CN103601716A - Benzothiophene substituted oxime ether compound and preparation method and application thereof - Google Patents
Benzothiophene substituted oxime ether compound and preparation method and application thereof Download PDFInfo
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- CN103601716A CN103601716A CN201310586192.4A CN201310586192A CN103601716A CN 103601716 A CN103601716 A CN 103601716A CN 201310586192 A CN201310586192 A CN 201310586192A CN 103601716 A CN103601716 A CN 103601716A
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- FNSIZIKIAILDKM-JLHYYAGUSA-N Cc(cccc1)c1/C(/C(NC)=O)=N\OC Chemical compound Cc(cccc1)c1/C(/C(NC)=O)=N\OC FNSIZIKIAILDKM-JLHYYAGUSA-N 0.000 description 1
- IIYFINSFZVFXCL-DHZHZOJOSA-N Cc(cccc1)c1/C(/C(OC)=O)=C\OC Chemical compound Cc(cccc1)c1/C(/C(OC)=O)=C\OC IIYFINSFZVFXCL-DHZHZOJOSA-N 0.000 description 1
- YCINJZQUXAFTQD-ZRDIBKRKSA-N Cc(cccc1)c1/C(/C(OC)=O)=N\OC Chemical compound Cc(cccc1)c1/C(/C(OC)=O)=N\OC YCINJZQUXAFTQD-ZRDIBKRKSA-N 0.000 description 1
- WATGRBLNQPCORS-UHFFFAOYSA-N Cc(cccc1)c1N(C(OC)=O)OC Chemical compound Cc(cccc1)c1N(C(OC)=O)OC WATGRBLNQPCORS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D333/58—Radicals substituted by nitrogen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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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- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a benzothiophene substituted oxime ether compound and a preparation method and application thereof, relating to a pesticide bactericide. The benzothiophene substituted oxime ether compound is novel in structure, high in efficiency, broad in spectrum, low in toxicity and high in degradability. The benzothiophene substituted oxime ether compound is an effective bactericide, has systematic activity, and can be used as a leaf and soil bactericide. The benzothiophene substituted oxime ether compound is capable of effectively controlling multiple plant diseases, such as powdery mildew of barley and wheat, powdery mildew of cucumber, rice blast, puccinia polysra, powdery mildew of grape, powdery mildew of apple, downy mildew of cucumber, anthracnose of cucumber, and downy mildew of grape. The benzothiophene substituted oxime ether compound is especially suitable for controlling of powdery mildew of wheat, puccinia polysra, downy mildew of cucumber and rice blast. The benzothiophene substituted oxime ether compound uses a single compound of a general formula I or a mixture of multiple compounds as an active component; the preparation method comprises the step of mixing the compound of the general formula I with at least one carrier; the weight percentage of the active component in the benzothiophene substituted oxime ether compound is 1-99 percent.
Description
Technical field
The present invention relates to agricultural bactericide, especially relate to a kind of thionaphthene substituted oximinoether kind compound and preparation method thereof application on control of crop disease with it.
Background technology
1999 Nian， U.S. ROHM AND HAAS (ROHM AND HASS) company has 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 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, 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 object of the invention is to replace indenyl with thionaphthene substituting group, efficient, the wide spectrum, low toxicity of a class formation novelty, a kind of thionaphthene substituted oximinoether kind compound that degradability is strong and preparation method thereof and application are provided.
The general structure of described thionaphthene substituted oximinoether kind compound is as follows:
Wherein:
R
1for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
2for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
3for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
4for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
5for hydrogen, C
1-C
4alkyl, C
3-C
6cycloalkyl, phenyl or substituted-phenyl;
Q is selected from one of group as follows:
Preferred R
1for hydrogen or fluorine; R
2for hydrogen or trihalogenmethyl; R
3for hydrogen, chlorine or C
1-C
4alkylthio; R
4for hydrogen; R
5for methyl; Q is selected from Q
1, Q
2, Q
3, Q
4or Q
5.
Described thionaphthene substituted oximinoether kind compound has very high biological activity, even still can obtain good sterilization effect under very low dosage.
The synthetic route of described thionaphthene substituted oximinoether kind compound is as follows:
Concrete synthetic method is as follows:
The compound of general formula III can be prepared by the following method:
In aqueous solvent, under sodium hydroxide exists, under room temperature condition, add sulfur alcohol, then add the compound shown in tetra-n-butyl ammonium bromide and general formula II, at 25～100 ℃, react to obtain the compound shown in general formula III.
The compound of general formula IV can be prepared by the following method:
In solvent acetone, under calcium oxide exists, under 25～60 ℃ of conditions, with the compound shown in general formula III and α-monochloroacetone, react to obtain the compound shown in general formula IV.
The compound of general formula V can be prepared by the following method:
In ethanol/water solution (V/V=2/1), under alkali sodium acetate exists, under 25～100 ℃ of conditions, with the compound shown in general formula IV and oxammonium hydrochloride, react to obtain the compound shown in general formula V.
General formula I-Q
1, I-Q
2and I-Q
3compound can prepare by the following method:
In solvent acetonitrile, under alkali salt of wormwood exists, under 25～100 ℃ of conditions, the general formula I-Q that reacts correspondingly with the compound shown in general formula V respectively with three different intermediate A, B or C
1, I-Q
2and I-Q
3shown compound.
General formula I-Q
4and I-Q
5compound can prepare by the following method:
In solvent methanol, under 25～80 ℃ of conditions, with general formula I-Q
2or I-Q
3general formula I-Q that shown compound reacts correspondingly with aqueous methylamine solution (25wt%) respectively
4and I-Q
5shown compound.
The present invention have the part of compounds of general formula III structure concrete structure formula, compound physical property,
1h NMR,
13c NMR data are as follows, are used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound (III-1): yellow liquid
1H?NMR(CDCl
3,400MHz)δ(ppm):1.37(t,J=7.2Hz,3H,CH
2CH
3),2.99(q,J=7.2Hz,2H,CH
2),7.28-7.33(m,1H,ArH),7.43(d,J=7.6Hz,1H,ArH),7.49-7.54(m,1H,ArH),7.84(dd,J=8.0,1.6Hz,ArH),10.39(s,1H,O=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):14.04,27.66,125.65,128.56,132.36,134.22,134.39,142.26,191.92.
Compound (III-2): faint yellow solid Mp:57.3～57.7 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.40(t,J=7.2Hz,3H,CH
2CH
3),2.96(q,J=7.2Hz,2H,CH
2),7.20(dd,J=8.0,1.2Hz,1H,ArH),7.26(d,J=8.0Hz,1H,ArH),7.38(t,J=8.0Hz,1H,ArH),10.62(s,1H,O=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):13.27,26.36,124.34,126.18,129.06,133.72,140.34,146.11,190.85.
Compound (III-3): yellow liquid
1H?NMR(CDCl
3,400MHz)δ(ppm):1.42(t,J=7.2Hz,3H,CH
2CH
3),3.05(q,J=7.2Hz,2H,CH
2),7.49(d,J=8.4Hz,1H,ArH),7.72(dd,J=8.4,1.6Hz,1H,ArH),8.06(d,J=1.2Hz,1H,ArH),10.33(s,1H,O=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):13.66,26.83,127.22,129.64,130.14,130.18,133.46,147.57,190.27.
Compound (III-4): yellow solid Mp:40.3～41.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.38(t,J=7.2Hz,3H,CH
2CH
3),1.40(t,J=7.2Hz,3H,CH
2CH
3),2.97(q,J=7.2Hz,2H,CH
2),3.04(q,J=7.2Hz,2H,CH
2),7.12(dd,J=8.0,2.0Hz,1H,ArH),7.21(d,J=1.6Hz,1H,ArH),7.72(d,J=8.4Hz,1H,ArH),10.26(s,1H,O=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):13.94,14.21,26.30,27.59,123.02,125.35,131.13,132.59,142.81,146.68,190.82.
Compound (III-5): faint yellow solid Mp:47.0～48.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.40(t,J=7.2Hz,3H,CH
2CH
3),3.03(q,J=7.2Hz,2H,CH
2),7.17-7.20(m,1H,ArH),7.24(d,J=1.6Hz,1H,ArH),7.80(d,J=8.4Hz,1H,ArH),10.36(s,1H,O=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):13.96,26.21,124.95,127.02,129.30,129.58,138.70,148.57,189.13.
The present invention have the part of compounds of general formula IV structure concrete structure formula, compound physical property,
1h NMR,
13c NMR data are as follows, are used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound (IV-1): faint yellow solid Mp:88.5～89 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.67(s,3H,O=C-CH
3),7.39-7.43(m,1H,ArH),7.45-7.49(m,1H,ArH),7.86-7.91(m,2H,ArH),7.94(d,J=0.4Hz,1H,C=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):11.87,122.31,123.65,123.98,124.48,125.63,139.38,139.78,140.36,152.36.
Compound (IV-2): do not purify and obtain sterling
Compound (IV-3): yellow oil
1H?NMR(CDCl
3,400MHz)δ(ppm):2.69(s,3H,O=C-CH
3),7.66-7.69(m,1H,ArH),7.97-8.00(m,2H,ArH),8.17(s,1H,C=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):27.17,123.36,123.41,123.79,123.82,124.09,129.53,138.99,146.42,192.20.
Compound (IV-4): yellow solid Mp:72.4～73.0 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.37(t,J=7.2Hz,3H,CH
2CH
3),2.64(s,3H,O=C-CH
3),3.04(q,J=7.2Hz,2H,CH
2),7.32(dd,J=8.4,2.0Hz,1H,ArH),7.72-7.74(m,1H,ArH),7.76(d,J=8.4Hz,1H,ArH),7.86(d,J=0.8Hz,1H,C=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):14.48,27.05,27.62,100.32,121.34,126.12,129.76,137.15,138.12,143.50,143.93,192.38.
Compound (IV-5): yellow solid Mp:101.0～101.8 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.66(s,3H,C-CH
3),7.38(dd,J=8.8,2.0Hz,1H,ArH),7.80(d,J=8.8Hz,1H,C=CH),7.85-7.86(m,1H,ArH),7.891(d,J=0.4Hz,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):27.11,122.93,126.47,127.05,129.29,134.17,137.88,143.90,144.90,192.25.
The present invention have the part of compounds of general formula V structure concrete structure formula, compound physical property,
1h NMR,
13c NMR data are as follows, are used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound (V-1): pale solid Mp:186.9～187.8 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.38(s,3H,O=C-CH
3),7.31-7.38(m,2H,ArH),7.48(s,1H,C=CH),7.74-7.80(m,2H,ArH),8.05(s,1H,N-OH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.16,122.65,123.97,124.31,124.81,125.95,139.71,140.15,140.74,152.78.
Compound (V-2): white solid Mp:197.1～197.4 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.40(s,3H,O=C-CH
3),7.27(t,J=8.0Hz,1H,ArH),7.34(dd,J=8.0,0.8Hz,1H,ArH),7.62(d,J=0.4Hz,1H,C=CH),7.67(dd,J=8.0,0.8Hz,1H,ArH),7.829(s,1H,N-OH).
13C?NMR(DMSO,100MHz)δ(ppm):12.06,121.15,121.93,124.80,126.56,129.33,138.05,141.30,141.80,152.68.
Compound (V-3): red oil
1H?NMR(CDCl
3,400MHz)δ(ppm):2.39(s,3H,O=C-CH
3),7.53(s,1H,C=CH),7.57(dd,J=8.4,1.2Hz,1H,ArH),7.88(dd,J=8.4,0.8Hz,1H,ArH),7.99(s,1H,ArH),8.02(s,1H,N-OH).
13CNMR(DMSO,100MHz)δ(ppm):11.86,121.01,121.05,121.83,121.86,122.82,123.35,127.37,138.97,142.60,152.03.
Compound (V-4): faint yellow solid Mp:166.6～166.9 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.34(t,J=7.2Hz,3H,CH
2CH
3),2.36(s,3H,O=C-CH
3),3.00(q,J=7.2Hz,2H,CH
2),7.30(dd,J=8.4,2.0Hz,1H,ArH),7.41(d,J=0.4Hz,1H,C=CH),7.64(d,J=8.4Hz,1H,ArH),7.71-7.72(m,1H,ArH),8.04(s,1H,N-OH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.15,14.71,28.44,122.41,123.65,124.33,126.49,134.89,137.83,141.26,140.96,152.67.
Compound (V-5): faint yellow solid Mp:227.3～229.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.35(s,3H,C-CH
3),7.30(dd,J=6.8,1.6Hz,1H,ArH),7.42(s,1H,C=CH),7.46(s,1H,N-OH),7.65(d,J=1.2Hz,1H,ArH),7.76(d,J=0.8Hz,1H,ArH).
13CNMR(DMSO,100MHz)δ(ppm):11.80,122.14,123.10,125.43,125.67,130.62,138.50,140.57,142.51,150.54.
The present invention have the part of compounds of general formula I structure concrete structure formula, compound physical property,
1h NMR,
13c NMR data are as follows, are used for further illustrating the present invention, but do not mean that restriction the present invention.
Compound (I-1): pale solid Mp:102.9～103.5 ℃
1H?NMR(CDCl
3,500MHz)δ(ppm):2.29(s,3H,N=C-CH
3),3.69(s,3H,C=C-OCH
3),3.82(s,3H,O=C-OCH
3),5.17(s,2H,O-CH
2),7.15-7.18(m,1H,ArH),7.28-7.36(m,4H,ArH),7.41(s,1H,S-C=CH),7.51-7.54(m,1H,ArH),7.59(s,1H,O-CH=C),7.70-7.77(m,2H,ArH).
13C?NMR(CDCl
3,125MHz)δ(ppm):12.87,51.97,62.27,75.16,110.70,122.54,123.36,124.14,124.64,125.69,127.95,128.22,128.91,131.27,132.18,136.89,139.76,140.33,141.21,151.17,160.25,168.36.
Compound (I-2): pale solid Mp:148.5～148.9 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.31(s,3H,N=C-CH
3),3.70(s,3H,C=C-OCH
3),3.83(s,3H,O=C-OCH
3),5.17(s,2H,O-CH
2),7.15-7.19(m,1H,ArH),7.21-7.26(m,1H,ArH),7.29-7.35(m,3H,ArH),7.50-7.53(m,1H,ArH),7.55(d,J=0.8Hz,1H,S-C=CH),7.597(s,1H,O-C=CH),7.64(dd,J=8.0,0.8Hz,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.74,51.96,62.25,75.28,110.66,121.01,121.28,124.61,126.28,128.01,128.22,128.92,129.12,131.29,132.20,136.73,138.04,141.43,142.24,150.97,160.26,168.33.
Compound (I-3): white solid Mp:120.4～121.3 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.30(s,3H,N=C-CH
3),3.70(s,3H,C=C-OCH
3),3.83(s,3H,O=C-OCH
3),5.18(s,2H,O-CH
2),7.16-7.19(m,1H,ArH),7.32-7.37(m,2H,ArH),7.46(s,1H,S-C=CH),7.50-7.55(m,2H,ArH),7.60(s,1H,O-C=CH),7.83-7.86(m,1H,ArH)7.98(s,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.79,51.98,62.28,75.37,110.69,121.13,121.18,121.86,121.89,122.96,123.04,128.08,128.25,128.97,131.33,132.24,136.70,139.35,143.38,143.58,150.74,160.27,168.35.
Compound (I-4): faint yellow solid Mp:129.8～130.1 ℃
1H?NMR(CDCl
3,500MHz)δ(ppm):1.33(t,J=2.0Hz,3H,CH
2CH
3),2.27(s,3H,N=C-CH
3),2.99(q,J=2.0Hz,2H,S-CH
2),3.69(s,3H,C=C-OCH
3),3.82(s,3H,O=C-OCH
3),5.16(s,2H,O-CH
2),7.15-7.18(m,1H,ArH),7.28(dd,J=6.8,1.2Hz,1H,ArH),7.30-7.36(m,3H,ArH),7.51-7.53(m,1H,ArH),7.59(s,1H,O-C=CH),7.60(d,J=6.8Hz,1H,ArH),7.69-7.70(m,1H,ArH).
13C?NMR(CDCl
3,125MHz)δ(ppm):12.81,14.72,28.54,51.94,62.25,75.17,110.72,122.56,123.00,124.16,126.44,127.94,128.20,128.90,131.28,132.18,134.43,136.43,136.88,140.85,141.14,151.09,160.23,168.33.
Compound (I-5): white solid Mp:144.0～144.5 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.27(s,3H,N=C-CH
3),3.69(s,3H,C=C-OCH
3),3.82(s,3H,O=C-OCH
3),5.16(s,2H,O-CH
2),7.15-7.18(m,1H,Ar-H),7.27(dd,J=8.8,1.6Hz,ArH),7.31-7.36(m,3H,ArH),7.50-7.53(m,1H,ArH),7.59(s,1H,O-C=CH),7.61(d,J=8.4Hz,1H,ArH),7.73(d,J=1.2Hz,1H,ArH)ppm.
13C?NMR(CDCl
3,100MHz)δ(ppm):12.78,51.97,62.28,75.25,110.67,122.13,122.68,124.88,125.51,128.01,128.23,128.91,131.29,131.78,132.19,136.77,138.20,141.41,141.90,150.88,160.25,168.33.
Compound (I-6): white solid Mp:114.5～117.8 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.27(s,3H,N=C-CH
3),3.84(s,3H,N-OCH
3),4.04(s,3H,O=C-OCH
3),5.14(s,2H,O-CH
2),7.19(dd,J=7.6,1.2Hz,1H,ArH),7.28-7.34(m,2H,ArH),7.36-7.40(m,1H,ArH),7.41(s,1H,C=CH),7.41-7.45(m,1H,ArH),7.51(m,J=7.8,0.8Hz,1H,ArH),7.70-7.76(m,2H?ArH)ppm.
13C?NMR(CDCl
3,100MHz)δ(ppm):12.82,53.25,64.15,75.38,122.54,123.56,124.17,124.64,125.75,128.12,128.86,129.23,129.74,130.18,136.12,139.68,140.38,140.94,149.86,151.60,163.66ppm.
Compound (I-7): yellow solid Mp:162.9～163.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.29(s,3H,N=C-CH
3),3.85(s,3H,N-OCH
3),4.05(s,3H,O=C-OCH
3),5.14(s,2H,O-CH
2),7.20(dd,J=7.6,1.6Hz,1H,ArH),7.21-7.25(m,1H,ArH),7.31(dd,J=7.6,0.8Hz,1H,ArH),7.36-7.40(m,1H,ArH),7.41-7.46(m,1H,ArH),7.51(dd,J=7.2,0.8Hz,1H,ArH),7.55(d,J=0.8Hz,1H,S-C=CH),7.61-7.65(m,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.71,53.25,64.15,75.50,121.03,121.49,124.63,126.36,128.19,128.87,129.17,129.25,129.74,130.21,135.98,137.99,141.50,141.99,149.82,151.41,163.65.
Compound (I-8): white solid Mp:77.9～82.6 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.27(s,3H,N=C-CH
3),3.84(s,3H,N-OCH
3),4.04(s,3H,O=C-OCH
3),5.15(s,2H,O-CH
2),7.19(dd,J=7.6,1.2Hz,1H,ArH),7.37-7.41(m,1H,ArH),7.41-7.44(td,J=7.6,1.6Hz,1H,ArH),7.45(s,1H,C=CH),7.50-7.54(m,2H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.72,53.24,64.14,75.58,121.15,121.20,121.93,123.03,123.16,128.23,128.90,129.27,129.75,130.23,135.93,139.26,143.29,143.42,149.82,151.16,163.64.
Compound (I-9): faint yellow solid Mp:113.7～114.8 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.33(t,J=7.2Hz,3H,CH
2CH
3),2.25(s,3H,N=C-CH
3),2.99(q,J=7.6Hz,2H,S-CH
2),3.84(s,3H,N-OCH
3),4.05(s,3H,O=C-OCH
3),5.13(s,2H,O-CH
2),7.19(dd,J=7.2,1.2Hz,1H,ArH),7.27(dd,J=8.0,1.2Hz,1H,ArH),7.35(s,1H,C=CH),7.36-7.40(m,1H,ArH),7.41-7.45(m,1H,ArH),7.50-7.53(m,1H?ArH),7.60(d,J=8.4Hz,1H,ArH),7.68-7.69(m,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.78,14.71,28.48,53.27,64.16,75.39,122.45,123.23,124.20,126.38,128.14,128.86,129.24,129.74,130.17,134.52,136.09,137.84,140.53,141.19,149.84,151.54,163.65.
Compound (I-10): faint yellow solid Mp:135.1～137.6 ℃
1H?NMR(CDCl
3,500MHz)δ(ppm):2.34(s,3H,N=C-CH
3),3.79(s,3H,N-OCH
3),3.80(s,3H,O=C-OCH
3),5.29(s,2H,O-CH
2),7.30-7.33(m,2H,ArH),7.36-7.39(m,3H,ArH),7.43(s,1H,S-C=CH),7.56-7.59(m,1H,ArH),7.70-7.76(m,2H,ArH).
13C?NMR(CDCl
3,125MHz)δ(ppm):12.96,53.85,62.48,72.48,122.54,123.60,124.17,124.67,125.78,127.17,128.75,129.00,129.53,135.98,137.76,139.67,140.33,140.95,151.61,156.13.
Compound (I-11): white solid Mp:115.6～116.8 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.36(s,3H,N=C-CH
3),3.79(s,3H,N-OCH
3),3.80(s,3H,O=C-OCH
3),5.30(s,2H,O-CH
2),7.21-7.26(m,1H,ArH),7.29-7.32(m,1H,ArH),7.36-7.402(m,3H,ArH),7.56-7.58(m,2H,ArH),7.62(d,J=8.0Hz,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.86,53.86,6246,72.63,121.03,121.53,124.65,126.38,127.23,128.81,129.01,129.17,129.53,135.81,137.76,137.99,141.45,142.00,151.42,156.12.
Compound (I-12): faint yellow solid Mp:89.5～93.3 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.34(s,3H,N=C-CH
3),3.79(s,3H,N-OCH
3),3.81(s,3H,O=C-OCH
3),5.31(s,2H,O-CH
2),7.36-7.40(m,3H,ArH),7.47(s,1H,S-C=CH),7.51-7.54(m,1H,ArH),7.55-7.58(m,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.87,23.75,53.84,62.44,72.71,121.15,121.19,121.92,121.95,123.03,123.20,128.84,129.02,129.56,135.74,137.79,139.25,143.31,151.17,156.12.
Compound (I-13): faint yellow solid Mp:93.6～95.3 ℃
1H?NMR(CDCl
3,500MHz)δ(ppm):1.33(t,J=2.0Hz,3H,CH
2CH
3),2.32(s,3H,N=C-CH
3),2.99(q,J=2.0Hz,2H,S-CH
2),3.79(s,3H,N-OCH
3),3.80(s,3H,O=C-OCH
3),5.28(s,2H,O-CH
2),7.26(dd,J=6.4,1.2Hz,1H,ArH),7.36-7.39(m,4H,ArH),7.56-7.58(m,1H,ArH),7.60(d,J=2.8Hz,1H,ArH),7.68(s,1H,O-C=CH).
13C?NMR(CDCl
3,125MHz)δ(ppm):12.90,14.69,28.49,53.83,62.45,72.51,122.47,123.25,124.19,126.42,127.21,128.75,128.99,129.54,134.60,135.96,137.78,137.85,140.57,141.17,151.54,156.14.
Compound (I-14): white solid Mp:137.8～139.4 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.26(s,3H,N=C-CH
3),2.88(d,J=4.8Hz,3H,N-CH
3),3.96(s,3H,N-OCH
3),5.13(s,2H,O-CH
2),6.72(d,J=3.2Hz,1H,NH),7.19-7.22(m,1H,ArH),7.29-7.43(m,5H,ArH),7.50(d,J=7.2Hz,1H,ArH),7.70-7.77(m,2H,ArH)ppm.
13C?NMR(CDCl
3,100MHz)δ(ppm):12.81,26.56,63.63,75.62,122.52,123.53,124.18,124.68,125.76,128.11,129.04,129.30,129.63,130.05,136.13,139.70,140.29,140.97,151.47,163.26ppm.
Compound (I-15): pale solid Mp:137.4～138.2 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.28(s,3H,N=C-CH
3),2.90(d,J=4.8Hz,3H,N-CH
3),3.97(s,3H,N-OCH
3),5.14(s,2H,O-CH
2),6.74(d,J=4.4Hz,1H,NH),7.19-7.21(m,1H,ArH),7.22-7.26(m,2H,ArH),7.31(dd,J=7.6,0.8Hz,1H,ArH),7.36-7.43(m,2H,ArH),7.49-7.51(m,1H,ArH),7.55(d,J=0.4Hz,1H,SC=CH),7.63(d,J=8.0Hz,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.72,26.58,63.65,75.76,121.02,121.45,124.67,126.37,128.17,129.09,129.19,129.29,129.65,130.04,136.03,138.03,141.45,142.07,151.28,151.48,163.25.
Compound (I-16): white solid Mp:130.4～131.2 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.29(s,3H,N=C-CH
3),2.93(d,J=4.8Hz,3H,N-CH
3),4.00(s,3H,N-OCH
3),5.18(s,2H,O-CH
2),6.78(d,J=4.8Hz,1H,NH),7.22-7.25(m,1H,ArH),7.39-7.47(m,2H,ArH),7.48(s,1H,C=CH),7.52-7.58(m,2H,ArH),7.70(dd,J=8.4,4.4Hz,1H,ArH),8.01(s,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.72,26.54,63.63,75.78,121.15,121.19,121.89,121.92,123.01,123.11,128.17,129.07,129.27,129.64,130.04,135.98,139.29,143.37,151.04,151.45,163.20.
Compound (I-17): faint yellow solid Mp:137.8～138.6 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):1.33(t,J=7.2Hz,3H,CH
2CH
3),2.24(s,3H,N=C-CH
3),2.89(d,J=5.2Hz,3H,N-CH
3)，2.99(q,J=7.2Hz,2H,S-CH
2),3.96(s,3H,N-OCH
3),5.13(s,2H,O-CH
2),6.72(d,J=4.4Hz,1H,NH),7.20(dd,J=7.2,1.2Hz,1H,ArH),7.28(dd,J=8.4,1.6Hz,1H,ArH),7.35(d,J=0.4Hz,1H,C=CH),7.36-7.43(m,2H,ArH),7.49-7.52(m,1H,ArH),7.61(d,J=8.4Hz,1H,ArH),7.69-7.70(m,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.77,14.71,26.57,28.49,63.64,75.63,122.47,123.20,124.21,126.41,128.13,129.05,129.30,129.63,130.04,134.55,136.12,137.88,140.59,141.12,151.41,151.49,163.26.
Compound (I-18): yellow solid Mp:93.3～94.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.34(s,3H,N=C-CH
3),2.90(d,J=4.8Hz,3H,NCH
3),3.73(s,3H,N-OCH
3),5.35(s,2H,O-CH
2),5.97(d,J=4.0Hz,1H,NH),7.29-7.37(m,5H,ArH),7.41(s,1H,O-C=CH),7.54-7.57(m,1H,ArH),7.70-7.75(m,2H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.96,27.11,62.24,72.61,122.52,123.42,124.15,124.64,125.71,125.80,128.31,128.62,129.23,136.77,139.01,139.72,140.31,141.21,151.34,158.52.
Compound (I-19): white solid Mp:124.5～125.2 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.36(s,3H,N=C-CH
3),2.90(d,J=4.8Hz,3H,NCH
3),3.72(s,3H,N-OCH
3),5.36(s,2H,O-CH
2),5.99(d,J=4.8Hz,1H,NH),7.30(t,J=8.0,1H,ArH),7.29(d,J=1.2Hz,1H,S-C=CH),7.31-7.36(m,3H,ArH,),7.53-7.56(m,2H,ArH)7.60-7.63(m,1H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.86,27.11,62.21,72.74,121.01,121.36,124.62,125.82,126.31,128.34,129.14,129.20,136.58,138.98,141.42,142.22,151.18,158.55.
Compound (I-20): faint yellow solid Mp:123.4～124.1 ℃
1H?NMR(CDCl
3,400MHz)δ(ppm):2.34(s,3H,N=C-CH
3),2.90(d,J=4.8Hz,3H,NCH
3),3.73(s,3H,N-OCH
3),5.37(s,2H,O-CH
2),5.99(d,J=4.8Hz,1H,NH),7.31-7.37(m,3H,ArH),7.45(s,1H,O-C=CH),7.51-7.55(m,2H,ArH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.88,27.10,62.20,72.83,121.12,121.16,121.85,121.88,123.01,125.75,127.13,128.29,128.69,129.16,136.51,139.06,139.31,143.36,143.56,150.91,158.51.
Compound (I-21): brown oil
1H?NMR(CDCl
3,400MHz)δ(ppm):1.33(t,J=2.0Hz,3H,CH
2CH
3),2.32(s,3H,N=C-CH
3),2.90(d,J=4.8Hz,3H,NCH
3),2.99(q,J=3.2Hz,2H,S-CH
2),3.73(s,3H,N-OCH
3),5.34(s,2H,O-CH
2),5.97(d,J=4.4Hz,1H,NH),7.27-7.37(m,5H,ArH),7.53-7.56(m,1H,ArH),7.59-7.61(d,J=8.4Hz,1H,ArH),7.68(s,1H,O-C=CH).
13C?NMR(CDCl
3,100MHz)δ(ppm):12.92,14.72,27.11,28.52,62.23,72.62,122.51,123.08,124.17,125.79,126.42,128.30,128.62,129.20,134.44,136.73,137.90,139.00,140.82,141.12,151.28,158.52.
Described a kind of thionaphthene substituted oximinoether kind compound can be applied in preparing sterilant or controlling 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 prevent and treat barley powdery mildew medicine, wheat powdery mildew medicine, powdery mildew of cucumber medicine, rice blast medicine, corn rust medicine, uncinula necator medicine, apple mildew medicine, cucumber downy mildew medicine, cucumber anthracnose medicine, downy mildew of garpe medicine; Be in particular control wheat powdery mildew medicine, corn rust medicine, cucumber anthracnose medicine and rice blast medicine; Described sterilant comprises fungicidal composition, and it is active ingredient that described fungicidal composition be take at least one compound of general formula I, and the compound that its preparation method is general formula I mixes with at least one carrier, and in fungicidal composition, the mass ratio of active ingredient is 1%～99%.
Effect of the present invention and benefit are:
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 store, transport or operation.Carrier can be solid or liquid, comprises the material that is generally gas but has been 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, silicon sodium soil, 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 thionaphthene resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax is as beeswax, paraffin.
Applicable liquid vehicle comprises water; 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 transportation, before using, by user, diluted.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, obtains conventionally containing 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.Other additives of the dispersion agent of 0.5%～15% weight, 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 than independent compound of Formula I the more activity of wide spectrum.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 example 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:
The preparation of 2-(ethylmercapto group) phenyl aldehyde (III-1)
In 25mL there-necked flask, add respectively water (12mL), sodium hydroxide (0.56g, 14mmol), sulfur alcohol (1.1mL, 14mmol), stirring at room 0.5h, and then add tetra-n-butyl ammonium bromide (0.06g), 1-chlorobenzaldehyde (1.15mL in reaction mixture, 10mmol), heating, induction stirring, temperature rises to 82 ℃, TLC detection reaction, stopped reaction after 6h.In reaction solution, add 60mL water, with the extraction of 3 * 60mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/12), obtains weak yellow liquid 1.66g, quantitative yield.
The preparation of the compound of example 2 general formula IV:
The preparation of 1-(thionaphthene-2-yl) ethyl ketone (IV-1)
In 25mL there-necked flask, add respectively 2-(ethylmercapto group) phenyl aldehyde (III-1,1.66g, 10mmol), monochloroacetone (1.0mL, 12.5mmol), acetone (10mL), calcium oxide (0.04g, 0.7mmol), heating, induction stirring, temperature rises to 60 ℃ of backflows, TLC detection reaction, stopped reaction after 10h.In reaction solution, add 60mL water, with the extraction of 3 * 60mL ethyl acetate, anhydrous sodium sulfate drying, decompression precipitation, through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/12), obtains faint yellow solid 1.76g, quantitative yield.
The preparation of the compound of example 3 general formula V:
The preparation of 1-(thionaphthene-2-yl) ethyl ketone oxime (V-1)
In the there-necked flask of 50mL, add respectively 1-(thionaphthene-2-yl) ethyl ketone (IV-1,2.06g, 12mmol), oxammonium hydrochloride (1.08g, 15mmol), sodium acetate (2.10g, 15mmol), ethanol/water (V/V=2/1) solution 18mL, heating, induction stirring, temperature rises to 77 ℃ of backflows, TLC detection reaction, stopped reaction after 2h.Hydrochloric acid to adding 50mL0.5mol/L in reaction solution, extracts by 2 * 50mL ethyl acetate.With anhydrous sodium sulfate drying, decompression precipitation, obtains pale solid 2.074g through recrystallization, yield 90.4%.
The preparation of the compound of example 4 general formula Is:
3-methoxyl group-2-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl ］ preparation of methyl acrylate (I-1)
In the there-necked flask of 25mL, add respectively 1-(thionaphthene-2-yl) ethyl ketone oxime (V-1,0.19g, 1.0mmol), (E)-methyl-2-(2-(chloromethyl) phenyl)-3-methoxy-methyl acrylate (intermediate A, 0.32g, 1.3mmol), salt of wormwood (0.36g, 1.6mmol), acetonitrile 6mL, heating, induction stirring, temperature rises to 80 ℃ of backflows, TLC detection reaction, stopped reaction after 11h.In reaction solution, add 20mL water, by 3 * 20mL ethyl acetate, extract.With anhydrous sodium sulfate drying, decompression precipitation, obtains product 0.343g, yield 86.7% through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/12).
The preparation of N-methoxyl group-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl] imino methyl acetate (I-6)
In the there-necked flask of 25mL, add respectively 1-(thionaphthene-2-yl) ethyl ketone oxime (V-1,0.28g, 1.5mmol), (E)-methyl-2-(2 – (brooethyl) phenyl)-2-methoxyimino methyl acetate (intermediate B, 0.57g, 2.0mmol), salt of wormwood (0.63g, 4.5mmol), acetonitrile 9mL, heating, induction stirring, temperature rises to 82 ℃ of backflows, TLC detection reaction, stopped reaction after 10h.In reaction solution, add 20mL water, by 3 * 20mL ethyl acetate, extract.With anhydrous sodium sulfate drying, decompression precipitation, obtains product 0.511g, yield 86.0% through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/12).
N-methoxyl group-N-[2-((1-(methylbenzene thiophthene-2-yl) ethylidene) amino oxygen methyl) phenyl] preparation of Urethylane (I-10)
In the there-necked flask of 25mL, add respectively 1-(thionaphthene-2-yl) ethyl ketone oxime (V-1,0.28g, 1.5mmol), N-2-2-bromomethylphenyl-N-methoxyl group Urethylane (intermediate C, 0.55g, 2.0mmol), salt of wormwood (0.63g, 4.5mmol), acetonitrile 9mL, heating, induction stirring, temperature rises to 82 ℃ of backflows, TLC detection reaction, stopped reaction after 5h.In reaction solution, add 20mL water, by 3 * 20mL ethyl acetate, extract.With anhydrous sodium sulfate drying, decompression precipitation, obtains product 0.515g, yield 89.3% through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/12).
N-methoxyl group-N-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl] preparation of imido grpup acetyl methylamine (I-14)
In the there-necked flask of 25mL, add respectively N-methoxyl group-N-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl] imino methyl acetate (I-6,0.39g, 1mmol), methylamine (the 0.5mL25wt% aqueous solution, 4mmol), methyl alcohol 6mL, heating, induction stirring, temperature rises to 80 ℃ of backflows, TLC detection reaction, stopped reaction after 6h.In reaction solution, add 20mL water, by 3 * 20mL ethyl acetate, extract.With anhydrous sodium sulfate drying, decompression precipitation, obtains product 0.376g, yield 95.1% through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/3).
N-methoxyl group-N-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl] preparation of carbamyl methylamine (I-18)
In the there-necked flask of 25mL, add respectively N-methoxyl group-N-[2-((1-(thionaphthene-2-yl) ethylidene) amino oxygen methyl) phenyl] Urethylane (I-10,0.38g, 1mmol), methylamine (the 0.5mL25wt% aqueous solution, 4mmol), methyl alcohol 6mL, heating, induction stirring, temperature rises to 80 ℃ of backflows, TLC detection reaction, stopped reaction after 24h.In reaction solution, add 20mL water, by 3 * 20mL ethyl acetate, extract.With anhydrous sodium sulfate drying, decompression precipitation, obtains product 0.108g, yield 28.2% through silica gel column chromatography separated (ethyl acetate/petroleum ether=1/3).
Other compound can be prepared with reference to aforesaid method.
Formulation Implementation example
Example 510% missible oil
10 parts of heavy Compound I-1 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 680% liquor
80 parts of (weight) Compound I-6 are mixed with the N-Methyl pyrrolidone of 20 parts (weight), obtain being applicable to take the very solution (active compound content is 80%) of small droplets form application.
Biological activity determination
Example 7 fungicidal activities are measured
With the compound of general formula I of the present invention, the various fungal diseases of plant are tested.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,
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 of " 0 " representative (conventionally using this is worth as basic survey standard), " 100 " represent without any scab.Test result is in Table 1～5.
The sterilization biological activity of thionaphthene substituted oximinoether kind methoxy-methyl acrylate class strobilurin compound.In Table 1.
Table 1
Note: " * " represents that crop is poisoned to death.
The fungicidal activity of thionaphthene substituted oximinoether kind N-methoxyl group-acetimidic acid methyl esters class strobilurin compound.In Table 2.
Table 2
Note: " * " represents that crop is poisoned to death.
The fungicidal activity of thionaphthene substituted oximinoether kind N-methoxyl group-Urethylane class strobilurin compound.In Table 3.
Table 3
Note: " * " represents that crop is poisoned to death.
The fungicidal activity of thionaphthene substituted oximinoether kind N-methoxyl group-imino-acetyl methylamine strobilurin compound.In Table 4.
Table 4
The fungicidal activity of thionaphthene substituted oximinoether kind N-methoxyl group-carbamyl methylamine strobilurin compound.In Table 5.
Table 5
Note: " * " represents that crop is poisoned to death.
Claims (10)
1. a thionaphthene substituted oximinoether kind compound, is characterized in that its general structure is as follows:
Wherein:
R
1for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
2for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
3for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
4for hydrogen, halogen, trihalogenmethyl, C
1-C
4alkyl, C
1-C
4alkoxyl group, C
1-C
4alkylthio, nitro or cyano group;
R
5for 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 thionaphthene substituted oximinoether kind compound as claimed in claim 1, is characterized in that described R
1for hydrogen or fluorine; R
2for hydrogen or trihalogenmethyl; R
3for hydrogen, chlorine or C
1-C
4alkylthio; R
4for hydrogen; R
5for methyl; Q is selected from Q
1, Q
2, Q
3, Q
4or Q
5.
3. the synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 1, is characterized in that described synthetic route is as follows:
4. a kind of synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 3, is characterized in that,
The compound of general formula III is prepared by the following method:
In aqueous solvent, under sodium hydroxide exists, under room temperature condition, add sulfur alcohol, then add the compound shown in tetra-n-butyl ammonium bromide and general formula II, at 25～100 ℃, react to obtain the compound shown in general formula III.
5. a kind of synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 3, is characterized in that,
The compound of general formula IV is prepared by the following method:
In solvent acetone, under calcium oxide exists, under 25～60 ℃ of conditions, with the compound shown in general formula III and α-monochloroacetone, react to obtain the compound shown in general formula IV.
6. a kind of synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 3, is characterized in that,
The compound of general formula V is prepared by the following method:
In ethanol/water solution, under alkali sodium acetate exists, under 25～100 ℃ of conditions, with the compound shown in general formula IV and oxammonium hydrochloride, react to obtain the compound shown in general formula V, the volume ratio of ethanol/water solution is 2/1.
7. a kind of synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 3, is characterized in that,
General formula I-Q
1, I-Q
2and I-Q
3compound prepare by the following method:
In solvent acetonitrile, under alkali salt of wormwood exists, under 25～100 ℃ of conditions, the general formula I-Q that reacts correspondingly with the compound shown in general formula V respectively with three different intermediate A, B or C
1, I-Q
2and I-Q
3shown compound.
8. a kind of synthetic route of thionaphthene substituted oximinoether kind compound as claimed in claim 3, is characterized in that,
General formula I-Q
4and I-Q
5compound prepare by the following method:
In solvent methanol, under 25～80 ℃ of conditions, with general formula I-Q
2or I-Q
3general formula I-Q that shown compound reacts correspondingly with the aqueous methylamine solution that is by mass percentage 25% respectively
4and I-Q
5shown compound.
9. the application of a kind of thionaphthene substituted oximinoether kind compound in preparing sterilant or controlling plant diseases medicine as claimed in claim 1.
10. application as claimed in claim 9, is characterized in that described sterilant includes but not limited to plant leaf surface sterilant, soil fungicides; Described controlling plant diseases medicine includes but not limited to prevent and treat barley powdery mildew medicine, wheat powdery mildew medicine, powdery mildew of cucumber medicine, rice blast medicine, corn rust medicine, uncinula necator medicine, apple mildew medicine, cucumber downy mildew medicine, cucumber anthracnose medicine, downy mildew of garpe medicine; Be in particular control wheat powdery mildew medicine, corn rust medicine, cucumber anthracnose medicine and rice blast medicine; Described sterilant comprises fungicidal composition, and it is active ingredient that described fungicidal composition be take at least one compound of general formula I, and the compound that its preparation method is general formula I mixes with at least one carrier, and in fungicidal composition, the mass ratio of active ingredient is 1%～99%.
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| CN103980179A (en) * | 2014-05-29 | 2014-08-13 | 厦门大学 | Indole-substituted oxime ether compounds as well as preparation method and application thereof |
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