CN109776327A - First chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, preparation method and application - Google Patents
First chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, preparation method and application Download PDFInfo
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Abstract
The invention belongs to chrysanthemum ester type compound fields, and in particular to a kind of first chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound further relates to the application of the preparation method and above compound of above-mentioned compound.First chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound of the invention is that progress esterification is obtained in solvent in the presence of organic base with polyfluoro benzylalcohol by first chloro chrysanthemum acyl chlorides.This has very high kill activity to sanitary insect pests such as mosquito, housefly and Groton bugs with bright provided compound；And be readily synthesized, production cost is low, is easy to industrialize, and synthesis complexity is substantially reduced；Furthermore the compound can effectively reduce the resistance and Environmental Residues problem of pest due to the dissymmetrical structure and polyfluoro alantol of chrysanthemumic acid part.
Description
Technical field
The invention belongs to chrysanthemum ester type compound fields, and in particular to a kind of first chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound,
Further relate to the application of the preparation method and above compound of above-mentioned compound.
Background technique
Pyrethroid be it is a kind of have the characteristics that efficiently, insecticidal spectrum it is wide, it is less toxic, to the bionical insecticide of safety of human and livestock,
Important function has been played in the plant protection such as health and epidemic prevention and grain and cotton vegetables and fruits.However, also being faced due to long-term and a large amount of uses
Some fatal problems:
Pyrethroid insecticides are largely used extensively, and pest is made generally to produce drug resistance.It is this kind of in order to control
The pests such as resistance mosquito, producer have to increase Drug level, and the moderately toxic bromine that will be only used in the past in terms of agricultural
Cyano chrysanthemate is also applied to household.However, this further results in pest resistance to insecticide enhancing, vicious circle.Influence them
Use duration.
Elliott etc. has once synthesized first chlorocyanohydrin ester, it is found that their insecticidal activity is suitable with bioresmethrin
(Elliott,M；Janes,N.F；Khambar,B.P.S Pesctic.Sic.1986,17,708).
Mitra, R.B. and Muramatsu, S. etc. also report the synthesis of the halogenated phenothrin of first, find its insecticidal activity
Slightly below permethrin, but it is only 1/10 (Mitra, R.B. of permethrin to the toxicity of fish；
Kulaarni,G.H.；Muljiani,Z.；Khanna,P.N.Synth.Comm.,1989,20(7),1139-1149；Ide,J.；
Nakada,Y.；Endo,R.；Muramatsu,S.；Konishi,K.；Mizuno,T.；Ohno,S.；Yamazaki,Y.；Endo,
H.；Fujita,K.Agric.Biol.Chem.,1983,47(4),927-928.).
The insecticidal activity of above-mentioned first halogen pyrethroids is all very low, it is difficult to meet public health and vector insect control and agricultural
Requirement of the plant protection to pyrethroid.Therefore, in fact, first chloro pyrethroids was not yet really utilized so far.
CN108264452A discloses a kind of ethers Pesticidal compound with similar pyrethroid ester structure, preparation side
Method is the following steps are included: using phenyl tetrafluoride halides shown in alcohol shown in formula B, formula C as raw material, the two item existing for NaH
It is dissolved under part in the atent solvents such as DMF, carries out etherificate synthetic reaction at room temperature and be prepared into described there is similar quasi- remove
The ethers Pesticidal compound of worm pyrethroids structure；The molar ratio of the pure and mild phenyl tetrafluoride halides is 1:1；
The applicant of above-mentioned patent application simultaneously has also applied for CN108250078A, a kind of pyrethroid compound,
Preparation method includes the following steps: the trans- -3- of 2,2- dimethyl -1R- (2,2- difluoroethylene base) cyclopropane-carboxylic acid or its is right
The acetyl halide compound answered, in organic solvent, and 2,3,5,6- tetrafluorobenzyl alcohols or 2,3,5,6- tetrafluoros carry out ester to xylyl alcohol
Change reaction, to obtain the pyrethroid compound.
Deficiency existing for the above patent application is that the activity of part of compounds still has much room for improvement.
It is new therefore, it is necessary to need to study a kind of high activity of a new generation, the pyrethroid of low-residual for public health
Kind.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of high activities, the pyrethroid new product of low-residual
Kind.Specifically: the present invention forms novel first chlorine by the structure of modification to traditional pyrethroid chrysanthemumic acid, alantol part
Chrysanthemumic acid polyfluoro benzylalcohol pyrethroids compound.The pharmacodynamic test of the mixture of the compound and its stereoisomer or its stereoisomer
Show it with good insecticidal activity.Simultaneously because the introducing of the multiple fluorine atoms in alantol part, can also reduce the anti-of pest
Property risk.
Above-mentioned pyrethroid compound provided by the present invention, i.e. first chlorine chrysanthemumic acid polyfluoro benzylalcohol pyrethroids, and its anti-
Control the application and invention which is intended to be protected on the sanitary insect pests such as mosquito, cockroach or housefly；
The innovative point of this patent is that first chlorine chrysanthemumic acid is combined the novel chrysanthemum of preparation by the innovation-of molecular structure with polyfluoro benzylalcohol
Ester compounds, part of compounds activity are better than effective cypermethrin, solve the previously reported low insecticidal activity of first Permethrin
Disadvantage.
A kind of first chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound provided by the present invention, general structure such as following formula I:
Alternatively, being the stereoisomer of above formula；
Wherein R is-H ,-F ,-CH3,-CH2OCH3。
Including at least more than one mixture of stereoisomer as described in claim 1, also wanted in the present invention
Within the scope of protection.
Above-mentioned first chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, selected from any one of following:
Cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane
Carboxylate；
Trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；
Trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropyl
Alkane carboxylate；
(1R) cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane carboxylic acid
Acid esters；
(1R) cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) ring
Carboxylate；
(1R) trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；
(1R) trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane
Carboxylate；
(1R) trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl)
Cyclopropanecarboxylcompound.
The preparation method of above-mentioned compound, comprising the following steps:
The polyfluoro benzylalcohol that the first chloro chrysanthemum acyl chlorides and structural formula that structural formula is II are III is in the presence of organic base in solvent
Middle carry out esterification；
The condition of above-mentioned esterification is: the molar ratio of first chloro chrysanthemum acyl chlorides and polyfluoro benzylalcohol is 0.8-1.5:1, reaction
For middle addition organic base as acid binding agent, reaction temperature is 0-35 DEG C.
Above-mentioned solvent is preferably any one of toluene, dimethylbenzene, hexamethylene, n-hexane etc.；
Organic base is tertiary amine, such as any one of pyridine, triethylamine.
Specifically, the preparation method of above-mentioned compound, includes the following steps: 2,2- dimethyl -3- (2- chloropropene
Base) cyclopropane dicarbonyl chloride, cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride, trans-2,2- dimethyl -3-
(E/Z-2- Chloroallyl, 1R-cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride or 1R-trans-2,2-
Any one of dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride and structural formula are the polyfluoro benzylalcohol of (III) organic
Esterification is carried out in the presence of alkali in solvent.
Above-mentioned compound or mixture is controlling or is killing the application in the vector in Public Hygienic Prevention, and
Invention which is intended to be protected；
Preferably, the vector in Public Hygienic Prevention is any one of mosquito, cockroach or housefly.
In above-mentioned application, the insecticide that the compound comprising Formulas I is prepared into as raw medicine, also claimed by the present invention
Within the scope of.
In above-mentioned application, insecticide includes coiled mosquito-repellent incense, electric mosquito repellent tablet, mosquito liquid, insect aerosol, powder
Any one of agent, granula, non-heated volatilization preparation, smoke preparation or poison bait.
For the present inventor when carrying out experiment of the invention, the considerations of being based on and thinking are as follows:
The introducing of fluorine atom is important directions (Qi Mingzhu, Zhou Jingmei, the ginger for developing novel pyrethroid in pyrethroids molecule
Friendly method, He Shuze, Wang Dongchao, He Hongjun, a kind of new pyrethroid compound and its preparation method and application [P], CN
101665433A,2010；Yang Zehua, Chen Hubiao, Xu Yongchen, some new pyrethroid compounds as derived from Tefluthrin
[P],CN 101638367A,2010).It is reported that the characteristics such as height hydrogen-like that fluorine atom has and high electronegativity, Ke Yiti
The bioactivity of high pyrethroids molecule and the drug resistance for reducing pest.For example, the cyfloxylate being derived from cypermethrin, it will
Trifluoromethyl introduces dichlor chrysanthemic acid double bond part instead of a chlorine atom, reduces molecule and melts boiling point, improve vapour pressure, has
There are extremely strong stomach toxicity and action of contace poison, the quick-acting and lasting period is long, belongs to the column of ultra high efficiency insecticide.Zou Xinzhuo etc. is fluorine-containing in research
" mixed fluorine efficacy " phenomenon (Teng Haixia, Guan Xixia, Xu Zijin, Zou Xinzhuo, time chrysanthemumic acid are also found when the insecticidal activity of pyrethroids
Synthesis and melange effect [J] of the 4- methyl containing fluoro-methylbenzyl ester, pesticide, 2006,45 (8), 531-532.), i.e. mixing contains Flumethrin pair
The insecticidal activity of resistant strain pest is higher than individual isomer.
The present inventor is on the basis of the molecular structure of serious analysis pyrethroid, it is believed that the first pyrethroids ester is due to it
Connect the methyl there are two supplied for electronic in the photosensitive center double bond of chrysanthemumic acid part, therefore, is easy to happen light degradation reaction, limits it and answer
Use range；And cypermethrin, bromine cyanogen are the dihalo pyrethroid of the high-efficiency low-toxicity of representative then on the basis of the first chrysanthemum monocarboxylate
The upper excessive stability for having considered double bond key increases residual in the environment so as to cause their mistake stabilization
Time, this exactly causes teratogenesis, mutagenicity or the one of the major reasons as incretion interferent.First chloro pyrethroids combines
The design feature of first chrysanthemum monocarboxylate and dihalo- pyrethroids, methyl and an electrophilic halogen containing a supplied for electronic in double bond.
Such structure between the first chrysanthemum monocarboxylate and dihalo- pyrethroids, has convenient photostability or biology to the stability of light
Degradability.Simultaneously because the introducing of the multiple fluorine atoms in alantol part, also can be improved insecticidal activity and reduces the resistance of pest.
The beneficial effects of the present invention are:
(1) this has very high kill to live the sanitary insect pests such as mosquito, housefly and Groton bug with the bright compound (I) being related to
Property；
(2) compound (I) of the present invention is readily synthesized, and production cost is low, is easy to industrialize；Effective cypermethrin is logical
Often by generating cypermethrin after dichlor chrysanthemic acid and the esterification of salt containing cyanogen and 3-Phenoxy-benzaldehyde, and configuration is carried out under alkaline condition and converts to obtain,
Compound (I) is directly esterified by acid with polyfluoro alantol, and synthesis complexity is substantially reduced；
(3) compound (I) of the present invention can effectively reduce due to the dissymmetrical structure and polyfluoro alantol of chrysanthemumic acid part
The resistance and Environmental Residues problem of pest.
Specific embodiment
Embodiment 1
Synthesize cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 2g, hexamethylene 40mL are added in the three-necked bottle of 100mL,
Cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 5.2g (25mmol), room temperature reaction 4 is slowly added dropwise
Hour.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, dry,
Light yellow viscous liquid is obtained after desolventizing, is obtained weak yellow liquid 8.0g after column chromatographs (petrol ether/ethyl acetate=20/1), is received
Rate 91%.1H NMR (400MHz, CDCl3)δ1.23,1.24,1.25,1.27(4s,-CH3,6H),1.77(2d,cyclo-H,J1
=8.4Hz, J2=5.8Hz, 1H), 1.87 (t, cyclo-H, J=8.5Hz, 0.3H), 2.10,2.13 (2s ,-CH3,3H),2.18
(t, cyclo-H, J=8.4Hz, 0.7H), 5.18-5.25 (m ,-OCH2, 2H), 5.81 (d ,=CH-, J=8.4Hz, 0.7H),
5.85 (d ,=CH-, J=8.5Hz, 0.3H), 7.07-7.16 (m, ArH, 1H)；HRMS cacld for C16H16O2ClF4
351.0775,found 351.0782.
Note: cis-2,3,5,6- ptfe benzyls 2, in 2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
" cis " refers to cis-；Trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
In " trans " refer to trans-, following embodiment is herewith explained.
Embodiment 2
Synthesize cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
2,3,4,5,6- five fluoro benzyl alcohol 4.95g (25mmol), triethylamine 2.5g, toluene are added in the three-necked bottle of 100mL
Cis-2 is slowly added dropwise in 40mL, and 2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g (29mmol), room temperature is anti-
It answers 4 hours.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, is done
It is dry, light yellow viscous liquid is obtained after desolventizing, obtains weak yellow liquid after column chromatographs (petrol ether/ethyl acetate=20/1)
9.0g, yield 96%.1H NMR (400MHz, CDCl3)δ0.98-1.24(m,-CH3,6H),1.62-1.75(m,cyclo-H,
1H),1.85-2.18(m,-CH3And cyclo-H, 4H), 5.11 (d ,=CH-, 0.7H), 5.65-5.85 (d ,=CH-,
0.3H, J=8.6Hz)；HRMS cacld for C23H22NO3FCl 414.1271,found 414.1272.HRMS cacld
for C16H15O2ClF5369.0681,found 369.0693。
Embodiment 3
Synthesize cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane carboxylic acid
Acid esters
It is added 4- methyl -2,3 in the three-necked bottle of 100mL, 5,6- tetrafluorobenzyl alcohol 4.85g (25mmol), pyridine 2.5g, two
Cis-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 5.2g (25mmol), room temperature is slowly added dropwise in toluene 40mL
Reaction 4 hours.Successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, it is dry, it takes off
Light yellow viscous liquid is obtained after solvent, obtains weak yellow liquid 8.5g, yield after column chromatographs (petrol ether/ethyl acetate=20/1)
93%.1H NMR (400MHz, CDCl3)δ1.22,1.23,1.25,1.26(4s,-CH3,6H),1.73-1.77(m,cyclo-H,
1H), 1.85 (t, cyclo-H, J=8.8Hz, 0.3H), 2.10-2.19 (m ,-CH3,cyclo-H,3.7H),5.14-5.22
(m,-OCH2, 2H), 5.80 (d ,=CH-, J=8.2Hz, 0.7H), 5.86 (d ,=CH-, J=8.5Hz, 0.3H)；HRMS
cacld for C17H18O2ClF4365.0931,found 365.0945.
Embodiment 4
Synthesize cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) ring
Carboxylate
4- methoxy -2,3,5,6- tetrafluorobenzyl alcohol 5.6g (25mmol), pyridine are added in the three-necked bottle of 100mL
Cis-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in 2.5g, dimethylbenzene 40mL
(29mmol) is reacted at room temperature 4 hours.It is successively molten with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium-chloride
Liquid washing, it is dry, light yellow viscous liquid is obtained after desolventizing, is obtained after column chromatographs (petrol ether/ethyl acetate=20/1) yellowish
Color liquid 9.5g, yield 96%.1H NMR (400MHz, CDCl3)δ1.22,1.23,1.25,1.26(4s,-CH3,6H),1.75
(2d,cyclo-H,J1=7.2Hz, J2=8.3Hz, 1H), 1.86 (t, cyclo-H, J=8.7Hz, 0.3H), 2.10-2.19
(m,-CH3,cyclo-H,3.7H),3.40(s,-OCH3,3H),4.59(s,-CH2 OCH3,2H),5.17-5.25(m,-OCH2-,
2H), 5.79 (d ,=CH-, J=8.6Hz, 0.7H), 5.86 (d ,=CH-, J=8.4Hz, 0.3H)；HRMS cacld for
C18H20O3ClF4395.1035,found 395.1050。
Embodiment 5
Synthesize trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 3g, n-hexane 40mL are added in the three-necked bottle of 100mL,
Trans-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 6g (30mmol) is slowly added dropwise, room temperature reaction 4 is small
When.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, dry, is taken off
Light yellow viscous liquid is obtained after solvent, obtains weak yellow liquid 8.5g, yield after column chromatographs (petrol ether/ethyl acetate=20/1)
97%.1H NMR (400MHz, CDCl3): δ 1.06,1.18 (2s ,-CH3,6H),1.41-1.44(m,cyclo-H,0.83H),
1.94-2.05(m,-CH3, cyclo-H, 3.17H), 2.22 (t, cyclo-H, J=6.0Hz, 0.82H), 2.29-2.38 (m,
cyclo-H,0.17H),5.08-5.18(m,-OCH2,=CH-, 2.83H), 5.23 (d ,=CH-, J=8.4Hz, 0.17H),
6.96-7.05(m,Ar-H,1H)；HRMS cacld for C16H16O2ClF4351.0775,found 351.0780。
Embodiment 6
Synthesize trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
The fluoro- 3- phenoxy benzaldehyde 5.4g (25mmol) of 4-, pyridine 3g, hexamethylene are added in the three-necked bottle of 100mL
40mL, potassium cyanide 2g (25mmol) formed saturated aqueous solution, be slowly added dropwise (1R) it is trans- -2,2- dimethyl -3- (2- chloropropene
Base) cyclopropane dicarbonyl chloride 6g (30mmol), it reacts at room temperature 4 hours.Organic phase successively use 20mL 5% sodium hydroxide solution,
5% hydrochloric acid solution and saturated sodium chloride solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, chromatographs (petroleum through column
Ether/ethyl acetate=20/1) after weak yellow liquid 9.6g, yield 93%.1H NMR (400MHz, CDCl3): δ 1.07,1.29
(2s,-CH3,6H),1.40-1.43(m,cyclo-H,1H),2.00(s,-CH3,3H),2.21(t,cyclo-H,J1=5.8Hz,
J2=7.2Hz, 1H), 5.08-5.24 (m ,=CH- ,-OCH2-,3H)；HRMS cacld for C16H15O2ClF5369.0681,
found 369.0695。
Embodiment 7
Synthesize trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane
Carboxylate
4- methyl -2,3,5,6- tetrafluorobenzyl alcohol 4.85g (25mmol), pyridine 3g, toluene are added in the three-necked bottle of 100mL
Trans-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 6g (30mmol) is slowly added dropwise in 40mL, room temperature reaction
4 hours.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, dry,
Light yellow viscous liquid is obtained after desolventizing, is obtained weak yellow liquid 9.0g after column chromatographs (petrol ether/ethyl acetate=20/1), is received
Rate 98%.1H NMR (400MHz, CDCl3): δ 1.16,1.29 (2s ,-CH3, 6H), 1.52 (d, cyclo-H, J=5.2Hz,
1H),2.10(s,-CH3,3H),2.28-2.33(m,cyclo-H,-CH3, 4H), 5.19-5.34 (m ,=CH- ,-OCH2-,3H)；
HRMS cacld for C17H18O2ClF4365.0931,found 365.0946。
Embodiment 8
Synthesize trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl)
Cyclopropanecarboxylcompound
Addition trans-4- methoxy -2,3 in the three-necked bottle of 100mL, 5,6- tetrafluorobenzyl alcohol 5.6g (25mmol),
Trans- -2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in pyridine 3g, hexamethylene 40mL
(30mmol) is reacted at room temperature 4 hours.Organic phase successively uses 5% sodium hydroxide solution, 5% hydrochloric acid solution and saturation chlorine of 20mL
Change sodium solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, after column chromatographs (petrol ether/ethyl acetate=20/1)
Obtain weak yellow liquid 9.5g, yield 96%.1H NMR (400MHz, CDCl3): δ 1.16,1.29 (4s ,-CH3,6H),1.50,
(1.52 2d, cyclo-H, J=5.3Hz, 1H), 2.04-2.02 (m, cyclo-H ,-CH3,3.2H),2.30-2.33(m,
cyclo-H,0.8H),3.40(s,-CH3,3H),4.58(s,-CH2O-, 2H), 5.19-5.34 (m ,=CH- ,-OCH2-,3H)；
HRMS cacld for C18H20O3ClF4395.1035,found 395.1045。
Embodiment 9
Synthesize (1R)-cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- chloropropene
Base) cyclopropanecarboxylcompound
4- methoxy -2,3,5,6- tetrafluorobenzyl alcohol 5.6g (25mmol), pyridine are added in the three-necked bottle of 100mL
(1R)-cis-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in 2.5g, toluene 40mL
(29mmol) is reacted at room temperature 4 hours.It is successively molten with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium-chloride
Liquid washing, it is dry, light yellow viscous liquid is obtained after desolventizing, is obtained after column chromatographs (petrol ether/ethyl acetate=20/1) yellowish
Color liquid 9.5g, yield 96%.1H NMR (400MHz, CDCl3)δ1.22,1.23,1.25,1.26(4s,-CH3,6H),1.75
(2d,cyclo-H,J1=7.2Hz, J2=8.3Hz, 1H), 1.86 (t, cyclo-H, J=8.7Hz, 0.3H), 2.10-2.19
(m,-CH3,cyclo-H,3.7H),3.40(s,-OCH3,3H),4.59(s,-CH2 OCH3,2H),5.17-5.25(m,-OCH2-,
2H), 5.79 (d ,=CH-, J=8.6Hz, 0.7H), 5.86 (d ,=CH-, J=8.4Hz, 0.3H).
Embodiment 10
Synthesize (1R)-trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- chlorine third
Alkenyl) cyclopropanecarboxylcompound
Addition trans-4- methoxy -2,3 in the three-necked bottle of 100mL, 5,6- tetrafluorobenzyl alcohol 5.6g (25mmol),
(1R)-trans-2,2- dimethyl -3- (2- Chloroallyl) cyclopropane dicarbonyl chloride is slowly added dropwise in pyridine 3g, hexamethylene 40mL
6g (30mmol) is reacted at room temperature 4 hours.Organic phase successively uses 5% sodium hydroxide solution, 5% hydrochloric acid solution and saturation of 20mL
Sodium chloride solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, chromatographs (petrol ether/ethyl acetate=20/1) through column
Weak yellow liquid 9.5g, yield 96% are obtained afterwards.1H NMR (400MHz, CDCl3): δ 1.16,1.29 (4s ,-CH3,6H),1.50,
1.52 (2d, cyclo-H, J=5.3Hz, 1H), 2.04-2.02 (m, cyclo-H ,-CH3,3.2H),2.30-2.33(m,
cyclo-H,0.8H),3.40(s,-CH3,3H),4.58(s,-CH2O-, 2H), 5.19-5.34 (m ,=CH- ,-OCH2-,3H)。
It is raw to survey application examples 1
To the killing effect of Culex pipiens pallens (Culex pipiens palens Coq) wriggler
Select following pyrethroids as representing, referring to method (Zhang Zong Ping, the insecticide of the World Health Organization (WHO) recommendation
Toxicity test, Science Press, 1988), with common test kind Culex pipiens pallens (Culex pipiens pallens Coq)
3 instar larvaes are as test object.Test ambient temperature: 25 DEG C；Illumination: illumination 16h, dark 8h are raised in control and medicament
In aqueous solution.Test method uses larva immersion method, by the access examination after concentration mix as needed of a certain amount of medical fluid and pure water
Worm, every processing set 3 repetitions, and processing investigates test worm death condition afterwards for 24 hours, records total borer population and dead borer population, calculate the death rate,
Its result is shown in table 1, with entry evaluation insecticidal activity.Wherein 1-10 compound is compound of the present invention
(I) typical example: compound involved in preparation embodiment 1-10.Simultaneously and cypermethrin and decis progress relative virus force
Comparison.
1 compound of table (I) is in 1ppm and 0.1ppm to the killing effect of Culex pipiens pallens wriggler
It is raw to survey application examples 2
To the insecticidal activity LC of Culex pipiens pallens (Culex pipiens palens Coq) wriggler50And LC90
Using larva immersion method, by a certain amount of medical fluid and pure water after concentration mixes as needed (0.008,0.006,
0.004,0.002,0.001mg/L) test worm is accessed, every processing sets 3 repetitions, and processing is investigated test worm death condition afterwards for 24 hours, obtained
The death rate, and calculate LC50And LC90, result is shown in table 2, to assess insecticidal activity.Wherein the 3rd, 4, No. 6-10 change
Close the typical example that object is compound of the present invention (I): preparation embodiment 3, compound involved in 4,6-10.It is simultaneously and high
Imitate the comparison that cypermethrin carries out relative virus force.
Insecticidal activity LC of 2 compound of table (I) to Culex pipiens pallens wriggler50And LC90
It is raw to survey application examples 3
The knockdown effect of No. 4 compound housefly and cockroach
No. 4 compound is cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- chlorine
Acrylic) cyclopropanecarboxylcompound, it is the mixture being made of multiple stereoisomers, it is the easiest in synthesis and right
The insecticidal activity of wriggler is higher, is 1.2 times of effective cypermethrin.Therefore, selecting No. 4 compound is representative, is tested pair
The knockdown effect of housefly and Groton bug.Housefly (Musca domestica), the sensitive strain of indoor raising, emergence 3-5 days
Adult, half male and half female.Test temperature: 26 ± 1 DEG C, humidity: 70 ± 10%.Test method: liquid film contact method.0.1% acetone
Medical fluid 1mL is spread evenly across in 500mL conical flask and forms a film, and after doing, is put into adult 20-25 head, observes knockdown time and knocks down number,
It is repeated 3 times in parallel.Groton bug (Blattela germanica), the sensitive strain of indoor raising, male insect.Test temperature
Degree: 22 ± 1 DEG C.Test method: liquid-film method.By 54mg/m2Metering, by acetone medical fluid be spread evenly across wide-mouth inner wall film forming,
After dry, adult 10 are put into, observe knockdown time and knocks down number, is repeated 3 times in parallel.Test result is as shown in table 3.
Knockdown effect of No. 4 compound of table 3 to housefly and Groton bug
| Housefly | Groton bug | |
| 95% fiducial limit of KT50 (dividing) | 3.82(3.61-3.98) | 6.21(6.04-6.48) |
It can be seen that this from the data in above table with the bright compound (I) being related to mosquito, housefly and Groton bug
Equal sanitary insect pests have very high kill activity: if 4,9 and 10 compound of embodiment is to the activity of family's common insect pests Culex pipiens pallens
Greater than effective cypermethrin.Effective cypermethrin is to be applied to the highest pyrethroids kind of domestic hygiene pest activity at present.
It is further an advantage of the invention that: compound (I) of the present invention is readily synthesized, and production cost is low, is easy to
Industrialization；Effective cypermethrin generates cypermethrin after being usually esterified by dichlor chrysanthemic acid and salt containing cyanogen and 3-Phenoxy-benzaldehyde, and in alkaline item
Configuration is carried out under part to convert to obtain.Compound (I) is directly esterified by acid with polyfluoro alantol, and synthesis complexity obviously drops
It is low.
Compound (I) of the present invention can effectively reduce evil due to the dissymmetrical structure and polyfluoro alantol of chrysanthemumic acid part
The resistance and Environmental Residues problem of worm.
Embodiment 11
Synthesize cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；?
2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 3g, n-hexane 40mL are added in the three-necked bottle of 100mL, be slowly added dropwise into
Cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g (30mmol) is reacted at room temperature 4 hours.It is organic
Mutually successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, it is dry, after desolventizing
Light yellow viscous liquid obtains weak yellow liquid 9.2g, yield 95% after column chromatographs (petrol ether/ethyl acetate=20/1).
Embodiment 12
Synthesize (1R) cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；2,3,4,5,6- five fluoro benzyl alcohol 4.5g (25mmol), pyridine 3g, n-hexane 40mL are added in the three-necked bottle of 100mL, slowly
(1R) cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid carboxylic acid chloride 6g (30mmol) is added dropwise, room temperature is anti-
It answers 4 hours.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution, is done
It is dry, light yellow viscous liquid is obtained after desolventizing, obtains weak yellow liquid after column chromatographs (petrol ether/ethyl acetate=20/1)
9.4g, yield 94%.
Embodiment 13
Synthesize (1R) cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropyl
Alkane carboxylate；
In the three-necked bottle of 100mL be added 4- methyl -2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 3g, just oneself
(1R)-cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in alkane 40mL
(30mmol) is reacted at room temperature 4 hours.Organic phase successively uses 5% sodium hydroxide solution, 5% hydrochloric acid solution and saturation chlorine of 20mL
Change sodium solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, after column chromatographs (petrol ether/ethyl acetate=20/1)
Obtain weak yellow liquid 9.3g, yield 96%.
Embodiment 14
Synthesize (1R) trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；
2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 3g, n-hexane 40mL are added in the three-necked bottle of 100mL,
(1R)-trans-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g (30mmol), room temperature is slowly added dropwise
Reaction 4 hours.Organic phase is successively washed with 5% sodium hydroxide solution of 20mL, 5% hydrochloric acid solution and saturated sodium chloride solution,
It is dry, light yellow viscous liquid is obtained after desolventizing, obtains weak yellow liquid after column chromatographs (petrol ether/ethyl acetate=20/1)
9.5g, yield 97%.
Embodiment 15
Synthesize (1R) trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane carboxylic acid
Acid esters；
2,3,4,5,6- five fluoro benzyl alcohol 4.5g (25mmol), pyridine 3g, n-hexane are added in the three-necked bottle of 100mL
(1R)-trans-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in 40mL
(30mmol) is reacted at room temperature 4 hours.Organic phase successively uses 5% sodium hydroxide solution, 5% hydrochloric acid solution and saturation chlorine of 20mL
Change sodium solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, after column chromatographs (petrol ether/ethyl acetate=20/1)
Obtain weak yellow liquid 9.4g, yield 94%.
Embodiment 16
(1R) trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane
Carboxylate；
In the three-necked bottle of 100mL be added 4- methyl -2,3,5,6- tetrafluorobenzyl alcohol 4.5g (25mmol), pyridine 3g, just oneself
(1R)-trans-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride 6g is slowly added dropwise in alkane 40mL
(30mmol) is reacted at room temperature 4 hours.Organic phase successively uses 5% sodium hydroxide solution, 5% hydrochloric acid solution and saturation chlorine of 20mL
Change sodium solution washing, it is dry, light yellow viscous liquid is obtained after desolventizing, after column chromatographs (petrol ether/ethyl acetate=20/1)
Obtain weak yellow liquid 9.3g, yield 96%.
Embodiment 17
About its readily degradable of ester type compound of the invention, the present inventor has done following experiment: using
Agilent6890/5975 type Gc/ms Analyser, in closed room (rooms of 3 about 15 square meters or so)
Cis-2 on point in 1-3 of the embodiment of the present invention, 3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropyl
Alkane carboxylate 20mL, cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound,
Cis-4- methyl -2,3,5,6- ptfe benzyls 2, phase made by 2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound
With the mosquito liquid of concentration；8 hours on continuity point, power-off stops kindling mosquito repellent incense, and measures the esters before and after the air in room
Close the concentration of object；Every mistake continued to measure the concentration of the ester type compound in room after 2 hours again；It configures above-mentioned when electric mosquito repellent liquid
The concentration of ester type compound is 0.6% or so；The electric mosquito repellent liquid consumed every night is 0.6g or so；Ester type compound therein contains
Amount is 0.036g or so, specific measurement such as following table；
When sampling, airtight test and traffic alignment are carried out to sampler, and open aspiration pump with 1.0L/min flow pumping
Gas 4-6min replaces the air of sampling system；It will with the silicone rubber tube of teflon hose or inner liner polytetrafluoroethylene film
Adsorption tube is connected to air sampler, in the flow velocity acquisition gaseous sample 20min to adsorption tube of 0.5mL/min, sampling is completed
Adsorption tube both ends open is sealed with pipe cap immediately afterwards；Enter the volatile organic matter of thermal desorption instrument cooperation GC/MS after the completion of sampling
Analysis；GC-MS instrument condition:
Chromatographic column: DB-1, the capillary chromatographic column of 30m × 0.25mm × 0.25 μm, carrier gas: helium, purity 99.999%,
Flow velocity 1mL/min；
Injector temperature: 270 DEG C, Splitless injecting samples；Flow divider, bypass flow 40mL/min, column temperature are opened after 1 minute
40 DEG C (keeping 2min), 230 DEG C (keeping 8min), column flow 10mL/min, ion source temperature 230 are risen to 20 DEG C/min
DEG C, level four bars temperature is 150 DEG C, and interface temperature is 270 DEG C.
Through detecting, air sample is taken twice before and after spraying the compound of the present invention, detects corresponding ester type compound
Amount it is as follows:
Passing through above data, it can be seen that the ester type compound in the present invention, degradation rate is higher, after 8 hours,
After its degradation rate has almost reached 50% or so, 10 hours, content is only 0.2mg/m3Left and right, after 12 hours, contains
Amount is only 0.1/m3Left and right.As it can be seen that its degradation rate of ester type compound of the invention is higher, residual is few.
Claims (10)
1. a kind of first chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, general structure such as following formula I:
Alternatively, being the stereoisomer of above formula；
Wherein R is-H ,-F ,-CH3,-CH2OCH3。
2. including at least more than one mixture of stereoisomer as described in claim 1.
3. a kind of first chlorine chrysanthemumic acid polyfluoro benzylalcohol pyrethroids class as described in any of claims 1, which is characterized in that the compound
Selected from any one of following:
Cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；
Trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
Trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane carboxylic acid
Acid esters；
(1R) cis-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) cis-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) cis-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) cis-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane
Carboxylate；
(1R) trans-2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) trans-2,3,4,5,6- pentafluorobenzyl 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropanecarboxylcompound；
(1R) trans-4- methyl -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane-carboxylic acid
Ester；
(1R) trans-4- methoxy -2,3,5,6- ptfe benzyls 2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropyl
Alkane carboxylate.
4. such as the preparation method of compound of any of claims 1-2, comprising the following steps:
The polyfluoro benzylalcohol that first chloro chrysanthemum acyl chlorides that structural formula is II and structural formula are III in the presence of organic base in solvent into
Row esterification；
5. the preparation method of compound as claimed in claim 4, it is characterised in that: first chloro chrysanthemum acyl chlorides rubs with polyfluoro benzylalcohol
, than being 0.8-1.5:1, reaction temperature is 0-35 DEG C for you.
6. the preparation method of compound as claimed in claim 4, it is characterised in that: 2,2- dimethyl -3- (2- Chloroallyl)
Cyclopropane dicarbonyl chloride, cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride, trans-2,2- dimethyl -3- (E/
Z-2- Chloroallyl, 1R-cis-2,2- dimethyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride or 1R-trans-2,2- bis-
Any one of methyl -3- (E/Z-2- Chloroallyl) cyclopropane dicarbonyl chloride and structural formula are the polyfluoro benzylalcohol of (III) in organic base
In the presence of esterification is carried out in solvent.
7. the preparation method of the compound as described in any one of claim 4-6, it is characterised in that: solvent is toluene, diformazan
Any one of benzene, hexamethylene, n-hexane；
Organic base is tertiary amine, such as any one of pyridine, triethylamine.
8. the compound or mixture as described in any one of claim 1-2 are being controlled or are being killed in Public Hygienic Prevention
Application in vector；
Preferably, the vector in Public Hygienic Prevention is any one of mosquito, cockroach or housefly.
9. application as claimed in claim 8, it is characterised in that: the insecticide that the compound comprising Formulas I is prepared into as raw medicine.
10. application as claimed in claim 8, it is characterised in that: insecticide includes coiled mosquito-repellent incense, electric mosquito repellent tablet, electric heating mosquito
Any one of fragrant liquid, insect aerosol, pulvis, granula, non-heated volatilization preparation, smoke preparation or poison bait.
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Application publication date: 20190521 |