CN108997307A - A kind of acrylonitrile di esters compound and its application - Google Patents
A kind of acrylonitrile di esters compound and its application Download PDFInfo
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- CN108997307A CN108997307A CN201810722372.3A CN201810722372A CN108997307A CN 108997307 A CN108997307 A CN 108997307A CN 201810722372 A CN201810722372 A CN 201810722372A CN 108997307 A CN108997307 A CN 108997307A
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- acrylonitrile
- compound
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- mite
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- -1 acrylonitrile di esters compound Chemical class 0.000 title claims abstract description 21
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 6
- 201000010099 disease Diseases 0.000 claims abstract description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 22
- 230000000975 bioactive effect Effects 0.000 claims 1
- 230000000361 pesticidal effect Effects 0.000 claims 1
- 241000426497 Chilo suppressalis Species 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 2
- 244000052616 bacterial pathogen Species 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 230000002147 killing effect Effects 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000000749 insecticidal effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SFYQTXFSGQMRSM-UHFFFAOYSA-N 3-chloro-2-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=C(Cl)C=CC=C1C(Cl)=O SFYQTXFSGQMRSM-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- RJQQYZYIJMBRNH-UHFFFAOYSA-N C(C)#N.C(C)(C)(C)C1=CC=CC=C1 Chemical compound C(C)#N.C(C)(C)(C)C1=CC=CC=C1 RJQQYZYIJMBRNH-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- 241000222201 Colletotrichum capsici Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000223195 Fusarium graminearum Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 241000813090 Rhizoctonia solani Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MXIUWSYTQJLIKE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoyl chloride Chemical compound FC(F)(F)C1=CC=CC=C1C(Cl)=O MXIUWSYTQJLIKE-UHFFFAOYSA-N 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- BWKGZHYPIUYSJQ-BUHFOSPRSA-N CCOC(/C(/O)=C(\c1ccc(C(C)(C)C)cc1)/C#N)=O Chemical compound CCOC(/C(/O)=C(\c1ccc(C(C)(C)C)cc1)/C#N)=O BWKGZHYPIUYSJQ-BUHFOSPRSA-N 0.000 description 1
- 241000426499 Chilo Species 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 1
- 240000008254 Rosa chinensis Species 0.000 description 1
- 235000000664 Rosa chinensis Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- APJLTUBHYCOZJI-VZCXRCSSSA-N cyenopyrafen Chemical compound CC1=NN(C)C(\C(OC(=O)C(C)(C)C)=C(/C#N)C=2C=CC(=CC=2)C(C)(C)C)=C1C APJLTUBHYCOZJI-VZCXRCSSSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of acrylonitrile di esters compounds, and general structure is as shown in I:R in formula are as follows:
Description
The invention belongs to agricultural insecticidal, mite killing and fungicide fields for technical field, and in particular to a kind of acrylonitrile di esters
Compound and its application.
Background technique agriculturally disease, worm, mite evil lead to crop failure and quality decline, at present its Prevention Technique mainly according to
Rely chemical pesticide.Due to the long-term a large amount of frequent uses of chemical pesticide, harmful organism causes to prevent to which create serious drug resistance
Effect reduces, and control cost increases.Desinsection, mite killing and the bactericidal agent for developing novel different role mechanism are to overcome or delay to have
The important means of evil biomolecule resistant.The moth fly nitrile of German schering company early stage research and development is vinyl cyanide insecticide, thereafter
The time of decades, the report of few vinyl cyanide insecticidal/acaricidal agents, CN1216530A, which is disclosed, as follows has pest, harmful mite
There is the acrylonitrile compound (KC) of preventive and therapeutic effect:
2002, Shibata et al. (Shibata Y, Ichikawan N, Hatano R, et al.Organic
Compound Having Cyano Group and Vermin Controlling Agent:JP,2004010577[P]
.2004-01-15 it) proposes a series of with desinsection (mite killing) active acrylonitrile compound A containing pyrazole heterocycle；When each
When substituent structure such as compound B, which has excellent killing ability to Tetranychus urticae.
Japanese Nissan chemical company has developed the novel propylene nitrile compounds (structural formula C) with good insecticidal,
Trade name NC-510, it is effective to acarid, especially have to sucking pest such as silkworm aphid and aphid etc. and efficiently kills
Deactivation, and and insecticide no interactions resistance at that time.2009, Japanese Nissan chemical company was proposed with excellent activity
Acaricide nitrile pyrrole mite ester (Cyenopyrafen, structural formula D).
Above compound and the compounds of this invention have certain similarity in structure, but in the prior art, such as originally
A kind of acrylonitrile di esters compound of invention and its application are not disclosed.
Summary of the invention
The purpose of the present invention is to provide a kind of acrylonitrile di esters compounds of structure novel, and it is common that it can be used for agricultural
Insect pest, mite evil, fungus damage effectively prevent.
Technical scheme is as follows:
The present invention provides a kind of acrylonitrile di esters compounds, and general structure is as shown in I:
R in formula are as follows:
Generalformulaⅰcompound of the present invention can be by reacting preparation as follows, and each group definition is the same in reaction equation.
The specific preparation method of intermediate and generalformulaⅰcompound is shown in present invention synthesis example.
Table 1 lists the structure and physical property of generalformulaⅰcompound.
The structure and physical property of 1 chemical compounds I of table
The advantages and positive effects of the present invention: generalformulaⅰcompound of the present invention is a kind of di esters acrylonitrile compound, is had
The simple advantage of structure novel, synthetic method, and both had the function of desinsection, mite killing, while having to crop Common Diseases
It is simultaneous to control effect.There is generalformulaⅰcompound of the present invention a medicine more to control, reduce control cost, overcome or delay the anti-medicine of harmful organisms
The unexpected comprehensive performances such as property.As New pesticides discovery kind, there is very wide exploitation and application prospect.Therefore,
The invention also includes the purposes that generalformulaⅰcompound is used to control agricultural insect pest, mite evil and disease.
The compounds of this invention is being prevented and treated worm, mite and when disease, can both can be used alone according to actual needs, can also be with
Other desinsections, mite killing or fungicide isoreactivity substance are applied in combination, to improve the comprehensive performance of product.
The invention also includes desinsection, mite killing and the bactericidal compositions using generalformulaⅰcompound as active component.The modularization
Closing object further includes agriculturally acceptable carrier.
Composition of the invention can be applied in the form of preparation.Generalformulaⅰcompound is dissolved or dispersed in as active component
In carrier or solvent, surfactant formulatory appropriate is added into missible oil, suspending agent, microemulsion or wettable powder etc..
It should be appreciated that various transformation and change can be carried out in the range of claim of the invention limits.
Specific embodiment
Following synthesis example and raw result of surveying can be used to further illustrate the present invention, but be not intended to limit the present invention.
Synthesize example:
The preparation of example 1, generalformulaⅰcompound:
(1) preparation of intermediate 3- (4- (tert-butyl) phenyl) -3- cyano-2-hydroxy ethyl acrylate:
100mL ethyl alcohol is added in 250mL three-necked flask, reaction flask is placed in cold-trap by 2.53g (0.11mol) sodium, is stirred
It is all reacted to sodium into sodium alkoxide.17.3g (0.1mol) is added into the alcohol sodium solution prepared to tert-butyl benzene acetonitrile, temperature control
17.52g (0.12mol) diethy-aceto oxalate, exothermic heat of reaction is slowly added dropwise at 0 DEG C in system, and solution becomes cloudy rear thin out yellow, stirring
4h is reacted, it is complete to tert-butyl benzene acetonitrile total overall reaction that TLC detects raw material, and has new product to generate, and filters, and revolving removes part second
Alcohol, adds the stirring of 500mL water, adjusts pH to 4-5 with dilute hydrochloric acid, and the extraction of 200mL ethyl acetate is added, and liquid separation retains organic
Phase, water phase use the extraction of 100mL ethyl acetate primary again, merge organic phase, and revolving is dry, obtains pale yellow oily liquid 25.9g, yield
94.9%, 10mL ethyl acetate is added, oil product is uniformly dissolved by heating, and petroleum ether to muddiness is added dropwise after cooling and is
Only, heating makes it dissolve uniformly, is placed on crystallisation by cooling in refrigerator, obtains faint yellow solid 3- (4- (tert-butyl) phenyl) -3- cyano -
2- hydroxyl ethyl acrylate 23.2g, yield 85.0% (in terms of to tert-butyl benzene acetonitrile), 67-70 DEG C of fusing point.
(2) preparation of o-trifluoromethyl chlorobenzoyl chloride:
9.50g (0.05mol) o-trifluoromethyl benzoic acid, 8.95g (0.075mol) chlorination are added into 250mL there-necked flask
Sulfoxide, 20mL toluene make solvent, and two drop DMF make catalyst, connect device for absorbing tail gas in bottleneck, be warming up to reflux, react 4h,
TLC detects that o-trifluoromethyl benzoic acid point disappears, and decompression steams solvent, obtains weak yellow liquid o-trifluoromethyl chlorobenzoyl chloride
9.95g, yield 95.4%.
(3) chemical compounds I1Preparation:
5.46g (0.02mol) 3- (4- (tert-butyl) phenyl) -3- cyano-2-hydroxy third is added into 250mL three-necked flask
Olefin(e) acid ethyl ester, 20mL ethyl acetate, 2.22g (0.11mol) triethylamine, by 4.48g (0.022mool) o-trifluoromethyl benzoyl
Chlorine is diluted with 20mL ethyl acetate to be slowly dropped in there-necked flask, is stirred to react 2h, TLC detects raw material 3- (4- (tert-butyl)
Phenyl) disappearance of -3- cyano-2-hydroxy ethyl acrylate, it filters, collects filtrate, wash organic phase with 1% sodium hydroxide solution,
Extra o-trifluoromethyl chlorobenzoyl chloride is washed away, liquid separation retains organic phase, and organic phase is washed twice with clear water again, separates organic phase
Dry with anhydrous sodium sulfate, revolving walks solvent ethyl acetate, obtains faint yellow oil product 8.62g, recrystallisation from isopropanol obtains white
Solid 3- (4- (tert-butyl) phenyl) -3- cyano -2- (2- (trifluoromethyl) benzoyloxy) ethyl acrylate 7.91g, yield
88.9% (in terms of 3- (4- (tert-butyl) phenyl) -3- cyano-2-hydroxy ethyl acrylate), 107~110 DEG C of fusing point.
1H NMR (500MHz, CDCl3- d), δ (ppm): 1.31 (s, 9H), 1.39-1.42 (t, 3H), 4.44-4.48 (q,
2H), 7.41-7.43 (d, 2H), 7.53-7.55 (d, 2H), 7.64-7.67 (t, 1H), 7.70-7.73 (t, 1H), 7.83-7.84
(d, 1H), on 7.94-7.96 (d, 1H) phenyl ring is 1.31 (s, 9H), methyl in ethyl acrylate structure to tert-butyl appearance
Appearance is 1.39-1.42 (t, 3H), and it is 4.44-4.48 (q, 2H), two phenyl ring that methylene, which is moved appearance to low field by oxygen atom,
Upper hydrogen peak is 7.41-7.43 (d, 2H), 7.53-7.55 (d, 2H), 7.64-7.67 (t, 1H), 7.70-7.73 (t, 1H), 7.83-
7.84 (d, 1H), 7.94-7.96 (d, 1H).
Other chemical compounds Is2~I10Preparation method and I1It is similar.The nuclear magnetic data of each compound is as follows:
Ⅰ2:1H NMR (500MHz, DMSO-d6), δ (ppm): 1.29 (s, 9H), 1.32~1.35 (t, 3H), 4.34~
4.38 (q, 2H), 7.45~7.48 (d, 2H), 7.63~7.66 (d, 2H), 7.67~7.68 (d, 2H), 8.00~8.02 (d,
2H)。
Ⅰ3:1H NMR (500MHz, DMSO-d6), δ (ppm): 1.28 (s, 9H) 1.30-1.33 (t, 3H), 4.29-4.33
(m, 2H), 7.40-7.42 (d, 2H), 7.64-7.66 (d, 2H).
Ⅰ4:1H NMR (500MHz, CDCl3- d), δ (ppm): 1.34 (s, 9H), 1.38-1.41 (t, 3H), 3.91 (s,
2H), 4.39-4.43 (q, 2H), 7.21-7.26 (m, 2H), 7.36-7.38 (d, 2H), 7.41-7.42 (m, 3H).
Ⅰ5:1H NMR (500MHz, CDCl3- d), δ (ppm): 1.34 (s, 9H), 1.40-1.43 (t, 3H), 4.44-4.49
(q, 2H), 7.46-7.48 (d, 2H), 7.57-7.59 (d, 2H), 7.67-7.68 (m, 1H), 7.94-7.95 (d, 2H).
Ⅰ6:1H NMR (500MHz, DMSO-d6), δ (ppm): 1.16~1.19 (t, 3H), 1.26 (s, 9H), 1.27~
1.32 (t, 3H), 2.57~2.61 (q, 2H), 3.99 (s, 3H), 4.34~4.39 (q, 2H), 7.52~7.54 (d, 2H), 7.62
~7.66 (d, 2H).
Ⅰ7:1H NMR (500MHz, DMSO-d6), δ (ppm): 1.33 (s, 9H), 1.39-1.42 (t, 3H), 4.40-4.43
(q, 2H), 6.68 (s, 1H), 7.46-7.48 (d, 2H), 7.57-7.59 (d, 2H), 7.67-7.68 (m, 1H), 7.94-7.95
(m, 1H), 8.59~8.60 (m, 1H).
Ⅰ8:1H NMR (500MHz, CDCl3- d), δ (ppm): 0.73-0.76 (t, 3H), 1.18 (s, 6H), 1.32 (s,
9H), 1.38-1.41 (t, 3H), 1.57-1.61 (q, 2H), 4.32-4.38 (q, 2H), 7.42-7.44 (d, 2H), 7.47-7.50
(d, 2H).
Ⅰ9:1H NMR (500MHz, DMSO-d6), δ (ppm): 1.01 (s, 6H), 1.24~1.26 (t, 3H), 1.27 (s,
9H), 2.00~2.01 (d, 1H), 2.24~2.25 (m, 1H), 4.16~4.19 (q, 2H), 6.73~6.75 (d, 1H), 7.49
~7.50 (d, 2H), 7.54~7.56 (d, 2H).
Ⅰ10:1H NMR (500MHz, DMSO-d6), δ (ppm): 0.72-0.75 (t, 3H), 1.08-1.16 (m, 2H), 1.30
(s, 9H), 1.32-1.34 (t, 3H), 1.42-1.48 (m, 2H), 3.30-3.33 (t, 2H), 4.35-4.41 (q, 2H), 7.57-
7.59 (m, 2H), 7.61-7.63 (m, 2H).
Biological activity determination:
Example 2, insecticidal activity assay
To striped rice borer determination of activity: using the drop method of NY/T 1154.1-2006 standard recommendation, mutual-through type Compound I into
Row active testing.Compound is dissolved respectively with the dimethyl sulfoxide (DMSO) of equivalent, respectively with 0.1% tween-now matched
80 aqueous solutions are diluted to 4 kinds of concentration, and blank is the Tween-80 aqueous solution of DMSO and 0.1%, are also diluted to 4 concentration.Use writing brush
Size, the consistent 4 age Chilo spp larvae of upgrowth situation for choosing artificial feeding are spare in culture dish.With 1 μ of capillary taking liquid
Polypide after drop is transferred to and raises under normal circumstances on polypide pronotary by L drop.Every group of processing test worm is 15, often
Handle 4 repetitions.Using the DMSO without medicament as blank control.It investigates test worm death condition afterwards for 24 hours, records dead borer population.It presses
According to formula (1) and (2), the corrected mortality of each processing is calculated.
In formula: P1--- the death rate, unit are percentage (%)；K --- indicate dead borer population；N --- indicate that processing is total
Borer population.
In formula: P2--- corrected mortality, unit are percentage (%)；Pt --- the processing death rate；P0--- blank control
The death rate.
If compareing the death rate < 5%, without correction；The death rate is compareed between 5%~20%, school should be carried out by formula (2)
Just；The death rate > 20% is compareed, test need to carry out again.Test result is as shown in table 2.
Killing activity data of 2 compound of Formula I of table to striped rice borer
As can be seen from Table 2, the compounds of this invention has killing effect to striped rice borer, and when Drug level is 200mg/L, I7、I8With
I10Corrected mortality to striped rice borer is 100%, I9Also higher corrected mortality (96.55%) is shown.With concentration
Gradually decrease to 25mg/L, I8And I10Still remain 100% corrected mortality.In 5mg/L, I8Corrected mortality be
83.51%, I10Corrected mortality be 86.34%, still show good insecticidal activity.
Example 3, acaricidal activity measurement
To Tetranychus cinnabarinus determination of activity: using spray-on process.It is sprayed using what international resistance Action Committee (IRAC) proposed
Method.The leaf dish that Kidney bean spire blade is broken into punch to 2 centimetres of diameter, with Airbrush spraying treatment, certain density survey
It is spraying in every leaf dish front and back sides to try compound, spray amount is 0.5 milliliter, and every processing accesses 20 test worms (3 age) after drying in the shade.Processing
It is put into the indoor culture of 24 DEG C, relative humidity 60%~70%, no light afterwards, investigation survival borer population after 48 hours calculates dead
Rate.(3 repetitions are done in test, are averaged)
In the test compound of part, following compounds are preferable to the preventive effect of Tetranychus cinnabarinus in concentration 50ppm, and the death rate exists
90% or more: I1、Ⅰ2、Ⅰ6、Ⅰ8、Ⅰ9、Ⅰ10.According to above method, chemical compounds I is chosen1、Ⅰ6、Ⅰ9、Ⅰ10It is carried out with known compound KC
The parallel determination of Tetranychus cinnabarinus activity is killed, test result is listed in table 3.
Table 3 kills Tetranychus cinnabarinus determination of activity
Example 4, bactericidal activity test
According to " farm-chemical indoor determination tests criterion fungicide ", using the sterilization of Plating measurement compound of Formula I
Effect.With Rhizoctonia solani Kuhn (Rhizoctonia solani), Colletotrichum capsici (Colletotrichum capsici),
Four kinds of fusarium graminearum (Gibberella zeae), Chinese rose Pseudoperonospora cubensis mycelia are test object, are divided into four groups, and be arranged
Blank control.Compound of Formula I is dissolved respectively with the dimethyl sulfoxide (DMSO) of equivalent, respectively spitting with 0.1% now matched
Warm -80 aqueous solutions are diluted to 50 μ g/L, and blank is the Tween-80 aqueous solution of DMSO and 0.1%, and DMSO is no more than the 2% of total amount.
1mL medical fluid is successively drawn from 11 bottles, injection has been melted in the sterile conical flask of sterilising medium in advance, sufficiently shaken up, so
Equivalent is poured into the culture dish that 3 diameters are 9cm afterwards, and the drug containing tablet that concentration is 50 μ g/L is made, and 3 repetitions are arranged and test,
And that uses no medicament does same treatment as blank control.The pathogen that will be cultivated above aseptically uses diameter 5mm
Sterilization punchers punching, cut bacteria cake from bacterium colony edge, with inoculator be inoculated in drug containing tablet center, mycelia is face-up,
Culture ware lid is covered, culture dish is put in the constant incubator of (24 ± 1) DEG C and is cultivated.Calliper to measure bacterium colony is used after 72h
Diameter is respectively measured once using crossing method diameter, surveys its average diameter.Opposite bacteriostasis rate is calculated according to following formula:
D=D1-D2......................................................(3)
In formula: D --- bacterium colony increases diameter；D1--- colony diameter；D2--- bacteria cake diameter.
In formula: I --- mycelial growth inhibition rate；D0--- blank control bacterium colony increases diameter；Dt--- chemicals treatment bacterium colony
Increase diameter.
According to experimental result, different agents are calculated to the mycelial growth inhibition rate for trying target bacterium by formula (3), (4)
(%).Test result is listed in table 4.
Table 4 kills germ active testing
By table 4 as it can be seen that the compounds of this invention shows certain bactericidal activity.
Claims (3)
1. a kind of acrylonitrile di esters compound, general structure is as shown in I:
R in formula are as follows:
2. a kind of purposes of acrylonitrile di esters compound according to claim 1, it is characterised in that generalformulaⅰcompound list
One uses or is applied in combination with other bioactive compound, has control efficiency to agriculturally pest, mite and disease.
3. a kind of Pesticidal combination, being containing compound of Formula I described in claim 1 can in active component and agricultural, forestry
The carrier of receiving.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4469688A (en) * | 1982-06-30 | 1984-09-04 | Union Carbide Corporation | Pesticidal cyano enol phosphates |
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
| CN1247530A (en) * | 1997-02-14 | 2000-03-15 | 石原产业株式会社 | Acrylonitrile compounds, process for their prodn. and pesticides containing them |
-
2018
- 2018-07-04 CN CN201810722372.3A patent/CN108997307A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4469688A (en) * | 1982-06-30 | 1984-09-04 | Union Carbide Corporation | Pesticidal cyano enol phosphates |
| CN1216530A (en) * | 1996-04-25 | 1999-05-12 | 日产化学工业株式会社 | Ethylene derivatives and pest controlling agents |
| CN1247530A (en) * | 1997-02-14 | 2000-03-15 | 石原产业株式会社 | Acrylonitrile compounds, process for their prodn. and pesticides containing them |
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