CN102442966A - N-substituted phenyl oxime ether compound containing heterocycle ketone as well as preparation and application to prevention and treatment of plant diseases and insect pests thereof - Google Patents
N-substituted phenyl oxime ether compound containing heterocycle ketone as well as preparation and application to prevention and treatment of plant diseases and insect pests thereof Download PDFInfo
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- CN102442966A CN102442966A CN201010501011XA CN201010501011A CN102442966A CN 102442966 A CN102442966 A CN 102442966A CN 201010501011X A CN201010501011X A CN 201010501011XA CN 201010501011 A CN201010501011 A CN 201010501011A CN 102442966 A CN102442966 A CN 102442966A
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- compound
- ketone
- phenyl
- substituted phenyl
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- -1 phenyl oxime ether compound Chemical class 0.000 title claims abstract description 38
- 241000607479 Yersinia pestis Species 0.000 title claims abstract description 11
- 201000010099 disease Diseases 0.000 title abstract description 11
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title abstract description 11
- 241000238631 Hexapoda Species 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 230000002265 prevention Effects 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 7
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 3
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 claims description 3
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 claims description 3
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 3
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
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- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
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- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
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- 230000002147 killing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
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- 239000001301 oxygen Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 10
- VEUMBMHMMCOFAG-UHFFFAOYSA-N 2,3-dihydrooxadiazole Chemical compound N1NC=CO1 VEUMBMHMMCOFAG-UHFFFAOYSA-N 0.000 description 8
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- IRFHMTUHTBSEBK-QGZVFWFLSA-N tert-butyl n-[(2s)-2-(2,5-difluorophenyl)-3-quinolin-3-ylpropyl]carbamate Chemical compound C1([C@H](CC=2C=C3C=CC=CC3=NC=2)CNC(=O)OC(C)(C)C)=CC(F)=CC=C1F IRFHMTUHTBSEBK-QGZVFWFLSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 6
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- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
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- 230000009885 systemic effect Effects 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an N-substituted phenyl oxime ether compound containing heterocycle ketone as well as preparation and an application to prevention and treatment of plant diseases and insect pests thereof. Substituted phenyl oxime is used as raw materials to take etherification reaction with the heterocycle ketone containing benzyl halogen under the effect of acid binding agents, and the N-substituted phenyl oxime ether compound containing the heterocycle ketone is obtained. The compound has the excellent sterilization activity and insect killing activity and can be applied to the prevention and the treatment of plant diseases and insect pests on various crops.
Description
Technical field
The invention belongs to agricultural insecticidal, sterilant field.Be specifically related to a kind of application that contains N-substituted-phenyl oximinoether and the preparation and the control plant pest of heterocyclic ketone.
Technical background
At present, the control of disease and pest is the core realm of pesticide science research all the time, and the generally use of agricultural chemicals makes most sick entomogenous fungi evils obtain administering effectively, has reduced the heavy losses that agricultural produces because of disease and pest.But along with the continuous expansion of agricultural chemicals application scale, the problems such as resistance that the desinsection of organic synthesis, sterilant in use produce more highlight, and the key that addresses these problems is at low toxicity desinsection, the sterilant of seeking and develop brand-new action target spot.
Methoxy acrylic ester compounds is one type of material with novel mechanism of action of the eighties of last century research nineties and exploitation.It mainly acts on is to suppress mitochondrial breathing, through getting in the pathogenic bacteria cell, with the Q of cytochrome b on the plastosome
0The site combines, the electron transport between blocking-up cytochrome b and the cytochrome c 1, thus suppress mitochondrial respiration, it is synthetic to destroy the germ energy.The fungicidal activity of this compounds wide spectrum is that other type sterilant is incomparable, and methoxy acrylic ester compounds also has outstanding insecticidal activity simultaneously.Characteristics such as this compounds has efficiently, low toxicity, wide spectrum, safety, environmental friendliness.
Oxime bacterium ester (trifloxystrobin) is typical case's representative of this compounds; Patent EP0460575, WO9524383 etc. disclose the structure of this compounds and the biological activity of wide spectrum; Substituted aryl oxime ether in its structure is the synthetic fragment of outstanding biologically active; This fragment has desinsection, kills full, sterilization, and the weeding isoreactivity is widely used in the initiative of novel pesticide.The heterocyclic ketones structure also is the synthetic fragment of biologically active, has at medicine, pesticide field and uses (Zappia, G. very widely; Menendez, P.; Delle, M.G.; Misiti, D.; Nevola, L.; Botta, B.Mini-Rev.Med.Chem.2007,7,389; Zappia, G.; Cancelliere, G.; Gacs, B.E.; Delle, M.G.; Misiti, D.; Nevola, L.; Botta, B.Curr.Org.Syn.2007,4,238.), its kind that success is developed in agricultural chemicals Wei oxazole bacterium ketone (Ulrich, G.; Helge, S.; Alison, C.; Alan, M.Pest Manag.Sci.2002,58,859).
Patent EP0704430 discloses a kind of compound (structure-1) of following structure, contains two azolactones in the agent structure of this compounds, has the agricultural bactericidal effect.
Structure-1 structure-2
Patent US5977149 discloses the disinfectant use in agriculture that a kind of agent structure is a heterocyclic ketone (structure-2), and the atom that heterocyclic ketone links to each other with phenyl ring is C or N.
Disclose among the patent US6642180B1 that a series of to contain biphenyl substituent be the compound of agent structure and the application in disinfectant use in agriculture with the heterocyclic ketone.
Disclose a kind of compound that comprises the heterocyclic ketone agent structure (structure-3) among the patent US2004/0063937A1 equally and be applied to agricultural bactericidal, the agent structure that comprises in representative instance Wei oxazolidone (structure-4):
Structure-3 structure-4
Before the present invention; We have also applied for one piece of Chinese patent; Application number is 201010221898.7 (2010.7.9), and this patent relates to a kind of application that contains N-substituted phenyl pyrazole compounds and the preparation and the control plant pest of heterocyclic ketone, and general formula is (structure-5) as follows:
R
(n)Middle n=1-5 replaces R
(n)Be selected from hydrogen, halogen, cyanic acid, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy, C
1-C
6Alkylthio, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkylamino, the halogen in the wherein said halogeno-group is selected from one or more in fluorine, chlorine, the bromine or iodine; Q is selected from one of following group:
The present invention is from the developing direction of novel pesticide; N-substituted phenyl pyrazole compounds to reporting in the above chapter patent carries out further structure of modification; Replace the phenylpyrazole fragment with phenyl oxime ether active fragments; Splice with the heterocyclic ketone main body, designed and synthesized a kind of N-substituted-phenyl oximinoether that contains heterocyclic ketone.Though disclosed compound has similar structures in this compounds and the patent before, exists significantly different.Through this compounds is carried out biological activity test, find that this compounds has desinsection, fungicidal activity preferably, being expected to exploitation becomes new varieties of pesticides.
Summary of the invention
The object of the present invention is to provide a kind of novel N-substituted-phenyl oximinoether that contains heterocyclic ketone that under very little dosage, just can control various disease and pests, it can be applied to agricultural and go up disease and insect pest with the control crop.
Technical scheme of the present invention is following:
The present invention provides a kind of N-substituted-phenyl oximinoether that contains heterocyclic ketone, shown in general formula I:
R
(n)Middle n=1-5 replaces R
(n)Be selected from hydrogen, halogen, cyanic acid, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy, C
1-C
6Alkylthio, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkylamino, the halogen in the wherein said halogeno-group is selected from one or more in fluorine, chlorine, the bromine or iodine; Z is selected from methyl or hydrogen; Q is selected from one of following group:
Can the present invention be described with the compound of listing in the following table 1, but not limit the present invention.
Table 1
| Numbering | R (n) | Z | Q |
| 1 | H | CH 3 | Q 1 |
| 2 | 4-Br | CH 3 | Q 1 |
| 3 | 3-CF 3 | CH 3 | Q 1 |
| 4 | 3-CF 3-4-Cl | CH 3 | Q 1 |
| 5 | 4-Cl | CH 3 | Q 1 |
| 6 | 2，4-(Cl) 2 | H | Q 1 |
| 7 | 3-F | CH 3 | Q 1 |
| 8 | 3-Cl-4-F | CH 3 | Q 1 |
[0028]
| 9 | 4-CH 3 | CH 3 | Q 1 |
| 10 | 3-CH 3 | CH 3 | Q 1 |
| 11 | 3-Cl-4-F | CH 3 | Q 2 |
| 12 | 2，4-(Cl) 2 | H | Q 2 |
| 13 | 3-CF 3 | CH 3 | Q 2 |
| 14 | 4-Cl | CH 3 | Q 2 |
| 15 | 4-Br | CH 3 | Q 2 |
| 16 | 4-Cl | H | Q 2 |
| 17 | 4-NO 2 | H | Q 2 |
| 18 | 4-F | H | Q 2 |
Among the present invention; The compound method of N-substituted-phenyl oximinoether that contains heterocyclic ketone is following: (amount of substance is a unit by the compound I I of 1 times of amount; Down with) compound III doubly measured with 1-2 is at acetone, acetonitrile or N; In the dinethylformamide solvent, be that acid binding agent at room temperature reacts the compound that obtained general formula I in 0.5-20 hour with alkali:
In the formula, X is a leavings group, is selected from chlorine, bromine or iodine.
Compound shown in the general formula I I can be obtained through bromo by the known compound thing, but reference literature Tetrahedron Lett.1988,29,5095, Synth.2007,16,2517 with chemistry circular 2006,9,74 etc.
The oximinoether of hydroxyl shown in the general formula III is made by currently known methods, but reference literature Org.Lett.2007, and 9 (18), 3599 with patent US6211413 etc.
The compound of originally issuing a statement has the excellent sterilizing activity; They have systemic activity and can be used as blade face and soil fungicides; Can be applicable to the disease on the various crops of control, be particularly suitable for preventing and treating the following plants disease: downy mildew of garpe, rice sheath blight disease, rice blast, early blight of tomato, tomato late blight, wheat rust, speckled leaf blotch, wheat powdery mildew, powdery mildew of cucumber, cucumber downy mildew, gray mold of cucumber etc.
Compound of the present invention has excellent insecticidal activity equally, is used to prevent and treat the insect on the various crops.For example can be used for preventing and treating mythimna separata, small cabbage moth, black peach aphid, carmine spider mite, Tetranychus urticae, ladybug, evil mite and culex pipiens pollens etc.
Embodiment
Following specific embodiment is used for further specifying the present invention.
Synthetic embodiment
Embodiment 1:3-(synthesizing of 2-((((1-phenyl ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 1)
Add compound (III-1) 0.41g (3.0mmol) in the 100mL four-hole boiling flask, sodium hydride 0.22g (4.5mmol, 50% content); With the anhydrous N of 20mL, dinethylformamide stirs 0.5h down in ice bath (0 ℃); The 15mL N that adds compound (II-1) 0.77g (3.00mmol) again; Dinethylformamide solution after continuing reaction 15h under the room temperature, adds the 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying; The pressure reducing and steaming solvent obtains yellow thick liquid, through column chromatography for separation purification (silica gel is filled, petrol ether/ethyl acetate); Obtain little yellow thick liquid, productive rate 79.3%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.25 (s, 3H, CH
3), 3.98 (t, J=7.96,2H, CH
2), 4.46 (t, J=7.85,2H, CH
2), 5.28 (s, 2H, CH
2), 7.22-7.29 (m, 2H, Ar-H), 7.33-7.39 (m, 5H, Ar-H), 7.54-7.57 (m, 1H, Ar-H), 7.60-7.63 (m, 2H, Ar-H).
Embodiment 2:3-(synthesizing of 2-((((1-(4-bromophenyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 2)
Add compound (III-2) 0.64g (3.0mmol) in the 100mL four-hole boiling flask; Sodium hydride 0.22g (4.5mmol, 50% content) and 20mL anhydrous acetonitrile; Stir 0.5h down in ice bath (0 ℃); The 15mL acetonitrile solution that adds compound (II-1) 0.77g (3.00mmol) again after continuing reaction 15h under the room temperature, is put the cold adding 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying; The pressure reducing and steaming solvent obtains yellow thick liquid, through column chromatography for separation purification (silica gel is filled, petrol ether/ethyl acetate); Obtain white solid, productive rate 82.0%, fusing point are 98-101 ℃.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.22 (s, 3H, CH
3), 3.99 (t, J=7.98,2H, CH
2), 4.48 (t, J=7.49,2H, CH
2), 5.28 (s, 2H, CH
2), 7.22-7.30 (m, 2H, Ar-H), 7.35-7.39 (m, 2H, Ar-H), 7.45-7.55 (m, 4H, Ar-H).
Embodiment 3:3-(synthesizing of 2-((((1-(3-trifluoromethyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 3)
III-3 II-1 3
Add compound (III-3) 0.61g (3.0mmol) in the 100mL four-hole boiling flask; Salt of wormwood 0.62g (4.5mmol); With the 20mL anhydrous propanone, under the reflux temperature (56 ℃) of acetone, stir 0.5h, add the 15mL acetone soln of compound (II-1) 0.77g (3.00mmol) again; After continuing reaction 15h under this temperature, put the cold adding 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying; The pressure reducing and steaming solvent obtains yellow thick liquid, through column chromatography for separation purification (silica gel is filled, petrol ether/ethyl acetate); Obtain little yellow thick liquid, productive rate 87.0%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 4.00 (t, J=7.94,2H, CH
2), 4.49 (t, J=7.94,2H, CH
2), 5.30 (s, 2H, CH
2), 7.22-7.31 (m, 2H, Ar-H), 7.36-7.41 (m, 2H, Ar-H), 7.47 (t, J=7.78,1H, Ar-H), 7.54-7.61 (m, 2H, Ar-H), 7.80 (d, J=7.89,1H, Ar-H), 7.88 (s, 1H, Ar-H).
Embodiment 4:3-(synthesizing of 2-((((1-(3-trifluoromethyl-4-chloro-phenyl-) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 4)
Add compound (III-4) 0.71g (3.0mmol) in the 100mL four-hole boiling flask, sodium hydride 0.22g (4.5mmol, 50% content); With the anhydrous N of 20mL, dinethylformamide stirs 0.5h down in ice bath (0 ℃); The 15mL N that adds compound (II-1) 0.77g (3.00mmol) again; Dinethylformamide solution after continuing reaction 15h under the room temperature, adds the 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent obtains yellow thick liquid, purifies (silica gel is filled, petrol ether/ethyl acetate) through column chromatography for separation, obtains product, yield 83.9%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.24 (s, 3H, CH
3), 3.99 (t, J=7.91,2H, CH
2), 4.49 (t, J=7.91,2H, CH
2), 5.30 (s, 2H, CH
2), 7.21-7.30 (m, 2H, Ar-H), 7.34-7.39 (m, 2H, Ar-H), 7.47 (d, J=8.46,1H, Ar-H), 7.53 (q, J=6.86,1H, Ar-H), 7.72 (q, J=8.37,1H, Ar-H), 7.94 (d, J=2.2,1H, Ar-H).
Embodiment 5:3-(synthesizing of 2-((((1-(4-chloro-phenyl-) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 5)
Compound method is with reference to embodiment 1.Productive rate 82.7%.
Nuclear magnetic data (
1HNMR, 500MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.22 (s, 3H, CH
3), 3.98 (t, J=7.90,2H, CH
2), 4.47 (t, J=7.90,2H, CH
2), 5.28 (s, 2H, CH
2), 6.96-7.11 (m, 2H, Ar-H), 7.28-7.33 (m, 2H, Ar-H), 7.35-7.39 (m, 2H, Ar-H), 7.53-7.56 (t, J=8.25,2H, Ar-H).
Embodiment 6:3-(synthesizing of 2-((((1-(2,4 dichloro benzene base) methylene radical) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 6)
Compound method is with reference to embodiment 1.Productive rate 85.1%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 4.01 (t, J=7.90,2H, CH
2), 4.50 (t, J=7.97,2H, CH
2), 5.28 (s, 2H, CH
2), 7.22-7.30 (m, 2H, Ar-H), 7.34-7.41 (m, 3H, Ar-H), 7.53 (d, J=7.4,1H, Ar-H), 7.79 (d, J=8.6,1H, Ar-H), 8.46 (s, 1H, CH).
Embodiment 7:3-(synthesizing of 2-((((1-(3-fluorophenyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 7)
Compound method is with reference to embodiment 1.Productive rate 79.8%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.23 (s, 3H, CH
3), 4.00 (t, J=7.94,2H, CH
2), 4.48 (t, J=7.94,2H, CH
2), 5.29 (s, 2H, CH
2), 7.00-7.07 (m, 1H, Ar-H), 7.22-7.44 (m, 6H, Ar-H), 7.47-7.56 (m, 1H, Ar-H).
Embodiment 8:3-(synthesizing of 2-((((1-(3-chloro-4-fluorophenyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 8)
Compound method is with reference to embodiment 1.Productive rate 80.3%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.21 (s, 3H, CH
3), 3.97 (t, J=7.92,2H, CH
2), 4.49 (t, J=7.90,2H, CH
2), 5.28 (s, 2H, CH
2), 7.11 (t, J=8.68,1H, Ar-H), 7.20-7.30 (m, 3H, Ar-H), 7.35-7.41 (m, 1H, Ar-H), 7.50-7.55 (m, 1H, Ar-H), 7.68 (q, J=7.10,1H, Ar-H).
Embodiment 9:3-(synthesizing of 2-((((1-(4-aminomethyl phenyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 9)
Compound method is with reference to embodiment 1.Productive rate 84.6%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.21 (s, 3H, CH
3), 3.80 (s, 3H, Ar-CH
3), 3.99 (t, J=7.94,2H, CH
2), 4.47 (t, J=7.94,2H, CH
2), 5.26 (s, 2H, CH
2), 6.86 (d, J=8.94,2H, Ar-H), 7.26-7.39 (m, 3H, Ar-H), 7.53-7.58 (m, 3H, Ar-H).
Embodiment 10:3-(synthesizing of 2-((((1-(3-aminomethyl phenyl) ethylidene) amino) oxygen) methyl) phenyl) oxazoline ketone-2-ketone (compound 10)
Compound method is with reference to embodiment 1.Productive rate 83.3%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.24 (s, 3H, CH
3), 2.36 (s, 3H, Ar-CH
3), 4.00 (t, J=7.97,2H, CH
2), 4.49 (t, J=7.89,2H, CH
2), 5.28 (s, 2H, CH
2), 7.11-7.19 (m, 1H, Ar-H), 7.23 (d, J=7.53,1H, Ar-H), 7.27-7.33 (m, 2H, Ar-H), 7.35-7.41 (m, 2H, Ar-H), 7.44 (s, 1H, Ar-H), 7.54-7.57 (m, 1H, Ar-H).
Embodiment 11:3-(2-((((1-(3-chloro-4-fluorophenyl) ethylidene) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 11) synthetic
Add compound (III-8) 0.56g (3.0mmol) in the 100mL four-hole boiling flask, sodium hydride 0.22g (4.5mmol, 50% content) and the anhydrous N of 20mL; Dinethylformamide; Stir 0.5h down in ice bath (0 ℃), add the 15mL N of compound (II-2) 0.81g (3.00mmol) again, dinethylformamide solution; After continuing reaction 15h under the room temperature, put the cold adding 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent obtains yellow thick liquid, purifies (silica gel is filled, petrol ether/ethyl acetate) through column chromatography for separation, obtains product, productive rate 87.1%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.17 (s, 3H, CH
3), 2.29 (s, 3H, CH
3), 5.34 (s, 2H, CH
2), 7.09 (t, J=8.70,1H, Ar-H), 7.31 (d, J=6.63,1H, Ar-H), 7.41-7.49 (m, 3H, Ar-H), 7.53 (d, J=5.07,1H, Ar-H), 7.66 (dd, J=7.14,1H, Ar-H).
Embodiment 12:3-(2-((((1-(2,4 dichloro benzene base) methylene radical) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 12) synthetic
Add compound (III-6) 0.57g (3.0mmol) in the 100mL four-hole boiling flask; The anhydrous N of salt of wormwood 0.62g and 20mL, dinethylformamide stirs 0.5h down in ice bath (0 ℃); The 15mL N that adds compound (II-2) 0.81g (3.00mmol) again; Dinethylformamide solution after continuing reaction 15h under the room temperature, is put the cold adding 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent obtains yellow thick liquid, purifies (silica gel is filled, petrol ether/ethyl acetate) through column chromatography for separation, obtains product, productive rate 81.9%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.32 (s, 3H, CH
3), 5.34 (s, 2H, CH
2), 7.20 (d, J=8.61,1H, Ar-H), 7.38 (s, 1H, Ar-H), 7.43-7.44 (m, 2H, Ar-H), 7.53-7.58 (m, 1H, Ar-H), 7.77 (d, J=8.58,1H, Ar-H), 8.44 (s, 1H, CH).
Embodiment 13:3-(2-((((1-(3-trifluoromethyl) ethylidene) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 13) synthetic
Add compound (III-3) 0.61g (3.0mmol) in the 100mL four-hole boiling flask; Salt of wormwood 0.62g (4.5mmol); With the 20mL anhydrous propanone, under the reflux temperature (56 ℃) of acetone, stir 0.5h, add the 15mL acetone soln of compound (II-2) 0.81g (3.00mmol) again; After continuing reaction 15h under this temperature, put the cold adding 50mL shrend reaction of going out.ETHYLE ACETATE (50mL * 3) extraction, organic layer is washed through saturated nacl aqueous solution, anhydrous magnesium sulfate drying, the pressure reducing and steaming solvent obtains yellow thick liquid, purifies (silica gel is filled, petrol ether/ethyl acetate) through column chromatography for separation, obtains product, productive rate 77.5%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.24 (s, 3H, CH
3), 2.28 (s, 3H, CH
3), 5.38 (s, 2H, CH
2), 7.40-7.50 (m, 4H, Ar-H), 7.54-7.60 (m, 2H, Ar-H), 7.79 (d, J=7.80,1H, Ar-H), 7.87 (s, 1H, Ar-H).
Embodiment 14:3-(2-((((1-(4-chloro-phenyl-) ethylidene) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 14) synthetic
Compound method is with reference to embodiment 11.Productive rate 85.1%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.19 (s, 3H, CH
3), 2.28 (s, 3H, CH
3), 5.35 (s, 2H, CH
2), 7.31 (t, J=7.82,2H, Ar-H), 7.41-7.42 (m, 3H, Ar-H), 7.54 (t, J=7.89,3H, Ar-H).
Embodiment 15:3-(2-((((1-(4-bromophenyl) ethylidene) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 15) synthetic
Compound method is with reference to embodiment 11.Productive rate 84.3%.
Nuclear magnetic data (
1HNMR, 300MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.19 (s, 3H, CH
3), 2.28 (s, 3H, CH
3), 5.35 (s, 2H, CH
2), 7.39-7.45 (m, 3H, Ar-H), 7.46-7.50 (m, 4H, Ar-H), 7.53-7.67 (m, 1H, Ar-H).
Embodiment 16: (E)-3-(2-((((1-(4-chloro-phenyl-) methylene radical) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 16) synthetic
Compound method is with reference to embodiment 11.Productive rate 81.6%.
Nuclear magnetic data (
1HNMR, 500MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.29 (s, 3H, CH
3), 5.31 (s, 2H, CH
2), 7.31 (tt, J=8.50,2H, Ar-H), 7.40-7.44 (m, 3H, Ar-H), 7.47 (tt, J=8.50,2H, Ar-H), 7.53-7.56 (m, 1H, Ar-H), 8.03 (s, 1H, CH).
Embodiment 17: (E)-3-(2-((((1-(4-nitrophenyl) methylene radical) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 17) synthetic
Compound method is with reference to embodiment 13.Productive rate 83.6%.
Nuclear magnetic data (
1HNMR, 500MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.32 (s, 3H, CH
3), 5.37 (s, 2H, CH
2), 7.42-7.45 (m, 3H, Ar-H), 7.54-7.56 (m, 1H, Ar-H), 7.70 (tt, J=9.00,2H, Ar-H), 8.13 (s, 1H, CH), 8.20 (tt, J=9.00,2H, Ar-H).
Embodiment 18: (E)-3-(2-((((1-(4-fluorophenyl) methylene radical) amino) oxygen) methyl) phenyl)-5-methyl isophthalic acid, 3,4-oxadiazole quinoline-2 (3H)-ketone (compound 18) synthetic
Compound method is with reference to embodiment 11.Productive rate 82.8%.
Nuclear magnetic data (
1HNMR, 500MHz, interior mark TMS, solvent C DCl
3) as follows: δ ppm 2.30 (s, 3H, CH
3), 5.32 (s, 2H, CH
2), 7.03-7.07 (m, 2H, Ar-H), 7.41-7.46 (m, 3H, Ar-H), 7.53-7.58 (m, 1H, Ar-H), 8.07 (s, 1H, CH).
Biological activity determination
Embodiment 19 fungicidal activities are measured
With The compounds of this invention the various fungus diseases of plant are tested.The method of experiment is following:
Adopt the potted plant measuring method of live body.The former medicine small amount of acetone dissolving of testing compound is diluted to required concentration with the water that contains 0.1% tween 80.Spray pesticide carries out the disease inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the fixed temperature and humidity incubator, makes and continue to infect, treat that fully assessment surveys is carried out in morbidity back (being generally week age).
The partial test result is following
aBacteriostasis rate is divided into four types: (-)＜50%, and (C) 51-70%, (B) 71-90%, (A)＞90%
At dosage is under the 1000ppm, and less than 50%, 9 pairs of sclerotinia rot of colzas of compound have medium restraining effect to test compounds, have reached the C level to the inhibiting rate of eliminating vegetable botrytis.There are 5 compounds that the inhibiting rate of rice blast has been reached the B level in the test, a little less than contrast medicament Strobilurin.
Embodiment 23 insecticidal activity assays
The compounds of this invention has carried out the insecticidal activity assay experiment to insect and mite class.Measuring method is following:
After the mixed solvent dissolving of new compound with acetone/methanol (1: 1), be diluted to required concentration with the water that contains 0.1% tween 80.
With small cabbage moth (Plutella xylostella) and carmine spider mite (Tetranychus cinna barinus) is target, adopts the airbrush spray method to carry out insecticidal activity assay, and the pressure position 10psi that the airbrush spraying is handled (is roughly equal to 0.7kg/cm
2), spouting liquid is 0.5mL.Handle the mortality ratio that 2-3 day is investigated target in the back.
The partial test result is following:
aMortality ratio is divided into four types: (-)＜50%, and (C) 51-70%, (B) 71-90%, (A)＞90%
From table, can find out under the 400ppm dosage that the kill ratio of 1 pair of small cabbage moth of compound has reached more than 60%.
Though the present invention has been detailed, yet it is not to be used to limit the present invention with preferred embodiment.Any those skilled in the art under the situation that does not break away from the spirit and scope of the present invention, should make various modifications and change.Therefore protection scope of the present invention should be regarded as appended claims institute restricted portion.
Claims (6)
1. N-substituted-phenyl oximinoether that contains heterocyclic ketone, shown in general formula I:
It is characterized in that: R
(n)Middle n=1-5 replaces R
(n)Be selected from hydrogen, halogen, cyanic acid, nitro, C respectively
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy, C
1-C
6Alkylthio, C
1-C
6Alkyl-carbonyl, C
1-C
6Alkoxy carbonyl, C
1-C
6Alkylamino, the halogen in the wherein said halogeno-group is selected from one or more in fluorine, chlorine, the bromine or iodine; Z is selected from methyl or hydrogen; Q is selected from one of following group:
2. compound method like any described compound I in the claim 1; It is characterized in that: (amount of substance is a unit by the compound I I of 1 times of amount; Down with) compound III doubly measured with 1-2 is at acetone, acetonitrile or N; In the dinethylformamide solvent, be that acid binding agent at room temperature reacts the compound that obtains general formula I with alkali.
In the formula, X is a leavings group, is selected from chlorine, bromine or iodine.
3. compound method as claimed in claim 2, the reaction acid binding agent is sodium hydride, yellow soda ash, salt of wormwood, sodium hydroxide or Pottasium Hydroxide.
4. compound method as claimed in claim 2, the reaction times is 0.5-48 hour.
5. application like the germ on the control crop of arbitrary described compound in the claim 1.
One kind as arbitrary described compound in the claim 1 the control pest on crop application.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030680A (en) * | 2010-10-20 | 2011-04-27 | 湖北省生物农药工程研究中心 | Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof |
| CN104151308A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation method and application of 1,2,3-thiadiazole pyrazole oxime ether compounds |
| CN107954898A (en) * | 2017-12-01 | 2018-04-24 | 西北农林科技大学 | Salicylaldoxime ester type compound and preparation method thereof, purposes |
Citations (2)
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|---|---|---|---|---|
| CN1188394A (en) * | 1995-06-20 | 1998-07-22 | 纳幕尔杜邦公司 | Arthropodicidal and fungicidal cyclic amides |
| WO2001034568A1 (en) * | 1999-11-05 | 2001-05-17 | Nippon Soda Co., Ltd. | Oxime o-ether compounds and fungicides for agricultural and horticultural use |
-
2010
- 2010-10-09 CN CN201010501011XA patent/CN102442966A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188394A (en) * | 1995-06-20 | 1998-07-22 | 纳幕尔杜邦公司 | Arthropodicidal and fungicidal cyclic amides |
| WO2001034568A1 (en) * | 1999-11-05 | 2001-05-17 | Nippon Soda Co., Ltd. | Oxime o-ether compounds and fungicides for agricultural and horticultural use |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030680A (en) * | 2010-10-20 | 2011-04-27 | 湖北省生物农药工程研究中心 | Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof |
| CN104151308A (en) * | 2014-07-03 | 2014-11-19 | 南通大学 | Preparation method and application of 1,2,3-thiadiazole pyrazole oxime ether compounds |
| CN104151308B (en) * | 2014-07-03 | 2017-12-29 | 南通大学 | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters |
| CN107954898A (en) * | 2017-12-01 | 2018-04-24 | 西北农林科技大学 | Salicylaldoxime ester type compound and preparation method thereof, purposes |
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