CN110078593A - A kind of synthetic method of sex pheromone of carpocapsa pomonella - Google Patents
A kind of synthetic method of sex pheromone of carpocapsa pomonella Download PDFInfo
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- CN110078593A CN110078593A CN201910194423.4A CN201910194423A CN110078593A CN 110078593 A CN110078593 A CN 110078593A CN 201910194423 A CN201910194423 A CN 201910194423A CN 110078593 A CN110078593 A CN 110078593A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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Abstract
The present invention relates to a kind of synthetic method of sex pheromone of carpocapsa pomonella, include the following steps: that methanol is added using sorbic acid methyl esters as raw material in (1), and intermediate A sorb base alcohol is obtained by 5% palladium carbon catalytic hydrogenating reduction；(2) the pure and mild acetic anhydride of intermediate A sorb base obtained in (1) is obtained into intermediate B sorb yl acetate in ethyl acetate, triethylamine and underwater reaction；(3) 6- Mecoral ethyl acetate and in the presence of triethylamine and trim,ethylchlorosilane reaction in toluene, after reaction, adds water, stirs, layering obtains intermediate C6- Mecoral trimethylsilyl ester；(4) intermediate B sorb yl acetate and intermediate C6- Mecoral trimethylsilyl ester react in toluene solution with sodium sand, and water and sulfuric acid, layering is then added dropwise, and rectifying obtains target product E8,12 carbon diene -1- alcohol of E10-.The present invention has the advantages that the present invention is short using be easy to get Material synthesis, reaction route and can be improved selectivity and product yield.
Description
Technical field
The present invention relates to the field of chemical synthesis, in particular to a kind of synthetic method of sex pheromone of carpocapsa pomonella.
Background technique
Insect sex pheromone is a certain gender individual secretion by insect in external, by the receptor institute of anisotropic individual of the same race
Receive, and anisotropic individual is caused to generate the trace level chemical substance that certain reproductive behavio(u)r is reacted.In the world, insects letter is utilized
The monitoring of breath element and isotropic prevention and treatment diseases and pests of agronomic crop have become a kind of practical and widely applied pest management technique.
Carpocapsa pononella (Laspey resia pom onella) belongs to Lepidoptera, steinernema section, adaptable wide, breeding
The features such as power is strong, harm is serious, difficulty of prevention and cure is big, belongs to China's one kind quarantine harmful organisms, and the most serious in the world
Eat into one of fruit pest.Chemical pesticide is mainly also to rely on for the basic means of prevention of pest in agricultural production at present, but
It is to bring many side effects using pesticide without limit for a long time, the generation of pest resistance to insecticide causes dosage and Drug level
It is continuously increased, cost improves year by year, and prevention and treatment is increasingly difficult；The ecological balance is destroyed, while pest control, a large amount of natural enemies are killed
Wound, causes the wildness of secondary property pest to cause harm；And pollution environment, a large amount of pesticide residues are in crops, soil and rivers,lakes and seas
In, it is enriched in human body further through the form of food chain, the mankind are caused to endanger again.Therefore, at present both at home and abroad in relation to research department
For door in new way, the new technology for making great efforts exploration and research control of insect, these researchs include: novel, efficient, less toxic, low residual
The development of the chemical insecticide stayed；The utilization of natural enemy insect and microbial pesticide；The application of insect sterilisation technology and insect hormone；
Wherein, using insect hormone, the pass of people is just being increasingly subject in particular with the research that insect sex pheromone carries out control of insect
Note and attention.
12 carbon diene -1- alcohol of E8, E10-, molecular formula: C12H22O, molecular weight: 182.3, No. CAS: 33956-49-9, it should
Substance have many advantages, such as in terms of preventing carpocapsa pononella specificity it is strong, it is efficient, pollution-free, do not hurt beneficial insect, fruit noresidue.At present
Corps diseases largely have been prevented and treated using insect sex pheromone in European and American developed countries, and have accomplished volume increase of guaranteeing the quality, green agriculture
Requirement.Since the synthetic route of the pheromones is longer, purification difficult, higher cost, prices are rather stiff for import, constrains
Popularization and use of the product in China.
Through retrieving, existing synthetic method mainly has:
1, Roelofs etc. (1971) has synthesized 12 carbon of sex pheromone E8, E10- using " Wittig reaction building alkene "
Diene -1- alcohol, but this route is too long, yield is low, the selectivity after isomerization is also bad.
2, Odinokov etc. (1985) is used using 1,4,92 last of the ten Heavenly stems trialkenyl trimethyl silanes as the alkene boron hydrogen of starting material
Change/method for oxidation has synthesized E8, and 12 carbon diene -1- alcohol of E10-, total recovery is higher, but starting material is difficult to obtain relatively.
3, yellow literary virtue etc. (1986) is with diphenyl allyl type ylide Ph2CH3P=CHCH=CHCH3With fatty aldehyde OHC
(CH2)6COOCH3For raw material, using Wittig reaction synthesis E8,12 carbon diene -1- alcohol of E10-, reaction route is as follows:
Yield 56%, stereoselectivity preferable 96%, disadvantage starting material is opposite to be difficult to obtain, and intermediate product quality is difficult to control.
4, it opens great waves etc. (2005) to react using Schlosser2Wittig, with 2 bromo octanol triphenylphosphine of ω and 2E2 butylene
Aldehyde (trans- crotonaldehyde) is raw material, in the presence of 2 lithium bromide of phenyl lithium, the stereoselective syntheses property information of carpocapsa pononella
Element, total recovery are about 30%, E, and E- content of isomer is up to 98%；The disadvantage is that (trans- crotonaldehyde) is hypertoxic, raw material is seldom arrived, and is received
Rate is relatively low.
5, Xinjiang Branch of China Academy of Sciences chemistry institute has used always sorb yl acetate dative since the nineties in last century
Family name's reagent is raw material, catalyzes and synthesizes 12 carbon diene -1- alcohol of E8, E10- through tetrachloro copper lithium, reaction route is as follows:
Total recovery is about 55% or more, E, and E- is different
Structure body content prepares the lure that becomes second nature and applies on the fruit tree of Xinjiang up to 98% or more, and achieving preferable control efficiency, (Lee protects
State and Mei Longzhu, 1999；Huang Guozheng and A Jiai Baeyer Chinese mugwort Sa, 2007).But low temperature is required to make in synthesis process, and big
The disadvantages of amount use sodium borohydride or potassium as reducing agent, and reducing condition is harsh, the time is long, copper lithium catalyst production requirement is absolutely
Anhydrous, otherwise reaction yield can sharply decline.
Therefore, it researches and develops a kind of short using be easy to get Material synthesis, reaction route and can be improved selectivity and product yield
The synthetic method of sex pheromone of carpocapsa pomonella is necessary.
Summary of the invention
It is short and can be improved using be easy to get Material synthesis, reaction route that the technical problem to be solved in the present invention is to provide a kind of
The synthetic method of the sex pheromone of carpocapsa pomonella of selectivity and product yield.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of synthetic method of sex pheromone of carpocapsa pomonella,
Its innovative point is: the synthetic method includes the following steps:
Step S1: using sorbic acid methyl esters as raw material, methanol is added, and centre is obtained by 5% palladium carbon catalytic hydrogenating reduction
Body A sorb base alcohol；
Step S2: by the pure and mild acetic anhydride of intermediate A sorb base obtained in step S1 in ethyl acetate, triethylamine and underwater
Reaction obtains intermediate B sorb yl acetate；
Step S3:6- Mecoral ethyl acetate and in the presence of triethylamine and trim,ethylchlorosilane reaction in toluene, instead
After answering, add water, stir, layering obtains intermediate C6- Mecoral trimethylsilyl ester；
Step S4: intermediate B sorb yl acetate and intermediate C6- Mecoral trimethylsilyl ester are in toluene solution and sodium
Sand reaction, is then added dropwise water and sulfuric acid, layering, and rectifying obtains target product E8,12 carbon diene -1- alcohol of E10-；It synthesizes road
Line is as follows:
Further, the mass ratio of sorbic acid methyl esters in the step S1, methanol, 5% palladium carbon and hydrogen is 1-2:1-3:
0.001-0.003-0.01-0.03。
Further, the mass ratio of sorb base alcohol in the step S2, ethyl acetate, triethylamine, acetic anhydride and water is 8-
9:15-25:8-15:8-15:20-50, reaction temperature is at 40-65 DEG C, and the reaction time is in 5-15h.
Further, in the step S3 6- Mecoral, ethyl acetate, triethylamine, trim,ethylchlorosilane and water quality
Than for 1-2:1-5:1-2:1-2:1-5, reaction temperature is at -10 DEG C -10 DEG C, and the reaction time is in 5-12.
Further, intermediate B sorb yl acetate, intermediate C6- Mecoral trimethylsilyl ester, first in the step S4
Benzene, sodium, water and sulfuric acid mass ratio are as follows: 1-2:1.5-3:1~5:0.5-1.5:1-5:1-2, reaction temperature be -10 DEG C -80 DEG C,
Reaction time is in 6-15h.
The present invention has the advantages that the synthetic method of sex pheromone of carpocapsa pomonella of the present invention, is successfully utilized cheap
Industrial raw materials expeditiously synthesize sex pheromone of carpocapsa pomonella E8,12 carbon diene -1- alcohol of E10-, and reaction route is short,
It being detected through GC, E, the purity of E- isomers is not less than 98%, Structural Identification is carried out to product with the methods of mass spectrum, nuclear-magnetism, infrared,
Comply fully with the structure of matter feature.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the E8 synthesized in embodiment 1,12 carbon diene -1- alcohol nuclear magnetic spectrum of E10-.
Fig. 2 is the E8 synthesized in embodiment 2,12 carbon diene -1- alcohol nuclear magnetic spectrum of E10-.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment 1
Intermediate A:
In the stainless steel autoclave of 500L dried and clean, sorbic acid methyl esters 100Kg, the methanol 300Kg that will be measured,
The palladium carbon 300g of cat:5% is put into, and stirring nitrogen replaces 3 times to anaerobic, is warming up to 50 DEG C, is passed through hydrogen to 6MPa, heat preservation is protected
Pressure reaction 12h cools 20 DEG C until reaction pressure no longer declines, and after pressure release processing, cat is filtered post activation reuse, filtrate
Concentration and recovery methanol, remaining yellow oily liquid are 98.05% by GC detection level.Amount of fluid are as follows: 90.2kg, yield exist
94.95%.
Intermediate B:
In the enamel reaction still of 500L dried and clean, sorb base alcohol 90.2kg, the ethyl acetate 200kg that will be measured,
Triethylamine 100kg, acetic anhydride 98kg investment, stirring are warming up to 55 DEG C, stop heating, control 55 DEG C, are stirred to react 12 hours, cold
But to room temperature, the water 300kg measured is added, stirs 30min, static layering, branch vibration layer, organic layer negative pressure is concentrated into solvent
Nothing, obtains sorb yl acetate, and GC detection level is 98.51%.Amount of fluid are as follows: 133.5kg, yield is 91.89%.
Intermediate C:
In the enamel reaction still of 1000L dried and clean, the 6- Mecoral that will measure: 150kg, ethyl acetate:
300kg, triethylamine: 115kg investment, stirring are cooled to 0 DEG C, and trim,ethylchlorosilane 137kg is added dropwise, and control temperature at 0 DEG C, are added dropwise
Terminate, 10 DEG C of stirring heat preservation, 8 hours, less than 0.5%, reaction terminates detection control 6- Mecoral, and 300kg water, stirring is added
30min, static layering, branch vibration layer, organic layer negative pressure are concentrated into solvent without obtaining 6- Mecoral trimethylsilyl ester, GC detection contains
Amount is 98.15%.Amount of fluid are as follows: 217.6kg, yield is 95.02%.
Target product synthesizes 12 carbon diene -1- alcohol of example 1:E8, E10-
In the enamel reaction still of 1500L dried and clean, into the toluene 400kg measured, nitrogen displacement, investment chopping
Clean metallic sodium 46kg, be warming up to 80 DEG C, quickly under stirring, ice water is cooling, is cooled to 10 DEG C, is added dropwise by intermediate B 137kg
With the mixture of intermediate C208.5kg.0-10 DEG C of dropwise addition of control, is added dropwise, is warming up to temperature 60 C, insulation reaction 12 is small
When, it is cooled to 0 DEG C, water 300kg, sulfuric acid 98kg is added dropwise, controls 20 DEG C of hydrolysis temperature, hydrolysis stirring 1 hour detects water layer pH value
3-4, layering, organic layer 200kg washing is primary, and branch vibration layer, organic layer negative pressure is concentrated into solvent without remaining liq enters rectifying
Tower rectifying, collects 10mmHg, and 118-120 DEG C of fraction detects E, E- content of isomer 99.5%, quantity as shown in Figure 1 are as follows:
141kg.Yield is 77.47%.Total recovery exists: 68%.
Embodiment 2
Intermediate A:
In the stainless steel autoclave of 500L dried and clean, sorbic acid methyl esters 100Kg, the methanol 200Kg that will be measured,
The palladium carbon 200g of cat:5% is put into, and stirring nitrogen replaces 3 times to anaerobic, is warming up to 60 DEG C, is passed through hydrogen to 5MPa, heat preservation is protected
Pressure reaction 12h cools 20 DEG C until reaction pressure no longer declines, and after pressure release processing, cat is filtered post activation reuse, filtrate
Concentration and recovery methanol, remaining yellow oily liquid are 97.15% by GC detection level.Amount of fluid are as follows: 88.2kg, yield exist
92.84%.
Intermediate B:
In the enamel reaction still of 500L dried and clean, sorb base alcohol 88.2kg, the ethyl acetate 150kg that will be measured,
Triethylamine 105kg, acetic anhydride 100kg investment, stirring are warming up to 60 DEG C, stop heating, control 60 DEG C, are stirred to react 10 hours,
It is cooled to room temperature, the water 200kg measured is added, stir 30min, static layering, branch vibration layer, organic layer negative pressure is concentrated into molten
Agent is without obtaining sorb yl acetate, GC detection level is 98.6%.Amount of fluid are as follows: 130.5kg, yield is 91.9%.
Intermediate C:
In the enamel reaction still of 1000L dried and clean, the 6- Mecoral that will measure: 150kg, ethyl acetate:
400kg, triethylamine: 125kg investment, stirring are cooled to 0 DEG C, and trim,ethylchlorosilane 145kg is added dropwise, and control temperature at 0 DEG C, are added dropwise
Terminate, 5 DEG C of stirring heat preservation, 8 hours, less than 0.5%, reaction terminates detection control 6- Mecoral, and 200kg water, stirring is added
30min, static layering, branch vibration layer, organic layer negative pressure are concentrated into solvent without obtaining 6- Mecoral trimethylsilyl ester, GC detection contains
Amount is 97.25%.Amount of fluid are as follows: 218.6kg, yield is 98.6%.
Target product synthesizes 12 carbon diene -1- alcohol of example 1:E8, E10-
In the enamel reaction still of 1500L dried and clean, into the toluene 500kg measured, nitrogen displacement, investment chopping
Clean metallic sodium 50kg, be warming up to 80 DEG C, quickly under stirring, ice water is cooling, is cooled to 0 DEG C, is added dropwise by intermediate B 137kg
With the mixture of intermediate C208.5kg.10-20 DEG C of dropwise addition of control, is added dropwise, is warming up to 80 DEG C of temperature, insulation reaction 8 is small
When, 5 DEG C are cooled to, water 400kg, sulfuric acid 100kg is added dropwise, controls 20 DEG C of hydrolysis temperature, hydrolysis stirring 1 hour detects water layer PH
Value 3-4, layering, organic layer 200kg washing is primary, and branch vibration layer, organic layer negative pressure is concentrated into solvent without remaining liq enters essence
Tower rectifying is evaporated, 20mmHg is collected, 145-155 DEG C of fraction detects E, E- content of isomer 98.5%, quantity as shown in Figure 2 are as follows:
140kg.Yield is 76.92%.Total recovery exists: 65.63%.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (5)
1. a kind of synthetic method of sex pheromone of carpocapsa pomonella, it is characterised in that: the synthetic method includes the following steps:
Step S1: using sorbic acid methyl esters as raw material, methanol is added, and intermediate A mountain is obtained by 5% palladium carbon catalytic hydrogenating reduction
Pears base alcohol；
Step S2: by the pure and mild acetic anhydride of intermediate A sorb base obtained in step S1 in ethyl acetate, triethylamine and underwater reaction
Obtain intermediate B sorb yl acetate；
Step S3:6- Mecoral ethyl acetate and in the presence of triethylamine and trim,ethylchlorosilane reaction in toluene, reaction knot
Shu Hou adds water, and stirring, layering obtains intermediate C6- Mecoral trimethylsilyl ester；
Step S4: intermediate B sorb yl acetate and intermediate C6- Mecoral trimethylsilyl ester are husky anti-with sodium in toluene solution
It answers, water and sulfuric acid, layering is then added dropwise, rectifying obtains target product E8,12 carbon diene -1- alcohol of E10-；Its synthetic route is such as
Under:
Cl(C6H12)OH+(CH3)3SiCl+(C2H5)3N→Cl(C6H12)OSi(CH3)3+(C2H5)3N·HCl
。
2. the synthetic method of sex pheromone of carpocapsa pomonella according to claim 1, it is characterised in that: mountain in the step S1
Pears acid methyl esters, methanol, 5% palladium carbon and hydrogen mass ratio be 1-2:1-3:0.001-0.003-0.01-0.03.
3. the synthetic method of sex pheromone of carpocapsa pomonella according to claim 1, it is characterised in that: mountain in the step S2
Pears base alcohol, ethyl acetate, triethylamine, acetic anhydride and water mass ratio be 8-9:15-25:8-15:8-15:20-50, reaction temperature
At 40-65 DEG C, the reaction time is in 5-15h.
4. the synthetic method of sex pheromone of carpocapsa pomonella according to claim 1, it is characterised in that: 6- in the step S3
Mecoral, ethyl acetate, triethylamine, trim,ethylchlorosilane and water mass ratio be 1-2:1-5:1-2:1-2:1-5, reaction temperature
At -10 DEG C -10 DEG C, the reaction time is in 5-12.
5. the synthetic method of sex pheromone of carpocapsa pomonella according to claim 1, it is characterised in that: in the step S4
Mesosome B sorb yl acetate, intermediate C6- Mecoral trimethylsilyl ester, toluene, sodium, water and sulfuric acid mass ratio are as follows: 1-2:
1.5-3:1~5:0.5-1.5:1-5:1-2, reaction temperature are -10 DEG C -80 DEG C, and the reaction time is in 6-15h.
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Cited By (1)
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| CN115304463A (en) * | 2022-08-11 | 2022-11-08 | 中国农业科学院植物保护研究所 | Preparation method of codling moth pheromone |
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