CN108727167A - A kind of preparation method of longicorn beetle aggregation pheromone - Google Patents

A kind of preparation method of longicorn beetle aggregation pheromone Download PDF

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CN108727167A
CN108727167A CN201810390288.6A CN201810390288A CN108727167A CN 108727167 A CN108727167 A CN 108727167A CN 201810390288 A CN201810390288 A CN 201810390288A CN 108727167 A CN108727167 A CN 108727167A
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hexyl
preparation
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compound represented
catalyst
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CN108727167B (en
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陈维
陈维一
吴新红
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Suzhou Ze Agricultural Biotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention discloses a kind of preparation method of longicorn beetle aggregation pheromone, and substitution reaction is carried out under alkaline condition and the first catalyst action and obtains compound；By compound in ionic liquid and under the action of the second catalyst, deprotection reaction is carried out, final compound is obtained.Synthetic method target product good yields of the present invention, operation are easy；Compared with prior art, used raw material sources are convenient, and cheap, production material cost is relatively low；Reaction makees solvent using ionic liquid, can dissolve reactant very well, and play the role of phase transfer catalyst, rapid reaction can be promoted to be smoothed out, and method is novel；After the completion of reaction, ionic liquid may be reused through washing and drying, and environmental friendly, safety is suitble to industrialized production.

Description

A kind of preparation method of longicorn beetle aggregation pheromone
Technical field
The present invention relates to a kind of field of compound preparation, and in particular to a kind of preparation method of longicorn aggregation pheromone.
Background technology
Longicorn beetle is a kind of great trunk borer of forest industry harmfulness, and distribution is very extensive, the distribution model more early recorded Enclose including Hebei, Beijing, Shandong, Jiangsu, Zhejiang, Shanxi, Shaanxi, Gansu, Hubei, Hunan, Sichuan, Guizhou, Fujian, Guangdong, The distribution record in Hong Kong, Hainan, Guangxi, later record includes Yunnan, Jiangxi, Jilin, Liaoning, Taiwan and Heilungkiang.Longicorn beetle Host it is extremely extensive, include at least 36 sections, mainly have Acer (Sapindaceae), Citrus (Rutaceae), Lagerstroemia (thousand bend Dish section), Populus (willow), Rosa (rose family), Salix (Salicaceae), Elm (Ulmaceae), citrus garden in south China The harm being particularly acute is caused with shelter belt.
Since longicorn beetle larva concealment is strong, host range is big, its difficulty of prevention and cure is caused to increase, with people to environment and The raising of food safety requirements, the free of contamination ecological Control Technology of green high-efficient increasingly have been favored by people.Utilize aggregation Pheromones carry out trapping longicorn and have been developed in recent years a kind of control method the most efficient, by using artificial synthesized Longicorn aggregation pheromone can be trapped and killed in trapper, to reduce longicorn population density, be integrated control longicorn most One of effective measures.
For longicorn beetle aggregation pheromone 4- (positive oxygroup in heptan)-n-butyl alcohol, only a kind of method is reported at present：
Reaction raw materials 1,4-butanediol is dissolved in a large amount of DMF solvents, and sodium hydrogen is added and is prepared into sodium alkoxide, 1- bromines are then added dropwise Heptane carry out at ether reaction come synthesize 4- (positive oxygroup in heptan)-n-butyl alcohol [A.Zhang et al.Z.Naturforsch.57c, 553-558(2002)]；The sodium hydrogen that the synthetic method uses is inflammable and explosive, and reaction will produce a large amount of hydrogen, therefore dangerous pole Greatly；Simultaneously because reaction is solvent using a large amount of DMF, a large amount of water, which need to be added, can extract product, and product yield is low, Wastewater flow rate is big, and environment influences high.
Due to longicorn beetle aggregation pheromone 4- (positive oxygroup in heptan) the good market prospects of-n-butyl alcohol, a kind of novelty is developed Synthetic method realize that its industrialized production is significantly.
Invention content
In view of this, the present invention provides, one kind is simple to operate, and securely and reliably, the lower longicorn beetle of production cost assembles The preparation method of pheromones 4- (positive oxygroup in heptan)-n-butyl alcohol,
In order to solve the above technical problems, the technical scheme is that using a kind of preparation side of longicorn beetle aggregation pheromone Method, including：Formulas I compound represented and Formula II compound represented are blended in ionic liquid, and in alkaline condition and Substitution reaction is carried out under one catalyst action obtains formula III compound represented；By the formula III compound represented in ion In liquid, and under the action of the second catalyst, deprotection reaction is carried out, formula IV compound represented is obtained；
Preferably, the ionic liquid is one or more in following compound：1- n-hexyl -3- methylimidazole chlorine Salt, 1- n-hexyl -3- methylimidazoles bromide, 1- n-hexyl -3- methylimidazoles salt compounded of iodine, 1- n-hexyl -3- methylimidazole tetrafluoro boron Hydrochlorate, 1- n-hexyl -3- methylimidazoles hexafluorophosphate, 1- n-hexyl -3- ethyl imidazol(e)s villaumite, 1- n-hexyl -3- ethyl miaows Azoles bromide, 1- n-hexyl -3- ethyl imidazol(e)s salt compounded of iodine, 1- n-hexyl -3- ethyl imidazol(e)s tetrafluoroborate, 1- n-hexyl -3- ethyls Limidazolium hexafluorophosphate.
Preferably, the ionic liquid is one or more in following compound：1- n-hexyl -3- methylimidazole chlorine Salt, 1- n-hexyl -3- methylimidazoles salt compounded of iodine, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates.
Preferably, the alkaline condition is by one or more offers in following compound：Potassium tert-butoxide, sodium hydroxide, Potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate.
Preferably, first catalyst is one or more in following compound：18 hat, six, 15 hat five, Sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetrabutylammonium iodide and tetrabutylammonium bromide.
Preferably, Formulas I compound represented provides compound, the Formula II compound represented and one of the alkaline condition The mass ratio of catalyst is 1：(1.0~1.5)：(1.0~1.5)：(0.01~0.05).
Preferably, a concentration of 0.5~5M of the reaction system of the substitution reaction.
Preferably, use the second catalyst one or more in following compound：Trifluoroacetic acid, methyl sulphur Acid, chlorosulfonic acid, concentrated hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid.
Preferably, formula III compound represented and the weight ratio of second catalyst are 1:0.01~0.05.
Preferably, the solution concentration of the deprotection reaction system is 1~8M.
It is an advantage of the invention that：Synthesis target product longicorn beetle aggregation pheromone 4- (positive oxygen in heptan is reacted using " one kettle way " Base)-n-butyl alcohol, using this synthetic method target product good yields, operation is easy；Compared with prior art, the present invention Used raw material sources are convenient, and cheap, production material cost is relatively low；Reaction makees solvent using ionic liquid, can be very Good dissolving reactant, and play the role of phase transfer catalyst, rapid reaction can be promoted to be smoothed out, method is novel；Reaction is completed Afterwards, ionic liquid may be reused through washing and drying, and environmental friendly, safety is suitble to industrialized production.
Description of the drawings
The nuclear magnetic spectrum of formula IV compound represented prepared by Fig. 1 embodiment of the present invention 1.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme of the present invention, With reference to embodiment The present invention is described in further detail.
Pass through research, it has been found that compared with conventional organic solvents, ionic liquid has the advantages that a series of protrusions： (1) liquid state range is wide, to 300 degrees Celsius or more, there is high thermal stability and chemical stability from below or near to room temperature；(2) Vapour pressure is very small, non-volatile, lost using, will not be evaporated in storage, can recycle, eliminate volatile organic Object (VOCs, i.e. volative organic compounds) problem of environmental pollution is closed, (3) conductivity is high, and electrochemical window is big, It can be used as the electrolyte of many substance electrochemical research；(4) by the design of zwitterion be adjusted its to inorganic matter, water, have The dissolubility of machine object and polymer, and its acidity is adjustable to super acid.(4) there is larger polarity Modulatory character, viscosity is low, close Degree is big, can form two-phase or heterogeneous system, is suitable as separation solvent or constitutes reaction-separation coupling new system；(5) to big Good solvability at all performances of inorganic and organic substance, and the dual function with solvent and catalyst are measured, it can conduct Many chemical reaction solvents or catalytic activity carrier.Due to these special natures of ionic liquid and performance, it is considered and surpasses Critical CO2 and aqueous two-phase constitute three big green solvents together, have broad application prospects.
On the basis of system research existing main preparation methods, to solve, a kind of longicorn beetle aggregation The preparation method of pheromones, including：Formulas I compound represented and Formula II compound represented are blended in ionic liquid, and Substitution reaction is carried out under alkaline condition and a catalyst action obtains formula III compound represented；Shown in the formula III Compound carries out deprotection reaction, obtains chemical combination shown in formula IV in ionic liquid, and under the action of the second catalyst Object；
Specific synthetic route is as follows：
It is raw material, reference literature using convenient sources, cheap tetrahydrofuran and methyl tertiary butyl ether(MTBE) in the present invention [J.Org.Chem.1981,46,3361-3364 and KR2017/4895] is prepared for 4- tert-butoxies -1-chlorobutane.
According to the present invention, first using Formula II compound represented and Formulas I compound represented as raw material, suitable alkali, Temperature, ionic liquid are to carry out substitution reaction in solvent, formula III compound represented is prepared.The temperature of the substitution reaction Ranging from 0~120 DEG C of degree, more preferably 60-120 DEG C of reaction temperature.The ionic liquid preferably is selected from one kind in following substance Or it is a variety of：1- n-hexyl -3- methylimidazole villaumites, 1- n-hexyl -3- methylimidazoles bromide, 1- n-hexyl -3- methylimidazoles Salt compounded of iodine, 1- n-hexyl -3- methyl imidazolium tetrafluoroborates, 1- n-hexyl -3- methylimidazoles hexafluorophosphate, 1- n-hexyls -3- Ethyl imidazol(e) villaumite, 1- n-hexyl -3- ethyl imidazol(e)s bromide, 1- n-hexyl -3- ethyl imidazol(e)s salt compounded of iodine, 1- n-hexyl -3- ethyls Tetrafluoroborate, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates；More preferably 1- n-hexyls -3- methylimidazole villaumites, 1- n-hexyl -3- methylimidazoles salt compounded of iodine, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates.The present invention is carried out using ionic liquid The dissolving of reaction raw materials can dissolve reactant, and play the role of phase transfer catalyst very well, can promote rapid reaction smoothly into Row, method are novel.
The alkaline condition is by one or more offers in following compound：Potassium tert-butoxide, sodium hydroxide, hydroxide Potassium, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate；Used catalyst be one kind in following substance or It is a variety of：18 hat, six, 15 hat five, sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetrabutylammonium iodide, tetrabutylammonium bromide. More preferably potassium tert-butoxide, potassium hydroxide, lithium hydroxide, cesium carbonate.
According to the present invention in order to promote reaction progress, invention also uses catalyst, the catalyst be potassium iodide, Tetrabutylammonium iodide or 18 hats six.
Preferably, the Formulas I compound represented provides compound and catalyst shown in alkaline condition compound, Formula VII Weight ratio be 1：(1.0~1.5)：(1.0~1.5)：(0.01~0.05).The dosage of the ionic liquid is.
After obtaining formula III compound represented, in the condition that suitable acid catalyst, temperature and ionic liquid are solvent Under, it carries out deprotection reaction (sloughing tert. butyl protection group) and obtains target product formula IV compound represented.Range of reaction temperature Preferably 0~100 DEG C, more preferably 20-60 DEG C；Used second catalyst is preferably a kind of or more in following substance Kind：Trifluoroacetic acid, pyrovinic acid, chlorosulfonic acid, concentrated hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid.More preferably hydrochloric acid or trifluoroacetic acid.
According to the present invention, ionic liquid used in the solvent preferably is selected from one or more of following substance：1- N-hexyl -3- methylimidazole villaumites, 1- n-hexyl -3- methylimidazoles bromide, 1- n-hexyl -3- methylimidazoles salt compounded of iodine, 1- just oneself Base -3- methyl imidazolium tetrafluoroborates, 1- n-hexyl -3- methylimidazoles hexafluorophosphate, 1- n-hexyl -3- ethyl imidazol(e) chlorine Salt, 1- n-hexyl -3- ethyl imidazol(e)s bromide, 1- n-hexyl -3- ethyl imidazol(e)s salt compounded of iodine, 1- n-hexyl -3- ethyl imidazol(e) tetrafluoro boron Hydrochlorate, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates.More preferably：1- n-hexyl -3- methylimidazole villaumites, 1- n-hexyls - 3- methylimidazoles salt compounded of iodine, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates；
It is an advantage of the invention that：Synthesis target product longicorn beetle aggregation pheromone 4- (positive oxygen in heptan is reacted using " one kettle way " Base)-n-butyl alcohol, using this synthetic method target product good yields, operation is easy；Compared with prior art, the present invention Used raw material sources are convenient, and cheap, production material cost is relatively low；Reaction makees solvent using ionic liquid, can be very Good dissolving reactant, and play the role of phase transfer catalyst, rapid reaction can be promoted to be smoothed out, method is novel；Reaction is completed Afterwards, ionic liquid may be reused through washing and drying, and environmental friendly, safety is suitble to industrialized production.
It is below the specific embodiment of the invention, elaborates the advantageous effect of preparation method of the present invention.
Embodiment 1：
100 milliliters of 1- n-hexyl -3- methylimidazole villaumites and 12 grams of n-heptanols are added in reaction bulb, are heated to 60 DEG C, so After 12 grams of potassium tert-butoxides are added portionwise, add 0.5 gram 18 hat six；After reaction 1 hour, 18 grams of 4- tert-butoxies -1- are added dropwise Chlorobutane, maintaining 60 DEG C, the reaction was complete (vapor detection).
It is cooled to room temperature, 15 milliliters of trifluoroacetic acids is added and are stirred to react complete (vapor detection)；Repeatedly extracted using petroleum ether It takes, merges organic phase, wash, dry, concentration, residue column chromatography purifies to obtain 10 grams of products, yield 53%.
Embodiment 2：
80 milliliters of 1- n-hexyl -3- methyl imidazolium tetrafluoroborates and 12 grams of n-heptanols are added in reaction bulb, are heated to 40 DEG C, 6 grams of potassium hydroxide are then added, add 1 gram of potassium iodide；After reaction 1 hour, 18 grams of 4- tert-butoxy -1- neoprenes are added dropwise Alkane, maintaining 40 DEG C, the reaction was complete (vapor detection).
It is cooled to room temperature, 10 milliliters of concentrated hydrochloric acids is added, be stirred to react complete (vapor detection)；Repeatedly extracted using ethyl acetate It takes, merges organic phase, wash, dry, concentration, residue column chromatography purifies to obtain 11 grams of products, yield 59%.
Embodiment 3：
200 milliliters of 1- n-hexyls -3- ethyl imidazol(e)s tetrafluoroborates and 50 grams of n-heptanols are added in reaction bulb, are heated to 60 DEG C, 65 grams of cesium carbonates are added, add 5 grams of tetrabutylammonium bromide；After 60 DEG C are stirred 1 hour, 75 grams of 4- tert-butoxies -1- are added Chlorobutane, being warming up to 100 DEG C, the reaction was complete (vapor detection).
50 DEG C are cooled to, is filtered while hot, 25 milliliter of 30% sulfuric acid solution is added in filtrate, being heated to 80 DEG C, the reaction was complete (vapor detection)；It is repeatedly fully extracted using petroleum ether, merges organic phase, washed, dry, concentration, residue is evaporated under reduced pressure to To 56 grams of products, yield 69%.
Embodiment 4：
50 milliliters of 1- n-hexyls -3- methylimidazoles salt compounded of iodine and 12 grams of n-heptanols are added in reaction bulb, are heated to 50 DEG C, then 6 grams of sodium hydroxides are added portionwise, after reacting 1 hour, 18 grams of 4- tert-butoxies -1-chlorobutanes are added dropwise, maintaining 50 DEG C, the reaction was complete (vapor detection).
It is cooled to room temperature, 10 milliliters of concentrated hydrochloric acids is added and are stirred to react complete (vapor detection)；It is repeatedly extracted using petroleum ether, Merge organic phase, wash, dry, concentration, residue column chromatography purifies to obtain 12 grams of products, yield 64%.
Embodiment 5：
40 milliliters of 1- n-hexyls -3- ethyl imidazol(e)s hexafluorophosphates and 12 grams of n-heptanols are added in reaction bulb, are heated to 80 DEG C, 3 grams of lithium hydroxides are then added, add 0.5 gram of 15 hat five；After reaction 1 hour, 18 grams of 4- tert-butoxies -1- are added dropwise Chlorobutane, maintaining 80 DEG C, the reaction was complete (vapor detection).
It is cooled to room temperature, 10 milliliters of pyrovinic acids is added, be stirred to react complete (vapor detection)；It is multiple using ethyl acetate Extraction merges organic phase, washes, dry, and concentration, residue column chromatography purifies to obtain 8.6 grams of products, yield 46%.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair The limitation of the present invention, protection scope of the present invention should be subject to claim limited range.For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change Protection scope of the present invention is also should be regarded as into retouching.

Claims (10)

1. a kind of preparation method of longicorn beetle aggregation pheromone, which is characterized in that including：
Step 1: Formulas I compound represented and Formula II compound represented are blended in ionic liquid, and in alkaline condition and Substitution reaction is carried out under first catalyst action obtains formula III compound represented；
Step 2: the formula III compound represented is taken off in ionic liquid, and under the action of the second catalyst Protection reaction, obtains formula IV compound represented；
2. preparation method according to claim 1, which is characterized in that the ionic liquid is independently selected from following compound It is one or more：1- n-hexyl -3- methylimidazole villaumites, 1- n-hexyl -3- methylimidazoles bromide, 1- n-hexyl -3- methyl Iodonium imidazolide salts, 1- n-hexyl -3- methyl imidazolium tetrafluoroborates, 1- n-hexyl -3- methylimidazoles hexafluorophosphate, 1- just oneself Base -3- ethyl imidazol(e)s villaumite, 1- n-hexyl -3- ethyl imidazol(e)s bromide, 1- n-hexyl -3- ethyl imidazol(e)s salt compounded of iodine, 1- n-hexyls -3- Ethyl imidazol(e) tetrafluoroborate, 1- n-hexyl -3- ethyl imidazol(e) hexafluorophosphates.
3. preparation method according to claim 1, which is characterized in that the ionic liquid is independently selected from following compound It is one or more：1- n-hexyl -3- methylimidazole villaumites, 1- n-hexyl -3- methylimidazoles salt compounded of iodine, 1- n-hexyl -3- ethyls Limidazolium hexafluorophosphate.
4. preparation method according to claim 1, which is characterized in that the alkaline condition is by one kind in following compound Or a variety of offers：Potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate.
5. preparation method according to claim 1, which is characterized in that first catalyst is in following compound It is one or more：
18 hat, six, 15 hat five, sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetrabutylammonium iodide and tetrabutylammonium bromide.
6. preparation method according to claim 1, which is characterized in that Formulas I compound represented provides the alkaline condition Compound, Formula II compound represented and a catalyst mass ratio be 1：(1.0~1.5)：(1.0~1.5)：(0.01~ 0.05)。
7. preparation method according to claim 1, which is characterized in that the reaction system a concentration of 0.5 of the substitution reaction ~5M.
8. preparation method according to claim 1, which is characterized in that use the second catalyst in following compound It is one or more：Trifluoroacetic acid, pyrovinic acid, chlorosulfonic acid, concentrated hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid.
9. preparation method according to claim 1, which is characterized in that formula III compound represented and second catalysis The amount of substance ratio of agent is 1:0.01~0.05.
10. preparation method according to claim 1, which is characterized in that the solution concentration of the deprotection reaction system is 1 ~8M.
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CN112042647A (en) * 2020-09-15 2020-12-08 中国林业科学研究院亚热带林业研究所 Attractant for adult anoplophora chinensis

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112042647A (en) * 2020-09-15 2020-12-08 中国林业科学研究院亚热带林业研究所 Attractant for adult anoplophora chinensis
CN112042647B (en) * 2020-09-15 2021-11-16 中国林业科学研究院亚热带林业研究所 Attractant for adult anoplophora chinensis

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