CN1043720C - Fungicide contg. fluorodiphenyl acrylamides - Google Patents

Fungicide contg. fluorodiphenyl acrylamides Download PDF

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CN1043720C
CN1043720C CN96115551A CN96115551A CN1043720C CN 1043720 C CN1043720 C CN 1043720C CN 96115551 A CN96115551 A CN 96115551A CN 96115551 A CN96115551 A CN 96115551A CN 1043720 C CN1043720 C CN 1043720C
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compound
och
disease
downy mildew
effect
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CN1167568A (en
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李宗成
刘长令
刘武成
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SHENYANG CHEMICAL INST MINISTR
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SHENYANG CHEMICAL INST MINISTR
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Abstract

The present invention relates to an acrylamide germicide containing fluoro-diphenyl. The general formula (I) of the germicide is disclosed in the specification. The germicide is used for controlling diseases caused by oomycetes subclass pathogenic bacteria, and has special effect on downy mildew, phytophthora root rot and pythium disease.

Description

Acrylamide germicide containing fluoro-diphenyl
Belong to disinfectant use in agriculture
German Patent Publication 3541716,3615488 all reported the diphenylprop acrylamide compound with bactericidal activity, and such compound is not good enough to the prevention effect of crop disease, in addition it is also necessary to the more excellent compound of activity.In preventing and treating cucumber downy mildew, metalaxyl, aliette, Bravo, the general prevention effect for the bactericide such as making every effort to overcome are not ideal enough.To meet the requirement on agriculture, gardening, the invention provides new acrylamide germicide containing fluoro-diphenyl and its preparation.
The formula of acrylamide germicide containing fluoro-diphenyl compound of the present invention is：
Figure C9611555100031
In above formula：R1、R2=C1~6Alkyl, C1~6Haloalkyl, C1~6Alkoxy -C1~6Alkyl, C1~6Halogenated alkoxy-C1~6Alkyl, C3~6Cycloalkyl, C3~6Cycloalkyl ,-C1~6Alkyl, C2~6Alkenyl, C2~6Alkynyl, (substitution) aryl, (substitution) aryl-C1~3Alkyl.R1、R2It may be the same or different, can also constitute five, six annulus.
R3=hydrogen, halogen, cyano group, nitro, triazolyl, pyrazolyl, imidazole radicals, C1~6Alkyl, C1~6Alkoxy.
X=oxygen, sulphur or NH.
Z=key or oxygen.
R4、R5=hydrogen, C1~6Alkyl, C2~6Alkenyl, C2~6Alkynyl, C1~6Alkoxy -C1~6Alkyl, C1~6Halogenated alkoxy-C2~6Alkenyl, C1~6Halogenated alkoxy-C2~6Alkynyl, C1~6Haloalkyl, C1~6Alkane (oxygen) base carbonyl, (substitution) amino-carbonyl, C3~6Cycloalkyl, C3~6Cycloalkyl-C1~6Alkyl, (substitution) aryl-C1~3Alkyl, (substitution) aryl carbonyl.R4、R5It may be the same or different, can also constitute five annulus or six annulus, such as triazolyl, pyrazolyl, imidazole radicals, nafoxidine, morpholine, piperidines, piperazine, pyridazine, isoxazolyl.
Alkyl, alkenyl, alkynyl in title compound refer to the straight or branched alkyl that straight or branched alkyl, alkenyl, alkynyl, haloalkyl can replace for halogen.
(substitution) aryl refers to halogen, cyano group, nitro, alkoxy, phenyl, carboxyl, alkoxy carbonyl, phenyl, naphthyl, pyridine radicals, pyrimidine radicals, triazolyl, pyrazolyl, imidazole radicals, the pyridazinyl of amido substitution, and the number of substituent is 0~5.
In the compound of the present invention, having with greater activity：
Compound 1,3- (4- fluorophenyls) -3- (3,4- Dimethoxyphenyls) acryloyl morpholine
Figure C9611555100041
Compound 2,3- (4- fluorophenyls) -3- (3- methoxyl group -4- ethoxyl phenenyls) acryloyl morpholine
Figure C9611555100051
Compound 3,3- (4- fluorophenyls) -3- (3- ethoxy-4-methoxyphenyls) acryloyl morpholine
Compound 4,3- (4- fluorophenyls) -3- (3,4- Dimethoxyphenyls)-N- methoxy-. N-methyl acrylamides
Compound 5,3- (4- fluorophenyls) -3- (3- ethoxy-4-methoxyphenyls)-N- methoxy-. N-methyl acrylamides
Figure C9611555100062
Compound 6,3- (4- fluorophenyls) -3- (3- methoxyl group -4- ethoxyl phenenyls)-N- methoxy-. N-methyl acrylamides
Figure C9611555100063
The title compound of the present invention can be made by the following method：
The reaction equation of method one is as follows：
The reaction equation of method two is as follows：
Figure C9611555100072
Method one and method two are to react 0.5-24 hours to be made at a temperature of 0 DEG C to solvent boiling point in atent solvent (benzene,toluene,xylene, ether, tetrahydrofuran, dimethylformamide) in the presence of highly basic (sodium hydroxide, potassium hydroxide, sodium hydride, potassium tert-butoxide, sodium tert-butoxide, sodium methoxide, caustic alcohol).
The reaction equation of method three is as follows：
Intermediate (V) reacts 0.5~24 hour at a temperature of 0 DEG C to solvent boiling point in atent solvent (benzene,toluene,xylene, ether, tetrahydrofuran, dimethylformamide, dichloromethane) and is made in the presence of chlorinating agent thionyl chloride, POCl3, phosphorus trichloride, oxalyl chloride, phosgene.
The reaction equation of method four is as follows：
Figure C9611555100082
(I) (X=O) is dissolved in atent solvent (dichloromethane, chloroform, dichloroethanes, tetrahydrofuran, benzene,toluene,xylene, chlorobenzene, dichloro-benzenes, ether, acetonitrile), with phosphorus pentasulfide in -25 DEG C to solvent boiling point thermotonus 0.5~24 hour in the presence of alkali (triethylamine, sodium hydroxide, potassium hydroxide, sodium acid carbonate, saleratus), title compound (I) is made after processing.
The formula (I) of the title compound of the present invention, including the compound shown in table 1~5：
Table 1
Figure C9611555100091
R1     R2      R3    X      Z     R4   R5CH3    CH3     H      O      -     CH3  CH3CH3    CH3     CN     O      -     CH3  CH3CH3    CH3     H      O      -     CH3  C2H5CH3    CH3     H      O      -     CH3  C3H7nCH3    CH3     H      O      -     CH3  C3H7iCH3    CH3     H      O      -     CH3  C4H9nCH3    CH3     H      O      -     CH3  C4H9iR1     R2      R3    X       Z     R4    R5CH3    CH3     H      O       -     CH3   C5H11nCH3    CH3     H      O       -     C2H5  C2H5CH3    CH3     H      O       -     C2H5  C3H7nCH3    CH3     H      O       -     C2H5  C3H7iCH3    CH3     H      O       -     C2H5  C4H9nCH3    CH3     H      O       -     C2H5  C4H9iCH3    CH3     H      O       -     C2H5  C5H11nCH3    CH3     H      O       -     C3H7n C3H7nCH3    CH3     H      O       -     C3H7n C3H7iCH3    CH3     H      O       -     C3H7n C4H9nCH3    CH3     H      O       -     C3H7n C4H9iCH3    CH3     H      O       -     C3H7n C5H11nCH3    CH3     H      O       -     C3H7i C3H7iCH3    CH3     H      O       -     C3H7i C4H9nCH3    CH3     H      O       -     C3H7i C4H9iCH3    CH3     H      O       -     C3H7i C5H11nCH3    CH3     H      O       -     C4H9n C4H9nCH3    CH3     H      O       -     C4H9n C4H9iCH3    CH3     H      O       -     C4H9n C5H11nCH3    CH3     H      O       -     CH3CH3    CH3     H      O       -     CH3CH3    CH3     H      O       -     CH3CH3    CH3     H      O       -     C2H5CH3    CH3     H      O       -     C3H7CH3    CH3     H      O       -     CH3   CH2CΞCHCH3    CH3     H      O       -     CH3   CH2CH=CH2CH3    CH3     H      O       -     CH3   CH2CΞCCH3CH3    CH3     H      O       -     CH3   CH2OCH3CH3    CH3     H      O       -     CH3   CH2CH2OCH3CH3    CH3     H      O       -     CH3   CH2OCH2CH3CH3    CH3     H      O       -     CH3   CH2CH2OC2H5CH3    CH3     H      O       -     CH3   CH2PhR1     R2      R3    X       Z     R4   R5CH3    CH3     H      O       -     CH3   CH2Ph-4-CICH3    CH3     H      O       -     CH3   CH2Ph-4-FCH3    CH3     H      O       -     CH3   CH2Ph-3,4-CI2CH3    CH3     H      O       -     CH3   CH2Ph-4-OCH3CH3    CH3     H      O       -     CH3   CH2Ph-4-CH3CH3    CH3     H      O       -     CH3   CH2(CH3)PhCH3    CH3     H      O       -     CH3   CH2CF3CH3    CH3     H      O       -     CH3   CH2PhCH3    CH3     H      O       -     CH3   CH2pH-4-CICH3    CH3     H      O       -     CH3   CH2ph-4-FCH3    CH3     H      O       -     CH3   CH2Ph-3,4-CI2CH3    CH3     H      O       -     C2H5 CH2CΞCHCH3    CH3     H      O       -     C2H5 CH2CH=CH2CH3    CH3     H      O       -     C2H5 CH2PhCH3    CH3     H      O       -     C2H5 CH2ΞCCH3CH3    CH3     H      O       -     C2H5 CH2OCH3CH3    CH3     H      O       -     C2H5 CH2CH2OCH3CH3    CH3     H      O       -     C2H5 CH2OCH2CH3CH3    CH3     H      O       -     C2H5 CH2CH2OC2H5CH3    CH3     H      O       -     C3H7 CH2CΞCHCH3    CH3     H      O       -     C3H7 CH2CH=CH2CH3    CH3     H      O       -     C3H7 CH2CΞCCH3CH3    CH3     H      O       -     C3H7 CH2PhCH3    CH3     H      O       O     CH3   CH3CH3    CH3     H      O       O     CH3   C2H5CH3    CH3     H      O       O     CH3   C3H7nCH3    CH3     H      O       O     CH3   C3H7iCH3    CH3     H      O       O     CH3   C4H9nCH3    CH3     H      O       O     CH3   C4H9iCH3    CH3     H      O       O     CH3   CH2OCH3CH3    CH3     H      O       O     CH3   CH2CH2OCH3CH3    CH3     H      O       O     CH3   CH2OCH2CH3R1    R2     R3    X      Z       R4         R5CH3   CH3    H      O      O       CH3     CH2CH2OC2H5CH3   CH3    H      O      O       CH3     CH2CΞCHCH3   CH3    H      O      O       CH3     CH2CH=CH2CH3   CH3    H      O      O       CH3     CH2CΞCCII3CH3   CH3    H      O      O       CH3     CH2PhCH3   CH3    H      O      O       CH3     CH2Ph-4-CICH3   CH3    H      O      O       CH3     CH2Ph-4-FCH3   CH3    H      O      O       CH3     CH2Ph-3,4-CI2CH3   CH3    H      O      O       CH3     CH2Ph-4-OCH3CH3   CH3    H      O      O       CH3     CH2Ph-4-CH3CH3   CH3    H      O      O       CH3     CH2(CH3)PhCH3   CH3    H      O      O       C2H5   CH3CH3   CH3    H      O      O       C2H5   C2H5CH3   CH3    H      O      O       C2H5   C3H7nCH3   CH3    H      O      O       C2H5   C3H7iCH3   CH3    H      O      O       C2H5   C4H9nCH3   CH3    H      O      O       C2H5   CH2CΞCHCH3   CH3    H      O      O       C2H5   CH2CH=CH2CH3   CH3    H      O      O       CH3     CH2CΞCCH3CH3   CH3    H      O      O       C2H5   CH2OCH3CH3   CH3    H      O      O       C2H5   CH2CH2OCH3CH3   CH3    H      O      O       C2H5   CH2OCH2CH3CH3   CH3    H      O      O       C2H5   CH2CH2OC2H5CH3   CH3    H      O      O       C2H5   CH2PhCH3   CH3    H      O      O       C2H5   CH2ph-4-CICH3   CH3    H      O      O       C2H5   CH2Ph-4-FCH3   CH3    H      O      O       C2H5   CH2Ph-3,4-CI2CH3   CH3    H      O      O       C2H5   CH2Ph-4-OCH3CH3   CH3    H      O      O       C2H5   CH2Ph-4-CH3CH3   CH3    H      O      O       C2H5   CH2(CH3)PhCH3   CH3    H      O      O      CH2OCH3 CH2=CHCH3   CH3    H      O      O      CH2OCH3 CH2PhR1    R2     R3   X     Z      R4        R5CH3   CH3    H     O     O   CH2OCH3      CH2OCH3CH3   CH3    H     O     O   CH2CH=CH2    CH3CH3   CH3    H     O     O   CH2CH=CH2    CH2CH=CH2CH3   CH3    H     O     O   CH2CH=CH2    C2H5CH3   CH3    H     O     O   CH2CH=CH2    C3H7nCH3   CH3    H     O     O   CH2CH=CH2    CH2PhCH3   CH3    H     O     O   CH2CH=CH2    CH2Ph-4-CICH3   CH3    H     O     O   CH2CH=CH2    CH2Ph-4-FCH3   CH3    H     O     O   CH2CΞCH      CH3CH3   CH3    H     O     O   CH2CΞCH      C2H5CH3   CH3    H     O     O   CH2CΞCH      CH2CΞCHCH3   CH3    H     O     O   CH2CΞCH      C3H7nCH3   CH3    H     O     O   CH2CΞCH      CH2OCH3CH3   CH3    H     O     O   CH2CΞCH      CH2CH2OCH3CH3   CH3    H     O     O   CH2CΞCH      CH2Ph-4-CICH3   CH3    H     O     O   CH2CΞCH      CH2Ph-4-FCH3   CH3    H     O     O   CH2Ph         CH3CH3   CH3    H     O     O   CH2Ph         C2H5CH3   CH3    H     O     O   CH2Ph         C3H7nCH3   CH3    H     O     O   CH2Ph         CH2CF3CH3   CH3    H     O     -   CH3           CH2ACH3   CH3    H     O     -   C2H5         CH2ACH3   CH3    H     O     -   C3H7         CH2ACH3   CH3    H     O     -   C3H7i        CH2ACH3   CH3    H     O     -   CH3           CH2BCH3   CH3    H     O     -   C2H5         CH2BCH3   CH3    H     O     -   C3H7         CH2BCH3   CH3    H     O     -   C3H7i        CH2BCH3   CH3    H     O     O   CH3           CH2ACH3   CH3    H     O     O   CH3           CH2BCH3   CH3    H     O     O   CH3           CH2DCH3   CH3    H     O     O   CH3           CH2E
Figure C9611555100141
Table 2R3=HX=OR4    R5                R6        R7        ZCH3    CH3                 H         H         -C2H5  C2H5              H         H         -C3H7n C3H7n              H         H         -C3H7i C3H7i              H         H         -CH3    C2H5               H         H         -CH3    C3H7i              H         H         -CH3    C4H9n              H         H         -CH3    CH3                 H         H         OC3H7n C3H7n              H         H         OCH3    CH3                 H         H         OC2H5  C2H5              H         H         OC3H7n C3H7n              H         H         OC3H7i CH2CΞCH            H         H         OCH3    CH2CH=CH2          H         H         OCH3    CH2Ph               H         H         OC2H5  C2H5              H         H         OR4         R5         R6        R7        ZC2H5     CH3          H         H         OC2H5     C3H7n       H         H         OC2H5     C3H7i       H         H         OCH3    CH2Ph-4-F       H         H         OC2H5  CH2Ph-4-F       H         H         OCH3       CH3          F         F         OC2H5     C2H5        F         F         OCH3       C2H5        F         F         OC3H7n    C3H7n       F         F         OC3H7i    C3H7i       F         F         OCH3       CH2CΞCH     F         F         OCH3       CH2Ph        F         F         OC2H5     CH3          F         F         OC2H5     C3H7n       F         F         OCH3       CH3          F         F         -C2H5     C2H5        F         F         -CH3       C2H5        F         F         -CH3       C3H7n       F         F         -CH3       CH2CCH       F         F         -C2H5     CH2CCH       F         F         -CH3       CH2Ph        F         F         -C3H7n    C3H7n       F         F         -CH3       CH2A         F         F         -CH3       CH2A F F-A=1,2,4- triazol-1-yls table 3
Figure C9611555100161
R3=H,CNX=OR1            R2                QCH3           CH3               Q1CH3           CH3               Q2CH3           CH3               Q3CH3           CH3               Q4CH3           CH3               Q5CH3           CH3               Q6CH3           CH3               Q7CH3           C2H5             Q1C2H5         CH3               Q2C2H5         CH3               Q3C2H5         CH3               Q4C2H5         CH3               Q5C2H5         CH3               Q6C2H5         CH3               Q7CH3           C2H5             Q2CH3           C2H5             Q3CH3           C2H5             Q4CH3           C2H5             Q5CH3           C2H5             Q6CH3           C2H5             Q7 Table 4Table 5
Figure C9611555100181
R3=H, CNX=OQ1-Q7 are with table 3R6 R7 Q R6 R7 QH H Q1 F F Q1H H Q2 F F Q2H H Q3 F F Q3H H Q4 F F Q4H H Q5 F F Q5H H Q6 F F Q6H H Q7 F F Q7
Example 1
The preparation of 3- (4- fluorophenyls) -3- (3,4- Dimethoxyphenyls) acryloyl morpholines (compound 1)
By 26 grams of (0.1 mole) 4- fluoro- 3 ', 4 '-dimethoxybenzophenone be added to got ready contain 380 milliliters of toluene, in the mixed liquor of 0.15~0.35 mole of sodium tert-butoxide of 30 milliliters of the tert-butyl alcohol, in the case where being heated to reflux stirring, 50 milliliters of toluene solutions containing 0.15~0.35 mole of acetyl morphine were added dropwise in 5~8 hours, back flow reaction separates the tert-butyl alcohol simultaneously, reacts 6~12 hours (TLC tracking).Reaction is finished, cooling, washes toluene layer, and anhydrous magnesium sulfate drying, precipitation, placement separate out crystallization, and recrystallizing methanol obtains 31.5~34.0 grams of (yields of product：88~95%).Fusing point：120~128 DEG C (Z/E mixture ratios 55/45).
IR (KBr tablettings)：1625cm-1(-CO-)
1H NMR (DMCO, internal standard tetramethylsilane 90MHz) δ：
=CH-CO- is suitable：6.21ppm, instead：6.35ppm
Cis and trans isomers can be by further isolated.
Example 1 is not intended to limit the present invention, and base its mixture of the present invention can be made using similar method.
The compound (I) of the present invention can be used alone and binary or ternary mix preparation application can be also made into one kind or two or more bactericide or insecticide.
The bactericide that can be mixed with the title compound (I) of the present invention has：
Captan, folpet, zineb, Mancozeb, thiram, difoltan, iprodione, methyl sclex, first and second sclexes, hexaconazole, nitrile bacterium azoles, Tebuconazole, Pencycuron, cymoxanil, biguanide spicy acid salt, prothiocarb, diethofencarb, ring bacterium amine, ester bacterium urea, olefin conversion, flutolanil, carbendazim, benomyl, triazolone, cyproconazole, thiophanate methyl, hydroxyisoxazole, butadiene morpholine, Propamocarb, metalaxyl, furalaxyl, M 9834, dislike acid amides, methasulfocarb, pyrifenox, fenpropidin, TH-164, BAS480F, BAS490F, ICIA5504, RH7592, MON24000, CGA219417, XRD-563, mepanipyrim, dimethomorph, fenpiclonil, seed dressing is strong, propiconazole, Bravo, basudin, copper sulphate, Euparen, aliette, hymexazol.
Insecticide that can be mixed with the compound (I) of the present invention has：
Fenisobromolate, dicofol, parathion-methyl, 1605, Folithion, diazinon, chlopyrifos, RH7988, RH5992, Methomyl, Cupric sulfate, dimehypo, Padan, sevin, Permethrin, cypermethrin, tetramethrin, Tefluthrin, cyfloxylate, fenvalerate, flufenoxuron, desinsection is grand, UC 62644, fenpyroximate (NNI850), MK239, AC303630 (azoles), imidacloprid (NTN33893), ICIA5682, Fipronil, NI-25, CGA215944, TIA304, GR-572, CGA157419, CGA184699, PH-7023, XRD-473, ABG-6215, fenazaquin, methamidophos, pyridaben (NC129), NC170, NC184, NC196, SU8801, clofentezine.
In the binary or ternary mixture that are made into, the ratio shared by title compound of the invention is 1%~99%.
The title compound of the present invention, can be made into emulsion, pulvis, wettable powder, granule, colloidal suspending agent.
Pulvis, wettable powder, the carrier used in granule have diatomite, clay, gypsum, talcum powder, kaolin：Solvent used in emulsion：The fatty alcohol of benzene,toluene,xylene, alkylbenzene, chlorinated aromatic hydrocarbons, C1~6, phenmethylol, cyclohexanol, acetone, butanone, methyl iso-butyl ketone (MIBK), cyclohexanone, dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, water etc..
Anion, cation or nonionic surfactant are added in preparation, surfactant can be with being emulsifying agent, dispersant or wetting agent.Dodecyl sodium sulfate, neopelex, polyoxyethylene groups fatty acid ester, polyoxyethylene groups fatty acid alcohol, polyoxyethylene groups fatty acid amine, ethoxy castor oil, sodium lignin sulfonate (potassium), carboxymethyl alcohol, polyvinyl alcohol, polyvinyl ester can for example be used.
Example 2
The compound 40 of the present invention, diatomite 53, C12-20Alcohol sulfuric ester 4,3 parts of neopelex (percetage by weight), above composition is uniformly mixed, and is crushed, is obtained the wettable powder containing active ingredient 40%.
Example 3
The compound 30 of the present invention, dimethylbenzene 33, dimethylformamide 30, polyxyethylated 7 parts of propyl ether (percetage by weight) uniformly mixes above composition, dissolves, obtains the emulsion containing active ingredient 30%.
Example 4
The compound 10 of the present invention, talcum powder 89, polyxyethylated 1 part of propyl ether (percetage by weight) uniformly mixes above composition, crushes, obtains the pulvis containing active ingredient 10%.
Example 5
The compound 5 of the present invention, clay 73, bentonite 20, dioctylthio sodium succinate 1,1 part of sodium phosphate (percetage by weight) uniformly mixes above composition, after fully crushing, and adds suitable quantity of water.It is sufficiently mixed, granulates again, after drying, obtains the granule containing active ingredient 5%.
Example 6
The compound 10 of the present invention, sodium lignin sulfonate 4, neopelex 1, xanthic acid 0.2,84.8 parts of water (percetage by weight), above composition is uniformly mixed, wet lapping is less than 1 micron to granularity, is obtained containing the colloidal suspending agent that active ingredient is 10%.
Example 7
The compounds of this invention 8, Mancozeb 50, kaolin 30, neopelex 4,8 parts of sodium lignin sulfonate (percetage by weight)；Mentioned component is mixed, after fully crushing, the wettable powder that mixture content is 58% is obtained.
Example 8
The compounds of this invention 10, propiconazole 30, kaolin 45, neopelex 6,9 parts of sodium lignin sulfonate (percetage by weight)；Above composition is uniformly mixed, after fully crushing, the wettable powder that mixture content is 40% is obtained.
The compound of the present invention, being compared compared with bactericide has good bioactivity, the disease produced available for preventing and treating by oomycetes subclass pathogen, to downy mildew, phytophthora root rot, rotten mildew has special efficacy, such as apple root cap epidemic disease, citrus epidemic disease, capsicum epidemic disease, pumpkin epidemic disease, the late blight of potato, tomato late blight, fig epidemic disease, tomato brown rot, onion epidemic disease, Cucumber Blight, the black cane blight of tobacco, cucumber downy mildew, downy mildew of garpe, strawberry root rot.Illustrated below by taking compound 1 as an example：
Example 9 suppresses cucumber downy mildew spore germination experiment
Reagent agent compound 1 (content be 9% missible oil) sets 100,50,25ppm, dimethomorph (the i.e. compound of commercialization in dimethomorph, that is, similar patent.Content is 50% wettable powder) 50ppm is set, separately set blank control.Fresh mould layer is taken to prepare sporangia suspension on the sick leaf of cucumber downy mildew, mixed with institute preparating liquid, often handle six repetitions, place in insulating box (25 DEG C), investigated after 24 hours, 18 visuals field of often processing investigation, record sprouts spore and do not sprout spore number, calculate and suppress spore germination rate (%), as a result with table 6.
The spore germination result of the test of table 6 shows：There is compound 1 higher suppression sporangium sprouting to act on, and inhibitory action is substantially better than dimethomorph, and compound 1,25,50,100ppm suppression spore germination rates are respectively 65.2%, 93.5%, 97.6%, and dimethomorph 50ppm is 42.5%.
The spore germination rate result of the test reagent agent concentration of 6 compound of table 1 sprouts spore and does not sprout spore spore germination rate suppression spore germination rate
(ppm) (individual) (individual) (%) (%)
25 198 660 23.1 65.2 compounds 1 50 45 990 4.3 93.5
The CK-383 194 66.4 of 100 17 1,044 1.6 97.6 dimethomorph 50 208 336 38.2 42.5-
The preventing and treating cucumber downy mildew protection of example 10 and therapeutic action experiment (interior)
Set 250 for reagent compound 1 (content be 9% missible oil), 200,150,100, five concentration of 75ppm, dimethomorph 150ppm is comparison medicament.Try material and select 2~3 leaf phases susceptible cucumber key seedling, three repetitions, protection test nineteen ninety-five September is handled, is inoculated with after 24 hours on the 17th, and therapeutic test September is inoculated with the 18th, is post-processed within 24 hours.Investigated after one week, nine grades of systems are recorded, calculate disease and refer to and preventive effect, the results are shown in Table 7：
The protective effect of 7 compound of table 1 and therapeutic action result
Protective effect therapeutic action
Drug concentration ... ... ... ...
(ppm) disease refers to preventive effect (%) disease and refers to preventive effect (%)
        250    0      100      0      100
200 0 100 0.01 98.1 compounds 1 150 0 100 0 100
        100    0      100     0.08    84.6
The CK-0.40-0.52 of 75 0.03 92.5 0.11 78.8 dimethomorph 150 0 100 0.19 63.5-
Protection and therapeutic test result show：The protecting effect of compound 1 is better than therapeutic effect, and 100ppm protective effects are 100%, and therapeutic action is that 84.6%75ppm protective effects are 92.5%, and therapeutic action is 78.8%；Find that the protective effect of compound 1 is basically identical with dimethomorph under 150ppm concentration simultaneously, but therapeutic action compound 1 is substantially better than dimethomorph：The therapeutic action of 150ppm compounds 1 is 100%, and dimethomorph is 63.5%；150ppm of the therapeutic effect also superior to dimethomorph when the concentration of compound 1 is 75ppm.
The compound 1 of example 11 is with dimethomorph preventing and treating cucumber downy mildew expression activitiy experiment (interior)
The experiment is divided and ruled the protective effect for the treatment of, and two kinds of medicaments set 150,100ppm, two concentration, often handle three repetitions, separately set blank control respectively.Try material and select 2~3 leaf phase cucumber seedlings.Handle investigation method ibid, the results are shown in Table 8.
The compound 1 of table 8 and dimethomorph expression activitiy result of the test
Protective effect therapeutic action
Drug concentration ... ... ... ...
(ppm) disease refers to preventive effect (%) disease and refers to preventive effect (%) compound 1 100 0.07 93 0.37 63
150 0.05 95 0.26 74 dimethomorphs 100 0.39 61 0.98 2
        150    0.21     79     0.76    24
CK       -     1.00     -      1.00    -
Compound 1 shows with dimethomorph expression activitiy result of the test：Compound 1 is treated is significantly better than that dimethomorph with protecting effect.The 100ppm protecting effects of compound 1 are 93%, and therapeutic effect is that 63%, 150ppm protecting effects are 95%, and therapeutic effect is 74%；Dimethomorph 100ppm protecting effects are 61%, and therapeutic effect is only that 2%, 150ppm protecting effects are 79%, and therapeutic effect is 24%.
The compound 1 of example 12 tests (interior) compared with bactericidal agent for preventing and treating cucumber downy mildew expression activitiy
The experiment is divided and ruled treatment and protective effect, compound 1 sets 200,100,75,50,25ppm5 concentration, comparison medicament metalaxyl, which sets 500ppm, aliette and sets 1000ppm, Bravo and set 1000ppm, general make every effort to overcome, sets 1000ppm.Often handle and once repeat, separately set blank control.Try material and select 2~3 leaf phase cucumber seedlings.Handle investigation method ibid, the results are shown in Table 9.
The compound 1 of table 9 is compared with fungicidal activity comparative test result drug concentration (ppm) protective effect/preventive effect (%) therapeutic action/preventive effect (%) compound 1 25 40.0 0.0
         50         60.0                40.0
         75         75.0                60.0
         100        90.0                75.0
The Bravo 1,000 90.0 75.0 of 200 100.0 90.0 metalaxyl, 500 60.0 40.0 aliette 1,000 75.0 40.0 is general to make every effort to overcome 1,000 90.0 0.0 CK 0.0 0.0
As can be seen from Table 9：The 100ppm of compound 1 protections are suitable with Bravo 1000ppm with therapeutic effect, but are substantially better than metalaxyl, aliette, the general prevention effect made every effort to overcome.
The protective effect of example 13 (field)
The protection test of field control cucumber downy mildew is carried out in the greenhouse of Hou Zhai villages of Shenyang City Dongling District Hun River township one.
Compound 1 (20% wettable powder) sets 200,400,600ppm tri- concentration, and general make every effort to overcome (66.5% aqua) of comparison medicament sets 800,1000,1200ppm.Blank control separately is set, 4 repetitions are often handled.Sample investigation.For the first time processing April 5, see primary infection focus；April 17, first meeting infection court are handled for the second time；Third time handles April 22.First time preventive effect investigates April 22, and second of preventive effect investigation third time preventive effect on April 29 investigates May 5.It the results are shown in Table 10
10 compound of table 1 field control cucumber cream viral disease protective effect pharmacodynamic results drug concentration (ppm) May 5 April 29 April 22
Disease, which refers to preventive effect (%) disease and refers to preventive effect (%) disease, refers to preventive effect (%)
200 0 100 0 100 0.03 97.0 compounds 1 400 0 100 0 100 0 100
          600       0    100     0    100     0      100
800 0.08 89.2 0.21 77.2 0.59 41.0 general make every effort to overcome * 1,000 0.06 91.6 0.16 82.6 0.42 58.0
          1200     0.03  95.9   0.10  89.1    0.32   68.0  CK           -       0.74   -     0.92   -      1.00   -
* it is general to make every effort to overcome (Schilling company commodity-i.e. Previcur, common name Propamocarb is propamocarb)
From table 10 we can see that：The protecting effect of compound 1 200,400,600ppm be substantially better than it is general make every effort to overcome 800,1000,1200ppm, as the difference of effect between two kinds of medicaments of extension of dispenser interval becomes apparent from.
The therapeutic action of example 14 (field)
The therapeutic test of field control cucumber downy mildew is carried out in the greenhouse of Shenyang City Shujiatun District one.
Compound 1 (20% wettable powder) sets 100,200,300ppm3 concentration, and a gram dew 1500ppm does comparison medicament, separately sets blank control.Three repetitions are often handled, for the first time processing May 13, for the second time processing May 20.Third time handles May 27, carries out preventive effect investigation June 3.It the results are shown in Table 11.
As can be seen from Table 11：The 100ppm therapeutic effects of compound 1 are slightly better than a gram dew 1500ppm, and compound 1 200,300ppm therapeutic effects are substantially better than a gram dew 1500ppm therapeutic effect.
The field control cucumber downy mildew therapeutic action pharmacodynamic results of 11 compound of table 1
Drug concentration (ppm) disease refers to preventive effect (%) compound 1 100 0.049 88.4
          200        0.011    97.4
300 0 100 grams of dew * * 1,500 0.076 81.9
CK         -         0.422     -
* grams of dew (E.I.Du Pont Company's commodity-cymoxanil is the mixture of DPX-3217 and Mancozeb)
The tomato late blight of example 15 (field)
The therapeutic test of field control tomato late blight is carried out in the greenhouse of Shenyang City Hun River station one.
Compound 1 (20% wettable powder) sets 200,400,600ppm3 concentration.Big raw (wettable powder of content 80%) 1300ppm does comparison medicament, separately sets blank control.Three repetitions are often handled, first time handles May 21, for the second time processing May 28, third time handles June 5, progress preventive effect investigation on June 20.
It the results are shown in Table 12.
The field control tomato late blight therapeutic action pharmacodynamic results of 12 compound of table 1
Disease refers to disease and refers to preventive effect (%) compound 1 200 0.74 5.56 80.9 before drug concentration (ppm) medicine
          400       0.74      2.59     91.1
600 1.11 2.22 94.9 big raw * * 1,300 1.11 5.56 87.3
CK         -        1.11      43.7      -
The big lifes of * *：U.S. Luo Men-Haars Co., Ltd's commodity：Mancozeb.
As can be seen from Table 12：The 400,600ppm of compound 1 is substantially better than big raw 1300ppm to the prevention effect of tomato late blight.

Claims (3)

1st, a kind of acrylamide germicide containing fluoro-diphenyl compound, chemical name is 3- (4- fluorophenyls) -3- (3,4- Dimethoxyphenyl) acryloyl morpholine (I)
Structural formula is；
Figure C9611555100021
2nd, fungicide compound (I) accounts for 1~99% in the biocide preparation of fungicide compound according to claim 1, preparation.
3rd, the fungicide compound according to claim I, the disease produced available for preventing and treating by oomycetes subclass pathogen, to cucumber downy mildew, grape downy mildew, citrus epidemic disease, capsicum epidemic disease, the late blight of potato, tomato late blight, onion epidemic disease, Cucumber Blight have special efficacy.
CN96115551A 1995-08-28 1996-08-21 Fungicide contg. fluorodiphenyl acrylamides Expired - Lifetime CN1043720C (en)

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