CN108558709A - A kind of preparation method of Monochamus alternatus Hope aggregation pheromone - Google Patents
A kind of preparation method of Monochamus alternatus Hope aggregation pheromone Download PDFInfo
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- CN108558709A CN108558709A CN201810390276.3A CN201810390276A CN108558709A CN 108558709 A CN108558709 A CN 108558709A CN 201810390276 A CN201810390276 A CN 201810390276A CN 108558709 A CN108558709 A CN 108558709A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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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
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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
Abstract
The present invention discloses a kind of preparation method of Monochamus alternatus Hope aggregation pheromone, including：Two kinds of compounds are blended in the first solvent, and carries out substitution reaction under alkaline condition and obtains third compound；Third compound and fourth compound are blended in the second solvent, and under the action of alkaline condition and the first catalyst, carry out substitution reaction, obtain the 5th compound；5th compound is mixed with third solvent, is deprotected under acid condition and the second catalyst action, obtains final compound, Monochamus alternatus Hope aggregation pheromone.The present invention obtains finished product hendecane epoxide ethyl alcohol using 2 tert-butoxy ethyl alcohol as starting material, through sulfonic acid esterification and positive undecyl alcohol substitution, deprotection reaction.This technological operation is simple and convenient, high income, at low cost, and weight is good, can meet industrialization production requirements.
Description
Technical field
The present invention relates to a kind of field of compound preparation, and in particular to a kind of preparation side of Monochamus alternatus Hope aggregation pheromone
Method.
Background technology
Pine nematode is a kind of destructive disease of pine tree.Pine tree once catches an illness, and just can not give treatment to, and lethal speed is fast,
Most fast 40 days can be withered, 3~5 years can cause full wafer pine forest to destroy, and be referred to as " cancer " of pine tree, and propagate fast
Speed, difficulty of prevention and cure are big.
It is Bursaphelenchus xylophilus to cause the main arch-criminal of pine nematode, and Monochamus alternatus Hope is the main media elder brother of pine nematode
Worm.In the diffusion of Bursaphelenchus xylophilus and during infect, Monochamus alternatus Hope plays carrying, propagation and the pass for assisting cause of disease intrusion host
Keyness acts on.Monochamus alternatus Hope itself is also fatal insect to pine tree simultaneously, and the Adult supplement nutrient needs of Monochamus alternatus Hope are gnawed
Spray skin causes host weak, and a large amount of brill moth tree vigo(u)rs of larva are weak or the trunk newly cuted down, cause pine tree in blocks withered.So
Longicorn insect density is reduced, harm can mitigate, and eliminate Monochamus alternatus Hope, so that it may to eradicate pine nematode.
Hendecane epoxide ethyl alcohol is Monochamus alternatus Hope aggregation pheromone, effectively Monochamus alternatus Hope can be made to assemble, and implements to trap,
Trapping Monochamus alternatus Hope, which is carried out, using Monochamus alternatus Hope aggregation pheromone has been developed in recent years a kind of prevention side the most efficient
Method is endangered in prevention and control Monochamus alternatus Hope, is played a significant role in terms of containment pine nematode propagation.
Preparation for Monochamus alternatus Hope aggregation pheromone hendecane epoxide ethyl alcohol, the method reported have the following two kinds：
1, using n,N-Dimethylformamide as solvent, the ethylene glycol of big equivalent is added, is carefully added into sodium hydrogen in batches, waits for sodium hydrogen
The reaction was complete, be added dropwise to 1- bromo-n-11s reacted prepare hendecane epoxide ethyl alcohol [J.Chem.Ecol.2010,36,
570-583]；Reaction system product extraction is difficult, and has disubstituted by-product to generate, and causes yield very low.
2, in ethylene glycol, it is carefully added into metallic sodium in batches and is prepared into sodium alkoxide, be then added dropwise and the progress of 1- bromo-n-11s is added
It reacts to prepare hendecane epoxide ethyl alcohol [Sci.Rep.2016,6,29300；Dyes and Pigments 2013,96,16-
24]；Similarly, since reaction system, with the presence of a large amount of ethylene glycol, product is difficult to extract, and reaction process also have it is more
High boiling diether substitution by-product generates, and yield is caused there was only 54% or so.
In above-mentioned production technology, it is that raw material is produced to be required for 1- bromo-n-11s, and not only price is very high for the raw material, and
And not large product can be supplied, it is difficult to realize amplification production；It is alkali that reaction, which will use metallic sodium and sodium hydrogen, and is produced
Journey will produce a large amount of hydrogen, and the security risk of production is high, so that the production greatly of hendecane epoxide ethyl alcohol is difficult.
Invention content
In view of this, the present invention provides, one kind is simple to operate, and securely and reliably, production cost is relatively low, it can be achieved that loose brown
Longicorn assembles the method for sex pheromone hendecane epoxide ethyl alcohol amplification production.
In order to solve the above technical problems, the technical scheme is that using a kind of preparation of Monochamus alternatus Hope aggregation pheromone
Method, including：
Formulas I compound represented and Formula II compound represented are blended in the first solvent, and in the first alkaline condition
Formula III compound represented is obtained by the reaction in lower progress sulfonic acid esterification；
The formula III compound represented and formula IV compound represented are blended in the second solvent, and in the second alkali
Property condition and the first catalyst under the action of, carry out substitution reaction, obtain Formula V compound represented；
Formula V compound represented is mixed with third solvent, is carried out under acid condition and the second catalyst action
Deprotection, obtains Formula IV compound represented, Monochamus alternatus Hope aggregation pheromone；
Wherein R be carbon atom number be 1~10 straight chained alkyl, carbon atom number be 1~10 branched alkyl, halogenated virtue
Perfume base, nitryl aromatic base, halogenated aromatic base, alkoxy aromatic perfume base.
Preferably, first solvent is one or more in following compound：Methyl tertiary butyl ether(MTBE), methyl tetrahydrochysene
Furans, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, 1,4- dioxane and water.
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, lithium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, triethylamine, pyridine and
DMAP。
Preferably, the Formula II compound represented is one or more in following substance：Mesyl chloride, second sulphonyl
Chlorine, the third sulfonic acid chloride, isopropyl sulfonic acid chloride, benzene sulfonyl chloride, paratoluensulfonyl chloride, 4-Nitrobenzenesulfonyl chloride, m-nitrobenzene sulfonyl chloride, neighbour
Nitrobenzene sulfonyl chloride, to Methoxybenzenesulfonyl chloride, to t-butylbenzenesulfonyl chloride and trifluoromethanesulfanhydride anhydride.
Preferably, second solvent is one or more in following compounds：Methyl tertiary butyl ether(MTBE), methyl tetrahydrochysene
Furans, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, 1,4- dioxane and water.
Preferably, the second alkaline condition by one or more offers in following compound：Potassium tert-butoxide, hydroxide
Sodium, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, sodium methoxide and sodium ethoxide.
Preferably, used first catalyst is one or more in following compound：Tetrabutylammonium bromide, four
Butyl ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyltrimethylammonium bromide, dodecyltriethylammonium
Ammonium bromide, dodecyl sodium sulfate, polyethylene glycol 200, polyethylene glycol 400,18- crown-s 6 and 15- crown-s 5.
Preferably, the acid condition is by one or more offers in following compound：Trifluoroacetic acid, hydrochloric acid, sulfuric acid,
Phosphoric acid, acetic acid.
Preferably, the third solvent is one or more in following compound：Methyl tertiary butyl ether(MTBE), methyl tetrahydrochysene
Furans, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, water, methanol, ethyl alcohol, isopropanol and
1,4- dioxane.
Preferably, second catalyst is selected from one or more of following compound：Tetrabutylammonium bromide, four fourths
Base ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyltrimethylammonium bromide, dodecyltriethylammonium bromine
Change ammonium, polyethylene glycol 200 and polyethylene glycol 400.
The primary improvements of the present invention are using 2- tert-butoxies ethyl alcohol as starting material, through sulfonic acid esterification and positive 11
Alcohol substitution, deprotection reaction obtain finished product hendecane epoxide ethyl alcohol.This technological operation is simple and convenient, high income, at low cost, weight
It measures, industrialization production requirements can be met.
Description of the drawings
The nuclear magnetic spectrum for preparing final product that Fig. 1, the embodiment of the present invention 1 provide.
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.
The present invention is using positive undecyl alcohol and 2- tert-butoxies ethyl alcohol as starting material, through sulfonic acid esterification, substitution, deprotection reaction
Obtain finished product；High using the purity of this technique institute productive target product, reaction condition is mild, high income, convenience easy to operate,
Securely and reliably, production cost is low, and amplification production may be implemented.
Monochamus alternatus Hope aggregation pheromone hendecane epoxide ethyl alcohol synthetic route of the present invention is as follows：
It is that raw material and Formula II compound represented are mixed with inexpensive, the 2- tert-butoxies ethyl alcohol that is easy to get (Formulas I compound represented)
It closes in the first solvent, and carries out substitution reaction under alkaline condition and obtain formula III compound represented；Wherein R is carbon atom
The branched alkyl that straight chained alkyl that number is 1~10, carbon atom number are 1~10, it is halogenated aromatic base, nitryl aromatic base, halogenated
Aromatic radical, alkoxy aromatic perfume base.
According to the present invention, the temperature range of the sulfonic acid esterification is at -20~100 DEG C；Formulas I compound represented and shape
The weight ratio of compound shown in compound and Formula II at the first alkaline condition is preferably：1：(1.1~1.5)：(1.1~
1.5)；Used first solvent is preferably one or more of following substance：Methyl tertiary butyl ether(MTBE), methyl tetrahydrochysene furan
Mutter, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, Isosorbide-5-Nitrae-dioxane and water, more preferably
For methyl tertiary butyl ether(MTBE), methyltetrahydrofuran, tetrahydrofuran, dichloromethane, glycol dimethyl ether and water, most preferably tetrahydrochysene
Furans, dichloromethane, the concentration of solute is preferably in first solvent：1~5M.
First alkaline condition is preferably by one or more offers in following compound：Potassium tert-butoxide, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, triethylamine, pyridine and
DMAP.More it is selected as sodium hydroxide, potassium hydroxide, lithium hydroxide, triethylamine, pyridine and DMAP, most preferably potassium hydroxide, three
Ethamine.
Formula II compound represented when R is different substituents with different configurations, it is a kind of in preferably following substance
Or it is a variety of：Mesyl chloride, ethyl sulfonic chloride, the third sulfonic acid chloride, isopropyl sulfonic acid chloride, benzene sulfonyl chloride, paratoluensulfonyl chloride, p-nitrophenyl sulphur
Acyl chlorides, m-nitrobenzene sulfonyl chloride, ortho-nitrophenyl sulfonic acid chloride, to Methoxybenzenesulfonyl chloride, to t-butylbenzenesulfonyl chloride, trifluoro methylsulphur
Acid anhydrides.More it is selected as mesyl chloride, benzene sulfonyl chloride, 4-Nitrobenzenesulfonyl chloride, trifluoromethanesulfanhydride anhydride.
After obtaining formula III compound represented, the formula III compound represented is mixed with formula IV compound represented
In the second solvent, and under the action of the second alkaline condition and the first catalyst, substitution reaction is carried out, is obtained shown in Formula V
Compound.Range of reaction temperature is preferably at 20~150 DEG C.Formula III compound represented and formula IV compound represented, first
Catalyst and the weight ratio for forming the compound of the first alkaline condition are (1.1~1.5)：1：(0.01-0.1)：(1.1~1.5).
Second solvent preferably is selected from one or more in following compounds：Methyl tertiary butyl ether(MTBE), methyltetrahydrofuran, tetrahydrochysene furan
It mutters, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, 1,4- dioxane and water.More preferably tetrahydrochysene furan
Mutter, DMF, butanone, water, Isosorbide-5-Nitrae-dioxane, the concentration of solute is preferably in second solvent：0.5~5M.
Second alkaline condition is preferably by one or more offers in following compound：Potassium tert-butoxide, sodium hydroxide,
Potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, sodium methoxide and sodium ethoxide.More it is selected as hydroxide
Potassium, potassium tert-butoxide, sodium ethoxide, cesium carbonate.
Used first catalyst preferably is selected from one or more in following compound：Tetrabutylammonium bromide, the tetrabutyl
Ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyltrimethylammonium bromide, dodecyltriethylammonium bromination
Ammonium, dodecyl sodium sulfate, polyethylene glycol 200, polyethylene glycol 400,18- crown-s 6 and 15- crown-s 5.More preferably tetrabutyl phosphonium bromide
Ammonium, benzyl triethyl ammonium bromide, dodecyltriethylammonium ammonium bromide, dodecyl sodium sulfate, polyethylene glycol 400.
Formula V compound represented is mixed with third solvent, is carried out under acid condition and the second catalyst action
Deprotection, obtains Formula IV compound represented, Monochamus alternatus Hope aggregation pheromone；The preferred deprotection reaction temperature range
At 30~100 DEG C；The acid condition is preferably by one or more offers in following compound：Trifluoroacetic acid, hydrochloric acid, sulphur
Acid, phosphoric acid, acetic acid.More preferably preferred acidic compound is trifluoroacetic acid and hydrochloric acid.The Formula V compound represented and second
The weight of catalyst and with the weight ratio of compound of manufacture acid condition it is preferably：1:1~6,
Preferably, the third solvent is one or more in following compound：Methyl tertiary butyl ether(MTBE), methyl tetrahydrochysene
Furans, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, butanone, toluene, water, methanol, ethyl alcohol, isopropanol and
1,4- dioxane.More preferably methanol, water, acetic acid, the concentration of solute is preferably in the third solvent：0.5~6M.
Preferably, second catalyst is selected from one or more of following compound：Tetrabutylammonium bromide, four fourths
Base ammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyltrimethylammonium bromide, dodecyltriethylammonium bromine
Change ammonium, polyethylene glycol 200 and polyethylene glycol 400.More preferably hydrochloric acid, trifluoroacetic acid.
After the completion of preparation, the present invention further preferably provides deduction step, by different raw material and preparation parameter, provides extraction
Take, dry, concentrating and etc. obtain Monochamus alternatus Hope aggregation pheromone of the purity 99% or more.
It is below the specific embodiment of the invention, elaborates technical solution of the present invention.
Embodiment 1：
59 grams of 2- tert-butoxies ethyl alcohol, 65 grams of triethylamines and 300 milliliters of dichloromethane are added in reaction bulb, are cooled to -20
DEG C, 156 grams of trifluoromethanesulfanhydride anhydrides are slowly added dropwise.It is added dropwise, is stirred to react 6 hours；Reaction, liquid separation, organic phase is quenched in cold water
It is dry, concentration.
Concentrate is transferred in 1 liter of autoclave pressure, is separately added into 300 milliliters of tetrahydrofurans, 95 grams of positive undecyl alcohols, 10 gram of four fourth
Base ammonium bromide and 110 grams of cesium carbonates are warming up to 120 DEG C, insulation reaction 3 hours after sealing；It is cooled to heating, filters and removes admittedly
Body, concentration remove solvent, and water and dichloromethane stirring, liquid separation is added.50 milliliters of trifluoroacetic acids, room temperature reaction are added in organic phase
Completely, 250 milliliters of water quenchings are added to go out reaction, liquid separation, water phase is extracted with dichloromethane, merges organic phase, is concentrated, is evaporated under reduced pressure to
To 56 grams of hendecane epoxide ethyl alcohol, product purity 99.6%.
As shown in Figure 1, the diffraction maximum of product manufactured in the present embodiment can prove that product manufactured in the present embodiment is that pine is brown
The aggregation pheromone of longicorn, i.e. Formula IV compound represented.
Embodiment 2：
118 grams of 2- tert-butoxies ethyl alcohol, 230 grams of benzene sulfonyl chlorides, 1.5 liters of methyl tertiary butyl ether(MTBE)s are added in reaction bulb, it is cooling
To 10 DEG C, 250 gram of 30% sodium hydrate aqueous solution is added dropwise；It is added dropwise, is stirred overnight, static liquid separation, organic phase is dried, dense
Contracting.
172 grams of positive undecyl alcohols, 20 grams of benzyl triethyl ammonium bromides and 800 milliliters of tetrahydrofurans are added in reaction bulb, are added
55 grams of sodium methoxides are heated to reflux 30 minutes；500 milliliters of the tetrahydrofuran solution that reaction product is walked in dropwise addition, continues to heat back
It flow to that the reaction was complete.Reaction solution is poured into ice water, dichloromethane extraction, concentration.
Concentrate is dissolved in 1 liter of methanol, and 150 milliliters of concentrated hydrochloric acids and 50 grams of tetrabutylammonium bromide are added, be heated to reflux to
Reaction terminates；Reaction solution pours into ice water, and dichloromethane extraction concentrates, and residue is evaporated under reduced pressure to obtain 190 grams of hendecane epoxide second
Alcohol, product purity 99.5%.
Embodiment 3：
118 grams of 2- tert-butoxies ethyl alcohol, 250 gram of 30% sodium hydrate aqueous solution, 1 liter of tetrahydrofuran are added in reaction bulb,
210 grams of paratoluensulfonyl chloride/500 milliliter tetrahydrofuran solutions are added dropwise in 0 DEG C or so of temperature control；It is added dropwise, is stirred overnight, it is static
Liquid separation, organic phase drying, concentration.
Above-mentioned concentrate is dissolved in 800 milliliters of tetrahydrofurans, be added 180 grams of positive undecyl alcohols, 50 grams of polyethylene glycol 400s and
It is abundant to be heated to 55 DEG C of reactions for 280 gram of 30% potassium hydroxide aqueous solution；Reaction solution is poured into ice water, dichloromethane extraction is dense
Contracting.
250 milliliters of concentrated hydrochloric acids and 50 grams of benzyltriethylammoinium chlorides, 45 DEG C of reactions are added in concentrate；Reaction terminates, and adds
Enter 500 milliliters of water, dichloromethane extraction, the drying of organic phase sodium sulphate concentrates, and vacuum distillation obtains 168 grams of hendecane epoxide second
Alcohol, purity 99.1%.
Embodiment 4：
59 grams of 2- tert-butoxies ethyl alcohol, 80 grams of triethylamines and 300 milliliters of toluene are added in reaction bulb, are cooled to 0 DEG C, slowly
65 grams of mesyl chlorides are added dropwise.It is added dropwise, is stirred to react 6 hours；Reaction, liquid separation, organic phase drying, concentration is quenched in cold water.
95 grams of positive undecyl alcohols, 10 grams of 18- crown-s 6 and 500 milliliters of DMF are added in reaction bulb, 78 grams of sodium ethoxides are added portionwise,
90 DEG C are warming up to react 1 hour；100 milliliters of DMF for walking reaction product in dropwise addition mutters solution, continues 60 DEG C of heat preservation to having reacted
Entirely.Reaction solution is poured into ice water, dichloromethane extraction.
50 milliliter of 30% aqueous sulfuric acid and 10 grams of polyethylene glycol 200s are added in above-mentioned dichloromethane solution, heat back
Stream reaction to complete, cooling, liquid separation, the drying of organic phase sodium carbonate, concentration, residue is evaporated under reduced pressure to obtain 58 grams of hendecane epoxides
Ethyl alcohol, purity 99.2%.
Embodiment 5：
110 grams of 4-Nitrobenzenesulfonyl chlorides, 600 milliliters of 2- tert-butoxies ethyl alcohol and 100 milliliters of water, temperature control are added in reaction bulb
20 DEG C, 115 gram of 30% potassium hydroxide aqueous solution is added dropwise；It is added dropwise, is stirred to react overnight；Ice water is poured into, is filtered after stirring, Gu
Body is dried in vacuo.
Solid is dissolved in 800 milliliters of Isosorbide-5-Nitrae-dioxane, and 95 grams of positive undecyl alcohols and 15 grams of dodecyl sodium sulfates are added,
90 DEG C are heated to, 75 grams of potassium tert-butoxides are added portionwise in 1 hour, and continues 90 DEG C of heat preservation and terminates to reaction.Vacuum distillation removes
Solvent, adds water and dichloromethane is sufficiently stirred, and liquid separation, water phase is extracted using dichloromethane, merges organic phase and concentrates.
Concentrate is dissolved in 250 milliliters of acetic acid, and 10 grams of dodecyltriethylammonium ammonium bromides and 20 milliliters of concentrated hydrochloric acids are added,
It is heated to 60 DEG C of reactions；Reaction terminates, and pours into ice water, petroleum ether extraction, the drying of organic phase sodium carbonate, concentration, and residue subtracts
Pressure distillation obtains 62 grams of hendecane epoxide ethyl alcohol, purity 99.6%.
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 Monochamus alternatus Hope aggregation pheromone, which is characterized in that including：
Formulas I compound represented and Formula II compound represented are blended in the first solvent, and under the first alkaline condition into
Formula III compound represented is obtained by the reaction in the esterification of row sulfonic acid；
The formula III compound represented and formula IV compound represented are blended in the second solvent, and in the second alkaline item
Under the action of part and the first catalyst, substitution reaction is carried out, Formula V compound represented is obtained；
Formula V compound represented is mixed with third solvent, remove-insurance is carried out under acid condition and the second catalyst action
Shield, obtains Formula IV compound represented, Monochamus alternatus Hope aggregation pheromone；
Wherein R be carbon atom number be 1~10 straight chained alkyl, carbon atom number be 1~10 branched alkyl, halogenated aromatic
Base, nitryl aromatic base, halogenated aromatic base, alkoxy aromatic perfume base.
2. preparation method according to claim 1, which is characterized in that first solvent in following compound one
Kind is a variety of：Methyl tertiary butyl ether(MTBE), methyltetrahydrofuran, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, fourth
Ketone, toluene, 1,4- dioxane and water.
3. preparation method according to claim 1, which is characterized in that first alkaline condition is by following compound
One or more offers：Potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, carbonic acid
Caesium, sodium methoxide, sodium ethoxide, triethylamine, pyridine and DMAP.
4. preparation method according to claim 1, which is characterized in that the Formula II compound represented is in following substance
It is one or more：Mesyl chloride, ethyl sulfonic chloride, the third sulfonic acid chloride, isopropyl sulfonic acid chloride, benzene sulfonyl chloride, paratoluensulfonyl chloride, to nitre
Base benzene sulfonyl chloride, m-nitrobenzene sulfonyl chloride, ortho-nitrophenyl sulfonic acid chloride, to Methoxybenzenesulfonyl chloride, to t-butylbenzenesulfonyl chloride and
Trifluoromethanesulfanhydride anhydride.
5. preparation method according to claim 1, which is characterized in that second solvent in following compounds one
Kind is a variety of：Methyl tertiary butyl ether(MTBE), methyltetrahydrofuran, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, fourth
Ketone, toluene, 1,4- dioxane and water.
6. preparation method according to claim 1, which is characterized in that institute's alkaline condition by following compound one kind or
A variety of offers：Potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, first
Sodium alkoxide and sodium ethoxide.
7. preparation method according to claim 1, which is characterized in that used catalyst is in following compound
It is one or more：Tetrabutylammonium bromide, tetrabutylammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyl three
Methyl bromide ammonium, dodecyltriethylammonium ammonium bromide, dodecyl sodium sulfate, polyethylene glycol 200, polyethylene glycol 400,18- crown-s
6 and 15- crown-s 5.
8. preparation method according to claim 1, which is characterized in that the acid condition is by one kind in following compound
Or a variety of offers：Trifluoroacetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid.
9. preparation method according to claim 1, which is characterized in that the third solvent in following compound one
Kind is a variety of：Methyl tertiary butyl ether(MTBE), methyltetrahydrofuran, tetrahydrofuran, glycol dimethyl ether, DMF, DMSO, dichloromethane, fourth
Ketone, toluene, water, methanol, ethyl alcohol, isopropanol and 1,4- dioxane.
10. preparation method according to claim 1, which is characterized in that second catalyst is in following compound
One or more：Tetrabutylammonium bromide, tetrabutylammonium iodide, benzyl triethyl ammonium bromide, benzyltriethylammoinium chloride, benzyl
Base trimethylammonium bromide, dodecyltriethylammonium ammonium bromide, polyethylene glycol 200 and polyethylene glycol 400.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079679A (en) * | 2020-09-01 | 2020-12-15 | 塔里木大学 | Asymmetric total synthesis method of sex pheromone (R, Z) -21-methyl-8-thirty-five carbene of longicorn |
| CN113072433A (en) * | 2021-03-30 | 2021-07-06 | 苏州华道生物药业股份有限公司 | Synthesis method of coffee carica longicorn pheromone 2- (4-heptyloxy-1-butoxy) -1-ethanol |
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| US20060008850A1 (en) * | 2004-07-02 | 2006-01-12 | Riggs-Sauthier Jennifer A | Combinatorial synthesis of PEG oligomer libraries |
| CN107805187A (en) * | 2017-09-30 | 2018-03-16 | 苏州华道生物药业股份有限公司 | The production technology of Monochamus alternatus aggregation pheromone hendecane epoxide ethanol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079679A (en) * | 2020-09-01 | 2020-12-15 | 塔里木大学 | Asymmetric total synthesis method of sex pheromone (R, Z) -21-methyl-8-thirty-five carbene of longicorn |
| CN112079679B (en) * | 2020-09-01 | 2022-10-11 | 塔里木大学 | Asymmetric total synthesis method of sex pheromone (R, Z) -21-methyl-8-thirty-five carbene of longicorn |
| CN113072433A (en) * | 2021-03-30 | 2021-07-06 | 苏州华道生物药业股份有限公司 | Synthesis method of coffee carica longicorn pheromone 2- (4-heptyloxy-1-butoxy) -1-ethanol |
| CN113072433B (en) * | 2021-03-30 | 2023-06-20 | 苏州华道生物药业股份有限公司 | Synthesis method of longicorn pheromone 2- (4-heptyloxy-1-butoxy) -1-ethanol |
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