CN102030649B - Propargyl fluoride pyrethroid compound and application thereof - Google Patents
Propargyl fluoride pyrethroid compound and application thereof Download PDFInfo
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Abstract
The invention provides a propargyl fluoride pyrethroid compound shown in formula (A), which has excellent pest control activity and can be used as an active ingredient for pest control. The invention also provides a preparation method of the compound in the and the application in pest control aspect. The compound is good in volatility and very good in the control effect of sanitary insect pests such as mosquitoes, flies, cockroaches and the like.
Description
Technical field
The invention belongs to the sterilant technical field, be specifically related to a kind of propargyl fluoride pyrethroid compound and application thereof.
Background technology
Pyrethroid coumpound has higher insecticidal activity aspect the preventive and curative health mosquito, it has efficiently, low toxicity, low residue, characteristics good with environmental compatible, in the sanitary insect pest prevention and control field, has obtained application widely.But known to some benzyl alcohol ester comparison pyrethrins more or less have some defects on basic insecticidal activity and vapour pressure, therefore need the more useful compound of exploitation.The effective ingredient that ester cpds shown in formula (1) can be used as mosquito control has been proposed in patent documentation CN86101408A and US5132469, US5017606.
In addition, JP 61-207361 communique and JP 7-29989 communique have also been put down in writing the benzyl ester class pyrethroid of introducing fluorine atom in benzyl.And patent documentation CN01823686.3 further discloses with the ester cpds shown in following formula (2).
Wherein R is H, CH
3, CH
2cH
3, CO
2cH
3, CO
2c
2h
5.
Within 2007, Sumitomo Chemical Co has related separately to the compound of time array structure in patent documentation CN200780016519.7 and CN200780002871.5,
Along with people are more and more higher to environmental requirement, the high reactivity of agricultural chemicals more and more causes people's attention.From the angle of environmental protection, use highly active agricultural chemicals can under the prerequisite that does not reduce drug effect, reduce the dose that need use, thereby reduce the toxicity to non-target organism, improve security, reduce the pollution of left drug to environment.Though existing compound has certain effect aspect desinsection, cost, drug effect aspect still can not meet real requirement, can not meet excellent insecticidal effect and the industrialization feasibility of compound simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of propargyl fluoride pyrethroid compound, this compound is in the situation that equal formulation rate, and its biological activity is high, to sanitary insect pest, control has extraordinary effect, insecticidal activity is high, and formulation rate is few, and cost is low and environmental pressure is little.
Second purpose of the present invention is to provide above-mentioned propargyl fluoride pyrethroid compound, and the method technique is simple, and cost is low.
The present invention also aims to provide the application of above-mentioned propargyl fluoride pyrethroid compound in the medication of preparation control sanitary insect pest health.
First purpose of the present invention is achieved by the following technical solution: a kind of propargyl fluoride pyrethroid compound, its chemical name is: 2,3,5,6-tetrafluoro-4-propargyl benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound, its structural formula is as shown in the formula shown in (A):
Because the above-mentioned fluorine-containing cyclopropanecarboxylcompound compound of the present invention has two asymmetric c atoms on cyclopropane ring on 1,3, on cyclopropane ring, the substituting group of 3 has double bond structure simultaneously, thereby produce a variety of steric isomers, as cis-trans-isomer and optically active isomer.
Compound of the present invention comprises steric isomer that they are all and composition thereof.
Below to structural formula of the present invention, be the propargyl fluoride pyrethroid compound of (A) each steric isomer is exemplified below:
The compound (1) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration.
The compound (2) of structural formula of the present invention (A), wherein on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can also be transconfiguration.
The compound (3) of structural formula of the present invention (A), wherein on cyclopropane ring on the 3-position configuration of the two keys on substituting group can also be the Z configuration.
The compound (4) of structural formula of the present invention (A), wherein on cyclopropane ring on the 3-position configuration of the two keys on substituting group can also be the E configuration.
The compound (5) of structural formula of the present invention (A), wherein on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (6) of structural formula of the present invention (A), wherein on cyclopropane ring, the absolute configuration of 1-position can also be the S configuration.
The compound (7) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration.
The compound (8) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration.
The compound (9) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (10) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
The compound (11) of structural formula of the present invention (A), wherein on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can also be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration.
The compound (12) of structural formula of the present invention (A), wherein on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can also be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration.
The compound (13) of structural formula of the present invention (A), wherein on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can also be transconfiguration, on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (14) of structural formula of the present invention (A), wherein on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can also be transconfiguration, on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
The compound (15) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (16) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
The compound (17) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (18) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
The compound (19) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (20) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the Z configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
The compound (21) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the R configuration.
The compound (22) of structural formula of the present invention (A), wherein on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position can be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group can also be the E configuration, and on cyclopropane ring, the absolute configuration of 1-position can be the S configuration.
Propargyl fluoride pyrethroid compound of the present invention, can be above-mentioned any, racemic modification that wherein a pair of enantiomer forms, appoint several or whole mixing.
Preferably, compound of the present invention is cis-configuration in the 1-position of carboxylic acid part cyclopropane ring and the substituent relative configuration of 3-position, the carbon-carbon double bond on carboxylic acid part cyclopropane ring 3 bit substituents be configured as Z or E configuration.Be above-claimed cpd (7,8).
Further preferred, compound of the present invention is cis-configuration in the 1-position of carboxylic acid part cyclopropane ring and the substituent relative configuration of 3-position, absolute configuration on the 1-position is the R-configuration, the carbon-carbon double bond on carboxylic acid part cyclopropane ring 3 bit substituents be configured as Z or E configuration.Be above-claimed cpd (15,17).
Preferably, compound of the present invention is transconfiguration in the 1-position of carboxylic acid part cyclopropane ring and the substituent relative configuration of 3-position, the carbon-carbon double bond on carboxylic acid part cyclopropane ring 3 bit substituents be configured as Z or E configuration.Be above-claimed cpd (11,12).
Further preferred, compound of the present invention is transconfiguration in the 1-position of carboxylic acid part cyclopropane ring and the substituent relative configuration of 3-position, absolute configuration on the 1-position is the R-configuration, the carbon-carbon double bond on carboxylic acid part cyclopropane ring 3 bit substituents be configured as Z or E configuration.Be above-claimed cpd (19,21).
Second purpose of the present invention is achieved by the following technical solution: the preparation method of above-mentioned propargyl fluoride pyrethroid compound, adopt compound (B) as follows or compound (B) to obtain corresponding acyl chlorides (C) through the chloride reagent chloride, again with 2,3,5,6-tetrafluoro-4-propargyl benzylalcohol (D) carries out esterification and obtains:
Wherein, described chloride reagent is phosphorus oxychloride or sulfur oxychloride.
Above-claimed cpd (B) comprises its cis Z, cis E, trans Z, trans E, dextrorotation cis Z, dextrorotation cis E, each configurations such as the trans Z of dextrorotation, the trans E of dextrorotation, and each different steric isomers of compound (B) can be by commercially available or synthetic by the several different methods of prior art.Be listed below:
When compound (B) is cis-E-3-(3,3, the fluoro-1-propenyl of 3-tri-)-during the 2-2-dimethyl cyclopropane carboxylic acid, it can prepare by the following method: the Z-cis one chlorine trifluoro chrysanthemumic acid of take is raw material, take hydrazine hydrate as reductive agent, under reaction solvent and catalyst action, control temperature and carry out Dehalogenation reduction reaction 0.5～30h for-5～95 ℃, then the purified processing of reaction product is obtained to E-cis trifluoro chrysanthemumic acid, reaction formula is:
Control temperature and carry out Dehalogenation reduction reaction 0.5～30h at-5～50 ℃ in preparation E-cis trifluoro chrysanthemumic acid process; The mol ratio of Z-cis one chlorine trifluoro chrysanthemumic acid and hydrazine hydrate is 1: 3-20; Reaction solvent is water, alcohol, organic acid or organic ester; Alcohol is methyl alcohol, ethanol or Virahol, and described acid is acetic acid, and described ester is ethyl acetate; The consumption of reaction solvent is Z-cis one chlorine trifluoro chrysanthemumic acid 4-10 times; The mixture that catalyzer is aluminum-nickel-chromium alloy and palladium carbon, the mass ratio of described aluminum-nickel-chromium alloy and Z-cis one chlorine trifluoro chrysanthemumic acid is 1: 45-55, the mass ratio of described palladium carbon and Z-cis one chlorine trifluoro chrysanthemumic acid is 1: 100-300; In palladium carbon, the quality percentage composition of palladium is 5-10%; The aluminum-nickel-chromium alloy is W-6 type Raney's nickel; Purification process contains following step: filtration, acidolysis, extraction, precipitation and recrystallization.
When compound (B) is cis-Z-3-(3,3, the fluoro-1-propenyl of 3-tri-)-during the 2-2-dimethyl cyclopropane carboxylic acid, by product 3-(3 in the time of can be by production cis one chlorine trifluoro chrysanthemumic acid, the fluoro-1-proyl of 3,3-tri-)-2,2-dimethyl cyclopropane carboxylic acid ester is raw material, through the selective catalytic hydrogenation preparation, as patent documentation CN101367722A.
When compound (B) is dextrorotation cis E or dextrorotation cis Z isomer, can by conventional method for splitting, prepare by corresponding cis E or cis Z configuration chrysanthemumic acid.
When compound (B) is trans E, trans Z, the trans E of dextrorotation, the trans Z isomer of dextrorotation, can prepare with reference to above-mentioned similar method, only need change starting raw material one chlorine trifluoro chrysanthemumic acid into corresponding cis and get final product.
In the preparation process of above-claimed cpd (A): the process of the chloride of compound (B) is: in compound (B), add DMF and toluene, the mol ratio of compound (B) and DMF is 1: 1.0-2.0, the mass ratio of compound (B) and toluene is 1: 1.0-3.0, be cooled to 5-15 ℃ and start to drip chloride reagent, compound (B) is 1.0-3.0 with the mol ratio of chloride reagent: 1,1.5-3h dropwise, insulation reaction 0.5-1.5h, standing 5-10h, divide and go spent acid to get final product.
In the preparation process of above-claimed cpd (A): described compound (C) with the esterification reaction process of compound (D) is: in compound (D), add pyridine and toluene, compound (D) is 1 with the mol ratio of pyridine: 1.0-1.5, compound (D) is 1 with the mass ratio of toluene: 1.0-8.0, start stirring, be cooled to 0-5 ℃ with frozen water, start to drip compound (C), compound (D) is 1 with the mol ratio of compound (C): 0.5-2.0, after dropwising, insulation reaction 2-4h, products therefrom removes toluene through the washing negative pressure can obtain compound (A).
In the preparation process of above-claimed cpd (A): the process that described washing negative pressure removes toluene is: the salt acid elution that products therefrom is first 3-8% with volumn concentration, and then the sodium carbonate solution that is 2-8% with quality percentage composition washing, finally wash with water to neutrality, under the 5-10mmHg negative pressure, the desolventizing temperature is that 105 ℃ of piptonychia benzene are complete.
In the preparation process of above-claimed cpd (A): the preparation of the alkylol cpd shown in formula (C) can be with reference to the preparation of the method described in patent documentation EP0196156A1, CN86101408A, US5132469 and US5017606, can also adopt other disclosed method preparation or is commercially available prod.
The application of propargyl fluoride pyrethroid compound of the present invention in the medication of preparation control sanitary insect pest health.
Sanitary insect pest of the present invention is preferably mosquito, fly or cockroach etc.; Of the present invention at sanitary insect pest being applied as aspect preventing and treating to take the compound that structural formula is (A) be active ingredient, be prepared into according to a conventional method the sterilant of various formulations, as coiled mosquito-repellent incense, electric mosquito repellent tablet, mosquito liquid, insect aerosol or filter paper ribbon formulation etc., for removing, kill mosquito, fly or cockroach.
The invention has the beneficial effects as follows: the compounds of this invention industrializing implementation feasibility is high, and has very excellent insecticidal effect.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited in following examples, and following reagent is commercially available if no special instructions.
Preparation Example 12,3,5,6-tetrafluoro-4-propargyl benzyl-cis-Z-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 7)
Drop into commercially available cis-(Z)-3-(the fluoro-1-propenyl of 3,3,3-tri-)-2 in the there-necked flask of a 250ml, 2-dimethyl cyclopropane carboxylic acid 50g, add DMF20g, toluene 50g, be cooled to 10 ℃ and start to drip phosphorus oxychloride, 2h dropwises, insulation reaction 1h, pour the standing 8h of pyriform funnel left and right into, divide and remove spent acid, obtain 1R-cis-(Z)-3-(3,3, the fluoro-1-propenyl of 3-tri-)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides, yield 98%.
In the there-necked flask of a 500ml, drop into commercially available 2, 3, 5, 6-tetrafluoro-4-propargyl benzylalcohol 54.5g, pyridine 22.7g, toluene 200g, start stirring, be cooled to 0～5 ℃ with frozen water, start to drip cis-Z-2 prepared by above-mentioned technique, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane dicarbonyl chloride, after dropwising, insulation reaction 3h, the salt acid elution that adds 150ml volumn concentration 5%, and then the sodium carbonate solution that is 5% with quality percentage composition washing, finally wash with water to neutrality, under the 10mmHg negative pressure, piptonychia benzene is complete, 105 ℃ of terminal precipitation temperature, can obtain 2, 3, 5, 6-tetrafluoro-4-propargyl benzyl-cis-Z-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 1) 100g, content 92.3%, yield 90.2%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
The compound of above-mentioned preparation on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is Z configurations.
Preparation Example 22,3,5,6-tetrafluoro-4-propargyl benzyl-cis-E-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 8)
In the reactor with condensing reflux, stirring and temperature control unit, add the commercially available Z-cis of 150.0g one chlorine trifluoro chrysanthemumic acid, the hydrazine hydrate of 480.0g 50%, 600g ethanol, 1.5g palladium carbon, 3.0g nickel, stir, and temperature is controlled at 5 ℃, reaction 10h, filter reactant acidolysis, extraction, precipitation, hexanaphthene recrystallization, obtain white solid cis-(E)-3-(the fluoro-1-propenyl of 3,3,3-tri-)-2,2-dimethyl cyclopropane carboxylic acid 115.5g, yield is 89%, 78.5 ℃ of fusing points.
The cis of the above-mentioned preparation of input-(E)-3-(the fluoro-1-propenyl of 3,3,3-tri-)-2 in the there-necked flask of a 250ml, 2-dimethyl cyclopropane carboxylic acid 50g, add DMF15g, toluene 80g, be cooled to 15 ℃ and start to drip phosphorus oxychloride, 2h dropwises, insulation reaction 2h, pour the standing 8h of pyriform funnel left and right into, divide and remove spent acid, obtain cis-(E)-3-(3,3, the fluoro-1-propenyl of 3-tri-)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides, yield 98%.
In the there-necked flask of a 500ml, drop into commercially available 2, 3, 5, 6-tetrafluoro-4-propargyl benzylalcohol 55.0g, pyridine 25.0g, toluene 200g, start stirring, be cooled to 0～5 ℃ with frozen water, start to drip cis-E-2 prepared by above-mentioned technique, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane dicarbonyl chloride, after dropwising, insulation reaction 3h, the salt acid elution that adds 150ml volumn concentration 5%, and then the sodium carbonate solution that is 5% with quality percentage composition washing, finally wash with water to neutrality, under the 10mmHg negative pressure, piptonychia benzene is complete, 105 ℃ of terminal precipitation temperature, can obtain 2, 3, 5, 6-tetrafluoro-4-propargyl benzyl-cis-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 2) 98.5g, content 94.3%, yield 90.8%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
The above-mentioned propargyl fluoride pyrethroid coumpound that is prepared into, its on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be cis-configuration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is E configurations.
Preparation Example 32,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-cis-Z-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 15)
In the there-necked flask of a 1000ml, drop into commercially available cis-(Z)-3-(3, 3, the fluoro-1-propenyl of 3-tri-)-2, 2-dimethyl cyclopropane carboxylic acid racemic modification 150g, dextrorotation PTE172g, toluene 600ml, anhydrous methanol 30mL, stir, be warming up to 80 ℃ to system be vitreous state, insulation 0.5h, while starting to be cooled to 40 ℃ of systems muddinesses, insulation 1h, continue to be cooled to 5 ℃ and be incubated again 0.5h, now system has a large amount of solids to separate out, filter, filter cake first adds the liquid caustic soda alkalization of 300g5%, resolving agent is reclaimed in the toluene extraction, water layer adds the hcl acidifying of 300g5% again, add the extraction of 500ml toluene, layering, oil-reservoir water is washed till neutrality, negative pressure purifies toluene, obtain dextrorotation-cis-(Z)-3-(3, 3, the fluoro-1-propenyl of 3-tri-)-2, 2-dimethyl cyclopropane carboxylic acid 68.0g, cis dextrorotatory form ratio 97%, yield 45.5%.
According to the method in Preparation Example 1, by dextrorotation-cis-Z-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane-carboxylic acid is prepared into acyl chlorides again with commercially available 2,3,5,6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-cis-Z-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 3) 102.1g, content 91.3%, yield 91.1%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
Above-mentioned be prepared into compound on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be cis-configuration, the configuration of the two keys on cyclopropane on 3 bit substituents is Z configurations, and on cyclopropane ring, the absolute configuration of 1-position is the R configuration.
Preparation Example 42,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-cis-E-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 17)
In the reactor with condensing reflux, stirring and temperature control unit, add the commercially available Z-cis of 300.0g one chlorine trifluoro chrysanthemumic acid, the hydrazine hydrate of 960.0g 50%, 1200g ethanol, 3.0g palladium carbon, 6.0g nickel, stir, and temperature is controlled at 5 ℃, reaction 10h, filter reactant acidolysis, extraction, precipitation, hexanaphthene recrystallization, obtain white solid cis-(E)-3-(the fluoro-1-propenyl of 3,3,3-tri-)-2,2-dimethyl cyclopropane carboxylic acid 230g, yield is 89%, 79.0 ℃ of fusing points.
In the there-necked flask of a 1000ml, drop into the cis of above-mentioned preparation-(E)-3-(3, 3, the fluoro-1-propenyl of 3-tri-)-2, 2-dimethyl cyclopropane carboxylic acid racemic modification 150g, dextrorotation PTE172g, toluene 600ml, anhydrous methanol 30mL, stir, be warming up to 80 ℃ to system be vitreous state, insulation 0.5h, while starting to be cooled to 40 ℃ of systems muddinesses, insulation 1h, continue to be cooled to 5 ℃ and be incubated again 0.5h, now system has a large amount of solids to separate out, filter, filter cake first adds the liquid caustic soda alkalization of 300g5%, resolving agent is reclaimed in the toluene extraction, water layer adds the hcl acidifying of 300g5% again, add the extraction of 500ml toluene, layering, oil-reservoir water is washed till neutrality, negative pressure purifies toluene, obtain dextrorotation-cis-(E)-3-(3, 3, the fluoro-1-propenyl of 3-tri-)-2, 2-dimethyl cyclopropane carboxylic acid 67.5g, cis dextrorotatory form ratio 97%, yield 45.2%.
According to the method in Preparation Example 1, by dextrorotation-cis-E-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane-carboxylic acid is prepared into acyl chlorides again with commercially available 2,3,5,6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-cis-E-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 3) 98.5g, content 93.5%, yield 90.0%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
Above-mentioned be prepared into compound on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be cis-configuration, the configuration of the two keys on cyclopropane on 3 bit substituents is E configurations, and on cyclopropane ring, the absolute configuration of 1-position is the R configuration.
Preparation Example 52,3,5,6-tetrafluoro-4-propargyl benzyl-trans-Z-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 11)
According to the method in Preparation Example 1, by commercially available trans-Z-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane-carboxylic acid is prepared into acyl chlorides again with commercially available 2,3,5,6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2,3,5,6-tetrafluoro-4-propargyl benzyl-trans-Z-2,2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 5) 103.5g, content 93.5%, yield 94.5%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
Above-mentioned be prepared into compound on cyclopropane ring the substituting group on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is Z configurations.
Preparation Example 62,3,5,6-tetrafluoro-4-propargyl benzyl-trans-E-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 12)
According to the method in Preparation Example 2, change starting raw material into a Z-trans chlorine trifluoro chrysanthemumic acid, can prepare trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane dicarbonyl chloride, by this acyl chlorides again with commercially available 2, 3, 5, the 6-four-function is trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane dicarbonyl chloride and 2, 3, 5, 6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2, 3, 5, 6-tetrafluoro-4-propargyl benzyl-trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 6) 96.5g, content 95.5%, yield 90.1%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
The above-mentioned propargyl fluoride pyrethroid coumpound that is prepared into, its on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is E configurations.
Preparation Example 72,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-trans-Z-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 19)
According to the method in Preparation Example 3, by trans-Z-2, 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane-carboxylic acid is split, obtain dextrorotation-trans-Z-2, 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane-carboxylic acid, by dextrorotation-trans-Z-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane-carboxylic acid is prepared into acyl chlorides again with commercially available 2, 3, 5, 6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2, 3, 5, 6-tetrafluoro-4-propargyl benzyl-dextrorotation-trans-Z-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 7) 99.5g, content 94.0%, yield 91.4%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
The above-mentioned propargyl fluoride pyrethroid coumpound that is prepared into, its on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is Z configurations, and on cyclopropane ring, the absolute configuration of 1-position is the R configuration.
Preparation Example 82,3,5,6-tetrafluoro-4-propargyl benzyl-dextrorotation-trans-E-2, the preparation of 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound (compound 21)
According to the method in Preparation Example 3, by trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane-carboxylic acid is split, obtain dextrorotation-trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane-carboxylic acid, by dextrorotation-trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropane-carboxylic acid is prepared into acyl chlorides again with commercially available 2, 3, 5, 6-tetrafluoro-4-propargyl benzylalcohol reaction, can obtain 2, 3, 5, 6-tetrafluoro-4-propargyl benzyl-dextrorotation-trans-E-2, 2-dimethyl-3-(2-Trifluoromethyl-1-ethene thiazolinyl) cyclopropanecarboxylcompound (compound 8) 97.5g, content 95.3%, yield 90.8%.The molecular formula of this compound is: C
19h
16f
7o
2, molecular weight: 409.3.
The above-mentioned propargyl fluoride pyrethroid coumpound that is prepared into, its on cyclopropane ring the substituent configuration on the 1-position and on cyclopropane ring the substituent configuration on the 3-position be transconfiguration, on cyclopropane ring, on the 3-position, the configuration of the two keys on substituting group is E configurations, and on cyclopropane ring, the absolute configuration of 1-position is the R configuration.
Test implementation example 1
Resulting compound in above-mentioned Preparation Example 1-8 and Es-esbiothrin are mixed with to the kerosin of different concns, then getting 3ml solution evenly is sprayed on the empty base of mosquito-repellent incense with micro-syringe, make coiled mosquito-repellent incense 1-9, the mosquito-repellent incense sample that will prepare by the method for stipulating in GB13917.4-92 carries out kill mosquito evaluation of pesticide effectiveness contrast to culex pipiens pollens, each tests triplicate, and observed mortality ratio after 24 hours, result is as table 1:
Table 1 the compounds of this invention and Es-allethrin effect exterminating mosquito are relatively
Result shows: above-mentioned each compound all has very high insecticidal activity, and the drug effect difference caused along anti-body is not remarkable, and the drug effect of dextrorotatory form is more than 1.6 times of raceme; Drug effect and the dimefluthrin of raceme are suitable.
Test implementation example 2
With the compound 1-8 containing 2mg, respectively with the long 35mm of 15mgBHT (2,6-di-t-butyl 4-methylphenol) dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: paper pulp fiber 50: 50), under room temperature, place 3 days, make electric mosquito repellent tablet.
The electric mosquito repellent tablet that aforesaid method is made carries out the evaluation of pesticide effectiveness contrast to mosquito with the prallethrin electric mosquito repellent tablet of at present the most frequently used 10mg/ sheet according to GB13917.5-92, adopts airtight drum device.Detailed process is as follows: by electric mosquito repellent tablet sample energising preheating 1h, 2h, 4h, 6h, 8h, draw 20 female culex pipiens fatigans with mosquito sucking tube, put into airtight drum test set, accurately smoked kill 1min, clock simultaneously, cut off the electricity supply after smoked, and remove the electric mosquito repellent sheet devices, record at regular intervals down and out examination mosquito number.The results are shown in Table 2:
Electric mat prepared by table 2 the compounds of this invention and alkynes the third the third chrysanthemum ester electric mat effects relatively
Result shows: electric mat prepared as former medicine by the compounds of this invention of take has extraordinary desinsection effect, and wherein the relative effectivenes of racemic modification is at more than 5 times of prallethrin anti-mosquito incense sheet; The relative effectivenes of electric mat prepared as former medicine by the compounds of this invention 15 (the trans body of dextrorotation) of take is at more than 9 times of prallethrin anti-mosquito incense sheet.
Test implementation example 3
By 0.2 part of compound 7 and 15 respectively with 0.3 part of BHT, the C14 aliphatic hydrocarbon Hybrid Heating of surplus, be prepared into vaporizer mosquito liquid, filling one-tenth electric liquid device then, wherein the active ingredient compound is 0.2w/w%.
The electric liquid device that aforesaid method is made and 1% prallethrin vaporizer mosquito liquid carry out evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device, by electric liquid device sample energising 2h, 36h, 84h, 168h, 336h, draw 20 female culex pipiens pollens with mosquito sucking tube, in embedding device, accurate smoked kill 1min, clock simultaneously, cut off the electricity supply after smoked, and remove the electric liquid device device, record at regular intervals down and out examination mosquito number.The results are shown in Table 3:
The comparison of vaporizer mosquito liquid prepared by table 3 the compounds of this invention and prallethrin vaporizer mosquito liquid effect
Result shows: the relative effectivenes of electric liquid device prepared as former medicine by the compounds of this invention 7 (racemic modification) of take is at more than 5 times of prallethrin anti-mosquito incense sheet; The relative effectivenes of electric liquid device prepared as former medicine by the compounds of this invention 15 (dextrorotation along Z) of take is at more than 10 times of prallethrin anti-mosquito incense sheet.
Test implementation example 4
Under heating, compound 8 and 17 is mixed and made into to certain density solution with dehydrated alcohol respectively, is placed in the inhalator jar that control valve is housed, then be filled with a certain amount of propellent, make insect aerosol.
The sample that aforesaid method is made carries out mosquito according to GB13917.2-92, fly, and the efficacy testing of Groton bug, adopt airtight drum device.Detailed process is as follows: will put into cylinder for the examination insect; after trying worm recovery normal activity; metered injection from insect aerosol tank of the present invention; extract baffle plate after 1min out and make to try worm and contact with medicament, timing immediately, and start record; record at regular intervals down and out examination borer population; to all for the examination worm, be transferred in clean dependent insect cage after 20min, check dead examination borer population after 24h, wherein Groton bug check 72h mortality ratio.The results are shown in Table 4:
Insect aerosol prepared by the table 4 the compounds of this invention insect killing effect to mosquito, fly, Groton bug
From above-mentioned experimental result: the aerosols of the compounds of this invention 8 and 17 preparations all have good insect killing effect to mosquito, fly, Groton bug.
The specific embodiment of more than enumerating is the explanation that the present invention is carried out.It is pointed out that above embodiment, only for the invention will be further described, does not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made, still belong to protection scope of the present invention.
Claims (1)
1. the preparation method of a propargyl fluoride pyrethroid compound, the chemical name of this propargyl fluoride pyrethroid compound is: 2,3,5,6-tetrafluoro-4-propargyl benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound, its structural formula is as shown in the formula shown in (A):
Wherein, described chloride reagent is phosphorus oxychloride or sulfur oxychloride, wherein said compound (C) with the esterification reaction process of compound (D) is: in compound (D), add pyridine and toluene, compound (D) is 1 with the mol ratio of pyridine: 1.0-1.5, compound (D) is 1 with the mass ratio of toluene: 1.0-8.0, start stirring, be cooled to 0-5 ℃ with frozen water, start to drip compound (C), compound (D) is 1 with the mol ratio of compound (C): 0.5-2.0, after dropwising, insulation reaction 2-4h, products therefrom removes toluene through the washing negative pressure can obtain compound (A).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101408A (en) * | 1985-03-06 | 1986-09-17 | 帝国化学工业公司 | The preparation of fluorobenzyl esters and application thereof |
| US5132469A (en) * | 1986-12-12 | 1992-07-21 | Imperial Chemical Industries Plc | Fluorobenzyl esters |
| CN1558893A (en) * | 2001-10-03 | 2004-12-29 | 大日本除虫菊株式会社 | Propargylbenzyl alcohol ester derivative, process for producing the same, and insecticide/insectifuge containing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101408A (en) * | 1985-03-06 | 1986-09-17 | 帝国化学工业公司 | The preparation of fluorobenzyl esters and application thereof |
| US5132469A (en) * | 1986-12-12 | 1992-07-21 | Imperial Chemical Industries Plc | Fluorobenzyl esters |
| CN1558893A (en) * | 2001-10-03 | 2004-12-29 | 大日本除虫菊株式会社 | Propargylbenzyl alcohol ester derivative, process for producing the same, and insecticide/insectifuge containing the same |
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