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WO1996013482A1 - Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire - Google Patents

Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire Download PDF

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Publication number
WO1996013482A1
WO1996013482A1 PCT/JP1994/001846 JP9401846W WO9613482A1 WO 1996013482 A1 WO1996013482 A1 WO 1996013482A1 JP 9401846 W JP9401846 W JP 9401846W WO 9613482 A1 WO9613482 A1 WO 9613482A1
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WIPO (PCT)
Prior art keywords
group
substituted
same
atom
different
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PCT/JP1994/001846
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English (en)
Japanese (ja)
Inventor
Masaru Shibata
Kazuhiko Sugiyama
Norihisa Yonekura
Junetsu Sakai
Yoshiyuki Kojima
Shigeru Hayashi
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Kumiai Chemical Industry Co., Ltd.
Ihara Chemical Industry Co., Ltd.
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Priority to CA002180000A priority Critical patent/CA2180000C/fr
Priority claimed from CA002180000A external-priority patent/CA2180000C/fr
Application filed by Kumiai Chemical Industry Co., Ltd., Ihara Chemical Industry Co., Ltd. filed Critical Kumiai Chemical Industry Co., Ltd.
Priority to BR9408433A priority patent/BR9408433A/pt
Priority to US08/666,474 priority patent/US5811424A/en
Priority to AU80044/94A priority patent/AU677726B2/en
Priority to PCT/JP1994/001846 priority patent/WO1996013482A1/fr
Publication of WO1996013482A1 publication Critical patent/WO1996013482A1/fr

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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07C333/18—Esters of dithiocarbamic acids
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
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    • C07K5/06—Dipeptides
    • C07K5/06008—Dipeptides with the first amino acid being neutral
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    • C07K5/06052—Val-amino acid
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    • C07C2601/14—The ring being saturated

Definitions

  • Amino acid amide derivatives their production method and agricultural and horticultural fungicides
  • the present invention relates to an amino acid amide derivative which is a novel compound not described in any literature, and a fungicide for agricultural and horticultural use containing the derivative as an active ingredient.
  • fungicides when used repeatedly, may show resistant bacteria to the drug and may not exhibit sufficient bactericidal activity.
  • it is efficient at a low concentration due to environmental problems.
  • the present inventors have synthesized various amino acid amide derivatives in order to develop a drug having a bactericidal activity superior to known bactericides, and studied the physiological activities thereof.
  • the compound of the present invention which binds a substituted or unsubstituted phenoxy group, a substituted or unsubstituted benzyloxy group, a substituted or unsubstituted alkoxy group, etc., has a low dose and a wide sterilization spectrum, especially The present inventors have found that they have an extremely excellent bactericidal activity against downy mildew and tomato blight and do not cause any harm to useful crops, and have completed the present invention.
  • R i is (a) a lower alkyl group (the groups may be the same or different from each other, and may be substituted at one or more positions with a nodogen atom, an alkoxy group or a cyano group) , (B) lower alkenyl group
  • a lower alkynyl group (d) a cycloalkyl group (this group may be substituted at one or more positions with a methyl group or a halogen atom) Good. ), (E) cycloalkyl'alkynole group, (f) cycloalkenyl group, (g) cyclic ether group, (h) phenyl group, wherein the group is a halogen atom, a lower alkyl group (the group may be the same or It may be substituted by a different halogen atom), a lower alkoxy group (the group may be substituted by the same or different halogen atoms), a cyano group or a nitro group.
  • R 2 represents a lower alkyl group, a lower alkenyl group, a cycloalkyl group or a phenyl group (the group may be substituted at one or more positions by a halogen atom);
  • R 3 represents a hydrogen atom or a lower alkyl group
  • R represents a hydrogen atom, a lower alkyl group or a cyano group
  • R ⁇ , R ⁇ and R 7 are the same or different and represent a hydrogen atom or a lower alkyl group
  • R ⁇ represents a hydrogen atom, a lower alkyl group, an aralkyl group, a phenyl group, an alkoxycarbonyl group or a cyano group,
  • ⁇ 1 and ⁇ are the same or different and represent an oxygen atom or a sulfur atom
  • Zeta 3 represents an oxygen atom, a sulfur atom,> NR i.
  • R 1. Is selected from the group consisting of hydrogen Hara A methyl group, a acetyl group, a benzoyl group, a methoxycarbonyl group or a methoxymethyl group. .), Sulf I group, sul Honiru group, Kiichi COO-, group - CONR 1 1 -.
  • R 1 x is showing a water atom or a lower alkyl group
  • Q is, (a) A phenyl group [the group is a halogen atom, a lower alkyl group (the group may be substituted with one or more same or different halogen atoms)], a lower alkoxy group (the group is May be substituted with one or different halogen atoms.), A cyano group, a nitro group, a lower alkoxycarbonyl group, a methylsulfonyl group, a methylsulfinyl group, a methylthio group (the group is May be the same or different, and may be substituted at one or more positions by a dimethylamino group, a phenylsulfonyl group, an acyl group or a phenyl group. ]
  • R G RB (Where, R 1 , RRRRRRR
  • Z 1 , Z z , Z 3 , Q, m, and n have the same meanings as in the first item)).
  • R i, R 2 , R 3 , R e , RRRR 1, Z 2 , Z 3 , Q, m and n have the same meaning as in the first term, and Y is a nitrogen atom, 4, 6 — dimethylpyrimidinylthio group, group R 1 ⁇ C ( ⁇ ) 0 — or group NC
  • a fungicide for agricultural and horticultural use containing these amino acid amide derivatives as an active ingredient.
  • the lower _alkyl group refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a Sobutyl, sec-butyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, 1- Examples thereof include an ethylpropyl group and a hexyl group.
  • a halogen atom is a fluorine atom, a chlorine atom, a bromine atom or Indicates a nitrogen atom.
  • the lower alkenyl group refers to a linear or branched alkenyl group having 2 to 6 carbon atoms, specifically, a vinyl group, a 1-propenyl group, a 2-propidinole group, an isobrozyl group. Examples thereof include a nitrile group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-1-propanol group, a 2-methylpropenyl group, and a 1-ethylvinyl group.
  • the lower alkynyl group is a straight-chain or branched alkynyl group having 2 to 6 carbon atoms, and specifically includes ethynyl, propynyl, butynyl, and 1-methyl-2-propynyl group. be able to.
  • the cycloalkyl group refers to a cycloalkyl group having 3 to 8 carbon atoms, and specifically includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. Examples can be provided.
  • the cycloalkenyl group is a cycloalkenyl group having 4 to 8 carbon atoms, and specific examples thereof include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. Can be.
  • the cyclic ether group refers to a cyclic ether group having 2 to 6 carbon atoms, and specific examples thereof include an oxylanyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. In monkey.
  • the heterocyclic group means a 5- or 6-membered ring containing one or two heteroatoms consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
  • a pyridinyl group, a pyrimidinyl group, a furyl The group and the phenyl group can be exemplified.
  • the fused heterocyclic group means a two-membered ring composed of a 5- or / and 6-membered ring containing one or two heteroatoms consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and specifically, a benzofuranyl group, Examples thereof include a benzophenyl group and a quinolinyl group.
  • an alkyl group R 1 is a straight-chain or branched-chain having a carbon number of 2-6, an alkenyl group having a straight-chain or branched-chain having 3 carbon atoms, carbon atoms 5 to 6 cycloalkyl groups or an optionally substituted phenyl group
  • R z is an ethyl group, a propyl group, an isopropyl group or a sec-butyl group
  • R 3 is a hydrogen atom or A methyl group
  • R 4 is a hydrogen atom or a methyl group
  • R ⁇ is a hydrogen atom or a methyl group
  • R e is a hydrogen atom or a methyl group
  • Q may be substituted.
  • M is an integer of 0 or 1
  • n is 0,
  • Z 1 , Z 2 and Z 3 are oxygen or sulfur atoms, and Those in which the amino acid is in the L form can be mentioned.
  • Some of the compounds of the present invention represented by the general formula [I] have two or more asymmetric carbon atoms in the molecule, and those compounds are obtained from various diastereomers and enantiomers which can be separated by an appropriate method. As is true, pure individual diastereomers and enantiomers and mixtures thereof are included in the compounds of the present invention.
  • the acid portion of the amino acid amide derivative is (2S) -butyric acid in the compounds 23 to 23 and the compounds 42 to 42.
  • the i-danied products (33, 345, 3464), the i-danied products (107, 1116, 1117), and the i-danied products (135, 395, 39 6), compound (228, 414, 415) and compound (452, 453, Each of the three compound groups 4) 5) is a diastereomer mixture and an individual diastereomer mixture.
  • the two compound groups [0 9, 4 10) are each a diastereomer mixture or one of the diastereomer mixtures.
  • Compound 108 is a mixture of four isomers, and compound 433 is a mixture of two isomers.
  • compound 504 In the compound 483 to compound 501, compound 504, compound 505, compound 510 to compound 518, compound 521 and compound 522, L-V al_DL—Ala, compound 502, compound 503, compound 508, compound 509, compound 519 and compound
  • Isopropyl group C 3 H 7 — i
  • tert-butyl group CH a — t
  • sec-butyl group C 4 H S — s
  • Isobutyl group C 4 H s — i, 6/1
  • Ri_0 C-NH-CH-C-NH-CH-CH 2 -0-Q
  • the compound of the present invention represented by the general formula [1] can be produced by the following method.
  • the compound of the present invention ⁇ I] is a compound having an activated amino acid derivative represented by the general formula [IX] or a carboxyl group thereof activated, if necessary, in the presence of a catalyst and Z or a base. It can be produced by reacting with an amine represented by the formula [X].
  • the compound in which the carboxyl group of the amino acid derivative represented by the general formula [IX] is activated includes, for example, an acid halide such as an acid chloride and a compound represented by the general formula [ ⁇ ]
  • 2-Trophenyl ester, 2-Tetrahedro Ranyl ester, 2-pyridyl Activated esters such as £ ster.
  • This reaction can also be carried out using a condensing agent such as, N'-dicyclohexylcarbodiimide, carbonyldiimidazole, 2-chloro1,3-dimethyldimethylimidazolide. .
  • This reaction is usually performed in a solvent. Any solvent that does not inhibit the reaction may be used, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, rigoline, benzene, toluene, and xylene.
  • Halogenated hydrocarbons such as benzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc., dimethyl ether, diisopropyl ether, Ethers such as ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane; ketones such as acetate, methylethylketone, methylisopropylketone, and methylisobutylketone; methyl acetate; acetic acid Esters such as ethyl, acetate, tripropane, benzonitrile, etc.
  • Ryls furthermore, non-protonic polar solvents such as dimethylsulfoxide, dimethylformamide, and sulfolane, and a mixed solvent obtained by combining solvents selected from these can be used.
  • those generally used in this type of reaction can be used.
  • sodium hydroxide, potassium hydroxide, etc. Alkaline earth metal hydroxides such as calcium metal hydroxide and calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate and carbonate Alkali metal bicarbonates such as potassium hydrogen, and furthermore, triethylamine, trimethylethylamine dimethinourealine, pyridine, N-methylmorpholin, N-methylbiperidine, 1,5 — Organic bases such as diazabicyclo [4.3.0] non-5-ene (DBN) and 1,8- diazabicyclo [5.4.0] Among them, tertiary amines such as triethylamine, pyridine and N-methylbiperidine are preferred.
  • Examples of the catalyst include 4-dimethylaminopyridine, 11-hydroxybenzotriazole, dimethylformamide and the like.
  • the reaction temperature is in the range of ⁇ 5 ° C. to 100 ° C., preferably in the range of 60 ° C. to 40 ° C.
  • the reaction time is usually 1 to 20 hours.
  • the compound represented by the general formula [] as a raw material is obtained, for example, by reacting L-parin with di (tert-butyl) dicarbonate in the presence of sodium hydrogen carbonate. It can be produced as N-tert-butoxycarbonyl-L-linoline.
  • N-benzyloxycarboyl is prepared by reacting DL-valin with levovobenzoxychloride in the presence of sodium bicarbonate.
  • the mixed acid anhydride is obtained by converting the amino acid derivative represented by the general formula [K] and bivaloyl chloride into an organic base. It can be produced by reacting in the presence of a kind. Further, ⁇ -nitrophenyl ester is produced by reacting an amino acid derivative represented by the general formula [IX] with ⁇ -nitrophenol in the presence of a condensing agent.
  • the compound [X] as a raw material is obtained by reacting benzonitrile with chloro mouth with 2-amino-12-methyl-11-propanol in the presence of sodium hydride.
  • R ', R z, R 3, R, R, R e, R ", R e, Z 1, Z 2, Z 3, Q, m and n represent the same meaning
  • Y is a nitrogen atom, 4, 6-.dimethylpyrimidinylthio group, Group R 1 OC (0) O — or group P h
  • the compound [1] of the present invention is obtained by converting a compound represented by the general formula [XI] into an amine represented by the general formula [I] or an inorganic compound such as a hydrochloride thereof, if necessary, in the presence of a base. It can be produced by reacting with an organic acid salt such as an acid salt or a tosylate salt.
  • This reaction is usually performed in a solvent.
  • Any solvent that does not inhibit the reaction may be used, and examples thereof include pentane, hexane, heptane, cyclohexane, petroleum ether, rigoline, benzene, toluene, and xylene.
  • Hydrocarbons such as dichloromethane, dichloroethane, cycloforman, carbon tetrachloride, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, etc.
  • Ethers such as ethyl ether, tetrahydrofuran, and dioxane; ketones such as acetate, methylethylketone, methylisopropylketone, and methylisobutylketone; esters such as methyl acetate and ethyl acetate; Acetonitol, propionitol, benzonitrile, etc.
  • Bok Lil include dimethyl sulfoxide, dimethyl Chiruhorumuami de, non pro tons polar solvents such as sulfolane, water and a mixed solvent combining solvents selected from these can and use Iruko a. . As the 9 bases, those commonly used in this type of reaction can be used.
  • alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkaline earth metal hydroxides such as calcium hydroxide, sodium carbonate and potassium carbonate
  • Alkali metal bicarbonates such as alkali metal carbonates, sodium hydrogencarbonate and potassium hydrogencarbonate, and triethylamine, trimethylamine.dimethylaniline, N-methylmorpholine , Pyridine, N-methylpiperidine, 1,5-diazabicyclo [4.3.0] non-5- (DBN), 1,8-diazabicyclo [5.4.0]
  • Organic bases such as 1-ene (DBU) and the like can be mentioned, and tertiary amines such as triethylamine, pyridine and N-methylbiperidine are preferable.
  • the reaction temperature is in the range of ⁇ 20 ° C. to 100 ° C., preferably 0 ° (up to 40 ° C.)
  • the reaction time is usually 30 minutes to 20 hours. Is achieved.
  • the compound represented by the general formula [ ⁇ ] as a raw material is a novel substance.
  • a carbamic acid ester of the compound [I] synthesized by the method of the production method A is used as an amino acid Amino
  • an acid such as liquid hydrogen fluoride, sulfonic acids, hydrogen chloride, hydrogen bromide, or formic acid. Can be manufactured.
  • the organic layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. Low-boiling substances were removed from the obtained oil to obtain 25 g (yield: 81%) of the desired product.
  • Refractive index (11 2 °): tooth 5 4 7 5
  • Boiling point 100 ° CZ 0.12 mmH g
  • L-Norinamide hydrochloride (0.9 g) is suspended in 50 ml of dichloromethan, and 15 ° C At C, 0.6 g of N-methylmorpholine was added, followed by 0.4 g of isopropaninole chloroformate. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. After the organic layer was dried over anhydrous magnesium sulfate, dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.23 g (yield) of the target compound as colorless granular crystals. Rate 13%). '
  • N-Phenoxysolevonil 4.0 g L-Norin Dissolved in 80 ml of methane and N-methisolepiperidine at 20 ° C
  • N 1- [2 — (4-cyanophenoxy)-1-methylethyl)-L-Norinamide (1.1 g) is suspended in 4 ml of dichloromethane, and the N- 0.4 g of methylmorpholine and then 0.7 g of phenyl thiothioformate were added. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.2 g (yield: 75%) of a target substance as a yellow candy substance.
  • N 1 [2— (4-cyanophenoxy) -11-methylethyl) 1-L-linoleamide (1.4 g) is suspended in 4 ml of dichloromethan, and at 15 ° C N- 0.5 g of methylmorpholine and then 0.9 g of phenyl dithioformate were added. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.4 g (yield 66%) of the target compound as a yellow candy.
  • N-methylmorpholine at 15 ° C.
  • phenol e.g., phenol
  • phenyl chloroformate e.g., phenol
  • the organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure.
  • the resulting residue was purified by silica gel column chromatography to obtain 2.3 g (yield: 54%) of the target compound as white crystals.
  • (2 S)-2-tert-butoxycarbonylaminobutyric acid 1.0 g was dissolved in 4 ml of dichloromethane, and 0.5 g of N-methylpiperidine was added at ⁇ 20 ° C., followed by stirring for 10 minutes. After addition of 0.7 g of isobutyl formate in the mouth, the mixture was stirred at 120 ° C for 1 hour. To this mixture was added 0.9 g of 2-((4-cyanophenoxy) -11-methylethylamine) at 160 ° C., and the mixture was stirred at room temperature for 20 hours. Water was added to the reaction mixture, and the dichloromethane layer was washed with a 5% aqueous sodium hydrogen carbonate solution and water in that order.
  • N 1 one [2 - (4 - click throat Benjiruokiji) - 1 - Mechiruechiru] one N 2 - preparation of I-Soviet propoxy carbonylation Lou L over burrs N'a mi de (Compound No. 2 4 6) Dissolve 1 g of N-isopropoxycarbonyl-L-Lin in 4 O ml of dichloromethan at 120 ° C and add N-methylbiperidine.
  • Og to dichloromethane 50 m Then, 2.1 g of m-chloroperbenzoic acid was added at 0 ° C, and the mixture was stirred at reflux temperature for 8 hours. Room After cooling to a temperature, the reaction mixture was filtered, and the dichloromethane solution was washed with a saturated aqueous solution of potassium carbonate and water.
  • N 1 i (2 - (4 one fluorophenylthio) one 1 - Mechisoree chill] one N 2 -.
  • I source propoxycarbonyl one L
  • Roh Li N'a Mi de 2 dissolved 2 g to Axis B
  • Lome data down 5 0 ml Then, 3.4 g of m-chloroperbenzoic acid was added at 0 ° C, and the mixture was stirred at reflux temperature for 8 hours.After cooling to room temperature, the reaction mixture was filtered and the dichloromethane solution was saturated. The organic layer was dried over anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography. Purification by chromatography gave 2.0 g (yield 83%) of the target product as white crystals.
  • N 1 [2-(4-cyanophenoxy) 1 1-methylethyl]-L-Norinamide hydrochloride (1.5 g) was suspended in 100 ml of dichloromethane. At 20 ° C., 1.0 g of N-methylmorpholine and then 0.7 g of 3-tetrahydrofurofuranyl chloroformate were added. After stirring at room temperature for 2 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.1 g of the target substance as a white powder.
  • N 1 (2-(4-cyanophenoxy) 1-1 -methylethyl)-L-linolenamide l Og was suspended in 50 ml of dichloromethan and the mixture was suspended at 115 ° C. 0.4 g of N-methylmorpholine, then black mouth Formic acid 3-methylcyclohexyl 0'.8 g was added. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.2 g (yield: 80%) of a target substance as white crystals.
  • N 1- (2- (4-cyanophenoxy) -1-1-methylethyl) 1-L-linoleamide (0.5 g) is suspended in 3 O ml of dichloromethane, and N-at 15 ° C. —0.2 g of methylmorpholine and then 0.2 g of propargyl formate in the mouth were added After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 0.5 g of the desired product as a white powder (yield). .
  • N 1- [2-(4- cyanophenoxy) 1-1-methylethyl] L-Linolinamide hydrochloride and 5 mL of the suspension were suspended in 150 ml of dichloromethan. — At 20 ° C, 1.0 g of N-methylmorpholine, then 2 g of chloroformic acid. —Methoxyxy 1 0.7 g of methylethyl was added. After stirring at room temperature for 2 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.337 g (yield: 20%) of a target product as white plate crystals.
  • the organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure.
  • the obtained residue was purified by silica gel column chromatography to obtain 1.0 g (yield: 18%) of the target substance as yellow plate-like crystals.
  • N 1- [2- (4-cyanophenoxy) 1 1 -methylethyl] -L-norinamide 1.5 g is suspended in 50 ml of dichloromethane and added at 15 ° C. Then, 0.6 g of N-methylmorpholine and then 1.2 g of 3,4-dimethinolephenyl chloroformate were added. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.7 g (yield: 74%) of a target product as white crystals.
  • N 1 [1-methyl-2- (4-nitrophenethyl) ethyl] — 0.9 g of L-linoleamide is suspended in 50 ml of dichloromethane and _15 ° At C, 0.3 g of N-methylmorpholine was added, followed by 0.4 g of ethyl thioformate. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain the desired product l.Og (yield: 79%) as yellow granular crystals.
  • L-Noryl mono-N- (4-cyclobenzyl) -DL-alanine amide hydrochloride 0.95 g is suspended in dichloromethane 50 ml, and N- 0.555 g of methylmorpholine and then 0.43 g of phenylchloroformate were added. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and the dichloromethane layer was washed with water. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.9 g (yield: 75%) of the desired product as a white powder.
  • N 1- (2-(4-cyanophenoxy) 1, 1 -dimethylethyl) 0.7 g of L-valinamide is dissolved in 40 ml of dichloromethan, and 15 ° C 0.24 g of N-methylmorpholine and 0.42 g of 3-fluorophenyl chloroformate were added at C. After stirring at room temperature for 15 hours, water was added to the reaction mixture, and dichloromethan was added. The organic layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain the target compound as colorless granular crystals. 0.53 g (yield 51%) was obtained.
  • the agricultural and horticultural fungicide of the present invention contains an amino acid amide derivative represented by the general formula [I] as an active ingredient.
  • an amino acid amide derivative represented by the general formula [I] as an active ingredient.
  • the compound of the present invention may be used as it is, but it is preferable to formulate and use the active ingredient in an appropriate dosage form according to the purpose.
  • the active ingredient is diluted with an inert liquid or solid carrier, and surfactants and other substances are added as necessary, and used in the form of powders, wettable powders, emulsions, granules, etc. it can.
  • the compounding ratio of the active ingredient is appropriately selected according to need, but it is 0.1 to 20% (weight) for powders and granules, and 5 to 80% (weight) for emulsions and wettable powders. ) Is appropriate.
  • Suitable carriers include, for example, solid carriers such as talc, bentonite, cretin, kaolin, diatomaceous earth, white carbon, vermiculite slaked lime, silica sand, ammonium sulfate, and urea; Liquid carriers such as pyralcol, xylene, cyclohexanone, and methylnaphthalene are exemplified.
  • surfactants and dispersants include dinaphthylmethansulfonate, alcohol sulfates, alkylarylsulfonates, ligninsulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkyl alcohols, and the like. And polyoxyethylene sorbitan monoalkylate.
  • auxiliary include carboxymethyl cellulose.
  • These formulated agricultural and horticultural fungicides of the present invention are diluted to an appropriate concentration and sprayed or directly applied.
  • the application rate of the agricultural and horticultural fungicide of the present invention varies depending on the type of the compound used, the target disease, the tendency of occurrence, the degree of damage, the environmental conditions, the dosage form used, and the like. For example, when used as such as powders and granules, it is appropriate to select an active ingredient from the range of 0.1 g to 5 kg per 10 ares, preferably from 1 g to 1 kg. Good. When used in liquid form such as emulsions and wettable powders, the amount should be appropriately selected from the range of 0.1 ppm to 100,000 ppm, preferably 10 to 3,000 ppm. Is good.
  • the fungicide for agricultural and horticultural use of the present invention can be used for seed treatment, foliage application, soil application, or water application. As a result, algae (Oomycetes), ascomycetes (As
  • Genus Pseud operonospora eg L
  • cucumber and ⁇ ⁇ Pseudoperonospora cubensis
  • genus Phytophthora such as Tomato plague
  • the genus La includes, for example, Plasmopara viticola. Further, the compound of the present invention may be mixed with other fungicides, insecticides, herbicides, plant growth regulators, fertilizers, and the like, if necessary.
  • the agricultural and horticultural fungicide of the present invention has an extremely high preventive effect against cucumber downy mildew, tomato blight, and budo downy mildew, and also has a high effect against potato blight. Having. Further, the agricultural / horticultural fungicide of the present invention exhibits an excellent therapeutically effective control effect by treating the pathogen after invading the plant. On the other hand, the agricultural and horticultural fungicide of the present invention does not cause phytotoxicity to crops, and also has the characteristics of being excellent in systemic migration, residual effect, and rain resistance. Next, the effect of the agricultural and horticultural fungicide of the present invention will be specifically described with reference to test examples. In the test, the following compounds were used as comparative drugs.
  • Comparative drug X N z -tert-butoxycarbonyl N 1- (2-phenoxexetil) 1-D-alanine amide (compound described in Japanese Patent Application Laid-Open No. Sho 62-89696)
  • Comparative drug Y N z one tert- Bed Tokishikarubo two Lou N 1 - (2 - off Eniruchioechiru) - D-Aranin'a mi de (JP 6 2 - 8 9 6 9 6 JP herein described compounds)
  • a conidia suspension of (Pseudoperono spora cubensis) was spray-inoculated and immediately placed in a moist chamber at 22 ° C for 24 hours. After air-drying, the wettable powder prepared according to Formulation Example 2 was diluted with the active ingredient to 500 ppm by water and sprayed with 10 ml per pot. After that, they were transferred to a greenhouse, and 7 days after inoculation, the diseased area of the entire pot was investigated.
  • Table 16 shows the results of the evaluation based on the criteria shown in Table 14 above. Table 16 Compound No. Evaluation Compound No. Evaluation Compound No. Evaluation
  • Test Example 3 Test for Preventive Effect on Tomato Blight A single tomato seedling (variety: Ponterosa) was transplanted into each unglazed pot having a diameter of 12 cm and grown in a greenhouse. When the double leaves of the seedlings spread to 6 to 7 leaves, the wettable powder prepared according to Formulation Example 2 was diluted with water to 500 ppm of the active ingredient, and each pot was filled with water. 20 ml was sprayed. After air-drying, a suspension of zoospores of Phytophthora infestans was sprayed and inoculated, immediately placed in a moist chamber at 22 ° C, and four days after inoculation, the diseased area of each leaflet was examined. The disease severity was evaluated based on the criteria in Table 17 and the damage was calculated from the disease severity and the number of leaves according to the following formula, and the control value was calculated from the following formula. . The results are shown in Table 18. Table 17
  • Bud seedlings (cultivar: Kyoho) cut and grown in unglazed pots with a diameter of 12 cm were pruned and grown in a greenhouse.
  • the wettable powder prepared according to Formulation Example 2 is diluted with water to 500 ppm of the active ingredient, and 20 m 1 per pot Was sprayed.
  • a conidia suspension of the downy mildew (Plasmopara viticola) was sprayed and inoculated, and immediately placed in a moist chamber at 22 ° C for 24 hours.
  • Table 20 shows the results of the evaluation based on the criteria shown in Table 14 above.
  • Test example 6 Cucumber and disease treatment effect test
  • Table 21 shows the results of the evaluation based on the criteria shown in Table 14 above. No. 21 ⁇ Compound number evaluation
  • One tomato seedling (variety: Ponterosa) was transplanted into each of the unglazed pots having a diameter of 12 cm, and grown in a greenhouse.
  • the wettable powder prepared according to Formulation Example 2 was diluted with water to 500 ppm of the active ingredient, and the weight per pot was 2 0 m 1 was sprayed.
  • a zoospore suspension of Phytophthora infestans was sprayed and inoculated, and immediately placed in a moist chamber at 22 ° C. The day after the inoculation, the diseased area of each leaflet was examined.
  • the disease severity was evaluated based on the criteria shown in Table 17 above, the degree of damage was determined from the corresponding number of leaves by the above formula, and the control value was further determined by the above formula. The results are shown in Table 22.
  • Bud seedlings (cultivar: Kyoho) cut and grown in unglazed pots with a diameter of 12 cm were pruned and grown in a greenhouse. At the time when 4 to 5 leaves of the seedlings have developed, the wettable powder prepared according to Formulation Example 2 is diluted with water to 500 ppm of the active ingredient, and 20 m / pot. Was sprayed.
  • the severity of the disease was evaluated based on the criteria in Table 17 above, and the damage was determined by the above formula from the disease severity and the number of leaves corresponding to the disease, and the control value was further calculated by the above formula. The results are shown in Table 23.

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Abstract

La présente invention concerne un dérivé amide d'acide aminé représenté par la formule générale (1). L'invention concerne également un bactéricide phytosanitaire dont le principe actif est ce dérivé. Dans la formule générale (1), R1 représente un alkyle inférieur qui peut être identique ou différent et peut être halogéné mais doit comporter au moins un atome de carbone; R2 représente un éthyle; R3 représente un hydrogène; R4 représente un hydrogène; R?5, R6 et R7¿ représentent chacun indépendamment un hydrogène ou un éthyle; R8 représente un hydrogène; Z1 et Z2 représentent chacun indépendamment un oxygène ou un soufre; Z3 représente un oxygène ou un soufre; Q représente un phényle; m représente un entier valant de 0 à 2; et n représente un entier valant 0 ou 1. Ce dérivé permet avantageusement de lutter puissamment contre les maladies des plantes, et en particulier le mildiou de la vigne et le mildiou de la pomme de terre sans nuire aux récoltes.
PCT/JP1994/001846 1994-10-27 1994-11-01 Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire WO1996013482A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002180000A CA2180000C (fr) 1994-10-27 1994-10-27 Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire
BR9408433A BR9408433A (pt) 1994-10-27 1994-11-01 Derivados de amidas de aminoácidos métodos para a sua produç o e fungicidas agrícolas ou hortícolas
US08/666,474 US5811424A (en) 1994-10-27 1994-11-01 Amino-acid amide derivatives, method for producing the same, and agricultural or horticultural fungicides
AU80044/94A AU677726B2 (en) 1994-10-27 1994-11-01 Amino acid amide derivative, process for producing the same, and agrohorticultural bactericide
PCT/JP1994/001846 WO1996013482A1 (fr) 1994-10-27 1994-11-01 Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire

Applications Claiming Priority (2)

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CA002180000A CA2180000C (fr) 1994-10-27 1994-10-27 Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire
PCT/JP1994/001846 WO1996013482A1 (fr) 1994-10-27 1994-11-01 Derive amide d'acide amine, son procede de production, et bactericide phytosanitaire

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH035451A (ja) * 1989-05-13 1991-01-11 Bayer Ag 有害生物防除剤及びその製法
JPH03153657A (ja) * 1989-11-01 1991-07-01 Bayer Ag 置換アミノ酸アミド誘導体類、それらの製造および使用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH035451A (ja) * 1989-05-13 1991-01-11 Bayer Ag 有害生物防除剤及びその製法
JPH03153657A (ja) * 1989-11-01 1991-07-01 Bayer Ag 置換アミノ酸アミド誘導体類、それらの製造および使用

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