CN108129301A - A kind of synthetic method of 3-M2BOL formic acid esters - Google Patents
A kind of synthetic method of 3-M2BOL formic acid esters Download PDFInfo
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- CN108129301A CN108129301A CN201711487459.9A CN201711487459A CN108129301A CN 108129301 A CN108129301 A CN 108129301A CN 201711487459 A CN201711487459 A CN 201711487459A CN 108129301 A CN108129301 A CN 108129301A
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- C—CHEMISTRY; METALLURGY
- 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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Abstract
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthetic method of 3 methyl, 2 butylene, 1 alcohol formic acid esters.The synthetic method of 3 methyl, 2 butylene, 1 alcohol formic acid esters of the present invention, on the basis of prior art processes, selection sodium hydrogensulfite is catalyst, further improve the yield of 3 methyl, 2 butylene, 1 alcohol formic acid ester products, more preferably reacted in the presence of selected ionic liquid, other than effectively promoting product yield, the reaction time is more effectively accelerated, obtains higher product yield within the shorter time.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of synthesis of 3-M2BOL formic acid esters
Method.
Background technology
Bisabolol (Bisabolol), also known as sweet tea bisabolol, bisabolol are that there are more sesquialters in nature
One of terpene compound.Bisabolol has two kinds of structures of α-body and β-body, and α-bisabolol is primarily present in yellow chamomile essential oil, tacamahac
In essential oil and the essential oil of certain Myoporums and Salvia；β-bisabolol is primarily present in cotton bud essential oil, corn oil, camphor tree
In cerebrol, frankincense oil.Bisabolol has preferable stability and skin-friendliness, is suitable for applying in cosmetics；Meanwhile
Bisabolol has anti-inflammatory, sterilizing, healing ulcer, a dissolving drug effects such as cholelith, thus purposes of the bisabolol in pharmaceuticals industry compared with
Extensively；In addition, due to the light happiness of bisabolol fragrance and a kind of preferable fixastive of stability, answering in spices and essence
With being also paid more and more attention；Skin can be protected and be cured to bisabolol, protect it from the influence of daily tension, can speed up skin
The healing process of skin, is particularly suitable for use as sensitive skin and body, is widely used in the personal nursing (shield of skin and body
Manage care product after liquid, aftershave lotion and solarization) formula in, in addition its anti-inflammatory, natural, security feature, becomes one kind and is used for
The common active constituent of skin nursing.
In the prior art, the preparation of bisabolol is mostly using 3-M2BOL formic acid esters as intermediate, with double penta
Alkene carries out condensation reaction and is made.3-M2BOL formic acid esters, also known as prenol formic acid esters, usually with 3- first
Base -2- butene-1-ols (prenol) carry out esterification with formic acid and are synthesized.It is entire anti-but in existing esterification technique
It should usually require 6 hours or so, and product yield is at most also only capable of reaching 90% or so.Importantly, in the prior art
The synthesis of 3-M2BOL formic acid esters is typically to be carried out during bisabolol synthesizes, such as Chinese patent
CN106831322A discloses a kind of production method of α-bisabolol, be during α-bisabolol is synthesized, first with
Prenol and formic acid are directly added into dipentene and dichloromethane progress α-opopanax through lactate synthesis prenol formic acid esters
The synthesis of alcohol.Not only the generated time of prenol formic acid esters is longer in whole process, yield is slightly lower, moreover, its final product
The synthetic yield of α-bisabolol also only has 68%, it is difficult to meet the needs of actual production.
Invention content
For this purpose, the technical problems to be solved by the invention are to provide a kind of conjunction of 3-M2BOL formic acid esters
Into method, to solve, the synthesis cycle of 3-M2BOL formic acid esters in the prior art is longer, synthetic ratio is slightly lower asks
Topic.
In order to solve the above technical problems, a kind of synthesis side of 3-M2BOL formic acid esters of the present invention
Method including taking the step of 3-M2BOL is with formic acid mixing, and adds sulphite as catalyst, be esterified anti-
It should.
The molar ratio of the 3-M2BOL and formic acid is 1：1.3-1.6.
The sulphite is sodium hydrogensulfite.
The additive amount of the sulphite is the 0.5-2wt% of 3-M2BOL material quantity.
The temperature of the esterification is 30-40 DEG C.
The reaction carries out in the presence of ion liquid solvent.
The ionic liquid is ionic liquid of alkyl guanidine salt.
The ionic liquid is N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid
([HOctTMG]CF3COO)。
The reaction time of esterification is 1-6h.
The invention also discloses a kind of production method of α-bisabolol, i.e., including the synthesis 3- methyl-2-butenes-
The step of 1- alcohol formic acid esters.
The synthetic method of 3-M2BOL formic acid esters of the present invention, on the basis of prior art processes
On, selection sodium hydrogensulfite is catalyst, further improves the yield of 3-M2BOL formic acid ester products.
The synthetic method of 3-M2BOL formic acid esters of the present invention preferably exists in selected ionic liquid
Under reacted, other than effectively promoting product yield, more effectively accelerate the reaction time, obtain within the shorter time more
High product yield；Moreover, more amazing be, in the technique for preparing α-bisabolol, exist in selected ionic liquid
Under prepare 3-M2BOL formic acid esters, with this system be directly added into dipentene carry out α-bisabolol preparation when,
In addition to except the product yield for effectively promoting 3-M2BOL formic acid esters and shortening the reaction time, α-red more can be effectively promoted
The yield of bisabol has unexpected technique effect.
Specific embodiment
It is prepared by 1 ionic liquid of embodiment
Ionic liquid needed for following examples of the present invention is N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl second
Hydrochlorate ionic liquid ([HOctTMG] CF3COO), synthetic method includes the following steps：
(1) 0.30mol tetramethylureas is taken to be dissolved in 175mL toluene, instill what is newly steamed under nitrogen protection and stirring condition
0.31mol POCl3, under room temperature react 10 hours after be added dropwise 0.70mol n-octyl amines, after be stirred at room temperature 34
Hour, it after 175mL water diluting reaction systems, is vigorously stirred 30 minutes, removes a layer solution, be charged with solid NaOH to making
System display alkalinity, then two layers of solution point, filters out solid, after filtrate layered, takes upper solution, be dissolved in ether
In, then use anhydrous Na2CO3Filtered after drying, solvent be evaporated off, raffinate is through being evaporated under reduced pressure to 0.10mol target products N, N, N ',
The synthesis of N '-tetramethyl-N "-octyl group guanidine (OctTMG).FTIR(KBr)：υmax：2922,2852,1611,1477,1430,
1383,1142cm-1；
(2) OctTMG and 0.30mol CF obtained by 0.30mol are taken3COOH carries out neutralization reaction and obtains 0.24mol targets
Product N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid ([HOctTMG] CF3COO)。FTIR
(KBr)：υmax：2929,2857,1706,1652,1513,1497,1394,1256,1178,1154,1037,644cm-1。
Embodiment 2
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in 3- methyl-2-butenes-
1- alcohol 86g and formic acid 60g (molar ratios 1：1.3) sodium hydrogensulfite 0.43g (0.5wt%), is added as catalyst, then will
Three-necked flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification
6h.After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesis α-red does not have
The technical study of medicine alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
94.3%.
Embodiment 3
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in 3- methyl-2-butenes-
1- alcohol 86g and formic acid 64.4g (molar ratios 1：1.4) sodium hydrogensulfite 0.86g (1wt%), is added as catalyst, then will
Three-necked flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification
5h.After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesis α-red does not have
The technical study of medicine alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
94%.
Embodiment 4
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in 3- methyl-2-butenes-
1- alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then will
Three-necked flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification
5h.After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesis α-red does not have
The technical study of medicine alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
94%.
Embodiment 5
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in 3- methyl-2-butenes-
1- alcohol 86g and formic acid 73.6g (molar ratios 1：1.6) sodium hydrogensulfite 1.72g (2wt%), is added as catalyst, then will
Three-necked flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification
4h.After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesis α-red does not have
The technical study of medicine alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
94.1%.
Embodiment 6
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 1h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
94.6%.
Embodiment 7
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 2h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
97.3%.
Embodiment 8
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 3h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
98%.
Embodiment 9
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 4h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
98.1%.
Embodiment 10
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 5h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
98.3%.
Embodiment 11
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in obtained in embodiment 1
N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid 100ml, and add in 3- methyl-2-butenes -1-
Alcohol 86g and formic acid 69g (molar ratios 1：1.5) sodium hydrogensulfite 1.29g (1.5wt%), is added as catalyst, then by three
Mouth flask is put into heating reaction (35 DEG C) in the heating mantle with magnetic agitation and opens magnetic agitation, carries out esterification 6h.
After reaction, reaction product is washed to neutrality, product (is referred to according to art methods《Dipentene synthesizes α-opopanax
The technical study of alcohol》, Deng Qian, etc.) product detection is carried out, calculating product 3-M2BOL formic acid esters yield is
98.5%.
Comparative example
Equipped with thermometer, reflux condensing tube, dropping funel 250mL three-necked flask, add in 3- methyl-2-butenes-
1- alcohol 86g and formic acid 69g (molar ratios 1：1.5), then three-necked flask is put into the heating mantle with magnetic agitation and is heated instead
Magnetic agitation should and be opened, carries out esterification 6h.After reaction, reaction product is washed to neutrality, product is according to existing
Technical method (refers to《Dipentene synthesizes the technical study of α-bisabolol》, Deng Qian, etc.) product detection is carried out, calculate product 3-
Methyl-2-butene -1- alcohol formic acid esters yield is 92%.
The synthesis of 1 α of application examples-bisabolol
Esterification 5h is carried out according to step in embodiment 4, after esterification is reached home, dipentene is added in reaction system
409g (dipentenes：Prenol molar ratio=3：1) with dichloromethane 540g, 75 DEG C are added dropwise catalyst (formic acid and phosphoric acid mole
Than being 1：2) 30g stirs condensation reaction, and (method refers to GC tracking and monitorings product《The technique of dipentene synthesis α-bisabolol is ground
Study carefully》, Deng Qian, etc.), final α-bisabolol yield 70%.
The synthesis of 2 α of application examples-bisabolol
Esterification 5h is carried out according to step in embodiment 6, after esterification is reached home, dipentene is added in reaction system
409g (dipentenes：Prenol molar ratio=3：1) with dichloromethane 540g, 75 DEG C are added dropwise catalyst (formic acid and phosphoric acid mole
Than being 1：2) 30g stirs condensation reaction, and (method refers to GC tracking and monitorings product《The technique of dipentene synthesis α-bisabolol is ground
Study carefully》, Deng Qian, etc.), final α-bisabolol yield 81%.
The synthesis of 3 α of application examples-bisabolol
Esterification 5h is carried out according to step in embodiment 8, after esterification is reached home, dipentene is added in reaction system
409g (dipentenes：Prenol molar ratio=3：1) with dichloromethane 540g, 75 DEG C are added dropwise catalyst (formic acid and phosphoric acid mole
Than being 1：2) 30g stirs condensation reaction, and (method refers to GC tracking and monitorings product《The technique of dipentene synthesis α-bisabolol is ground
Study carefully》, Deng Qian, etc.), final α-bisabolol yield 83%.
Compare application examples
Esterification 6h is carried out according to step in comparative example 1, after esterification is reached home, dipentene is added in reaction system
409g (dipentenes：Prenol molar ratio=3：1) with dichloromethane 540g, 75 DEG C are added dropwise catalyst (formic acid and phosphoric acid mole
Than being 1：2) 30g stirs condensation reaction, and (method refers to GC tracking and monitorings product《The technique of dipentene synthesis α-bisabolol is ground
Study carefully》, Deng Qian, etc.), final α-bisabolol yield 68%.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of synthetic method of 3-M2BOL formic acid esters, which is characterized in that including take 3- methyl-2-butenes-
The step of 1- alcohol is with formic acid mixing, and sulphite is added as catalyst, carry out esterification.
2. the synthetic method of 3-M2BOL formic acid esters according to claim 1, which is characterized in that the 3-
The molar ratio of methyl-2-butene -1- alcohol and formic acid is 1：1.3-1.6.
3. the synthetic method of 3-M2BOL formic acid esters according to claim 1 or 2, which is characterized in that institute
Sulphite is stated as sodium hydrogensulfite.
4. the synthetic method of 3-M2BOL formic acid esters according to claim 3, which is characterized in that the Asia
The additive amount of sulfate is the 0.5-2wt% of 3-M2BOL material quantity.
5. according to the synthetic method of claim 1-4 any one of them 3-M2BOL formic acid esters, feature exists
In the temperature of the esterification is 30-40 DEG C.
6. according to the synthetic method of claim 1-5 any one of them 3-M2BOL formic acid esters, feature exists
In the reaction carries out in the presence of ion liquid solvent.
7. the synthetic method of 3-M2BOL formic acid esters according to claim 6, which is characterized in that it is described from
Sub- liquid is ionic liquid of alkyl guanidine salt.
8. the synthetic method of the 3-M2BOL formic acid esters described according to claim 6 or 7, which is characterized in that institute
Ionic liquid is stated as N, N, N ', N '-tetramethyl-N "-octyl group guanidine trifluoromethyl acetate ion liquid.
9. according to the synthetic method of claim 1-8 any one of them 3-M2BOL formic acid esters, feature exists
In the reaction time of esterification is 1-6h.
10. a kind of production method of α-bisabolol, which is characterized in that synthesize 3- including claim 1-9 any one of them
The step of methyl-2-butene -1- alcohol formic acid esters.
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| CN201711487459.9A CN108129301B (en) | 2017-12-30 | 2017-12-30 | Synthetic method of 3-methyl-2-butene-1-alcohol formate |
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| CN201711487459.9A CN108129301B (en) | 2017-12-30 | 2017-12-30 | Synthetic method of 3-methyl-2-butene-1-alcohol formate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101434639A (en) * | 2008-12-17 | 2009-05-20 | 中国农业科学院油料作物研究所 | Green technological process for preparing sterol fatty acid ester |
| CN106831322A (en) * | 2017-01-10 | 2017-06-13 | 南宁辰康生物科技有限公司 | A kind of production method of α bisabolols |
-
2017
- 2017-12-30 CN CN201711487459.9A patent/CN108129301B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049332A (en) * | 1989-08-08 | 1991-02-20 | 纳贝斯高·布兰股伦有限公司 | The preparation method of neoalkyl triol triesters |
| CN101434639A (en) * | 2008-12-17 | 2009-05-20 | 中国农业科学院油料作物研究所 | Green technological process for preparing sterol fatty acid ester |
| CN106831322A (en) * | 2017-01-10 | 2017-06-13 | 南宁辰康生物科技有限公司 | A kind of production method of α bisabolols |
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| 杨娟娟: ""亚硫酸氢钠催化合成丙烯酸正丁酯"", 《课外阅读（中下）》 * |
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Application publication date: 20180608 Assignee: GUANGXI NANNING LVJING FUNCTIONAL POLYMER MATERIALS Co.,Ltd. Assignor: GUANGXI ZHUANG AUTONOMOUS REGION FORESTRY Research Institute Contract record no.: X2022450000395 Denomination of invention: Synthesis of 3-methyl-2-butene-1-alkoxylate Granted publication date: 20210302 License type: Common License Record date: 20221226 |