CN105541771B - A kind of preparation method of the amylene acid lactones of δ 3 - Google Patents
A kind of preparation method of the amylene acid lactones of δ 3 Download PDFInfo
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- CN105541771B CN105541771B CN201610039926.0A CN201610039926A CN105541771B CN 105541771 B CN105541771 B CN 105541771B CN 201610039926 A CN201610039926 A CN 201610039926A CN 105541771 B CN105541771 B CN 105541771B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The present invention relates to a kind of preparation method of the amylene acid lactones of δ 3, specific method obtains reaction solution A, the reaction solution A in 100~150 DEG C of 5~10h of back flow reaction for the pentenoate of 5 chlorine 3, carboxylic acid and carboxylate and the amylene acid lactones of δ 3 is obtained after isolating and purifying；The pentenoate of 5 chlorine 3, carboxylic acid, the mol ratio of carboxylate are 1:2~5:1~2, the pentenoate of 5 chlorine 3 is the one or more in the amylene-4 acid methyl ester of 5 chlorine 3, the pentenoic acid ethyl ester of 5 chlorine 3, the amylene propyl propionate of 5 chlorine 3 and the amylene acid butyl ester of 5 chlorine 3.Synthetic route of the present invention is short, reaction condition is gentle, preparation technology is simple, safe, cost is low, is easy to industrialized production, while has the advantages of discarded object is few, clean environment firendly；The amylene acid lactone high incomes of δ 3, the purity of this method preparation are high.
Description
Technical field
The present invention relates to a kind of preparation method of organic intermediate, and in particular to the preparation method of δ -3- amylene acid lactones,
Belong to chemical technology field.
Background technology
Lactone is important organic compound and intermediate, has wide application in pharmaceutical synthesis and essence and flavoring agent field
Prospect, such as gamma lactone and delta-lactone are applied to superior cosmetics, food and tobacco industry field.In δ -3- penetenoic acids
Ester contains multiple active groups, is also widely used in pharmaceutical synthesis and essence and flavoring agent synthesis.
The preparation method for recording δ -3- amylene acid lactones is had no in prior art literature, is only disclosed in similar products δ-penta
The documents of the preparation method of ester.Such as Chinese patent " a kind of production method of δ-valerolactone ", publication number：103980241, it is public
Open day：2014.08.13, a kind of production method of δ-valerolactone is disclosed：1,5-PD raw material is dehydrated in drying tower,
Ensure that water content is less than 1wt%；Enter after dried 1,5-PD is mixed with hydrogen in vaporizer, hydrogen and 1,5- penta
The mol ratio of glycol is 10~5:1；Hydrogen after vaporization and 1,5-PD are entered in dehydrogenation reactor, normal pressure, 230~
Under the conditions of 270 DEG C, 1,5-PD is converted into δ-valerolactone in the presence of dehydrogenation, described dehydrogenation is extremely
Include 15~35wt% of copper, 0.2~2.0wt% of silver, 1~5wt% of rare earth element, 20~60wt% of carrier less.Chinese patent " one
The method that kind prepares δ-valerolactone with load type nano gold catalyst ", publication number：101157677, publication date：2008.04.09
Disclose a kind of production method of δ-valerolactone：Solvent is made with tributyl phosphate, 1,5-PD is urged in load type nano gold
At agent effect and 80~160 DEG C, oxidation reaction generation δ-valerolactone occurs with 0.8~1.3Mpa pressure-airs.It is but above-mentioned existing
The method for preparing δ-valerolactone for having technology to record, is not suitable for the preparation of δ -3- amylene acid lactones, it is therefore necessary to find one
Kind high income, the δ -3- amylene acid lactone preparation methods that cost is low, pollution is small.
The content of the invention
It is an object of the invention to provide a kind of preparation method of δ -3- amylene acid lactones, the preparation method are simple and easy to do, dirty
Contaminate that small, cost is low, suitable for industrialized production；δ -3- amylene acid lactones high income, the purity of this method preparation are high.
Realize the technical scheme is that：
A kind of preparation method of δ -3- amylene acid lactones, it is characterised in that comprise the following steps：
1) 5- chloro- 3- pentenoates, carboxylic acid and carboxylate obtains reaction solution A in 100~150 DEG C of 5~10h of back flow reaction,
The chemical equation that the back flow reaction includes is；
The R is C1~C4 alkyl, and the M be metallic element, the R ' for C1~C3 alkyl, preferably methyl,
One kind in ethyl, propyl group；
2) the reaction solution A obtains δ -3- amylene acid lactones after isolating and purifying.
The method of the present invention isolated and purified is to be depressurized at vacuum -0.088Mpa~-0.09Mpa, 80~110 DEG C
Untill being concentrated into no distillate, then be cooled to 35~45 DEG C, concentrate be filtered to remove insoluble matter, filtrate vacuum-
0.097Mpa~-0.098Mpa, to without distillate untill, collection distillate is produced in δ -3- penetenoic acids for distillation at 150~190 DEG C
Ester.
The chloro- 3- pentenoates of 5- of the present invention are the chloro- 3- amylene-4 acid methyl esters of 5-, the chloro- 3- pentenoic acid ethyl esters of 5-, 5- chloro-
One or more in the chloro- 3- amylenes acid butyl ester of 3- amylenes propyl propionate, 5-；The chloro- 3- pentenoates of 5- of the present invention use 1,
3- butadiene and chloro-formate obtain in catalysts and solvents through the acylated step of addition reaction one.
M of the present invention is one kind in Li, Na, K.
The chloro- 3- pentenoates of 5- of the present invention, carboxylic acid, the mol ratio of carboxylate are 1:2~5:1~2.
The beneficial effects of the present invention are:
1st, the present invention is using the chloro- 3- pentenoates of 5- as predominant starting material, 5- chloro- 3- pentenoates, carboxylic acid and carboxylate
One-step synthesis δ -3- amylene acid lactones, synthetic route is short, and finished product δ -3- amylene acid lactones high income, purity are high, δ -3- penetenoic acids
Lactone yield is between 77.6%~91.8%, and purity is between 96%~98%.
2nd, the chloro- 3- pentenoates of initiation material 5- of the present invention use 1,3- butadiene and chloro-formate in catalysts and solvents
Middle to be obtained through the acylated step of addition reaction one, the chloro- 3- pentenoates costs of prepared 5- are low, can further reduce δ -3- of the present invention
The preparation cost of amylene acid lactone.
3rd, preparation method of the present invention is simple, reaction condition is gentle, and carboxylic acid and carboxylate used are conventional chemical material, production
It is safe and be easy to control, it is easy to industrialized production.
4th, preparation method discarded object of the present invention is few, and the generated ester byproducts material of reaction is reclaimed by being concentrated under reduced pressure,
Clean environment firendly.
Embodiment
To allow those skilled in the art to be better understood from the present invention and can be practiced, with reference to specific implementation
The present invention is further elaborated for example.
First, part of the embodiment of the present invention
Embodiment 1
5- chloro- 3- amylene-4 acid methyl esters 1mol, sodium acetate 1mol and acetic acid 2mol are added in reactor, at 100~105 DEG C
It is stirred at reflux reaction 10h；Reaction solution is -0.09Mpa in vacuum, untill no distillate is concentrated under reduced pressure at 80~100 DEG C, then
Be cooled to 38 DEG C, concentrate be filtered to remove insoluble matter, filtrate is -0.098Mpa in vacuum, distilled at 150~190 DEG C to
Untill without distillate, 80 grams of δ -3- amylene acid lactones are obtained, GC (Gas Chromatography, gas-chromatography, abbreviation GC) is pure
Spend for 97%.
Embodiment 2
5- chloro- 3- pentenoic acid ethyl esters 1mol, potassium acetate 1.5mol and acetic acid 5mol are added in reactor, at 110~115 DEG C
Under be stirred at reflux reaction 8h；Reaction solution is -0.09Mpa in vacuum, untill no distillate is concentrated under reduced pressure at 80~100 DEG C,
41 DEG C are cooled to again, concentrate are filtered to remove insoluble matter, filtrate is -0.098Mpa in vacuum, is distilled at 150~180 DEG C
Untill without distillate, 84 grams of δ -3- amylene acid lactones are obtained, GC purity is 98%.
Embodiment 3
5- chloro- 3- amylenes acid butyl ester 1mol, propionic acid lithium 2mol and n-butyric acie 2mol are added in reactor, at 145~150 DEG C
Under be stirred at reflux reaction 5h；Reaction solution is -0.088Mpa in vacuum, and no distillate is concentrated under reduced pressure at 100~110 DEG C and is
Only, then 40 DEG C are cooled to, concentrate are filtered to remove insoluble matter, filtrate is -0.097Mpa in vacuum, is steamed at 150~180 DEG C
Evaporate untill without distillate, obtain 76 grams of δ -3- amylene acid lactones, GC purity is 96%.
Embodiment 4
5- chloro- 3- amylenes propyl propionate 1mol, sodium propionate 1.2mol and propionic acid 3mol are added in reactor, at 120~125 DEG C
Under be stirred at reflux reaction 5h；Reaction solution is -0.088Mpa in vacuum, and no distillate is concentrated under reduced pressure at 100~110 DEG C and is
Only, then 45 DEG C are cooled to, concentrate are filtered to remove insoluble matter, filtrate is -0.098Mpa in vacuum, is steamed at 160~180 DEG C
Evaporate untill without distillate, obtain 83 grams of δ -3- amylene acid lactones, GC purity is 97%.
Embodiment 5
5- chloro- 3- pentenoic acid ethyl esters 1mol, potassium butyrate 1.3mol and propionic acid 3mol are added in reactor, at 115~120 DEG C
Under be stirred at reflux reaction 6h；Reaction solution is -0.089Mpa in vacuum, untill no distillate is concentrated under reduced pressure at 90~110 DEG C,
40 DEG C are cooled to again, concentrate are filtered to remove insoluble matter, filtrate is -0.097Mpa in vacuum, is distilled at 160~190 DEG C
Untill without distillate, 79 grams of δ -3- amylene acid lactones are obtained, GC purity is 97%.
Embodiment 6
5- chloro- 3- amylenes acid butyl ester 1mol, potassium butyrate 1.8mol and n-butyric acie 5mol are added in reactor, 115~120
Reaction 8h is stirred at reflux at DEG C；Reaction solution is -0.09Mpa in vacuum, and no distillate is concentrated under reduced pressure at 90~110 DEG C and is
Only, then 39 DEG C are cooled to, concentrate are filtered to remove insoluble matter, filtrate is -0.098Mpa in vacuum, is steamed at 150~190 DEG C
Evaporate untill without distillate, obtain 85 grams of δ -3- amylene acid lactones, GC purity is 98%.
Embodiment 7
5- chloro- 3- pentenoic acid ethyl esters 1mol, lithium acetate 1.2mol and propionic acid 2mol are added in reactor, at 135~140 DEG C
Under be stirred at reflux reaction 6h；Reaction solution is -0.089Mpa in vacuum, and no distillate is concentrated under reduced pressure at 100~110 DEG C and is
Only, then 35 DEG C are cooled to, concentrate are filtered to remove insoluble matter, filtrate is -0.097Mpa in vacuum, is steamed at 150~190 DEG C
Evaporate untill without distillate, obtain 81 grams of δ -3- amylene acid lactones, GC purity is 96%.
Embodiment 8
5- chloro- 3- amylenes propyl propionate 1mol, potassium acetate 1.6mol and propionic acid 4mol are added in reactor, at 125~130 DEG C
Under be stirred at reflux reaction 7h；Reaction solution is -0.09Mpa in vacuum, untill no distillate is concentrated under reduced pressure at 100~110 DEG C,
40 DEG C are cooled to again, concentrate are filtered to remove insoluble matter, filtrate is -0.098Mpa in vacuum, is distilled at 160~180 DEG C
Untill without distillate, 90 grams of δ -3- amylene acid lactones are obtained, GC purity is 98%.
2nd, experimental sections
The weight and yield of the target product δ -3- amylene acid lactones of the embodiment of the present invention 1~8 are respectively by weighing and calculating
Obtain, its purity is detected using gas chromatography.The testing result of the target product δ -3- amylene acid lactones of embodiment 1~8 is shown in Table
1。
Target product δ -3- amylene acid lactone the testing results of 1 embodiment of table 1~8
For the target product δ -3- amylene acid lactone yields of the embodiment of the present invention 1~8 between 77.6%~91.8%, product is pure
Between degree 96%~98%, the δ -3- amylenes acid lactones not only high income, and purity is also high of preparation method preparation of the present invention.
Claims (6)
1. a kind of preparation method of δ -3- amylene acid lactones, it is characterised in that comprise the following steps：
1) 5- chloro- 3- pentenoates, carboxylic acid and carboxylate be in 100~150 DEG C of 5~10h of back flow reaction, obtains reaction solution A, described
The chemical equation that back flow reaction includes is；
The R is C1~C4 alkyl, and the M is metallic element, and the R ' is C1~C3 alkyl；
2) the reaction solution A obtains δ -3- amylene acid lactones after isolating and purifying.
2. the preparation method of δ -3- amylene acid lactones according to claim 1, it is characterised in that：The side isolated and purified
Method is untill being concentrated under reduced pressure into no distillate at vacuum -0.088Mpa~-0.09Mpa, 80~110 DEG C, then is cooled to 35
~45 DEG C, concentrate is filtered to remove insoluble matter, filtrate is steamed at vacuum -0.097Mpa~-0.098Mpa, 150~190 DEG C
Evaporate untill without distillate, collect distillate and produce δ -3- amylene acid lactones.
3. the preparation method of δ -3- amylene acid lactones according to claim 1, it is characterised in that：The chloro- 3- amylenes of 5-
Acid esters is the chloro- 3- amylene-4 acid methyl esters of 5-, the chloro- 3- pentenoic acid ethyl esters of 5-, the chloro- 3- amylenes propyl propionates of 5-, the chloro- 3- amylenes acid butyl esters of 5-
In one or more.
4. the preparation method of δ -3- amylene acid lactones according to claim 1, it is characterised in that：The R ' is methyl, second
One kind in base, propyl group.
5. the preparation method of δ -3- amylene acid lactones according to claim 1, it is characterised in that：The M is in Li, Na, K
One kind.
6. the preparation method of δ -3- amylene acid lactones according to claim 1, it is characterised in that：The chloro- 3- amylenes of 5-
Acid esters, carboxylic acid, the mol ratio of carboxylate are 1:2~5:1~2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD222023A1 (en) * | 1983-09-14 | 1985-05-08 | Univ Schiller Jena | PROCESS FOR PREPARING 3-UNSATURATED DEHYDROPYRANONES |
| CN102653531A (en) * | 2011-03-04 | 2012-09-05 | 上海爱普植物科技有限公司 | Synthesis method of massoia lactone |
-
2016
- 2016-01-21 CN CN201610039926.0A patent/CN105541771B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD222023A1 (en) * | 1983-09-14 | 1985-05-08 | Univ Schiller Jena | PROCESS FOR PREPARING 3-UNSATURATED DEHYDROPYRANONES |
| CN102653531A (en) * | 2011-03-04 | 2012-09-05 | 上海爱普植物科技有限公司 | Synthesis method of massoia lactone |
Non-Patent Citations (5)
| Title |
|---|
| A simple catalytic system for the substitutive carbonylation of allyl alcohols to β,γ-unsaturated acids or esters;Bartolo Gabriel et al.;《Journal of Molecular Catalysis A: Chemical》;19961231;第111卷;第43-48页 * |
| Ring-chain equilibria of R-but-3-enoate esters —A quantum mechanical study of direct and indirect ring-closing reactions;Michael B. Burt et al.;《Can. J. Chem.》;20101022;第80卷;第1094-1103页 * |
| Synthesis of 2,6-Dideoxysugars via Ring-Closing Olefinic Metathesis;Peter R. Andreana et al.;《Organic Letters》;20021001;第4卷(第22期);第3875-3878页 * |
| Synthesis of β,γ-Unsaturated Valerolactones;Yasushi Nakashima et al.;《Synthetic Communications》;19791231;第9卷(第10期);第889-894页 * |
| 亚铜催化的溴代烯酸分子内偶联反应的研究;张月;《万方数据知识服务平台 学位论文》;20071119;第1-68页 * |
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