WO1997019908A1 - Phenylalanine derivatives, optically active substances, salts or coordination compounds thereof, and their use as fungicides - Google Patents

Phenylalanine derivatives, optically active substances, salts or coordination compounds thereof, and their use as fungicides Download PDF

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Publication number
WO1997019908A1
WO1997019908A1 PCT/JP1996/003484 JP9603484W WO9719908A1 WO 1997019908 A1 WO1997019908 A1 WO 1997019908A1 JP 9603484 W JP9603484 W JP 9603484W WO 9719908 A1 WO9719908 A1 WO 9719908A1
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group
groups
alkyl
phenyl
halo
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PCT/JP1996/003484
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French (fr)
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Naoya Yamamoto
Koji Umimoto
Tsutomu Nishiguchi
Koji Baba
Tatsuo Tabuchi
Masanori Yoshida
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Nihon Nohyaku Co., Ltd.
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Priority to AU77105/96A priority Critical patent/AU7710596A/en
Publication of WO1997019908A1 publication Critical patent/WO1997019908A1/en

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    • 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
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C07C311/19—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to phenylalanine derivatives, salts thereof, their optically active
  • JP-A-49-109536 describes phenylalanine
  • the present invention provides novel fungicides for fruit gardening used for controlling
  • the present invention relates to fungicides for fruit gardening containing as an active ingredient any of phenylalanine derivatives represented by the following general formula (I), salts thereof, and their optically active substances or coordination compounds:
  • R 1 is a hydrogen atom or a (C 1 -C 8 )alkyl group
  • R 2 is a hydrogen atom; a (C 1 -C 8 )alkyl group; a (C 1 -C 6 )alkoxycarbonyl group; an unsubstituted (C 1 -C 6 )alkylcarbonyl group; a substituted (C 1 -C 6 )alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C 1 -C 6 )alkyl group; a substituted phenyl(C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )
  • substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups,
  • halo(C 1 -C 6 )alkoxy groups carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups, halo(C 1 -C 6 )alkoxy groups, carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group
  • R 1 and R 2 being able to be taken together to represent a (C 1 -C 6 )alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group
  • R 3 is a group represented by the formula: OR 4
  • R 4 is a hydrogen atom; a (C 1 -C 18 )alkyl group; a halo(C 1 -C 8 )alkyl group; a (C 2 -C 6 )alkenyl group; a
  • phenyl(C 2 -C 6 )alkenyl group unsubstituted phenyl(C 2 -C 6 )alkenyl group; a substituted phenyl(C 2 -C 6 )alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo ⁇
  • R 5 is a hydrogen atom; a (C 1 -C 8 )alkyl group; a cyclo(C 3 -C 8 )alkyl group; a (C 2 -C 6 )alkenyl group; a
  • R 6 is a hydrogen atom, a (C 1 -C 6 )alkyl group or a (C 2 -C 6 )alkenyl group, R 5 and R 6 being able to be taken together to represent a (C 1 -C 6 )alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C 1 -C 6 )alkylene group being able to form a ring and have on the ring one or more substituents which may be the same or different and are selected from the group consisting of (C 1 -C 6 )alkyl groups, carboxyl
  • R 7 is a hydrogen atom, a (C 1 -C 6 )alkyl group, a cyclo(C 3 -C 8 )alkyl group, a cyclo(C 3 -C 8 )alkyl(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl group, a hydroxy(C 1 -C 6 )alkyl group, an amino(C 1 -C 6 )alkyl group, an unsubstituted phenyl(C 1 -C 6 )alkyl group, or a substituted phenyl(C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms. nitro group, cyano group, (C 1 -C 6 )alkyl groups,
  • R 8 is a hydrogen atom, a
  • (C 1 -C 6 )alkyl group an unsubstituted phenyl(C 1 -C 6 )alkyl group, or a substituted phenyl(C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups, halo(C 1 -C 6 )alkoxy groups, carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1), X is a halogen atom, a nitro group, a cyano group, a hydroxyl group
  • R 1 is a hydrogen atom or a (C 1 -C 8 )alkyl group
  • R 2 is a hydrogen atom; a (C 1 -C 8 )alkyl group; a (C 1 -C 6 ) alkoxycarbonyl group; an unsubstituted (C 1 -C 6 )alkylcarbonyl group; a substituted (C 1 -C 6 )alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C 1 -C 6 )alkyl group; a substituted phenyl (C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )
  • substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups,
  • halo(C 1 -C 6 )alkoxy groups carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups, halo(C 1 -C 6 )alkoxy groups, carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group
  • R 1 and R 2 being able to be taken together to represent a (C 1 -C 6 )alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group
  • R 3' is a group represented by the formula:
  • R 4' is a hydrogen atom, a (C 3 -C 18 )alkyl group; a halo(C 1 -C 8 )alkyl group; a (C 2 -C 6 )alkenyl group; a (C 2 -C 6 )alkynyl group; a cyclo(C 3 -C 8 )alkyl group; a cyclo(C 3 -C 8 )alkyl(C 1 -C 6 )alkyl group; a hydroxy(C 1 -C 6 )alkyl group; a (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl group; a
  • halo(C 1 -C 6 )alkoxy groups carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C 1 -C 6 )alkyl group; or an aromatic heterocyclic (C 1 -C 6 )alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, provided that when each of R 1 and R 2 is a hydrogen atom, R 4' is other than hydrogen atom, tert-butyl group and benzyl group), a group represented by the formula:
  • R 5 is a hydrogen atom; a (C 1 -C 8 )alkyl group; a cyclo(C 3 -C 8 )alkyl group; a (C 2 -C 6 )alkenyl group; a
  • (C 2 -C 6 )alkynyl group an unsubstituted cyano(C 1 -C 6 )alkyl group; a substituted cyano(C 1 -C 6 )alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups and phenyl group; a (C 1 -C 6 )alkoxy (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl group; an unsubstituted amino(C 1 -C 6 )alkyl group; a substituted amino(C 1 -C 6 )alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C 1 -C 6 )alkyl groups; an unsubstituted phenyl group
  • phenoxy(C 1 -C 6 )alkyl group unsubstituted phenoxy(C 1 -C 6 )alkyl group; a substituted phenoxy(C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups,
  • halo(C 1 -C 6 )alkoxy groups carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C 1 -C 6 )alkyloxy group; a substituted phenyl(C 1 -C 6 )alkyloxy group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups, halo(C 1 -C 6 )alkoxy groups, carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylened
  • (C 1 -C 6 )alkyl group or a (C 2 -C 6 )alkenyl group R 5 and R 6 being able to be taken together to represent a (C 1 -C 6 )alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C 1 -C 6 )alkylene group being able to form a ring and have on the ring one or more
  • substituents which may be the same or different and are selected from the group consisting of (C 1 -C 6 )alkyl groups, carboxyl group, ( C 1 -C 6 )alkoxycarbonyl groups, phenyl group, phenyl(C 1 -C 6 )alkyloxycarbonyl groups and phenyl(C 1 -C 6 )alkyloxy groups, provided that R 1 , R 2 , R 5 and R 6 are not hydrogen atoms at the same time, and that when R 1 is a tert-butoxycarbonyl group and R 5 is a benzyl group, R 6 is other than methyl group) or a group represented by the formula:
  • R 7 is a hydrogen atom, a (C 1 -C 6 )alkyl group, a cyclo(C 3 -C 8 )alkyl group, a cyclo(C 3 -C 8 )alkyl(C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl group, a hydroxy(C 1 -C 6 )alkyl group, an amino(C 1 -C 6 )alkyl group, an unsubstituted phenyl(C 1 -C 6 )alkyl group, or a substituted phenyl(C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups,
  • R 8 is a hydrogen atom, a
  • (C 1 -C 6 )alkyl group an unsubstituted phenyl(C 1 -C 6 )alkyl group, or a substituted phenyl (C 1 -C 6 )alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C 1 -C 6 )alkyl groups, halo(C 1 -C 6 )alkyl groups, (C 1 -C 6 )alkoxy groups, halo(C 1 -C 6 )alkoxy groups, carboxyl group, (C 1 -C 6 )alkoxycarbonyl groups, (C 1 -C 6 )alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1, provided that when each of R 1 and R 2 is a hydrogen atom, R 7 is other than methyl group and isobutyl
  • (C 1 -C 18 )alkyl group means a linear or branched alkyl group of 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
  • halo(C 1 -C 6 )alkyl group means a substituted alkyl group of 1 to 6 carbon atoms having as the substituent(s) one or more halogen atoms including fluorine atom, chlorine atom, bromine atom and iodine atom which may be the same or different, for example, trifluoromethyl or tetrafluoroethyl.
  • the cyclo(C 3 -C 6 )alkyl group includes cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.
  • the (C 2 -C 6 )alkenyl group includes alkenyl groups of 2 to 6 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 4-butenyl, etc.
  • the alkynyl group includes alkynyl groups of 2 to 6 carbon atoms, such as ethenyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc.
  • the hydroxy(C 1 -C 6 )alkyl group includes hydroxymethyl, hydroxyethyl, etc.
  • the (C 1 -C 6 )alkoxy- (C 1 -C 6 )alkyl group includes methoxymethyl, ethoxymethyl, etc.
  • the (C 1 -C 6 )alkoxy(C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl group includes methoxymethoxymethyl, ethoxymethoxymethyl, etc.
  • the (C 1 -C 6 )alkylthio(C 1 -C 6 )alkyl group includes methyl- thiomethyl, ethylthiomethyl, etc.
  • the carboxy( C 1 -C 6 )alkyl group includes carboxymethyl, carboxyethyl, etc.
  • the (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 )alkyl group includes methoxycarbonylmethyl, ethoxycarbonylmethyl, etc.
  • the cyano(C 1 -C 6 )alkyl group includes cyanomethyl, 1-cyano-1-methylethyl, etc.
  • the substituted amino(C 1 -C 6 )alkyl group having one or more substituents which may be the same or different and are selected from (C 1 -C 6 )alkyl groups includes methylaminomethyl, methylaminoethyl, dimethylaminomethyl, dimethylaminoethyl, etc.
  • the phenoxy(C 1 -C 6 )alkyl group includes phenoxymethyl. phenoxyethyl, etc.
  • the phenyl (C 1 -C 6 )alkyloxy (C 1 -C 6 )alkyl group includes, for example, substituted alkyl groups having a benzyloxy group, a phenethyloxy group or the like as the substituent.
  • the phenylthio(C 1 -C 6 )alkyl group includes phenylthiomethyl, phenylthioethyl, etc.
  • the aromatic heterocyclic substituted (C 1 -C 6 )alkyl group includes pyridylmethyl, pyrimidylmethyl, thienylmethyl, furylethyl, etc.
  • the phenyl (C 1 -C 6 )alkyloxy group includes benzyloxy, phenethyloxy, etc.
  • the (C 1 -C 6 )alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain may form, for example, a pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino group together with the nitrogen atom to which the
  • (C 1 -C 6 )alkylene group is bonded, and the pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino group may be substituted by a (C 1 -C 6 )alkyl group, a (C 1 -C 6 )alkoxycarbonyl group or a substituted or
  • the phenylalanine derivative of the general formula (I) of the present invention is an amino acid, it has D-form and L-form.
  • the phenylalanine derivative is a dipeptide, it has diastereomers as stereoisomers.
  • the phenylalanine derivative of the general formula (I) of the present invention includes mixtures of the above-mentioned optically active
  • the phenylalanine derivative of the general formula (I) of the present invention may form a salt.
  • the salt there can be usually exemplified salts with organic or inorganic bases or acids, for example, salts formed by addition of an acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, phosphoric acid, perchloric acid, thiocyanic acid, boric acid, formic acid, acetic acid, haloacetic acid, propionic acid, glycolic acid, citric acid, tartaric acid, succinic acid, gluconic acid, lactic acid, malonic acid, fumaric acid,
  • an acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, phosphoric acid, perchloric acid, thiocyanic acid, boric acid, formic acid, acetic acid, haloacetic acid, propionic acid, glycolic acid, citric acid, tartaric acid, succinic acid, glu
  • anthranilic acid benzoic acid, cinnamic acid, p-toluenesulfonic acid, alkylbenzenesulfonic acid,
  • naphthalenesulfonic acid sulfanilic acid or the like
  • salts with organic bases such as amines
  • salts with alkaline earth metal such as sodium, potassium, etc., or metals such as aluminum, etc.
  • alkaline earth metal such as sodium, potassium, etc., or metals such as aluminum, etc.
  • derivative of the general formula (I) of the present invention may form also a metal coordination compound, for example, a coordination compound with zinc, nickel, cobalt, copper, iron or the like.
  • each of R 1 and R 2 is preferably a hydrogen atom or a (C 1 -C 6 )alkyl group, particularly preferably a hydrogen atom
  • R 3 is preferably -OR 4 wherein R 4 is preferably a hydrogen atom, a (C 1 -C 6 )alkyl group, a cyclo(C 3 -C 8 )alkyl group, a phenyl(C 1 -C 6 )alkyl group or a substituted phenyl(C 1 -C 6 )alkyl group, particularly preferably a (C 1 -C 6 )alkyl group or a benzyl group
  • X is preferably a halogen atom.
  • the phenylalanine derivative of the general formula (I) of the present invention can be produced, for example, by any of the processes illustrated below.
  • R 1 , R 2 , R 3 , R 4 , R 5 and m are as defined above
  • R6 is the same as R 5 or is CH(R 7 )(CH 2 ) n COOR 8 (wherein R 7 , R 8 and n are as defined above)
  • R 1' is a benzyloxycarbonyl group or a tert-butoxycarbonyl group
  • Bn is a benzyl group
  • TsOH is p-toluenesulfonic acid
  • Hal is a halogen atom.
  • examples of inert solvent suitable for each production step are water and all inert solvents which are not changed under the reaction conditions.
  • inert solvents are alcohols (e.g. methanol, ethanol, n-propanol and isopropanol), ethers (e.g. diethyl ether, dioxane, diisopropyl ether, tetrahydrofuran, glycol monomethyl ether and glycol dimethyl ether), chlorinated hydrocarbons (e.g. chloroform and dichloromethane), amides (e.g.
  • reaction temperature ranges from -20oC to the boiling point of the solvent.
  • reaction time may be chosen in the range of 0.5 hour to 24 hours.
  • D,L-amino acids can be produced by a process based on the content of Journal of the Chemical Society, 1951, p.2071.
  • p-Toluenesulfonic acid salt of the phenylalanine derivative can be
  • Optically active substances of the phenylalanine derivative can be separated from their racemic modification by a high performance liquid chromatography according to a method described in
  • Optically active substances also can be prepared through optical resolution method using optically active amines or acids as a optically resoluting agent.
  • the starting compound i.e., the compound of the general formula (II) or (V) is a well-known
  • Bn and TsOH are as defined above, Et is an ethyl group, Ac is an acetyl group, Bzo is a benzyloxycarbonyl group, and Boc is a tert-butoxycarbonyl group.
  • the phenylalanine derivatives of the general formula (I) of the present invention are useful as agricultural fungicides and are excellent particularly as fungicides for fruit trees for controlling, for example, Alternaria leaf spot, scab and black spot.
  • the phenylalanine derivative and optionally an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into a suitable preparation form such as a solution, a suspension, an oil formulation, an emulsifiable concentrate, dust, granules, a wettable powder, tablets, pellets, a paste or an aerosol through dissolution, dispersion, suspension, mixing, impregnation, adsorption or sticking.
  • a suitable inert carrier any of solid, liquid and gaseous carriers may be used.
  • soybean flour there can be exemplified soybean flour, wood flour, bark flour, saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction residue of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid clay), talcs (e.g. talc and
  • silica powders or flakes e.g. diatomaceous earth, silica sand, mica, synthetic silicates, and synthetic, high-dispersion silicic acid
  • activated carbon powdered sulfur, powdered pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, calcium phosphate powder and other inorganic or mineral powders
  • chemical fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride and urea
  • carriers may be used alone or as a mixture thereof.
  • the liquid carrier is that which itself has solubility or which is without such solubility but is capable of dispersing an active ingredient with the aid of an adjuvant.
  • cyclohexanone ethers such as ethyl ether, dioxane, tetrahydrofuran and Cellosolve; aliphatic hydrocarbons such as gasoline and kerosene; aromatic hydrocarbons such as benzene, toluene, solvent naphtha and methylnaphthalene; halogenated hydrocarbons such as dichloroethane and chloroform; esters such as ethyl acetate and diisopropyl phthalate; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; and dimethyl sulfoxide.
  • ethers such as ethyl ether, dioxane, tetrahydrofuran and Cellosolve
  • aliphatic hydrocarbons such as gasoline and kerosene
  • aromatic hydrocarbons such as benzene, toluene, solvent naphtha and methylnaphthalene
  • the gaseous carrier includes, for example, Freon, butane gas, dimethyl ether, carbonic acid gas and LPG (liquefied petroleum gas).
  • the following adjuvants can be exemplified. They are used depending upon purposes and used alone or in combination in some cases, or need not be used at all.
  • surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monooleate, alkylaryl sorbitan monolaurates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, ligninsulfonates and higher alcohol sulfate esters.
  • adjuvants such as casein, gelatin, starch, alginic acid, CMC, gum arabic, agar, polyvinyl alcohols, turpentine, bran oil, bentonite, lignin, and sulfite liquor.
  • adjuvants such as waxes, stearic acid and alkyl phosphates.
  • Adjuvants such as naphthalenesulfonic acid condensation products and phosphates may be used as a peptizer for dispersible products.
  • Defoaming agents such as silicon oils may also be added.
  • the applying dosage of the active ingredient, i.e., the phenylalanine derivative is varied depending on various factors such as a purpose, a plant to be treated, a growth state of the plant, tendency of disease occurence, weather, environmental conditions, a preparation form, an
  • the content of the active ingredient may be varied as required. In dusts or granules, the content is usually 0.5 to 20%. In emulsifiable concentrates, suspensions or wettable powders, the content is 0.1 to 90% .
  • the fungicide for fruit gardening containing the compound of the present invention as an active ingredient may be used in admixture with other ingredients
  • the desired effect of the present inventive fungicide for fruit gardening containing the compound of the present invention as an active ingredient can be obtained by applying the fungicide at a season at which the diseases are expected to occur, before their occurrence or at the time when their occurrence is confirmed.
  • Typical examples of the phenylalanine derivative of the general formula (I) of the present invention are given in Table 1 but they are not intended in any way to limit the scope of the present invention.
  • Et, Bn, Bzo, Boc and TsOH are as defined above, Me is a methyl group, i-Pr is an isopropyl group, i-Bu is an isobutyl group, t-Bu is a tert-butyl group, Ph is a phenyl group, Bz is a benzoyl group, and DSA is a dodecylbenzenesulfonic acid.
  • Q 1 through Q 7 denote the following substituents:
  • Table 2 shows NMR data of the compounds having a physical property expressed by the word "paste" in Table 1.
  • reaction mixture was poured into ice water and a saturated aqueous sodium hydrogencarbonate solution was added, and the desired compound was extracted with ethyl acetate.
  • the organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 0.26 g of crystals of the desired compound .
  • Each compound of the invention 50 parts Xylene 40 parts
  • An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect dissolution.
  • Granules were prepared by mixing the above ingredients uniformly, and kneading the resulting mixture together with a suitable amount of water, followed by granulation and drying.
  • Formulation Example 5
  • Each compound of the invention 20 parts Mixture of kaolin and synthetic, 75 parts high-dispersion silicic acid
  • a wettable powder was prepared by mixing uniformly and grinding the above ingredients.
  • Potted apple plants were sufficiently sprayed with a 200 ppm liquid chemical containing each compound of the present invention as active ingredient. Twentyfour hours after the spraying, the plants were

Abstract

The present invention provides a phenylalanine derivative represented by general formula (I), [wherein R1 is H or an alkyl group, R2 is H, an alkyl group, an alkoxycarbonyl group, a phenylalkyl group or the like, R?1 and R2¿ being able to be taken together to represent an alkylene group which may contain O or N between adjacent carbon atoms of the carbon chain, or a phthaloyl group, R?3 is OR4, N(R5)-R6¿ or NHCH(R7)(CH2)nCOOR?8 (R4, R5, R6, R7 and R8¿ are as defined in the specification], a salt thereof, their optically active substances or coordination compounds, and a novel fungicide for fruit gardening containing any of them as an active ingredient.

Description

DESCRIPTION
PHENYLALANINE DERIVATIVES, OPTICALLY ACTIVE SUBSTANCES, SALTS OR COORDINATION COMPOUNDS THEREOF, AND THEIR USE AS FUNGICIDES
FIELD OF THE INVENTION
The present invention relates to phenylalanine derivatives, salts thereof, their optically active
substances or coordination compounds, fungicides for fruit gardening containing any of these compounds as an active ingredient, and a method for application of the fungicides.
BACKGROUND ART
JP-A-49-109536 describes phenylalanine
derivatives as effective in controlling rice blast and sheath blight but does not describe their effect against diseases in fruit gardening.
SUMMARY OF THE INVENTION
Apple alternaria leaf spot and scab, pear
black spot, etc. are typical diseases to be controlled in fruit growing. The present invention provides novel fungicides for fruit gardening used for controlling
these diseases in fruit growing. DISCLOSURE OF THE INVENTION
The present invention relates to fungicides for fruit gardening containing as an active ingredient any of phenylalanine derivatives represented by the following general formula (I), salts thereof, and their optically active substances or coordination compounds:
Figure imgf000004_0001
[wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl (C1-C6)alkyloxycarbonyl group; or a substituted phenyl(C1-C6)alkyloxycarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, R3 is a group represented by the formula: OR4
(wherein R4 is a hydrogen atom; a (C1-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; a cyclo(C3-C8)alkyl group; a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a (C1-C6)alkylthio(C1-C6)alkyl group; a carboxy(C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl ( C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from
(C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylene¬dioxy groups, phenyl group and phenoxy group; an
unsubstituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo¬
(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio¬(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenyl carbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo¬(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom), a group represented by the formula:
N(R5)-R6
(wherein R5 is a hydrogen atom; a (C1-C8)alkyl group; a cyclo(C3-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6) alkynyl group; an unsubstituted cyano(C1-C6)alkyl group; a substituted cyano(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups and phenyl group; a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C1-C6)alkyl groups; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6) alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxy group; a substituted phenyl(C1-C6)alkyloxy group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; or a guanidyl(C1-C6)alkyl group, and R6 is a hydrogen atom, a (C1-C6)alkyl group or a (C2-C6)alkenyl group, R5 and R6 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C1-C6)alkylene group being able to form a ring and have on the ring one or more substituents which may be the same or different and are selected from the group consisting of (C1-C6)alkyl groups, carboxyl group,
(C1-C6)alkoxycarbonyl groups, phenyl group, phenyl¬
(C1-C6)alkyloxycarbonyl groups and phenyl(C1-C6)alkyloxy groups) or a group represented by the formula:
NHCH(R7)(CH2)nCOOR8
(wherein R7 is a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8)alkyl group, a cyclo(C3-C8)alkyl(C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a hydroxy(C1-C6)alkyl group, an amino(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms. nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R8 is a hydrogen atom, a
(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1), X is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a (C1-C6)alkyl group, a
halo(C1-C6)alkyl group or a (C1-C6)alkoxy group, and m is an integer of 1 or 2], a method for application of the fungicides for fruit gardening, and novel compounds included in the compounds of the general formula (I) and not known in any literature, phenylalanine derivatives represented by the general formula (Ia):
Figure imgf000011_0001
[wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6) alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an
unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl (C1-C6)alkyloxycarbonyl group; or a substituted phenyl (C1-C6)alkyloxycarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, and R3' is a group represented by the formula:
OR4 '
(wherein R4' is a hydrogen atom, a (C3-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a (C2-C6)alkynyl group; a cyclo(C3-C8)alkyl group; a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)-alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a (C1-C6)¬alkylthio(C1-C6)alkyl group; a carboxy(C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from
(C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl (C1-C6)alkyl group; a substituted phenyl (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, ( C1-C6 )alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenylcarbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, provided that when each of R1 and R2 is a hydrogen atom, R4' is other than hydrogen atom, tert-butyl group and benzyl group), a group represented by the formula:
N(R5)-R6
(wherein R5 is a hydrogen atom; a (C1-C8)alkyl group; a cyclo(C3-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; an unsubstituted cyano(C1-C6)alkyl group; a substituted cyano(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups and phenyl group; a (C1-C6)alkoxy (C1-C6)alkoxy(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C1-C6)alkyl groups; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)¬alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an
unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxy group; a substituted phenyl(C1-C6)alkyloxy group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; or a guanidyl- (C1-C6)alkyl group, and R6 is a hydrogen atom, a
(C1-C6)alkyl group or a (C2-C6)alkenyl group, R5 and R6 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C1-C6)alkylene group being able to form a ring and have on the ring one or more
substituents which may be the same or different and are selected from the group consisting of (C1-C6)alkyl groups, carboxyl group, ( C1-C6)alkoxycarbonyl groups, phenyl group, phenyl(C1-C6)alkyloxycarbonyl groups and phenyl(C1-C6)alkyloxy groups, provided that R1, R2, R5 and R6 are not hydrogen atoms at the same time, and that when R1 is a tert-butoxycarbonyl group and R5 is a benzyl group, R6 is other than methyl group) or a group represented by the formula:
NHCH(R7)(CH2)nCOOR8
(wherein R7 is a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8)alkyl group, a cyclo(C3-C8)alkyl(C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a hydroxy(C1-C6)alkyl group, an amino(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R8 is a hydrogen atom, a
(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1, provided that when each of R1 and R2 is a hydrogen atom, R7 is other than methyl group and isobutyl group, and that when R1 is a benzyloxycarbonyl group, R7 is a hydrogen atom and n is 0, R8 is other than ethyl group)],
salts thereof, and optically active substances or coordination compounds of the phenylalanine derivatives or salts.
In the present specification, the term
" (C1-C18)alkyl group" means a linear or branched alkyl group of 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,
1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl or the like. The term "halo(C1-C6)alkyl group" means a substituted alkyl group of 1 to 6 carbon atoms having as the substituent(s) one or more halogen atoms including fluorine atom, chlorine atom, bromine atom and iodine atom which may be the same or different, for example, trifluoromethyl or tetrafluoroethyl. The cyclo(C3-C6)alkyl group includes cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. The (C2-C6)alkenyl group includes alkenyl groups of 2 to 6 carbon atoms, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 4-butenyl, etc. The alkynyl group includes alkynyl groups of 2 to 6 carbon atoms, such as ethenyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc. The hydroxy(C1-C6)alkyl group includes hydroxymethyl, hydroxyethyl, etc. The (C1-C6)alkoxy- (C1-C6)alkyl group includes methoxymethyl, ethoxymethyl, etc. The (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group includes methoxymethoxymethyl, ethoxymethoxymethyl, etc. The (C1-C6)alkylthio(C1-C6)alkyl group includes methyl- thiomethyl, ethylthiomethyl, etc. The carboxy( C1-C6 )alkyl group includes carboxymethyl, carboxyethyl, etc. The (C1-C6)alkoxycarbonyl(C1-C6)alkyl group includes methoxycarbonylmethyl, ethoxycarbonylmethyl, etc. The cyano(C1-C6)alkyl group includes cyanomethyl, 1-cyano-1-methylethyl, etc. The substituted amino(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from (C1-C6)alkyl groups includes methylaminomethyl, methylaminoethyl, dimethylaminomethyl, dimethylaminoethyl, etc. The phenoxy(C1-C6)alkyl group includes phenoxymethyl. phenoxyethyl, etc. The phenyl (C1-C6)alkyloxy (C1-C6)alkyl group includes, for example, substituted alkyl groups having a benzyloxy group, a phenethyloxy group or the like as the substituent. The phenylthio(C1-C6)alkyl group includes phenylthiomethyl, phenylthioethyl, etc. The aromatic heterocyclic substituted (C1-C6)alkyl group includes pyridylmethyl, pyrimidylmethyl, thienylmethyl, furylethyl, etc. The phenyl (C1-C6)alkyloxy group includes benzyloxy, phenethyloxy, etc. The (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain may form, for example, a pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino group together with the nitrogen atom to which the
(C1-C6)alkylene group is bonded, and the pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino group may be substituted by a (C1-C6)alkyl group, a (C1-C6)alkoxycarbonyl group or a substituted or
unsubstituted benzyl group.
When the phenylalanine derivative of the general formula (I) of the present invention is an amino acid, it has D-form and L-form. When the phenylalanine derivative is a dipeptide, it has diastereomers as stereoisomers. The phenylalanine derivative of the general formula (I) of the present invention includes mixtures of the above-mentioned optically active
substances or diastereomers, and the individual
optically active substances. The phenylalanine derivative of the general formula (I) of the present invention may form a salt. As the salt, there can be usually exemplified salts with organic or inorganic bases or acids, for example, salts formed by addition of an acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, phosphoric acid, perchloric acid, thiocyanic acid, boric acid, formic acid, acetic acid, haloacetic acid, propionic acid, glycolic acid, citric acid, tartaric acid, succinic acid, gluconic acid, lactic acid, malonic acid, fumaric acid,
anthranilic acid, benzoic acid, cinnamic acid, p-toluenesulfonic acid, alkylbenzenesulfonic acid,
naphthalenesulfonic acid, sulfanilic acid or the like; salts with organic bases such as amines; and salts with alkaline earth metal such as sodium, potassium, etc., or metals such as aluminum, etc. The phenylalanine
derivative of the general formula (I) of the present invention may form also a metal coordination compound, for example, a coordination compound with zinc, nickel, cobalt, copper, iron or the like.
Preferable examples of the substituents of the phenylalanine derivative represented by the general formula (I) of the present invention are as follows: each of R1 and R2 is preferably a hydrogen atom or a (C1-C6)alkyl group, particularly preferably a hydrogen atom, R3 is preferably -OR4 wherein R4 is preferably a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8)alkyl group, a phenyl(C1-C6)alkyl group or a substituted phenyl(C1-C6)alkyl group, particularly preferably a (C1-C6)alkyl group or a benzyl group, and X is preferably a halogen atom.
The phenylalanine derivative of the general formula (I) of the present invention can be produced, for example, by any of the processes illustrated below.
Scheme I
Process A
Figure imgf000023_0001
Process B
Figure imgf000023_0002
Process C
Figure imgf000024_0001
wherein R1, R2, R3, R4, R5 and m are as defined above, R6 is the same as R5 or is CH(R7)(CH2)nCOOR8 (wherein R7, R8 and n are as defined above), R1' is a benzyloxycarbonyl group or a tert-butoxycarbonyl group, Bn is a benzyl group, TsOH is p-toluenesulfonic acid, and Hal is a halogen atom.
In this production process, examples of inert solvent suitable for each production step are water and all inert solvents which are not changed under the reaction conditions. Preferable examples of such inert solvents are alcohols (e.g. methanol, ethanol, n-propanol and isopropanol), ethers (e.g. diethyl ether, dioxane, diisopropyl ether, tetrahydrofuran, glycol monomethyl ether and glycol dimethyl ether), chlorinated hydrocarbons (e.g. chloroform and dichloromethane), amides (e.g. dimethylformamide, dimethylamine and hexamethyl-phosphorylamide), glacial acetic acid, dimethyl sulfoxide, acetonitrile and pyridine. In each reaction, although one of the reactants may be used in excess, it is preferably used in an amount of 1
equivalent per equivalent of the other. The reaction temperature ranges from -20ºC to the boiling point of the solvent. The reaction time may be chosen in the range of 0.5 hour to 24 hours.
Of the phenylalanine derivatives represented by the general formula (I), D,L-amino acids can be produced by a process based on the content of Journal of the Chemical Society, 1951, p.2071. p-Toluenesulfonic acid salt of the phenylalanine derivative can be
produced by a process based on the content of
"Fundamentals and Practice of Peptide Synthesis", p. 43, Maruzen Co., Ltd. Optically active substances of the phenylalanine derivative can be separated from their racemic modification by a high performance liquid chromatography according to a method described in
Journal of Chromatography, Vol. 405, p. 145 (1887).
Optically active substances also can be prepared through optical resolution method using optically active amines or acids as a optically resoluting agent.
The starting compound, i.e., the compound of the general formula (II) or (V) is a well-known
substance and can be produced, for example, by the following conventional process described in Journal of the Chemical Society, 1951, p.2071. Scheme II
Figure imgf000026_0001
wherein Bn and TsOH are as defined above, Et is an ethyl group, Ac is an acetyl group, Bzo is a benzyloxycarbonyl group, and Boc is a tert-butoxycarbonyl group.
The phenylalanine derivatives of the general formula (I) of the present invention are useful as agricultural fungicides and are excellent particularly as fungicides for fruit trees for controlling, for example, Alternaria leaf spot, scab and black spot.
For formulating the phenylalanine derivative of the general formula (I) of the present invention into an agricultural and horticultural fungicide, the phenylalanine derivative and optionally an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into a suitable preparation form such as a solution, a suspension, an oil formulation, an emulsifiable concentrate, dust, granules, a wettable powder, tablets, pellets, a paste or an aerosol through dissolution, dispersion, suspension, mixing, impregnation, adsorption or sticking. As the inert carrier, any of solid, liquid and gaseous carriers may be used. As the solid carrier, there can be exemplified soybean flour, wood flour, bark flour, saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction residue of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid clay), talcs (e.g. talc and
pyrophyllite), silica powders or flakes (e.g. diatomaceous earth, silica sand, mica, synthetic silicates, and synthetic, high-dispersion silicic acid), activated carbon, powdered sulfur, powdered pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, calcium phosphate powder and other inorganic or mineral powders, chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride and urea), and compost. These
carriers may be used alone or as a mixture thereof.
The liquid carrier is that which itself has solubility or which is without such solubility but is capable of dispersing an active ingredient with the aid of an adjuvant. The following are examples of the liquid carrier and can be used alone or as a mixture thereof. Water; alcohols such as methanol, isopropanol and ethylene glycol; ketones such as acetone and
cyclohexanone; ethers such as ethyl ether, dioxane, tetrahydrofuran and Cellosolve; aliphatic hydrocarbons such as gasoline and kerosene; aromatic hydrocarbons such as benzene, toluene, solvent naphtha and methylnaphthalene; halogenated hydrocarbons such as dichloroethane and chloroform; esters such as ethyl acetate and diisopropyl phthalate; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile; and dimethyl sulfoxide.
The gaseous carrier includes, for example, Freon, butane gas, dimethyl ether, carbonic acid gas and LPG (liquefied petroleum gas).
As the adjuvant, the following adjuvants can be exemplified. They are used depending upon purposes and used alone or in combination in some cases, or need not be used at all. To emulsify, disperse, dissolve and/or wet an active ingredient, there can be used surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monooleate, alkylaryl sorbitan monolaurates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, ligninsulfonates and higher alcohol sulfate esters.
Further, to stabilize the dispersion of an active ingredient, tackify it and/or bind it, there may be used adjuvants such as casein, gelatin, starch, alginic acid, CMC, gum arabic, agar, polyvinyl alcohols, turpentine, bran oil, bentonite, lignin, and sulfite liquor.
To improve the flowability of a solid product, there may be used adjuvants such as waxes, stearic acid and alkyl phosphates.
Adjuvants such as naphthalenesulfonic acid condensation products and phosphates may be used as a peptizer for dispersible products.
Defoaming agents such as silicon oils may also be added.
When the phenylalanine derivative of the general formula (I) of the present invention is applied as a fungicide for fruit gardening, the applying dosage of the active ingredient, i.e., the phenylalanine derivative is varied depending on various factors such as a purpose, a plant to be treated, a growth state of the plant, tendency of disease occurence, weather, environmental conditions, a preparation form, an
application method, an application site and an application time. It is properly chosen in the range of 0.1 g to 1 kg per 10 ares.
The content of the active ingredient may be varied as required. In dusts or granules, the content is usually 0.5 to 20%. In emulsifiable concentrates, suspensions or wettable powders, the content is 0.1 to 90% .
The fungicide for fruit gardening containing the compound of the present invention as an active ingredient may be used in admixture with other
agricultural and horticultural fungicides in order to expand both spectrum of controllable diseases and the period of time when effective applications are possible or to reduce the dosage. The desired effect of the present inventive fungicide for fruit gardening containing the compound of the present invention as an active ingredient can be obtained by applying the fungicide at a season at which the diseases are expected to occur, before their occurrence or at the time when their occurrence is confirmed.
Typical examples of the phenylalanine derivative of the general formula (I) of the present invention are given in Table 1 but they are not intended in any way to limit the scope of the present invention. In Table 1, Et, Bn, Bzo, Boc and TsOH are as defined above, Me is a methyl group, i-Pr is an isopropyl group, i-Bu is an isobutyl group, t-Bu is a tert-butyl group, Ph is a phenyl group, Bz is a benzoyl group, and DSA is a dodecylbenzenesulfonic acid. Q1 through Q7 denote the following substituents:
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0003
,
Figure imgf000031_0002
, , .
Figure imgf000031_0004
General formula (I):
Figure imgf000031_0005
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Table 2 shows NMR data of the compounds having a physical property expressed by the word "paste" in Table 1.
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
EXAMPLES OF THE INVENTION
The present invention is concretely illustrated with the following examples, formulation examples and test examples, which should not be
construed as limiting the scope of the invention.
Example 1
Production of N-(p-toluenesulfonyl)-4-fluorophenylalanine (compound 1)
In 10 ml of ethanol was dissolved 0.35 g of N-(p-toluenesulfonyl)-4-fluorophenylalanine benzyl ester, followed by adding thereto 0.08 g of 10% Pd-C, and the resulting mixture was subjected to hydrogenation at ordinary temperature and atmospheric pressure. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure. Ether was added to the concentrate to effect crystallization and the crystals were filtered and then washed with ether to obtain 0.24 g of crystals of the desired compound.
Physical property: m.p. 142 - 143ºC.
Yield: 87%.
Example 2
Production of 4-fluorophenylalanine cyclo-hexylamide acetate (compound 6)
In a mixed solvent of ethanol, acetic acid and water in volumes of 10 ml, 1 ml and 1 ml, respectively, was dissolved 0.45 g of N-(benzyloxycarbonyl)-4-fluorophenylalanine cyclohexylamide, followed by adding thereto 0.18 g of 10% Pd-C, and the resulting mixture was subjected to hydrogenation at ordinary temperature and atmospheric pressure. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure. Hexane was added to the concentrate to effect crystallization and the crystals were filtered and then washed with hexane to obtain 0.26 g of crystals of the desired compound.
Physical property: m.p. 115 - 116ºC.
Yield: 72%.
Example 3
Production of N-( tert-butoxycarbonyl)-4-fluorophenylalanine benzylamide (compound 9)
In 15 ml of dried tetrahydrofuran were
dissolved 0.52 g of N-(tert-butoxycarbonyl)-4-fluorophenylalanine and 0.26 ml of triethylamine, followed by adding thereto 0.25 ml of isobutyl chloroformate under ice-cooling. After stirring for 30 minutes, 0.21 ml of benzylamine was added and the resulting mixture was stirred at room temperature for another 3 hours. After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 0.49 g of crystals of the desired compound.
Physical property: m.p. 169 - 170ºC.
Yield: 72%. Example 4
Production of 4-fluorophenylalanine benzylamide (compound 10)
To 0.40 g of N-(tert-butoxycarbonyl)-4-fluorophenylalanine benzylamide was added 5 ml of trifluoroacetic acid, and the resulting mixture was stirred at room temperature for 1 hour. After
completion of the reaction, the reaction mixture was poured into ice water and a saturated aqueous sodium hydrogencarbonate solution was added, and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 0.26 g of crystals of the desired compound .
Physical property: m.p. 67 - 68ºC.
Yield: 91%.
Example 5
Production of N-(benzyloxycarbonyl)-4-fluorophenylalanine cyclohexylamide (compound 19)
In 15 ml of dried tetrahydrofuran were
dissolved 1.0 g of N-(benzyloxycarbonyl)-4-fluorophenyl- alanine and 0.44 ml of triethylamine, followed by adding thereto 0.42 ml of isobutyl chloroformate under ice-cooling. After stirring for 30 minutes, 0.4 ml of cyclohexylamine was added and the resulting mixture was stirred at room temperature for another 3 hours. After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 0.78 g of crystals of the desired compound.
Physical property: m.p. 183 - 184ºC.
Yield: 62%.
Example 6
Production of N-(p-toluenesulfonyl)-4-fluorophenylalanine benzyl ester (compound 23)
In 30 ml of dried dichloromethane were
dissolved 1.5 g of 4-fluorophenylalanine benzyl ester p-toluenesulfonate and 1.00 ml of triethylamine, followed by adding thereto 0.71 g of p-toluenesulfonyl chloride under ice-cooling. After stirring at room temperature for 24 hours, the reaction mixture was poured into ice water and the desired compound was extracted with dichloromethane. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with ether to obtain 0.65 g of crystals of the desired compound. Physical property: m.p. 130 - 131ºC.
Yield: 45%.
Example 7
Production of N-(4-tert-butylbenzyl)-4-fluorophenylalanine benzyl ester (compound 27)
In 15 ml of tetrahydrofuran were dissolved 1.0 g of 4-fluorophenylalanine benzyl ester p-toluenesulfonate and 0.65 ml of triethylamine, followed by adding thereto 0.53 g of 4-tert-butylbenzyl bromide, and the resulting mixture was stirred at room temperature for 24 hours. After completion of the reaction, the desired compound was extracted with ethyl acetate, and the organic layer was washed with a saturated aqueous sodium hydrogencarbonate solution, dried, and then concentrated under reduced pressure. The oil thus obtained was purified by a silica gel column chromatography to obtain 0.18 g of the desired compound.
Physical property: paste. Yield: 19%.
NMR[CDCl3/TMS, δ values (ppm)]
1.31(9H, s), 2.93(2H, m), 3.55(1H, t),
3.60(1H, d), 3.76(1H, d), 5.07(2H, m),
6.90(2H, m), 7.05(2H, m), 7.14(2H, d),
7.24(2H, m), 7.30(2H, d), 7.35(3H, m).
Example 8
Production of N-(benzyloxycarbonyl)-4-fluorophenylalanine isoamyl ester (compound 30) In 15 ml of dried dichloromethane were
dissolved 1.00 g of N-(benzyloxycarbonyl)-4-fluorophenylalanine, 0.07 g of dimethylaminopyridine and
0.69 ml of isoamyl alcohol, followed by adding thereto 0.66 g of 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride under ice-cooling. After stirring at room temperature for 24 hours, the reaction mixture was poured into ice water, and the desired compound was extracted with ethyl acetate. The organic layer was washed with 1N HCl, dried, and then concentrated under reduced pressure, and the oil thus obtained was purified by a silica gel column chromatography to obtain 1.16 g of the desired compound.
Physical property: paste. Yield: 95%.
NMR[CDCl3/TMS, δ values (ppm)]
0.89(6H, m), 1.12(0.5H, m), 1.32(0.5H, m), 1.48(1H, m), 1.60(1H, m), 3.09(2H, m),
3.93(1H, m), 4.11(1H, m), 4.62(1H, m),
5.09(2H, m), 5.22(1H, d), 6.95(2H, m),
7.06(2H, m), 7.35(5H, m).
Example 9
Production of N-(benzyloxycarbonyl)-4-fluorophenylalanyl-piperidine-4-carboxylic acid
(compound 40)
In 6 ml of aqueous ethanol was dissolved 0.5 g of ethyl N-(benzyloxycarbonyl)-4-fluorophenylalanyl-piperidine-4-carboxylate, followed by adding thereto 0.05 g of lithium hydroxide, and the resulting mixture was stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was poured into ice water and acidified with 1N HCl, and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with ether to obtain 0.44 g of the desired compound.
Physical property: m.p. 180 - 181ºC.
Yield: 94%.
Example 10
Production of N-(benzyloxycarbonyl)-4-fluorophenylalanyl-valine benzyl ester (compound 44)
In 40 ml of dried tetrahydrofuran were
dissolved 2.0 g of N-(benzyloxycarbonyl)-4-fluorophenylalanine and 2.62 ml of triethylamine, and 0.83 ml of isobutyl chloroformate was added and then stirred for 30 minutes. Then, 2.39 g of valine benzyl ester p-toluenesulfonate was added, and the resulting mixture was stirred at room temperature for another 24 hours. After completion of the reaction, the reaction mixture was poured into ice water and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 0.63 g of crystals of the desired compound. Physical property: m.p. 120 - 122ºC.
Yield: 20%.
Example 11
Production of 4-fluorophenylalanyl-valine (compound 45)
In a mixed solvent of ethanol, acetic acid and water in volumes of 20 ml, 1 ml and 1 ml, respectively, was dissolved 1.00 g of N-(benzyloxycarbonyl)-4-fluorophenylalanyl-valine benzyl ester, followed by adding thereto 0.20 g of 10% Pd-C, and the resulting mixture was subjected to hydrogenation at ordinary temperature and atmospheric pressure. After completion of the reaction, the catalyst was filtered off and the filtrate was concentrated under reduced pressure. Ether was added to the concentrate to effect crystallization and the crystals were filtered and then washed with hexane to obtain 0.30 g of the desired compound.
Physical property: m.p. 142 - 145ºC.
Yield: 54%. Example 12
Production of 4-fluorophenylalanine (D,L-amino acid) (compound 168)
In 100 ml of ethanol was dissolved 1.44 g of metallic sodium, followed by adding thereto 12.38 g of diethyl acetamidomalonate and 8.24 g of 4-fluorobenzyl chloride, and the resulting mixture was stirred with heating for 7 hours. After completion of the reaction, ice water was added to the reaction mixture and the crystals precipitated were filtered and washed with water to obtain 14.0 g of crystals. The crystals obtained were dissolved in 50 ml of a 47% aqueous hydrobromic acid solution and the resulting solution was stirred with heating for 8 hours. The reaction solution was neutralized with concentrated aqueous ammonia under ice-cooling, and the crystals thus precipitated were filtered and then washed with water to obtain 4.9 g of crystals of the desired compound.
Physical property: m.p. 253 - 257ºC (decomp.).
Yield: 47%.
Example 13
Production of 4-fluorophenylalanine benzyl ester p-toluenesulfonate (TsOH salt, compound 181)
In 60 ml of toluene, 11.0 g of 4-fluorophenylalanine, 80 ml of benzyl alcohol and 12.6 g of p-toluenesulfonic acid monohydrate were stirred with heating for 6 hours by using a Dean-Stark trap. After completion of the reaction, 100 ml of ether was added to the reaction mixture and the crystals precipitated were filtered and then washed with hexane to obtain 23.2 g of crystals of the desired compound.
Physical property: m.p. 158 - 159ºC.
Yield: 87%. Reference Example 1
Production of N-(benzyloxycarbonyl)-4-fluorophenylalanine
In 30 ml of a 2M aqueous sodium hydroxide solution was dissolved 4.9 g of 4-fluorophenylalanine, followed by adding dropwise thereto 5.0 g of benzyloxycarbonyl chloride under ice-cooling, and the resulting solution was stirred at 10ºC for 3 hours. The reaction solution was washed with ether, after which the aqueous layer was acidified with 1N HCl and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with ether to obtain 7.13 g of crystals of the desired compound.
Physical property: m.p. 120 - 122ºC.
Yield: 84%.
Reference Example 2
Production of N-(tert-butoxycarbonyl)-4-fluorophenylalanine
in 80 ml of a 1M aqueous sodium hydroxide solution was dissolved 10.1 g of 4-fluorophenylalanine, followed by adding dropwise thereto 13.2 g of di-tert-butyl dicarbonate under ice-cooling, and the resulting solution was stirred overnight at room temperature. The reaction solution was washed with ether, after which the aqueous layer was acidified with citric acid and the desired compound was extracted with ethyl acetate. The organic layer was dried and then concentrated under reduced pressure, and the crystals thus obtained were washed with hexane to obtain 4.9 g of the desired compound.
Physical property: m.p. 253 - 257ºC (decomp.).
Yield: 47%.
Formulation examples are described below. In the formulation examples, parts are all by weight.
Formulation Example 1
Each compound of the invention 50 parts Xylene 40 parts
Mixture of polyoxyethylene 10 parts nonylphenyl ether and
alkylbenzenesulfonate
An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect dissolution.
Formulation Example 2
Each compound of the invention 0.5 part Xylene 0.8 part
Illuminating kerosine 98.7 parts An oil formulation was prepared by mixing uniformly the above ingredients to effect dissolution. Formulation Example 3
Each compound of the invention 3 parts Clay powder 82 parts
Diatomaceous earth powder 15 parts A dust was prepared by mixing uniformly and grinding the above ingredients.
Formulation Example 4
Each compound of the invention 5 parts Mixed powder of bentonite and clay 90 parts Calcium stearate 1 part
Granules were prepared by mixing the above ingredients uniformly, and kneading the resulting mixture together with a suitable amount of water, followed by granulation and drying. Formulation Example 5
Each compound of the invention 20 parts Mixture of kaolin and synthetic, 75 parts high-dispersion silicic acid
Mixture of polyoxyethylene 5 parts nonylphenyl ether and calcium
alkylbenzenesulfonate
A wettable powder was prepared by mixing uniformly and grinding the above ingredients.
Test Example 1
Controlling effect on apple Alternaria leaf spot The leaves of apple plants were sufficiently sprayed with a 200 ppm liquid chemical containing each compound of the present invention as active ingredient, and then inoculated with a suspension of spores of Alternaria leaf spot fungus (Alternaria mali) by spaying. The plants were placed in a moist chamber at 15ºC for 1 day and then in a room thermostated at 15ºC for 3 days, to cause the disease sufficiently. Thereafter, the lesion area of each leaf was measured and then compared with that on the untreated plot, whereby the effect was judged according to the following criterion.
Figure imgf000062_0001
The results obtained are shown in Table 3. Test Example 2
Controlling effect on apple scab
Potted apple plants were sufficiently sprayed with a 200 ppm liquid chemical containing each compound of the present invention as active ingredient. Twentyfour hours after the spraying, the plants were
inoculated with a suspension of spores of scab fungus (Venturia inaegualis) by spraying. The plants were placed in a moist chamber at 17ºC for 1 day and then in a room thermostated at 17ºC for 10 days, to cause the disease sufficiently. Thereafter, the lesion area of each leaf was measured and then compared with that on the untreated plot, whereby the effect was judged according to the same criterion as described in Test Example 1. The results obtained are shown in Table 3.
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001

Claims

1. A phenylalanine derivative represented by the general formula (Ia):
Figure imgf000070_0001
wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)-alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, ( C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxy carbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl (C1-C6)alkyloxycarbonyl group; or a substituted phenyl(C1-C6)alkyloxycarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, and R3' is a group represented by the formula:
OR4' (wherein R4' is a hydrogen atom; a (C3-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a (C2-C6)alkynyl group; a cyclo(C3-C8)alkyl group;
a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a (C1-C6)alkylthio(C1-C6)alkyl group; a carboxy(C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from
(C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsub stituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenylcarbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, provided that when each of R1 and R2 is a hydrogen atom, R4' is other than hydrogen atom, tert-butyl group and benzyl group), a group represented by the formula:
N(R5)-R6
(wherein R5 is a hydrogen atom; a (C1-C8)alkyl group; a cyclo(C3-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; an unsubstituted cyano(C1-C6)alkyl group; a substituted cyano(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups and phenyl group; a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C1-C6)alkyl groups; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6) alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an
unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxy group; a substituted phenyl(C1-C6)alkyloxy group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; or a guanidyl(C1-C6)alkyl group, and R6 is a hydrogen atom, a
(C1-C6)alkyl group or a (C2-C6)alkenyl group, R5 and R6 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C1-C6)alkylene group being able to form a ring and have on the ring one or more
substituents which may be the same or different and are selected from the group consisting of (C1-C6)alkyl groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, phenyl group, phenyl(C1-C6)alkyloxycarbonyl groups and phenyl(C1-(6)alkyloxy groups, provided that R1, R2, R5 and R6 are not hydrogen atoms at the same time, and that when R1 is a tert-butoxycarbonyl group and R5 is a benzyl group, R6 is other than methyl group) or a group represented by the formula:
NHCH(R7)(CH2)nCOOR8
(wherein R7 is a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8) alkyl group, a cyclo(C3-C8)alkyl (C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a hydroxy (C1-C6)alkyl group, an amino(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R8 is a hydrogen atom, a
(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1, provided that when each of R1 and R2 is a hydrogen atom, R7 is other than methyl group and isobutyl group, and that when R1 is a benzyloxycarbonyl group, R7 is a hydrogen atom and n is 0, R8 is other than ethyl group).
2. A phenylalanine derivative according to claim 1, wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 sub- stituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxycarbonyl group; or a substituted phenyl(C1-C6) alkyloxycarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, and R3' is a group represented by the formula:
OR4'
(wherein R4' is a hydrogen atom; a (C3-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a (C2-C6)alkynyl group; a cyclo(C3-C8)alkyl group; a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group;
a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)alkylthio(C1-C6)alkyl group; a carboxy(C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from
(C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl (C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo- (C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio-(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenylcarbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl (C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, provided that when each of R1 and R2 is a hydrogen atom, R4' is other than hydrogen atom, tert-butyl group and benzyl group).
3. A phenylalanine derivative according to claim
1 or 2, which is an optically active substance.
4. A phenylalanine derivative according to claim
1, 2 or 3, which is a chemically acceptable salt.
5. A phenylalanine derivative according to claim 1 or 2, which is a coordination compound.
6. A fungicide for fruit gardening comprising as an active ingredient a phenylalanine derivative
represented by the general formula (I):
Figure imgf000082_0001
wherein R1 is a hydrogen atom or a (C1-C8) alkyl group, R2 is a hydrogen atom; a (C1-C8) alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylene dioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxycarbonyl group; or a substituted phenyl(C1-C6)alkyloxycarbonyl group having on the ring 1 to 5
substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6) alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, R3 is a group represented by the formula:
OR4 (wherein R4 is a hydrogen atom; a (C1-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; a cyclo(C3-C6)alkyl group; a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a (C1-C6)alkylthio(C1-C6)alkyl group; a carboxy (C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from
(C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6) alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an
unsubstituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenylcarbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo¬(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy group, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom), a group represented by the formula:
N(R5)-R6
(wherein R5 is a hydrogen atom; a (C1-C8)alkyl group; a cyclo(C3-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; an unsubstituted cyano(C1-C6)alkyl group; a substituted cyano(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C1-C6)alkyl groups, (C1-C6) alkoxy groups and phenyl group; a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C1-C6)alkyl groups; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy(C1-C6)alkyl group; a substituted phenoxy(C1-C6)¬alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylene dioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxy group; a substituted phenyl(C1-C6)alkyloxy group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; or a guanidyl(C1-C6)alkyl group, and R6 is a hydrogen atom, a (C1-C6)alkyl group or a (C2-C6) alkenyl group, R5 and R6 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C1-C6)alkylene group being able to form a ring and have on the ring one or more substituents which may be the same or different and are selected from the group consisting of (C1-C6)alkyl groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, phenyl group, phenyl¬
(C1-C6)alkyloxycarbonyl groups and phenyl(C1-C6)alkyloxy groups) or a group represented by the formula:
NHCH(R7)(CH2)nCOOR8
(wherein R7 is a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8)alkyl group, a cyclo(C3-C8)alkyl(C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a hydroxy (C1-C6)alkyl group, an amino(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R8 is a hydrogen atom, a
(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, and n is 0 or 1), X is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a (C1-C6)alkyl group, a
halo(C1-C6)alkyl group or a (C1-C6)alkoxy group, and m is an integer of 1 or 2.
7. A fungicide for fruit gardening according to claim 6, wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl (C1-C6) alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl group; a substituted phenylcarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylsulfonyl group; a substituted phenylsulfonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo( C1-C6 )alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyloxycarbonyl group; or a substituted phenyl(C1-C6) alkyloxycarbonyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group, R1 and R2 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, or a phthaloyl group, R3 is a group represented by the formula:
OR4
(wherein R4 is a hydrogen atom; a (C1-C18)alkyl group; a halo(C1-C8)alkyl group; a (C2-C6)alkenyl group; a
(C2-C6)alkynyl group; a cyclo(C3-C8)alkyl group; a cyclo(C3-C8)alkyl(C1-C6)alkyl group; a hydroxy(C1-C6)alkyl group; a (C1-C6)alkoxy(C1-C6)alkyl group; a
(C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; a (C1-C6)¬alkylthio(C1-C6)alkyl group; a carboxy(C1-C6)alkyl group; a (C1-C6)alkoxycarbonyl(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or different and are selected from (C1-C6)alkyl groups; a cyano(C1-C6)alkyl group; an unsubstituted phenyl group; a substituted phenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an
unsubstituted phenyl(C2-C6)alkenyl group; a substituted phenyl(C2-C6)alkenyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenoxy- (C1-C6)alkyl group; a substituted phenoxy(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, ( C1-C6 ) alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylthio(C1-C6)alkyl group; a substituted phenylthio(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; an unsubstituted phenylcarbonyl(C1-C6)alkyl group; a substituted phenylcarbonyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom), X is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group or a
(C1-C6)alkoxy group, and m is an integer of 1 or 2.
8. A fungicide for fruit gardening according to claim 7, wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom or a (C1-C8)alkyl group, R3 is a group represented by the formula:
OR4
(wherein R4 is a hydrogen atom, a (C1-C8)alkyl group, a cyclo(C3-C8)alkyl group, a (C2-C6)alkenyl group, a
(C2-C6)alkynyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group, an unsubstituted phenyl(C1-C6)alkyl group, or a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups,
halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups,
halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group), X is a halogen atom, and m is an integer of 1 or 2.
9. A fungicide for fruit gardening according to claim 6, 7 or 8, wherein the phenylalanine derivative is an optically active substance.
10. A fungicide for fruit gardening according to claim 6, 7, 8 or 9, wherein the phenylalanine derivative is a chemically acceptable salt.
11. A fungicide for fruit gardening according to claim 6, 7, 8 or 9, wherein the phenylalanine derivative is a coordination compound.
12. A method for applying a plant disease
controller which comprises applying a fungicide for fruit gardening according to any of claims 6 to 11 in an effective dosage for controlling diseases of fruit crops.
AMENDED CLAIMS
[received by the International Bureau on 14 April 1997 (14.04.97);
original claims 1 and 2 amended; remaining
claims unchanged (6 pages)]
selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1- C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; a diphenyl(C1-C6)alkyl group; or an aromatic heterocyclic (C1-C6)alkyl group having on the ring one or more heteroatoms which may be the same or different and are selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom, provided that when each of R1 and R2 is a hydrogen atom, R4' is other than hydrogen atom, tert-butyl group and benzyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 2-, 3- or 4-position of the phenyl ring, R2 is other than a methylcarbonyl group, an ethylcarbonyl group and a chloromethylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 2-position of the phenyl ring, R2 is other than a trifluoromethylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 3-position of the phenyl ring, R2 is other than a phenylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a tert-butoxycarbonyl group; when R1 is a hydrogen atom, R4' is an ethyl group and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a phenylmethoxycarbonyl group; and when R1 is a hydrogen atom, R4' is a benzyl group and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a tert-butoxycarbonyl group), a group represented by the formula: N(R5)-R6
(wherein R5 is a hydrogen atom; a (C1-C8)alkyl group; a cyclo(C3-C8)alkyl group; a (C2-C6)alkenyl group; a (C2-C6)alkynyl group; an unsubstituted cyano(C1-C6)alkyl group; a substituted cyano(C1-C6)alkyl group having one or more substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups and phenyl group; a (C1-C6)alkoxy(C1-C6)alkoxy(C1-C6)alkyl group; an unsubstituted amino(C1-C6)alkyl group; a substituted amino(C1-C6)alkyl group having 1 or 2 substituents which may be the same or be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups, (C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylenedioxy groups, phenyl group and phenoxy group; or a guanidyl-(C1-C6)alkyl group, and R6 is a hydrogen atom, a (C1-C6)alkyl group or a (C2-C6)alkenyl group, R5 and R6 being able to be taken together to represent a (C1-C6)alkylene group which may contain an oxygen atom or a nitrogen atom between adjacent carbon atoms of the carbon chain, and said (C1-C6)alkylene group being able to form a ring and have on the ring one or more substituents which may be the same or different and are selected from the group consisting of (C1-C6)alkyl groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, phenyl group, phenyl(C1-C6)alkyloxycarbonyl groups and phenyl(C1-C6)alkyloxy groups, provided that R1, R2, R5 and R6 are not hydrogen atoms at the same time, and that when R1 is a tert-butoxycarbonyl group and R5 is a benzyl group, R6 is other than methyl group; when each of R1, R5 and R6 is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 2-, 3- or 4-position of the phenyl ring, R2 is other than an ethyl group; and when each of R1 and R6 is a hydrogen atom, R5 is a benzyl group and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than an ethylcarbonyl group) or a group represented by the formula:
NHCH(R7)(CH2)nCOOR8 (wherein R7 is a hydrogen atom, a (C1-C6)alkyl group, a cyclo(C3-C8)alkyl group, a cyclo(C3-C8)alkyl(C1-C6)alkyl group, a (C1-C6)alkoxy(C1-C6)alkyl group, a hydroxy-
other than hydrogen atom, tert-butyl group and benzyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 2-, 3- or 4-position of the phenyl ring, R2 is other than a methylcarbonyl group, an ethylcarbonyl group and a chloromethylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 2-position of the phenyl ring, R2 is other than a trifluoromethylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 3-position of the phenyl ring, R2 is other than a phenylcarbonyl group; when each of R1 and R4' is a hydrogen atom and a
fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a tert-butoxycarbonyl group; when R1 is a hydrogen atom, R4' is an ethyl group and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a phenylmethoxycarbonyl group; and when R1 is a hydrogen atom, R4' is a benzyl group and a fluorine atom on a phenyl ring of the formula (Ia) is substituted at 4-position of the phenyl ring, R2 is other than a tert-butoxycarbonyl group).
3. A phenylalanine derivative according to claim 1 or 2, which is an optically active substance.
4. A phenylalanine derivative according to claim 1, 2 or 3, which is a chemically acceptable salt.
5. A phenylalanine derivative according to claim 1 or 2, which is a coordination compound.
6. A fungicide for fruit gardening comprising as an active ingredient a phenylalanine derivative represented by the general formula (I):
Figure imgf000101_0001
wherein R1 is a hydrogen atom or a (C1-C8)alkyl group, R2 is a hydrogen atom; a (C1-C8)alkyl group; a (C1-C6)alkoxycarbonyl group; an unsubstituted (C1-C6)alkylcarbonyl group; a substituted (C1-C6)alkylcarbonyl group having as the substituent(s) one or more halogen atoms which may be the same or different; an unsubstituted phenyl(C1-C6)alkyl group; a substituted phenyl(C1-C6)alkyl group having on the ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, nitro group, cyano group, (C1-C6)alkyl groups, halo(C1-C6)alkyl groups,
(C1-C6)alkoxy groups, halo(C1-C6)alkoxy groups, carboxyl group, (C1-C6)alkoxycarbonyl groups, (C1-C6)alkylene
PCT/JP1996/003484 1995-11-29 1996-11-28 Phenylalanine derivatives, optically active substances, salts or coordination compounds thereof, and their use as fungicides WO1997019908A1 (en)

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