CN103980179A - Indole-substituted oxime ether compounds as well as preparation method and application thereof - Google Patents

Indole-substituted oxime ether compounds as well as preparation method and application thereof Download PDF

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CN103980179A
CN103980179A CN201410232317.8A CN201410232317A CN103980179A CN 103980179 A CN103980179 A CN 103980179A CN 201410232317 A CN201410232317 A CN 201410232317A CN 103980179 A CN103980179 A CN 103980179A
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compound
arh
general formula
cdcl
nmr
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吐松
谢亚强
李军
卢英华
叶李艺
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses indole-substituted oxime ether compounds as well as a preparation method and application thereof, relating to pesticide bactericides. The indole-substituted oxime ether compounds are effective bactericides. The compounds have internal absorption performance, can be used for foliage and soil bactericides, can be used for effectively preventing and treating various plant diseases, and comprise plant foliage bactericides, soil bactericides and the like, wherein crop diseases include but are not limited to corn rust, rice blast, gray mold, barley powdery mildew, wheat powdery mildew, apple powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber anthracnose, grape powdery mildew and grape downy mildew. The indole-substituted oxime ether compounds are used as active components, and can be used for forming composite bactericides with other carriers, diluents and other bactericides. The indole-substituted oxime ether compounds have very high biological activities, and can obtain very good sterilization effects even by using very low dose, so that the indole-substituted oxime ether compounds can be used for preparing the bactericides.

Description

A kind of indoles substituted oximinoether kind compound and preparation method thereof and application
Technical field
The present invention relates to agricultural bactericide, especially relate to a kind of indoles substituted oximinoether kind compound and preparation method thereof and application.
Background technology
1999, U.S.'s ROHM AND HAAS (ROHM AND HASS) company reported phenyl propenylidene oximinoether kind bactericide, sterilant, and the patent No. is: EP936213, and its structural formula is as follows:
2000, LG-DOW benefit agriculture (DOW AGROSCIENCES) company also reported a class aryl rings propyl substituted oximinoether kind bactericide agent, and the patent No. is: US6063956, and its structural formula is as follows:
2002, LG-DOW benefit agriculture (DOW AGROSCIENCES) company reported again the agent of another kind of aryl rings propyl substituted oximinoether kind bactericide, and the patent No. is: WO2002046142, and its structural formula is as follows:
It is reported, the compound of these unsaturated oxime ether structures has broad spectrum of activity, can be used for preventing on various crops by multiple fungus-caused diseases such as Phycomycetes, Oomycete, Ascomycetes and deuteromycetes.Rear two series bactericidal agents have replaced the aryl propenylidene of disclosed compound in EP936213 with aryl rings propyl, it is reported that this compounds has broad-spectrum sterilization activity equally, wheat leaf rust, wheat powdery mildew, tomato late blight, rice blast and other plurality of plant diseases are all had to good preventive effect.
2006, to tell the people such as pine and reported a class indene substituted oximinoether kind bactericide agent, China Patent Publication No. is CN1824648, its structural formula is as follows:
This compounds has broad-spectrum sterilization activity equally, and part of compounds is better than commercial sterilant of part to the preventive effect effect of rice blast, wheat powdery mildew and other plurality of plant diseases, for example, BAS490F and SYP-Z071, its structural formula is as follows:
Summary of the invention
The first object of the present invention is to provide indoles substituted oximinoether kind compound.
The second object of the present invention is to provide the preparation method of indoles substituted oximinoether kind compound.
The 3rd object of the present invention is to provide indoles substituted oximinoether kind compound in the application of preparing in sterilant.
The described general formula I that indoles substituted oximinoether kind compound is provided is:
Wherein:
R 1for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 2for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 3for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 4for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R5 is hydrogen, C 1– C 4alkyl, C 3– C 6cycloalkyl, phenyl or substituted-phenyl;
R 6for hydrogen, C 1– C 4alkyl, C 3– C 6cycloalkyl, phenyl or substituted-phenyl;
Q is selected from one of group as follows:
In preferred general formula I, preferably:
R 1for hydrogen;
R 2for hydrogen, fluorine or chlorine;
R 3for hydrogen, fluorine or chlorine;
R 4for hydrogen;
R 5for methyl;
R 6for hydrogen, methyl;
Q is selected from one of group as follows:
The preparation method of described indoles substituted oximinoether kind compound is as follows:
Reaction formula 1:
Reaction formula 2:
Reaction formula 3:
Reaction formula 4:
In reaction formula 1, in the mixed solution of solvent methyl-sulphoxide and water, under additive exists, under 25～150 DEG C of conditions, obtain the compound shown in general formula III with the compound shown in general formula II and reaction of sodium azide; Compound shown in general formula III and trifluoroacetic anhydride, under the existence of pyridine, in methylene dichloride, under 0～80 DEG C of condition, react to obtain the compound shown in general formula IV; Compound shown in general formula IV and monochloroacetone, under the existence of alkali salt of wormwood, in poly(oxyethylene glycol) 400 solvent, under 25～150 DEG C of conditions, react to obtain the compound shown in general formula V;
Described additive can be selected from the bromo-phenyl aldehyde of the chloro-2-of 4-, L-AA sodium and DL-proline.
In reaction formula 2, in solvent acetonitrile, under alkali salt of wormwood exists, under 25～80 DEG C of conditions, obtain the compound shown in general formula VI with the compound shown in general formula V and iodomethane reaction; Compound shown in general formula VI and oxammonium hydrochloride, under alkali sodium acetate exists, in ethanol/water, under 25～80 DEG C of conditions, react to obtain the compound shown in general formula VII; Or, with compound and oxammonium hydrochloride shown in general formula V, under alkali sodium acetate exists, in ethanol/water, under 25～80 DEG C of conditions, react to obtain the compound shown in general formula VII
In reaction formula 3, in solvent acetonitrile, under alkali salt of wormwood exists, under 25～85 DEG C of conditions, the general formula I – Q that reacts correspondingly with the compound shown in general formula VI respectively with 3 different intermediate A, B or C 1, I – Q 2with I – Q 3shown compound;
In reaction formula 4, in solvent methanol, under 25～80 DEG C of conditions, with general formula I – Q 2or I – Q 3the general formula I – Q that shown compound reacts correspondingly with aqueous methylamine solution respectively 4with I – Q 5shown compound.
Described indoles substituted oximinoether kind compound can be used for preparing to prevent and treat in crop pest preparation applying.
The indoles substituted oximinoether kind compound of general formula I of the present invention is effective sterilant, and these compounds have interior absorption and can be used for blade face and soil fungicides, can effectively prevent and treat plurality of plant diseases, comprises plant leaf surface sterilant, soil fungicides etc.Described crop pest includes but not limited to corn rust, rice blast, gray mold, barley powdery mildew, wheat powdery mildew, apple mildew, powdery mildew of cucumber, cucumber downy mildew, cucumber anthracnose, uncinula necator, downy mildew of garpe, is particularly suitable for preventing and treating wheat powdery mildew, corn rust, cucumber anthracnose, cucumber downy mildew, rice blast and gray mold.
Described indoles substituted oximinoether kind compound can form fungicidal composition as active ingredient together with other carrier or thinner, and in Bactericide composition, the mass percentage content of indoles substituted oximinoether kind compound is 1%～99%.
Described indoles substituted oximinoether kind compound is as active ingredient and other sterilant composition compound disinfectant, and in compound disinfectant, the mass percent of indoles substituted oximinoether kind compound is 1%～99%.
Described indoles substituted oximinoether kind compound has very high biological activity, even if still can obtain good sterilization effect under very low dosage, therefore described indoles substituted oximinoether kind compound can be used for preparing sterilant.
The present invention have the part of compounds of general formula III structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound Ⅲ – 1: yellow solid Mp:37.6～38.2 DEG C
1H?NMR(CDCl 3,400MHz):δ6.11(s,2H,NH 2),6.64(d,J＝8.0Hz,1H,ArH),6.72-6.77(m,1H,ArH),7.28-7.33(m,1H,ArH),7.48(dd,J＝8.0,1.6Hz,1H,ArH),9.87(s,1H,O＝CH)； 13C?NMR(CDCl 3,100MHz):115.9,116.4,118.8,135.2,135.7,149.8,194.1.
Compound Ⅲ – 2: faint yellow solid Mp:81.8～82.2 DEG C
1H?NMR(CDCl 3,400MHz):δ6.21(s,2H,NH 2),6.66(d,J＝1.6Hz,1H,ArH),6.71(dd,J＝8.4,1.6Hz,1H,ArH),7.40(d,J＝8.4Hz,1H,ArH),9.82(s,1H,O＝CH)； 13C?NMR(CDCl 3,100MHz):δ115.8,117.3,117.7,137.3,141.9,150.8,193.3.
Compound Ⅲ – 3: yellow oil
1H?NMR(CDCl 3,400MHz):δ6.31(s,2H,NH 2),6.31(dd,J＝10.8,2.0Hz,1H,ArH),6.42-6.47(m,1H,ArH),7.46(dd,J＝8.0,6.4Hz,1H,ArH),9.79(s,1H,O＝CH)； 13C?NMR(CDCl 3,100MHz):δ102.0(d,J CF＝24.7Hz),105.2(d,J CF＝23.4Hz),116.4(d,J CF＝0.9Hz),139.0(d,J CF＝12.5Hz),152.5(d,J CF＝23.5Hz),167.6(d,J CF＝252.9Hz),192.9.
Compound Ⅲ – 4: yellow oil
1H?NMR(CDCl 3,400MHz):δ6.00(s,2H,NH 2),6.62(dd,J＝9.2,4.0Hz,1H,ArH),7.06-7.12(m,1H,ArH),7.18(dd,J＝8.4,3.2Hz,1H,ArH),9.81(s,1H,O＝CH)； 13C?NMR(CDCl 3,100MHz):δ117.8(d,J CF＝6.6Hz),118.5(d,J CF＝5.2Hz),119.8(d,J CF＝21.2Hz),123.8(d,J CF＝21.2Hz),146.8(d,J CF＝1.2Hz),154.4(d,J CF＝234.5Hz),193.1.
The present invention have the part of compounds of general formula IV structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound Ⅳ – 1: faint yellow solid Mp:68.9～69.6 DEG C
1H?NMR(CDCl 3,400MHz):δ7.38-7.43(m,1H,ArH),7.68-7.74(m,1H,ArH),7.79(dd,J＝7.6,1.6Hz,1H,ArH),8.68(d,J＝8.4Hz,1H,ArH),9.98(s,1H,O＝CH),12.19(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ30.0,120.8,122.9,125.6,136.4,136.7,138.5,156.3,195.9.
Compound Ⅳ – 2: faint yellow solid Mp:58.5～59.0 DEG C
1H?NMR(CDCl 3,500MHz):δ7.38(dd,J＝6.4,1.6Hz,1H,ArH),7.71(d,J＝6.4Hz,1H,ArH),8.75(d,J＝1.2Hz,1H,ArH),9.94(s,1H,O＝C-H),12.24(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ114.2,117.1,121.1,121.2,125.9,137.2,139.3,143.5,194.8.
Compound Ⅳ – 3: faint yellow solid Mp:47.6～48.2 DEG C
1H?NMR(CDCl 3,400MHz):δ7.06-7.12(m,1H,ArH),7.80(dd,J＝8.8,6.0Hz,1H,ArH),8.46(dd,J＝11.2,2.4Hz,1H,ArH),9.93(s,1H,O＝C-H),12.39(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ108.8(d,J CF＝28.7Hz),112.9(d,J CF＝22.7Hz),115.6(d,J CF＝286.8Hz),119.7,138.8(d,J CF＝11.6Hz),140.9(d,J CF＝13.5Hz),156.5(d,J CF＝76.0Hz),167.4(d,J CF＝259.6Hz),194.5.
Compound Ⅳ – 4: faint yellow solid Mp:96.3～97.0 DEG C
1H?NMR(CDCl 3,400MHz):δ7.04-7.46(m,1H,ArH),7.50(dd,J＝7.6,3.2Hz,1H,ArH),8.72(dd,J＝9.2,4.8Hz,1H,ArH),9.94(s,1H,O＝C-H),12.01(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ115.8(d,J CF＝326.9Hz),122.0(d,J CF＝22.7Hz),122.9(d,J CF＝6.9Hz),123.7(d,J CF＝21.9Hz),124.0(d,J CF＝5.5Hz),134.7(d,J CF＝2.9Hz),156.0(d,J CF＝37.9Hz),159.5(d,J CF＝247.2Hz),194.6.
The present invention have the part of compounds of general formula V structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound V-1: brown solid Mp:139.7～140.6 DEG C
1H?NMR(CDCl 3,400MHz):δ2.60(s,3H,CH 3),7.13-7.17(m,1H,ArH),7.20(dd,J＝2.4,0.8Hz,1H,N-C＝CH),7.32-7.37(m,1H,ArH),7.43(dd,J＝8.0,0.8Hz,1H,ArH),7.71(dd,J＝8.0,0.8Hz,1H,ArH),9.24(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ26.2,110.2,112.5,121.3,123.4,126.7,127.9,135.7,137.7,190.9.
Compound V-2: yellow solid Mp:150.3～150.8 DEG C
1H?NMR(CDCl 3,400MHz):δ2.61(s,3H,CH 3),7.12(dd,J＝8.4,1.6Hz,1H,ArH),7.17(dd,J＝2.4,0.8Hz,1H,N-C＝CH),7.44-7.45(m,1H,ArH),7.62(d,J＝8.8Hz,1H,ArH),9.49(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ26.2,110.1,112.4,122.4,124.3,126.4,132.6,136.3,138.0,190.8.
Compound V-3: brown color solid Mp:145.2～145.4 DEG C
1H?NMR(CDCl 3,400MHz):δ2.61(s,3H,CH 3),7.08-7.14(m,1H,ArH),7.16(d,J＝1.2Hz,1H,N-C＝CH),7.34(dd,J＝8.8,2.0Hz,1H,ArH),7.39(dd,J＝9.2,4.4Hz,1H,ArH),9.49(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ26.2,107.4(d,J CF＝23.2Hz),109.9(d,J CF＝5.5Hz),113.7(d,J CF＝9.5Hz),115.9(d,J CF＝26.9Hz),128.0(d,J CF＝10.3Hz),134.4,137.0,158.5(d,J CF＝235.7Hz),191.0.
Compound V-4: brown color solid Mp:187.3～187.7 DEG C
1H?NMR(CDCl 3,400MHz):δ2.61(s,3H,CH 3),7.08-7.14(m,1H,ArH),7.16(d,J＝1.2Hz,1H,N-C＝CH),7.34(dd,J＝8.8,2.4Hz,1H,ArH),7.39(dd,J＝8.8,4.4Hz,1H,ArH),9.45(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ26.2,107.4(d,J CF＝23.1Hz),109.9(d,J CF＝5.6Hz),113.6(d,J CF＝9.4Hz),115.9(d,J CF＝26.9Hz),128.0(d,J CF＝10.2Hz),134.4,137.0,158.9(d,J CF＝235.7Hz),191.0.
The present invention have the part of compounds of general formula VI structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound VI-1: brown solid Mp:92.5～93.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.61(s,3H,C-CH 3),4.07(s,3H,N-CH 3),7.13-7.17(m,1H,ArH),7.28(s,1H,N-C＝CH),7.36-7.38(m,2H,ArH),7.69(d,J＝8.0Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ28.3,32.5,110.7,112.3,121.0,123.2,126.1,126.2,135.2,140.4,192.0.
Compound VI-2: brown color solid Mp:147.1～147.9 DEG C
1H?NMR(CDCl 3,400MHz):δ2.64(s,3H,C-CH 3),3.95(s,3H,N-CH 3),7.25(s,1H,N-C＝CH),7.40(dd,J＝8.4,2.0Hz,1H,ArH),7.62(d,J＝7.2Hz,1H,ArH),7.96(d,J＝2.4Hz,1H,ArH)； 13CNMR(CDCl 3,100MHz):δ20.5,55.4,110.5,126.8,126.9,127.4,127.4,132.0,142.9,152.3,154.3.
Compound VI-3: yellow solid Mp:106.6～107.1 DEG C
1H?NMR(CDCl 3,400MHz):δ2.59(s,3H,C-CH 3),4.03(s,3H,N-CH 3),6.90-6.95(m,1H,ArH),7.03(dd,J＝10.0,2.0Hz,1H,ArH),7.27(s,1H,N-C＝CH),7.63(dd,J＝8.8,5.6Hz,1H,ArH),7.96(d,J＝2.4Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ28.1,32.7,96.6(d,J CF＝28.2Hz),110.8(d,J CF＝25.5Hz),112.5(d,J CF＝1.2Hz),122.6,124.6(d,J CF＝10.5Hz),136.0(d,J CF＝3.6Hz),140.8(d,J CF＝12.2Hz),162.4(d,J CF＝242.1Hz),191.4.
Compound VI-4: yellow solid Mp:83.6～84.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.60(s,3H,C-CH 3),4.05(s,3H,N-CH 3),7.10-7.16(m,1H,ArH),7.22(s,1H,N-C＝CH),7.28-7.33(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ28.3,32.7,107.1(d,J CF＝23.0Hz),111.7,111.8(d,J CF＝3.1Hz),115.3(d,J CF＝26.9Hz),126.0(d,J CF＝10.3Hz),136.3,136.7(d,J CF＝71.4Hz),158.9(d,J CF＝235.6Hz),191.9.
The present invention have the part of compounds of general formula VII structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound VII-1: yellow solid Mp:161.5～162.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.35(s,3H,C-CH 3),3.94(s,3H,N-CH 3),6.77(d,J＝0.8Hz,1H,N-C＝CH),7.08-7.13(m,1H,ArH),7.26-7.29(m,1H,ArH),7.31-7.34(m,1H,ArH),7.59-7.63(m,1H,ArH),7.83(s,1H,N-OH)； 13C?NMR(CDCl 3,100MHz):δ13.8,33.2,105.3,110.1,120.2,121.4,123.5,127.3,135.6,139.7,151.9.
Compound VII-2: yellow solid Mp:163.7～164.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.34(s,3H,C-CH 3),3.91(s,3H,N-CH 3),6.73(d,J＝0.4Hz,1H,N-C＝CH),7.07(dd,J＝8.4,1.6Hz,1H,ArH),7.32(d,J＝0.8Hz,1H,ArH),7.50(d,J＝8.4Hz,1H,ArH),7.54(s,1H,N-OH)； 13C?NMR(CDCl 3,100MHz):δ13.6,33.4,105.3,110.1,121.0,122.2,125.7,129.4,136.3,140.1,151.6.
Compound VII-3: yellow solid Mp:164.3～164.7 DEG C
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,C-CH 3),3.88(s,3H,N-CH 3),6.74(d,J＝0.4Hz,1H,N-C＝CH),6.84-6.90(m,1H,ArH),7.00(dd,J＝10.0,2.4Hz,1H,ArH),7.51(dd,J＝8.8,5.6Hz,1H,ArH),7.84(s,1H,N-OH)； 13C?NMR(CDCl 3,100MHz):δ13.7,33.5,96.3(d,J CF＝26.3Hz),105.4,109.2(d,J CF＝24.7Hz),122.3(d,J CF＝10.2Hz),123.7,136.2(d,J CF＝3.9Hz),139.9(d,J CF＝11.9Hz),151.6,161.0(d,J CF＝237.9Hz).
Compound VII-4: yellow solid Mp:158.9～159.4 DEG C
1H?NMR(CDCl 3,400MHz):δ2.34(s,3H,C-CH 3),3.92(s,3H,N-CH 3),6.71(s,1H,N-C＝CH),6.99-7.04(m,1H,ArH),7.21-7.26(m,2H,ArH),7.77(s,1H,N-OH)； 13C?NMR(CDCl 3,100MHz):δ13.8,33.4,105.0(d,J CF＝4.9Hz),105.8(d,J CF＝23.2Hz),110.8(d,J CF＝9.6Hz),112.0(d,J CF＝26.2Hz),127.3(d,J CF＝10.3Hz),136.3,137.0,151.7,158.3(d,J CF＝233.6Hz).
Compound VII-5: white solid Mp:146.9～147.8 DEG C
1H?NMR(DMSO,400MHz):δ2.15(s,3H,CH 3),6.71(d,J＝1.6Hz,1H,N-C＝CH),6.93-6.98(m,1H,ArH),7.07-7.11(m,1H,ArH),7.37(d,J＝8.0Hz,1H,ArH),7.50(d,J＝7.6Hz,1H,ArH),11.15(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ11.8,105.0,111.3,120.4,121.5,124.3,128.3,133.9,137.1,150.6.
The present invention have the part of compounds of general formula I structure concrete structure formula, compound physical property, 1h NMR (CDCl 3, 400MHz), 13c NMR (CDCl 3, 100MHz) and data are as follows, and be used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound I – 1: yellow solid Mp:113.4～114.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.29(s,3H,N＝C-CH 3),3.66(s,3H,C＝C-OCH 3),3.78(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),5.15(s,2H,O-CH 2),6.71(d,J＝1.2Hz,1H,N-C＝CH),7.05-7.09(m,1H,ArH),7.15-7.18(m,1H,ArH),7.21-7.25(m,1H,ArH),7.26-7.36(m,3H,ArH),7.48-7.51(m,1H,ArH),7.56-7.59(m,1H,ArH),7.58(s,1H,O-CH＝C)； 13C?NMR(CDCl 3,100MHz):δ14.2,33.2,51.9,62.2,74.8,105.0,110.0,110.8,120.0,121.2,123.3,127.2,127.8,128.1,128.8,131.3,132.1,135.7,137.6,139.7,150.1,160.1,168.4；HRMS(ESI)calcd?for[C 23H 24N 2NaO 4] +(M+Na +):415.1628；found:415.1620.
Compound I – 2: yellow solid Mp:107.8～108.3 DEG C
1H?NMR(CDCl 3,400MHz):δ2.27(s,3H,N＝C-CH 3),3.67(s,3H,C＝C-OCH 3),3.75(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),5.15(s,2H,O-CH 2),6.67(s,1H,N-C＝CH),7.04(dd,J＝8.4,1.6Hz,1H,ArH),7.15-7.19(m,1H,ArH),7.27(d,J＝0.8Hz,1H,ArH),7.29-7.36(m,2H,ArH),7.42-7.50(m,2H,ArH),7.59(s,1H,O-CH＝C)； 13C?NMR(CDCl 3,100MHz):δ14.2,33.4,51.9,62.2,74.9,104.9,110.0,110.8,120.8,122.1,125.7,127.8,128.1,128.8,129.2,131.3,132.1,136.4,137.5,140.1,149.8,160.1,168.3；HRMS(ESI)calcd?for[C 23H 23ClN 2NaO 4] +(M+Na +):449.1239；found:449.1229.
Compound I – 3: faint yellow solid Mp:119.0～119.5 DEG C
1H?NMR(CDCl 3,400MHz):δ2.27(s,3H,N＝C-CH 3),3.67(s,3H,C＝C-OCH 3),3.74(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),5.14(s,2H,O-CH 2),6.68(s,1H,N-C＝CH),6.81-6.87(m,1H,ArH),6.94(dd,J＝10.0,2.0Hz,1H,ArH),7.15-7.18(m,1H,ArH),7.31-7.34(m,2H,ArH),7.46-7.50(m,2H,ArH),7.59(s,1H,O-CH＝C)； 13C?NMR(CDCl 3,100MHz):δ14.1,33.5,51.9,62.2,74.8,96.3(d,J CF＝26.3Hz),105.0,108.9(d,J CF＝24.7Hz),110.8,122.1(d,J CF＝10.1Hz),123.7,127.8,128.1,128.8,131.3,132.1,136.3(d,J CF＝3.8Hz),137.6,139.9(d,J CF＝12.0Hz),149.9,160.1,160.8(d,J CF＝237.6Hz),168.4；HRMS(ESI)calcd?for[C 23H 23FN 2NaO 4] +(M+Na +):433.1534；found:433.1526.
Compound I – 4: faint yellow solid Mp:102.8～103.4 DEG C
1H?NMR(CDCl 3,400MHz):δ2.28(s,3H,N＝C-CH 3),3.67(s,3H,C＝C-OCH 3),3.77(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),5.15(s,2H,O-CH 2),6.65(s,1H,N-C＝CH),6.95-7.00(m,1H,ArH),7.15-7.22(m,3H,ArH),7.29-7.36(m,2H,ArH),7.47-7.50(m,1H,ArH),7.59(s,1H,O-CH＝C)； 13C?NMR(CDCl 3,100MHz):δ14.3,33.4,51.9,62.2,74.9,104.6(d,J CF＝4.9Hz),105.7(d,J CF＝23.2Hz),110.7(d,J CF＝9.5Hz),110.8,111.7(d,J CF＝26.3Hz),127.2(d,J CF＝10.3Hz),127.8,128.1,128.8,131.3,132.1,136.3,137.1,137.5,149.9,158.1(d,J CF＝233.1Hz),160.1,168.4；HRMS(ESI)calcd?for[C 23H 23FN 2NaO 4] +(M+Na +):433.1534；found:433.1529.
Compound I – 5: brown crystal Mp:115.7～116.2 DEG C
1H?NMR(CDCl 3,400MHz):δ2.23(s,3H,N＝C-CH 3),3.72(s,3H,C＝C-OCH 3),3.81(s,3H,O＝C-OCH 3),5.12(s,2H,O-CH 2),6.67(d,J＝1.2Hz,1H,N-C＝CH),7.03-7.12(m,1H,ArH),7.16-7.22(m,3H,ArH),7.31-7.35(m,2H,ArH),7.49-7.51(m,1H,ArH),7.60(s,1H,O-CH＝C),7.95-7.99(m,1H,ArH),9.03(s,1H,NH)； 13C?NMR(CDCl 3,100MHz):δ12.3,52.1,62.2,74.4,103.8,110.9,111.3,120.0,121.3,123.8,127.9,128.3,129.0,131.2,132.2,134.4,137.0,137.4,148.5,160.3,168.7；HRMS(ESI)calcd?for[C 22H 22N 2NaO 4] +(M+Na +):401.1472；found:401.1469.
Compound I – 6: yellow solid Mp:89.0～89.6 DEG C
1H?NMR(CDCl 3,400MHz):δ2.27(s,3H,N＝C-CH 3),3.75(s,3H,N-CH 3),3.79(s,3H,O＝C-OCH 3),4.01(s,3H,N-OCH 3),5.13(s,2H,O-CH 2),6.72(s,1H,N-C＝CH),7.05-7.09(m,1H,ArH),7.18-7.20(m,1H,ArH),7.21-7.29(m,2H,ArH),7.35-7.39(m,1H,ArH),7.39-7.44(m,1H,ArH),7.48(dd,J＝7.6,0.8Hz,1H,ArH),7.57(d,J＝8.0Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.2,33.1,53.2,64.1,75.1,105.2,110.0,120.0,121.3,123.4,127.2,128.0,128.9,129.1,129.6,130.2,135.4,137.0,139.7,150.0,150.6,163.6；HRMS(ESI)calcd?for[C 22H 23N 3NaO 4] +(M+Na +):416.1581；found:416.1565.
Compound I – 7: faint yellow solid Mp:99.0～99.7 DEG C
1H?NMR(CDCl 3,400MHz):δ2.25(s,3H,N＝C-CH 3),3.70(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),4.02(s,3H,N-OCH 3),5.12(s,2H,O-CH 2),6.68(d,J＝0.8Hz,1H,N-C＝CH),7.04(dd,J＝8.4,1.6Hz,1H,ArH),7.20(dd,J＝7.2,1.6Hz,1H,ArH),7.26-7.27(m,1H,ArH),7.38-7.49(m,4H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.1,33.4,53.2,64.1,75.2,105.1,110.0,120.8,122.1,125.7,128.0,128.9,129.1,129.3,129.6,130.2,136.2,136.9,140.1,149.9,150.2,163.6；HRMS(ESI)calcd?for[C 22H 22ClN 3NaO 4] +(M+Na +):450.1191；found:450.1196.
Compound I – 8: white crystal Mp:123.0～124.3 DEG C
1H?NMR(CDCl 3,400MHz):δ2.24(s,3H,N＝C-CH 3),3.69(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),4.01(s,3H,N-OCH 3),5.12(s,2H,O-CH 2),6.80(d,J＝0.4Hz,1H,N-C＝CH),6.80-6.86(m,1H,ArH),6.93(dd,J＝10.0,2.0Hz,1H,ArH),7.20(dd,J＝7.2,1.2Hz,1H,ArH),7.35-7.44(m,2H,ArH),7.45-7.49(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.0,33.4,53.2,64.1,75.1,96.2(d,J CF＝26.2Hz),105.2,109.0(d,J CF＝24.6Hz),122.1(d,J CF＝10.2Hz),123.6,128.0,128.9,129.1,129.6,130.2,136.0(d,J CF＝3.9Hz),136.9,139.9(d,J CF＝12.1Hz),150.0,150.3,161.0(d,J CF＝237.8Hz),163.6；HRMS(ESI)calcd?for[C 22H 22FN 3NaO 4] +(M+Na +):434.1487；found:434.1492.
Compound I – 9: faint yellow solid Mp:90.5～92.1 DEG C
1H?NMR(CDCl 3,400MHz):δ2.25(s,3H,N＝C-CH 3),3.72(s,3H,N-CH 3),3.80(s,3H,O＝C-OCH 3),4.01(s,3H,N-OCH 3),5.12(s,2H,O-CH 2),6.65(d,J＝0.4Hz,1H,N-C＝CH),6.95-7.01(m,1H,ArH),7.15-7.22(m,2H,ArH),7.35-7.44(m,2H,ArH),7.47(dd,J＝7.6,1.2Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.2,33.4,53.2,64.1,75.2,104.8(d,J CF＝4.9Hz),105.7(d,J CF＝23.1Hz),110.7(d,J CF＝9.6Hz),111.8(d,J CF＝26.3Hz),127.2(d,J CF＝10.3Hz),128.0,128.9,129.1,129.6,130.2,136.3,136.8,136.9,150.0,150.3,158.2(d,J CF＝233.4Hz),163.6；HRMS(ESI)calcd?for[C 22H 22FN 3NaO 4] +(M+Na +):434.1487；found:434.1487.
Compound I – 10: brown solid Mp:93.5～94.1 DEG C
1H?NMR(CDCl 3,400MHz):δ2.35(s,3H,N＝C-CH 3),3.76(s,3H,N-OCH 3),3.77(s,3H,O＝C-OCH 3),3.82(s,3H,H-N-CH 3),5.30(s,2H,O-CH 2),6.74(s,1H,N-C＝CH),7.06-7.10(m,1H,ArH),7.21-7.26(m,1H,ArH),7.28(d,J＝8.0Hz,1H,ArH),7.35-7.40(m,3H,ArH),7.54-7.57(m,1H,ArH),7.58(d,J＝8.0Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.4,33.2,53.8,62.3,72.4,105.3,110.0,120.1,121.3,123.4,127.2,127.5,128.5,129.0,129.4,135.4,136.5,137.6,139.7,150.6,156.1；HRMS(ESI)calcd?for[C 21H 23N 3NaO 4] +(M+Na +):404.1586；found:404.1581.
Compound I – 11: yellow solid Mp:98.8～99.0 DEG C
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,N＝C-CH 3),3.76(s,3H,N-OCH 3),3.77(s,3H,O＝C-OCH 3),3.78(s,3H,H-N-CH 3),5.29(s,2H,O-CH 2),6.70(d,J＝0.8Hz,1H,N-C＝CH),7.05(dd,J＝8.4,1.2Hz,1H,ArH),7.27-7.28(m,1H,ArH),7.34-7.40(m,3H,ArH),7.48(d,J＝8.4Hz,1H,ArH),7.52-7.55(m,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.4,33.4,53.8,62.4,72.5,105.2,110.0,120.9,122.1,125.7,127.6,128.6,129.0,129.3,129.4,136.2,136.3,137.6,140.1,150.3,156.1；HRMS(ESI)calcd?for[C 21H 22FClN 3NaO 4] +(M+Na +):438.1191；found:438.1188.
Compound I – 12: yellow oil
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,N＝C-CH 3),3.76(s,3H,N-OCH 3),3.77(s,3H,O＝C-OCH 3),3.78(s,3H,H-N-CH 3),5.29(s,2H,O-CH 2),6.71(s,1H,N-C＝CH),6.81-6.87(m,1H,ArH),6.94(dd,J＝10.0,2.0Hz,1H,ArH),7.35-7.40(m,3H,ArH),7.48(dd,J＝8.4,5.2Hz,1H,ArH),7.53-7.55(m,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.3,33.5,53.8,62.4,72.5,96.3(d,J CF＝26.3Hz),105.3,109.0(d,J CF＝24.7Hz),122.2(d,J CF＝10.1Hz),123.6,127.6,128.6,129.0,129.4,136.0(d,J CF＝3.8Hz),136.4,137.6,140.0(d,J CF＝12.0Hz),150.3,156.1,161.0(d,J CF＝237.9Hz)；HRMS(ESI)calcd?for[C 21H 22FN 3NaO 4] +(M+Na +):422.1487；found:422.1486.
Compound I – 13: brown oil
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,N＝C-CH 3),3.76(s,3H,N-OCH 3),3.78(s,3H,O＝C-OCH 3),3.79(s,3H,H-N-CH 3),5.30(s,2H,O-CH 2),6.68(d,J＝0.8Hz,1H,N-C＝CH),6.95-7.01(m,1H,ArH),7.17-7.23(m,2H,ArH),7.35-7.40(m,3H,ArH),7.53-7.55(m,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.4,33.4,53.8,62.4,72.5,104.9(d,J CF＝4.9Hz),105.6(d,J CF＝23.2Hz),110.7(d,J CF＝9.6Hz),111.9(d,J CF＝26.2Hz),127.2(d,J CF＝10.3Hz),127.6,128.6,129.0,129.4,136.3,136.3,136.8,137.6,150.4,156.1,158.2(d,J CF＝233.5Hz).HRMS(ESI)calcd?for[C 21H 22FN 3NaO 4] +(M+Na +):422.1487；found:422.1481.
Compound I – 14: white solid Mp:163.6～164.2 DEG C
1H?NMR(CDCl 3,400MHz):δ2.26(s,3H,N＝C-CH 3),2.86(d,J＝5.2Hz,3H,H-N-CH 3),3.76(s,3H,C-N-CH 3),3.93(s,3H,N-OCH 3),5.13(s,2H,O-CH 2),6.71(d,J＝0.4Hz,1H,N-C＝CH),6.73-6.74(m,1H,NH),7.05-7.10(m,1H,ArH),7.18-7.21(m,1H,ArH),7.22-7.25(m,1H,ArH),7.28(d,J＝7.6Hz,1H,ArH),7.34-7.43(m,2H,ArH),7.47-7.50(m,2H,ArH),7.57(d,J＝7.6Hz,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.2,26.5,33.2,63.6,75.2,105.1,110.0,120.0,121.2,123.4,127.2,127.9,129.1,129.1,129.5,129.9,135.5,137.0,139.7,150.4,151.6,163.2；HRMS(ESI)calcd?for[C 22H 24N 4NaO 3] +(M+Na +):415.1741；found:415.1738.
Compound I – 15: faint yellow solid Mp:169.4～170.5 DEG C
1H?NMR(CDCl 3,400MHz):δ2.24(s,3H,N＝C-CH 3),2.88(d,J＝5.2Hz,3H,H-N-CH 3),3.71(s,3H,C-N-CH 3),3.93(s,3H,N-OCH 3),5.12(s,2H,O-CH 2),6.66(d,J＝0.8Hz,1H,N-C＝CH),6.74-6.76(m,1H,NH),7.03(dd,J＝8.4,2.0Hz,1H,ArH),7.19(dd,J＝7.2,1.6Hz,1H,ArH),7.25-7.27(m,1H,ArH),7.34-7.43(m,2H,ArH),7.45-7.49(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.1,26.5,33.4,63.6,75.3,105.0,110.0,120.8,122.1,125.7,127.9,129.0,129.2,129.3,129.5,129.9,136.4,137.0,140.1,150.1,151.6,163.2；HRMS(ESI)calcd?for[C 22H 23ClN 4NaO 3] +(M+Na +):449.1351；found:449.1353.
Compound I – 16: yellow solid Mp:167.9～168.7 DEG C
1H?NMR(CDCl 3,400MHz):δ2.24(s,3H,N＝C-CH 3),2.88(d,J＝4.8Hz,3H,H-N-CH 3),3.70(s,3H,C-N-CH 3),3.93(s,3H,N-OCH 3),5.12(s,2H,O-CH 2),6.67(d,J＝0.4Hz,1H,N-C＝CH),6.74-6.76(m,1H,NH),6.81-6.86(m,1H,ArH),6.93(dd,J＝10.0,2.0Hz,1H,ArH),7.20(dd,J＝7.2,1.2Hz,1H,ArH),7.36-7.41(m,2H,ArH),7.45-7.49(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.1,26.5,33.5,63.6,75.2,96.3(d,J CF＝26.3Hz),105.1,109.0(d,J CF＝24.6Hz),122.1(d,J CF＝10.1Hz),123.7,127.9,129.0,129.1,129.5,129.9,136.1(d,J CF＝3.8Hz),137.0,139.9(d,J CF＝12.0Hz),150.2,151.6,161.0(d,J CF＝237.6Hz),163.2；HRMS(ESI)calcd?for[C 22H 23FN 4NaO 3] +(M+Na +):433.1646；found:433.1644.
Compound I – 17: yellow solid Mp:139.0～139.8 DEG C
1H?NMR(CDCl 3,400MHz):δ2.25(s,3H,N＝C-CH 3),2.88(d,J＝5.2Hz,3H,H-N-CH 3),3.72(s,3H,C-N-CH 3),3.93(s,3H,N-OCH 3),5.13(s,2H,O-CH 2),6.65(d,J＝0.4Hz,1H,N-C＝CH),6.75-6.77(m,1H,NH),6.95-6.70(m,1H,ArH),7.16-7.22(m,3H,ArH),7.34-7.43(m,2H,ArH),7.47-7.49(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.2,26.5,33.4,63.6,75.3,104.6(d,J CF＝5.0Hz),105.7(d,J CF＝23.2Hz),110.7(d,J CF＝9.5Hz),111.8(d,J CF＝26.3Hz),127.2(d,J CF＝10.4Hz),127.9,129.0,129.1,129.5,129.9,136.3,137.0,137.0,150.2,151.6,158.1(d,J CF＝233.3Hz),163.1；HRMS(ESI)calcd?for[C 22H 23FN 4NaO 3] +(M+Na +):433.1646；found:433.1645.
Compound I – 18: brown oil
1H?NMR(CDCl 3,400MHz):δ2.35(s,3H,N＝C-CH 3),2.89(d,J＝0.4Hz,3H,N-CH 3),3.67(s,3H,C-N-CH 3),3.83(s,3H,N-OCH 3),5.36(s,2H,O-CH 2),5.97-5.98(m,1H,NH),6.73(d,J＝0.4Hz,1H,N-C＝CH),7.06-7.10(m,1H,ArH),7.21-7.26(m,1H,ArH),7.27-7.29(m,1H,ArH),7.31-7.38(m,3H,ArH),7.51-7.55(m,1H,ArH),7.58(d,J＝8.0Hz,1H,ArH),7.69-7.72(m,1H,ArH)； 13CNMR(CDCl 3,100MHz):δ14.4,27.1,33.3,62.1,72.5,105.1,110.0,120.0,121.2,123.3,125.7,127.2,128.2,128.4,129.0,135.6,137.1,139.0,139.7,150.3,158.5；HRMS(ESI)calcd?for[C 21H 24N 4NaO 3] +(M+Na +):403.1741；found:403.1738.
Compound I – 19: faint yellow solid Mp:92.9～93.6 ° C
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,N＝C-CH 3),2.89(d,J＝4.8Hz,3H,N-CH 3),3.68(s,3H,C-N-CH 3),3.79(s,3H,N-OCH 3),5.36(s,2H,O-CH 2),5.98-6.00(m,1H,NH),6.69(d,J＝0.8Hz,1H,N-C＝CH),7.04(dd,J＝8.4,1.6Hz,1H,ArH),7.26-7.28(m,1H,ArH),7.31-7.38(m,3H,ArH),7.47(d,J＝8.4Hz,1H,ArH),7.51-7.54(m,1H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.4,27.1,33.5,62.1,72.7,105.1,110.0,120.8,122.1,125.7,125.7,128.2,128.5,128.9,129.2,136.4,136.9,139.0,140.1,150.0,158.5；HRMS(ESI)calcd?for[C 21H 23ClN 4NaO 3] +(M+Na +):437.1351；found:437.1345.
Compound I – 20: brown solid Mp:99.4～101.3 DEG C
1H?NMR(CDCl 3,400MHz):δ2.33(s,3H,N＝C-CH 3),2.89(d,J＝4.8Hz,3H,N-CH 3),3.68(s,3H,C-N-CH 3),3.77(s,3H,N-OCH 3),5.35(s,2H,O-CH 2),5.98-6.00(m,1H,NH),6.70(s,1H,N-C＝CH),6.81-6.87(m,1H,ArH),6.94(dd,J＝10.0,2.0Hz,1H,ArH),7.30-7.38(m,3H,ArH),7.46-7.54(m,2H,ArH)； 13C?NMR(CDCl 3,100MHz):δ14.3,27.1,33.6,62.1,72.6,96.3(d,J CF＝26.2Hz),105.2,109.0(d,J CF＝24.7Hz),122.1(d,J CF＝10.1Hz),123.6,125.8,128.2,128.5,128.9,136.2(d,J CF＝3.7Hz),137.0,139.0,139.9(d,J CF＝11.9Hz),150.1,158.5,161.0(d,J CF＝237.7Hz)；HRMS(ESI)calcd?for[C 21H 23FN 4NaO 3] +(M+Na +):421.1646；found:421.1649.
Compound I – 21: brown solid Mp:93.7～94.4 DEG C
1H?NMR(CDCl 3,500MHz):δ2.33(s,3H,N＝C-CH 3),2.89(d,J＝5.0Hz,3H,N-CH 3),3.68(s,3H,C-N-CH 3),3.81(s,3H,N-OCH 3),5.36(s,2H,O-CH 2),5.98(d,J＝4.5Hz,1H,NH),6.67(s,1H,N-C＝CH),6.96-7.00(m,1H,ArH),7.17-7.22(m,2H,ArH),7.31-7.38(m,3H,ArH),7.51-7.53(m,1H,ArH)； 13C?NMR(CDCl 3,125MHz):δ14.4,27.1,33.5,62.1,72.7,104.8(d,J CF＝4.9Hz),105.7(d,J CF＝22.9Hz),110.7(d,J CF＝9.6Hz),111.8(d,J CF＝26.3Hz),125.8,127.3(d,J CF＝10.8Hz),128.2,128.5,129.0,136.3,137.0,137.1,139.1,150.1,158.2(d,J CF＝233.5Hz),158.5；HRMS(ESI)calcd?for[C 21H 23FN 4NaO 3] +(M+Na +):421.1646；found:421.1641.
Described a kind of indoles substituted oximinoether kind compound can be preparing sterilant or prevent from applying in Plant diseases medicine.
Described sterilant includes but not limited to plant leaf surface sterilant, soil fungicides; Described controlling plant diseases medicine includes but not limited to control of maize rust medicine, rice blast medicine, barley powdery mildew medicine, wheat powdery mildew medicine, gray mold medicine, apple mildew medicine, powdery mildew of cucumber medicine, cucumber downy mildew medicine, cucumber anthracnose medicine, uncinula necator medicine, downy mildew of garpe medicine; Be in particular control wheat powdery mildew medicine, corn rust medicine, cucumber anthracnose medicine, cucumber downy mildew medicine, rice blast medicine and gray mold medicine; Described sterilant comprises fungicidal composition, and affiliated fungicidal composition is taking at least one compound of general formula I as active ingredient, and the compound that its preparation method is general formula I mixes with at least one carrier, and in fungicidal composition, the weight of active ingredient is 1%～99%.
Described carrier can be solid carrier, liquid vehicle or is generally gas but has been compressed into material of liquid etc.
Described solid carrier can be selected from least one in plant, seed, soil, silicate, talcum, pure aluminium silicate, montmorillonite, mica, calcium carbonate, calcium sulfate, ammonium sulfate, synthetic silica, synthetic calcium silicate, synthetic aluminium silicate, natural resin, synthetic resins, solid polystream phenol, pitch, paraffin etc., and described soil can be selected from the one in natural clay, synthesis of clay, diatomite, attapulgite etc.; Described liquid vehicle can be selected from the one in water, alcohol, ketone, ether, petroleum fractions, chlorinated hydrocarbon, aromatic hydrocarbons etc.
Beneficial effect of the present invention is as follows:
Carrier is the material that meets following condition: it and activeconstituents are convenient to be applied to pending site after preparing, for example, can be plant, seed or soil; Or be conducive to storage, transport or operation.Carrier can be solid or liquid, comprises the material that is generally gas but be compressed into liquid, can use any carrier used in configuration fungicidal composition conventionally.
Applicable solid carrier comprises natural and synthetic clay and silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Calcium carbonate, calcium sulfate, ammonium sulfate, synthetic silicon oxide and synthetic calcium silicate or pure aluminium silicate; Element is as carbon and sulphur; Natural or synthetic resin is as indoles resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax is as beeswax, paraffin.
Applicable liquid vehicle comprises water, alcohol, ketone, ether, petroleum fractions, chlorinated hydrocarbon; Alcohol is as Virahol and ethanol; Ketone is as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons is as benzene,toluene,xylene; Petroleum fractions is as kerosene and mineral oil; Hydrochloric ether is as tetracol phenixin, tetrachloroethylene and trieline, and conventionally, the mixture of these liquid is also applicable to.
Fungicidal composition be conventionally processed into concentrated form and with this for transport, before using, diluted by user.In composition, contain a small amount of tensio-active agent and contribute to dilution.Like this according to having preferably tensio-active agent of a kind of carrier in composition of the present invention at least.For example composition has two kinds of carriers at least, and wherein at least one is tensio-active agent.Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be the tensio-active agent of non-ionic or ion.The example of applicable tensio-active agent comprises sodium salt or the calcium salt of polyacrylic acid and xylogen sulfuric acid; In molecule, contain the lipid acid of at least 12 carbon atoms or the condenses of acid amides and oxyethane and/or propylene oxide.The condenses of glycol, Sorbic Acid, sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; Fatty alcohol or alkylphenol as paraoctyl phenol or or condenses to octyl group cresylol and oxyethane and/or propylene oxide; The vitriol of these condensess and sulfonate; In molecule, at least contain the sulfuric acid of 10 carbon atoms or the alkaline earth salt of sulphonate, particular certain cancers, for example sodium lauryl sulfate, the secondary alkane ester of sulfuric acid sodium, sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium, alkyl aryl sulfonic acid ester sodium, as sodium dodecylbenzene salt.
Fungicidal composition of the present invention can be processed into multiple formulation as required, for example wettable powder, pulvis, granule and solution, the agent of emulsible agriculture institute, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 25% conventionally, the activeconstituents of 50% or 75% weight, and conventionally, except solid inert carrier, also contain the dispersion agent of 3%～10% weight, and if desired can add the stablizer of 0%～10% weight and/or other additives as permeate agent or tackiness agent.Pulvis may be molded to the pulvis enriching agent that has the similar composition of wettable powder but there is no dispersion agent conventionally, more further with solid carrier dilution, is conventionally contained the composition of 0.5%～10% heavy activity component.Pulvis is prepared into conventionally has 10 and 100 order (1.676～0.152mm) sizes, and available agglomerating or implantttion technique preparation, conventionally, granula containing the activeconstituents of 0.5%～75% weight and 0%～10% weight additive as stablizer, tensio-active agent, slowly-releasing modifying agent.So-called " dry powder can flow " has again the relatively little granulometric composition of relative high density activeconstituents.Outside can emulsion concentrate desolventizing, conventionally contain when needed cosolvent, 1%～50%W/V activeconstituents, other additive of 2%～20%W/V emulsifying agent and 2%～20%W/V is as stablizer, permeate agent and corrosion inhibitor.Suspension thickner contains the activeconstituents of 10%～75% weight conventionally.The dispersion agent of 0.5%～15% weight, other additives of 0.1%～10% weight are as defoamer, corrosion inhibitor, stablizer, permeate agent and tackiness agent.
By add other one or more sterilant in composition, can there is the more activity of wide spectrum than independent compound of Formula I.In addition the fungicidal activity that, other sterilant can mutual-through type I compound has synergism.Also can be by compound of Formula I and other Mixture Use of Insecticides, or simultaneously and another kind of sterilant and other Mixture Use of Insecticides.The example that can be included in the Fungicidal compounds in the present composition has: cyanogen bacterium azoles, triadimefon, F-1991, derosal, Baijunling, king's ketone, Bordeaux mixture, fuberidazole, the pungent salt of biguanides, hymexazol, Fujione, kasugamycin, zinc manganese ethylenebisdithiocarbamate, maneb, zineb, Polyoxin, propineb, thiophanate methyl, thiram, tridemorph, rare morpholide etc.
Embodiment
Following examples and biological activity determination result can be used to further illustrate the present invention, but do not mean that restriction the present invention.
The preparation of the compound of example 1 general formula III:
2-amino-4-chlorobenzaldehyde (Ⅲ – 2) preparation
In 100mL there-necked flask, add respectively the bromo-phenyl aldehyde of the chloro-2-of 4-(II-2,4.52g, 20mmol), L-AA sodium (0.59g, 3.0mmol), DL-proline (0.46g, 4mmol), sodiumazide (2.42g, 36mmol) and N, mixed solution (the V/V=9/1 of dinethylformamide/water, 45mL), heating, induction stirring, temperature rises to 70 DEG C, TLC detection reaction, stopped reaction after 4.5h.In reaction solution, add 200mL water, extract by 2 × 100mL ethyl acetate, with 100mL saturated aqueous common salt washing oil phase, the water of using again the extraction of 2 × 100mL ethyl acetate to merge, merges all oil phase anhydrous sodium sulfate dryings, decompression precipitation, separate (ethyl acetate/petroleum ether=1/12 through silica gel column chromatography, V/V), obtain faint yellow solid 1.80g, yield 57.9%.
The preparation of the compound of example 2 general formula IV:
The preparation of the fluoro-N-of 2,2,2-tri-(2-formyl radical phenyl) ethanamide (IV – 1)
In 100mL there-necked flask, add respectively methylene dichloride (12mL), pyridine (1.6mL, 20mmol) with 2-aminobenzaldehyde (Ⅲ – 2,1.20g, 10mmol), ice bath, induction stirring, the temperature of question response mixed solution is lower than 4 DEG C, be that 1mL disposable syringe slowly adds trifluoroacetic anhydride (2.4mL, 16mmol) in reaction mixture with range, control temperature of reaction below 4 DEG C, treat that trifluoroacetic anhydride adds complete, room temperature reaction, TLC detection reaction, stopped reaction after 12h.In reaction solution, add 50mL water, extraction, then water is extracted by 2 × 40mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12 through silica gel column chromatography, V/V), obtain 1.75g faint yellow solid, yield 76.7%.
The preparation of the compound of example 3 general formula V:
1-(1H-indoles-2-yl) ethyl ketone (Ⅴ – 1) preparation
In 50mL there-necked flask, add respectively intermediate 2; the fluoro-N-of 2,2-tri-(2-formyl radical phenyl) ethanamide (IV – 1,1.95g; 9mmol), monochloroacetone (1.0mL; 11mmol), Anhydrous potassium carbonate (3.81g, 27mmol) and PEG-4000 (30mL), heating; induction stirring; temperature rises to 100 DEG C, TLC detection reaction, stopped reaction after 3.0h.In reaction solution, add 60mL water, with the extraction of 3 × 60mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12, V/V) through silica gel column chromatography, obtains brown solid 1.07g, yield 74.5%.
The preparation of the compound of example 4 general formula VI:
1-(1-methyl-indoles-2-yl) ethyl ketone (Ⅵ – 1) preparation
In 25mL there-necked flask, add respectively intermediate 1-(1H-indoles-2-yl) ethyl ketone (Ⅴ – 1,1.59g, 10mmol), Anhydrous potassium carbonate (1.38g, 10mmol), potassiumiodide (2.0mL, 32mmol) and anhydrous acetonitrile (10mL), nitrogen balloon pressurization, heating, induction stirring, temperature rises to 70 DEG C, TLC detection reaction, stopped reaction after 72.0h.In reaction solution, add 30mL water, with the extraction of 3 × 30mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12, V/V) through silica gel column chromatography, obtains brown solid 1.08g, yield 62.2%.
The preparation of the compound of example 5 general formula VII:
(E)-1-(1-methyl-indoles-2-yl) ethyl ketone oxime (Ⅶ – 1) preparation
In the there-necked flask of 25mL, add respectively 1-(1-methyl-indoles-2-yl) ethyl ketone (Ⅵ – 1,0.86g, 5mmol), oxammonium hydrochloride (0.52g, 7.5mmol), sodium acetate (0.62g, 7.5mmol) and ethanol/water mixed solution (V/V=2/1,10mL), heating, induction stirring, temperature rises to 77 DEG C of backflows, TLC detection reaction, stopped reaction after 1h.To the hydrochloric acid that adds 25mL0.5mol/L in reaction mixture, with the extraction of 2 × 30mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, obtains yellow solid 0.92g through recrystallization, yield 98.3%.
The preparation of the compound of example 6 general formula Is:
The preparation of (E, E)-methyl 3-methoxyl group-2-(2-((((1-(1-methyl-indoles-2-yl) ethylidene) amino) oxygen base) methyl) phenyl) methyl acrylate (I – 1)
In the there-necked flask of 25mL, add respectively (E)-1-(1-methyl-indoles-2-yl) ethyl ketone oxime (VII-1,0.28g, 1.5mmol), (E)-methyl 2-(2-(chloromethyl) phenyl)-3-methoxy-methyl acrylate (intermediate A, 0.49g, 2.0mmol), Anhydrous potassium carbonate (0.62g, 4.5mmol) and anhydrous acetonitrile (9mL), heating, induction stirring, temperature rises to 82 DEG C of backflows, TLC detection reaction, stopped reaction after 11.0h.In reaction solution, add 30mL water, with the extraction of 3 × 30mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12, V/V) through silica gel column chromatography and obtains yellow solid product 0.50g, yield 81.4%.
The preparation of (E, E)-methyl 2-(2-((((1-(1-methyl-indoles-2-yl) ethylidene) amino) oxygen base) methyl) phenyl)-2-methoxyimino acetic ester (I-6)
In the there-necked flask of 25mL, add respectively 1-(1-methyl-indoles-2-yl) ethyl ketone oxime (VII-1,0.28g, 1.5mmol), (E)-methyl-2-(2-(brooethyl) phenyl)-2-methoxyimino acetic ester (intermediate B, 0.57g, 2.0mmol), Anhydrous potassium carbonate (0.62g, 4.5mmol) and anhydrous acetonitrile (9mL), heating, induction stirring, temperature rises to 82 DEG C of backflows, TLC detection reaction, stopped reaction after 17.0h.In reaction solution, add 30mL water, with the extraction of 3 × 30mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12, V/V) through silica gel column chromatography and obtains yellow solid product 0.51g, yield 91.3%.
(E) preparation of-N-methoxyl group-N-(2-((1-(1-methyl-indoles-2-yl) ethylidene) amino oxygen methyl) phenyl) carboxylamine methyl ester (I-10)
In the there-necked flask of 25mL, add respectively (E)-1-(1-methyl-indoles-2-yl) ethyl ketone oxime (VII-1,0.28g, 1.5mmol), methyl (2-(brooethyl) phenyl) methoxyl group Urethylane (intermediate C, 0.55g, 2.0mmol), Anhydrous potassium carbonate (0.62g, 4.5mmol) and anhydrous acetonitrile (9mL), heating, induction stirring, temperature rises to 82 DEG C of backflows, TLC detection reaction, stopped reaction after 9.5h.In reaction solution, add 30mL water, with the extraction of 3 × 30mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/12, V/V) through silica gel column chromatography and obtains brown solid product 0.55g, yield 86.9%.
The preparation of (E, E)-2-(2-((1-(1-methyl-indoles-2-yl) ethylidene) amino oxygen methyl) phenyl)-2-methoxyimino-N-methylacetamide (I-14)
In the there-necked flask of 25mL, add respectively (E, E)-methyl 2-(2-((((1-(1-methyl-indoles-2-yl) ethylidene) amino) oxygen base) methyl) phenyl)-2-methoxyimino acetic ester (I-6,0.39g, 1.0mmol), methylamine (the 0.5mL25wt% aqueous solution, 4mmol) and methyl alcohol (6mL), heating, induction stirring, temperature rises to 80 DEG C of backflows, TLC detection reaction, stopped reaction after 1.0h.In reaction solution, add 20mL water, with the extraction of 3 × 20mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/3, V/V) through silica gel column chromatography and obtains white solid product 0.28g, yield 71.6%.
(E) preparation of-1-methoxyl group-3-methyl isophthalic acid-(2-((((1-(1-methyl-indoles-2-yl) ethylidene) amino) oxygen base) methyl) phenyl) urea (I – 18)
In the there-necked flask of 25mL, add respectively (E)-N-methoxyl group-N-(2-((1-(1-methyl-indoles-2-yl) ethylidene) amino oxygen methyl) phenyl) carboxylamine methyl ester (I-10,0.38g, 1.0mmol), methylamine (the 0.5mL25wt% aqueous solution, 4mmol) and methyl alcohol (6mL), heating, induction stirring, temperature rises to 80 DEG C of backflows, TLC detection reaction, stopped reaction after 48.0h.In reaction solution, add 20mL water, with the extraction of 3 × 20mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, separates (ethyl acetate/petroleum ether=1/3, V/V) through silica gel column chromatography and obtains brown oil 0.16g, yield 42.7%.
Other compound can be prepared with reference to aforesaid method.
Below provide formulation examples:
Example 710% missible oil
10 parts of heavy Compound I-5 are dissolved in the following mixture of 90 parts of weights: this mixture, containing 90 parts of heavy dimethylbenzene, 6 parts of heavy polyoxyethylene nonylphenol ethers, 2 parts of heavy calcium dodecylbenzene sulphonates and the oxyethane of 2 parts of weights and the affixture of Viscotrol C (mol ratio 40/1), is prepared missible oil (active compound content is 10%).
Example 880% liquor
80 parts of (weight) compound I – 7 are mixed with the N-Methyl pyrrolidone of 20 parts (weight), obtain being applicable to the solution (active compound content is as 80%) so that very small droplets form is applied.
Biological activity determination
Example 9 fungicidal activities are measured
The various fungal diseases of plant are tested with the compound of general formula I of the present invention.The program of test is as follows: plant is tried to material and carry out potted plant.The former medicinal a small amount of DMF of testing compound dissolves, and is diluted with water to required concentration, and preparation is diluted with water to required concentration.Spray pesticide, to plant examination material, carries out disease inoculation after 24h.After inoculation, plant is placed in fixed temperature and humidity incubator, makes to infect and continue, after contrasting abundant morbidity, carry out assessment surveys.The most serious occurring degree (being conventionally worth as basic survey standard using this) of " 0 " representative, " 100 " represent without any scab.
The structural formula of indoles substituted oximinoether kind methoxy-methyl acrylate class Strobilurin compound is as follows:
The sterilization biological activity of indoles substituted oximinoether kind methoxy-methyl acrylate class Strobilurin compound is referring to table 1.
Table 1
Note: " ///" represent not test.
The structural formula of indoles substituted oximinoether kind N-methoxyl group-Urethylane class strobilurin compound is as follows:
The fungicidal activity of indoles substituted oximinoether kind N-methoxyl group-Urethylane class strobilurin compound is in table 2.
Table 2
The structural formula of indoles substituted oximinoether kind N-methoxyl group-carbamyl methylamine strobilurin compound is as follows:
The fungicidal activity of indoles substituted oximinoether kind N-methoxyl group-carbamyl methylamine strobilurin compound is in table 3.
Table 3
The structural formula of indoles substituted oximinoether kind N-methoxyl group-acetimidic acid methyl esters class strobilurin compound is as follows:
The fungicidal activity of indoles substituted oximinoether kind N-methoxyl group-acetimidic acid methyl esters class strobilurin compound is in table 4.
Table 4
The structural formula of indoles substituted oximinoether kind N-methoxyl group-imino-acetyl methylamine strobilurin compound is as follows:
The fungicidal activity of indoles substituted oximinoether kind N-methoxyl group-imino-acetyl methylamine strobilurin compound is in table 5.
Table 5
Note: " ///" represent not test.

Claims (10)

1. an indoles substituted oximinoether kind compound, is characterized in that its general formula is as follows:
Wherein:
R 1for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 2for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 3for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R 4for hydrogen, halogen, trihalogenmethyl, C 1– C 4alkyl, C 1– C 4alkoxyl group, nitro or cyano group;
R5 is hydrogen, C 1– C 4alkyl, C 3– C 6cycloalkyl, phenyl or substituted-phenyl;
R 6for hydrogen, C 1– C 4alkyl, C 3– C 6cycloalkyl, phenyl or substituted-phenyl;
Q is selected from one of group as follows:
2. a kind of indoles substituted oximinoether kind compound as claimed in claim 1, is characterized in that,
R 1for hydrogen;
R 2for hydrogen, fluorine or chlorine;
R 3for hydrogen, fluorine or chlorine;
R 4for hydrogen;
R 5for methyl;
R 6for hydrogen, methyl;
Q is selected from one of group as follows:
3. a kind of preparation method of indoles substituted oximinoether kind compound as claimed in claim 1, is characterized in that concrete steps are as follows: 1) reaction formula 1:
2) reaction formula 2:
3) reaction formula 3:
4) reaction formula 4:
In reaction formula 1, in the mixed solution of solvent methyl-sulphoxide and water, under additive exists, under 25～150 DEG C of conditions, obtain the compound shown in general formula III with the compound shown in general formula II and reaction of sodium azide; Compound shown in general formula III and trifluoroacetic anhydride, under the existence of pyridine, in methylene dichloride, under 0～80 DEG C of condition, react to obtain the compound shown in general formula IV; Compound shown in general formula IV and monochloroacetone, under the existence of alkali salt of wormwood, in poly(oxyethylene glycol) 400 solvent, under 25～150 DEG C of conditions, react to obtain the compound shown in general formula V; Described additive is selected from the bromo-phenyl aldehyde of the chloro-2-of 4-, L-AA sodium and DL-proline;
In reaction formula 2, in solvent acetonitrile, under alkali salt of wormwood exists, under 25～80 DEG C of conditions, obtain the compound shown in general formula VI with the compound shown in general formula V and iodomethane reaction; Compound and oxammonium hydrochloride shown in compound shown in general formula V or general formula VI, under alkali sodium acetate exists, in ethanol/water, under 25～80 DEG C of conditions, reacts to obtain the compound shown in general formula VI;
In reaction formula 3, in solvent acetonitrile, under alkali salt of wormwood exists, under 25～80 DEG C of conditions, the general formula I – Q that reacts correspondingly with the compound shown in general formula VI respectively with 3 different intermediate A, B or C 1, I – Q 2with I – Q 3shown compound;
In reaction formula 4, in solvent methanol, under 25～80 DEG C of conditions, with general formula I – Q 2or I – Q 3the general formula I – Q that shown compound reacts correspondingly with aqueous methylamine solution respectively 4with I – Q 5shown compound.
As claimed in claim 1 a kind of indoles substituted oximinoether kind compound in the application of preparing in sterilant.
5. application as claimed in claim 4, is characterized in that described sterilant is plant leaf surface sterilant or soil fungicides.
6. application as claimed in claim 5, is characterized in that described plant leaf surface sterilant includes but not limited to corn rust, rice blast, gray mold, barley powdery mildew, wheat powdery mildew, apple mildew, powdery mildew of cucumber, cucumber downy mildew, cucumber anthracnose, uncinula necator, downy mildew of garpe sterilant.
7. application as claimed in claim 4, it is characterized in that described indoles substituted oximinoether kind compound forms fungicidal composition as active ingredient together with carrier or thinner, in Bactericide composition, the mass percentage content of indoles substituted oximinoether kind compound is 1%～99%.
8. application as claimed in claim 4, is characterized in that described indoles substituted oximinoether kind compound is as active ingredient and other sterilant composition compound disinfectant, and in compound disinfectant, the mass percent of indoles substituted oximinoether kind compound is 1%～99%.
9. application as claimed in claim 7, is characterized in that described carrier is solid carrier, liquid vehicle or is generally gas but has been compressed into the material of liquid.
10. application as claimed in claim 9, it is characterized in that described solid carrier is selected from least one in plant, seed, soil, silicate, talcum, pure aluminium silicate, montmorillonite, mica, calcium carbonate, calcium sulfate, ammonium sulfate, synthetic silica, synthetic calcium silicate, synthetic aluminium silicate, natural resin, synthetic resins, solid polystream phenol, pitch, paraffin, described soil is selected from the one in natural clay, synthesis of clay, diatomite, attapulgite; Described liquid vehicle is selected from the one in water, alcohol, ketone, ether, petroleum fractions, chlorinated hydrocarbon, aromatic hydrocarbons.
CN201410232317.8A 2014-05-29 2014-05-29 Indole-substituted oxime ether compounds as well as preparation method and application thereof Pending CN103980179A (en)

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