CN105061412A - Fluorine-containing N-furoamide compound and application thereof - Google Patents
Fluorine-containing N-furoamide compound and application thereof Download PDFInfo
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- CN105061412A CN105061412A CN201510559792.0A CN201510559792A CN105061412A CN 105061412 A CN105061412 A CN 105061412A CN 201510559792 A CN201510559792 A CN 201510559792A CN 105061412 A CN105061412 A CN 105061412A
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- furfuryl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 9
- 239000011737 fluorine Substances 0.000 title claims abstract description 9
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 9
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical class NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 2
- 230000000749 insecticidal effect Effects 0.000 abstract description 7
- 230000002045 lasting effect Effects 0.000 abstract description 4
- 230000003405 preventing effect Effects 0.000 abstract description 3
- 230000005945 translocation Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 241000426497 Chilo suppressalis Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 3-difluoroethoxy-pyrazol acid amide compounds Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000255777 Lepidoptera Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical compound NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- FNELVJVBIYMIMC-UHFFFAOYSA-N Ethiprole Chemical compound N1=C(C#N)C(S(=O)CC)=C(N)N1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl FNELVJVBIYMIMC-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical class CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 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 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 210000004681 ovum Anatomy 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- DKORSYDQYFVQNS-UHFFFAOYSA-N propyl methanesulfonate Chemical compound CCCOS(C)(=O)=O DKORSYDQYFVQNS-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 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
- 239000004576 sand Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
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)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a fluorine-containing N-furoamide compound with a structure as shown in the general formula I, wherein R1 is selected from C1 or CH3; R2 is selected from OCH2CHF2 or OCH2CF2HF2. The compound as shown in the general formula I is excellent in insecticidal activity, relatively strong in uptake and translocation functions and capable of improving the preventing and controlling effects and prolonging the lasting period and can be used for preventing and controlling agricultural or forest pests.
Description
Technical field the invention belongs to agricultural insecticide field, is specifically related to a kind of fluorine-containing N-furfuryl amides and application thereof.
The resistance problem of background technology harmful organism is the main contributor that it is difficult to administer, and development of new pesticide control is the important channel administering resistance.Rynaxypyr compounds (ryanodine receptor inhibitor class) is the efficient pesticides of the control lepidoptera pest developed in recent years.Patent CN103130769B discloses the 3-difluoroethoxy-pyrazol acid amide compounds (KC1) with excellent insecticidal activity:
Patent CN103755681B discloses a kind of 3-(2,2,3,3-tetrafluoro propoxy-)-pyrazol acid amide compounds (KC2) with excellent insecticidal activity:
Though compound has similarity with the compounds of this invention on precursor structure disclosed in above-mentioned patent, in the prior art, fluorine-containing N-furfuryl amides (formula I) of the present invention has no open.
Summary of the invention
The object of the present invention is to provide the fluorine-containing N-furfuryl amides that a kind of novel structure, good combination property, cost accounting are low, may be used for the control of agricultural or forestry primary pest.
Technical scheme of the present invention is as follows:
A kind of fluorine-containing N-furfuryl amides, structure is such as formula shown in I:
In formula: R
1be selected from Cl or CH
3; R
2be selected from OCH
2cHF
2or OCH
2cF
2hF
2.
Formula I can be prepared by the following method, and in reaction formula, each group definition is the same.
Namely formula II and III compound back flow reaction in ethyl acetate or toluene solvant obtains formula I, and the embodiment of the present invention is shown in formula II compound and compound III preparation.Table 1 lists structure and the physical properties of partial Formula I.
The structure of table 1 partial Formula I and physical properties
| Compound | R 1 | R 2 | Outward appearance; Fusing point (DEG C) |
| 1 | Cl | OCH 2CHF 2 | White solid, 111-114 DEG C |
| 2 | CH 3 | OCH 2CHF 2 | White solid, 94-97 DEG C |
| 3 | Cl | OCH 2CF 2CHF 2 | Pale solid, 155-159 DEG C |
| 4 | CH 3 | OCH 2CF 2CHF 2 | Pale solid, 110-114 DEG C |
Advantage of the present invention and positively effect:
Borer pest (as striped rice borer etc.) is difficult to contact medicament after piercing plant materials, and conventional contact killing type medicament is invalid to it.Especially at " ethiprole " because of after toxicity problem is prohibited from using, market lacks the efficient medicament of control borer pest.According to the requirement of modern agriculture to low public hazards, ultra-high efficiency, long holding effect agricultural chemicals, the agricultural chemicals preventing and treating this class pest must have stronger Uptake and translocation function, and this is the basis of improving prevention effect and extending the lasting period.The present inventor is studied by lot of experiments, the furyl with hydrophilic and oleophilic parents effect is introduced in pesticide molecules structure, unexpectedly significantly extend the lasting period (see table 3) of control striped rice borer, and there is minimizing spraying times, reduction expenses for prevention and control, huge advantage such as minimizing environmental pollution, time and labour saving etc.Meanwhile, the compounds of this invention is also significantly better than contrast known compound (KC1 and KC2) to the insecticidal activity of lepidoptera pest small cabbage moth.The compounds of this invention is to human body and beneficial organism toxicity is low, dosage is little, Environmental compatibility is good, meets the requirement of modern agriculture to low public hazards, ultra-high efficiency, long holding effect, possesses the potentiality that exploitation becomes ultra-high efficiency, the green type sterilant of long holding effect.
When the compounds of this invention is for controlling insect pest purposes, can be used alone, also can use with other active substance combination, to improve the comprehensive function of product.
The present invention also comprises the insect-killing composition using compound of Formula I as active ingredient, also comprises acceptable carrier in agricultural or forestry in this insect-killing composition.
It is clearly understood that, in the scope of the claims in the present invention, can various conversion and change be carried out.
Embodiment
Following synthesis example, formulation examples and raw test-results of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthesis example
The preparation of example 1, compound 1
(1) synthesis of 2-amino-N-furfuryl benzamide
16.3g (0.1mol) isatoic anhydride and 180mL water is added in 250mL reaction flask, instillation 14.55g (0.15mol) chaff amine (2-furylamine), normal-temperature reaction 12h, suction filtration, filter cake washs with tap water (10mL × 2), dry to obtain white solid 18.4g, yield 85%.
(2) synthesis of amino-3, the 5-bis-chloro-N-furfuryl benzamide of 2-
21.6g (0.1mol) 2-amino-N-furfuryl benzamide and 150g ethyl acetate is added in 250mL reaction flask, temperature control less than 15 DEG C drips SULPHURYL CHLORIDE 33.75g (0.25mol), drip complete temperature control 15 DEG C reaction 4 ~ 5h, thin-layer chromatography (TLC) detection disappears to raw material point, suction filtration, filter cake, with ethyl acetate (20mL × 2) washing, dries to obtain white solid 22.37g, yield 78.5%.
(3) synthesis of compound 1
2.85g (0.01mol) 2-amino-3 is added in 100mL reaction flask, 5-bis-chloro-N-furfuryl benzamide and 10mL ethyl acetate, the 6mL diluted ethyl acetate liquid of instillation 3.54g (0.011mol) 1-(3-chloropyridine-2-base)-3-difluoroethoxy-1H-pyrazoles-5-formyl chloride (by method preparation in CN103130769A), be warming up to backflow, back flow reaction 3h, be down to room temperature suction filtration, filter cake washs with 2mL ethyl acetate, dry, weigh to obtain white solid 4.08g, yield 71.5%.
The preparation of example 2, compound 2
(1) the chloro-8-methyl isophthalic acid of 6--H-benzo [the d] [synthesis of 1,3] oxazine-2,4-diketone
The chloro-3-tolyl acid of 18.5g (0.1mol) 2-amino-5-and 100mL ethyl acetate is added in 100mL reaction flask, instillation 2g pyridine, temperature control less than 40 DEG C drips the ethyl acetate solution 50mL of 14.85g (0.05mol) solid phosgene, 40 DEG C of reaction 4h, suction filtration, filter cake washs with ethyl acetate 10mL × 2, dries to obtain white solid 19.92g, yield 94.2%.
(2) synthesis of the chloro-3-methyl of 2-amino-5--N-furfuryl benzamide
21.15g (0.1mol) 6-chloro-8-methyl isophthalic acid-H-benzo [d] [1 is added in 250mL reaction flask, 3] oxazines-2,4-diketone and 180mL water, instillation 14.55g (0.15mol) chaff amine (2-furylamine), normal-temperature reaction 12h, suction filtration, filter cake is with 10mL × 2 tap water, dry to obtain white solid 22.48g, yield 85%.
(3) synthesis of compound 2
2.64g (0.01mol) 2-amino-5-chloro-3-methyl-N-furfuryl benzamide and 10mL ethyl acetate is added in 100mL reaction flask, the 6mL diluted ethyl acetate liquid of instillation 3.54g (0.011mol) 1-(3-chloropyridine-2-base)-3-difluoroethoxy-1H-pyrazoles-5-formyl chloride (by method preparation in CN103130769A), be warming up to backflow, back flow reaction 3.5h, be down to room temperature suction filtration, filter cake washs with 2mL ethyl acetate, dry, weigh to obtain white solid 4.69g, yield 80.1%.
The preparation of example 3, compound 3
(1) synthesis of 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--1H-pyrazole-5-ethyl formate
26.7g (0.1mol) 1-(3-chloropyridine-2-base)-3-hydroxyl-1H-pyrazole-5-ethyl formate (with reference to the preparation of CN102285963A method) is added respectively in the there-necked flask of 250mL, 16.56g (0.12mol) salt of wormwood (powder) and 100mL toluene, 20mLDMSO, instillation 27.30g (0.13mol) 2, 2-tetrafluoro propyl Methanesulfonate (reacted by C3-Fluoroalcohol and methylsulfonyl chloride and prepare), backflow 4-5h, thin-layer chromatography (TLC) detects raw material point and disappears, suction filtration, with 50mL toluene wash filter cake, 90 DEG C steam solvent in filtrate, obtain red-brown oily matter, be directly used in next step reaction.
(2) synthesis of 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--1H-pyrazoles-5-formic acid:
Previous step whole product 100mL dissolve with methanol is added in 250mL there-necked flask, add the NaOH solution 40mL of 20%, 40-50 DEG C is stirred 2h, and thin-layer chromatography detects raw material point and disappears, add 60mL water, steam most of methyl alcohol, adjust pH to 2-3 with concentrated hydrochloric acid, white solid is separated out, suction filtration, washing, drying obtains product 1-(3-chloropyridine-2-base)-3-difluoroethoxy-1H-pyrazoles-5-formic acid 26.56g, yield 76%.
(3) synthesis of 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--1H-pyrazoles-5-formyl chloride
34.9g (0.1mol) 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--pyrazoles-5-formic acid and 100g toluene is added in 250mL there-necked flask, instillation 2dDMF, drip 23.8g (0.2mol) sulfur oxychloride, drip finish be warming up to backflow.Back flow reaction 4-5h, steams toluene, obtains brown oil 36.7g, yield 100%.
(4) synthesis of compound 3
2.85g (0.01mol) 2-amino-3 is added in 100mL reaction flask, 5-bis-chloro-N-furfuryl benzamide and 10mL toluene, the 4mL dilution with toluene liquid of instillation 4.02g (0.011mol) 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--1H-pyrazoles-5-formyl chloride, be warming up to backflow, back flow reaction 3h, be down to room temperature suction filtration, filter cake washs with 2mL ethyl acetate, dry, weigh to obtain pale solid 4.88g, yield 79.6%.
The preparation of example 4, compound 4
Chloro-3 methyl-N-furfuryl benzamide and the 10mL toluene of 2.64g (0.01mol) 2-amino-5-are added in 100mL reaction flask, the 4mL dilution with toluene liquid of instillation 4.02g (0.011mol) 1-(3-chloropyridine-2-base)-3-tetrafluoro propoxy--1H-pyrazoles-5-formyl chloride, be warming up to backflow, back flow reaction 3h, be down to room temperature suction filtration, filter cake, with the washing of 2mL ethyl acetate, is dried, weigh to obtain pale solid 4.85g, yield 81.5%.
1hNMR (500MHz, DMSO-d
6), δ (ppm) data are as follows:
Compound 1:4.316-4.327 (d, 2H), 4.545-4.511 (t, 2H), 6.240-6.246 (d, 1H), 6.364 (s, 1H), 6.291-6.509 (t, 1H) 6.818 (s, 1H), 7.493-7.496 (d, 1H), 7.528 (s, 1H), (7.535-7.563 q, 1H), 7.624-7.830 (d, 1H), 8.094-8.110 (d, 1H), 8.462-8.472 (d, 1H), 8.857-8.879 (t, 1H), 10.341 (s, 1H).
Compound 2:2.169 (s, 3H), 4.335-4.346 (d, 2H), 4.449-4.515 (t, 2H), (6.234-6.239 d, 1H), 6.361 (s, 1H), 6.296-6.514 (t, 1H) 6.750 (s, 1H), 7.348-7.352 (d, 1H), (7.485-7.488 d, 1H), 7.529 (s, 1H), 7.543-7.559 (q, 1H), (8.096-8.113 d, 1H), 8.459-8.476 (d, 1H), 8.780-8.802 (t, 1H), 10.135 (s, 1H).
Compound 3:4.318-4.329 (d, 2H), 4.735-4.790 (t, 2H), 6.234-6.239 (d, 1H), (6.359 s, 1H), 6.610-6.812 (t, 1H) 6.843 (s, 1H), 7.493-7.496 (d, 1H), 7.528 (s, 1H), (7.544-7.567 q, 1H), 7.847-7.851 (d, 1H), 8.096-8.113 (d, 1H), 8.466-8.475 (d, 1H), 8.852-8.874 (t, 1H), 10.361 (s, 1H).
Compound 4:2.165 (s, 3H), 4.329-4.340 (d, 2H), 4.731-4.787 (t, 2H), (6.228-6.233 d, 1H), 6.355 (s, 1H), 6.576-6.771 (t, 1H) 6.7690 (s, 1H), 7.347 (s, 1H), (7.485 s, 1H), 7.522 (s, 1H), 7.540-7.566 (q, 1H), (8.101-8.117 d, 1H), 8.462-8.471 (d, 1H), 8.780-8.802 (t, 1H), 10.154 (s, 1H).
Biological activity determination
Example 5 insecticidal activity assay
1. kill small cabbage moth determination of activity:
Adopt leaf dipping method.Adopt the leaf dipping method that international resistance Action Committee (IRAC) proposes.With the liquid to be measured prepared, 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 straight type pipe that the markd 10cm of tool is long, access 2 age diamondback moth larvae 30, build the mouth of pipe with gauze.Test process be placed in standard treatment chamber, 48h check result touches polypide to pull out pin, and motionless person is dead.Calculate mortality ratio.3 repetitions are done in test, and average, test-results is in table 2.
Table 2 kills small cabbage moth determination of activity
Illustrated by table 2 result, the compounds of this invention is significantly better than known compound KC1, KC2 to small cabbage moth insecticidal activity at low concentrations.
2. the water prevention chilo suppressalis test of pesticide effectiveness:
Select the field that paddy growth, soil moisture content, water and fertilizer condition are consistent, be divided into test site and blank district, each plot area 150m
2, do not establish repetition.Sample sand mill to be tested is ground to form the water suspending agent of 5% effective content, dilute 500 times of liquid, with workers and peasants-16 type knapsack hand sprayer in 1 generation striped rice borer ovum incubate the dispenser of Sheng phase, investigated killed strain number respectively at after medicine 10 days, 20 days, 30 days----withered sheath, withered heart strain number.Method adopts parallel method often to process investigation 20 point, looks into 100 caves altogether, and the record total strain number of investigation and killed strain number, calculate prevention effect.
Test-results is in table 3.
Striped rice borer test-results prevented and treated by table 3
As can be known from Table 3, the insecticidal effect of the compounds of this invention to striped rice borer is better than contrast agents, and its lasting period is more outstanding.
Claims (3)
1. a fluorine-containing N-furfuryl amides, structure is as shown in general formula I:
In formula: R
1be selected from Cl or CH
3; R
2be selected from OCH
2cHF
2or OCH
2cF
2hF
2.
2., according to the purposes of a kind of fluorine-containing N-furfuryl amides according to claim 1, it is characterized in that this compound is used as to control the sterilant of crop pest.
3. an insect-killing composition is active ingredient and acceptable carrier in agricultural or forestry containing compound of Formula I according to claim 1.
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Application publication date: 20151118 |