CN105541771A - Preparation method for delta-3-pentadienoic lactone - Google Patents
Preparation method for delta-3-pentadienoic lactone Download PDFInfo
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- CN105541771A CN105541771A CN201610039926.0A CN201610039926A CN105541771A CN 105541771 A CN105541771 A CN 105541771A CN 201610039926 A CN201610039926 A CN 201610039926A CN 105541771 A CN105541771 A CN 105541771A
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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 invention discloses a preparation method for delta-3-pentadienoic lactone. The preparation method specifically comprises the following steps: performing reflux reaction on 5-chloro-3-pentenoic ester, carboxylic acid and carboxylate at 100 to 150 DEG C for 5 to 10 hours to obtain a reaction liquid A; separating and purifying the reaction A to obtain the delta-3-pentadienoic lactone, wherein the 5-chloro-3-pentenoic ester, the carboxylic acid and the carboxylate are in the molar ratio of 1:(2-5):(1-2); the 5-chloro-3-pentenoic ester is one or more of 5-chloro-3-methyl pentenoate, 5-chloro-3-ethyl pentenoate, 5-chloro-3-propyl pentenoate and 5-chloro-3-butyl pentenoate. The preparation method is short in synthetic route, mild in reaction conditions, simple in preparation process, high in safety and low in cost, facilities industrial production, and meanwhile, has the advantages of little waste, cleanness and environment friendliness. The delta-3-pentadienoic lactone prepared by the preparation method is high in yield and high in purity.
Description
Technical field
The present invention relates to a kind of preparation method of organic intermediate, be specifically related to the preparation method of δ-3-pentenoic acid lactone, belong to chemical technology field.
Background technology
Lactone is important organic compound and intermediate, has broad application prospects, be applied to the fields such as superior cosmetics, food and tobacco industry as gamma lactone and delta-lactone at pharmaceutical synthesis and essence and flavoring agent field.δ-3-pentenoic acid lactone contains multiple active group, is also widely used in pharmaceutical synthesis and essence and flavoring agent synthesis.
Have no the preparation method recording δ-3-pentenoic acid lactone in prior art document, only have the documents of the preparation method disclosing analogous products δ-valerolactone.As Chinese patent " a kind of production method of δ-valerolactone ", publication number: 103980241, publication date: 2014.08.13, discloses a kind of production method of δ-valerolactone: dewatered in drying tower by 1,5-PD raw material, ensures that water-content is lower than 1wt%; Enter in vaporizer after being mixed with hydrogen by dried 1,5-PD, the mol ratio of hydrogen and 1,5-PD is 10 ~ 5:1; By the hydrogen and 1 after vaporization, 5-pentanediol enters in dehydrogenation reactor, under normal pressure, 230 ~ 270 DEG C of conditions, by 1 under the effect of dehydrogenation catalyst, 5-pentanediol is converted into δ-valerolactone, and described dehydrogenation catalyst at least comprises copper 15 ~ 35wt%, silver 0.2 ~ 2.0wt%, rare earth element 1 ~ 5wt%, carrier 20 ~ 60wt%.Chinese patent " a kind of load type nano gold catalyst prepares the method for δ-valerolactone ", publication number: 101157677, publication date: 2008.04.09, disclose a kind of production method of δ-valerolactone: make solvent with tributyl phosphate, by 1,5-pentanediol, at load type nano gold catalyst effect and 80 ~ 160 DEG C, generates δ-valerolactone with 0.8 ~ 1.3Mpa high-pressure air generation oxidizing reaction.But the method preparing δ-valerolactone that above-mentioned prior art is recorded, is not suitable for the preparation of δ-3-pentenoic acid lactone, be therefore necessary to find that a kind of yield is high, cost is low, pollute little δ-3-pentenoic acid lactone preparation method.
Summary of the invention
The object of this invention is to provide a kind of preparation method of δ-3-pentenoic acid lactone, this preparation method be simple and easy to do, pollute little, cost is low, is suitable for suitability for industrialized production; δ-3-pentenoic acid lactone yield prepared by the method is high, purity is high.
Realizing technical scheme of the present invention is:
A preparation method for δ-3-pentenoic acid lactone, is characterized in that comprising the following steps:
1) the chloro-3-pentenoate of 5-, carboxylic acid and carboxylate salt are at 100 ~ 150 DEG C of back flow reaction 5 ~ 10h, and obtain reaction solution A, the chemical equation that described back flow reaction comprises is;
Described R is the alkyl of C1 ~ C4, and described M is metallic element, the alkyl that described R ' is C1 ~ C3, is preferably the one in methyl, ethyl, propyl group;
2) described reaction solution A obtains δ-3-pentenoic acid lactone after separation and purification.
The method of separation and purification of the present invention is at vacuum tightness-0.088Mpa ~-0.09Mpa, be evaporated at 80 ~ 110 DEG C without till overhead product, be cooled to 35 ~ 45 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is at vacuum tightness-0.097Mpa ~-0.098Mpa, be distilled at 150 ~ 190 DEG C without till overhead product, collect overhead product and namely obtain δ-3-pentenoic acid lactone.
5-of the present invention chloro-3-pentenoate is one or more in 5-chloro-3-amylene-4 acid methyl ester, 5-chloro-3-pentenoic acid ethyl ester, 5-chloro-3-pentenoic acid propyl ester, 5-chloro-3-pentenoic acid butyl ester; The chloro-3-pentenoate of 5-of the present invention adopts 1,3-butadiene and chloro-formic ester to obtain through acidylate addition reaction one step in catalysts and solvents.
M of the present invention is the one in Li, Na, K.
The mol ratio of the chloro-3-pentenoate of 5-of the present invention, carboxylic acid, carboxylate salt is 1:2 ~ 5:1 ~ 2.
Beneficial effect of the present invention is:
1, the present invention with the chloro-3-pentenoate of 5-for predominant starting material, the chloro-3-pentenoate of 5-, carboxylic acid and carboxylate salt one-step synthesis δ-3-pentenoic acid lactone, synthetic route is short, finished product δ-3-pentenoic acid lactone yield is high, purity is high, δ-3-pentenoic acid lactone yield is between 77.6% ~ 91.8%, and purity is between 96% ~ 98%.
2, the chloro-3-pentenoate of starting raw material 5-of the present invention adopts 1; 3-divinyl and chloro-formic ester obtain through acidylate addition reaction one step in catalysts and solvents; prepared 5-chloro-3-pentenoate cost is low, can reduce the preparation cost of δ-3-pentenoic acid lactone of the present invention further.
3, preparation method of the present invention is simple, reaction conditions is gentle, and carboxylic acid used and carboxylate salt are conventional chemical material, production security high and be convenient to control, be easy to suitability for industrialized production.
4, preparation method's waste of the present invention is few, reacts the ester byproducts material generated and is reclaimed by concentrating under reduced pressure, clean environment firendly.
Embodiment
Can better understand the present invention for making those skilled in the art and can be implemented, below in conjunction with specific embodiment, the present invention is further elaborated.
One, embodiment of the present invention part
Embodiment 1
5-chloro-3-amylene-4 acid methyl ester 1mol, sodium-acetate 1mol and acetic acid 2mol is added, stirring and refluxing reaction 10h at 100 ~ 105 DEG C in reactor; Reaction solution is-0.09Mpa in vacuum tightness, be evaporated at 80 ~ 100 DEG C without till overhead product, be cooled to 38 DEG C again, crossed by concentrated solution and filter insolubles, filtrate is-0.098Mpa in vacuum tightness, is distilled to without till overhead product at 150 ~ 190 DEG C, obtain 80 grams of δ-3-pentenoic acid lactones, GC (GasChromatography, gas-chromatography are called for short GC) purity is 97%.
Embodiment 2
5-chloro-3-pentenoic acid ethyl ester 1mol, Potassium ethanoate 1.5mol and acetic acid 5mol is added, stirring and refluxing reaction 8h at 110 ~ 115 DEG C in reactor; Reaction solution is-0.09Mpa in vacuum tightness, be evaporated at 80 ~ 100 DEG C without till overhead product, be cooled to 41 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.098Mpa in vacuum tightness, be distilled to without till overhead product at 150 ~ 180 DEG C, obtain 84 grams of δ-3-pentenoic acid lactones, GC purity is 98%.
Embodiment 3
5-chloro-3-pentenoic acid butyl ester 1mol, propionic acid lithium 2mol and butanic acid 2mol is added, stirring and refluxing reaction 5h at 145 ~ 150 DEG C in reactor; Reaction solution is-0.088Mpa in vacuum tightness, be evaporated at 100 ~ 110 DEG C without till overhead product, be cooled to 40 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.097Mpa in vacuum tightness, be distilled to without till overhead product at 150 ~ 180 DEG C, obtain 76 grams of δ-3-pentenoic acid lactones, GC purity is 96%.
Embodiment 4
5-chloro-3-pentenoic acid propyl ester 1mol, Sodium Propionate 1.2mol and propionic acid 3mol is added, stirring and refluxing reaction 5h at 120 ~ 125 DEG C in reactor; Reaction solution is-0.088Mpa in vacuum tightness, be evaporated at 100 ~ 110 DEG C without till overhead product, be cooled to 45 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.098Mpa in vacuum tightness, be distilled to without till overhead product at 160 ~ 180 DEG C, obtain 83 grams of δ-3-pentenoic acid lactones, GC purity is 97%.
Embodiment 5
5-chloro-3-pentenoic acid ethyl ester 1mol, potassium butyrate 1.3mol and propionic acid 3mol is added, stirring and refluxing reaction 6h at 115 ~ 120 DEG C in reactor; Reaction solution is-0.089Mpa in vacuum tightness, be evaporated at 90 ~ 110 DEG C without till overhead product, be cooled to 40 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.097Mpa in vacuum tightness, be distilled to without till overhead product at 160 ~ 190 DEG C, obtain 79 grams of δ-3-pentenoic acid lactones, GC purity is 97%.
Embodiment 6
5-chloro-3-pentenoic acid butyl ester 1mol, potassium butyrate 1.8mol and butanic acid 5mol is added, stirring and refluxing reaction 8h at 115 ~ 120 DEG C in reactor; Reaction solution is-0.09Mpa in vacuum tightness, be evaporated at 90 ~ 110 DEG C without till overhead product, be cooled to 39 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.098Mpa in vacuum tightness, be distilled to without till overhead product at 150 ~ 190 DEG C, obtain 85 grams of δ-3-pentenoic acid lactones, GC purity is 98%.
Embodiment 7
5-chloro-3-pentenoic acid ethyl ester 1mol, Lithium Acetate 1.2mol and propionic acid 2mol is added, stirring and refluxing reaction 6h at 135 ~ 140 DEG C in reactor; Reaction solution is-0.089Mpa in vacuum tightness, be evaporated at 100 ~ 110 DEG C without till overhead product, be cooled to 35 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.097Mpa in vacuum tightness, be distilled to without till overhead product at 150 ~ 190 DEG C, obtain 81 grams of δ-3-pentenoic acid lactones, GC purity is 96%.
Embodiment 8
5-chloro-3-pentenoic acid propyl ester 1mol, Potassium ethanoate 1.6mol and propionic acid 4mol is added, stirring and refluxing reaction 7h at 125 ~ 130 DEG C in reactor; Reaction solution is-0.09Mpa in vacuum tightness, be evaporated at 100 ~ 110 DEG C without till overhead product, be cooled to 40 DEG C again, concentrated solution is crossed and filters insolubles, filtrate is-0.098Mpa in vacuum tightness, be distilled to without till overhead product at 160 ~ 180 DEG C, obtain 90 grams of δ-3-pentenoic acid lactones, GC purity is 98%.
Two, experimental sections
The weight of the embodiment of the present invention 1 ~ 8 target product δ-3-pentenoic acid lactone and yield are respectively by weighing and calculate, and its purity adopts vapor-phase chromatography to detect.The detected result of embodiment 1 ~ 8 target product δ-3-pentenoic acid lactone is in table 1.
Table 1 embodiment 1 ~ 8 target product δ-3-pentenoic acid lactone detected result
The embodiment of the present invention 1 ~ 8 target product δ-3-pentenoic acid lactone yield is between 77.6% ~ 91.8%, and between product purity 96% ~ 98%, not only yield is high for δ-3-pentenoic acid lactone prepared by preparation method of the present invention, and purity is also high.
Claims (6)
1. a preparation method for δ-3-pentenoic acid lactone, is characterized in that comprising the following steps:
1) the chloro-3-pentenoate of 5-, carboxylic acid and carboxylate salt are at 100 ~ 150 DEG C of back flow reaction 5 ~ 10h, and obtain reaction solution A, the chemical equation that described back flow reaction comprises is;
Described R is the alkyl of C1 ~ C4, and described M is metallic element, the alkyl that described R ' is C1 ~ C3;
2) described reaction solution A obtains δ-3-pentenoic acid lactone after separation and purification.
2. the preparation method of δ-3-pentenoic acid lactone according to claim 1, it is characterized in that: the method for described separation and purification is at vacuum tightness-0.088Mpa ~-0.09Mpa, be evaporated at 80 ~ 110 DEG C without till overhead product, be cooled to 35 ~ 45 DEG C again, concentrated solution is crossed and filters insolubles, filtrate, at vacuum tightness-0.097Mpa ~-0.098Mpa, is distilled at 150 ~ 190 DEG C without till overhead product, collects overhead product and namely obtains δ-3-pentenoic acid lactone.
3. the preparation method of δ-3-pentenoic acid lactone according to claim 1, is characterized in that: described 5-chloro-3-pentenoate is one or more in 5-chloro-3-amylene-4 acid methyl ester, 5-chloro-3-pentenoic acid ethyl ester, 5-chloro-3-pentenoic acid propyl ester, 5-chloro-3-pentenoic acid butyl ester.
4. the preparation method of δ-3-pentenoic acid lactone according to claim 1, is characterized in that: described R ' is methyl, one in ethyl, propyl group.
5. the preparation method of δ-3-pentenoic acid lactone according to claim 1, is characterized in that: described M is the one in Li, Na, K.
6. the preparation method of δ-3-pentenoic acid lactone according to claim 1, is characterized in that: the mol ratio of the chloro-3-pentenoate of described 5-, carboxylic acid, carboxylate salt is 1:2 ~ 5:1 ~ 2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610039926.0A CN105541771B (en) | 2016-01-21 | 2016-01-21 | A kind of preparation method of the amylene acid lactones of δ 3 |
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| CN201610039926.0A CN105541771B (en) | 2016-01-21 | 2016-01-21 | A kind of preparation method of the amylene acid lactones of δ 3 |
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| CN105541771B CN105541771B (en) | 2017-11-10 |
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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 |
|---|
| BARTOLO GABRIEL ET AL.: "A simple catalytic system for the substitutive carbonylation of allyl alcohols to β,γ-unsaturated acids or esters", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| MICHAEL B. BURT ET AL.: "Ring-chain equilibria of R-but-3-enoate esters —A quantum mechanical study of direct and indirect ring-closing reactions", 《CAN. J. CHEM.》 * |
| PETER R. ANDREANA ET AL.: "Synthesis of 2,6-Dideoxysugars via Ring-Closing Olefinic Metathesis", 《ORGANIC LETTERS》 * |
| YASUSHI NAKASHIMA ET AL.: "Synthesis of β,γ-Unsaturated Valerolactones", 《SYNTHETIC COMMUNICATIONS》 * |
| 张月: "亚铜催化的溴代烯酸分子内偶联反应的研究", 《万方数据知识服务平台 学位论文》 * |
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