CN109776368A - A kind of novel thiol pyrethroids chemical modification object and its preparation method and application - Google Patents
A kind of novel thiol pyrethroids chemical modification object and its preparation method and application Download PDFInfo
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- CN109776368A CN109776368A CN201910088511.6A CN201910088511A CN109776368A CN 109776368 A CN109776368 A CN 109776368A CN 201910088511 A CN201910088511 A CN 201910088511A CN 109776368 A CN109776368 A CN 109776368A
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Abstract
The invention discloses a kind of novel thiol pyrethroids chemical modification objects and its preparation method and application.The present invention mainly by transfluthrin an end position chlorine atom and ester group be transformed, one end position chlorine atom is substituted for trifluoromethyl to replace, in addition ester group is substituted for the structure of mercaptan ester group, form the novel thiol pyrethroids class compound structure of the structure containing mercaptan of a series of novel.These novel thiol pyrethroids chemical modification objects can be improved metabolic stability and reduce the toxicity of environment, and certain insecticidal effect is shown for larva, part mercaptan pyrethroids chemical modification object is to the insecticidal activity and Biphenthrin of adult mosquito substantially in the same concentration rank simultaneously, it shows effect exterminating mosquito similar with Biphenthrin, and can effectively solve existing pyrethroid insecticides drug resistance serious problem outstanding.In addition, the present invention has reaction process simple, reaction step is few, and the yield of synthesis is higher, and reaction time is short, the advantages such as reproducible.
Description
Technical field
The invention belongs to the technical field of pesticide of Medicine small molecule structural modification.More particularly, to a kind of novel thiol
Pyrethroids chemical modification object and its preparation method and application.
Background technique
The hygrothermal environment of summer to mosquito breeding and haunt and bring good condition.Mosquito as one of " four pests "
Bring great puzzlement to daily life, not only mosquito drone cry will influence people daily rest,
Working and learning, and people usually indoors or field be easy to by Adult female mosquito bite to skin, it is easy to draw
Red swelling of the skin is played, pain, which is itched, feels bad.Even more serious problem is that mosquito can propagate dengue fever, Japanese Type-B encephalitis, yellow fever, malaria
Up to more than the 80 kinds of diseases such as disease and filariasis.Therefore, mosquito eradication keeps away the important measures that mosquito is pre- mosquito-proof matchmaker's infectious disease, research and development one
The effective insecticide of money has the product of repelling effect to seem very necessary in summer.Such a product not only needs
It plays good mosquito eradication or mosquito repellent, while with greater need for being that harm for human body is small, being even safe from harm, for
Environment does not have long-term residual and any pollution.
Pyrethroid insecticides are the insecticide of a kind of biomimetic type synthesis, such as etrafluorine ethofenprox, can be used for mosquito
The prevention and treatment of worm harm, and have many advantages, such as high specificity, insecticidal activity height and the small preventing and controlling field in mosquito of toxic
In be widely used.Pyrethroid coumpound is initially to study chrysanthemum at United Kingdom National Research And Development Corp (NRDC)
Extract be found when there are natural insecticidal properties.The research team has synthesized the pyrethroid stable to light first
Compound, and chrysanthemum extract property before is unstable, just loses insecticidal activity after light-exposed.The pyrethroid of early stage synthesis
The racemic mixture that ester type compound is made of many isomers is not to all have insecticidal activity.Tradition
Viewpoint thinks, pyrethroid insecticides have bioactivity, low environment and the food residue degree, relatively of broad-spectrum high efficacy
Low mammalian toxicity.But more and more research discovery pyrethroids can interfere the normal function of organism, to the mankind
Sizable threat is caused with the health of animal.Some researches show that being exposed in the environment containing pyrethroid for a long time can be to people
The health of body especially children has an adverse effect.And as some traditional pyrethroid insectides are long-term a large amount of single
Use, the pests such as mosquitos and flies produce apparent drug resistance for pesticide, it is therefore desirable to a kind of raising metabolic stability and reduction
Environmental toxicity, new type structure pesticide compound.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the above-mentioned prior art and deficiencies, provide a kind of raising metabolism
Stability and reduction environmental toxicity, new type structure novel thiol pyrethroids chemical modification object.
It is a further object to provide a kind of preparation methods of novel thiol pyrethroids chemical modification object.
It is also another object of the present invention to provide above-mentioned mercaptan pyrethroids chemical modification object or use sulphur made from the above method
Alcohol pyrethroids chemical modification object as or application in terms of preparing insecticide.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of novel thiol pyrethroids chemical modification object, shown in structural formula such as following formula (I):
Wherein, R is to contain monosubstituted or polysubstituted aromatic ring class group.
Further, in preferred embodiments of the present invention, the aromatic ring class group is containing phenyl ring and/or thiphene ring
Aromatic ring class group, or be the aromatic ring class group containing furan nucleus.
Further, in preferred embodiments of the present invention, R is-CH3、F、Cl、-CH3O or-CF3。
Further, in preferred embodiments of the present invention, the aromatic ring class group is
The present invention mainly by transfluthrin an end position chlorine atom and ester group be transformed, by end position
Chlorine atom is substituted for trifluoromethyl substitution, and in addition ester group is substituted for the structure of mercaptan ester group, form the sulfur-bearing of a series of novel
The novel thiol pyrethroids class compound structure of alcohol structure.These new compounds can be improved metabolic stability and reduce environment
Toxicity, and certain insecticidal effect is shown for larva, at the same have part novel thiol pyrethroids chemical modification object at
The insecticidal activity of mosquito and complicated Biphenthrin show kill similar with Biphenthrin substantially in the same concentration rank
Worm effect, this class formation have excellent transformation potential.
The invention further relates to the preparation methods of novel thiol pyrethroids chemical modification object, comprising the following steps:
S1. in protective gas atmosphere, super dry dichloromethane solvent is added into lanbda-cyhalothric acid, at room temperature,
After stirring and dissolving, ethanedioly chloride is added, after stirring 30~35min at room temperature, n,N-Dimethylformamide is added, in room
Temperature stirring is lower to react 0.8~1h；
S2. product is dried under vacuum conditions, and super dry dichloromethane solvent is added in protective gas atmosphere, in room
Under the conditions of temperature after stirring and dissolving, anhydrous pyridine is added, after being stirred to react 25~30min, adds cyclic annular methyl mercaptan, is esterified
React 2~3h；
S3. crude product is obtained by washing extraction drying after completion of the reaction, then is purified by silica gel column chromatography, can obtained
To novel thiol pyrethroids chemical modification object.
Further, in preferred embodiments of the present invention, in step S1, the object of the lanbda-cyhalothric acid and ethanedioly chloride
The amount ratio of matter is 1:2~4.
Further, in preferred embodiments of the present invention, in step S2, the substance of lanbda-cyhalothric acid and anhydrous pyridine
The ratio of amount is 1:1~2；The mass ratio of the material example of lanbda-cyhalothric acid and ring class methyl mercaptan is 1:1~2.
Further, in preferred embodiments of the present invention, the ring class methyl mercaptan is selected to methyl beneze methane thiol, to chlorine
Beneze methane thiol, 2- furans methyl mercaptan, 3- trifluoromethyl benzyl mercaptan, 4- fluorine benzyl mercaptan, 2- chloro benzyl mercaptan, 4- methoxybenzyl mercaptan,
The rings class mercaptan such as benzyl mercaptan or 2- thiophene methyl mercaptan.
Further, in preferred embodiments of the present invention, the additional amount of the n,N-Dimethylformamide is 0.1mL.
Further, in preferred embodiments of the present invention, the protective gas is nitrogen.
Above-mentioned novel benzyl mercaptan pyrethroids chemical modification object or the novel thiol pyrethroids chemistry being prepared using the above method
Modifier is preparing the application in insecticide, also within protection scope of the present invention.
Novel thiol pyrethroids chemical modification object of the present invention prepare anti-mosquito, mosquito repellent, prevention and/or malaria control,
It has a good application prospect in drug in terms of the diseases such as encephalitis B, yellow fever, malaria and filariasis.In addition, described new
Type mercaptan pyrethroids chemical modification object can also be applied in pesticide chemicals and/or daily hygiene.
Further, in preferred embodiments of the present invention, the insecticide is anti-mosquito or culicifuge.
Further, in preferred embodiments of the present invention, the mosquito in the mosquito eradication or culicifuge is aedes albopictus
And/or Culex quinquefasciatus.
Compared with prior art, the invention has the following advantages:
(1) present invention is chemically modified the structure of methothrin, obtains a series of new mercaptan pyrethroids chemical modification
Object, these new compounds show certain insecticidal activity, and can be improved metabolic stability and reduce environmental toxicity, can
To be widely used in the field application of desinsection mosquito eradication, new safe and efficient, stable compound is provided for desinsection, is effectively solved
Certainly drug resistance problems.
(2) present invention has reaction process simple, and reaction step is few, and the yield of synthesis is higher, and reaction time is short, repeated
The advantages such as good, have a good application prospect and wide development space in pesticide field.
Detailed description of the invention
Fig. 1 is desinsection mosquito eradication kinetic test result of the analyte derivative object to female adult mosquito of the embodiment of the present invention 5.
Fig. 2 is the oxidation stability of mercaptan pyrethroids derivative L CA-COS-01 and transfluthrin.
Fig. 3 is drug to Aedes Albopictus Larva treated resemblance；Wherein, a figure is that 1 instar larvae is normally cultivated
For 24 hours, b figure be drug LCA-COS-05 processing 1 instar larvae for 24 hours.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Unless
It illustrates, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
The preparation of 1 novel thiol pyrethroids chemical modification object (LCA-COS-01) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-01), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and be stirred to react 30min, be eventually adding doubling dose to methyl beneze methane thiol 227mg (1.645mmol),
Under room temperature under nitrogen protective condition, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-01, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-01, colorless and transparent thick liquid, Rf=0.45 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 75%.
2, result
(1) compound L CA-COS-01, shown in molecular structural formula such as formula (1):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.16 (d, J=8.1Hz, 2H), 7.11 (d, J=7.9Hz, 2H), 6.97-6.88 (m,
1H), 4.17-4.05 (m, 2H), 2.31 (d, J=12.5Hz, 5H), 1.30 (d, J=7.2Hz, 6H)13C NMR(101MHz,
CDCl3)δ194.14,137.06,134.29,129.66,129.37,128.65,122.02,119.07,41.69,33.79,
33.43,31.34,28.33,21.09,14.86. high resolution mass spectrum HRMS (APCI): C17H18ClF3OSNa(385.06112)[M+
Na]+=385.06113.
The preparation of 2 novel thiol pyrethroids chemical modification object (LCA-COS-02) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-02), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and be stirred to react 30min, be eventually adding doubling dose to chlorobenzene methyl mercaptan 205mg (1.645mmol), in room
Under the conditions of warm nitrogen protection, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-02, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-02, colorless and transparent thick liquid, Rf=0.48 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 70%.
2, result
(1) compound L CA-COS-02, shown in molecular structural formula such as formula (2):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.26-7.22 (m, 2H), 7.22-7.14 (m, 2H), 6.88 (d, J=8.3Hz, 1H),
4.13-4.01 (m, 2H), 2.34-2.25 (m, 2H), 1.28 (d, J=14.4Hz, 6H)13C NMR(101MHz,CDCl3)δ
193.91,136.26,133.32,130.26,129.63,128.94,122.35,119.18,41.83,34.04,33.10,
31.64,28.44,14.98. high resolution mass spectrum HRMS (APCI): C16H16Cl2F3OSNa(383.02455)[M+H]+=
383.02396。
The preparation of 3 novel thiol pyrethroids chemical modification object (LCA-COS-03) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-03), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) product of previous step reaction activation in the round-bottomed flask after reaction 1h is done in vacuum revolving evaporimeter revolving
It is dry, and reduce outside air as far as possible in operation and enter in round-bottomed flask, protection gas then is done with nitrogen, is added super dry
Dichloromethane solvent is placed on blender after stirring and dissolving at room temperature, is subsequently added into the anhydrous pyridine of doubling dose
0.133mL (1.645mmol), and it is stirred to react 30min, it is eventually adding the 2- furans methyl mercaptan 187mg of doubling dose
(1.645mmol) is stirred to react 2h under room temperature under nitrogen protective condition；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-03, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-03, colorless and transparent thick liquid, Rf=0.42 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 72%.
2, result
(1) compound L CA-COS-03, shown in molecular structural formula such as formula (3):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.32 (dd, J=1.9,0.9Hz, 1H), 6.90 (d, J=8.5Hz, 1H), 6.29
(dd, J=3.3,1.9Hz, 1H), 6.20 (d, J=3.2Hz, 1H), 4.22-4.09 (m, 2H), 2.35-2.25 (m, 2H), 1.31
(s,3H),1.28(s,3H).13C NMR(101MHz,CDCl3)δ193.44,150.32,142.22,129.50,122.17,
119.03,110.63,107.93,41.72,33.90,31.49,28.29,26.11,14.84 high resolution mass spectrum HRMS
(APCI):C14H15ClF3O2SNa(339.04279)[M+H]+=339.04285.
The preparation of 4 novel thiol pyrethroids chemical modification object (LCA-COS-04) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-04), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the 3- trifluoromethyl benzyl mercaptan 316mg (1.645mmol) of doubling dose,
Under room temperature under nitrogen protective condition, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-04, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-04, colorless and transparent thick liquid, Rf=0.43 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 70%.
2, result
(1) compound L CA-COS-04, shown in molecular structural formula such as formula (4):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.57-7.48 (m, 2H), 7.43 (dt, J=15.2,7.7Hz, 2H), 6.93-6.85
(m, 1H), 4.16 (q, J=14.1Hz, 2H), 2.38-2.27 (m, 2H), 1.32 (s, 3H), 1.28 (s, 3H)13C NMR
(101MHz,CDCl3)δ193.58,138.72,132.13,131.02,129.38,129.10,125.52,124.15,
122.44,121.81,119.02,41.69,33.99,33.12,31.61,28.27,14.77 high resolution mass spectrum HRMS
(APCI):C17H16ClF6OS(417.05090)[M+H]+=417.05096.
The preparation of 5 novel thiol pyrethroids chemical modification object (LCA-COS-05) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-05), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the 4- fluorine benzyl mercaptan 316mg (1.645mmol) of doubling dose, in room temperature
Under the conditions of nitrogen protection, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-05, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-05, colorless and transparent thick liquid, Rf=0.45 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 65%.
2, result
(1) compound L CA-COS-05, shown in molecular structural formula such as formula (5):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.24 (dd, J=8.5,5.4Hz, 2H), 6.98 (t, J=8.6Hz, 2H), 6.93-
6.87 (m, 1H), 4.10 (d, J=5.0Hz, 2H), 2.31 (d, J=8.2Hz, 2H), 1.31 (s, 3H), 1.28 (s, 3H)13C
NMR(101MHz,CDCl3)δ194.04,162.18,133.45,130.56,130.48,129.69,121.89,120.745,
115.76,115.54,41.83,34.00,33.05,31.58,28.43,14.97. high resolution mass spectrum HRMS (APCI):
C16H16ClF4OS(367.05410)[M+H]+=367.05423.
The preparation of 6 novel thiol pyrethroids chemical modification object (LCA-COS-06) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-06), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the 2- chloro benzyl mercaptan 261mg (1.645mmol) of doubling dose, in room temperature
Under the conditions of nitrogen protection, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-06, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-06, colorless and transparent thick liquid, Rf=0.45 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 68%.
2, result
(1) compound L CA-COS-06, shown in molecular structural formula such as formula (6):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.40 (dt, J=7.5,3.9Hz, 1H), 7.36 (dt, J=7.4,3.7Hz, 1H),
7.21 (td, J=5.8,2.7Hz, 2H), 6.96-6.87 (m, 1H), 4.32-4.17 (m, 2H), 2.31 (d, J=7.5Hz, 2H),
1.30(s,3H),1.28(s,3H).13C NMR(101MHz,CDCl3)δ193.92,135.47,134.21,131.17,
129.70,128.99,127.19,121.87,120.71,41.82,34.00,31.70,31. 59,28.42,14.96. high-resolution
Mass spectrum HRMS (APCI): C16H16Cl2F3OS(383.02455)[M+H]+=383.02478.
The preparation of 7 novel thiol pyrethroids chemical modification object (LCA-COS-07) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-07), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the 4- methoxybenzyl mercaptan 254mg (1.645mmol) of doubling dose,
Under room temperature under nitrogen protective condition, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-07, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-07, colorless and transparent thick liquid, Rf=0.45 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 66%.
2, result
(1) compound L CA-COS-07, shown in molecular structural formula such as formula (7):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR(400MHz,Chloroform-d)δ7.22–7.14(m,2H),6.96–6.89(m,1H),6.87–6.79(m,2H),
4.15–4.04(m,2H),3.79(s,3H),2.34–2.26(m,2H),1.31(s,3H),1.29(s,3H).13C NMR
(101MHz,CDCl3)δ194.22,158.88,129.90,129.68,129.37,121,71,1200.54,114.09,
55.26,41.71,33.78,33.19,31.32,28.31,14.85. high resolution mass spectrum HRMS (APCI): C17H18ClF3O2SK
(417.02997)[M+K]+=417.02961.
The preparation of 8 novel thiol pyrethroids chemical modification object (LCA-COS-08) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-08), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the benzyl mercaptan 204mg (1.645mmol) of doubling dose, in room temperature under nitrogen
Under protective condition, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-08, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-08, colorless and transparent thick liquid, Rf=0.48 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 72%.
2, result
(1) compound L CA-COS-08, shown in molecular structural formula such as formula (8):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR(400MHz,Chloroform-d)δ7.38–7.32(m,1H),7.32–7.26(m,4H),7.00–6.90(m,1H),
4.24–4.09(m,2H),2.38–2.29(m,2H),1.34(s,3H),1.31(s,3H).13C NMR(101MHz,CDCl3)δ
194.03,137.39,129.62,128.77,128.68,127.33,121.73,120.56,41.69,33.83,33.67,
31.40,28.32,14.86. high resolution mass spectrum HRMS (APCI): C16H17ClF3OS(349.06352)[M+H]+=
349.06354。
The preparation of 9 novel thiol pyrethroids chemical modification object (LCA-COS-09) of embodiment
1, the preparation of novel thiol pyrethroids chemical modification object (LCA-COS-09), comprising the following steps:
(1) lanbda-cyhalothric acid of 200mg (0.824mmol) is weighed first in the round-bottomed flask of 50mL, in nitrogen protection
Under conditions of, with syringe measure the super dry anhydrous methylene chloride of 15mL in flask and stirring make it completely dissolved after, then
Ethanedioly chloride 0.210mL (2.473mmol), the stir about 30min of triplication is added, 0.1mL then is added with the syringe of 1mL
Anhydrous grade n,N-Dimethylformamide (DMF), reaction can generate a large amount of bubble, then react 1h at room temperature；
(2) it will react in the round-bottomed flask after 1h and react the product of activation in vacuum revolving evaporimeter revolving drying, and
Outside air is reduced in operating process as far as possible to enter in round-bottomed flask, then does protection gas with nitrogen, super dry dichloromethane is added
Alkane solvents are placed on blender after stirring and dissolving at room temperature, are subsequently added into the anhydrous pyridine 0.133mL of doubling dose
(1.645mmol), and it is stirred to react 30min, it is eventually adding the 2- thiophene methyl mercaptan 214mg (1.645mmol) of doubling dose, in room
Under the conditions of warm nitrogen protection, it is stirred to react 2h；
(3) reaction end (solvent: petroleum ether: ethyl acetate=50:1) is detected with TLC, it is dry etc. by washing extraction
Step obtains the crude product of compound L CA-COS-09, by silica gel column chromatography purifying (eluant, eluent: petroleum ether: ethyl acetate=
100:1) obtain compound L CA-COS-09, colorless and transparent thick liquid, Rf=0.45 (solvent: petroleum ether: ethyl acetate=
50:1), yield: 70%.
2, result
(1) compound L CA-COS-09, shown in molecular structural formula such as formula (9):
(2) pass through nuclear magnetic resonance1H NMR、13C NMR analysis, high resolution mass spectrum and fusing point etc. carry out Structural Identification.1H
NMR (400MHz, Chloroform-d) δ 7.18 (dd, J=5.1,1.3Hz, 1H), 6.98-6.87 (m, 3H), 4.34 (q, J=
14.7Hz,2H),2.37–2.25(m,2H),1.32(s,3H),1.30(s,3H).13C NMR(151MHz,CDCl3)δ193.78,
140.09,129.68,126.96,126.74,125.37,122.05,121.41,41.82,34.07,31.70,28.39,
28.32,14.98. high resolution mass spectrum HRMS (APCI): C14H15ClF3OS2(355.01995)[M+H]+=355.01993.
10 larva desinsection mosquito eradication active testing of embodiment
Aedes albopictus children mosquito (Aedes has been carried out using 24 well plate methods come compound of the measuring method to Examples 1 to 9
Albopictus larva) insecticidal activity test.
The test of larva half lethal concentration: this experiment pass through sterile 24 orifice plate to novel thiol pyrethroids and its chemical modification object into
The active testing gone to Aedes Albopictus Larva half lethal concentration.
Experiment obtains the sample after being diluted of 12 gradients using acetone (Aceton) solvent using doubling dilution first
Product compound, 985 μ L are then added into each orifice plate with liquid-transfering gun goes chlorine water and the food solns (fish of 13mg/mL of 5 μ L
Powdered food solution), and the larva (5~10) of 5 or more 1 ages is added into each orifice plate.It is added into each orifice plate
The sample compound of 8 concentration gradients of 10 μ L, each sample concentration is in parallel in triplicate；It is placed on 26~28 DEG C of room temperature condition
After lower culture for 24 hours, the death rate or lethality of each orifice plate are recorded.And all novel thiol pyrethroids derivatives are counted to 1
The semilethal rate LC of instar larvae50Value, statistical result see the table below 1.
1 novel thiol pyrethroids derivative of table tests the killing activity of 1 instar larvae of mosquito
Note: every group of experiment is repeated 3 times, and data indicate average value (n=3) ± standard deviation in table.LC50It is dense for median lethal
Degree.Mosquito selection is the aedes albopictus of sensitive strain, and it is 01~No. 09 that compound number, which can simplify,.The dead larvae of blank group
Rate is within 5%.
Carry out measuring method by using 24 well plate methods and aedes albopictus children mosquito (Aedes has been carried out to Examples 1 to 9
Albopictus larva) insecticidal activity test result illustrate, novel thiol pyrethroids derivant structure pair of the invention
There is killing effect in the larva of aedes albopictus, especially 05,06 and 08 3 group of derivative of embodiment shows to have larva
Excellent insecticidal activity, the i.e. structure of part ortho position substitution in novel thiol pyrethroids derivative phenyl ring have Aedes Albopictus Larva
There is highly effective insecticidal effect.
11 adult mosquito desinsection mosquito eradication active testing of embodiment
Aedes albopictus female adult mosquito has been carried out to the compound of Examples 1 to 9 using CDC bottle bioassay experiment
The insecticidal activity of (Aedes albopictus female adult mosquito) is tested.Novel thiol pyrethroids derivative is to female
Property adult mosquito insecticidal activity experiment test and result it is as shown in table 2 below.Table 3 indicates two positive group Biphenthrins and phenyl tetrafluoride chrysanthemum
Ester tests the insecticidal activity of female adult mosquito.The adult mosquito death rate general control of blank group is within 2%.
The active testing of female adult mosquito: carrying out in female adult mosquito experiment, by it is all go out pupas after adult mosquito with 10% syrup
With dechlorination Aquaponic 3~5 days or so, it is then blood sucking using female adult mosquito and then isolate female mosquito.Adult mosquito experiment uses
Standard CD C bottle bioassay (contact method), experiment are obtained using acetone (Aceton) solvent using doubling dilution first
Sample compound after to being diluted of 10 gradients, then each sample compound does high, normal, basic 3 groups of different concentration, each
Concentration is repeated 3 times in parallel, and the sample solution of 1mL is added into each favour bottle, is uniformly coated on the inner bottle of entire favour bottle
On wall, placement is protected from light dry 2~3h in ventilating and cooling place or so, after it is completely dried, is added 15~25 into each favour bottle
Only or above female adult mosquito, every the The dead quantity of 15 minutes record mosquitoes, and it is derivative finally to count novel thiol pyrethroids
Object is shown in Table 2 and table 3 to the lethality in different time periods of female adult mosquito 30min, 60min and 120min etc. 3, statistical result.
2 novel thiol pyrethroids derivative of table tests female adult mosquito using CDC bottle bioassay
Note: every group of experiment is repeated 3 times, and data indicate average value (n=3) ± standard deviation in table.μ g/bottle indicates every
Additional amount in a favour bottle.Then the high, normal, basic three different concentration of 1600,200 and 12.5 μ g/bottle of every group of sample is simultaneously
Count the lethality of respective concentration and corresponding time point.
The positive group of table 3 tests the CDC bottle bioassay of aedes albopictus female adult mosquito
Note: every group of experiment is repeated 3 times, and data indicate average value (n=3) ± standard deviation in table.μ g/bottle indicates every
Additional amount in a favour bottle.Then Biphenthrin and transfluthrin is taken to take 1600,12.5 and 1.56 μ g/ as a control group
The high, normal, basic three different concentration of bottle and the lethality for counting respective concentration and corresponding time point.
Aedes albopictus female adult mosquito (Aedes has been carried out by using CDC bottle bioassay experiment
Albopictus female adult mosquito) insecticidal activity test and result illustrate that novel thiol pyrethroids is derivative
Object still has quite excellent killing activity to female adult mosquito under the low consistency conditions of 12.5 μ g/bottle, and with the time
Passage, the effect of desinsection also gradually increases.And it can be in compared with two positive controls close to identical rank.It should
Mercaptan pyrethroids analog derivative structure has structure simple, and it is convenient easy to synthesize, the advantages such as synthesis cost is cheap.
The experiment of 12 adult mosquito desinsection mosquito eradication kinetic test of embodiment
According to 5 adult mosquito desinsection mosquito eradication active testing of embodiment as a result, choosing the sample of the best embodiment 5 of effect exterminating mosquito
Derivative carries out dynamic experiment test with the compound of 4 various concentration gradients, and all operations are identical as embodiment 11,
Survival/The dead quantity of female adult mosquito inside favour bottle was surveyed at interval of 15 minutes, and finally made the cause at corresponding time point
Dead rate, follow-on test 120 minutes.And by calculating and counting, the curve of the death rate of female adult mosquito at any time such as Fig. 1 is drawn out
It is shown.
It is as shown in Figure 1 to female adult mosquito desinsection mosquito eradication kinetic test experimental result to obtain No. 05 derivative.It can by Fig. 1
Know, such novel thiol pyrethroids LCA-COS-05 sample has excellent desinsection mosquito eradication activity to female adult mosquito, and with sample
The increase of product concentration, insecticidal activity gradually increase.In addition over time, under conditions of same concentration, female adult mosquito
The death rate is also to gradually increase, and is shown over time, novel thiol pyrethroids derivative of the invention to female at
The desinsection mosquito eradication activity of mosquito is enhancing.To sum up it can be concluded that, novel thiol pyrethroids chemical modification object of the invention is to larva
Toxicity is lower, but more excellent for the insecticidal activity of adult mosquito, substantially can be with positive group in rank relatively.
The test of 13 metabolic stability of embodiment
1, the test method of oxidation of drug stability
Any LCA-COS-01 number chosen in thiol synthesis pyrethroids derivative is a, and chooses transfluthrin
It is b as standard control group #；20mg is respectively weighed, is dissolved in the methanol solvate of 2mL, stirring 15min dissolves it sufficiently；
Then the oxydol H of 200 μ L 30% is respectively taken with liquid-transfering gun2O2, and start, 60min after stopping meter primary every 15min timing
When, it is c that blank control group, which is dissolved in number in the methanol solvate of 2mL with LCA-COS-01,.With the stability of TLC detection compound
Then the sample of three groups of tests of number a, b and c is carried out TLC detectionization by (solvent: petroleum ether: ethyl acetate=50:1)
Close the stability contrast of object.
2, result
Experiment discovery, as shown in Fig. 2, when sample LCA-COS-01 is dissolved in 2mL methanol, when the hydrogen peroxide of 200 μ L is added,
LCA-COS-01 will generate a large amount of white bubble immediately, and transfluthrin control group generates micro white bubble, still
After 15min hydrogen peroxide oxidation, when using TLC plate contact plate (solvent: petroleum ether: ethyl acetate=50:1), blank
Control group c group is held essentially constant, and is a unique point, is Rf=0.45；At this point, being substantially not visible in a group contact plate original
Raw material point, i.e. the LCA-COS-01 of a group is all oxidized and disappears；B group point plate sample, which has raw material point also, other impurity
Point illustrates transfluthrin control group by hydrogen peroxide partial oxidation；Measurement is primary again after 60min, and effect is surveyed with 15min substantially
That tries is consistent.
For synthesis, the oxidation stability of transfluthrin is better than mercaptan pyrethroids；Simultaneously according to embodiment 10 and implementation
It can be concluded that, mercaptan pyrethroids may be worse than Biphenthrin and phenyl tetrafluoride chrysanthemum in larva insecticidal activity in anti-mosquito activity in example 11
The positive controls of ester, but in adult mosquito activity, capable of reaching identical grade substantially, (this also embodies the system of its effect not
Together, cause out function and effect it is different), illustrate that mercaptan pyrethroids chemical modification object of the invention more tends to living to the desinsection of adult mosquito
Property, there is good killing effect to adult mosquito in practical applications, practical application promotional value is high.
14 cytotoxicity Pretreatment Test of embodiment
1, detection method for cytotoxicity of gas-liquid
Cell (selecting human liver cancer cell model HepG2) is inoculated into the cell density of 3000 cells/every hole, 80 μ L
In 96 orifice plates.After inoculation 24 hours, 20 μ L transfluthrins and LCA-COS-05 compound solution is added, and (sample concentration is
100μg/mL).The test cell activity after compound is handled 48 hours.Staurosporicae (MCE) is used as interior in plate
Portion's control group after incubation, the MTT (5mg/mL, Yeasen) in 10 holes μ L/ is added into each hole of cell plates, cell plates are existed
37 DEG C of incubation 4h.Discard the supernatant of cell liquid plate, and to the aerial DMSO that 120 holes μ L/ are added of each of cell plates.Shake hole
Plate 10min, with Envision (PekinElmer), absorbing wavelength is that 570nm is measured OD value.
2, result
Experiment discovery, which can normally grow substantially in 96 orifice plates, and sample LCA-COS-05 chemical combination
Object is smaller to the toxic of HepG2；Its cell survival can be higher, survival of the sample LCA-COS-05 compound to the cell model
Rate is 85% or more.Illustrate that mercaptan pyrethroids chemical modification object of the invention can reduce environmental toxicity, can be widely applied to kill
In the field application of worm mosquito eradication, new safe and efficient, stable compound is provided for desinsection.
15 drug of embodiment tests preliminary experiment to aedes albopictus resistance activity
1, the drug resistance test method of mosquito
Biphenthrin processing: make (150 μ L) using the positive group Biphenthrin of 1mg/mL and act in 300mL aqueous solution
The larva processing 15min or so (0.5mg/L) of 3 ages, then filters out larva, is put into and fresh goes in chlorine water to be trained
It supports, the death rate 50%~60% or so, cultivated by the larva of remaining survival.To must turn out come female adult mosquito by using
CDC bottle bioassay experiment has carried out aedes albopictus female adult mosquito (Aedes albopictus female adult
Mosquito insecticidal activity test)；The female adult mosquito with Biphenthrin resistance is carried out using the method for embodiment 11
Test the drug resistance to drug.Selection Biphenthrin and sample sets LCA-COS-05 are tested, and the concentration of simultaneous selection
Concentration for 100 μ g/bottle is tested.
2, result
Discovery is tested after testing 120min, the lethality of mercaptan pyrethroids LCA-COS-05 medicine group antagonism adult mosquito is 90%
More than, the death rate is very high；However the Biphenthrin of the concentration to the lethality of the female adult mosquito with anti-medicine 5% with
Interior, the death rate is very low.Illustrate that mercaptan pyrethroids LCA-COS-05 sample is turned out the drug resistance mosquito come to such and still had
There is efficient insecticidal activity, but under equal conditions, Biphenthrin has the drug resistance of height to the female adult mosquito of such anti-medicine.
Illustrate that mercaptan pyrethroids chemical modification object of the invention can effectively solve the problems, such as existing pyrethroid insecticides drug resistance.
16 drug of embodiment is to Aedes Albopictus Larva treated resemblance
1, method
One group of concentration (taking 2 μm of ol/mL) is chosen in medicine group LCA-COS-05 mercaptan pyrethroids chemical modification object to 1 age children
Worm test toxicity for 24 hours after (using the method for embodiment 10), amplify 20 times by fluorescence microscope, and take pictures and observe larva
Growth and lifestyle, it is seen that the larva growthform after drug effect.
2, result
From figure 3, it can be seen that the larva figure that acetone blank control group is added is normal, vegetative activity is very active, but
It is the phenomenon that larva after the effect of drug LCA-COS-05 mercaptan pyrethroids chemical modification object will appear teratogenesis, larva body is long to be become
It is short, and the big lower part of the body of head is small, deformity, vegetative activity is low, and in the aqueous phase system of growth, activity is more slack.Illustrate of the invention
Mercaptan pyrethroids chemical modification object has the function of certain lethal or teratogenesis to larva, can be widely applied to desinsection mosquito eradication neck
Domain.
The preferred embodiment that the above specific embodiment is of the invention for ease of understanding and illustrates, but the invention is not limited to
Above-described embodiment does not mean that the present invention must rely on above-described embodiment and could implement.Person of ordinary skill in the field
It is the addition of equivalence replacement and auxiliary element to raw material selected by the present invention, specific it will be clearly understood that any improvement in the present invention
The selection etc. of mode, all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of novel thiol pyrethroids chemical modification object, which is characterized in that shown in the following formula (I) of its structural formula:
,
Wherein, R is to contain monosubstituted or polysubstituted aromatic ring class group.
2. novel thiol pyrethroids chemical modification object according to claim 1, which is characterized in that the aromatic ring class group be containing
There is the aromatic ring class group of phenyl ring and/or thiphene ring, or is the aromatic ring class group containing furan nucleus.
3. novel thiol pyrethroids chemical modification object according to claim 1, which is characterized in that R is-CH3、F、Cl、-CH3O
Or-CF3。
4. novel thiol pyrethroids chemical modification object according to claim 1, which is characterized in that the aromatic ring class group is、、、、、、、Or。
5. a kind of preparation method of novel thiol pyrethroids chemical modification object, which comprises the following steps:
S1. in protective gas atmosphere, super dry dichloromethane solvent is added into lanbda-cyhalothric acid, at room temperature, stirring
After dissolution, ethanedioly chloride is added, after stirring 30~35 min at room temperature, n,N-Dimethylformamide is added, in room temperature
Stirring is lower to react 0.8~1 h；
S2. product is dried under vacuum conditions, and super dry dichloromethane solvent is added in protective gas atmosphere, in room temperature
Under the conditions of after stirring and dissolving, anhydrous pyridine is added, after being stirred to react 25~30 min, adds cyclic annular methyl mercaptan, is esterified
React 2~3 h；
S3. crude product is obtained by washing extraction drying after completion of the reaction, then is purified by silica gel column chromatography, can be obtained new
Type mercaptan pyrethroids chemical modification object.
6. preparation method according to claim 5, which is characterized in that in step S1, the lanbda-cyhalothric acid and oxalyl
The mass ratio of the material of chlorine is 1:2~4.
7. preparation method according to claim 5, which is characterized in that in step S2, lanbda-cyhalothric acid and anhydrous pyridine
The ratio of the amount of substance is 1:1~2；The mass ratio of the material example of lanbda-cyhalothric acid and ring class methyl mercaptan is 1:1~2.
8. the Claims 1 to 4 any novel benzyl mercaptan pyrethroids chemical modification object or any side of claim 5~7
The novel thiol pyrethroids chemical modification object that method is prepared as or prepare application in insecticide.
9. application according to claim 8, which is characterized in that the insecticide is anti-mosquito or culicifuge.
10. application according to claim 9, which is characterized in that the mosquito in the mosquito eradication or culicifuge is aedes albopictus
And/or Culex quinquefasciatus.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2025951A (en) * | 1978-06-26 | 1980-01-30 | Ciba Geigy Ag | Dihalovinylcyclopropanethiolic acid esters and their use in pest control |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| US4486355A (en) * | 1979-02-14 | 1984-12-04 | Imperial Chemical Industries Plc | Halogenated benzyl alcohols and halides |
| CN86108309A (en) * | 1985-11-08 | 1987-06-17 | 纳慕尔杜邦公司 | The phenoxypyridines base ester and the intermediate thereof that are used for desinsection and kill mite |
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2019
- 2019-01-18 CN CN201910088511.6A patent/CN109776368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2025951A (en) * | 1978-06-26 | 1980-01-30 | Ciba Geigy Ag | Dihalovinylcyclopropanethiolic acid esters and their use in pest control |
| US4486355A (en) * | 1979-02-14 | 1984-12-04 | Imperial Chemical Industries Plc | Halogenated benzyl alcohols and halides |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| CN86108309A (en) * | 1985-11-08 | 1987-06-17 | 纳慕尔杜邦公司 | The phenoxypyridines base ester and the intermediate thereof that are used for desinsection and kill mite |
Non-Patent Citations (1)
| Title |
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| HUAZHANG HUANG 等: "Development of Pyrethroid Substrates for Esterases Associated with Pyrethroid Resistance in the Tobacco Budworm, Heliothis virescens (F.)", 《J.AGRIC.FOOD CHEM.》 * |
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