CN107954864A - A kind of preparation method of tricyclodecenyl esters - Google Patents
A kind of preparation method of tricyclodecenyl esters Download PDFInfo
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- CN107954864A CN107954864A CN201710989656.4A CN201710989656A CN107954864A CN 107954864 A CN107954864 A CN 107954864A CN 201710989656 A CN201710989656 A CN 201710989656A CN 107954864 A CN107954864 A CN 107954864A
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- preparation
- acid
- carboxylic acid
- tricyclodecenyl esters
- sulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of tricyclodecenyl esters, and it is 100~120 DEG C to be included in excessive carboxylic acid in the presence of fluorine antimony sulfonic acid and dicyclopentadiene addition reaction, reaction temperature.The preparation method product of the tricyclodecenyl esters is not required to wash, and has the advantages that technique is simple, environmental-friendly and high income.
Description
Technical field
The present invention relates to a kind of preparation method of tricyclodecenyl esters.
Background technology
Tricyclodecenyl esters refer mainly to the ester obtained by carboxylic acid and dicyclopentadiene addition, a kind of widely used fine chemistry
Product, can be used as spices and medical synthesis material, be mainly used in synthetic perfume industry, essential oil industry, compound perfume industry and food
Product perfume industry.
Most common tricyclodecenyl esters such as cyclacet, existing production technology are：With dicyclopentadiene and greatly
Excessive acetic acid or aceticanhydride are measured, addition reaction is carried out as catalyst with perchloric acid, the vinegar with alkali neutralization excess is needed after reaction
Acid and acid anhydrides, while need washing to remove the salinity in organic phase again, the yield of product reduces while producing a large amount of waste water.
Patent 200780025813.4 discloses the method for preparing tricyclodecenyl esters, and C2-C4 is catalyzed using trifluoromethanesulfonic acid
Addition reaction between carboxylic acid and dicyclopentadiene.Although this method uses the C2-C4 carboxylic acids for being approximately equal to molar ratio and bicyclic penta 2
Alkene reaction, but after reacting after still need to use alkali neutralization, and use salt water washing organic phase, required isomers ＞ in product after washing
90wt.%
To solve the above-mentioned problems, the yield of tricyclodecenyl esters is improved, reduces water pollution, we are seeking a kind of preferable always
Technical solution.
The content of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, so as to provide, a kind of technique is simple, environmental-friendly and yield
The preparation method of high tricyclodecenyl esters.
A kind of preparation method of cyclacet, is included in excessive carboxylic acid and bicyclic penta 2 in the presence of fluorine antimony sulfonic acid
Alkene addition reaction, reaction temperature are 100~120 DEG C.Carboxylic acid of the present invention is that have at most four carbon atom, including second
Acid, propionic acid, butyric acid and isobutyric acid, and ester obtained by the more carboxylic acid additions of carbon number is without industrial required fragrance, first
The ester of sour addition has other peculiar smell, and acetic acid is most common carboxylic acid, in the present invention preferred acetic acid.
Acetic acid of the present invention can be glacial acetic acid, can also acid anhydrides and water reaction generation, can also be this hair
The acetic acid containing micro ester being distilled to recover after bright reaction, Han Liang≤90wt.%, raw material are easy to get.Used acetic acid is excessive
, preferably the amount ratio of the material of acetic acid and dicyclopentadiene is 1.5~2：1, excessive acetic acid can be distilled to recover after the reaction
Applied mechanically to next group.
Fluorine antimony sulfonic acid is super acids, provides proton ability in the reaction, interrupts dipentadiene carbon-carbon double bond and causes double penta 2
Alkene and carboxylic acid addition, using commercial product.The amount that fluorine antimony sulfonic acid is used in the present invention is catalyst dosage, preferably fluorine antimony sulphur
The mass ratio of acid and dicyclopentadiene is 0.1~1:100, more preferably the mass ratio of fluorine antimony sulfonic acid and dicyclopentadiene for 0.1~
0.5:100.Fluorine antimony sulfonic acid can use the alkali neutralization for being approximately equal to equivalent after the reaction, and preferably sodium, the carbonate of potassium neutralizes, is not required to wash
Wash, stayed in after product rectifying kettle it is residual in.
Based on above-mentioned, the addition reaction is added drop-wise to dicyclopentadiene in the mixed liquor of carboxylic acid and fluorine antimony sulfonic acid.More
It is added drop-wise to again after preferably dicyclopentadiene is mixed with carboxylic acid in the mixed liquor of carboxylic acid and fluorine antimony sulfonic acid.Because the present invention is urging
The lower reaction of agent effect is violent, maintains 100~110 DEG C in order to reduce accessory substance and more preferable heat dissipation, reaction temperature, drips
After can improve reaction temperature to 110~120 DEG C to reduce the reaction time, time for adding is limited with temperature control, can also be broken
It is continuous to be added dropwise.React after carboxylic acid is distilled off, Han Liang≤98% of tricyclodecenyl esters in chromatography product.
The present invention has prominent substantive distinguishing features and significant progress compared with the prior art, specifically, of the invention
Addition reaction uses fluorine antimony sulfonic acid as catalyst, and alkali neutralization is used after reaction, but is not required to wash, and technique is simple, technique green and production
Product high income.Furtherly, the present invention is not high to reactant carboxylic acid purity requirement, and raw material is easy to get.Further step is said, mistake in the present invention
The carboxylic acid of amount can be with recovery, and raw material availability is high, and production cost is low.It is with high income, production cost is low and technique is green
The advantages of color.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
The 3820g cyclopentadiene that mass fraction is 95% is added drop-wise to 4190g acetic acid and 20g fluorine antimony sulfonic acid at 102~104 DEG C
Mixed liquor in, while be added dropwise while stir.After being added dropwise to complete, 115~117 DEG C are warming up to, insulation, middle control samples cyclopentadiene content
For 0.16% when, stop insulation.Input 11.7g natrium carbonicum calcinatums are stirred into product, catalyst neutralisation.By the generation of neutralization
Thing filtering and then vacuum distillation obtain acetic acid 2491g, crude product cyclacet 5503g, and acetic acid tricyclic is obtained after rectifying
Ubidecarenone 4405g, content 98.2%, yield 90.7%.
Embodiment 2
Recycle acetic acid 2830g and survey moisture, calculate the aceticanhydride amount that need to be added（g）=moisture（g）* 40, aceticanhydride 5.7g are thrown
Half an hour is stirred after entering reaction kettle, 4g fluorine antimony sulfonic acid input wherein stirring 10min is stirred evenly.
3820g cyclopentadiene and 1360g glacial acetic acid that mass fraction is 95% are mixed, 15min is stirred, makes cyclopentadiene
It is uniformly mixed with glacial acetic acid.
The mixture of 5180g cyclopentadiene and glacial acetic acid is added drop-wise to 2839.7g acetic acid and fluorine antimony at 105~107 DEG C
In the mixed liquor of sulfonic acid, stirred when being added dropwise, when final time for adding is 8.3 small.After being added dropwise to complete, 115~117 are warming up to
DEG C, insulation, when middle control sampling cyclopentadiene content is 0.18%, stops insulation, soaking time come to 2.3 it is small when.Put into 2.4g
Natrium carbonicum calcinatum is stirred into product, catalyst neutralisation.The product filtering and then vacuum distillation of neutralization are obtained into acetic acid
2478g, crude product cyclacet 5513g, obtain cyclacet 4313g, content 98.5%, yield after rectifying
For 89.1%.
Finally it should be noted that:The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
It can modify to the embodiment of the present invention or equivalent substitution is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical solution, it should all cover among the claimed technical solution scope of the present invention.
Claims (6)
1. a kind of preparation method of tricyclodecenyl esters, it is included in excessive carboxylic acid in the presence of fluorine antimony sulfonic acid and dicyclopentadiene addition
Reaction, reaction temperature are 100~120 DEG C.
2. the preparation method of tricyclodecenyl esters according to claim 1, it is characterised in that：The carboxylic acid is C2~C4 carboxylics
Acid.
3. the preparation method of tricyclodecenyl esters according to claim 1 or 2, it is characterised in that：Carboxylic acid and dicyclopentadiene
Material amount ratio be 1.5~2：1.
4. according to the preparation method of the tricyclodecenyl esters described in claim 3, it is characterised in that：Fluorine antimony sulfonic acid and dicyclopentadiene
Mass ratio is 0.1~1:100.
5. according to the preparation method of the tricyclodecenyl esters described in claim 4, it is characterised in that：The addition reaction is by bicyclic penta
Diene is added drop-wise in the mixed liquor of carboxylic acid and fluorine antimony sulfonic acid.
6. according to the preparation method of the tricyclodecenyl esters described in claim 5, it is characterised in that：The addition reaction is by bicyclic penta
Diene is added drop-wise in the mixed liquor of carboxylic acid and fluorine antimony sulfonic acid again after being mixed with carboxylic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710989656.4A CN107954864A (en) | 2017-10-23 | 2017-10-23 | A kind of preparation method of tricyclodecenyl esters |
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| CN201710989656.4A CN107954864A (en) | 2017-10-23 | 2017-10-23 | A kind of preparation method of tricyclodecenyl esters |
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| CN201710989656.4A Pending CN107954864A (en) | 2017-10-23 | 2017-10-23 | A kind of preparation method of tricyclodecenyl esters |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912410A (en) * | 2019-03-28 | 2019-06-21 | 浙江师范大学 | Prepare method, the reaction intermediate and preparation method thereof of tricyclo decene alcohol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008008836A2 (en) * | 2006-07-11 | 2008-01-17 | Wellman, Inc. | Composite solid phase polymerization catalyst |
| CN101679195A (en) * | 2007-06-05 | 2010-03-24 | 美礼联专用化学品公司 | Process for making tricyclodecenyl esters |
| CN103193639A (en) * | 2012-01-10 | 2013-07-10 | 南昌洋浦天然香料香精有限公司 | Synthetic method of perfume verdyl acetate |
-
2017
- 2017-10-23 CN CN201710989656.4A patent/CN107954864A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008008836A2 (en) * | 2006-07-11 | 2008-01-17 | Wellman, Inc. | Composite solid phase polymerization catalyst |
| CN101679195A (en) * | 2007-06-05 | 2010-03-24 | 美礼联专用化学品公司 | Process for making tricyclodecenyl esters |
| CN103193639A (en) * | 2012-01-10 | 2013-07-10 | 南昌洋浦天然香料香精有限公司 | Synthetic method of perfume verdyl acetate |
Non-Patent Citations (2)
| Title |
|---|
| 上海日用化学工业研究所: "乙酸三环癸烯酯的合成(实验室工作小结)", 《上海日用化工》 * |
| 张贺等: "乙酸三环癸烯酯的合成工艺研究", 《化学工程师》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912410A (en) * | 2019-03-28 | 2019-06-21 | 浙江师范大学 | Prepare method, the reaction intermediate and preparation method thereof of tricyclo decene alcohol |
| CN109912410B (en) * | 2019-03-28 | 2022-02-15 | 浙江师范大学 | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof |
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