CN106748641A - A kind of method of synthesis 4- decylenic acids - Google Patents
A kind of method of synthesis 4- decylenic acids Download PDFInfo
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- CN106748641A CN106748641A CN201510827681.3A CN201510827681A CN106748641A CN 106748641 A CN106748641 A CN 106748641A CN 201510827681 A CN201510827681 A CN 201510827681A CN 106748641 A CN106748641 A CN 106748641A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/27—Preparation of carboxylic acid esters from ortho-esters
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Abstract
The invention discloses a kind of method of synthesis 4- decylenic acids, with 1-OCOL and ortho-acetate as raw material, it is heated to reflux under conditions of catalyst, while distilling out the ethanol of generation, vacuum distillation again removes excessive ortho-acetate, last rectifying obtains pure 4- decenoates, and 4- decenoates are heated to reflux in the basic conditions, and redistillation goes out the alcohol compound of hydrolysis, regulation pH=7, extraction, distillation, last rectifying obtains pure 4- decylenic acids.The present invention provides a kind of process that pure 4- decylenic acids are obtained by Claisen rearrangement reactions, with synthesis technique it is simple the characteristics of.
Description
Technical field
The invention belongs to technical field of food additives, more specifically, it relates to a kind of synthetic method of 4- decylenic acids.
Background technology
Decylenic acid is the important compound of a class, particularly 4- decylenic acids, and it is the accreditation of flavorant manufacture NAB National Association 0f Broadcasters of the U.S.
Safe edible spices (registration number is 3914).It has strong milk fragrance, is milk, cream, cheese essence it is important
Raw material, the local flavor to improving and improving food plays the role of important.
In the preparation method of existing decylenic acid, the predominantly synthesis of 5 (6)-decylenic acids seldom relates to 4- decylenic acids
Synthesis.For example：The Chinese patent (documents 1) of Publication No. CN1266841A, discloses a kind of 5 (6)-decylenic acids
Synthesis, its process route is with cyclohexanone and butyraldehyde as raw material, by alkaline condensation, selective hydrogenation, hydrogen peroxide ring expansion
It is lactone, finally dehydration obtains 5 (6)-decylenic acids under acid condition again；Authorization Notice No. is the Chinese patent of CN1291966C
(documents 2), there is provided one kind prepares the new method of 5 (6)-decylenic acids, are in multiphase bifunctional catalyst with cyclohexanone
Palladium/alundum (Al2O3) effect is lower and butyraldehyde is condensed, is dehydrated, hydrogenates, and one-step method realizes the preparation of butyl alkyl ketone, butyl alkyl
Ketone is again lactone by hydrogen peroxide ring expansion, and finally open loop obtains 5 (6)-decylenic acids in acid condition；Authorization Notice No. is
The Chinese patent (documents 3) of CN1184186C, there is provided a kind of new technique for preparing decylenic acid, is with aldehydes and ring
Ketone carries out selective hydrogenation using palladium for raw material carries out the product after alkaline condensation as catalyst, and the product of selective hydrogenation is through 20%
Peracetic acid oxidation after, carclazyte open loop through being processed with phosphoric acid is obtained decylenic acid, such as with hutanal and cyclohexanone as raw material, makes
Obtain 5 (6)-decylenic acids, it is also possible to valeral and cyclopentanone as raw material, 4 (5)-decylenic acids are obtained.
It can thus be seen that the synthesis of 5 (6)-decylenic acids is related generally in documents 1~3, and synthesis technique is complicated；
Although and be related to the preparation of 4- decylenic acids in documents 3, what it was obtained is the mixing of 4- decylenic acids and 5- decylenic acids
Thing, and pure 4- decylenic acids can not be prepared, and synthesize the method for pure 4- decylenic acids and be not reported so far.
The content of the invention
In view of the shortcomings of the prior art, obtain pure by Claisen rearrangement reactions it is an object of the invention to provide one kind
4- decylenic acids process, with synthesis technique it is simple the characteristics of.
Process route of the invention is as follows：
The process that the present invention is provided, comprises the following steps：
A kind of method of synthesis 4- decylenic acids, it is characterised in that comprise the following steps：
(1) preparation of 4- decenoates
With 1-OCOL and ortho esters as raw material, it is heated to reflux under conditions of catalyst, while distilling out the ethanol of generation, is reacted
After end, vacuum distillation removes excessive ortho esters, then rectifying obtains pure 4- decenoates；
(2) preparation of 4- decylenic acids
4- decenoates react in the basic conditions, after reaction terminates, distill out the alcohol compound of hydrolysis, adjust anti-with pH adjusting agent
It is 6.5~7.5 to answer liquid, then by steps such as extraction, distillations, steams extract, and last rectifying obtains pure 4- decylenic acids.
Preferably, the structural formula of ortho esters described in step (1) is Formulas I：, wherein R1、R2And R3Carbon number be 1~5.
Preferably, described ortho esters is trimethyl orthoacetate, triethly orthoacetate.
By using above-mentioned technical proposal,
Preferably, the catalyst described in step (1) is formic acid, acetic acid, propionic acid and its homologue.
Preferably, the mol ratio of the 1-OCOL, ortho esters and catalyst described in step (1) is 50: 60~150: 3.
Preferably, the structural formula of described 4- decylenic acids is Formula II：.
Preferably, in step (1), the reaction time is 2~4 hours, reaction temperature is 70~150 DEG C.
Preferably, in step (2), the reaction time is 3.5~4.5 hours, reaction temperature is 0~100 DEG C.
Preferably, in step (2), the reaction time is 4 hours, reaction temperature is 65~100 DEG C.
The present invention has the advantages that：
1st, the present invention prepares pure 4- decylenic acids by substitution reaction, Claisen rearrangement reactions, hydrolysis, and centre is without by-product
The generation of thing, requires no purification step, enormously simplify production technology, easy to operate；The generation for not having accessory substance be due to
Reactions steps are few, and required raw material is few, and solvent is gentle, and reaction condition is gentle etc..
Will not be introduced into makes the derivant of generation accessory substance in reaction, solvent
2nd, raw material is cheap, reduces production cost.
3rd, the reaction condition in step (1) and step (2), it is easy to control, and will not cause danger.
4th, the solvent used during extraction in step (2) is typically chosen Conventional solvents ethyl acetate, and the boiling point of ethyl acetate is
77 DEG C, it is easy to remove, therefore the dissolvent residual of product is extremely low, product quality is secure.
5th, the loss of product is mainly derived from necessary loss during purification, therefore reaction has a yield higher, product have compared with
Purity high.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the 4- decylenic acids of present invention synthesis.
Specific embodiment
Embodiment one：
(1) preparation of 4- decenoates
1-OCOL 12.82g and triethly orthoacetate 32.45g, propionic acid 0.44g mix, and are heated to 70 DEG C, while distilling birth
Into ethanol, react about 2 hours reaction terminate.Vacuum distillation removes excessive triethly orthoacetate.Then obtained with oil pump rectifying
To the 4- decenoate 19.83g of liquid, yield 99.7%.
(2) preparation of 4- decylenic acids
6.4g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoates 19.83g heating
To 100 DEG C, react 4.5 hours, reaction terminates.Reflux is changed to distilling apparatus, the ethanol of hydrolysis is slowly steamed, until
There is no ethanol to steam, reaction solution becomes clear.The aqueous solution configured with the water of the 10mL concentrated sulfuric acids and 26mL is neutralized to neutrality
(PH=7) ethyl acetate extraction (75mL*2), is added, collected organic layer is washed once, and anhydrous magnesium sulfate is dried, mistake
Filter, washing, then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 15.67g, is trans 4- through analytical proof
Decylenic acid, total recovery 92.1%.
Embodiment two：
(1) preparation of 4- decenoates
1-OCOL 12.82g and triethly orthoacetate 64.90g, propionic acid 0.44g mix, and are heated to 150 DEG C, while distilling birth
Into ethanol, react about 3 hours reaction terminate.Vacuum distillation removes excessive triethly orthoacetate.Then obtained with oil pump rectifying
To the 4- decenoate 19.86g of liquid, yield 99.9%.
(2) preparation of 4- decylenic acids
6.5g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoates 19.86g heating
To 65 DEG C, back flow reaction 4 hours, reaction terminates.Reflux is changed to distilling apparatus, the ethanol of hydrolysis is slowly steamed, directly
Steamed to no ethanol, reaction solution becomes clear.During the aqueous solution configured with the water of the 10mL concentrated sulfuric acids and 26mL is neutralized to
Property (PH=7), add ethyl acetate extraction (75mL*2), collected organic layer, washing once, anhydrous magnesium sulfate dry,
Filtering, washing, then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 15.95g, is trans 4- through analytical proof
Decylenic acid, total recovery 93.7%.
Embodiment three：
(1) preparation of 4- decenoates
1-OCOL 12.82g and triethly orthoacetate 42.05g, propionic acid 0.44g mix, and are heated to 100 DEG C, while distilling birth
Into ethanol, react about 4 hours reaction terminate.Vacuum distillation removes excessive triethly orthoacetate.Then obtained with oil pump rectifying
To the 4- decenoate 19.82g of liquid, yield 99.2%.
(2) preparation of 4- decylenic acids
6.4g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoate 19.82g normal temperature
Reaction 3.5 hours, reaction terminates.Reflux is changed to distilling apparatus, the ethanol of hydrolysis is slowly steamed, until without ethanol
Steam, reaction solution becomes clear.The aqueous solution configured with the water of the 10mL concentrated sulfuric acids and 26mL is neutralized to neutral (PH=7),
Ethyl acetate extraction (75mL*2) is added, collected organic layer is washed once, and anhydrous magnesium sulfate is dried, filtering, washing,
Then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 15.76g, is trans 4- decylenic acids through analytical proof, total to receive
Rate 92.6%.
Example IV：
(1) preparation of 4- decenoates
1-OCOL 12.82g and trimethyl orthoacetate 24.03g, propionic acid 0.44g mix, and 80 DEG C are heated to, while distilling out generation
Methyl alcohol, react about 2 hours reaction terminate.The excessive trimethyl orthoacetate of vacuum distillation, then obtains the 4- last of the ten Heavenly stems with oil pump rectifying
E pioic acid methyl ester 18.3g, yield 98.7%.
(2) preparation of 4- decylenic acids
6.4g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoates 18.3g to be heated to
70 DEG C, react 4 hours.Reflux is changed to distilling apparatus, the methyl alcohol of hydrolysis is slowly steamed, until no methyl alcohol steam for
Only, reaction solution becomes clear, and reaction terminates.During the aqueous solution configured with 10 milliliters of concentrated sulfuric acids and 26 milliliters of water is neutralized to
Property (PH=7), add ethyl acetate extraction (75mL*2), collected organic layer, washing once, anhydrous magnesium sulfate dry,
Filtering, washing, then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 16.9g, is trans 4- through analytical proof
Decylenic acid, total recovery 98.8%.
Embodiment five：
(1) preparation of 4- decenoates
1-OCOL 12.82g and trimethyl orthoacetate 50.93g, propionic acid 0.44g mix, and are heated to 125 DEG C, while distilling birth
Into methyl alcohol, react about 2 hours reaction terminate.The excessive trimethyl orthoacetate of vacuum distillation, then obtains 4- with oil pump rectifying
Decenoate 18.4g, yield 99.5%.
(2) preparation of 4- decylenic acids
6.4g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoates 18.4g to be heated to
70 DEG C, react 4.5 hours.Reflux is changed to distilling apparatus, the methyl alcohol of hydrolysis is slowly steamed, until no methyl alcohol is steamed
Untill, reaction solution becomes clear, and reaction terminates.The aqueous solution configured with 10 milliliters of concentrated sulfuric acids and 26 milliliters of water is neutralized to
Neutral (PH=7), adds ethyl acetate extraction (75mL*2), and collected organic layer is washed once, and anhydrous magnesium sulfate is dried,
Filtering, washing, then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 16.6g, is trans 4- through analytical proof
Decylenic acid, total recovery 97.3%.
Embodiment six：
(1) preparation of 4- decenoates
1-OCOL 12.82g and trimethyl orthoacetate 35.50g, propionic acid 0.44g mix, and 80 DEG C are heated to, while distilling out generation
Methyl alcohol, react 3 hours reaction terminate.The excessive trimethyl orthoacetate of vacuum distillation, then obtains 4- decene with oil pump rectifying
Sour methyl esters 18.1g, yield 97.9%.
(2) preparation of 4- decylenic acids
6.4g potassium hydroxide and 110mL water mix, and stirring to potassium hydroxide is completely dissolved, and add 4- decenoates 18.1g to be heated to
80 DEG C, react 4 hours.Reflux is changed to distilling apparatus, the methyl alcohol of hydrolysis is slowly steamed, until no methyl alcohol steam for
Only, reaction solution becomes clear, and reaction terminates.During the aqueous solution configured with 10 milliliters of concentrated sulfuric acids and 26 milliliters of water is neutralized to
Property (PH=7), add ethyl acetate extraction (75mL*2), collected organic layer, washing once, anhydrous magnesium sulfate dry,
Filtering, washing, then rotation steams ethyl acetate, then rectification under vacuum obtains 4- decylenic acid 16.7g, is trans 4- through analytical proof
Decylenic acid, total recovery 98.1%.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment,
All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that general for the art
For logical technical staff, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (9)
1. a kind of method of synthesis 4- decylenic acids, it is characterised in that comprise the following steps：
(1) preparation of 4- decenoates
With 1-OCOL and ortho esters as raw material, it is heated to reflux under conditions of catalyst, while distilling out the ethanol of generation, is reacted
After end, vacuum distillation removes excessive ortho esters, then rectifying obtains pure 4- decenoates；
(2) preparation of 4- decylenic acids
4- decenoates react in the basic conditions, after reaction terminates, distill out the alcohol compound of hydrolysis, adjust anti-with pH adjusting agent
It is 6.5~7.5 to answer liquid, then by steps such as extraction, distillations, steams extract, and last rectifying obtains pure 4- decylenic acids.
2. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that the knot of ortho esters described in step (1)
Structure formula is Formulas I：, wherein R1、R2And R3Carbon number be 1~5.
3. the method for synthesis 4- decylenic acids according to claim 2, it is characterised in that described ortho esters be trimethyl orthoacetate,
Triethly orthoacetate.
4. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that the catalyst described in step (1) is
Formic acid, acetic acid, propionic acid and its homologue.
5. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that the 1- octenes -3- described in step (1)
The mol ratio of alcohol, ortho esters and catalyst is 50: 60~150: 3.
6. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that the structural formula of described 4- decylenic acids is formula
II：.
7. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that in step (1), the reaction time is 2~
4 hours, reaction temperature was 70~150 DEG C.
8. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that in step (2), the reaction time is 3.5~
4.5 hours, reaction temperature was 0~100 DEG C.
9. the method for synthesis 4- decylenic acids according to claim 1, it is characterised in that in step (2), the reaction time is 4
Hour, reaction temperature is 65~100 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837671A (en) * | 1995-11-10 | 1998-11-17 | Givaudan-Roure (International) Sa | Organoleptic compound and composition |
| CN101157608A (en) * | 2007-11-20 | 2008-04-09 | 敖枝平 | Method for preparing 4-pentenoic acid |
| CN101665426A (en) * | 2009-09-29 | 2010-03-10 | 上海立科化学科技有限公司 | Method for preparing 2-alkyl carboxylic acid |
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2015
- 2015-11-24 CN CN201510827681.3A patent/CN106748641A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837671A (en) * | 1995-11-10 | 1998-11-17 | Givaudan-Roure (International) Sa | Organoleptic compound and composition |
| CN101157608A (en) * | 2007-11-20 | 2008-04-09 | 敖枝平 | Method for preparing 4-pentenoic acid |
| CN101665426A (en) * | 2009-09-29 | 2010-03-10 | 上海立科化学科技有限公司 | Method for preparing 2-alkyl carboxylic acid |
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