, C6-Cgcycloalkenyicarbonyl or C3-Cβcycloalkyl-Cι-
C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Cι-C8alkylamino, C2-Cτdialky!amino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C2-CBalkoxycarbonyl,
C -Cιocycloalkoxycarbonyl, d-C8alkylaminocarbonyl or C2-C8dialkylaminocarbonyl, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Ci-Csalkyl, CrC5alkoxy, Ci-Csalkylcarbonyl, d-Csalkylcarbonyloxy, d-C6alkoxycarbonyl, aminocarbonyl, d-Cealkylaminocarbonyl or
C2-C8dialkyiaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C4alkyl, d-C4alkoxy, d-C4alkylcarbonyl, Cι-C alkoxycarbonyl, aminocarbonyl,
Cι-C6alkylamino or d-C5alkylcarboπyloxy, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Ci-Cealkylcarbonyl, biphenyl-d-C6alkylcarbonyl, naphthyl-d-
C6alkylcarbonyl, phenyl-C^Cβalkenylcarbonyl, biphenyl-C2-C6alkenylcarbonyl or naphthyl-
C2-C6alkenylcarbonyl, it being possible for these substituents to be substituted by d-
C4alkyl, d-C alkoxy, Cι-C4alkylthio, C -C haloalkyl, Cι-C4alkylcarbonyl, halogen, cyano, amino, nitro, -COOR7, CrCsalkoxycarbonyl, hydroxyl, d-C4alkylsulfonyl, d-
C5alkylaminocarbonyl or C2-C6dialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C alkyl,
Cι-C4alkoxy, d-C4alkylthio, -COOH, -CONH2l Cι-C5alkylaminocarbonyl, C2-Cτdialkyl- aminocarbonyl, d-C4alkylcarbonyl or d-C5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-C4alkyl, d-C alkoxy, halogen, cyano or nitro, or
R2 and R3 independently of one another are amino, Cι-C4alkylamino, C2-Cβdialkylamino, phenylamino, d-Csalkylcarbonylamino, Cι-C5alkoxycarbonylamino, hydroxyl, d-C4alkoxy,
Cι-C5alkylcarbonyloxy or phenoxy,
R5 is hydrogen, C -Cβalkyl, Cι-C6haloalkyl, C2-C6alkoxyalkyl, Cι-C6cyanoalkyl, phenyl, haiophenyl, Ci-C4alkoxyphenyl, phenyl-d-C4alkyl, Cι-C4alkylcarbonyl, benzoyl, halobenzoyl, d-C alkylamino, C2-C6dialkylamino, C3-C6trialkylsilyl, C3-Cβcycloalkyl, C2-
C4alkenyl or C3-C4alkynyl,
R7 is hydrogen, d-C alkyl, Cι-C4haloalkylr d-C4cyanoalkyl, phenyl, haiophenyl,
C2-C4alkoxyalkyl, heterocyclyl or haloheterocyclyl, Rθ and R9 independently of one another are hydrogen, phenyl, haiophenyl, Cι-C4alkyl, d-C4haloalkyl, d-C4cyanoalkyl, d-dalkenyl, C3-C4alkynyl or C2-C4alkoxyalkyl, or
R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by Cι-C alkyl,
R10 and R independently of one another are hydrogen, phenyl, haiophenyl, d-dalkyl, d-C4haloalkyl, Cι-C cyanoalkyl, C3-C4alkenyl, C3-C4alkynyl, C2-C4alkoxyalkyl, formyl, d-C alkylcarbonyl or phenylcarbonyl, it being possible for the phenyl moiety therein to be substituted by Cι-C4alkyl, halogen, Cι-C alkoxy, hydroxyl, cyano, nitro or Cι-C alkoxy- carbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by d-C4 alkyl.
Preferred amongst this group of compounds of the formula I are those in which R2 and R3 independently of one another are hydrogen, d-C6alkyl, Cι-C6alkyl which is substituted by halogen, hydroxyl, amino, ammonium, tri-Cι-C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by Ci-Csalkylcarbonyloxy, phenylcarbonyloxy, d-C6alkylamino, Cι-C5alkoxycarbonyl or C2-C6dialkylamino, or R2 and R3 independently of one another are formyl, Cι-C8alkylcarbonyl, d-dalkenyl- carbonyl, C4-C9cycloalkylcarbonyl, Ce-Cgcycloalkenylcarbonyl or C3-dcycloalkyl-Cι- C6aikylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl, amino, -COOH or -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C5alkyl, d-C5alkoxy or d-Cβalkoxy- carbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CrC4alkyl, d-C alkoxy or CrC4alkoxycarbonyl, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Cι-C6alkylcarbonyl, biphenyl-d-C6alkylcarbonyl, naphthyl-Cι- C6alkylcarbonyl, phenyl-C2-C6alkenylcarbonyl, biphenyl-C2-C6alkenylcarbonyl or naphthyl- C2-C6alkenylcarbonyl, it being possible for these substituents to be substituted by d- dalkyl, d-C alkoxy, Cι-C4alkylthio, Cι-C4haloalkyl, Cι-C4alkylcarbonyl, halogen, cyano, amino, nitro, -COOH, Ci-Csalkoxycarbonyl, hydroxyl or Cι-C4alkylsulfonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, Cι-C4alkyl, d-dalkoxy, d-dalkylthio, -COOH or d-C5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Cι-C4alkyl, Cι-C alkoxy, halogen or cyano.
Compounds amongst this group which are of particular interest are those in which R2 and
R3 are hydrogen, or
R2 and R3 independently of one another are formyl, d-C8alkylcarbonyl, C2-
C8alkenylcarbonyl, d-Cgcycloalkylcarbonyl, C6-C9cycloalkenylcarbonyl or C3-C8cycloalkyl- d-C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl or amino, or
R2 and R3 are phenylcarbonyl, it being possible for the phenyl ring to be substituted by C dalkyl, Cι-C4alkoxy, C C4alkylthio, d-C4haloalkyl, halogen, cyano, nitro, -COOH, Cι-
C5akoxycarbonyl, hydroxyl or Cι-C alkylsulfonyl.
A further preferred group of compounds of the formula I is the group in which X is O or
S(O)x where x is 0, 1 or 2, and
R is methyl which is substituted by halogen, cyano, nitro or OR5, or
R4 is C2-C8alkyl, C2-C8alkenyl, C3-C8alkynyl, C3-C8cycloalkyl, C5-C8cycloalkenyl,
C3-C8cycloalkyl-Cι-C4alkyl or d-C4alkyl-C3-C8cycloalkyl, it being possible for these substituents herein to be substituted by halogen, cyano, nitro, =O or -OR5, or
R4 is phenyl which is substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl,
Cι-C alkyl, Cι-C4alkyloxy, Cι-C4alkylthio, d-C4haloalkyl, d-C4haloalkoxy, d-
C4haloalkylthio, C2-C6alkoxycarbonylalkoxy, Cι-C4alkylsulfιnyl, Cι-C4alkylsulfonyl, d-
Cealkyloxycarbonyl, Cι-C6alkyicarbonyl, -CONH2, formyl, Cι-C5alkylaminocarbonyl, C2- ddialkylaminocarbonyl, Cι-C alkylamino, C2-C6dialkylamino,
C3-C6trialkylsilyl, d-C6alkylcarbonylamino, d-C6alkylcarbonyloxy, phenoxy, halophenoxy or
Pyridyloxy, or
R4 is biphenyl, naphthyl, heterocyclyl, Cι-C4alkylphenyl, C C4alkylnaphthyl, phenyl-d-
C4alkyl or naphthyl-Cι-C alkyl, it being possible for the substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, Cι-C alkyl, Cι-C4alkyloxy, d-C alkylthio, d-C4haloalkyl, Cι-C4haloalkoxy, d-C haloalkylthio, C2-C6alkoxycarbonylalkoxy, d-C4alkyl- sulfinyl, Cι-C4alkylsulfonyl, Cι-C6alkyloxycarbonyl, d-C6alkylcarbonyl, -CONH2, formyl, C
C5alkylaminocarbonyl, C2-Cτdialkylaminocarbonyl,
C3-C6trialkylsilyl, Cι-C6alkylcarbonylamino, d-Cβalkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and
R5 is hydrogen, d-C6alkyl, Cι-C6haloalkyl, C2-Cealkoxyalkyl, d-Cecyanoalkyl, phenyl, haiophenyl, Cι-C4alkoxyphenyl, phenyl-d-C alkyl, Cι-C alkylcarbonyl, benzoyl, halobenzoyl, d-C4alkylamino, C2-C6dialkylamino, C3-Cetrialkylsilyl, C3-C6cycloalkyl, C2-
C4alkenyl or C3-C alkynyl.
Outstanding compounds of the formula I amongst this group are those in which X is O or S, and
R is methyl which is substituted by halogen or cyano, or
R4 is C2-C8alkyl, C2-C8alkenyl, C3-C8alkynyl, C3-Cβcycloalkyl, Cs-Cβcycloalkenyl, C3-Cβ- cycloalkyl-Cι-C4alkyl or Ci-dalkyl-drCβcycloalkyI, it being possible for the substituents herein to be substituted by halogen or cyano, or
RJ4 is phenyl which is substituted by halogen, cyano, nitro, amino, Cι-C4alkyl, Cι-C4alkyloxy, d-C alkylthio, C1-C4haloalkyl, Cι-C haloalkoxy, C2-C6alkoxycarbonylalkoxy, Cι-C4alkyl- sulfonyl, Cι-Cβalkyloxycarbonyl, d-C6alkylcarbonyl, formyl, Cι-C alkyiamino,
C2-C6dialkylamino,
C3-C6trialkylsilyl or C2-C6alkylcarbonyloxy, or
R4 is biphenyl, naphthyl, heterocyclyl, d-dalkylphenyl, Cι-C4alkylnaphthyl, phenyl-d-
C4alkyl or naphthyl-d-C4alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, d-dalkyl, Cι-C4alkyloxy, d-C alkylthio, d-C haloalkyl, d-C4haloalkoxy, C2-Cβalkoxycarbonylalkoxy, Cι-C4alkylsulfonyl, d-C8alkyloxycarbonyl, d-C6alkylcarbonyl, C3-C6trialkylsilyl or Cι-C6alkylcarbonyloxy, very preferably X being O and R being phenyl which is substituted by halogen, cyano, nitro, amino, Cι-C4alkyl, d-C4alkyloxy, Cι-C4alkylthio, Cι-C haloalkyl, halomethoxy, Ci-
C4alkyl-sulfonyl, Cι-C alkylamino or d-ddialkylamino.
Other compounds of the formula I which must be emphasized are those in which R1S, Rι6, R17, Riβ and Rι9 independently of one another are Cι-C alkyl, C2-C4alkenyl, Cι-C4alkoxy, fluorine, chlorine, bromine, phenyl, d-C alkoxy-Cι-C alkoxy, trimethylsilyl, di-Cι-C4alkyl- amino, di-Ci-dalkylamino-d-dalkyl, morpholinyl-d-C4alkyl, d-C4alkylthio, d-C4- alkylsulfinyl, Cι-C4alkyl.sulfonyl, d-C4alkylcarbonyl, d-C4alkoxy-C,-C4alkyl, 1 -(Cι-C4alkyl)- dioxolanyl, 1-phenyldioxolanyl, trifluoromethyl, hydroxyl, phenoxy, phenoxycarbonyl, C3- Cβcycloalkyl, Cι-C alkylperhydroazinyl, R2 is hydrogen, R3 is hydrogen or methylcarbonyl, X is O or S and R4 is phenyl, naphthyl, pyridyl, Ci-dhaloalkoxy, d-C8alkoxy, Cι-C4-alkylthio,
cyclohexyl, thienyl or the group , or is phenyl, naphthyl, pyridyl or thienyl,
Figure imgf000021_0001
each of which is substituted by d-C4alkyl, Cι-C alkoxy, fluorine, chlorine, nitro, cyano, C3- C6cycloalkyloxycarbonyl, d-C6alkylthio, Cι-C4hydroxycarbonyl, alkylsulfonyl, di-d-C alkylamino, d-C alkylsulfonyl or trifluormethyl.
An outstanding group of compounds of the formula I is the group in which R is the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , C2, C3, C4, C5, C6, D1 , D2 or D3, but preferably the groups A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1, C2, C3, C4, C5 or C6.
Other compounds of the formula I which are especially preferred are those in which Rι5, R16, R17, R18 and Rι9 independently of one another are halogen, d-Cβalkyl or d-Cealkoxy, preferably fluorine, chlorine, d-C4alkyl or d-C4alkoxy.
Compounds of the formula I which are of particular interest are those in which Rι5 is fluorine when R, is A1 , B1 , B2, B3, C1 , C2 or C6.
The compounds of the formula I can be prepared in various ways via process steps known per se using known starting materials.
For example, compounds of the formula I can be prepared by reacting an S,S- diorganosulfodiimide with an O.O'-diaryl N-cyanoimidocarbonate and subsequently subjecting the product to cyclization under acidic conditions:
Figure imgf000021_0002
ln the above diagram, Ri has the abovementioned meaning, R is R or another group which is suitable for the reaction, for example methyl or benzyl, and Ar is an aryl group, for example phenyl. Such processes are described, for example, in Winfried Jϋrgler's Ph.D. thesis, 1988, Philipps-Universitat, Marburg/L, Germany.
Compounds of the formula I can furthermore be prepared by starting from a trihalogenated thiatriazine of the formula II
Figure imgf000022_0001
in which Hal radicals independently of one another are fluorine, bromine or, in particular, chlorine, and reacting this trihalogenated thiatriazine with the corresponding organometallic compound of the formula III
RrM (III)
in which Ri has the abovementioned meanings and M is a mono- or polyvalent metal atom, which, depending on the valence, can have attached to it an appropriate number of Ri groups, in order to introduce the phenyl ring.
Compounds of the formula II and their preparation are described, for example, in Chem. Ber. (1991) 124 1347-1352 and Z. Chem. (1976) 16358-359.
Examples of suitable metals are, in particular, lithium, magnesium, zinc, aluminium, silicon, tin, and furthermore also manganese and titanium. Besides one or more Ri groups, the polyvalent metal atoms can also have attached to them further substituents such as halogen, cyano, d-C4alkyl, tetrafluoroborate or halogenated or unhalogenated alkanesulfonates. The organometallic compound of the formula III can furthermore be used in combination with salts such as aluminium chloride, zinc chloride, tin chloride, cerium chloride, aluminium bromide and/or copper bromide, aluminium chloride, aluminium bromide and zinc chloride being preferred.
The compounds of the formula III can be prepared by customary methods, for example
• by reacting the corresponding halide Ri-halogen with the metal M,
• by halogen/metal exchange reaction of the corresponding halide Rrhalogen, halogen preferably being bromine or iodine, with a reactive organometallic compound, such as an alkyllithium compound, for example n-butyl-, s-butyl- or t-butyllithium,
• by treating the corresponding aromatic Ri-H with a strong base, for example lithium diisopropylamide, lithium bis(trimethylsilyl)amide, lithium tetramethylpiperidide, n-butyl-, s-butyl- or t-butyllithium, and the like. Aromatics of the formula Ri-H which are especially suitable for this reaction are those which carry a function which facilitates deprotonation and/or which influence orientation (see, for example, Snieckus V. Chem. Rev. (1990) 90, 879-933),
• by subjecting an organometallic compound prepared as described above to a transmetalation with a derivative of another metal, for example a halide,
• some of the compounds of the formula III and their solutions are commercially available. As a rule, the organometallic compound is not isolated but is reacted directly with the thiatriazine halide, in the presence or absence of a metal salt.
The group R, may be introduced in an aprotic solvent such as a hydrocarbon, for example hexane, heptane or toluene, or an ether such as dioxane, diethyl ether or, in particular, tetrahydrofuran, at temperatures from -100CC to 150°C, in particular -80°C to 50°C (depending on the solvent).
Alternatively, the group Ri may be introduced by means of a Friedel-Crafts reaction between the aromatic R H and a compound of the formula It in the presence or absence of a catalyst such as a Lewis acid (for example AICI3, SnCI4 and the like) or activated clay (for example montmorillonite). This reaction can be carried out in an aprotic solvent such as a hydrocarbon, for example nitrobezene, benzene, carbon tetrachloride and the like, or an ether, such as diethyl ether or tetrahydrofuran at temperatures from -50°C to 120°C, in particular -10°C to 60°C (depending on the solvent).
Compounds of the formula IV (IV),
Figure imgf000024_0001
in which RT has the abovementioned meaning and Hal radicals independently of one another are fluorine, chlorine or bromine, with the exception of the compounds 1-(4- methylphenyl)-3,5-dichlorothiatriazine, 1 -(4-hydroxyphenyl)-3,5-dichlorothiatriazine, 1 -(4- methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(4-chlorophenyl)-3,5-dichlorothiatriazine, 1 -(2- hydroxy-5-tert-butylphenyl)-3,5-dichlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3,5- dichlorothiatriazine and 1 -(4-hydroxy-3-methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3,5-dichlorothiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)-3,5- dichlorothiatriazine, 1-(2-hydroxy-3,5-dimethylphenyl)-3,5-dichlorothiatriazine and 3,5- dichloro-1-(2,3,4,5,6-pentafluorophenyl)thiatriazine, which have been obtained by reacting the compounds of the formula II with the compounds of the formula III, are novel and thus also subject-matter of the invention.
The substituents -NR2R3- and -XR4- can subsequently be introduced into the compound of the formula IV in any sequence in order to obtain the compounds of the formula I.
The reaction of the compounds of the formula IV with the compounds of the formula V
H-XR4 (V),
in which X and R have the abovementioned meaning to give the compounds of the formula VI
Figure imgf000025_0001
is advantageously carried out in such a way that, prior to the reaction with the compounds of the formula IV, the compounds of the formula V are pretreated with a base such as metal hydride, for example lithium hydride, sodium hydride or potassium hydride, a metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic salt such as sodium carbonate or potassium carbonate, preferably in equivalent amounts. Alternatively, the reaction mixture of the compounds of the formulae IV and V may also be treated with the abovementioned bases. Solvents which are suitable for this step are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene, ethers such as tetrahydrofuran, dioxane or diethyl ether, and also tertiary amides such as dimethylformamide. It is also possible to employ a mixture of these solvents with water, in which case it is advantageous to use a phase transfer catalyst. As a rule, the reaction temperatures are between -50°C and 100°C, preferably between 0°C and 40°C.
The compounds of the formula V are known and can be prepared in a manner known to those skilled in the art.
With the exception of the compounds 1 -(4-methylphenyl)-3-phenoxy-5-chlorothiatriazine, 1-(4-methoxyphenyl)-3-(2,3,4,5,6-pentafluorophenoxy)-5-chlorothiatriazine, 1-(4-chlorophenyl)-3-(2,3,4,5,6-pentafiuorophenoxy)-5-chlorothiatriazine, 1 -(4-methoxyphenyl)-3-(2,3,4-trichlorophenoxy)-5-chlorothiatriazine, 1 -(4-chlorophenyl)- 3-(2,3-dichlorophenoxy)-5-chlorothiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-(2,5- difluorophenoxy)-5-chlorothiatriazine, 3-chloro-5-(2,5-difluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)-thiatriazine and 3-chloro-5-(2,3,4,5,6-pentafluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl) -thiatriazine , the compounds of the formula VI are novel and also subject-matter of the present invention.
They can be converted into the end products of the formula I by conversion with a compound of the formula VII Mι-NR2R3 (VII)
in which R2 and R3 have the abovementioned meanings and M is hydrogen or a metal atom such as lithium, sodium, potassium or calcium, the process advantageously being carried out in the presence of a base. If R2 and/or R3 are hydrogen, M1 is preferably hydrogen. If R2 or R3 is an acyl group, Mi is preferably lithium, sodium or potassium.
Solvents which are suitable for this reaction are hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as chlorobenzene or dichloromethane, ethers such as diethyl ether, dioxane or tetrahydrofuran, alcohols such as ethanol or isopropanol, esters such as ethyl acetate, nitriles such as acetonitrile, or water. The reaction temperatures are in the range of from -70°C to 100°C, in particular 0°C to 40°C.
If Mi has the meaning of hydrogen, an acid binder is preferably used in order to scavenge the Hal acid. This may be, for example, a second equivalent of the compound of the formula VII, or a tert-amine such as triethylamine, pyridine, or an inorganic base such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate. In the event that R2, R3 and Mi are hydrogen, an excess of base may be used. If required, the process may be carried out under pressure.
The compounds of the formula VII and their preparation are described in the literature.
If the compound of the formula IV is to be reacted first with the base of the formula VII, then, again, the reaction conditions to be followed for the reaction of compound VI with compound VII must be maintained. The resulting compounds of the formula VIII
Figure imgf000026_0001
in which R^ R2 and R3 have the abovementioned meanings and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1-(4-methylphenyl)-3-amino-5-chloro- thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-chlorothiatriazine, 1 -(4-methoxyphenyl)-3-amino- 5-chlorothiatriazine, 1 -(4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(2-hydroxy-5-tert- butylphenyl)-3-amino-5-chlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3-amino-5- chlorothiatriazine, 1 -(4-hydroxy-3-methoxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)- 3-amino-5-chlorothiatriazine, 1-(2-hydroxy-3,5-dimethylphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-chlorothiatriazine, 3-amino-5-chloro-1 - (4-amino-2,3,5,6-tetrafluorophenyl)thiatriazine and 3-amino-5-chloro-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine, are also novel and subject-matter of the present invention.
The further reaction of the compounds of the formula (VIII) with the compounds of the formula (V) is carried out analogously to the procedure in the reaction of the compounds of the formulae (IV) and (V). However, a catalytic amount up to an excess of an amine such as trimethylamine is additionally added to the reaction mixture.
The end products of the formula I can be isolated in the customary manner by concentrating and/or evaporating the solvent and purified by recrystaiiization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatographic methods.
Other compounds of the formula I may be prepared by customary derivatization of compounds of the formula I. The same applies to the intermediates of the formula IV, VI and VIII.
All application methods conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and a variety of methods and techniques, for example controlled release of active ingredient, are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them. To this end, a solution of the active ingredient is applied to mineral carriers for granules or to polymerized granules (urea/formaldehyde), and these are dried. If required, an additional coating may be applied (coated granules) which allows the active ingredient to be released in a controlled manner over a specific period. The compounds of the formula I can be employed as pure active ingredients, i.e. as obtained upon synthesis, but they are preferably processed in the customary manner with the auxiliaries conventionally used in the art of formulation to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The application methods, such as spraying, atomizing, dusting, wetting, scattering or pouring, and the type of composition, are selected to suit the intended aims and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I, or at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) may furthermore additionally be used in the preparation of the formulations.
The following are examples of suitable solvents: aromatic hydrocarbons, preferably the fractions C8 to d2, for example xylene mixtures or substituted naphthalenes, phthalate esters such as di butyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethyiformamide, or epoxidized and unepoxidized vegetable oils such as epoxidized coconut oil or soya oil; or water.
Solid carriers which are used for example for dust and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorptive polymers. Suitable paniculate, absorptive carriers for granules are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and non-sorptive carrier materials, for example, calcite or sand. Moreover, a large number of pregranulatθd materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues. Suitable surface-active compounds are non-ionic, cation ic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Soaps which are suitable are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (do-da), for example the sodium or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tallow oil. Furthermore mention must also be made of the fatty acid methyltaurine salts.
However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
As a rule, the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives have preferably 2 sulfonyl groups and a fatty acid radical of 8 to 22 C atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfuric acid, of dibutylnaphthalenesuffonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.
Furthermore phosphates, for example salts of the phosphoric ester of p-nonylphenol-(4-14)- ethylene oxide adducts, or phospholipids, are also suitable. Non-ionic surfactants which are suitable are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of alkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkyl phenols.
Other non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds normally have 1 to 5 ethylene glycol units per polypropylene glycol unit.
Examples of non-ionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Other substances which are also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are mainly quaternary ammonium salts which have, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of haiides, methylsulfates or ethylsulfates, examples being stearyltrimethylammonium chloride or benzyldi(2- chloroethyl)ethylammonium bromide.
The surfactants conventionally used in the art of formulations which can also be used in the compositions according to the invention are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch [Surfactants Guide]", Carl Hanser Veriag, MunichVienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol I— 111, Chemical Publishing Co., New York, 1980-81. As a rule, the herbicidal formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.
While concentrated compositions are now preferred as commercial products, the end consumer uses, as a rule, dilute compositions.
The compositions may also comprise further additives such as stabilizers, for example free or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, adhesives and fertilizers or other active ingredients.
Preferred formulations have, in particular, the following compositions: (% = percent by weight)
Emulsifiable concentrates: Active ingredient: 1 to 90%, preferably 5 to 50% Surfactant: 5 to 30%, preferably 10 to 20% Solvent 15 to 94%, preferably 70 to 85%
Dusts:
Active ingredient: 0.1 to 50%, preferably 0.1 to 1%
Solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates: Active ingredient: 5 to 75%, preferably 10 to 50% Water: 94 to 24%, preferably 88 to 30% Surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders: Active ingredient: 0.5 to 90%, preferably 1 to 80%
Surfactant: 0.5 to 20%, preferably 1 to 15%
Solid carrier: 5 to 95%, preferably 15 to 90%
Granules:
Active ingredient: 0.1 to 30%, preferably 0.1 to 15%
Solid carrier: 99.5 to 70%, preferably 97 to 85%
As a rule, the active ingredients of the formula I are successfully applied to the plant or its environment at rates of application of from 0.001 to 5 kg, in particular between 0.005 and 2 kg. The dosage required for the desired activity can be determined by experiments. It depends on the type of activity, the development stage of the crop plant and of the weed, and on the application (location, timing, method) and can, due to these parameters, vary within wide ranges.
The compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties, which allow them to be used in crops of useful plants, in particular in cereals, cotton, soya beans, sugar beet, sugar cane, plantations, oil seed rape, maize and rice.
Crops are also to be understood as meaning those which have been made tolerant to herbicides, or classes of herbicides, by conventional breeding or genetic engineering methods. The weeds to be controlled can be both mono- and dicotyledon weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The Examples which follow illustrate the invention in greater detail without imposing any limitation thereon.
The nomenclature used in the following text is based on the numbering shown below: 6
N N- λ
S N 4
N
Preparation Examples:
Example H1 : Preparation of 3.5-dichloro-1- 2-methylphenyl)thiatriazine: A 2 M solution of o-tolylmagnesium bromide in tetrahydrofuran (150 ml) is added dropwise with intensive stirring and cooling at a temperature of -20°C to a solution of 40.9 g of ZnCI2 (0.3 mol) in 500 ml of absolute tetrahydrofuran. The resulting mixture is stirred for 45 minutes at a temperature of -20°C and subsequently cooled to a temperature of -70°C. A solution of 61.3 g of trichlorothiatriazine (0.3 mol) in 50 ml of tetrahydrofuran is subsequently added to this reaction mixture dropwise with stirring and cooling at a temperature held between -70CC and -60°C. The reaction mixture is subsequently slowly warmed to room temperature. After 500 ml of water has been added and the reaction mixture has been poured into 1.5 I of water, the resulting suspension is placed on a suction filter. The residue obtained is washed with water and dried. After further washing with cold diethyl ether and drying, 3,5-dichloro-1-(2-methylphenyl)thiatriazine is obtained in the form of yellow crystals of melting point 140-142°C.
Example H2: Preparation of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro- 1 -(2-methylphenyl)thiatriazine (39.0 g, 0.150 mol) in 700 ml of tetrahydrofuran at a temperature of 0°C. When passing-in is complete, the reaction mixture is concentrated by half in vacuo, diluted with water to 1 I and stirred. The resulting suspension is filtered with suction, until the filter residue is washed with water and dried. This gives 3-amino-5-chloro- 1 -(2-methylphenyl)thiatriazine in the form of white crystals of melting point 196°C (decomposition).
Example H3: Preparation of 3-amino-1-(2-methylphenyl)-5-(4-(3-oxobutvD- phenoxy)thiatriazine:: A mixture of 2.4 g of 3-amino-5-chloro-1-(2-methylphenyl)thiatriazine (0.010 mol), 1.8 g of 4-hydroxyphenyl)-2-butanone (0.011 mol) and 70 ml of dichloromethane is treated with 6.0 ml of 2 N sodium hydroxide solution (0.012 mol) and 1.5 g of trimethylamine solution (40% in water). The reaction mixture is subsequently stirred for 2 days at a temperature of 20°C. The organic phase is subsequently dried over sodium sulfate and evaporated. After chromatographic pre-purification on silica with a hexane/ethyl acetate mixture (1 :1) and recrystallization from this mixture, 3-amino-1-(2-methylphenyl)-5-(4-(3-oxobutyl)- phenoxy)thiatriazine is obtained in the form of white crystals of melting point 186-188°C.
Example H4: Preparation of 3.5-dichloro-1- 2.5-dichlorophenyl)thiatriazine: A solution of 43.7 g of 1 ,4-dichloro-2-iodobenzene (0.16 mol) in 200 ml of absolute tetrahydrofuran is treated at a temperature of from -70°C to -65°C with a solution of 0.16 mol of n-butyllithium in 100 ml of hexane. Then, a solution of 21.8 g of ZnCI2 in 150 ml of absolute tetrahydrofuran is added dropwise. After the mixture has been stirred for 5 minutes, a solution of 32.7 g of trichlorothiatriazine in 50 ml of absolute tetrahydrofuran is added dropwise at this temperature. After the reaction mixture has come to room temperature, it is placed on a suction filter and the residue obtained is washed with diethyl ether and ethyl acetate. The filtrate is washed in succession with water, sodium bicarbonate solution, water and saturated NaCI solution, dried over sodium sulfate and evaporated. The resulting residue is stirred with pentane, during which process crystals form. After filtration with suction, washing with pentane and drying, 3,5-dichloro-1-(2,5-dichlorophenyl)- thiatriazine crystals are obtained which have a melting point of 200-203°C (decomposition).
Example H5: Preparation of 3-amino-5-chloro-1-(2.5-dichlorophenvDthiatriazine: Ammonia is passed into a vigorously stirred solution of 2.2 g of 3,5-dichloro-1 -(2,5- dichlorophenyl)thiatriazine (0.007 mol) in 80 ml of tetrahydrofuran at a temperature of 0CC. When the starting material has reacted completely, the reaction mixture is treated with ethyl acetate and water. The organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. When the liquid is reduced, crystals precipitate. The suspension is placed on a suction filter and the residue obtained is washed with a small amount of diethyl ether and with pentane and dried. White crystals of 3-amino- 5-chloro-1-(2,5-dichlorophenyl)thiatriazine of melting point 225-227°C (decomposition) are isolated. Example H6: Preparation of 3-amino-5-(3.5-bistrifluoromethylphenoxy)-1 -(3.5- dimethylphenvDthiatriazine.
A mixture of 2.54 g of 3-amino-5-chloro-1-(3,5-dimethylphenyl)thiatriazine (0.010 mol) and 2.53 g of 3,5-bistrifluoromethylphenol (0.011 mol) in 70 ml of dichloromethane is added with 5.5 ml of 2 N sodium hydroxide solution (0.011 mol) and 1.5 g of trimethylamine solution (40% in water). The mixture is stirred for 18 hours at a temperature of 20°C. The dichloromethane is distilled off and the residue obtained is stirred with water. The suspension is placed on a suction filter and the residue obtained is washed with water and subsequently dried. This gives 3-amino-5-(3,5-bistrifluoromethylphenoxy)- 1-(3,5-dimethylphenyl)thiatriazine in the form of white crystals of melting point 222-223cC (decomposition).
Example H7: Preparation of 3.5-dichloro-1-(2.4.6-trimethylphenylUhiatriazine: A 1 M solution of 2-mesitylmagnesium bromide in diethyl ether (100 ml) is added dropwise with vigorous stirring and cooling at a temperature of 20°C to a solution of 13.6 g of ZnCI2 (0.1 mol) in 200 ml of absolute tetrahydrofuran. The mixture obtained is subsequently stirred for 45 minutes at a temperature of 20°C and then cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine (0.1 mol) in 20 ml of tetrahydrofuran is added dropwise to this reaction mixture with stirring and cooling at a temperature kept between -70°C and -60°C. After the reaction mixture has been heated slowly, it is filtered with suction. The residue is washed with diethyl ether and the filtrate is extracted with water, sodium bicarbonate solution and saturated NaCI solution. The organic phase is dried over sodium sulfate and concentrated. Trituration of the residue with pentane results in the formation of yellow crystals of 3,5-dichloro-1 -(2,4,6-trimethyiphenyl)thiatriazine which, after washing with pentane and subsequent drying, have a melting point of 98-100°C.
Example H8: Preparation of 3-amino-5-chloro-1-(2.4.6-trimethylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 3,5-dichloro-1 -(2,4,6-trimethyl- phenyl)thiatriazine (10.1 g, 0.035 mol) in 200 ml of tetrahydrofuran at a temperature of 0°C. When the addition is complete, the reaction mixture is treated with ethyl acetate and water. After extraction, the organic phase is washed with water and subsequently with saturated NaCI solution and dried over sodium sulfate. The solution is then concentrated until a viscous suspension is formed which is filtered with suction. After the residue has been washed with cold ethyl acetate and subsequently with diethyl ether and dried, pale yellow crystals of 3-amino-5-chloro-1-(2,4,6-trimethylphenyl)thiatriazine which have a melting point of 167°C (decomposition) are isolated.
Example H9: Preparation of 3-amino-1-(2.4.6-trimethylphenyl)-5-(2.3.5.6-tetrafluoro- 4-trifluoromethylphenoxy)thiatriazine:
A mixture of 1.07 g of 3-amino-5-chloro-1-(2,4,6-trimethylphenyl)thiatriazine (0.004 mol), 40 ml of dichloromethane and 1 g of 2,3,5,6-tetrafluoro-4-trifiuoromethylphenol (0.0043 mol) is treated with 2 N sodium hydroxide solution (0.0044 mol) and 0.6 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 4 days at a temperature of 20°C. The organic phase is separated off and dried over sodium sulfate. After evaporation, chromatographic pre-purification on silica with a hexane/ethyl acetate mixture (3:1) and recrystallization from this mixture, 3-amino-1-(2,4,6-trimethylphenyl)-5-(2,3,5I6-tetrafluoro- 4-trifluoromethylphenoxy)thiatriazine crystals of melting point 206-208°C are obtained.
Example H10: Preparation of 3.5-dichloro-1-(2.3.5.6-tetramethylphenylUhiatriazine: A solution of 13.6 g of ZnCI2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,5,6-tetramethylphenylmagnesium bromide (prepared with 21.3 g of 1-bromo-2,3,5,6-tetramethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 100 ml of absolute tetrahydrofuran) at a temperature of -20°C. The mixture is subsequently stirred for 1 hour at a temperature of 20°C and then cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is subsequently added dropwise to the mixture at a temperature of from -70°C to -65°C. The reaction mixture is subsequently allowed to come to room temperature and then transferred into 1 litre of water. The suspension is placed on a suction filter, and the residue obtained is washed with water, dried with suction and then washed with pentane and dried. This gives 3,5-dichloro-1-(2,3,5,6-tetramethylphenyl)thiatriazine in the form of yellow crystals of melting point 138-140°C.
Example H11 : Preparation of 3-amino-5-chloro-1-(2.3.5.6-tetramethylphenylHhiatriazine. Ammonia is passed into a vigorously stirred solution of 15.2 g of 3,5-dichloro- 1-(2,3,5,6-tetramethylphenyl)thiatriazine (0.0503 mol) in 300 ml of tetrahydrofuran at a temperature of 0°C. After the starting material has reacted completely, the reaction mixture is treated with water. The suspension is placed on a suction filter, and the residue is washed with water, dried with suction, washed with diethyl ether and dried. This gives 3- amino-5-chloro-1 -(2,3,5,6-tetramethylphenyl)thiatriazine in the form of white crystals of melting point 185°C (decomposition).
Example H12: Preparation of 3-amino-5-(2-bromophenoxy)-1-(2.3.5,6-tetramethylphenyl)- thiatriazine:
A mixture of 2.1 g of 3-amino-5-chloro-1-(2,3,5,6-tetramethylphenyl)thiatriazine (0.0075 mol) and 1.43 g of 2-bromophenol (0.0082 mol) in 70 ml of dichloromethane is treated with 4.5 ml of 2 N sodium hydroxide solution (0.009 mol) and 1.1 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 70 hours at a temperature of 20°C. The dichloromethane is subsequently distilled off and the residue is stirred with water. The resulting suspension is placed on a suction filter, and the residue is washed with water, dried with suction, washed with pentane and dried. This gives 3-amino-5-(2- bromophenoxy)-1-(2,3,5,6-tetramethylphenyl)thiatriazine in the form of white crystals of melting point 212-214°C.
Example H13: Preparation of 3.5-dichloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine: A solution of 13.6 g of ZnCI2 (0.100 mol) in 200 ml of absolute tetrahydrofuran is treated with a solution of 2,3,4,5,6-pentamethylphenylmagnesium bromide (prepared with 22.7 g of 1-bromo-2,3,4,5,6-pentamethylbenzene (0.100 mol) and 2.64 g of magnesium (0.110 mol) in 130 ml of absolute tetrahydrofuran) at a temperature of -20°C. The mixture is stirred for 30 minutes at a temperature of 20°C and subsequently cooled to a temperature of -70°C. A solution of 20.4 g of trichlorothiatriazine in 10 ml of absolute tetrahydrofuran is then added dropwise to the mixture at a temperature of from -70°C to -65CC. The reaction mixture is allowed to come to room temperature, with stirring, and is subsequently transferred into 1 litre of water. The suspension is then placed on a suction filter and the residue obtained is washed with water, dried with suction, washed with pentane and dried. This gives 3,5-dichloro-1 -(2,3,4,5,6-pentamethylphenyl)thiatriazine in the form of yellow crystals of melting point 140-142CC. Example H14: Preparation of 3-amino-5-chloro-1-(2.3.4.5.6-pentamethylphenyl)thiatriazine: Ammonia is passed into a vigorously stirred solution of 14.0 g of 3,5-dichloro- 1-(2,3,4,5,6-pentamethylphenyl)thiatriazine (0.0443 mol) in 300 ml of tetrahydrofuran at a temperature of 0°C. After the starting material has reacted completely, the reaction mixture is evaporated and the residue obtained is treated with water. The suspension is placed on a suction filter and the residue obtained is washed with water, dried with suction and then washed with diethyl ether and dried. This gives 3-amino-5-chloro-1 -(2,3,4,5,6- pentamethylphenyl)thiatriazine in the form of yellowish crystals of melting point 189°C (decomposition).
Example H15: Preparation of 3-amino-5-(2.3.4.5.6-pentafluorophenoxy)-1 -(2,3.4.5.6- pentamethylphenyDthiatriazine:
A mixture of 2.2 g of 3-amino-5-chloro-1-(2,3,4,5,6-pentamethylphenyl)thiatriazine (0.0075 mol) and 1.5 g of 2,3,4,5,6-pentafluorophenol (0.0082 mol) in 70 ml of dichloromethane is treated with 4.5 ml of 2 N sodium hydroxide solution (0.009 mol) and 1.1 g of trimethylamine solution (40% in water). The mixture is subsequently stirred for 70 hours at a temperature of 20°C. The suspension is filtered and the residue obtained is washed with water. The organic phase is separated from the filtrate and dried over sodium sulfate. After evaporation of the solution, chromatographic pre-purification of the crude product on silica with a hexane/ethyl acetate mixture (3:1) and recrystallization from the abovementioned mixture, 3-amino-5-(2,3,4,5,6-pentafluorophenoxy)- 1-(2,3,4,5,6-pentamethylphenyl)thiatriazine is obtained in the form of white crystals of melting point 210-211°C.
Example H16: Preparation of methyl 2-ri-(3.5-difluorophθnyl)-5-chloro-1λ 4-(1.2.4.6)- thiatriazin-3-ylamino1-3-methyl-pentanoate (Example B5.052): A cooled suspension of 1.27 g of L-isoleucine methyl ester hydrochloride in 15 ml of tetrahydrofuran is treated with 14 ml of propylene oxide and 2.1 g of 3,5-dichloro- 1-(3,5-difluorophenyl)1 4-(1 ,2,4,6)thiatriazine in 3 ml of tetrahydrofuran and 0.68 ml of 1 ,8-diazabicyclo[5.4.0]undec-7-ene(1 ,5-5) (DBU). The resulting solution is held at a temperature of 20°C until the reaction is complete. The mixture is subsequently evaporated, and the residue is taken up in ethyl acetate, washed with water, dried and filtered through silica gel. This gives methyl 2-[1-(3,5-difluorophenyl)-5-chloro-1λ 4-(1,2,4,6)thiatriazin- 3-ylamino]-3-methylpentanoate (diastereomer mixture) in the form of a colourless resin of nD 501.5005.
Example H17: Preparation of methyl 2-ri-(3.5-difluorophenyl)-5-pentafluorophenoxy-1λ 4- (1.2.4.6)thiatriazin-3-ylamino1-3-methylpentanoate (Compound B6.009): 1.6 g of the product obtained in Example H16 are dissolved in 35 ml of dichloromethane, and the solution is treated with 0.65 ml of trimethylamine solution (45%, aqueous) and 27.3 ml of a 0.145 molar solution of pentafluorophenol in dichloromethane. 2 ml of 2 N sodium hydroxide solution are subsequently added dropwise with stirring and cooling, and the mixture is stirred at a temperature of 20°C until the reaction is complete. It is then treated with dichloromethane and ice-water, and extracted with dichloromethane, and the extracts are washed with water, dried and evaporated. After purification under silica gel (hexane/ethyl acetate 8:2), the residue yields methyl 2-[1 -(3,5,-difluorophenyl)-5- pentafluorophenoxy-1λ 4-(1 ,2,4,6)thiatriazin-3-ylamino]-3-methylpentanoate (diastereomer mixture) in the form of a colourless resin of no501.5139.
Example H19: Preparation of 2.2.2-trichloro-1-ri-(4-bromophenyl)-5-pentafluorophen- oxy-1λ -(1.2.4.6)-thiatriazin-3-ylaminoethanol (Compound A6.034)
A suspension of 262 mg of 1-(4-bromophenyl)-5-pentafluorophenoxy-3-amino-1λ
-(1 ,2,4,6)thiatriazine in 12 ml of dichloromethane is treated with 0.3 ml of anhydrous chloral and refluxed with stirring until the reaction is complete. The mixture is then evaporated in vacuo and the residue is filtered through silica gel (hexane/ethyl acetate 8:2). This gives
2,2,2-trichloro-1 -[1 -(4-bromophenyl)-5-pentafluorophenoxy-1 λ 4 -(1 ,2,4,6)thiatriazin-3- ylaminoethanol (diastereomer mixture) in the form of a white solid of melting point 187-
188°C.
Example H20: Preparation of 2.6-dichloro-N-f1-(3-chloro-4-methvtphenyl)- pentafluorophenoxy-1λ 4 -(1.2.4.6)thiatriazin-3-yηisonicotinamide (Compound B6.033): A solution of 1.5 g 2,6-dichloroisonicotinoyl chloride in 6 ml of acetonitrile is added dropwise to a stirred solution of 2.5 g of 1-(3-chloro-4-methylphenyl)-5-pentafluorophenoxy-3-amino- 1 λ 4 -(1 ,2,4,6)thiatriazine in 16 ml of pyridine under a nitrogen atmosphere at a temperature of from -5 to 0°C , and the resulting solution is stirred for 30 hours at a temperature of 0°C. The reaction mixture is then diluted with ethyl acetate, transferred into ice-water and is extracted rapidly with ethyl acetate while adding saturated sodium chloride solution. The extracts are dried over sodium sulfate and evaporated, and the residue is purified on silica gel (hexane/ethyl acetate 7:3). This gives 2,6,-dichloro-N-[1-(3-chloro-4-methylphenyl)- pentafluorophenoxy-1λ 4 -(1,2,4,6)-thiatriazin-3-yl]isonicotinamide of melting point 196- 198°C.
Other compounds which can be prepared analogously are those listed in the Tables which follow.
Table A1 : Compounds of the formula la:
Figure imgf000041_0001
R«
Figure imgf000041_0005
Figure imgf000041_0002
A1.002 A2 CH3
Figure imgf000041_0003
Figure imgf000041_0006
Figure imgf000041_0004
A1.005 A2 CH3 F 203
0~ y (decomp.)
F A1.006 A3 CH3 /=\ 239-241
A1.007 A1 CH3 . =\ ... 186-188
O^H(CH2)2COCH3 Comp. Ri Rl5 No.
A1.008 A2 CH3
A1.009 A3 CH3
Figure imgf000042_0001
A1.011 A3 SCH3
A1.012 A3 n-C4H9
A1.013 A3 i-C3H7
Figure imgf000042_0002
A1.016 A3 n-C4H9
A1.017 A3 SO2CH3
Figure imgf000042_0003
115
i-C3H7
Figure imgf000043_0008
Figure imgf000043_0001
Figure imgf000043_0007
Figure imgf000043_0002
A1.020 A3 i-C3H7 192-194
A1.021 A3 n-C4Hs 159-160
A1.022 A3 n-C3H7 220-225
A1.023 A3 C2H5 222-223
Figure imgf000043_0003
Figure imgf000043_0004
A1.025 A3 n-C3H7 193-195
Figure imgf000043_0005
A1.026 A3 SOCH3 F
F
Figure imgf000043_0006
R15 XR Physical data M.p. °C
Figure imgf000044_0006
Figure imgf000044_0001
Figure imgf000044_0002
A1.035 A3 CH=CH2 188-191
Figure imgf000044_0003
Figure imgf000044_0004
A1.037 A3 SO2CH3
Figure imgf000044_0005
H5 XR4 Physical data M.p. °C
Figure imgf000045_0002
Figure imgf000045_0001
Figure imgf000045_0003
Figure imgf000046_0001
XR4 Physical data M.p. °C
Figure imgf000047_0001
OCH(CF3)2
Figure imgf000047_0005
F F
F F
Figure imgf000047_0002
A1.067 A2 O-t-C4H9 OCH2C7F15
Figure imgf000047_0003
A1.070 A3 Br F F 182-183
°- F& F F
A1.071 A3 OC6H5 S-i-C3H7 A1.072 A3 OC2H5 OCH(CF3)2
0-(
CH,
A1.073 A3 OC2H5 OCH2C6F5
Figure imgf000047_0004
A1.075 A3 COC6H5
°" ~Ci=3 XR4 Physical data
M.p. °C
Figure imgf000048_0001
OCH2C3F7
Figure imgf000048_0002
°^ COOCH,CCH
Figure imgf000048_0006
Figure imgf000048_0003
Figure imgf000048_0004
A1.084 A3 C(CH3)=CH2 F F
F F
Figure imgf000048_0005
A1.086 A3 Si(CH3)3
0-^ N02
Figure imgf000049_0001
R15 XR4 Physical data M.p. °C
Figure imgf000050_0007
CF3 196-198
Figure imgf000050_0001
A1 .098 A3 CβH5 F F 250-252
°-β- ■'F
A1.099 A3 C «6Hns 250-252
Figure imgf000050_0002
Figure imgf000050_0003
A1 .102 A3 CH2-O-CH2-CH=CH2 149-151
Figure imgf000050_0004
Figure imgf000050_0005
A1 .105 A3 CH2OCH2CH=CH(CH3) 128-130
Figure imgf000050_0006
Figure imgf000051_0001
Figure imgf000052_0001
R 15
Figure imgf000053_0005
f-C4Hg
Figure imgf000053_0004
Figure imgf000053_0001
Figure imgf000053_0002
A1 .126 A2 — C≡C— H
> /=<
F
A1.127 A3 — C≡C— Si(CH3),
Figure imgf000053_0003
Table A2: Compounds of the formula lb:
Figure imgf000054_0004
Figure imgf000054_0001
Comp. RT R1S XR4 Physical
No. data
M.p. °C
Figure imgf000054_0002
A2.002 A2 CH3 F F
°- - F&F F'
Figure imgf000054_0003
A2.006 A3 CH3
0- ^)-t-C4H9
A2.007 A1 CH3 0-< -(CH2)2COCH3
Figure imgf000055_0001
R15 XR4 Physical data
M.p. °C
Figure imgf000056_0001
n-C4H9
>
F
Figure imgf000056_0002
n-CaH? F F
O-O- -ΪF F F
Figure imgf000056_0004
Figure imgf000056_0003
Comp. R, R1S XR4 Physical
No. data
M.p. °C
Figure imgf000057_0001
A2.031 A3 SOCH3 -
CβH13/
Figure imgf000057_0002
Figure imgf000058_0001
Comp. R, R15 XR4 Physical
No. data
M.p. °C
Figure imgf000059_0001
A2.051 A1 COCH
S-
Figure imgf000059_0002
Figure imgf000059_0006
Figure imgf000059_0003
Figure imgf000059_0004
A2.060 A2 v O
C '2' H '55 O N-'
Figure imgf000059_0005
Figure imgf000060_0003
Figure imgf000060_0001
Figure imgf000060_0004
,
Figure imgf000060_0002
Comp. Ri Rιs XR4 Physical
No. data
M.p. °C
Figure imgf000061_0006
Figure imgf000061_0001
Figure imgf000061_0007
Figure imgf000061_0002
Figure imgf000061_0003
A2.081 A3 CH2-N^ 0-<^-COOCH2CCH
A2.082 A2 SO-i-C3H7 F F
F F A2.083 A3 F F F
° F F~F
Figure imgf000061_0004
A2.086 A3 Si(CH3)3
Figure imgf000061_0005
Comp. RT R15 XR4 Physical
No. data
M.p. °C
Figure imgf000062_0001
Figure imgf000062_0005
Figure imgf000062_0003
Figure imgf000062_0002
A2.093 A1 C-C3 3Hrl5 o CP3
CF,
Figure imgf000062_0004
A2.095 A3 C(CH3)=CH2 0^\^
A2.096 A2 CH3 F
° F Table A3: Compounds of the formula IVa
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0002
Figure imgf000066_0001
Table A4: Compounds of the formula Via
Figure imgf000067_0001
Figure imgf000067_0002
Figure imgf000068_0001
Figure imgf000069_0001
Comp. Rt R15 XR4 Physical
No. data
M.p. °C
Figure imgf000070_0001
A4.031 A3 SOCHa
Figure imgf000070_0002
A4.032 A3 SO2CH3
Figure imgf000070_0003
Figure imgf000071_0001
Figure imgf000072_0002
Figure imgf000072_0001
A4.061 A2 °-
CaHs ^ Comp. R1 R1S XR4 Physical
No. data
M.p. °C
Figure imgf000073_0001
A4.064 A2 CF3 OCH(CF3)2
Figure imgf000073_0002
A4.067 A2 O-t-C4H9 OCH2C7F15
Figure imgf000073_0003
A4.071 A3 OC6H5 S-i-C3H7
A4.072 A3 OC2H5 OCH(CF3)2
CH3
A4.073 A3 OC2H5 OCH2C6F5
A4.074 A3 C6H5 OC6H5
A4.075 A3 COC6H5
°~0~CF3 XFU Physical data
M.p. °C
Figure imgf000074_0001
Figure imgf000074_0003
Figure imgf000074_0002
Figure imgf000074_0004
Figure imgf000075_0004
Figure imgf000075_0001
Figure imgf000075_0002
A4.094 A2 SOC2H5 F F
O^ F
F F
Figure imgf000075_0003
Table A5: Compounds of the formula Villa
(Villa)
Figure imgf000076_0001
Figure imgf000076_0002
NR22Rn3 Physical data M.p. °C
NH2 NH2
Figure imgf000077_0001
NH2 NH2 NH2 NH2 NH2 196-197 NH2 NH2 NH2 NH2
Figure imgf000077_0002
NH2
NH2 NH2 NH2
NH2 NH2 NH2 NH2 NH2 NH2 NH2 NH2
Figure imgf000077_0003
NH2
Figure imgf000078_0001
115 NR ι22Rπ3 Physical data M.p. °C
Figure imgf000079_0004
Figure imgf000079_0001
A5.067 A3 CH2OCH3 NH2 160 A5.068 A3 CH2OCH3 NHCH(OH)CCI3
Figure imgf000079_0002
A5.070 A3 O-CH2-CH=CH2 NH2 150
A5.071 A2 — C≡C— H NH2
A5.072 A2 — C≡C— H NHCH(OH)CCI3
A5.073 A2 O-CH2-CH=CH2 NH2 127-129
A5.074 A3 CF(CH3)2 NH2
A5.075 A3 CF(CH3)2 NHCH(OH)CCI3
A5.076 A3 CβHs NHCH(OH)CCI3
A5.077 A3 — C≡C— n-C3H7 NH2
A5.078 A3 — C≡C— t-C4H9 NH2
p.)
Figure imgf000079_0003
Figure imgf000080_0002
Figure imgf000080_0001
Table A6: Compounds of the formula Ic:
NR2R3
N=
R; N (IC)
* //
OR4
Comp. RT RIS R4 NR2R3 Physical data
M.p.
Figure imgf000081_0004
Figure imgf000081_0001
A6.005 A2 F C 'βFr,s NHCH(OH)CCI3
A6.006 A3 F C 6F' , 5 172-173°C
A6.007 A1 CH3 C6H4(CF3-3)
Figure imgf000081_0002
A6.008 A2 CH3 C6F5 NHCOCCI3
A6.009 A3 CH3 C6H3F2(2,5-) NHCH(OH)CCI3
A6.010 A2 C2H5 C6H4(NO2-4) NHCOCCI3
A6.01 1 A3 C2H5 C6H4F(2-)
A6.012 A2 CF3 C6H3CI3(2,3,6-)
Figure imgf000081_0003
Comp. RT R 15 R4
A6.013 A3 CF3 C6H4(CH3-4)
A6.014 A2 t-butyl CβF5
Figure imgf000082_0005
A6.015 A3 t-butyl CβFs NHCH(OH)CCI3 61-62°C
Figure imgf000082_0001
A6.017 A2 OCH3 C6HF4 (2,3,5,6-)
Figure imgf000082_0002
A6.018 A3 OCH3 CH4Br (4-) NHCH(OH)CCI3
A6.019 A2 Br CeH3F2(2,5-)
Figure imgf000082_0003
A6.020 A3 F NHCH(OH)CCI3
Figure imgf000082_0004
A6.021 A3 ,CH3 C6FS NHCH(OH)CCI3
Figure imgf000083_0005
A6.025 A3
Figure imgf000083_0001
NHCOCI3
A6.026 A3 C6H5 C •»6F' , 5 NHCH(OH)CCI3 95-103°C
Figure imgf000083_0002
A6.028 A3 Br C6H2CI2(2,6-) NHCH(OH)CCI3
Figure imgf000083_0003
A6.030 A3 t-butyl
Figure imgf000083_0004
Comp. R, R15 R4 NR2R3 Physical data
M.p.
A6.032 A3 CH3 CH4(CH3-4)
Figure imgf000084_0001
A6.033 A2 t-butyl C6H4(Si(CH3)3(-4)) NHCH(OH)CCI3
A6.034 A3 Br C6F5 NHCH(OH)CCI3 187-189°C
Table B1 : Compounds of the formula la:
Figure imgf000085_0001
Comp. R, R15 Riβ XR4 Physical
No. data
M.p. °C
Figure imgf000085_0002
B1.004 B3 Cl Cl
**$
B1 .005 B6 CH3 CH3 OCH2CH(CF3)2
B1.006 B2 CH3 CH3 O, r
B1.007 B5 Cl Cl F F 195-197
OHghF
F F B1.008 B6 CH3 CH3 F 233
0~(\ // (decomp.)
F
Figure imgf000086_0001
Figure imgf000087_0001
Rιs R16 XR4 Physical data
M.p. °C
Figure imgf000088_0004
Figure imgf000088_0001
Figure imgf000088_0002
B1.037 B3 o^>
H3C02C
Figure imgf000088_0003
Figure imgf000088_0005
Comp. R, R15 R16 XR4 Physical
No. data
M.p. °C
Figure imgf000089_0001
B1 .047 B3 OCH3 CH3 OC8H17
Figure imgf000089_0002
B1 .052 B1 CON(C2H5)2 OCH,SI(CH&
Figure imgf000089_0003
Figure imgf000089_0004
Comp. R, 115 116 XR4 Physical No. data M.p. °C
B1.054 B1 NHCOCH3
°-©- NO,
B1.055 B1 CON(C2H5)2 OCH3
Figure imgf000090_0001
B1.056 B1 -CN OCH3 oP S02-C2H5
Figure imgf000090_0002
B1.059 B1 -CN Cl c- _
Figure imgf000090_0003
B1.061 B1 -CN OCH3 o SCH,
B1.062 B2 CH3 CH3 >-0~oc<H*
B1.063 B1 -CN OC2H5
N-
Figure imgf000090_0004
B1.065 B2 CF3 NHCH3
Figure imgf000090_0005
\ιs R16 XR4 Physical data
M.p. °C
Figure imgf000091_0005
Figure imgf000091_0006
Figure imgf000091_0001
Figure imgf000091_0002
B1.071 B3 CF3 OCH2C6F5
B1.072 B4 CF3 CF3 SCβHs
B1.073 B3 NHCOCH3 Cl
Figure imgf000091_0003
Figure imgf000091_0004
230
Figure imgf000091_0007
Comp. RT R,5 Rl6
No.
Figure imgf000092_0001
B1.080 B1 Cl Cl
B1.081 B4 Cl Cl
Figure imgf000092_0002
B1.083 B5 OCH3 Cl
B1.084 B6 F
B1.085 B2 OCH3 OCH3
B1.086 B5 Cl CH3
B1.087 B4 F
Figure imgf000092_0003
Comp. R, R15 R16 XR4 Physical
No. data
M.p. °C
Figure imgf000093_0001
Table B2: Compounds of the formula lb:
Figure imgf000094_0001
Figure imgf000094_0002
Comp. R, R15 R16 XR4 Physical
No. data
M.p. °C
Figure imgf000095_0001
B2.012 B3 CH3 CH3
OH^-CF3
Figure imgf000095_0002
B2.018 B5 F 0-(^)-(CH2)2COOH R15 R16 XR4 Physical data
M.p. °C
Figure imgf000096_0004
Figure imgf000096_0001
B2.020 B2
Figure imgf000096_0005
Figure imgf000096_0002
Figure imgf000096_0006
Cl
Figure imgf000096_0003
Figure imgf000096_0007
Figure imgf000097_0001
Comp. RT R15 R16 XR,, Physical
No- data
M.p. °C
B2.042 B3 OCH3 CH3
°& F F F
Figure imgf000098_0001
B2.046 B2 CH3 OCH3 F F
°- -F
F& F'
B2.047 B3 OCH3 CH3 OC8H,7
Figure imgf000098_0002
B2.052 B1 CON(C2H5)2 0CH2si(CH,)3 C2H5 oP Comp. Ri R15 R16 XR Physical
No. data
M.p. °C
Figure imgf000099_0001
B2.054 B1 NHCOCH3 F
B2.055 B1 CON(C2H5)2 OCH3
Figure imgf000099_0002
Figure imgf000099_0004
B2.061 B1 -CN OCH3 °P SCH.
Figure imgf000099_0003
B2.063 B1 -CN OC2H5 s=\
N-7 Comp. RT R,5 R16 XR4 Physical
No. data
M.p. °C
Figure imgf000100_0001
B2.065 B2 CF3 NHCH3
^N
B2.066 B6 Cl Cl i-Q
S-t-C4H9
B2.067 B1 -CN CF3 S-i-C3H7 B2.068 B4 F CF3 OCH2CN
B2.069 B4 CF3 NHCOCH3
°^ t-C„HQ
Figure imgf000100_0002
B2.071 B3 F CF3 OCH2C6F5
B2.072 B4 CF3 CF3 SC6H5
B2.073 B3 NHCOCH3 Cl
Figure imgf000100_0003
Figure imgf000100_0004
B2.075 B3 CF3 CH2OC4H9 OCF, o J
B2.076 B4 OCH3 OCH3 S-c-CHn
Figure imgf000100_0005
-99
Table B3: Compounds of the formula IVa
Figure imgf000101_0001
Figure imgf000101_0002
Figure imgf000102_0001
Comp. Ri R15 R16 Physical
No. data
M.p. °C
B3.048 B3 NHCOCH3 Cl
B3.049 B4 Cl OCH3
B3.050 B3 CF3 CH2OC4H9
B3.051 B4 OCH3 OCH3
B3.052 B6 F F resin
B3.053 B4 F F resin
B3.054 B2 F Cl resin
B3.055 B5 OCH3 Cl resin
B3.056 B5 CH3 Cl resin
B3.057 B5 CF3 F
B3.058 B5 C≡CH Cl
B3.059 B6 C2H5 CH3
B3.060 B6 CH3 F
B3.061 B1 F F
B3.062 B5 Br Br
B3.063 B6 Br Cl
B3.064 B5 C=CCH3 βr
B3.065 B6 Cl O C3H7
Table B4: Compounds of the formula Via
Figure imgf000104_0001
Comp. Ri R1S Rie XR4 Physical
No. data
M.p. °C
Figure imgf000104_0002
B4.005 B6 CH3 CH3 OCH2CH(CF3)2
Figure imgf000104_0003
B4.007 B5 Cl Cl F F
F F
Figure imgf000104_0004
B4.009 B6 CH3 CH3 O, y Comp. R, R15 R16 XR4 Physical
No- data
M.p. °C
Figure imgf000105_0001
B4.015 B6 CH3 CH3 CF,
0- CF3
Figure imgf000105_0002
Figure imgf000106_0002
Figure imgf000106_0001
Comp. Ri R15 R16 XR Physical
No. data
M.p. °C
Figure imgf000107_0001
Figure imgf000107_0002
Figure imgf000108_0003
Figure imgf000108_0001
B4.052 B1 CON(C2Hs)2 ocH,si<t»w. C2HS
Figure imgf000108_0002
Figure imgf000109_0001
Comp. R, R15 R16 XR4 Physical
No. data
M.p. °C
B4.066 B6 Cl Cl
°-Q S-t-C4Hg
Figure imgf000110_0004
Figure imgf000110_0001
Figure imgf000110_0002
B4.075 B3 CF3 CH2OC4H9 OCF3 o-&
B4.076 B4 OCH3 OCH3 S-C-CHn
Figure imgf000110_0003
Table B5: Compounds of the formula Villa
(Villa)
Figure imgf000111_0001
Comp. Ri R15 R 16
No.
B5.001 B2 OCH3 OCH3
Figure imgf000111_0003
NH2 NH2 NH2 NH2 NH2
NH2 192-193 (decomp.)
NH2 NH2 NH2 196-198 NH2 275 NH2 NH2
Figure imgf000111_0002
NH2
Figure imgf000112_0001
Comp. RT R15 *16 NR22Rπ3 Physical
No. data M.p. °C
50
Figure imgf000113_0004
NH 1.5005)
Figure imgf000113_0001
B5.054 B5 CH3 Cl NHCH(OH)CCI3
Figure imgf000113_0002
Figure imgf000113_0005
N
Figure imgf000113_0003
e NR22R":3 Physical data M.p. °C
Cl NHCH(OH)CCI3
F NHCH(OH)CCI3
Figure imgf000114_0004
Figure imgf000114_0001
B5.068 B6 F F NHCH(OH)CCI3
Figure imgf000114_0002
B5.070 B6 NH, 179-180 (decomp.)
B5.071 B4 NH2 167 (decomp.)
B5.072 B2 Cl NH2 193 (decomp.)
Figure imgf000114_0003
B5.074 B6 CH3 NHCH(OH)CCI3 115 r R»ii6
Figure imgf000115_0001
B5.076 B2
B5.077 B5 OCH3 Cl
Figure imgf000115_0002
Table B6: Compounds of the formula Ic
NR2R3
,"=<
N (Ic)
OR.
Comp. RT R15 116 a. NR2R3 Physical data M.p.
B6.001 B2 OCH3 OCH3 CH3CI2(2,5-)
Figure imgf000116_0001
B6.002 B5 Cl Cl C6H3CI2(2,4-) NHCH(OH)CCI3 resin
resin
Figure imgf000116_0002
B6.005 B3 CH3 Cl C '6F' ,5 NHCH(OH)CCI3
B6.006 B5 F C6H3F2(2,5-)
Figure imgf000116_0003
B6.007 B6 F C 6F~5 NHCH(OH)CCI3 resin
Figure imgf000116_0004
Comp. Ri. R 15 " R1i6 NR22Rπ3. Physical data M.p.
B6.009 B6 F C βFδ no501.5139
Figure imgf000117_0001
Figure imgf000117_0006
Figure imgf000117_0002
Figure imgf000117_0003
B6.015 B5 Cl CH3 Cβ 6Fr,5 nD S01.5295
B6.016 B5 Cl CH3 C6 6F1 5 nD 501.5302
Figure imgf000117_0004
B6.017 B5 CH3 Cl CH3(CI-2,NO2-5) NHCH(OH)CCI3 B6.018 B5 Cl CH3 CF5 NHCH(OH)CCI3 no50! .5320
Figure imgf000117_0005
Comp. Ri R15 ^16
B6.020 B5 F CH3
B6.021 B6 C 2H« I5 CHa
Figure imgf000118_0004
B6.022 B5 CH3 F CH4(OCH3-2) NHCH(OH)CCI3 B6.023 B6 F F CF5 NHCH(OH)CCI3 nD S01.5262
B6.024 B4 CF3 CF3 C6H2F3(3,4,5-) NHCH(OH)CCI3
B6.025 B5 CF3 CF3 CβH2CI3(3,4,5-)
Figure imgf000118_0001
B6.026 B5 Br Br CβH2Cl3(3,4,5-) NHCH(OH)CCI3
B6.027 B6 F C 'β6F~,5 no50! .5295
Figure imgf000118_0002
Cl
B6.028 B6 Br Br CeH2CI3(3,4,5-) NH- N
Cl
B6.029 B6 Br Cl CH2F3(3,4,5-) NHCH(OH)CCI3
Figure imgf000118_0003
B6.031 B6 Br Cl C6HF4(2,3,5,6-) NHCH(OH)CCI3 Comp. Ri R15 e R4 NR22R» l;3 Physical data M.p.
B6.032 B6 Br Cl CHF4(2,3,5,6-)
B6.033 B5 Cl CH3 C6 6F' ,5 196-198° C
Figure imgf000119_0001
Figure imgf000119_0002
B6.035 B6 Br Cl CH2F3(2,3,4-) NHCH(OH)CCI3
B6.036 B5 H Br C6H3F2(2,5-) NHCH(OH)CCI3
///
B6.037 B6 F C6H3F2(2,5-)
B6.038 B5 F CH3 C6H3F2(2,5-)
B6.039 B5 Cl CH3 C6HF4(2,3,5,6-)
Figure imgf000119_0003
B6.040 B6 Cl O-iPropyl C6H3F2(2,6-) NHCH(OH)CCI3 Table C1: Compounds of the formula la:
Figure imgf000120_0001
Figure imgf000120_0003
Figure imgf000120_0002
OH XR Physical data
Figure imgf000121_0001
183-185
Figure imgf000121_0002
NC o^ ^N>
0-^ N
Figure imgf000121_0003
0-n-C4Hg
Figure imgf000121_0004
op 16 117 XFI4 Physical data
CH3 CH2OH
SC(CH3)3 CH3
Figure imgf000122_0001
Figure imgf000122_0002
CHa oO> n-C4H
CH, CH3
Figure imgf000122_0003
Figure imgf000122_0004
F F
Cl Cl 141 -143
F F
Figure imgf000122_0005
Figure imgf000122_0007
C2He OC2 2H^5 °Pt CH,
C1.032 C2 NHCO2-t-C4H9 n-C3H7 n-C3H7
Figure imgf000122_0006
C1.033 03 OCHa CH, CF3 o F,PC - NO,
Figure imgf000123_0005
Figure imgf000123_0001
Figure imgf000123_0002
Figure imgf000123_0004
Figure imgf000123_0003
01.04603 -CN
Figure imgf000123_0006
Comp. i R 16 Rl7 XR4 Physical No. data
C1.047 C3 CON(C2H5)2 Cl Cl
Figure imgf000124_0001
Figure imgf000124_0002
Comp. Ri R15
No.
C1.060 C6 NHCOC2Hs
Figure imgf000125_0001
C1.062 03
Figure imgf000125_0002
C1.065 03
C1.066 C1 Cl
C1.067 03 CH,
Figure imgf000125_0003
C1.071 01 OCHa
Figure imgf000125_0004
Comp. i R15 Ri6
No.
Figure imgf000126_0001
01.074 C5 CH3 OC3H7
Figure imgf000126_0002
Figure imgf000126_0007
C1.076 C1 Cl
O- 1
Figure imgf000126_0008
Figure imgf000126_0003
Figure imgf000126_0004
C1.08304 CHa oco-t.-C4.H9 CHa Cl
Cl
Figure imgf000126_0005
C1.085C6 OC3H7 OC3H7 COOH s SC5H11 o ^
Figure imgf000126_0006
*.16 R17 XR4 Physical data
M.p. °C
Figure imgf000127_0003
CH3 CH3 0_^>_CF
3
C1.089C1 -NHCOO-t-CH9
Figure imgf000127_0001
Figure imgf000127_0002
Figure imgf000127_0004
o
Figure imgf000128_0004
Figure imgf000128_0001
C1.110C3 -NHCOO-t-C4H9 CH3 Cl
Figure imgf000128_0002
F F
C1.11103 NHCON(CH3)2 Cl CF3
F F
01.112 C3 Cl F -NHCOO-t-C4t-
Figure imgf000128_0003
RlE *16
Cl OC2H5
Figure imgf000129_0001
Figure imgf000129_0006
OCH, OCH3 OCH3 o ^N
OCH, OCH3 OCHa
Figure imgf000129_0002
Figure imgf000129_0005
Figure imgf000129_0003
01.124 C6 Cl O-i-C3H7 172-173
Figure imgf000129_0004
Comp. Ri R^ R16 Rι XR4 Physical
No. data
M.p. °C
Figure imgf000130_0001
ci
Table C2: Compounds of the formula lb:
Figure imgf000131_0001
Comp. i R15 Ri6 R17 XR4 Physical
No. data
M.p. °C
Cl
C2.001 C1 CH3 CH3 CHa op Cl
Figure imgf000131_0002
C2.003C3 CH3 CH3 CH, o-Q
Figure imgf000131_0003
C2.005C5 CH3 CH3 CH3
OCH3
02.006 C6 CH3 CH3 CH3 o CH3
C2.007C1 CH3 CH3 CH3 o- -a
Cl
Figure imgf000131_0004
Figure imgf000132_0001
XR4 Physical data
Figure imgf000133_0001
F F
Figure imgf000133_0007
F F
02.025 C1 SO2-f-C4Hc OCH3 CH3
C2.026C2 CONfCuHste CH3 CH3
Figure imgf000133_0002
Figure imgf000133_0003
C2.029 C5 N(CH3)2 CH3 F
Figure imgf000133_0004
Figure imgf000133_0005
C2.031 C1 OCON(CH3)2 C2H5 OC2H5 °-Q- -'CH,
-N
C2.032 C2 NHco2-t-c4H9 n-C3H7 n-C3H7 T s S
C2.033 C3 OCH, CH, CF3
Figure imgf000133_0006
Comp. Ri *15 "16 *17 XR4 Physical No. data M.p. °C
02.034 C4 CH3 CH3 (CH20)2CH3 oO
Figure imgf000134_0001
C2.038C4 OC(CH3)3 OCH3 OCH3 F F
OH^CI
F F
C2.039C1 F F F 0-^-C02C2H5
Figure imgf000134_0002
C2.042C1 OCH2CH3 CH3 CH3 C 3
Figure imgf000134_0003
02.04603 -CN CHa CH, SCβHs Comp. Ri R 15 R 16 *17 XR4 Physical No. data
C2.047 C3 CON(C2H5)2 Cl Cl
Figure imgf000135_0001
Figure imgf000135_0002
Figure imgf000136_0001
Physical data M.p. °C
Figure imgf000137_0001
Comp. Ri Ru R« 17 XR4 Physical No. data M.p. °C
C2.088 C2 NHCON(CH3)2 CH3 CH,
»^ CF,
C2.089C1 -NHCOO-t-CHg
Figure imgf000138_0001
F F
C2.09004
O^-F
F F
Figure imgf000138_0002
Figure imgf000138_0003
SC5H„
C2.100C4 CON(C2H5)2 CF3 CF, o Comp. Ri R15 R16 R17 XR4 Physical
No. data
M.p. °C
C2.101C4 Cl Cl OCH,
0p~?
F F
Figure imgf000139_0001
C2.104C3 Cl CH3 NHCON(CH3)2
Figure imgf000139_0002
C2.105 C2 NHCOC6H5 F F J ^ s S
Figure imgf000139_0003
C2.110C3 -NHcoo-t-c4HS CH3 Cl
C2.111C3 NHCON(CH3)2 Cl CF3
02.112 C3 Cl F -NHcoo.t-c4H9
Figure imgf000139_0004
Comp. i R15 Riβ R1 XR4 Physical
No- data
Figure imgf000140_0001
Table C3: Compounds of the formula IVa
Figure imgf000141_0001
Figure imgf000141_0002
Figure imgf000142_0001
Figure imgf000143_0001
*15 '16 Rl Physical data
M.p. °C
Cl OC2H5 CH3 resin F F F resin F F Cl F F OCH3 F F F resin OCH3 OCH3 OCH3 resin
Figure imgf000144_0001
F Cl O-i-C3H7 resin
Table C4: Compounds of the formula Via
Cl
Rr— S N (Via)
N
XR.
Comp. i R15 Riβ R17 XR Physical
No. data
M.p.°C
Cl
C4.00101 CHa CHa CHa op Cl
Figure imgf000145_0001
04.003 C3 CHa CHa CH 3 o >
C4.004C4 CH3 CH3 CH3
Figure imgf000145_0002
C4.005C5 CH3 CH3 CH2
OCH3
Figure imgf000145_0003
C4.007C1 CH3 CH3 CH3 0^ . -Cl
Cl l
Figure imgf000145_0004
Figure imgf000146_0001
Comp. Ri Ri. *16 Ri; XR4 Physical No. data
Figure imgf000147_0001
C4.023 C5 CH3 SC(CH3)3 CH3 o
Figure imgf000147_0002
C4.02501 SOrC(CHJ, OCHa CHa
C4.02602 CON(C2H5)2 CH3 CHa
Figure imgf000147_0003
Figure imgf000147_0004
C4.031 01 OCON(CH3)2 C2H5 OC2H5
°-Q- CH,
04.032 C2 NHCO^t^H n-C3H7 n-C3H7 s-
04.03303 OCH3 CHa CF3 o NO,
F,C Comp. i Ris "16 "17 XR4 Physical No. data
M.p.°C
04.034 C4 CHa CH3 (CH20)2CH3
Figure imgf000148_0001
04.03505 CH3 CH3 F F
F F
Figure imgf000148_0002
C4.038C4 OC(CH3)3 OCH3 OCH2
Figure imgf000148_0003
C4.03901 F
°- -C0 2 C 2 H 5
C4.040 C1 -CN OCHa OCH3
Figure imgf000148_0004
Figure imgf000148_0005
C4.04201 OCH2CH3 CHa CH 0- >-N02 C 3
C4.04306 NH2 CHa CHa
C02C2H5
C4.044C2 CON(CH3)2 F
Figure imgf000148_0006
Figure imgf000148_0007
C4.046C3 -CN CH3 CH3 SC6H5 Comp. Ri s *ιe 11 No.
C4.047 C3 CON(C2H5)2 Cl
Figure imgf000149_0001
Figure imgf000149_0007
Figure imgf000149_0002
04.051 01
Figure imgf000149_0003
C4.05301 -NHCO-t-C4Hg CH3 Cl o-Q
CN
Figure imgf000149_0004
04.056 C3 Cl CHa -CN SCH,
04.05701 OCH3 C0N(CH3)2 OCH3 OCH2CF3
Figure imgf000149_0005
04.05901 OCH3 CON(CH2). OCH3
Figure imgf000149_0006
Comp. Ri R15 Rιβ R1 XR4 Physical
No- data
M.p.°C
C4.060C6 NHCOC2H5 CH3 Cl H3
Figure imgf000150_0001
F F
C4.061 C3 Cl CF3
F F C4.062C3 F OCH3 CON(C2H5)2
Figure imgf000150_0002
Figure imgf000150_0003
04.065 C3 F OCH3 CON(C2H5)2 Cl
04.066 C1 Cl Cl OCH2CH-CH2
C4.067C3 CH3 NHCH2OCH; CH3
Figure imgf000150_0004
Figure imgf000150_0005
C4.070C3 Cl CH3 Cl
Figure imgf000150_0006
C4.071C1 OCH3 iJC -@ OCH3 0- -CH2-t-C4H6 Comp. Ri R15 R16 R17 X Physical
No. data
M.p.°C
Figure imgf000151_0001
04.07405 CHa OC3H7 Cl 0"^-t-C4H,
C4.07503 OCHa OC2H5 >-<Q>-(CH2) 2COCH3
0J
C4.077 C1 OCH2CF3 -CN OCH2CF3 OCH2CF3
C4.078 C2 OC5Hn Br CH3 SCH2C6H5
C4.079 C5 Br C6H5 Br OC6H5
C4.080 C2 OCH3 OCH3 CH20-t-C4Hg OCH2C7F15
C4.081 C5 CH3 O-t-C4H9 CH3 N(C2H5)2
04.082 C4 -CN CF3 CF3 '^Tf^Y^
C4.083 C4 CH3 OCO-t-C4H CH3
Figure imgf000151_0003
04.08406 Cl Br Cl
C4.085 C6 OC3H7 OC3H7 COOH
Figure imgf000151_0004
Figure imgf000151_0005
Comp. i R 15 R 16 R 17 XR4 Physical No. data
M.p.°C
C4.088 C2 NHCON(CH )2 CH3 CHa "O- CF,
C4.089 C1 -NHCoo-t-CtHg
Figure imgf000152_0001
C4.09004 F F
F F
Figure imgf000152_0002
C4.09304 -NHC00-t-C4Hg CF3 OCHa
Figure imgf000152_0003
C4.09704 t-C4H9 CH3 CH3 OC6H
Figure imgf000152_0004
04.10004 CON(C2H5)2 CF3 CFa
Figure imgf000152_0005
Comp. i 5 6 Rll XR4 Physical No. data
M.p.°C
C4.101C4 F F
Cl Cl OCHa O-^F
Figure imgf000153_0001
C4.103C4 C2Hδ C2H5 C2H5 o-Q
S02-C2Hs
C4.104C3 Cl CH3 NHCON(CH3)2
C o,H
C4.105C2 NHCOC6H5 F F
C4.106C1 OCH2CF3 -CN OCH2CF3
Figure imgf000153_0002
Figure imgf000153_0003
C4.110 C3 -NHC00-t-C4Hg CH3 Cl -
C6H13/
C4.111 C3 NHCON(CH3)2 Cl CF,
C4.112C3 Cl -NHCOO-t-C4Hg
Figure imgf000153_0004
Comp. Ri R15 R16 R17 XR4 Physical
No. data
M.p.°C
Figure imgf000154_0001
Table C5: Compounds of the formula Villa
(Villa)
Figure imgf000155_0001
Figure imgf000155_0002
Comp. Ri R15 Riβ R17 NR2R3 Physical No. data
M.p. °C
C5.023 C4 OCH3 OCH3 OCH3 NH2
05.024 C4 F F F NH2
C5.025 04 OC(CH3)3 OCH3 OCH3 NH2
05.026 01 F F F NH2
05.027 01 -CN OCH3 OCH3 NH2
C5.028 C2 NH2 CH3 Cl NH2
C5.029 01 OCH2CH3 CH3 CH3 NH2
C5.030 C6 NH2 CH3 CH3 NH2
C5.031 02 CON(CH3)2 F F NH2
C5.032 C3 F F F NH2
C5.033 C3 -CN CH3 CH3 NH2
05.034 03 CON(C2H5)2 Cl Cl NH2
C5.035 C3 CF3 Cl Cl NH2
C5.036 C3 OCH3 OCH3 -CN NH2
C5.037 03 -CN F F NH2
C5.038 01 -NHCO-t-C4Hg CH3 Cl NH2
C5.039 02 -CN OCH3 OCH3 NH2
C5.040 03 Cl Cl CF3 NH2
C5.041 C3 Cl CH3 -CN NH2
C5.042 C1 OCH3 CON(CH3) OCH3 NH2
C5.043 03 OCH3 OH -CN NH2
C5.044 01 OCH3 CON(CH2) OCH3 NH2
05.045 06 NHCOCzHs CH3 Cl NH2
C5.046 C3 F Cl CF3 NH2
05.047 03 F OCH3 CON(C2H5)2 NH2
C5.048 C3 Cl Cl Cl NH2
C5.049 03 OCH3 OC2H5 _<0 NH2
0
C5.050 C1 Cl Cl OCH2CH=CH2 NH2
05.051 C3 CH3 NHCH2OCH CH3 NH2
C5.052 03 OCH2C6H5 OCH3 -CHO NH2
05.053 05 CH3 OC3H7 Cl NH2
C5.054 03 Cl CH3 Cl NH2
Figure imgf000157_0001
Figure imgf000158_0001
157 -
Table C6: Compounds of the formula (Ic):
NR2R3
,N=<
R; N (Ic)
N— ^
OR.
Figure imgf000159_0002
C6.007 03 F CeH4(CN-3)
06.008 C5 F C6H4(CF3-3)
C6.009 05 F C '66R~5
Figure imgf000159_0001
Comp. R, R15 H6 Rl7 FU NR22Rπ3 Physical data
M.p.
Figure imgf000160_0001
C6.011 05 F Cl O-i-propyl CβF5
06.012 05 F CH3 Br C6H4(CF3-4)
C6.013 C5 F Cl O-i-propyl OC6H3F2(2,5-)
Figure imgf000160_0002
Table D1 : Compounds of the formula la:
Figure imgf000161_0001
R« 116 "1
Figure imgf000161_0005
-CN OCH3 OCH3
D1.002 D1 CH3 CH3 OH
D1.003 D1 -CN Cl OCH3
D1.004 D1 CON(C2H5)2 OCH3 OCH3
Figure imgf000161_0002
D1.006 D1
Figure imgf000161_0003
Figure imgf000161_0004
D1.008 D1 OCON(C2H5)2 CH3 CH3
Figure imgf000161_0006
Comp. RT R15 He 117
No.
Figure imgf000162_0001
D1 .010 D2 CON(C2H5)2 OCH3 OCH3
D1.011 D3 OC2Hs OC2 2H« I;5 OC2Hs
Figure imgf000162_0002
D1.013 D1 CH3 CH3 CH3
D1 .014 D2 OCON(C2Hs)2 j-C3H7 Cl
D1.015 D3 NHCOO1-C4H9 F NCH3COt-C«Hβ
D1.016 D1 OCH2OCH3
Figure imgf000162_0003
D1.018 D1 NHCOOt-C«H9 OCH3 OCH3
D1.019 D1 Cl F F
Figure imgf000162_0004
Comp. R, R15 R 16 Rl7 R 18 XR4 Physical
No. data M.p.°C
D1.020 D1 CH3 CH3 N(CH3)2 N(CH3)2
Figure imgf000163_0001
Figure imgf000163_0002
D1 .023 D1 CH3 CH2N(C2HS)2 OC3H7 CH3 oP
C2H5
D1.024 D2 NHSO2C6Hs CH3 CH3 CH3
D1.025 D1 CH3 OC2H5 OC2H5 t-C4H9
Figure imgf000163_0003
Figure imgf000163_0004
D1.028 D1 OCH3 CHa CH3 OCH3 F F
F F
D1.029 D1 CH3 CH3 OCH3 OCH3 0p F F
F F Comp. R, R15 Riβ R Riβ XR4 Physical
No. data
M.p.°C D 1.030 D2 CH3 CH3 CH3 175-178
D1.031 D2
D1.032 D1 NH,
D1.033 D1 CH3 CH3 OCH2 2C«βHπs
D1.034 D3 CH3 CH3 CH3
D1.035 D3 CH3 Br CH3
Figure imgf000164_0004
D1.036 D3 CH3 CH2OCH3 CH3 CH3
D1.037 D3
D1.038 D1 OCH3 COoC- OCH3 OCH3
Figure imgf000164_0001
Figure imgf000164_0005
D1.039 D3 CH3 NHCOt- CH3 CH3
Figure imgf000164_0003
D1.040 D1 -CN OCH3 OCH3 OCH3
Figure imgf000164_0002
Comp. R, R15 R16 R Riβ XR4 Physical
No. data
M.p.°C
D1.041 D2 CH3 CH3 CH3 212-214
D1.042 D1 CH3 CH3 OH
D1.043 D1 -CN Cl OCH3
Figure imgf000165_0003
D1.046 D1 CON(i- CH3
Figure imgf000165_0001
D1.047 D3 F
D1.048 D1 OCON(C2H5)2 CH3 CHa
Figure imgf000165_0002
D1.050 D2 CON(C2H5)2 OCH3 OCH3
D1.051 D3 OC2H6 OC2H5 OC2H5
Figure imgf000165_0004
Comp. Ri R15 Ri6 R17 Riβ XR4 Physical
No. data
M.p.°C
Figure imgf000166_0001
D1.053 D2 CH3 CH3 CH3 CH3 o 215-216
Br D1.054 D1 CH3 CH3 CH3 CH3
Figure imgf000166_0002
D1.055 D2 OCON(C2H5)2 j-CgH Cl CH3 oP
F3C
D1.056 D3 NHCOOt-C4H9 F
Figure imgf000166_0003
Figure imgf000166_0004
D1.058 D3 OCH3 OCH3 OCH3 r~ F F
F F D1.059 D1 NHCOOt-C4H9 OCH3 OCH3 OCH3 OC8H17
Figure imgf000166_0005
D1.061 D1 CH3 CH3 N(CH3)2 N(CH3)2
Figure imgf000166_0006
D1.062 D1 -CN F F F O^ o 0 Comp. R R15 »16 '17 118 XR4 Physical
No. data M.p.°C
Figure imgf000167_0001
D1.064 D1 CH3 CH2N(CaH5)2 0C3H7 CHa
Figure imgf000167_0002
D1.065 D2 NHSOaCβHs CH3 CH3 CHa
Cl Cl
D1.066 D1 CH3 OC2H5 OC2H5 t-C4H9
Figure imgf000167_0003
Figure imgf000167_0004
D1.068 D2 Cl Cl Cl Cl
S02-C2H5
D1 .069 D1 OCHa CH3 CHa OCHa
D1 .070 D1 CH3 CH3 OCH3 OCHa
Figure imgf000167_0005
D1.071 D2 CH3 CH3 CHa CH3 s
D1.072 D2 F F F F OCH2CH(CF3)2
D1.073 D1 NH2 F F F 0.
D1 .074 D1 CHa CH3 OCH2CeHs CH3 F F
°P F F F Comp. RT 115 H Rl7 No.
Figure imgf000168_0001
D 1.076 D3 CH3 Br CH3
Figure imgf000168_0004
D1.077 D3 CH3 CH2OCH3 CH3 CH oP
D1.078 D3
D1.079 D1 OCH3 CO2c- OCH3
Figure imgf000168_0002
D1.080 D3 CH3 NHCOt- CH3
Figure imgf000168_0003
Figure imgf000168_0005
Table D2: Compounds of the formula lb:
Figure imgf000169_0001
Comp. R R15 6
No.
D2.001 D1 -CN OCH3
Figure imgf000169_0002
D2.003 D1 -CN Cl
D2.004 D1 CON(C2Hs)2 OCH3
Figure imgf000169_0003
D2.006 D1
Figure imgf000169_0004
Figure imgf000169_0005
Figure imgf000169_0006
Figure imgf000170_0001
Comp. Ri R15 ie 117 118 XR4 Physical
No. data M.p. °C
D2.018 D1 NHCOOt-C4H9 OCH3 OCH3 OCH3 o^)>
D2.019 D1 Cl »-o- NO,
D2.020 D1 CH3 CH3 N(CH3)2 N(CH3)2
Figure imgf000171_0001
Figure imgf000171_0002
D2.023 D1 CHa CH2N(C2H5)2 OC3H7 CH3
Figure imgf000171_0003
D2.024 D2 NHSO2C6H5 CH3 CH3 CHa
D2.025 D1 CH3 OCaHg OCaHs t-C H9
Figure imgf000171_0004
D2.027 D2 Cl Cl Cl Cl
Figure imgf000171_0005
Comp. Ri R15
No.
D2.028 D1 OCH3
D2.029 D1 CHa
D2.030 D2 CH3
Figure imgf000172_0001
D2.032 D1 NH2
D2.033 D1 CH3
D2.034 D3 CH3
D2.035 D3 CH3
Figure imgf000172_0003
0 ~?
F F D2.036 D3 CH3 CH2OCH3 CH3 CH3
Figure imgf000172_0002
D2.037 D3 F F F F Cl op Cl Comp. RT R15 R16 R17
No.
D2.038 D1 OCH3 CO2c-C6H 1 1 OCH3
D2.039 D3 CH3 NHCOt-C4H9 CH3
Figure imgf000173_0006
D2.040 D1 -CN OCH3 OCH3 OCH3
Figure imgf000173_0001
Figure imgf000173_0002
D2.043 D1 -CN Cl
D2.044 D1 CON(C2H5)2 OCH3
Figure imgf000173_0003
D2.046 D1 CON(i- CH3
Figure imgf000173_0007
C3H )2
Figure imgf000173_0004
D2.048 D1 OCON(C2H5)2 CH3 CH3 OCH3
Figure imgf000173_0005
Comp. Rt R15 R16 R17 Riβ XR4 Physical
No. data
M.p.
°C
Figure imgf000174_0001
D2.050 D2 CON(C2H5)2 OCH3 OCH3 OCH3 Cl
O-c^-α Cl D2.051 D3 OC2H5 OC2H5 OC2H5
Figure imgf000174_0002
D2.052 D3 Cl CF o ^
D2.053 D2 CH3 CH3 CH3 CH3 0- ^
Br D2.054 D1 CH3 CH3 CH3 CH3
Figure imgf000174_0003
D2.055 D2 OCON(C2H5)2 j-C3H7 Cl CH3
F3C
D2.056 D3 NHCOOt-C4H9 f NCH3C0t-C4H9 CF3
Figure imgf000174_0004
Figure imgf000174_0005
D2.058 D3 OCH3 OCH3 OCH3
Figure imgf000174_0006
D2.059 D1 NHCOOt-C4H9 OCH3 OCH3 OCH3 OC8H17 Comp. Ri R15 R16 R17 Riβ XR Physical
No. data
M.p.
°C
Figure imgf000175_0001
D2.061 D1 CH3 CH3 N(CH3)2 N(CH3)2
Figure imgf000175_0002
Figure imgf000175_0003
D2.064 D1 CH3 CH2N(C2H5)2 OC3H7 CH3
D2.065 D2 NHSO2C6H5 CH3 CH3 CH3
Figure imgf000175_0004
D2.066 D1 CH3 OC2H5 OC2H5 'c^ oP NO,
Figure imgf000175_0005
D2.069 D1 OCH3 CH3 CH3 OCH3 0p F F
F F
Figure imgf000176_0004
D2.074 D1 CH3 CH3 OCH2C6H5 CH3
Figure imgf000176_0001
Figure imgf000176_0002
D2.076 D3 CH3 Br CH3 CH3 O^^
^ ^
D2.077 D3 CH3 CH2OCH3 CH3 CH o
CH3
Figure imgf000176_0003
D2.079 D1 OCH3 COjC-CeHu OCH3 OCH3
°^ F3
D2.080 D3 CH3 NHCOt-C4Hβ CH3 CH3 CH3 op Cl Table D3: Compounds of the formula IVa
Figure imgf000177_0001
Figure imgf000177_0002
Figure imgf000178_0001
Comp. Ri R15 R16 Physical
No. data
M.p. °C D3.050 B3 CF3 CH2OC4H9
D3.051 B4 OCH3 OCH3
D4: Com ounds of the formula Via
Figure imgf000180_0003
D4.005 D2 CH3 CH3 CH3 o^>
OCH,
Figure imgf000180_0001
D4.007 D1 CH3 CH3 CH3 OH^-CI
Cl
Figure imgf000180_0002
R15 R16 R17 Ria XR4 Physical data M.p. °C
CH3 CH3 CH3 F F o-Q
Figure imgf000181_0004
Figure imgf000181_0001
Figure imgf000181_0002
D4.012 D3 CH3 CH3 CH3 CH3
O -Q
Figure imgf000181_0003
D4.017 D2 CH3 CH3 CHa o N02
D4.018 D3 Cl Cl Cl
N
D4.019 D1 OCH2OCH3 Si(CH3)3 OCH2OCH3 oO- NO, R16 Rι7 Rιβ XR4 Physical data M.p. °C CH3 CH(CH3)2
Figure imgf000182_0001
Figure imgf000182_0005
Cl
O
Cl
D4.022 D1 OC(CH3)3 OCH3 OCH3
D4.023 D2 CH3 SC(CH3)3 CH3
Figure imgf000182_0002
D4.024 D3 Cl Cl CH3 F F
F F
D4.025 D1 S02-C(CH3)3 OCH3 CH3
D4.026 D2 CON(C2Hs)2 CH3 CH3
Figure imgf000182_0003
Figure imgf000182_0004
R15 R16 R17 Riβ XR4 Physical data
Figure imgf000183_0001
Figure imgf000183_0005
CH3 Cl CHa F F
F F
D4.031 D1 OCON(CH3)2 c2H5 OC2H5 °P CH
D4.032 D2 OCH3 OCH3 OCH3
Figure imgf000183_0002
D4.033 D3 OCH3 CH3 CF3
0-^-NO2 3C
Figure imgf000183_0003
Table D5: Compounds of the formula Villa
Figure imgf000183_0004
Figure imgf000183_0006
Figure imgf000184_0001
Figure imgf000185_0001
Table E1 : Compounds of the formula la:
Figure imgf000186_0001
XFU Physical data
M.p. "C
CH3 CH3
Figure imgf000186_0005
Figure imgf000186_0002
Figure imgf000186_0003
E1.004 CH3 CH2θC4H9 CH3 CH2OC4H9 CH3
Figure imgf000186_0004
E1.005 CH3 CH2N(CH3)2 CH3 CH2 (C2H6)2 CH3 o OCH3
E 1.006 C2H5 CHzOCsH CaHs CH2OC3H7 C2H5 oP
CH3
E1.007 CON(CH3)2 Cl Cl OC3H7 OCH3 o^ ~cι
Cl R16 R1 Riβ R19 R4 Physical data
M.p. °C
Figure imgf000187_0008
CH3 OCH3 CHa OCH3 l
Figure imgf000187_0001
E1.009 F F F F F F F
°
E1.010 NH2 Cl Cl Cl Cl
Figure imgf000187_0002
E1.01 1 CH3 CH3 Br CH3 CH3 CH3
0-
CH3
Figure imgf000187_0003
E1.013 OCH3 COCH3 0-t-C4H9 CH3 OCH3
Figure imgf000187_0004
Figure imgf000187_0005
E1.016 F F CH3 F F F F
0p~?
F F
Figure imgf000187_0006
E1.018 Cl
^-N
N02
Figure imgf000187_0007
R 19 XRA Physical data M.p. °C i-CaH7
Figure imgf000188_0008
Figure imgf000188_0001
Figure imgf000188_0002
E1.022 Cl Cl OCH3 Cl Cl
Figure imgf000188_0003
Figure imgf000188_0004
E1.025 OCH2CβH5 Cl CaHs Cl CH3
Figure imgf000188_0005
Figure imgf000188_0006
E1.028 CH3 CHO OCHa 0CH3 0CH3
Figure imgf000188_0007
E1.029 COOH F F
F F 1i9 XFU Physical data
M.p. °C
Figure imgf000189_0005
SCH3 SCH3 SCH3 SCH3
E1.031 CH3 CH3 CH3 CH3 CH3
Figure imgf000189_0001
Figure imgf000189_0006
E1.038 OCO-t-C4H9 Cl CH3 Cl C2H5
Figure imgf000189_0002
E1.039 OCH3 CH3 CH3
Figure imgf000189_0003
Figure imgf000189_0004
Riβ Ru Riβ Rn
Figure imgf000190_0008
CH3 CH3 CH3 CH3
Figure imgf000190_0007
Figure imgf000190_0001
Figure imgf000190_0002
E1.043 OCOCH3 CH3 CH3 Cl CH3 θ }-t-C4H9
E1.044 OCHa OCH3 OSi(CH3)2-t- CH ,3, 0O -^, O UCCHH33 /=\
Figure imgf000190_0003
E1.046 Cl OCH3 CONHC4H9 OCH3 Cl
Figure imgf000190_0004
Figure imgf000190_0005
E1.049 OCH3 CH3 CH3 S0 N(C2H5)2 CH3 o-O F Cl
Figure imgf000190_0006
Figure imgf000191_0002
Table E2: Compounds of the formula lb:
Figure imgf000191_0001
XR4
Figure imgf000192_0005
Figure imgf000192_0001
Figure imgf000192_0002
E2.004 CH3 CH2OC4H9 CH3 CH2OC4Hg CH3
Figure imgf000192_0003
E2.005 CH3 CH2N(CH3)2 CH3 CHaN(C2Hβ)2 CH3 op OCH3
E2.006 C2H5 CH2OC3H7 C2H5 CH20C3H7 C2H5 o CH3
E2.007 CON(CH3)2 ci Cl OC3H7 OCH3 o-^-α
Cl
E2.008 OCH3 CH3 OCH3 CH3 OCH3
Figure imgf000192_0004
E2.009 F F F F F F F
° F E2.010 NH2 Cl Cl Cl Cl 0-n-C4H9 oP Comp. '15 R 16 Rl7 R 18 V9 XR4
No. E2.01 1 CH3 CH3 Br CH3
Figure imgf000193_0001
E2.013 OCH3 COCH3 O-t-C4H9 CH3
Figure imgf000193_0002
E2.018 F F Cl
E2.019 OH CH3 CH3 OH
E2.020 i-C3H7 N(CH3)CO- i-C3H7 N(CH3)CO- i
Figure imgf000193_0003
E2.021 F F OH F
Figure imgf000193_0004
o Comp. Ri. R 16 Rl7 1β "19 XR4
No. E2.022 Cl Cl OCH3 Cl Cl
Figure imgf000194_0001
Figure imgf000194_0002
E2.025 OCH2 2C-.6βHπ5 Cl C2 2Hri5 Cl CH3
E2.026 NHCON(CH3)2
Figure imgf000194_0003
Figure imgf000194_0004
E2.028 CH3 CHO OCH3 OCH3 OCH3 F F
F F
Figure imgf000194_0005
E2.030 SCH3 SCH3 SCH3 SCH3 SCH3 F F
0p ?
F F
E2.031 CH3 CH3 CH3 CH3 CH3
Figure imgf000194_0006
Comp. R15 Ri6 Rι Riβ R19 Λ *
No. E2.032 OH Cl CH3 Cl CH3 °P CH,
E2.033 NH, s^
E2.034 OCH3 CHO OCH3 CH3 OCH3 o^ NO,
F3C
E2.035 C2H5 N
Figure imgf000195_0001
E2.036
Figure imgf000195_0002
E2.037 F F Si(CH3)3 F F F o-
F E2.038
Figure imgf000195_0003
E2.039 OCH3 CH3 CH3
Figure imgf000195_0004
Figure imgf000195_0005
E2.041 CH3 CH3 CH3 CH3 CH3
Figure imgf000195_0006
E2.042 F F F F F F F
F F op F
Figure imgf000196_0001
Comp. R15 R16 R17 Riβ R19 XR
No. E2.054 Cl OCH3 CON(CaH5)2 OCH3 Cl
E2.055 CH3 C2H5 CH3 CH3 CH3
Figure imgf000197_0001
Figure imgf000197_0002
E2.057 OCO (C2H5)2 CH3 CH3 oco fCsHs), CH3
Figure imgf000197_0003
Table E3: Compounds of the formula la:
Cl
E.— S N (IVa) x — /
Cl
Comp. R 6 ^17 118 H9 Physical No. data M.p. °C
E3.001 CH3 CH3 CH, CH, CH3 CH3
(CH r.
Figure imgf000198_0001
Figure imgf000199_0001
Figure imgf000200_0003
Figure imgf000200_0001
Riβ R19 XR4
Figure imgf000200_0002
Figure imgf000200_0004
Cl Cl F op F Comp. Rιs R16 u Riβ R19 XR4
No.
Figure imgf000201_0001
E4.004 CH3 CH2OC4H9 CH3 CH2OC4H9 CH3
E4.005 CH3 CH2N(CH3)2 CH3 CH2N(C2H5)2 CH3
Figure imgf000201_0002
E4.006 C2 2H1 15 CH2OCaH7 C2Hs CH2OC3H7 C2 2Hri5 0-
CH3
E4.007 CON(CH3)2 Cl Cl OC3H7 OCH3 o- -ci
Cl
E4.008 OCHa CH3 OCH3 CH, OCH3
Figure imgf000201_0003
Figure imgf000201_0004
E4.010 NH2 Cl Cl Cl Cl
E4.011 CH3 CH3 Br CH3 CH3
Figure imgf000201_0005
Figure imgf000201_0006
E4.013 OCHa COCHa O-t-C4H9 CH3 OCH3
Figure imgf000201_0007
Riβ R19 XR4
Figure imgf000202_0008
Figure imgf000202_0001
E4.016 F F CH3 F F F F
F F
Figure imgf000202_0002
E4.018 Cl °P
Figure imgf000202_0003
E4.020 i-C3H7 N(
Figure imgf000202_0004
Figure imgf000202_0005
E4.022 Cl Cl OCH3 Cl Cl
Figure imgf000202_0006
Figure imgf000202_0007
E4.024 Cl Cl SCH3 Cl Cl F F
0- }-F
F F t18 nig XR4
Cl CH3
Figure imgf000203_0007
Figure imgf000203_0001
Figure imgf000203_0002
E4.028 CH3 CHO OCH3 OCH3 OCH3
Figure imgf000203_0003
Figure imgf000203_0004
E4.030 SCH3 SCH3 SCH3 SCH3 SCH3 F F
°V F T F
E4.031 CH3 CH3 CH3 CH3 CH3
Figure imgf000203_0005
E4.032 OH Cl CHa Cl CH3 -CH,
E4.033 NH2 s^
E4.034 OCH3 CHO OCH3 CH3 OCH3
Figure imgf000203_0006
E4.035 C2H5 N(CH3)COO- c2H5 N(CH3)COO- C2H5 l"C4H9 t-C4H9 o-Q 19 XR4
Figure imgf000204_0006
Figure imgf000204_0001
ci CH3 Cl C ■ 22Hns
Figure imgf000204_0002
Figure imgf000204_0003
CH3 CH3 CH3 CH3
Figure imgf000204_0007
Figure imgf000204_0005
E4.043 OCOCHa CH3 CH3 Cl CH3
Figure imgf000204_0004
E4.044 OCH3 OCH3 OSi(CH3)2 CH3 O^, OCH3 =\
X J 0-(N VfCH COC
-t-C4H9 '0-* v- 22
E4.045 F F Br
O F P,C Comp. R15 R16 R17 Riβ R19 XR
NO. E4.046 Cl OCH3 CONHC4H9 0CH3 Cl F F
°p F F-F
Figure imgf000205_0001
E4.049 OCH3 CH3 CH3 S02N(C2H5)2 CH3 o - F Cl
Figure imgf000205_0002
E4.051 F F CF3 F F
E4.052 CO N(C2H5)2 CH3 CH3 CH3 CH3
Figure imgf000205_0003
E4.053 CH3 CH3 CH3 CH3 CH3
NC
E4.054 Cl OCH3 C0N(C2H5)2 QCH3 Cl
E4.055 CH3 C2 2Hπ5 CH3 CH3 CH3
Figure imgf000205_0004
E4.056 CF3 CFa OC2H5 0- ^CH2-t-C4Hg Comp. R15 R16 R 17 t18 119 XR4
No. E4.057 oco N(C2H5)2 CHa CH3 OCO N(C2HS)2 CHa
Figure imgf000206_0001
Table E5: Compounds of the formula Villa
(Villa)
Figure imgf000206_0002
Comp. 15 R 16 Rl7 *1β NR2Rs Physic,
V|8 data No. .p. °C
Figure imgf000206_0003
Figure imgf000207_0001
Comp. Ru *16 Rl7 ie R19 NR2R3 Physic. data No. M.p. °C
Figure imgf000208_0001
E5.040 OCOCHa CH3 CH3 Cl CH3 NH2 E5.041 OCH3 OCH3 OSi(CH3)2-t- CH3 O OCH3 NH2
Figure imgf000208_0002
E5.042 F F Br F F NH2 E5.043 Cl OCH3 CONHC4H9 OCHa Cl NH2 E5.044 -CN F F F F NH2 E5.045 Cl Cl CβHs Cl Cl NH2 E5.046 OCHa CH3 CH3 Sθ2N(C2H5)2 CH3 NH2
Figure imgf000208_0003
E5.048 F F CF3 F F NH2
E5.049 CO N(C2H5)2 CH3 CH3 CH3 CH3 NH2 E5.050 Cl OCH3 CO N(C2H5)2 OCHa Cl NH2
E5.051 CH3 C2Hs CH3 CH3 CHa NH2
E5.052 CF3 F CF3 OC2H5 F NH2
E5.053 oco N(C2H5)2 CH3 CH3 OCO N(C2H5)2 CH3 NH2
F rmulation Exam l ive in redients the formula I % = ercent b wei ht
Figure imgf000209_0001
Emulsions of any desired concentration can be prepared from such concentrates by diluting them with water.
F2. Solutions a) b) c) d)
Active ingredient in accordance with Tables 5 %
1 -Methoxy-3-(3-methoxy- propoxy)propane
Polyethylene glycol MW 400 20 %
N-Methyl-2-pyrrolidone
Figure imgf000209_0002
Aromatic hydrocarbon 75 % 60 % mixture C8-C12
The solutions are suitable for use in the form of microdrops.
F3. Wettable powders a) b) c) d)
Active ingredient in accordance with Tables 5 % 25 % 50 % 80 %
Sodium lignosulfonate 4 % - 3 % Sodium lauryl sulfate 2 % 3 % - 4 %
Sodium diisobutylnaphthalenesulfonate - 6 % 5 % 6 %
Octylphenol polyglycol ether - 1 % 2 %
(7-8 mol of EO)
Highly disperse silica 1 % 3 % 5 % 10 %
Kaolin 88 % 62 % 35 %
The active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
Active ingredient in accordance with Tables 0.1 % Highly disperse silica 0.9 %
Inorganic carrier 99.0 %
Figure imgf000210_0001
(0 0.1 - 1 mm), for example CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo.
F5. Coated granules a) b) c)
Active ingredient in accordance with Tables 0.1 %
Polyethylene glycol MW 200 1.0 %
Highly disperse silica 0.9 %
Inorganic carrier 98.0 %
Figure imgf000210_0002
(0 0.1 - 1 mm), for example CaCO3 or SiO2
In a mixer, the finely ground active ingredient is applied uniformly to the carrier which has been moistened with polyethylene glycol. This gives dust-free coated granules. F6. Extruder granules a) b) c) d)
Active ingredient in accordance with Tables 0.1 %
Sodium lignosulfonate 1.5 %
Carboxymethylcellulose 1.4 %
Kaolin 97.0 %
Figure imgf000211_0001
The active ingredient is mixed with the additives, and the mixture is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
F7. Dusts a) b) c)
Active ingredient in accordance with Tables 0.1 % Talc 39.9 %
Kaolin 60.0 %
Figure imgf000211_0002
The ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
Active ingredient in accordance with Tables
Ethylene glycol
Nonyl phenol polyglycol ether
(15 mol of EO)
Sodium lignosulfonate
Carboxymethylcellulose
37% aqueous formaldehyde solution
Silicone oil emulsion
Water
Figure imgf000211_0003
The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by diluting it with water.
Biological Examples
Example B1 : Herbicidal action before emergence of the plants (pre-emergence action) Monocotyledon and dicotyledon test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on in the form of an aqueous suspension (25% wettable powder, Example F3, b)), corresponding to a dosage of 2 kg of a.i./ha (500 I of water/ha). The test plants are subsequently grown in the greenhouse under optimal conditions. After a test period of 3 weeks, the experiment is evaluated using a nine- point scale (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal activity. In this experiment, the compounds of the formula I show a good to very good herbicidal action. Examples of the herbicidal activity of the compounds of the formula I are given in the Table which follows:
Table B1 : Pre-emergence action:
Table Example Avena Setaria Sinapis Stellaria
A 1 4 5 A 2 2 1 A 3 2 5 A 5 3 3 A 9 1 1 A 10 2 6 A 11 4 2 A 13 4 2 A 15 3 9 2 A 16 6 4 2 A 19 2 3 1 A 20 4 7 2 Table Example Avena Setaria Sinapis Stellaria
Figure imgf000213_0001
Table Example Avena Setaria Sinapis Stellaria
Figure imgf000214_0001
The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F1 to F2 and F4 to F8.
Example B2: Post-emergence herbicidal action
Monocotyledon and dicotyledon test plants are grown in the greenhouse in plastic pots containing standard soil and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension of the test substances of the formula I, prepared with a 25% wettable powder (Example F3, b)), which corresponds to a dosage of 2 kg of a.i./ha (500 1 of water/ha). The test plants are subsequently grown on in the greenhouse under optimal conditions. After a test period of approximately 18 days, the experiment is evaluated using a nine-point scale (1 = complete damage, 9 = no action). Scores of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action. In this experiment, a good to very good herbicidal activity is shown by the compounds of the formula I. Examples of the herbicidal activity of the compounds of the formula I are given in the Table which follows:
Table B2: Post-emergence action:
Table Example Avena Setaria Sinapis Sellaria
A1 1 1 5 2 3
A1 2 1 2 1 2
A1 5 2 5 2 3 Table Example Avena Setaria Sinapis Sellaria
Figure imgf000215_0001
The same results are obtained when the compounds of the formula I are formulated in accordance with Examples F1 to F2 and F4 to F8.

Claims

What is claimed is:
1. A compound of the formula
Figure imgf000217_0001
in which Ri is a group
Figure imgf000217_0002
Figure imgf000217_0003
Figure imgf000218_0001
Figure imgf000218_0002
Figure imgf000218_0003
Figure imgf000218_0004
R2 and R3 independently of one another are hydrogen, Cι-C6alkyl, d-C6alkyl which is substituted by S(O)nRe, halogen, cyano, nitro, CrCβalkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d-C4alkylammonium, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by Cs-Cβcycloalkyl, d-Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cι-C6alkylamino, d-Csalkoxycarbonyl, C2-Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NRι0Rn, C C4alkyl, formyl, d-C alkylcarbonyl, -COOR7, Cι-C4alkylthio, d-C4alkylsulfonyl or -CONRβRg, or
R2 and R3 independently of one another are C2-Cealkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, d-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-Cι-C4alkylammonium, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or QrCβcycloalkyl, CrCsalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cι-C6alkylamino, C2-C alkoxycarbonyl, C2-Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NRι0Rn, Cι-C4alkyl, formyl, Cι-C4alkylcarbonyl, -COOR7, d-C4alkylthio, d-C4alkylsulfonyl or -CONR8R9, or
R2 and R3 independently of one another are C3-Cβalkynyi, C3-C6alkynyl which is substituted by halogen, cyano, nitro, Cι-C8alkoxy, C3-Cβtriaf kylsilyl , hydroxyl, amino, ammonium, tri-d-dalkylammonium, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or C3-C8cycloalkyl, d-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cι-C6alkylamino, CrC5alkoxycarbonyl, C2-C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NR10Rn, Cι-C alkyl, formyl, Cι-C alkylcarbonyl, -COOR7, d-C4alkylthio, Cι-C4alkylsulfonyl or -CONR8R9, or R2 and R3 independently of one another are formyl, d-C15alkylcarbonyl, C2-Cι5alkenylcarbonyl, C -C9cycloalkylcarbonyl, Cβ-Cgcycloalkenylcarbonyl or C3- C8cycloalkyl-C Cβalkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, d-C6alkylamino, C2-Cι2dialkylamino, -COOH, -COOR∞, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-Cβalkoxycarbonyl, C4-Cι0cycloalkoxycarbonyl, Cι-C8alkylaminocarbonyl or C2-C12dialkylaminocarbonyl, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Cι-C3alkyl, d-C5alkoxy, d-C5alkylcarbonyl, d-Csalkylcarbonyloxy, Cι-C6alkoxycarbonyl, aminocarbonyl, d-C6alkylaminocarbonyl or C^Cndialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C5alkyl, Crdalkoxy, Cι-C3alkylcarbonyl, Cι-Cβalkoxycarbonyl, aminocarbonyl, Ci-Cβalkylamino or Cι-C5alkylcarbonyloxy, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-d-Cβalkylcarbonyl, biphenyl-d-C6alkylcarbonyl, naphthyl-
Cι-C6alkylcarbonyl, phenyl-C2-C6alkenylcarbonyl, biphenyl-CrCβalkenylcarbonyl, naphthyl-
C2-C6alkenylcarbonyl, phenyl-Ca-Cβalkynylcarbonyl, biphenyl-C3-C6alkynylcarbonyl or naphthyl-C3-C6alkynylcarbonyl, it being possible for these substituents to be substituted by
Ci-Csalkyl, CrCsalkoxy, d-Csalkylthio, d-C5haloalkyl, d-C5alkylcarbonyl, halogen, cyano, amino, nitro, -COOR7, Ci-Cβalkoxycarbonyl, hydroxyl, Cι-C5alkylsurfinyl, d-C5alkylsulfonyl,
CrC8alkylaminocarbonyl or C2-d2dialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C5aikyl, Cι-C5alkoxy,
Cι-C5alkylthio, -COOH, -CONH2, d-Cβalkylaminocarbonyl, C2-Cιodialkylaminocarbonyl,
C C5alkylcarbonyl or Cι-C5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Cι-C5alkyl, Cι-C5alkoxy, halogen, cyano or nitro, or
R2 and R3 independently of one another are amino, Cι-C6alkylamino, C2-C8dialkylamino, phenylamino, naphthylamino, d-Cβalkylcarbonylamino, d-doalkoxycarbonylamino, hydroxyl, d-Cβalkoxy, Ci-Cealkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy,
X is O or S(O)x, in which x is 0, 1 or 2, and
R is C -C8alkyl, C2-Cβalkenyl, C3-C8alkynyl, C3-Cβcycloalkyl, Cs-Cβcycloalkenyl,
C3-C8cycloalkyl-Cι-C alkyl or Cι-C4alkyl-C3-C8cycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or -OR5, or
R4 is phenyl, biphenyl, naphthyl, heterocyclyl, d-C4alkylphenyl, d-dalkylnaphthyl, phenyl-
Cι-C alkyl or naphthyl-d-C4alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, d-C10alkyl, Crdoalkyloxy, C
C6alkylamino, di-C2-Cβalkylamino, d-C10alkylthio, Cι-C10haloalkyl, Cι-Cιohaloalkoxy, d-
Ciohaloalkylthio, C2-C10alkoxycarbonylalkoxy, CrCealkylsulfinyl, d-C6alkylsulfonyl, C
C6alkyloxycarbonyl, Ci-Cβalkylcarbonyl, -CONH2, formyl, Cι-C7alkylaminocarbonyl, C2- ddialkylaminocarbonyl, C3-C6trialkylsilyl, Cι-Cιoalkylcarbonylamino, C
C10alkylcarbonyloxy, phenoxy, halophenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Cι-C alkyl, Cι-C4alkoxy, cyano, nitro or amino, or 2 adjacent substituents on the phenyl or naphthyl ring R4 form a carbocyclic or heterocyclic ring which can be substituted by halogen, cyano, nitro, amino, -COOH, =O, Cι-C10alkyl. Cι-Cιoalkoxy, d-C10alkylthioP d- dohaloalkyl, hydroxyl, C3-C10alkoxy-carbonylalkoxy, d-C6alkylsulfinyl, d-Cealkylsulfonyl, C2-C6alkyloxycarbonyl, C2-C6alkyl-carbonyl, -CONH2, formyl, C2-Cτalkylaminocarbonyl, C3- Cndialkylaminocarbonyl, C3-C6trialkylsilyl, C2-C10alkylcarbonylamino, d- Cioalkylcarbonyloxy, phenoxy, pyridyloxy or pyridyloxy which is substituted by halogen, Ci- C alkyl, Cι-C4alkoxy, cyano, nitro or amino,
R5 is hydrogen, d-C6alkyl, Cι-C6haloalkyl, 02-Csalkoxyalkyl, Ci-Cecyanoalkyl, phenyl, phenyl-d-C4alkyl, formyl, C2-C7alkylcarboπyl, C2-C7alkoxycarbonyl, Ci-Cβalkyl¬ aminocarbonyl, d-Cβdialkylaminocarbonyl, benzoyl, halobeπzoyl, Ci-Cβalkylamino, C2-Cβdialkylamino, -N=CH2, -N=CH-d-C alkyl, -N=C(Cι-C alkyl)2l tri(d-C4alkyl)silyl, C3-C7cycloalkyl, C2-C7alkenyl or C3-C7alkynyl, heterocyclyl, n is 0, 1 or 2,
R6 is hydrogen or cyano when n is 0 or
R6 is Cι-C5alkyl, CrC5alkenyl, C3-C5alkynyl, CrCβalkoxyalkyl, Ci-Cshaioalkyl, d-Cδhydroxyalkyl, phenyl, phenyl-C C alkyl, heterocyclyl, heterocyclyl-Cι-C4alkyl or d-C^ycloalkyl,
R7 is hydrogen, d-C12alkyl, d-Cι2haloalkyl, d-Cenitroalkyl, Cι-Cβcyanoalkyl, phenyl, C2-Cιoalkoxyalkyl, C2-Cιoalkylcarbonylalkyl, C2-Cιoalkoxycarbonyialkyl, heterocyclyl, Cs-CTcycloalkyl, C3-dhalocycloalkyl, -N=CH2, -N=CH-Cι-C4alkyl, -N=C(d-C alkyl)2 or C2-C6dialkylamino,
Re and R9 independently of one another are hydrogen, phenyl, Ci-Cβalkyl, Cι-C8haloalkyl, d-C8alkoxy, phenoxy, C2-C7cyanoalkyl, C3-C7alkenyl, Ca-Cralkynyl, C2-C8alkoxyalkyl, Cι-C6alkylamino or C2-C6dialkylamino, or
R8 and R9 together with the nitrogen atom to which they are bonded form a three- to seven- membered heterocycle which can contain one or two further hetero atoms and, in turn can be substituted by d^alkyl groups or halogen,
R10 and Rn independently of one another are hydrogen, phenyl, Cι-C8alkyl, CrCβhaloalkyl, CrCsalkoxy, phenoxy, C2-C7cyanoalkyl, C3-C7alkenyl, C3-C7alkynyl, C2-C8alkoxyalkyl, Cι-C6alkylamino, (Cι-Cβalkylamino)carbonyl, C2-C6dialkylamino, (C2- C6dialkylamino)carbonyl, formyl, (Cι-Cτalkyl)carbonyl, (d-Cβalkoxy)carbonyl, phenylcarbonyl, phenoxycarbonyl, benzyloxycarbonyl, heterocyclylcarbonyl, heterocyclyloxycarbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which can contain one or two further hetero atoms and, in turn, can be substituted by C1-6alkyl groups or halogen, Rι2 is d-Cβalkyl, Cι-C8alkoxy, d-Cβalkenyloxy, Cι-C8alkynyloxy, Cι-C8haloalkyl, phenyl, phenyloxy,
Figure imgf000222_0001
R13 and Rι4 independently of one another are hydrogen, d-C6alkyl, C2-Cβalkylcarbonyl or phenyl, and
Ris, Riβ, R17, Riβ and R19 independently of one another are Cι-C10alkyl, C3-Cβcycloalkyl,
Figure imgf000222_0002
d-Cβalkyl-d-Cβcycloalkyl, C2-C10alkenyl, d-Cβcycloalkyl- C2-C4alkenyl, C2-C6alkenyl-C3-Cβcycloalkyl, C2-Cιoalkynyl, C3-C6cycloalkyl-C2-C alkynyl, C2-C6alkynyl-d-C6cycloalkyl, Cs-Cβcycloalkenyl, Cs-C6cycloalkenyl-Cι-C4alkyl, d-C6alkyl- C5-Cecycloalkenyl, Cs-Cβcycloalkenyl-Cg-C^lkenyl, CrCealkenyl-Cs-Cβcycloalkenyl, C5-C6cycloalkenyl-C2-C alkynyl, C2-Cealkynyl-C5-Cecycloalkenyl, C3-C6cycloalkyl- C3-C6cycloalkyl, Cs-Cβcycloalkenyl-Cs-Cβcycloalkenyl, Ca-Cβcycloalkyl-Cs-Cβcycloalkenyl, C5-Cβcycloalkenyl-C3-C6cycloalkyl, d-Cβalkynyl-d-Cβalkenyl or C2-Cβalkenyl-C2-C8alkynyl, phenyl, phenyl-Cι-C alkyl, phenyl-C2-C4alkenyl, phenyl-C2-C4alkynyl, heterocyclyl, heterocyclyl-Cι-C4alkyl, heterocyclyl-d-C^lkenyl or heterocyclyl-d-C4alkynyl, it being possible for the substituents R15, Riβ. R17, Ris and Rig independently of one another to be substituted by halogen, cyano, azido, nitro, -OR5, =O, -S(O)nRβ, -COOR7, -CONR8RB, -NR10Rιι, =NRι2 or =N-NR13Rι , or
R15, R16, Ri7, Riβ and R19 independently of one another are halogen, cyano, azido, nitro, -OR5, -S(O)nR6, -COOR7, -CONRβR9, -NR10R11, tri(d-C4alkyl)silyl, di(d-C4alkyl)- (C -C4alkoxy)silyl, -B(OH)2 , -B(d-C4alkoxy)2 , tri(C1-C4alkyl)silyl, tri(Cι-C4alkyl)silyl- d-C6alkyl, tri(C -C4alkyl)silyl-C2-Cealkenyl, tri(Cι-C alkyl)silyl-C2-C8alkynyl, tri(d-C alkyl)- stannyl, tr d-dalky stannyl-Ci-Cealkyl, tri(d-C alkyl)stannyl-C2-Cβalkenyl, tri(Cι-C4alkyl)- stannyl-C2-C8alkynyl, and
R∞ is Cι-C12alkyl,
Figure imgf000222_0003
Cι-C6nitroalkyl, Ci-CβcyanoalkyI, phenyl, C^doalkoxyalkyl, C2-Cιoalkylcarbonylalkyl, CrCioalkoxycarbonylalkyl, heterocyclyl, 03-Cτcycloalkyl, C3-C7halocycloalkyl, -N=CH2, -N=CH-Cι-C4alkyl, -N=C(d-C4alkyl)2 or C2-C6dialkylamino, and the salts of the compounds of the formula I, with the exception of the compounds 1 -(4-hydroxyphenyl)-3-amino-5-(2,5-difluorophenoxy)thiatriazine, 1 -(4-methylpheπyl)-3- amino-5-phenoxythiatriazine, 1-(4-methoxyphenyl)-3-amino-5-(2,3,4,5,6-pentafluoro- phenoxy)thiatriazine, 1-(4-methoxyphenyl)-3-amino-5-(2,3,4-trichlorophenoxy)thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-(2,3,4,5,6-pentafluorophenoxy)thiatriazine, 1 -(4-chlorophenyl)- 3-amino-5-(2,3-dichlorophenoxy)thiatriazine, 1-(2-hydroxy-5-tert-butylphenyl)-3-amino-5- (2,5-difluorophenoxy)thiatriazine, 1 -(4-hydroxy-3-methylphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(4-hydroxy-3-methoxyphenyl)-3-amino-5-(2,5- difluorophenoxy)thiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethoxy-4-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethyl-2-hydroxyphenyl)-3-amino-5-(2,5- difluorophenyloxy)thiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-(2,5- difluorophenyloxy)thiatriazine, 3-amino-1-(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2,3,4,5,6- pentafluorophenoxy)thiatriazine, 3-amino-1 -(4-amino-2,3,5,6-tetrafluorophenyl)-5-(2, 4, 6- trichlorophenoxy)thiatriazine, 3-amino-1-(4-amino-2,3,5I6-tetrafluorophenyl)-5-(2,5- difluorophenoxy)thiatriazine, 3-amino-5-(2,5-difluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine and 3-amino-5-(2,3,4I5I6-pentafluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine.
2. A compound according to Claim 1 , wherein R2 and R3 independently of one another are hydrogen, d-Cealkyl, Ci-Csalkyl which is substituted by S(O)nRe, halogen, cyano, nitro, Ci-Cβalkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d-C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3-C8cycloalkyl, d-Csalkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cι-C6alkylamino, d-C5alkoxycarbonyl, C2-C 2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -OR5, -NR10Rπ, d-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR7, d-C alkylthio, d-C4alkylsulfonyl or -CONRβRg, or
R2 and R3 independently of one another are C2-Cealkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, d-C8alkoxy, C3-Cβtriaikylsilyl, hydroxyl, amino, ammonium, tri-Cι- dalkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C8cycloalkyl, C2-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, Cι-Cβalkylamino, C2-C5alkoxycarbonyl, C2-C12dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR10R11, d-C4alkyl, formyl, Cι-C4alkylcarbonyl, -COOR7, d-C4alkylthio, Cι- dalkylsulfonyl or -CONRβRg, or
R2 and R3 independently of one another are C3-C6alkynyl, C3-C6alkynyl which is substituted by halogen, cyano, nitro, d-C8alkoxy, C3-Cβthalkylsilyl, hydroxyl, amino, ammonium, tri-C dalkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C3-C8cycloalkyl, Cι-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-C6alkylamino, d-Csalkoxycarbonyl, C2-Cι2dialkylamino, phenyl, naphthyl, phenoxy, naphthoxy, biphenyl, biphenyloxy, phenthio or naphthio, it being possible for the abovementioned aromatic rings to be substituted by halogen, cyano, nitro, -ORs, -NR10R11, Cι-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR7, d-C4alkylthio, d- C alkylsulfonyl or -CONRβRg, or
R2 and R3 independently of one another are formyl, Cι-Ci5alkyicarbonyl, C2-dsalkenyl- carbonyl, C4-C9cycloalkylcarbonyl, C6-C9cycloalkenylcarbonyl or Ca-Cβcycloalkyl-d-Cealkyl- carbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, Cι-Cβalkylamino, C2-Cι2dialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-Cβalkoxycarbonyl, C4-C10cycloalkoxycarbonyl, d-Cθalkylaminocarbonyl or C2-C12dialkylaminocarbonyl, or R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, Cι-C5alkyl, d-C5alkoxy, Cι-C5alkylcarbonyl, d-C3alkylcarbonyloxy, Cι-C6alkoxycarbonyl, aminocarbonyl, Ci-Cβalkylaminocarbonyl or CrCπdialkylaminocarbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, Ci-Csalkyl, CrCsalkoxy, d-C5alkylcarbonyl, Cι-C6alkoxycarbonyl, aminocarbonyl, Cι-C6alkylamino or d-C5alkylcarbonyloxy, or R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Ci-Cβalkylcarbonyl, biphenyl-Ci-Cβalkylcarbonyl, naphthyl-Cr C6alkylcarbonyl, phenyl-C2-C6alkenylcarbonyl, biphenyl-Cϋ-Cβalkenylcarbonyl, naphthyl-C2- C6alkenylcarbonyl, phenyl-C3-C6aikynylcarbonyl, biphenyl-C3-Cβalkynylcarbonyl or naphthyl- C3-C6alkynylcarbonyl, it being possible for these substituents to be substituted by C Csalkyl, d-C5alkoxy, CrC5alkylthio, Cι-C5haloalkyl, d-Gsalkylcarbonyl, halogen, cyano, amino, nitro, -COOR7, Cι-C8alkoxycarbonyl, hydroxyl, Cι-C5alkylsulfinyl, CrC5alkylsulfonyl, d-C6alkyl-aminocarbonyl or C2-Cι2dialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl or naphthyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, d-C5alkyl, CrCsalkoxy, CrC5alkylthio, -COOH, -CONH2, CrC6alkylaminocarbonyl, C2-Cιodialkylaminocarbonyl, CrC5alkylcarbonyl or d-C5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Ci-Csalkyl, CrC5alkoxy, halogen, cyano or nitro, or R2 and R3 independently of one another are amino, CrC6alkylamino, C2-C8dialkylamino, phenylamino, naphthylamino, d-Cβalkylcarbonylamino, CrC10alkoxycarbonylamino, hydroxyl, CrC6alkoxy, CrC6alkylcarbonyloxy, phenoxy, biphenyloxy or naphthoxy, and is, R16, Ri7, Riβ and R19 independently of one another are d-Cioalkyl, C3-Cβcycloalkyl, C3-C6cycloalkyl-CrC alkyl, d-Cβalkyl-d-Cβcycloalkyl, C2-Cιoalkenyl, d-Cβcycloalkyl-d- C alkenyl, C2-C6alkenyl-C3-C6cycloalkyl, d-Cι0alkynyl, C3-Cecycloalkyl-C2-C4alkynyl, C2-C6alkynyl-C3-C6cycloalkyl, C3-C6cycloalkenyl, C5-C6cycloalkenyl-Ci-C4alkyl, d-Cβalkyl-Cs- Cβcycloalkenyl, Cs-Cβcycloalkenyl-d-dalkenyl, C2-Cealkenyl-C5-Cecycloalkenyl, C5-C6cycloalkenyl-d-C4alkynyl , C2-C6alkynyl-C5-Cβcycloalkenyl, C3-C6cycloalkyl-C3- C6cycloalkyl, Cs-Cβcycloalkenyl-Cs-Cβcycloalkenyl, Cs-Cβcycloalkyl-Cs-Cβcycloalkenyl, C5-C6cycloalkenyl-C3-C6cycloalkyl, C2-C8alkynyl-C2-Cβalkenyl or C2-C8alkenyl-C2-C8alkynyl, phenyl, phenyl-CrC4alkyl, phenyl-d-C alkenyl, phenyl-d-C4alkynyl, heterocyclyl, heterocyclyl-CrC4alkyl, heterocyclyl-C2-C alkenyl or heterocyclyl-CrC4alkynyl, it being possible for the substituents Rι5, R16, R17, Riβ and R19 to be substituted by halogen, cyano, azido, nitro, -OR5, =O, -S(O)nR6l -COOR7, -CONR8R9, -NR10R11, =NRι2 or =N-NRι3R14, or Ris, Riβ, R17, R18 and R g independently of one another are halogen, cyano, azido, nitro, -ORs, -S(O)nR6, -COOR7, -CONRβR9, -NRι0Rn, tri(d-C4alkyl)silyl, di(d-C4alkyl)-(Cr C4alkoxy)silyl, -B(OH)2 or -B(d-C4alkoxy)2.
3. A compound according to Claim 1 , wherein Ris, Riβ, R17, Riβ and Rι9 independently of one another are Cι-Cιoalkyl, C3-Cecycloalkyl, C2-Cιoalkenyl, C2-Cιoalkynyl, C5-
Cβcycloalkenyl, C2-C8alkynyl-d-C8alkenyl or d-Cβalkenyl-C2-C8alkynyl, phenyl, phenyl-d-
C4alkyl, phenyl-C2-C4alkenyl, heterocyclyl, heterocyclyl-C C alkyl or heterocyclyl -C2-
C4alkenyl, it being possible for Rι5, Rι6, Rι7, Rι8 and Rι9 independently of one another to be substituted by halogen, cyano, -OR5, =O, -S(O)nR6, -COOR7, -CONR8R9 or -NRioRn, or is, Riβ, Ri7, RIB and Rι9 independently of one another are halogen, cyano, -OR5, -S(O)nRe,
-COOR7, -CONRβR9 or -NR10Rn,
R5 is hydrogen, d-Cβalkyl, C Cβhaloalkyl, C2-C5alkoxyalkyl, phenyl, phenyl-CrC4alkyl,
C2-dalkylcarbonyl, CrCβalkylaminocarbonyl, C2-C8dialkylaminocarbonyl, tri(CrC4alkyl)silyl,
C2-Cτalkenyl or C3-C alkynyl or heterocyclyl,
Re is hydrogen when n is 0, or
R6 is Ci-Csalkyl, phenyl, phenyl-C C alkyl or heterocyclyl,
R7 is hydrogen, d-Cβalkyl, CrC6haloalkyl, CrC6cyanoalkyl, C2-Cioalkoxycarbonylalkyl, heterocyclyl, C3-C6cycloalkyl or C2-C6dialkylamino, R8 and R9 independently of one another are hydrogen or CrC8alkyl, or R8 and R9 together with the nitrogen atom to which they are bonded form a three to seven- membered heterocycle which may contain one or two further hetero atoms and which may be substituted by d-βalkyl groups,
R10 and Rn independently of one another are hydrogen, phenyl, CrCβalkyl, C3-C7alkenyl, (d-CealkylaminoJcarbonyl, (C2-C6dialky!amino)carbonyl, (d-C7alkyl)carbonyl, (CrC6alkoxy)carbonyl or heterocyclylcarbonyl, or
R10 and R together with the nitrogen atom to which they are bonded form a three- to seven-membered heterocycle which may contain one or two further hetero atoms and which may be substituted by C1-6 alkyl groups.
4. A compound according to Claim 1 , wherein R2 and R3 independently of one another are hydrogen, CrCβalkyl, d-C6alkyl which is substituted by halogen, cyano, nitro, CrC4alkoxy, d-Cβtrialkylsilyl, hydroxyl, amino, ammonium, tri-CrC4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-C8cycloalkyl, Cι-C5alkylcarbonyloxy, phenylcarbonyloxy, naphthylcarbonyloxy, d-dalkylamino, C -C5alkoxycarbonyl, C2-C6dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NRι0Rn, d-C alkyl, formyl, d-dalkylcarbonyl, -COOR7, CrC alkylthio, d-C4alkylsulfonyl or -CONR8Rg, or
R2 and R3 independently of one another are C2-C6alkenyl, C2-C6alkenyl which is substituted by halogen, cyano, nitro, d-C4alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrCβalkylamino, CrCsalkoxycarbonyl, d-Cβdialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NR10Rιι, d-C4alkyl, formyl, d-C4alkylcarbonyl, -COOR , d-C alkylthio, d-C4alkylsulfonyl or -CONR8R9, or
R2 and R3 independently of one another are C3-Cβalkynyl, C3-Cβalkynyl which is substituted by halogen, cyano, nitro, Cι-C8alkoxy, C3-C6trialkylsilyl, hydroxyl, amino, ammonium, tri-d- C alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by d-Cβalkylamino, C2-C5alkoxycarbonyl, C2-C6dialkylamino or phenyl, it being possible for the phenyl ring to be substituted by halogen, cyano, nitro, -OR5, -NR10R11, d-dalkyl, formyl, Cι-C alkylcarbonyl, -COOR7, d-C4alkylthio, d-C4alkylsulfonyl or -CONRaRg, or R2 and R3 independently of one another are formyl, C C8alkylcarbonyl, C2-C8alkenyl- carbonyl, C -C9cycloalkylcarbonyl, C6-C9cycloalkenylcarbonyl or C3-C8cycloalkyl-Cr
C6alkyicarbonyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, hydroxyl, amino, CrC6alkylamino, d-C^ialkylamino, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by C2-C8alkoxycarbonyl,
C -Cιocycloalkoxycarbonyl, d-C8alkylaminocarbonyl or C2-C8dialkylaminocarbonyl, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, CrC5alkyl, Cι-C5alkoxy, d-Csalkylcarbonyl,
CrC5alkylcarbonyloxy, CrC6alkoxycarbonylr aminocarbonyl, C C6alkylaminocarbonyl or
C2-C8dialkylaminocarbonyl, or heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, CrC alkyl, CrC4alkoxy, CrC4alkylcarbonyl, CrC4alkoxycarbonyl, aminocarbonyl,
CrC6alkylamino or CrCsalkylcarbonyloxy, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-Ci-Cβalkylcarbonyl, biphenyl-CrC6alkylcarbonyl, naphthyl-d-
C6alkylcarbonyl, phenyl-C2-C6alkenylcarbonyl, biphenyl-C2-C6alkenylcarbonyl or naphthyl-
C2-C6alkenylcarbonyl, it being possible for these substituents to be substituted by C
C4alkyl, CrC4alkoxy, d-dalkylthio, d-C4haloalkyl, d-C4alkylcarbonyl, halogen, cyano, amino, nitro, -COOR7, d-Csalkoxycarbonyl, hydroxyl, Cι-C4alkylsulfonyl, d-
C5alkylaminocarbonyl or drCβdialkylaminocarbonyl, or
R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, CrC4alkyl,
Crdalkoxy, d-C4alkylthio, -COOH, -CONH2, CrC5alkylaminocarbonyl, C2-ddialkyl- aminocarbonyl, d-dalkylcarbonyl or CrC5alkoxycarbonyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by d-dalkyl, d-dalkoxy, halogen, cyano or nitro, or
R2 and R3 independently of one another are amino, d-dalkylamino, C2-C6dialkylamino, phenylamino, CrC5alkyicarbonylamino, CrC5alkoxycarbonylamino, hydroxyl, d-C4alkoxy,
CrC5alkylcarbonyloxy or phenoxy,
R5 is hydrogen, CrC6alkyl, d-Cβhaloalkyl, CrC6alkoxyalkyl, d-Cβcyanoalkyl, phenyl, haiophenyl, CrC alkoxyphenyl, phenyl-d-C alkyl, CrC alkylcarbonyl, benzoyl, halobenzoyl, Cι-C4alkylamino, C2-Cedialkylamino, C3-C6trialkylsilyl, C3-C6cycloalkyl, C2-
C4alkenyl or C3-C alkynyl,
R7 is hydrogen, CrC alkyl, C C haloalkyl, CrC cyanoalkyl, phenyl, haiophenyl,
C2-C4alkoxyalkyl, heterocyclyl or haloheterocyclyl, R8 and R9 independently of one another are hydrogen, phenyl, haiophenyl, CrC alkyl, d-dhaloalkyl, d-C4cyanoalkyl, C3-C alkenyl, C3-C4alkynyl or C2-C alkoxyalkyl, or
R8 and R9 together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by d-C alkyl,
R10 and Rn independently of one another are hydrogen, phenyl, haiophenyl, d-C4alkyl,
Crdhaloalkyl, d-C cyanoalkyl, C3-C alkenyl, 03-dalkynyl, C2-C alkoxyalkyl, formyl, d-C4alkylcarbonyl or phenylcarbonyl, it being possible for the phenyl moiety therein to be substituted by d-dalkyl, halogen, d-C4alkoxy, hydroxyl, cyano, nitro or C C alkoxy- carbonyl, or
R10 and Rn together with the nitrogen atom to which they are bonded form a heterocycle which can be substituted by CrC alkyl.
5. A compound according to Claim 4, wherein R2 and R3 independently of one another are hydrogen, CrC6alkyl, d-C6alkyl which is substituted by halogen, hydroxyl, amino, ammonium, tri-CrC4alkylammonium, -COOH, -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or by CrC5alkylcarbonyloxy, phenylcarbonyloxy, CrC6alkylamino, CrC5alkoxycarbonyl or d-Cβdialkylamino, or R2 and R3 independently of one another are formyl, CrC8alkylcarbonyl, C2-C8alkenyl- carbonyl, C4-C9cycloalkylcarbonyl, Cβ-Cgcycloalkenylcarbonyl or C3-C8cycloalkyl-CrCβalkyl- carbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl, amino, -COOH or -COOM, in which M is ammonium or an alkali metal or alkaline earth metal atom, or
R2 and R3 independently of one another are heterocyclyl, heterocyclylcarbonyl, heterocyclyl which is substituted by halogen, cyano, nitro, d-C5alkyl, CrC alkoxy or CrC6alkoxy- carbonyl, or are heterocyclylcarbonyl which is substituted by halogen, cyano, nitro, d-C4alkyl, CrC4alkoxy or d-C4alkoxycarbonyl, or
R2 and R3 independently of one another are phenylcarbonyl, biphenylcarbonyl, naphthylcarbonyl, phenyl-CrC6alkylcarbonyl, biphenyl-d-Cβalkyicarbonyl, naphthyl-d- Cβalkylcarbonyl, phenyl-C2-C6alkenylcarbonyl, biphenyl-C2-C6alkenylcarbonyl or naphthyl- C2-C6alkenylcarbonyl, it being possible for these substituents to be substituted by d- C alkyl, d-C4alkoxy, d-C4alkylthio, CrC4haloalkyl, Crdalkylcarbonyl, halogen, cyano, amino, nitro, -COOH, CrC5alkoxycarbonyl, hydroxyl or d-C4alkylsulfonyl, or R2 and R3 independently of one another are phenyl, naphthyl or heterocyclyl, it being possible for these substituents to be substituted by halogen, cyano, d-C alkyl, d-C4alkoxy, CrC4alkylthio, -COOH or CrC5alkoxycarboπyl, or
R2 and R3 together with the nitrogen atom to which they are bonded form a heterocyclic ring which can be substituted by Cι-C alkyl, d-C alkoxy, halogen or cyano.
6. A compound according to Claim 5, wherein R2 and R3 are hydrogen, or
R2 and R3 independently of one another are formyl, d-C8alkylcarbonyl, C2-C8alkenyl- carbonyl, C -C9cycloalkylcarbonyl, Cβ-Cgcycloalkenylcarbonyl or C3-CBcycloalkyl-Cr C6alkylcarbonyl, it being possible for these substituents to be substituted by halogen, cyano, hydroxyl or amino, or
R2 and R3 are phenylcarbonyl, it being possible for the phenyl ring to be substituted by d-C alkyl, C C4alkoxy, d-dalkylthio, CrC4haloalkyl, halogen, cyano, nitro, -COOH, d-Csalkoxycarbonyl, hydroxyl or d-C4alkylsulfonyl.
7. A compound according to Claim 1 , wherein X is O or S(O)x where x is 0, 1 or 2, and R4 is methyl which is substituted by halogen, cyano, nitro or OR5, or
R* is CsrCβalkyl, C2-C8alkenyl, C3-C8alkynyl, C3-C8cycloalkyl, C5-C8cycloalkenyl, C3-C8cycloalkyl-CrC4alkyl or CrC4alkyl-C3-C8cycloalkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, =O or -OR5 , or R« is phenyl which is substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, CrC4alkyl, CrC alkyloxy, CrC4alkylthio, d-C+haloalkyl, C C4haloalkoxy, d- C4haloalkylthio, C2-C6alkoxycarbonylalkoxy, Crdalkylsulfinyl, C C alkylsulfonyl, Cr C6alkyloxycarbonyl, Ci-Cβalkylcarbonyl, -CONH2, formyl, CrC5alkylaminocarbonyl, C2- ddialkyiaminocarbonyl, d-C4alkylamino, CrC6dialkylamino,
C3-Cetrialkylsilyl, Ci-Cβalkylcarbonylamino, d-Cβalkylcarbonyloxy, phenoxy, halophenoxy or Pyridyloxy, or
FU is biphenyl, naphthyl, heterocyclyl, d-C4alkylphenyl, d-dalkylnaphthyl, phenyl-d- C4alkyl or naphthyl-d-C alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, -COOH, hydroxyl, CrC4alkyl, d-C4alkyloxy, CrC4alkylthio, d-C4haloalkyl, CrC haloalkoxy, Cι-C4haloalkylthio, C2-C6alkoxycarbonylalkoxy, d-C4alkylsulfinyl, CrC alkylsulfonyl, CrCealkyloxycarbonyl, CrC6alkylcarbonyl, -CONH2, formyl, CrC5alkylaminocarbonyl, d-C^ialkylaminocarbonyl, C3-Cβtrialkylsilyl, CrC6alkylcarbonylamino, CrC6alkylcarbonyloxy, phenoxy, halophenoxy or pyridyloxy, and
R5 is hydrogen, CrC8alkyl, d-Cβhaloalkyl, C2-C6alkoxyalkyl, CrC6cyanoalkyl, phenyl, haiophenyl, Ci-C4alkoxyphenyl, phenyl-CrC alkyl, d-C4alkylcarbonyl, benzoyl, halobenzoyl, d-C4alkylamino, C2-C6dialkylamino, d-Cetrialkylsilyl, Ca-Cβcycloalkyl, C2- Ctalkenyl or C3-C4alkynyl.
8. A compound according to Claim 7, wherein X is O or S, and R is methyl which is substituted by halogen or cyano, or
R» is d-Cβalkyl, CrCβalkenyl, C3-Cβalkynyl, C3-CβCycloalkyl, C5-C8cycloalkenyl, C3-Cβ- cycloalkyl-Cι-C alkyl or Cι-C4alkyl-C3-C8cycloaikyl, it being possible for these substituents to be substituted by halogen or cyano, or
R is phenyl which is substituted by halogen, cyano, nitro, amino, Cι-C alkyl, Cι-C alkyloxy, d-C alkylthio, d-C4haloalkyl, d-C4haloalkoxy, C2-C6alkoxycarbonylalkoxy,
CrC4alkylsulfonyl, CrC6alkyloxycarbonyl, CrCβalkylcarbonyl, formyl, d-C4alkylamino,
C2-C6dialkylamino,
C3-C6trialkylsilyl or C2-C6alkylcarbonyloxy, or
R4 is biphenyl, naphthyl, heterocyclyl, d-C4alkylphenyl, CrC4alkylnaphthyl, phenyl-d-
C4alkyl or naphthyl-Ci-04alkyl, it being possible for these substituents to be substituted by halogen, cyano, nitro, amino, d-C alkyl, CrC4alkyloxy, CrC alkylthio, Cι-C haloalkyl, d-C4haloalkoxy, C2-C6alkoxycarbonylalkoxy, d-C4alkylsulfonyl, CrC6alkyloxycarbonyl,
CrCβalkylcarbonyl, C3-Cβtrialkylsilyl or CrC6alkylcarbonyloxy.
9. A compound according to Claim 8, wherein X is O and R4 is phenyl which is substituted by halogen, cyano, nitro, amino, d-C alkyl, d-C alkyloxy, Cι-C4alkylthio, d-C4haloalkyl, halomethoxy, CrC4alkylsulfoπyl, d-C4alkylamino or C2-C6dialkylamino.
10. A compound according to Claim 1 , wherein R15, R16, R17, Ri8 and Rι9 independently of one another are CrC4alkyl, C2-C4alkenyl, Cι-C4alkoxy, fluorine, chlorine, bromine, phenyl, CrC alkoxy-CrC4alkoxy, trimethylsilyl, di-CrC alkylamino, di-CrC alkylamino-CrC4alkyl, morpholinyl-CrC4alkyl, CrC alkylthio, Cι-C alkylsulfinyl, Cι-C4alkylsulfonyl, d-C4alkyl- carbonyl, CrC4alkoxy-Cι-C4alkyl, 1 -(Cι-C4alkyl)dioxolanyl, 1-phenyldioxolanyl, trifluoromethyl, hydroxyl, phenoxy, phenoxycarbonyl, Cs-Cβcycloalkyl, Crdalkyl- perhydroazinyl, R2 is hydrogen, R3 is hydrogen or methylcarbonyl, X is O or S and R4 is phenyl, naphthyl, pyridyl, CrC7haloalkoxy, CrCθalkoxy, d-C4-alkylthio, cyclohexyl, thienyl
or the group , or is phenyl, naphthyl, pyridyl or thienyl, each of which is
Figure imgf000231_0001
substituted by C C4alkyl, d-C4alkoxy, fluorine, chlorine, nitro, cyano, C3-C6cyclo- alkyloxycarbonyl, CrC6alkylthio, d-C4hydroxycarbonyl, alkylsulfonyl, di-d-C alkylamino, Cι-C4alkylsulfonyl or trifluoromethyl.
11. A compound according to Claim 1 , wherein Ri is a group A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , C2, 03, 04, C5, 06, D1 , D2 or D3.
12. A compound according to Claim 1 , wherein Ri is a group A1 , A2, A3, B1 , B2, B3, B4, B5, B6, C1 , 02, C3, 04, 05 or 06.
13. A compound according to Claim 1 , wherein R15, R16, Rι7, Rm and Rig independently of one another are halogen, CrC6alkyl or d-C6alkoxy.
14. A compound according to Claim 1 , wherein Rι5, Rι6, Rι7, Riβ and R19 independently of one another are fluorine, chlorine, d-C alkyl or C C alkoxy.
15. A compound according to Claim 1 , wherein Rι5 is fluorine when Ri is A1 , B1 , B2, B3, C1 , 02 or C6.
16. A process for the preparation of a compound according to Claim 1 , which comprises (1 ) reacting a compound of the formula II
Figure imgf000231_0002
in which Hal radicals independently of one another are fluorine, bromine or chlorine with an organometallic compound of the formula III RrM (III),
in which Ri has the meaning given in Claim 1 and M is a mono- or polyvalent metal atom, (2a) reacting the resulting compound of the formula IV
Figure imgf000232_0001
in which Ri has the meaning given in Claim 1 and Hal radicals independently of one another are fluorine, chlorine or bromine with the compound of the formula V
H-XR4 (V),
in which X and R4 have the abovementioned meaning to give the compounds of the formula VI
Figure imgf000232_0002
and
(3a) then converting this product with the compounds of the formula VII
M NR2R3 (VII), in which R2 and R3 have the abovementioned meanings and Mi is hydrogen or a metal atom into the end product of the formula I; or (2b) reacting the compounds of the formula IV with the compounds of the formula VII to give the compounds of the formula VIII
Figure imgf000233_0001
in which R^ R2 and R3 have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, and
(3b) then converting this product with the compounds of the formula V into the end products of the formula I.
17. A herbicidal and plant growth-inhibiting composition which contains one or more compounds of the formula according to claim 1.
18. A composition according to Claim 17, which comprises between 0.1% and 95% of active ingredient of the formula I.
19. A method of controlling undesirable vegetation, which comprises applying an active ingredient of the formula I according to Claim 1 , or a composition comprising this active ingredient, in an effective amount to the plants or their environment.
20. A method according to Claim 19, wherein an amount of between 0.001 and 5 kg, in particular between 0.005 and 2 kg, of active ingredient is applied per hectare.
21. A method of inhibiting plant growth, which comprises applying an active ingredient of the formula I according to Claim 1 , or a composition comprising this active ingredient, in an effective amount to the plants or their environment.
22. A method according to Claim 19 for the selective pre- or post-emergence control of weeds and crops of useful plants.
23. The use of a composition according to Claim 17 for the selective pre- or post- emergence control of weeds in crops of useful plants.
24. A compound of the formula IV
Figure imgf000234_0001
in which Ri has the meaning given in Claim 1 and Hal radicals independently of one another are fluorine, chlorine or bromine, with the exception of the compounds 1-(4- methylphenyl)-3,5-dichlorothiatriazine, 1 -(4-hydroxyphenyl)- 3,5-dichlorothiatriazine, 1 -(4- methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(4-chlorophenyl)-3,5-dichlorothiatriazine, 1 -(2- hydroxy-5-tert-butylphenyl)-3,5-dichlorothiatriazine, 1-(4-hydroxy-3-methylphenyl)-3,5- dichlorothiatriazine and 1 -(4-hydroxy-3-methoxyphenyl)-3,5-dichlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxy- phenyl)-3,5-dichlorothiatriazine, 1 -(3,5-dimethoxy-4-hydroxyphenyl)- 3,5-dichlorothiatriazine, 1 -(2-hydroxy-3,5-dimethylphenyl)-3,5-dichlorothiatriazine and 3,5-dichloro-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine.
25. A compound of the formula VI
Figure imgf000234_0002
in which R1 ( R4 and X have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1-(4-methylphenyl)-3-phenoxy-5-chloro- thiatriazine, 1 -(4-methoxyphenyl)-3-(2,3,4,5,6-pentafluorophenoxy)-5-chlorothιatriazine, 1 - (4-chlorophenyl)-3-(2,3,4,5,6-pentafluorophenoxy)-5-chlorothiatriazine, 1-(4- methoxyphenyl)-3-(2,3,4-trichlorophenoxy)-5-chlorothiatriazine, 1-(4-chlorophenyl)-3-(2,3- dichlorophenoxy)-5-chlorothiatriazine, 1-(3,5-dimethyl-4-hydroxyphenyl)-3-(2,5- difluorophenoxy)-5-chlorothiatriazine, 3-chloro-5-(2,5-difluorophenoxy)-1-(2,3,4,5,6-penta- fluorophenyl)thiatriazine and 3-chloro-5-(2,3,4,5,6-pentafluorophenoxy)-1 -(2,3,4,5,6- pentafluorophenyl)thiatriazine.
26. A compound of the formula VIII
Figure imgf000235_0001
in which R1 t R2 and R3 have the meanings given in Claim 1 and Hal is fluorine, chlorine or bromine, with the exception of the compounds 1-(4-methylphenyl)-3-amino-5-chloro- thiatriazine, 1 -(4-chlorophenyl)-3-amino-5-chlorothiatriazine, 1 -(4-methoxyphenyl)-3-amino- 5-chlorothiatriazine, 1 -(4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(2-hydroxy-5-tert- butylphenyl)-3-amino-5-chlorothiatriazine, 1 -(4-hydroxy-3-methylphenyl)-3-amino-5- chlorothiatriazine, 1 -(4-hydroxy-3-methoxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5- dimethyl-4-hydroxyphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5-dimethoxy-4-hydroxyphenyl)- 3-amino-5-chlorothiatriazine, 1-(2-hydroxy-3,5-dimethylphenyl)-3-amino-5-chlorothiatriazine, 1 -(3,5-dimethyl-4-hydroxyphenyl)-3-dimethylamino-5-chlorothiatriazine, 3-amino-5-chloro-1 - (4-amino-2,3,5,6-tetrafluorophenyl)thiatriazine and 3-amino-5-chloro-1 -(2,3,4,5,6-penta- fluorophenyl)thiatriazine.
Abstract:
Compounds of the formula I
Figure imgf000236_0001
in which Ri is a group
Figure imgf000236_0002
Figure imgf000236_0003
Figure imgf000237_0001
Figure imgf000237_0002
Figure imgf000237_0003
Figure imgf000237_0004
and R2, R3, X, R« and R 5 have the meanings given in Claim 1 are well suited for use as herbicides.
PCT/EP1996/005727 1996-01-05 1996-12-19 Substituted 1,2,4,6-thiatriazines useful as herbicides WO1997025319A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU13757/97A AU1375797A (en) 1996-01-05 1996-12-19 Substituted 1,2,4,6-thiatriazines useful as herbicides
BR9612409A BR9612409A (en) 1996-01-05 1996-12-19 1,2,4,6-Substituted thiatriazines useful as herbidides
EP96944022A EP0873328A1 (en) 1996-01-05 1996-12-19 Substituted 1,2,4,6-thiatriazines useful as herbicides
JP9512986A JP2000505052A (en) 1996-01-05 1996-12-19 Substituted 1,2,4,6-thiatriazines useful as herbicides

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
CH36/96 1996-01-05
CH3496 1996-01-05
CH37/96 1996-01-05
CH34/96 1996-01-05
CH3696 1996-01-05
CH3796 1996-01-05
CH3396 1996-01-05
CH35/96 1996-01-05
CH3596 1996-01-05
CH33/96 1996-01-05

Publications (1)

Publication Number Publication Date
WO1997025319A1 true WO1997025319A1 (en) 1997-07-17

Family

ID=27508763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/005727 WO1997025319A1 (en) 1996-01-05 1996-12-19 Substituted 1,2,4,6-thiatriazines useful as herbicides

Country Status (5)

Country Link
EP (1) EP0873328A1 (en)
JP (1) JP2000505052A (en)
AU (1) AU1375797A (en)
BR (1) BR9612409A (en)
WO (1) WO1997025319A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101384568B (en) * 2006-02-15 2012-12-12 雅培制药有限公司 Novel acetyl-coa carboxylase (acc) inhibitors and their use in diabetes, obesity and metabolic syndrome

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075117A2 (en) * 1981-08-28 1983-03-30 BASF Aktiengesellschaft 2H-1,2,4,6-thiatriazine-1,1-dioxides, process for their preparation and their use as herbicides
WO1996001814A1 (en) * 1994-07-07 1996-01-25 Ciba-Geigy Ag Herbicidal 1,2,4,6-thiatriazines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0075117A2 (en) * 1981-08-28 1983-03-30 BASF Aktiengesellschaft 2H-1,2,4,6-thiatriazine-1,1-dioxides, process for their preparation and their use as herbicides
WO1996001814A1 (en) * 1994-07-07 1996-01-25 Ciba-Geigy Ag Herbicidal 1,2,4,6-thiatriazines

Also Published As

Publication number Publication date
BR9612409A (en) 1999-07-13
AU1375797A (en) 1997-08-01
EP0873328A1 (en) 1998-10-28
JP2000505052A (en) 2000-04-25

Similar Documents

Publication Publication Date Title
US6268308B1 (en) Herbicidal S-substituted 1,2,4,6-thiatriazines
AU768156B2 (en) N2-phenylamidine derivatives
US5447945A (en) Nematicidal compositions
SU1309910A3 (en) Method of producing derivatives of delta-square-1,2,4-triazolyn-5-one
CA1333395C (en) Isoxazole (isothiazole)-5-carboxamides
EP0103660A1 (en) Pyridine-1-oxides, herbicidal compositions thereof and herbicidal methods for applying the compounds
IE45170B1 (en) Urea or thiourea compounds
BG61632B1 (en) Selective herbicide
KR800000505B1 (en) Process for preparing thia diazolyl-imidazoliinones
GB2043062A (en) N-(heterocyclyl)-acetanilide derivatives and herbicidal and plant growth regulating compositions containing them
EP0873328A1 (en) Substituted 1,2,4,6-thiatriazines useful as herbicides
EP0364396A1 (en) Neumaticides and fungicides
EP0084673B1 (en) Aminothiadiazoles, process for their preparation and their use in combating unwanted plant growth
NZ206870A (en) 2-(3-pyridyl)-1,3,4-thiadiazole and 5-(3-pyridyl)-1,2,4-thiadiazole derivatives and pesticidal compositions
AU636788B2 (en) Novel sulfonylureas
US6268311B1 (en) 1-Amino-3-benzyluracils
CA1092109A (en) 1,2,4-oxadiazin-5-one derivatives
US20020103168A1 (en) Fungicide phenylimine derivatives
US4179441A (en) Fungidal and herbicidal 2-substituted-3-oxa-3aλ4, 4-dithia-6-halo-1,5-diazapentalene
EP0769011B1 (en) Herbicidal 1,2,4,6-thiatriazines
US5087288A (en) Herbicidal thioparaconic acid derivatives
US5721192A (en) Aminosulfonyl ureas
EP0726260A1 (en) Herbicidal (1,2,4)thiadiazoles
CA1219282A (en) Fungicidal n - polyhaloalkyl - or vinyl - thio substituted - ethane - sulfonamide compounds
CA1158654A (en) Fungicidal 3-(n-thionoacyl-n-arylamino) lactones and thiolactones

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE GE HU IL IS JP KP KR LC LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK TR TT UA US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996944022

Country of ref document: EP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1997 512986

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1996944022

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996944022

Country of ref document: EP