CN103694219A - 3-halogenated ethoxy pyrazole amide compound and application thereof - Google Patents
3-halogenated ethoxy pyrazole amide compound and application thereof Download PDFInfo
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- -1 3-halogenated ethoxy pyrazole amide compound Chemical class 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 11
- 229910052794 bromium Chemical group 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000001475 halogen functional group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 241000255777 Lepidoptera Species 0.000 abstract description 2
- 230000005923 long-lasting effect Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007787 solid Substances 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241000272639 Brachycaudus mimeuri Species 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 241000238631 Hexapoda Species 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241001124076 Aphididae Species 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- 241000256247 Spodoptera exigua Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 3
- WNABMWFLKQEGCP-UHFFFAOYSA-N 2-amino-3,5-dibromobenzoic acid Chemical compound NC1=C(Br)C=C(Br)C=C1C(O)=O WNABMWFLKQEGCP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000016068 Berberis vulgaris Nutrition 0.000 description 3
- 241000335053 Beta vulgaris Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- PNALOBAQBMAHBZ-UHFFFAOYSA-N benzenecarbothiohydrazide Chemical compound NNC(=S)C1=CC=CC=C1 PNALOBAQBMAHBZ-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 240000007124 Brassica oleracea Species 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 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 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- LBTYNQNVZNPATH-UHFFFAOYSA-N 2-amino-3-bromobenzamide Chemical compound NC(=O)C1=CC=CC(Br)=C1N LBTYNQNVZNPATH-UHFFFAOYSA-N 0.000 description 1
- 235000006008 Brassica napus var napus Nutrition 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241001674939 Caulanthus Species 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 102000042094 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 1
- 108091052345 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 1
- 210000004894 snout Anatomy 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 230000009885 systemic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005303 weighing Methods 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
- 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
Abstract
The invention discloses a 3-halogenated ethoxy pyrazole amide compound. The structure of the compound is expressed by the formula I; in the formula, R1 is selected from CH3, Cl or Br; R2 is selected from Cl or Br; R3 is selected from CH3,CH2C[triple bond]CH; X is selected from Cl or Br; Y is O or S. The compound of the formula I has excellent insecticidal activity, in particular has such characteristics as high prevention effect, long lasting period and environmental friendliness for crop lepidoptera pests, and can be applied to the prevention of several pests difficult to be treated in agriculture.
Description
Technical field
The invention belongs to agricultural insecticide field, relate to a kind of 3-halo oxyethyl group pyrazol acid amide compounds and application thereof.
Background technology
Insect pest causes crop production reduction or quality to reduce.The common insecticides of pest control is owing to being used continually in a large number, all generation in various degree resistance.Along with the enhancing of people's environmental protection and Consciousness of food security and the raising of labor cost, wish that new insecticide variety has the characteristics such as ultra-high efficiency, long holding effect, low resistance, safety and environmental protection.
PCT patent application WO2003/015519 discloses the Compound I I(KC as follows with insecticidal activity):
This compound is the novel pesticide that can meet above-mentioned characteristic.This sterilant is different from existing sterilant insecticidal mechanism by suppressing insect ryanodine receptor, with common insecticides without cross resistance.
PCT patent application WO2006/023783 discloses the following polyfluoro compound III in generation:
Chinese patent CN101967139A and CN102285963A disclose respectively 3-fluoro methoxyl group and 3-methoxy pyrazolecarboxamide compound (formula IV and formula V).
Although the disclosed compound of above-mentioned patent structurally has similarity with the compounds of this invention, in the prior art, 3-halo oxyethyl group pyrazol acid amide compounds (formula I) and biological activity thereof have no open as described in the present invention.
Summary of the invention
The 3-halo oxyethyl group pyrazol acid amide compounds that the object of the present invention is to provide a kind of novel structure, it can be used for the control of agricultural or forestry pest.
Technical scheme of the present invention is as follows:
A kind of 3-halo oxyethyl group pyrazol acid amide compounds structure is as shown in general formula I:
In formula: R
1be selected from CH
3, Cl or Br;
R
2be selected from Cl or Br;
R
3be selected from CH
3, CH (CH
3)
2, CH
2c ≡ CH;
X is selected from Cl or Br;
Y is O or S.
Compound of Formula I of the present invention can be prepared by the following method, and in reaction formula, each group definition is the same.
Intermediate A and the intermediate B 3h that refluxes in acetonitrile or ethyl acetate makes the compounds of this invention (formula I).Intermediate A and intermediate B method for making are shown in that the present invention synthesizes example.
Table 1 has been listed structure and the physical properties of part compound of Formula I.
The structure of table 1 Compound I and physical properties
Compound I | R 1 | R 2 | R 3 | X | Y | Outward appearance | Fusing point |
I a | CH 3 | Cl | CH 3 | Br | O | White powder | 170~172℃ |
I b | CH 3 | Cl | CH 3 | Br | S | Yellow powder | 155~157℃ |
I c | Cl | Cl | CH(CH 3) 2 | Br | O | White powder | 171~174℃ |
I d | CH 3 | Cl | CH(CH 3) 2 | Br | O | White powder | 183~185℃ |
I e | Cl | Cl | CH 3 | Br | O | White powder | 196~198℃ |
I f | Cl | Cl | CH 3 | Br | S | Yellow powder | 200~203℃ |
I g | CH 3 | Cl | CH 3 | Cl | O | White powder | 179~181℃ |
I h | CH 3 | Br | CH 3 | Cl | O | White powder | 216~219℃ |
I i | Br | Br | CH 3 | Cl | S | White powder | 209~211℃ |
I j | CH 3 | Cl | CH 2C≡CH | Br | O | White powder | 224~226℃ |
Although the compounds of this invention has similar precursor structure to above-mentioned known compound, but electronegativity and fat-soluble difference due to pyrazole ring 3-bit substituent, affect its transporting in insect body and the suitability of being combined with action site, thereby cause its bioactive marked difference.And in the prior art, compound transporting and suitability of being combined with action site in insect body are unpredictable, need a large amount of creative works just can know.
Advantage of the present invention and positively effect:
In the compounds of this invention, the introducing of pyrazole ring 3-position halo oxyethyl group has increased substantially systemic activity and the lasting period of compound on plant materials, as the compounds of this invention I
aat identical working concentration (67ppm), prevent and treat in the snout moth's larva of rice test the compounds of this invention I with known compound II
alasting period reach 32 days, and the lasting period of Compound I I only has 18 days, has realized the overlength lasting period of January without worm.The compounds of this invention is having a clear superiority in known compound III and compound IV aspect cost and production difficulty; The compounds of this invention is significantly higher than known compound KC(in Table 2 to the insecticidal activity of small cabbage moth).Therefore, the compounds of this invention has advantages of that insecticidal activity is high, production difficulty is little, cost is low.The compounds of this invention is formulated new variety as agricultural chemicals, and its beyond thought high reactivity, long lasting period and lower production cost demonstrate obvious superiority aspect pest control.Therefore the compounds of this invention also comprises the purposes of controlling insect pest.
The compounds of this invention, when pest control, can be used separately according to practical situation, also can use with other agrochemical active substance combination, to improve the over-all properties of product.The present invention also comprises a kind of insect-killing composition, contains the compounds of this invention as acceptable carrier in active ingredient and agricultural or forestry in composition.
Composition of the present invention can preparation form use: compound of Formula I as solubilization of active ingredient be scattered in carrier or solvent in, add proper amount of surfactant and be mixed with missible oil, soluble liquid, suspension agent etc.
Should be clear and definite, in claim limited range of the present invention, can carry out various conversion and change.
Embodiment
Following synthetic example and the raw experimental result of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthetic example:
Example 1, Compound I
apreparation:
(1) N-methyl-2-amino-3-methyl-5-chloro benzamide is synthetic
In the there-necked flask of 250mL, add respectively 0.05mol (9.27g) N-methyl-2-amino-3-methyl-5-chloro phenylformic acid, ethyl acetate 100mL, solid phosgene 0.025mol (7.42g), drip 3 pyridines, at 40 ℃, react 4h, react complete, the unreacted solid phosgene of discharge is heated to reflux, cooling, suction filtration, obtains solid b, dries, the 10.04g that weighs, yield 95%.In 250mL there-necked flask, add 0.04mol (8.46g) b, 100mL acetonitrile, at 0~5 ℃, slowly drip 25% aqueous methylamine solution 9.92g, react complete, steam most of solvent, and mixture is poured in 100mL water, separate out a large amount of solids, suction filtration is dried, and obtains product N-methyl-2-amino-3-methyl-5-chloro benzamide 7.15g, yield 90%.
(2) synthesizing of 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazole-5-ethyl formate:
In the there-necked flask of 250mL, add respectively 0.05mol (13.37g) 1-(3-chloropyridine-2-yl)-3-hydroxyl-1H-pyrazole-5-ethyl formate (with reference to method preparation in CN10228596.3A) and 0.065mol (8.97g) salt of wormwood, add acetonitrile 100mL, add again 0.055mol (10.34g) 1,2-ethylene dibromide, backflow 3h, react complete, suction filtration, boil off solvent, obtain product 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazole-5-ethyl formate 16.83g, yield 90%.
(3) synthesizing of 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formic acid:
In the there-necked flask of 250mL, add 0.05mol(18.70g) 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazole-5-ethyl formate, use 50mL dissolve with ethanol, add water 50mL, then add 0.075mol(3.00g) sodium hydroxide, stirring at normal temperature 2h, react complete, steam ethanol, with concentrated hydrochloric acid, adjust pH to 2-3, separate out white solid, suction filtration, washing, dry 1-(3-chloropyridine-2-yl that obtains)-3-bromo oxyethyl group-1H-pyrazoles-5-formic acid 15.92g, yield 92%.
(4) synthesizing of 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formyl chloride:
In the there-necked flask of 100mL, add successively 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formic acid 0.02mol(6.92g), toluene 50mL, sulfur oxychloride 0.06mol(7.2g) and, backflow 4h.React complete, steam toluene and sulfur oxychloride, obtain 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formyl chloride 7.14g, yield 98%.
(5) Compound I
asynthetic:
In the there-necked flask of 100mL, add successively N-methyl-2-amino-3-methyl-5-chloro benzamide 0.01mol(1.98g), acetonitrile 40mL, 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formyl chloride 0.012mol(4.37g), back flow reaction 3h, react complete, steam solvent 20mL, cooling, suction filtration, the dry Compound I of weighing to obtain
a3.70g, yield 72%.
Example 2, Compound I
bpreparation:
(1) N-methyl-2-amino-3-methyl-5-chloro thiobenzamide:
In the there-necked flask of 250mL, add 0.05mol(9.92g) N-methyl-2-amino-3-methyl-5-chloro benzamide (synthetic method is shown in example 1), with 100mL tetrahydrofuran (THF), dissolve, under normal temperature, add thiophosphoric anhydride 0.03mol(6.66g), be warming up to 40 ℃, reaction 1h, react the complete solvent that steams, sodium hydroxide solution with 20% adjusts pH to neutral, ethyl acetate extraction, with saturated common salt washing extraction liquid 2-3 time, anhydrous magnesium sulfate drying, steams solvent, obtain N-methyl-2-amino-3-methyl-5-chloro thiobenzamide 10.00g, yield 94%.
(2) Compound I
bsynthetic:
In the there-necked flask of 100mL, add successively N-methyl-2-amino-3-methyl-5-chloro thiobenzamide 0.01mol(2.14g), acetonitrile 40mL, 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formyl chloride (synthetic method is shown in example 1) 0.012mol(4.37g), back flow reaction 3h, react complete, steam solvent 20mL, cooling, suction filtration obtains product I
a, the dry 3.74g that weighs, yield 69%.
Example 3, Compound I
isynthetic:
Synthesizing of (1) 3,5-dibromoanthranilic acid:
In the there-necked flask of 250mL, add 0.05mol(15.10g) methyl o-aminobenzoate, with 100mL acetic acid, dissolve, under normal temperature, drip 0.1mol(16.00g) bromine, reaction 4h, has a large amount of solids to separate out, suction filtration, washing.Solid transfer, in 250mL there-necked flask, is used to 50mL dissolve with ethanol, adds 50mL water, then add 0.075mol(3g) sodium hydroxide, normal-temperature reaction 2h, steam ethanol, concentrated hydrochloric acid acidifying, separates out white solid, suction filtration, dry, obtain 3,5-dibromoanthranilic acid 13.72g, yield 93%.
(2) N-methyl-3,5-dibromo-o aminobenzamide synthetic:
In the there-necked flask of 250mL, add respectively 0.05mol (14.75g) 3,5-dibromoanthranilic acid, ethyl acetate 100mL, solid phosgene 0.025mol (7.42g), drips 3 pyridines, reacts 4h at 40 ℃, react complete, be heated to reflux and discharge unreacted solid phosgene, lower the temperature, suction filtration, obtain solid e, dry the 14.92g that weighs, yield 93%.In 250mL there-necked flask, add 0.04mol (12.83g) intermediate e, 100mL acetonitrile, at 0~5 ℃, slowly drip 25% aqueous methylamine solution 9.92g, react complete, steam most of solvent, and mixture is poured in 100mL water, separate out a large amount of solids, suction filtration is dried, and obtains product N-methyl-3,5-dibromo-o aminobenzamide 11.33g, yield 92%.
(3) N-methyl-3, the amino thiobenzamide of the bromo-2-of 5-bis-synthetic:
In the there-necked flask of 250mL, add 0.05mol(15.40g) N-methyl-3, the bromo-2-aminobenzamide of 5-bis-, with 100mL tetrahydrofuran (THF), dissolve, under normal temperature, add thiophosphoric anhydride 0.03mol(6.66g), be warming up to 40 ℃, reaction 1h, react the complete solvent that steams, the sodium hydroxide solution with 20% adjusts pH to neutral, ethyl acetate extraction, with saturated common salt washing extraction liquid 2-3 time, anhydrous magnesium sulfate drying, steams solvent, obtains N-methyl-3, the amino thiobenzamide 14.90g of the bromo-2-of 5-bis-, yield 92%.
(4) synthesizing of 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazole-5-ethyl formate:
In the there-necked flask of 250mL, add respectively 0.05mol (13.37g) 1-(3-chloropyridine-2-yl)-3-hydroxyl-1H-pyrazole-5-ethyl formate and 0.065mol (8.97g) salt of wormwood, add 1,2-ethylene dichloride 100mL, backflow 3h, react complete, suction filtration, boils off solvent, obtain product 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazole-5-ethyl formate 15.65g, yield 95%.
(5) synthesizing of 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazoles-5-formic acid:
In the there-necked flask of 250mL, add 0.05mol(16.47g) 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazole-5-ethyl formate, use 50mL dissolve with ethanol, add water 50mL, then add 0.075mol(3.00g) sodium hydroxide, stirring at normal temperature 2h, react complete, steam ethanol, with concentrated hydrochloric acid, adjust pH to 2-3, separate out white solid, suction filtration, washing, dry 1-(3-chloropyridine-2-yl that obtains)-3-chloro oxyethyl group-1H-pyrazoles-5-formic acid 14.02g, yield 93%.
(4) synthesizing of 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazoles-5-formyl chloride:
In the there-necked flask of 100mL, add successively 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazoles-5-formic acid 0.02mol(6.92g), toluene 50mL, sulfur oxychloride 0.06mol(7.2g) and, backflow 4h.React complete, steam toluene and sulfur oxychloride, obtain 1-(3-chloropyridine-2-yl)-3-bromo oxyethyl group-1H-pyrazoles-5-formyl chloride 6.58g, yield 98%.
(4) Compound I
isynthetic:
In the there-necked flask of 100mL, add successively N-methyl-3, the amino thiobenzamide 0.01mol(3.24g of the bromo-2-of 5-bis-), acetonitrile 40mL, 1-(3-chloropyridine-2-yl)-3-chloro oxyethyl group-1H-pyrazoles-5-formyl chloride 0.012mol(4.03g), back flow reaction 3h, reacts complete, steams solvent 20mL, cooling, suction filtration obtains product I
i, the dry 4.67g that weighs, yield 75%.
According to above method, can prepare other compounds in general formula I of the present invention.
The nuclear magnetic data of part of compounds is as follows:
Compound I
a:
1h NMR(500MHz, DMSO): δ/ppm2.122 (s, 3H), 2.684-2.701 (d, 3H); 4.555-4.620 (t, 2H), 4.812-4.923 (t, 2H); 7.377-7.381 (d, 1H), 7.474 (d, 1H); 7.569-7.594 (q, 1H), 8.173-8.189 (d, 1H); 8.210 (s, 1H), 8.376-8.385 (d, 1H); 8.452-8.461 (d, 1H), 10.326 (s, 1H);
Compound I
b:
1h NMR(500MHz, DMSO): δ/ppm2.120 (s, 3H), 2.651-2.662 (d, 3H); 4.546-4.615 (t, 2H), 4.820-4.941 (t, 2H); 7.381-7.396 (d, 1H), 7.467 (d, 1H); 7.555-7.580 (q, 1H), 8.167-8.173 (d, 1H); 8.221 (s, 1H), 8.367-8.380 (d, 1H); 8.434-8.458 (d, 1H), 10.320 (s, 1H);
Compound I
c:
1h NMR(500MHz, DMSO): δ/ppm1.084-1.095 (d, 6H), 3.807-3.812 (t; 2H), 4.560-4.613 (t, 2H); (7.421-7.581 t, 3H), 7.945 (s; 1H), 8.169 (s, 1H); (8.445 s, 1H), 8.638 (s; 1H), 10.245 (s, 1H);
Compound I
d:
1h NMR(500MHz, DMSO): δ/ppm1.067-1.081 (d, 6H), 2.212 (s, 3H); 4.48746-4.510 (t, 2H), 4.734-4.803 (t, 2H); 7.525-7.531 (d, 1H), 7.568-7.584 (t, 1H); 7.813-7.818 (d, 1H), 8.153-8.171 (d, 1H); 8.230 (s, 1H), 8.335-8.358 (d, 1H); 8.448-8.461 (d, 1H), 10.273 (s, 1H);
Compound I
e:
1h NMR(500MHz, DMSO): δ/ppm2.682-2.711 (d, 3H), 4.553-4.619 (t; 2H), 4.762-4.781 (t, 2H), 7.503-7.512 (d; 1H), 7.570-7.593 (q, 1H), 7.825-7.829 (d; 1H), 8.261-8.274 (d, 1H), 8.330 (s; 1H), 8.380-8.392 (d, 1H), 8.460-8.469 (d; 1H), 10.212 (s, 1H);
Compound I
f:
1h NMR(500MHz, DMSO): δ/ppm2.591-2.632 (d, 3H), 4.569-4.625 (t; 2H), 4.771-4.784 (t, 2H), 7.534-7.564 (d; 1H), 7.576-7.601 (q, 1H), 7.846-7.897 (d; 1H), 8.270-8.284 (d, 1H), 8.328 (s; 1H), 8.375-8.382 (d, 1H), 8.473-8.480 (d; 1H), 10.322 (s, 1H);
Compound I
g:
1h NMR(500MHz, DMSO): δ/ppm2.114 (s, 3H), 2.671-2.696 (d, 3H); 4.523-4.581 (t, 2H), 4.755-4.832 (t, 2H); 7.273-7.281 (d, 1H), 7.354 (d, 1H); 7.475-7.537 (q, 1H), 8.003-8.119 (d, 1H); 8.140 (s, 1H), 8.256-8.345 (d, 1H); 8.442-8.456 (d, 1H), 10.343 (s, 1H);
Compound I
h:
1h NMR(500MHz, DMSO): δ/ppm2.314 (s, 3H), 2.653-2.686 (d, 3H); 4.555-4.590 (t, 2H), 4.762-4.883 (t, 2H); 7.193-7.261 (d, 1H), 7.344-7.432 (d, 1H); 7.465-7.585 (q, 1H), 8.130-8.199 (d, 1H); 8.240 (s, 1H), 8.261-8.336 (d, 1H); 8.482-8.556 (d, 1H), 10.280 (s, 1H);
Compound I
i:
1h NMR(500MHz, DMSO): δ/ppm2.596-2.641 (d, 3H), 4.643-4.698 (t; 2H), 4.962-4.985 (t, 2H), 7.332-7.418 (d; 1H), 7.567-7.623 (q, 1H), 7.845-7.881 (d; 1H), 8.171-8.234 (d, 1H), 8.234 (s; 1H), 8.480-8.502 (d, 1H), 8.480-8.519 (d; 1H), 10.352 (s, 1H);
Compound I
j:
1h NMR(500MHz, DMSO): δ/ppm2.327 (s, 3H), 3.381-3.931 (d, 2H); 4.555-4.620 (t, 2H), 4.812-4.923 (t, 2H), 5.632 (s; 1H), 7.377-7.381 (d, 1H), 7.474 (d, 1H); 7.569-7.594 (q, 1H), 8.173-8.189 (d, 1H); 8.210 (s, 1H), 8.376-8.385 (d, 1H); 8.452-8.461 (d, 1H), 10.326 (s, 1H);
Biological activity determination:
Example 4, insecticidal activity assay
1. the compounds of this invention is to beet armyworm determination of activity:
Adopt leaf dipping method.The leaf dipping method that adopts international resistance Action Committee (IRAC) to propose.With the liquid to be measured preparing, with straight peen ophthalmology tweezers dipping cabbage leaves, time 3-5 second, get rid of remaining liquid, each 1, totally 3, each sample, is successively placed in treatment paper by sample flag sequence.After liquid is dry, put into the long straight type pipe of the markd 10cm of tool, 30 of access beet exigua larvaes in 2 age, build the mouth of pipe with gauze.Test is processed and is placed in standard treatment chamber, and 72h check result is touched polypide to pull out pin, and motionless person is dead.Calculate mortality ratio.(3 repetitions are done in test, average)
In part test compound, following compounds is better to the preventive effect of beet armyworm when concentration 1ppm, and mortality ratio is more than 90%: I
a, I
b, I
c, I
d, I
e, I
f, I
g, I
h, I
i, I
j; In part test compound, following compounds is better to beet armyworm preventive effect when 0.1ppm, and mortality ratio is more than 90%: I
a, I
b, I
d, I
f, I
j; According to above method, choose Compound I
a, known compound II(KC) carry out the active replicate(determination) of killing beet noctuids.Test-results is in Table 2.
Table 2 killing beet noctuids determination of activity table
2. the compounds of this invention is to black peach aphid determination of activity:
6 centimetres, cut-off footpath culture dish, at the bottom of ware, cover one deck filter paper, and drip appropriate tap water moisturizing, clip suitable size (3 centimetres of diameters) and the long wild cabbage sheet that has 15-30 aphid from the cabbage plant of cultivation black peach aphid, removal has the aphid of aphid wing and face of blade, fall to wipe after radix, blade back is upwards placed in culture dish, with the processing of spraying of hand-held airbrush atomizer, every processing repeats for 3 times, processing is placed in standard observation ward, and 48 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
In part test compound, following compounds is better to the preventive effect of black peach aphid when concentration 50ppm, and mortality ratio is more than 90%: I
a, I
b, I
c, I
e, I
f,, I
h, I
i, I
j; According to above method, choose Compound I
b, known compound II kills the active replicate(determination) of black peach aphid.Test-results is in Table 3.
Table 3 kills black peach aphid determination of activity table
Table 2 and table 3 insecticidal test result show, with Compound I I(KC) to compare, the compounds of this invention all has more excellent insecticidal effect to lepidoptera pest (beet armyworm) and sucking pest (aphid).
Claims (3)
2. formula I compound according to claim 1 is for the purposes of pest control.
3. an insect-killing composition, contains compound of Formula I claimed in claim 1 as acceptable carrier in active ingredient and agricultural or forestry.
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