GB2289893A - 3-(Tetrahydrophthalimido)cinnamyl alcohol derivatives as herbicidal, desiccation and defoliation agents - Google Patents

3-(Tetrahydrophthalimido)cinnamyl alcohol derivatives as herbicidal, desiccation and defoliation agents Download PDF

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GB2289893A
GB2289893A GB9511199A GB9511199A GB2289893A GB 2289893 A GB2289893 A GB 2289893A GB 9511199 A GB9511199 A GB 9511199A GB 9511199 A GB9511199 A GB 9511199A GB 2289893 A GB2289893 A GB 2289893A
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carbonyl
alkyl
alkoxy
haloalkyl
halogen
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GB2289893B (en
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Ralf Klintz
Gerhard Hamprecht
Elisabeth Heistracher
Peter Schaefer
Dem Bussche-Huennefeld Chr Von
Peter Muenster
Karl-Otto Westphalen
Matthias Gerber
Helmut Walter
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
    • 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
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • 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
    • A01N47/12—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, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
    • C07C205/26—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups and being further substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/68—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

3-Tetrahydrophthalimidocinnamyl alcohol derivatives I <IMAGE> [where R<1> is halogen, NO2, CN, CF3; R<2> is H, halogen; R<3> is H, CN, halogen, C1-C6-alkyl; R<4> is H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy; R<5> and R<6> are H, C1-C6-alkyl, C1-C6-haloalkyl, unsubst. or subst. phenyl; R<7> is H, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-haloalkylcarbonyl, C3-C8-cycloalkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynlcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-haloalkoxycarbonyl, C3-C8-cycloalkoxycarbonyl, C1-C6-alkylthiocarbonyl, C1-C6-haloalkylthiocarbonyl, C3-C8-cycloalkylthiocarbonyl, C1-C6-alkylamiocarbonyl, C1-C6-haloalkylaminocarbonyl, C3-C8-cycloalkylamino-carbonyl, C1-C6-alkylcarbonyloxy -C1-C6-alkylcarbonyl, C1-C6-alkylcarbonylthio -C1-C6-alkylcarbonyl, C1-C6-alkoxy-carbonyl -C1-C6-alkylcarbonyl, C1-C6-alkythiocarbonyl -CC1-C6-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-alkyl-aminosulfonyl, di-(C1-C6-alkyl)aminosulfonyl; unsubst. or subst. phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl or phenylthiocarbonyl; or 3- to 8-membered, saturated, unsaturated or aromatic heterocyclyl carbonyl having 1 to 3 heteroatoms and bonded via -CO-] and their agriculturally utilizable salts are useful as herbicides and for desiccation/defoliation of plants. The corresponding amino (III, claim 16) and nitro (VU, claim 17) compounds are also claimed.

Description

. 3-Tetrahydrophthalimidocinnamyl alcohol derivatives The present invention provides- novel 3-tetrahydrophthalimido- cinnamyl alcohol derivatives of the formula I
where the substituents have the following meanings: R1 is halogen, nitro, cyano or trifluoromethyl; R2 is hydrogen or halogen; R3 is hydrogen, cyano, halogen or C1-C6-alkyl; R4 is hydrogen, halogen, Cl-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or the phenyl group, which can be unsubstituted or can carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl; R7 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C3-C8-cycloalkyl)carbonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkynl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-haloalkoxy)carbonyl, (C3-C8-cycloalkoxy)carbonyl, (C1-C6-alkylthio)carbonyl, (C1-C6-haloalkyl)thiocarbonyl, (C3-C8-cycloalkylthio)carbonyl, (C1-C6-alkyl)amino carbonyl, (C1-C6-haloalkyl)aminocarbonyl, (C3-C8 cycloalkyl)aminocarbonyl, (C1-C6-alkyl ) carbonyl- oxy-(C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonylthio (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6 alkyl)carbonyl, (C1-C6-alkylthio)carbonyl (C1-C6-alkyl)carbonyl, (C1-C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, di-(C1-Cc-alkyl)aminosulfonyl, the phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl or phenylthiocarbonyl group, it being possible for the phenyl ring, if desired, to carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-Cs-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (Cl-C6-alkoxy)carbonyl, or a 3- to 8-membered, saturated, unsaturated or aromatic heterocycle bonded via a carbonyl group and which contains one to three heteroatoms as ring members, selected from the group consisting of two oxygen atoms, two sulfur atoms, two nitrogen atoms and one nitrogen atom which carries a methyl group, and the agriculturally utilizable salts of the compounds I, where these exist.
The invention additionally provides - the use of the compounds I as herbicides and for the desicca tion and/or defoliation of plants, - herbicidal compositions and compositions for the desiccation and/or defoliation of plants, which contain the compounds I as active substances, - processes for preparing these herbicidal compositions and compositions for the desiccation and/or defoliation of plants, and - processes for controlling undesirable plant growth and for the desiccation and/or defoliation of plants using the com pounds I.
In addition, the invention provides.: novel 3-aminocinnamyl alcohol derivatives of the formula III and novel 3-nitrocinnamyl alcohol derivatives of the formula VI
where the substituents have the following meanings: R1 is halogen, nitro, cyano or trifluoromethyl; R2 is hydrogen or halogen; R3 is hydrogen, cyano, halogen or C1-C6-alkyl; R4 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or the phenyl group, which can be unsubstituted or can carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl; R7 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C3-C8-cycloalkyl)carbonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkynyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-haloalkoxy) carbonyl, (C3-Ce-cycloalkoxy)carbonyl, (C1-Cs-alkylthio)carbonyl, (C1-C6-haloalkyl)thiocarbonyl, (C3-C8-cycloalkylthio)carbonyl, (C1-C6-alkyl)amino carbonyl, (C1-C6-haloalkyl) aminocarbonyl, (C3-C9- cycloalkyl)aminocarbonyl, (C1-C6-alkyl ) carbonyl- oxy-(C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonylthio (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl-(C1-C6 alkyl)carbonyl, (C1-C6-alkylthio)carbonyl, (C1-C6-alkyl) carbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, di-(C1-C6-alkyl)aminosulfonyl, the phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl or phenylthio carbonyl group, it being possible for the phenyl ring, if desired, to carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, (C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl, or a 3- to 8-membered, saturated, unsaturated or aromatic heterocycle bonded via a carbonyl group and which contains one to three heteroatoms as ring members, selected from the group consisting of two oxygen atoms, two sulfur atoms, two nitrogen atoms and one nitrogen atom which carries a methyl group, and the salts of the compounds III and VI, where these exist It is already known from JP-OS-59/155358 that compounds of the formula IIa
where X and Y are hydrogen or methyl and Ra is a lower alkyl group, in particular methyl or ethyl, are herbicidally active.
Additionally, inter alia, cinnamic acids and cinnamic acid esters of the formulae IIb and IIc
where Rb is hydrogen or fluorine, Hal is chlorine or bromine and RC is hydrogen or C1-C4-alkyl and Rd is hydrogen, C1-C6-alkyl, C5/C6-cycloalkyl, (C1-C4-alkoxy) - or (C1-C4-alkylthio ) -C2-C4-alkyl, and their use as herbicides are to be inferred from EP-A 300 387.
The selectivity of these known herbicides with respect to weeds, however, may only be satisfactory to a limited extent.
It is an object of the present invention to make available novel herbicidally active compounds which have good tolerability for the crop plants and with-which undesirable plants can be pecifi- cally controlled better than previously.
We have now found that this object is achieved by the 3-tetrahydrophthalimidocinnamyl alcohol derivatives of the formula I. We have furthermore found herbicidal compositions which contain the compounds I and have a very good action. We have additionally found processes for preparing these compositions and processes for controlling undesirable plant growth using the compounds I.
The compounds I according to the invention are additionally suitable for the defoliation and desiccation of parts of plants for eg. cotton, potato, rape, sunflower, soybean or field beans, in particular for cotton. With respect to this, compositions for the desiccation and/or defoliation of plants, processes for preparing these compositions and processes for the desiccation and/or defoliation of plants using the compounds I have been found.
With respect to the use of the 3-tetrahydrophthalimidocinnamyl alcohol derivatives I as herbicidal compounds, R1 is preferably halogen such as fluorine, chlorine, bromine or iodine, in particular chlorine; R2 is preferably hydrogen, fluorine or chlorine; R3 is preferably hydrogen and R4 is preferably halogen or C1-C4-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, in par ticular methyl.
The organic molecular moieties mentioned for the substituents R to R7 or as radicals on phenyl rings - such as the meaning halogen - are collective terms for individual lists of the separate group members. All carbon chains, ie. all alkyl, alkylcarbonyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, haloalkynyl, alkoxy, alkox ycarbonyl and alkylthio moieties can be straight-chain or branched. Halogenated substituents preferably carry one to five identical or.different halogen atoms.
Specific examples are: - halogen: fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine; - C1-C6-alkyl and the alkyl moieties of (C1-Cs-alkyl) carbonyl, (C1-C6-alkylamino)carbonyl, (C1-C6-alkylsulfonyl, C1-C6-alkyl aminosulfonyl, di-(Cl-C6-alkyl)aminosulfonyl, (C1-C6-alkyl ) - carbnonyloxy-(C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonyl, thio- ( C1-C6-alkyl ) carbonyl, (Cl-C6-alkoxy)carbonyl-(Cl-C6- alkyl)carbonyl (C1-C6-alkylthio)carbonyl-(C1-C6-alkyl) carbonyl: methyl, ethyl, n-propyl, l-methylethyl, n-butyl, l-methyl propyl, 2-methylpropyl, l,l-dimethylethyl, n-pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl propyl, l-ethylpropyl, n-hexyl, l,l-dimethylpropyl, 1, 2-dimethylpropyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2-ethyl butyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, l-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl, preferably methyl, ethyl and l-methylethyl; C3-C6-alkenyl: prop-l-en-l-yl, prop-2-en-1-yl, 1-methyl ethenyl, n-buten-l-yl, n-buten-2-yl, n-buten-3-yl, l-methyl prop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methyl prop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-l-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, l-methyl but-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, l-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methyl but-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1, 2-dimethylprop-1-en-1-yl, 1, 2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl-, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methyl pent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methyl pent-2-en-1-yl, 3-methylpent-2-en-l-yl, 4-methylpent 2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methyl pent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent 4-en-1-yl, 4-methylpent-4-en-1-yl, 1, l-dimethylbut-2-en-l-yl , 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-l-yl, l-ethylbut-l-en-l-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut 1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1 1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-en-methyl prop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and l-ethyl-2-methylprop-2-en-1-yl, preferably ethenyl and prop-2-en-1-yl; - the alkenyl moiety of (C2-C6-alkenyl)carbonyl: vinyl and C3-C6-alkenyl as mentioned above; - C3-C6-alkynyl: prop-l-yn-l-yl, prop-2-yn-3-yl, n-but-1-yn-1-yl-, n-but-1-yn-4-yl-, n-but-2-yn-1-yl, n-pent-l-yn-l-yl, n-pent-l-yn-3-yl, n-pent-1-yn-4-yl, n-pent-l-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-1-yl, 3-methylbut-1 yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-l-yn-l-yl, n-hex-l-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-l-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent l-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, preferably ethyl and prop-2-yn-1-yl; - the alkynyl moiety of (C2-C6-alkynyl)carbonyl: ethynyl and C3-C6-alkynyl as mentioned above; - C1-C6-haloalkyl and the haloalkyl moiety of (C1-C6-haloalkyl ) - carbonyl, (C1-C6-haloalkyl ) thiocarbonyl and (C1-C6-haloalkyl ) - aminocarbonyl: C1-C6-alkyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and/or bromine, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, penta fluoroethyl, 3-chloropropyl, heptafluoropropyl, preferably trifluoromethyl, chloromethyl and dichloromethyl; Cl-C6-alkoxy and the alkoxy moiety of (Cl-C6-alkoxy)carbonyl and (Cl-C6-alkoxy)carbonyl-(Cl-C6-alkyl)carbonyl: methoxy, ethoxy, n-propoxy, l-methylethoxy, n-butoxy, l-methylpropoxy, 2-methylpropoxy, l,l-dimethylethoxy, n-pentoxy, l-methyl butoxy, 2-methylbutoxy, 3-methylbutoxy, l,l-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, l-ethylpropoxy, n-hexoxy, l-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, l,l-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, l-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2, 2-trimethyipropoxy, l-ethyl l-methylpropoxy and l-ethyl-2-methylpropoxy, preferably methoxy, ethoxy and 2-methylethoxy; - the haloalkoxy moiety of (C1-C6-haloalkoxy)carbonyl: C1-C6-alkoxy as mentioned above, which is partially or completely substituted by fluorine, chlorine and/or bromine, eg. chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chloro difluoromethoxy, l-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2, 2-trifluoroethoxy, 2-chloro-2-fluoro ethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoro ethoxy, 2,2, 2-trichloroethoxy, pentafluoroethoxy, 3-chloro propoxy and heptafluoropropoxy; - the alkylthio moiety of (C1-C6-alkylthio)carbonyl and (C1-C6-alkylthio)carbonyl-(C1-C6-alkyl)carbonyl: methylthio, ethylthio, n-propylthio, l-methylethylthio, n-butylthio, l-methylpropylthio, 2-methylpropylthio, l,l-dimethylethyl thio, n-pentylthio, l-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2, 2-dimethylpropylthio, l-ethylpropylthio, n-hexylthio, l,l-dimethylpropylthio, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio, 1, 2-dimethylbutyl thio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, l-ethylbutyl thio, 2-ethylbutylthio, 1,1, 2-trimethylpropylthio, 1,2,2-tri methylpropylthio, l-ethyl-l-methylpropylthio and l-ethyl-2-methylpropylthio, preferably methylthio and -ethylthio; - the cycloalkyl moiety of (C3-C9-cycloalkyl)carbonyl, (C3-C9-cycloalkyl) oxycarbonyl, (C3-C8-cycloalkyl)thiocarbonyl and of (C3-C9-cycloalkyl) aminocarbonyl: cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl and cyclooctylcarbonyl, preferably cyclopentyl and cyclohexylcarbonyl.
The phenyl, phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl and phenylthiocarbonyl group can carry one of the following radicals on any substitutable C atom of the phenyl ring: - cyano, nitro, - halogen, preferably fluorine or chlorine; - C1- or C2-alkyl, preferably methyl; - C1- or Cz-haloalkyl, preferably trifluoromethyl and trichloro methyl; - C1-C4-alkoxy, preferably methoxy or ethoxy; - C1-C4-alkoxycarbonyl, preferably methoxycarbonyl or ethoxycar bonyl.
The phenyl rings are preferably unsubstituted or carry a nitro, halogen, trifluoromethyl, methoxy or ethoxy substituent.
Among the 3- to 8-membered, saturated, unsaturated or aromatic heterocycles, the following rings are particularly preferred: - saturated and partially unsaturated, 4- to 6-membered heterocycles which, in addition to C atoms, in each case carry one or two ring members selected from the group consisting of an oxygen or sulfur atom and one or two nitrogen atoms and one or two -N(CH3)- groups, in particular oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, tetra hydrothienyl, tetrahydrothiopyranyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxa diazolidinyl, 1,3,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1,3,4-thiadiazolidinyl, 1,2,4-triazolidinyl, 1,3,4-triazolidinyl, 2,3-dihydrofuryl, dihydropyranyl, 2,4-dihydrofuryl, 2,3-dihydrothienyl, 2,4-dihydrothienyl, dihydrothiopyranyl, 2,3-pyrrolinyl, 2,4-pyrrolinyl, 2,3-isoxazolinyl, 3,4-isoxazolinyl, 4, 5-isoxazolinyl, 2,3-isothiazolinyl, 3, 4-isothiazolinyl, 4,5-isothiazolinyl, 2,3-dihydropyrazolyl, 3,4-dihydropyrazolyl, 4,5-dihydro pyrazolyl, 2,3-dihydrooxazolyl, 3, 4-dihydrooxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-triazolyl and 1,3,4-triazolyl, 1,3-dioxolanyl, piperidinyl, tetrahydro pyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl, 1,3,5-tetrahydrotriazinyl and 1,2, 4-tetrahydrotriazinyl; - 5- or 6-membered aromatic heterocycles having 1 or 2 heteroatoms selected from a group consisting of 2 nitrogen atoms and an oxygen or sulfur atom, in particular 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol 3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxa diazol-2-yl, 1,3, 4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl.
Among the heterocyclic substituents R7 bonded via a. carbonyl group, tetrahydrofuranylcarbonyl, tetrahydropyranylcarbonyl and tetrahydrothiopyranylcarbonyl are very particularly preferred.
Both the 3-tetrahydrophthalimidocinnamyl alcohol derivatives of the formula I and the 3-aminocinnamyl alcohol derivatives III and the 3-nitrocinnamyl alcohol derivatives VI can be present in the form of their agriculturally utilizable salts, in particular if R7 is hydrogen.
Suitable agriculturally utilizable salts in general are the salts of those bases which do not adversely affect the herbicidal action of I.
Suitable basic salts are particularly those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts, and those of the transition metals, preferably manganese, copper, zinc and iron salts, as well as the ammonium salts which can carry one to three Cl-C4-alkyl or hydroxy-C1-C4-alkyl substituents and/or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl-(2-hydroxyethyl)ammonium salts, in addition the phosphonium salts, the sulfonium salts, preferably tri-(C1-C4-alkyl)sulfonium salts, and the sulfoxonium salts, preferably tri- ( C1-C4-alkyl) sulfoxonium salts.
The substituted 3-tetrahydrophthalimidocinnamyl alcohol derivatives of the formula I are obtainable in various ways, to be specific preferably by one of the following processes: a) reaction of 3,4,5,6-tetrahydrophthalic anhydride with a 3-aminocinnamyl alcohol derivative of the formula III in a solvent:
Suitable solvents are, for example, short-chain alkanoic acids such as acetic acid, propionic acid and isobutyric acid, the esters of these alkanoic acids, eg. ethyl acetate, relatively high-boiling hydrocarbons such as toluene and xylene, and dimethylformamide. Mixtures of the solvents mentioned are also suitable.
The reaction is normally carried out at a reaction temperature from 250C up to the boiling point of the respective reaction mixture, preferably at from 40 to 110 C. When carrying out the reaction in an aprotic solvent, it is recommended that water formed during the reaction is continuously removed.
Expediently, approximately stoichiometric amounts of anhydride and of 3-aminocinnamyl alcohol derivative III are used or, eg. to optimize the conversion of III, an excess of anhydride up to approximately 10 mol*.
Depending on the 3-aminocinnamyl alcohol derivative III used, the addition of a condensing agent such as thionyl chloride, phosphorus oxychloride or phosgene, or an acid can have an accelerating effect on the reaction.
Acids utilizable for this purpose are, in particular, organic acids, eg. alkanecarboxylic acids such as acetic and propionic acid, sulfonic acids such as methanesulfonic and p-toluenesulfonic acid, or mineral acids such as hydrochloric acid, sulfuric acid and nitric acid.
The amount of condensing agent and/or acid is not critical.
Even a catalytic amount of eg. 0.01 mol equivalents can already positively affect the reaction course. On the other hand, there is also the possibility of using such a large excess that the condensing agent or the acid simultaneously serve as solvents.
For those compounds of the formula I in which R7 is (C1-C6-alkyl ) carbonyl, (C3-Ca-cycloalkyl)carbonyl or (C2-C6-alkenyl)carbonyl, it has proven particularly advantageous to react a-ljcompound of the formula III where R7 is hydrogen with 3,4,5,6-tetrahydrophthalic anhydride in a (Ci-Cs-alkyl)carboxylic acid, (C3-C8-cycloalkyl)carboxylic acid or (C2-C6-alkenyl) carboxylic acid or in an inert solvent in the presence of these acids. b) Reduction of an ester, aldehyde or ketone of the formula IV to compounds I where R7 is hydrogen:
O R2 O R2 R1 \ reluctant R1 'N. - > AS Dy < N-q t R1 ~ o 9 N 9 R o C (R4) R8 C=C(R4)CHR5 R9 R6 HoH R3 R3 IV R3 R3 I (R7 = H) Rs is hydroxyl, lower alkoxy, phenoxy or one of the meanings of R5 or R6.
If Re has one of the meanings of R5 or R6, compounds I are obtained in which one of the substituents R5 and R6 likewise has this meaning and the other substituent is hydrogen.
The use of starting materials of the formula IV where R8 is hydroxyl, lower alkoxy or phenoxy leads to compounds I in which R5 and R6 are hydrogen.
The reduction is customarily carried out in an inert solvent or diluent, for example in an aliphatic, cyclic or aromatic hydrocarbon such as n-pentane, petroleum ether, cyclohexane, benzene, toluene and o-, m- or p-xylene, in an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, dimethoxyethane or tetrahydrofuran, in an aliphatic or aro matic;halohydrocarbon such as dichloromethane, chloroform, chlorobenzene, 1,2-dichloroethane or dichlorobenzene, in an alcohol such as ethanol, methanol or tert-butanol, in an amide such as dimethylformamide or N-methylpyrrolidone, or in an amine such as ammonia. Mixtures of these solvents are also suitable.
Suitable reductants are eg. metal hydrides such as lithium and sodium hydride, silanes such as diethylsilane, boranes such as diborane, borane complexes with eg. pyridine or dimethyl sulfide, and also aluminum hydride, diisobutylaluminum hydride, complex metal hydrides such as lithium aluminum hydride, lithium, sodium or zinc borohydride and sodium cyanoborohydride, alkali metals such as sodium and potassium in the presence of an alcohol, as well as hydrogen in the presence of a noble metal catalyst, eg. palladium or plati num.
Depending on the starting compound IV, it can be particularly advantageous to work in the presence of a catalyst or of an auxiliary promoting the chemoselectivity of the reaction.
Suitable catalysts and/or auxiliaries are eg. lanthanoid salts such as cerium trichloride, terbium trichloride and samarium halides, or other metal halides, eg. zinc chloride, aluminum trichloride, cesium fluoride, dicyclopentadienylti tanium dichloride, vanadium trichloride, boron trifluoride etherate or titanium tetrachloride. With respect to the exact reaction procedure when using a catalyst or auxiliary, refer ence may be made, for example, to the references assembled by R.C. Larock in Comprehensive Organic Transformations, 1st Edition 1989, VCH Publishers, Inc., p. 537ff and p. 549ff.
The starting compound IV and the reductant are expediently employed in approximately equimolar amounts; to optimize the reaction course, however, it can be advantageous to use one of the two components in excess, approximately up to 10 times the molar amount.
The reaction temperature is dependent on the starting com pound IV used. It is very generally from -78 to approximately 100'C, preferably from -700C to the reflux temperature of the solvent used. c) Alkylation or acylation of a compound of the formula I in which R7 is hydrogen:
Alkylation or I (R7 = H) , I (R7 * H) acylation Suitable acylating agents are, in particular, acid chlorides R7-C1, where R7 is not hydrogen, alkyl, alkenyl or alkynyl.
The free acids R7-oB of the carboxylic acid chlorides, their anhydrides (R7)20 and also isocyanates (for the preparation of I where R7 = alkyl, cycloalkylaminocarbonyl or the phenylaminocarbonyls) are also suitable. When using the free acids, then working in the presence of a condensing agent such as carbonyldiimidazole and dicyclohexyl carbodiimide is recommended, as a rule approximately equimolar amounts of acid and condensing agent being particularly expedient.
The alkylation is expediently carried out in the presence of an inert organic solvent, in particular in an aprotic sol vent, eg. an aliphatic or cyclic ether, preferably 1,2-dimethoxyethane, tetrahydrofuran or dioxane, an aliphatic ketone, preferably acetone, amides, preferably dimethylform amide, or sulfoxides, preferably dimethyl sulfoxide.
For acylation with one of the abovementioned halides, said solvents are likewise suitable. It is particularly advanta geous to work in the presence of a base such as sodium hydride using an aprotic solvent.
The reaction can in general be carried out at a temperature from O C up to the boiling point of the reaction mixture. It is preferably carried out at from 0 to 40 C.
The compounds of the formula III are novel. They can be prepared, eg. by the processes described under method b) or c). Starting materials used for this purpose are compounds of the formula V or III where R7 = hydrogen:
In addition, the compounds of'the formula III can also be prepared from 3-nitrocinnamyl alcohol derivatives of the formula VI
in a manner known per se (cf. eg. DE-A 37 24 399) by hydrogena tin'of the nitro group by means of hydrogen on a metal catalyst such as Raney nickel, palladium or platinum, or by reduction with a reductant, eg. a tin(II) salt or iron.
The compounds of the formula VI are likewise novel and in turn can be prepared analogously to the methods b) or c) described above. Starting materials for this purpose are eg. compounds of the formula VII or VI where R7 = hydrogen:
Additionally, the compounds VI can be prepared in a manner known per se by nitration of allylbenzenes VIII
Further methods which may be mentioned with which compounds of the formula I, III or VI can be prepared would be, for example, alkylation with an oganometallic reagent, the Wittig reaction or the Peterson olefination.
The reactions described above are expediently all carried out at atmospheric pressure or under the autogenous pressure of the respective reaction mixture.
The reaction mixtures are customarily worked up by methods known per se, for example by removing the solvent, partitioning the residue in a mixture of water and a suitable organic solvent and isolating the product from the organic phase.
If not stated otherwise, the starting materials and auxiliaries needed for the preparation of the 3-tetrahydrophthalimidocinnamyl alcohol derivatives I, the 3-aminocinnamyl alcohol derivatives III and the 3-nitrocinnamyl alcohol derivatives VI are known or can be prepared by methods known per se.
The 3-tetrahydrophthalimidocinnamyl alcohol derivatives I, 3-aminocinnamyl alcohol derivatives III and 3-nitrocinnamyl alcohol derivatives VI can be obtained during preparation as isomer mixtures which, however, can be separated into the pure isomers if desired by the methods customary for this purpose such as crystallization or chromatography, also on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting materials.
Alkali metal salts of the 3-tetrahydrophthalimidocinnamyl alcohol derivatives I, the 3-aminocinnamyl alcohol derivatives III and the 3-nitrocinnamyl alcohol derivatives VI can be obtained by treating compounds I, III or VI where R7 = hydrogen with sodium hydroxide, potassium hydroxide, sodium hydride or potassium hydride in aqueous solution or in an organic solvent such as methanol, ethanol, acetone or toluene.
Salt formation normally takes place with sufficient speed even at about 20 C.
The salt can be isolated eg. by precipitating with a suitable inert solvent or by evaporating the solvent.
The salts of the 3-tetrahydrophthalimidocinnamyl alcohol derivatives I, the 3-aminocinnamyl alcohol derivatives III and the 3-nitrocinnamyl alcohol derivatives VI, whose metal ion is not an alkali metal ion, can customarily be prepared by double decomposition of the corresponding alkali metal salt in aqueous solution. In this way, in general metal salts of the compounds I can be prepared which are insoluble in water.
Other metal salts such as manganese, copper, zinc, iron, calcium, magnesium and barium salts can be prepared from the sodium salts in a customary manner, as well as ammonium and phosphonium salts by means of ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
The compounds I and their agriculturally utilizable salts are suitable as herbicides, both as isomer mixtures and in the form of the pure isomers. They can control broad-leaved weeds and grass weeds very effectively in crops such as wheat, rice, maize, soybeans and cotton without significantly damaging the crop plants. This effect occurs especially at low application rates.
Depending on the particular application method, the compounds I or herbicidal compositions containing them can additionally be employed. in a further number of crop plants for eliminating undesired plants. Examples of suitable crops are the following: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinif era and Zea mays.
Moreover, the compounds I can be employed in crops which have been made largely resistant to the action of I by breeding and/or by means of genetic engineering methods.
In addition, the substituted 3-tetrahydrophthalimidocinnamyl alcohol derivatives I are also suitable for the desiccation and/or defoliation of plants.
As desiccants, they are suitable in particular for the desiccation of the above-ground parts of crop plants such as potato, rape, sunflower and soybeans. A completely mechanized harvesting of these important crop plants is thus made possible.
Additionally of economic interest is the facilitation of harvesting, which is made possible by the temporally concentrated dropping or reduction of the power of adhesion to the tree in the case of citrus fruits, olives or other varieties and types of pomes, drupes and indehiscent fruit. The same mechanism, ie. the promotion of the formation of separating tissue between the fruit or leaf and stem part of the plant is also essential for a highly controllable defoliation of useful plants, in particular cotton.
Additionally, the shortening of the time interval in which the individual cotton plants become ripe leads to an enhanced fiber quality after harvesting.
The compounds I and the herbicidal compositions containing them can be applied by spraying, nebulizing, atomizing, scattering or watering, for example in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting compositions, scattering compositions or granules. The application forms depend entirely on the intended use; in any case if possible they should ensure the finest dispersion of the active compounds according to the invention.
Suitable inert auxiliaries for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, and also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraf fins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. amines such as N-methylpyrrolidone and water.
Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by addition of water. For the preparation of emulsions, pastes or oil dispersions, the substrates can be homogenized in water, as such or dissolved in an oil or solvent, by means of wetting agents, adherents, dispersants or emulsifiers.
However, concentrates also consisting of active substance, wetting agent, adherent, dispersant or emulsifier and possibly solvent or oil can be prepared which are suitable for dilution with water.
Suitable surface-active substances are the alkali metal, alkaline earth metal or ammonium salts of aromatic sulfonic acids, eg. lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and also of fatty acids, al kylsulfonates and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and also salts of sulfated hexa-, heptaand octadecanols, and also of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.
Powders, scattering and dusting compositions can be prepared by mixing or joint grinding of the active substances with a solid carrier.
Granules, eg. coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal meal, tree bark, wood and nutshell meal, cellulose powder or other solid carriers.
The concentrations of the active compounds I in the ready-toapply preparations can be varied within wide ranges, for example between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight. The active compounds are in this case employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following formulation examples illustrate the production of such preparations: I. 20 parts by weight of the compound No. I.01 are dissolved in a mixture which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the addition product of from 8 to 10 mol of ethylene oxide to 1 mol of oleic acid N-mono ethanolamide, 5 parts by weight of calcium salt of dodecyl benzenesulfonic acid and 5 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil.
By pouring out the solution and finely dispersing it in 100,000 parts by weight of water an aqueous dispersion is ob tained which contains 0.02% by weight of the active compound.
II. 20 parts by weight of the compound No. I.05 are dissolved in a mixture which consists of 40 parts by weight of cyclohexa none, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 mol of ethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil. By pour ing the solution into 100,000 parts by weight of water and finely dispersing it an aqueous dispersion is obtained which contains 0.02% by weight of the active compound.
111.20 parts by weight of the active compound No. 1.10 are dis solved in a mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280 C and 10 parts by weight of the addition product of 40 mol of ethylene oxide to 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely dispersing it an aqueous disper sion is obtained which contains 0.02% by weight of the active compound.
IV. 20 parts by weight of the active compound No. I.12 are well mixed with 3 parts by weight of the sodium salt of diiso butylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silicic acid gel and ground in a hammer mill. By finely dispersing the mixture in 20,000 parts by weight of water a spray liquor is obtained which contains 0.1% by weight of the active compound.
V. 3 parts by weight of the active compound No. I.20 are mixed with 97 parts by weight of finely divided kaolin. In this manner a dusting composition is obtained which contains 3% by weight of the active compound.
VI. 20 parts by weight of the active compound No. I.09 are intimately mixed with 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
The application of-the active compounds I or of the herbicidal compositions can be carried out pre-emergence or post-emergence.
If the active compounds are less tolerable to certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of the spray equipment such that the leaves of the sensitive crop plants are not affected if possible, while the active compounds reach the leaves of undesired plants growing under them or the uncovered soil surface (post-directed, lay-by).
The application rate of active compound, depending on the control target, time of year, target plants and growth stage, is from 0.001 to 3.0, preferably from 0.01 to 1, kg/ha of active substance (a.s.).
To widen the spectrum of action and to achieve synergistic effects, the substituted 3-tetrahydrophthalimidocinnamyl alcohol derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives which carry eg. a carboxyl or carbimino group in the 2-position, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, aryloxy- or heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others.
Additionally, it may be useful to apply the compounds I on their own or jointly in combination with other herbicides and additionally with other crop protection agents, for example with compositions for controlling pests or phytopathogenic fungi or bacteria.
Also of interest is the miscibility with mineral salt solutions, which are employed for eliminating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
Preparation examples Example 1 4-Chloro-3-(2-chloro-3-hydroxypropenyl)nitrobenzene {No. VI.1) 25 ml of a 1.0 molar solution of diisobutylaluminum hydride in toluene, diluted with 30 ml of tetrahydrofuran, were added dropwise at -70 to -75 C in the course of 30 minutes to a solution of 2.9 g of 4-chloro-3-(2-chloro-2-ethoxycarbonylethenyl)nitrobenzene in 120 ml of tetrahydrofuran. After stirring at -70 - -75 C for 5 hours, the mixture was warmed to 25 C in the course of 12 hours. As complete reaction was still not to be observed, diisobutylaluminum hydride (10.0 ml of a 1.0 M sol. in toluene) was added again at -70 - -75'C. After stirring at -70 - -75 C for a further 5 hours, the reaction mixture was warmed to about 200C again in the course of 12 hours. 50 ml of a 10% hydrochloric acid were then added, after which the mixture was stirred for a further 12 hours. The product was extracted from the separated aqueous phase using 50 ml of toluene. The combined organic phases were washed twice with 50 ml of water, dried over sodium sulfate and finally concentrated. Yield: 2.5 g (as an oil).
Example 2 4-Chloro-3-(3-hydroxy-2-methylpropenyl)nitrobenzene {No. VI.3) 17 g of sodium borohydride, dissolved in 150 ml of water, were added dropwise to a solution of 67.65 g of 4-chloro-3-(2-formylpropenyl)nitrobenzene in 600 ml of methanol. The mixture was then stirred for a further 5 hours, after which 40 ml of conc. hydrochloric acid were added. The low-boiling components were then removed. The residue was taken up using 200 ml of a mixture of ethyl acetate and water (approximately 1:1). The organic phase was separated off from the mixture obtained, washed with water and dried over sodium sulfate. After removing the solvent, 68.3 g of the product were obtained. M.p.: 82-84 C.
Further 3-nitrocinnamyl alcohol derivatives VI which were prepared or can be prepared in the same manner are listed in Table 1 which follows: Table 1
(R1 = Cl; R3 = H)
No. R2 R4 R5 R6 R7 Physical data (m.p. (0C]) VI.1 H Cl H H H oil VI.2 H H H H H 90 - 92 VI.3 H CH3 H H H 82 - 84 Example 3 4-Chloro-3-(2-chloro-3-hydroxypropenyl)aniline {No. III.1} 5.0 g of 4-chloro-3-(2-chloro-3-hydroxypropenyl)nitrobenzene, prepared according to Example 1, were hydrogenated in 150 ml of ethanol using Raney nickel as the catalyst. The product was obtained as an oil.
Example 4 4-Chloro-3-(2-chloro-3-hydroxypropenyl)aniline {No. III.1} A solution of 2.6 g of 4-Chloro-3-(2-chloro-2-ethoxycarbopnyl- ethenyl)nitrobenzene in 30 ml of tetrahydrofuran was added under nitrogen to a suspension of 0.46 g of lithium aluminum hydride in 120 ml of tetrahydrofuran. The reaction mixture was stirred for 2 hours at approximately 20 C and then treated with 50 ml of a 10% strength by weight sodium hydroxide solution. The aqueous phase was then separated off and washed twice with 100 ml of ether each time. The combined organic phases were in turn washed three times with 50 ml of water each time, then dried over sodium sulfate and finally concentrated. Yield: 1.5 g (as an oil).
Further 3-aminocinnamyl alcohol derivatives III which were prepared or can be prepared in the same way are listed in Table 2 which follows: Table 2
III (R1 = chlorine; R3 = hydrogen)
No. R2 R4 R5 RE R7 Physical data (trip. [OCI) III.1 H C1 oil III.2 H CH3 H H H oil Example 5 N-[4-Chloro-3-(2-chloro-3-hydroxypropenyl)phenyl]-3,4,5,6-tetrahydrophthalimide {No. I.06) 2.2 g of 4-chloro-3-(2-chloro-3-hydroxypropenyl)aniline were added to a solution of 1.5 g of 3,4,5,6-tetrahydrophthalic anhydride and 0.5 g of p-toluenesulfonic acid in 200 ml of toluene.
After refluxing the reaction mixture for 20 hours, it was concentrated to dryness. The crude product was purified by means of flash chromatography (eluent: first dichloromethane, then successively dichloromethane/ethyl acetate 9:1). Yield: 1.5 g (as an oil).
Example 6 N-[3-(3-Acetoxy-2-chloropropenyl)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide {No. I.07} 1.09 g of 4-chloro-3-(2-chloro-3-hydroxypropenyl)aniline were added to a solution of 0.76 g of 3,4,5,6-tetrahydrophthalic anhydride in 50 ml of glacial acetic acid. The reaction mixture was then refluxed for 20 hours, after which 50 ml of water were added. The aqueous phase was then separated off and extracted twice with 100 ml of dichloromethane each time. The combined organic phases were dried over sodium sulfate and then concentrated. After flash chromatography (eluent: dichloromethane), in addition to 0.2 g of N-[4-chloro-3-(2-chloro-3-hydroxypro penyl)phenyl]-3,4,5,6-tetrahydrophthalimide (oil), 1.0 g of the desired product was obtained. M.p.: 84 - 87 C.
Example 7 N-[3-(3-Acetoxy-2-chloropropenyl)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide CI.07) 0.9 g of acetyl chloride, dissolved in 20 ml of toluene, was added to a solution of 3.5 g of N-[4-chloro-3-(2-chloro-3-hyd roxypropenyl )phenyl ]-3,4,5, 6-tetrahydrophthalimide and 1.2 g of triethylamine in 80 ml of toluene. After stirring at approximately 20 C for 5 hours, the organic phase was washed three times with 30 ml of water each time, dried over sodium sulfate and concentrated. The product was crystallized by careful addition of diisopropyl ether. Yield: 2.0 g.
Further substituted 3-tetrahydrophthalimidocinnamyl alcohol derivatives of the formula I which were prepared or can be prepared in the same way are listed in Table 3 which follows: Table 3
I (R = chlorine; R = hydrogen)
No. R R4 R5 R6 R7 M.p.[ C] I.01 H CH3 H H -H 66-77 I.02 H CH3 H H -CO-CH3 oil I.03 H CH3 H H -CO-CH2CH3 79-81 I.04 H CH3 H H -CO-NH-CH3 oil I.05 H CH3 H H -CO-NH-C6H5 60-62 I.06 H Cl H H -H oil I.07 H Cl H H -CO-CH3 84-87 I.08 H Cl H H -CO-CH2Cl 99-100 I.09 H Cl H H -SO2-CH3 oil
No. R R4 R5 R6 R7 M.p.[ C] I.10 H Cl H H -CO-C2H5 94-97 I.11 H Cl H H -CO-n-C4H9 63-68 I.12 H Cl H H -CO-i-C3H7 60-64 I.13 H Cl H H -CO-CH2-C(CH3)=CH2 77-86 I.14 H Cl H H -CO-(CH2)2-CO-OCH3 62-67 I.15 H Cl H H -CO-CH2-O-CO-CH3 114-123 I.16 H Cl H H -CO-CH2-S-CO-CH3 111-119 I.17 H Cl H H -CO-cyclopropyl 94-102 I.18 H Cl H H -CO-(tetrahydrothio- 99-102 pyran-3-yl) I.19 H Cl H H -CO-OCH2H5 70-77 I.20 H Cl H H -CO-SCH3 98-105 I.21 H Cl H H -CO-NH-C2H5 103-104 Application examples It was possible to show the herbicidal action of the 3-tetrahydrophthalimidocinnamyl alcohol derivatives of the formula I by means of greenhouse tests: The cultivation containers used were plastic flower pots containing loamy sand with about 3.0% humus as substrate. The seeds of the test plants were sown separately according to species.
In pre-emergence treatment the active compounds suspended or emulsified in water were applied directly after sowing by means of finely dispersing nozzles. The containers were lightly watered to promote germination and growth, and then covered with transparent plastic hoods until the plants had taken root. This covering causes a uniform germination of the test plants if this had not been adversely affected by the active compounds.
For the purpose of post-emergence treatment, the test plants were raised, according to growth form, initially to a growth height of from 3 to 15 cm and only then treated with the active compounds suspended or emulsified in water. For this purpose, the test plants were either sown directly and cultivated in the same containers or they were first raised separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for the post-emergence treatment was 0.125 or 0.063 kg/ha of a.s..
The plants were kept species-specifically at temperatures of 10 25 C or 20 - 350C respectively. The test period ranged from 2 to 4 weeks. During this time the plants were tended and their reaction to the individual treatments was assessed.
Assessment was carried out according to a scale from 0 to 100.
100 here means no emergence of the plants or complete destruction at least of the above-ground parts and 0 means no damage or normal course of growth.
The plants used in the greenhouse tests consist of the following species: Botanical name Common name Galium aparine Catchweed bedstraw Ipomoea subspecies Morning-glory Polygonum persicaria Lady's-thumb Solanum nigrum Black nightshade At an application rate of 0.125 or 0.063 kg/ha of a.s., undesired broad-leaved plants can be very effectively controlled postemergence using the compounds Nos. I.10, I.12 and I.20.
Application examples for the desiccative/defoliant activity of the compounds I: The test plants used were young, 4-leaved (without seed leaves) cotton plants which were raised under greenhouse conditions (rel. atmospheric humidity from 50 to 70%; day/night temperature 27/20'C).
The leaves of the young cotton plants were treated with aqueous preparations of the active compounds (with addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac LF 700, based on the spray mixture) until dripping wet. The amount of water applied was the equivalent of 1000 1/aha. After 13 days, the number of leaves shed the degree of defoliation were determined in %.
No leaf fall occurred in the case of the untreated control plants.

Claims (19)

  1. Claims 1. A 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I
    where the substituents have the following meanings: R1 is halogen, nitro, cyano or trifluoromethyl; R2 is hydrogen or halogen; R3 is hydrogen, cyano, halogen or C1-C6-alkyl; R4 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, Cl-C6-haloalkyl or the phenyl group, which can be unsubstituted or can carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl, R7 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C3-C8-cycloalkyl)carbonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkynyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-haloalkoxy)carbonyl, (C3-C8-cycloalkoxy)carbonyl, (C1-Cs-alkylthio)carbonyl, (C1-Cs-haloalkyl)thiocarbbnyl (C3-C8-cycloalkylthio)carbonyl, (C1-C6-alkyl)aminocarbo nyl, (C1-Cs-haloalkyl)aminocarbonyl, (C3-C-cyclo- alkyl)aminocarbonyl, (C1-Cs-alkyl)carbonyloxy- (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonylthio (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl-(C1-C6 alkyl)carbonyl, (C1-C6-alkylthio)carbonyl-(C1-C6-alkyl) carbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, di- (c1-c6-alkyl) aminosulfonyl, the phenylcarbonyl, phenylamino carbonyl, phenoxycarbonyl or phenylthiocarbonyl group, it being possible for the phenyl ring, if desired, to carry one to three radicals selected from the group consisting of cyano, nitro, halogen, Cl-C-alkyl, Cl-C6-haloalkyl, Cl-C6-alkoxy and (C-C6- alkoxy)carbonyl, or a 3- to 8-membered, saturated, unsaturated or aromatic heterocycle bonded via a carbonyl group and which con tains one to three hetero atoms as ring members, selected from the group consisting of two oxygen atoms, two sulfur atoms, two nitrogen atoms and one nitrogen atom which carries a methyl group, and the agriculturally utilizable salts of the compounds I, where these exist.
  2. 2. A 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I as claimed in claim 1, where Rl is halogen.
  3. 3. A 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I as claimed in claim 1, where R2 is hydrogen, fluorine or chlorine.
  4. 4. A 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I as claimed in claim 1, where R3 is hydrogen.
  5. 5. A 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I as claimed in claim 1, where R4 is halogen or Cl-C4-alkyl.
  6. 6. A 3-tetrahydrophthalimidocinnamyl alcohol derivative identified hereinbefore as any of Nos. I.01 to I.21 inclusive.
  7. 7. The use of the 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I and of the agriculturally utilizable salts of I, as claimed in any of claims 1 to 6, as herbicides.
  8. 8. The use of the 3-tetrahydrophthalimidocinnamyl alcohol derivative of the formula I and of the agriculturally utilizable salts of I, as claimed in any of claims 1 to 6, for the desiccation and/or defoliation of plants.
  9. 9. A herbicidal composition, containing a herbicidally active amount of at least one 3-tetrahydrophthalimi-docinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, and at least one inert liquid and/or solid carrier, and if desired at least one adjuvant.
  10. 10. A composition for the desiccation and/or defoliation of plants, containing an amount of at least one 3-tetra-hydrophthalimidocinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, having desiccant and/or defoliant activity, and at least one inert liquid and/or solid carrier, and if desired at least one adjuvant.
  11. 11. A process for preparing a herbicidally active composition which comprises mixing a herbicidally active amount of at least one 3tetrahydrophthalimidocinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, and at least one inert liquid and/or solid carrier, and if desired at least one adjuvant.
  12. 12. A process for preparing a composition having desiccant and/or defoliant activity, which comprises mixing an amount of at least one 3tetrahydrophthalimidocinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, having desiccant and/or defoliant activity, and at least one inert liquid and/or solid carrier, and if desired at least one adjuvant.
  13. 13. A method of controlling undesired plant growth, which comprises allowing a herbicidally effective amount of at least one 3tetrahydrophthalimidocinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, to act on plants, their habitat or on seed.
  14. 14. A method for the desiccation and/or defoliation of plants, which comprises allowing an amount of at least one 3tetrahydrophthalimidocinnamyl alcohol derivative of the formula I or agriculturally utilizable salt of I, as claimed in any of claims 1 to 6, having defoliant and/or desiccant activity, to act on plants.
  15. 15. A method as claimed in claim 14, wherein cotton is treated.
  16. 16. A 3-aminocinnamyl alcohol derivative of the formula III
    where the substituents have the following meanings: R1 is halogen, nitro, cyano or trifluoromethyl; R2 is hydrogen or halogen; R3 is hydrogen, cyano, halogen or C1-C6-alkyl; R4 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or the phenyl group, which can be unsubstituted or can carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl; R7 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, (C1-C6-alkyl) carbonyl, (C1-Cs-haloalkyl)carbonyl, (C3-C8-cycloalkyl)carbonyl, (C2-C6-alkenyl)carbonyl, (C2-C6-alkynyl ) carbonyl, (C1-Cs-alkoxy) carbonyl, (C1-C6-haloalkoxy)carbonyl, (C3-C8-cycloalkoxy)carbonyl, (C1-C6-alkylthio)carbonyl, (C1-C6-haloalkyl)thiocarbonyl, (C3-C8-cycloalkylthio)carbonyl, (C1-C6-alkyl)aminocarbo nyl, (C1-Cs-haloalkyl) aminocarbonyl, (C3-Cs-cyclo alkyl)aminocarbonyl, (C1-C6-alkyl ) carbonyloxy- (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonylthio (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl-(C1-C6 alkyl)carbonyl, (C1-C6-alkylthiocarbonyl-(C1-C6-alkyl) carbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, di-(C1-C6-alkyl)aminosulfonyl, the phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl or phenylthio carbonyl group, it being possible for the phenyl ring, if desired, to carry one to three radicals selected from the group consisting of cyano, nitro, halogen, Cl-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy) carbonyl, or a 3- to 8-membered, saturated, unsaturated or aromati heterocycle bonded via a carbonyl group and which con tains one to three hetero atoms as ring members, selected from the group consisting of two oxygen atoms, two sulft atoms, two nitrogen atoms and one nitrogen atom which carries a methyl group, and the salts of the compounds III, where these exist.
  17. 17. A 3-nitrocinnamyl alcohol derivative of the formula VI
    where the substituents have the following meanings: R1 is halogen, nitro, cyano or trifluoromethyl; R2 is hydrogen or halogen; R3 is hydrogen, cyano, halogen or C1-C6-alkyl; R4 is hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; R5 and R6 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or the phenyl group, which can be unsubstituted or can carry one to three radicals selected from the group consisting of cyano, nitro, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and (C1-C6-alkoxy)carbonyl; R7 is hydrogen, C1-C6-alkyl, C3-C6-alkenyl; C3-C6-alkynyl, (C1-C6-alkyl)carbonyl, (C1-C6-haloalkyl)carbonyl, (C3-C8-cycloalkyl)carbonyl, (C2-C6-alkenyl)carbonyl, (Cz-Cs-alkynyl)carbonyl, (C1-Cs-alkoxy)carbonyl, (C1-C6-haloalkoxy)carbonyl, (C3-C8-cycloalkoxy)carbonyl, (C1-C6-alkylthio)carbonyl, (C1-C6-haloalkyl)thiocarbonyl (C3-C8-cycloalkylthio)carbonyl, (C1-C6-alkyl)aminocarbo nyl, (Cl-C6-haloalkyl) aminocarbonyl, (C3-C8-cyclo- alkyl)aminocarbonyl, (C1-C6-alkyl ) carbonyloxy- (C1-C6-alkyl)carbonyl, (C1-C6-alkyl)carbonylthio-(C1-C6 alkyl)carbonyl, (C1-C6-alkoxy)carbonyl-(C1-C6-alkyl)carbonyl, (C1 C6-alkylthio)carbonyl-(C1-C6-alkyl)-carbonyl, C1-C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, di-(C1-C6-alkyl)aminosulfonyl, the phenylcarbonyl, phenylaminocarbonyl, phenoxycarbonyl or phenylthio-carbonyl group, it being possible for the phenyl ring, if desired, to carry one to three radicals selected from the group consisting of cyano, nitro, halogen, Cl-C6-alkyl, c-c6- haloalkyl, C1-C6-alkoxy and (C-C6-alkoxy)carbonyl, or a 3- to 8 membered, saturated, unsaturated or aromatic heterocycle bonded via a carbonyl group and which contains one to three hetero atoms as ring members, selected from the group consisting of two oxygen atoms, two sulfur atoms, two nitrogen atoms and one nitrogen atom which carries a methyl group, and the salts of the compounds VI.
  18. 18 3-Aminocinnamyl alcohol derivatives and 3-nitrocinnamyl alcohol derivatives as hereinbefore individually mentioned or referred to.
  19. 19. The use of 3-nitrocinnamyl alcohol and 3-aminocinnamyl alcohol derivatives as claimed in any of claims 16 to 18 for the preparation of 3-tetrahydrophthalimidocinnamyl alcohol derivatives.
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EP0300387A2 (en) * 1987-07-23 1989-01-25 BASF Aktiengesellschaft Phenyl alkenylcarboxylic acids and their esters

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DE3603789A1 (en) * 1986-02-07 1987-08-13 Basf Ag N-SUBSTITUTED 3,4,5,6-TETRAHYDROPHTHALIMIDES
IL82657A0 (en) * 1986-06-03 1987-11-30 Rhone Poulenc Agrochimie N-(5-substituted methylene)phenyl herbicides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0300387A2 (en) * 1987-07-23 1989-01-25 BASF Aktiengesellschaft Phenyl alkenylcarboxylic acids and their esters

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GB9511199D0 (en) 1995-07-26
FR2720743B1 (en) 1997-02-21
FR2720743A1 (en) 1995-12-08
CH689621A5 (en) 1999-07-15
DE19517597A1 (en) 1995-12-07
GB2289893B (en) 1998-04-08

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