CN109912410B - Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof - Google Patents
Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof Download PDFInfo
- Publication number
- CN109912410B CN109912410B CN201910241116.7A CN201910241116A CN109912410B CN 109912410 B CN109912410 B CN 109912410B CN 201910241116 A CN201910241116 A CN 201910241116A CN 109912410 B CN109912410 B CN 109912410B
- Authority
- CN
- China
- Prior art keywords
- tricyclodecenyl
- trifluoroacetate
- reaction
- alcohol
- dicyclopentadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a method for preparing tricyclodecenyl alcohol, a reaction intermediate and a preparation method thereof. The preparation method of the tricyclodecenyl alcohol comprises the following steps: addition reaction of dicyclopentadiene and trifluoroacetic acid to obtain tricyclodecenyl trifluoroacetate, and hydrolysis with potassium carbonate to obtain tricyclodecenyl alcohol. The preparation method has the advantages of low reaction temperature, short time, less reaction pollutants and environmental friendliness, and the yield of the product tricyclodecenyl alcohol can reach 94 percent, and the purity can reach 98 percent.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for preparing tricyclodecenyl alcohol, a reaction intermediate and a preparation method thereof.
Background
Tricyclodecenyl alcohol is a component having vanilla and camphor odor that can be used as a fragrance. It can also be used as alcohol-containing component of unsaturated esters in the production of paints and synthetic resins. The tricyclodecenyl alcohol is also an important chemical raw material, and unsaturated polyester modified by the tricyclodecenyl alcohol can be self-polymerized without adding an active diluent; the tricyclodecenyl alcohol and the ethylene glycol are condensed to prepare ether, and the saturated polyester resin has low viscosity and good performance.
Numerous patents and literature disclose methods for hydrating dicyclopentadiene to make tricyclodecenyl alcohol, the process route being as follows:
octagonine and Korean dream bamboo subjects reported dicyclopentadiene and 20-25% H at about 100 ℃2SO4The tricyclodecenyl alcohol is produced through hydration reaction, and the yield is 75-85% (CN 101423459; CN 102659733). Although the method is simple, a large amount of sulfuric acid is needed in the hydration process, and environmental pollution is caused; and the product needs to be purified by reduced pressure distillation.
Furthermore, Japanese patent reports that hydration of dicyclopentadiene is catalyzed by a solid acid (Amberlyst 15), but the solid acid is expensive and not suitable for industrial production (JP 2008208062).
Disclosure of Invention
The invention aims to provide a method for preparing tricyclodecenyl alcohol, a reaction intermediate and a preparation method thereof aiming at the defects of the prior art.
The technical scheme provided by the invention is as follows:
a process for preparing tricyclodecenyl alcohol comprising: addition reaction of dicyclopentadiene and trifluoroacetic acid to obtain tricyclodecenyl trifluoroacetate, and hydrolysis with potassium carbonate to obtain tricyclodecenyl alcohol.
The reaction equation in the present invention is as follows:
the addition esterification reaction of dicyclopentadiene and trifluoroacetic acid has the advantages of low temperature, short time, high yield, no need of solvent, less reaction pollutants and environmental friendliness. Secondly, the reaction intermediate, namely the tricyclodecenyl trifluoroacetate is solid, and is purified by recrystallization, and after hydrolysis by potassium carbonate, the yield of tricyclodecenyl alcohol can reach 94 percent, and the purity can reach 98 percent.
Preferably, the feeding molar ratio of the dicyclopentadiene to the trifluoroacetic acid is 1: 1-2.
Preferably, the addition reaction occurs in the absence of a solvent.
Preferably, the reaction temperature of the addition reaction is 30-50 ℃.
Preferably, the reaction time of the addition reaction is 5-10 min.
Preferably, the addition reaction is completed and then extraction, washing, drying and recrystallization are carried out to obtain the tricyclodecenyl trifluoroacetate.
Preferably, the hydrolysis comprises dissolving tricyclodecenyl trifluoroacetate in methanol, adding potassium carbonate and stirring.
Preferably, after the hydrolysis is completed, the methanol is concentrated to dryness, and then extracted, washed and dried to obtain tricyclodecenyl alcohol.
The invention also provides tricyclodecenyl trifluoroacetate which has the following structural formula:
the invention also provides a preparation method of the tricyclodecenyl trifluoroacetate, which comprises the following steps: the dicyclopentadiene and trifluoroacetic acid are subjected to addition reaction to obtain tricyclodecenyl trifluoroacetate.
Preferably, the feeding molar ratio of the dicyclopentadiene to the trifluoroacetic acid is 1: 1-2.
Preferably, the addition reaction occurs in the absence of a solvent.
Preferably, the reaction temperature of the addition reaction is 30-50 ℃.
Preferably, the reaction time of the addition reaction is 5-10 min.
Preferably, the addition reaction is completed and then extraction, washing, drying and recrystallization are carried out to obtain the tricyclodecenyl trifluoroacetate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a method for preparing tricyclodecenyl alcohol by adding dicyclopentadiene and trifluoroacetic acid and then hydrolyzing, which greatly reduces the cost compared with the common synthesis method of tricyclodecenyl alcohol.
(2) In the invention, the reaction intermediate, namely the tricyclodecenyl trifluoroacetate, is a solid, and can be recrystallized and purified, and the purity of the product, namely the tricyclodecenyl alcohol, obtained by simple hydrolysis can reach 98 percent, and the product, namely the tricyclodecenyl alcohol, does not need to be purified by reduced pressure distillation.
(3) The preparation method has the advantages of high reaction yield, simple post-treatment, low environmental pollution and good application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 6.3g (0.055mol) of trifluoroacetic acid was slowly added dropwise thereto while controlling the reaction temperature at about 30 ℃. After the dropwise addition, the system was stirred and reacted for 10 min. 30mL of water was added to the reaction system, extraction was performed with dichloromethane (20mL x2), the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give a white solid, which was recrystallized from anhydrous ethanol to give 10.5g of tricyclodecenyl trifluoroacetate in a yield of 85%.
Characterization of reaction intermediates:1H NMR(600Hz,CDCl3)δ:5.74-5.76(m,1H),5.46-5.45(m,1H),4.91-4.90(m,1H),2.63-2.58(m,2H),2.27-2.26(m,1H),2.19-2.10(m,2H),1.96-1.86(m,2H),1.56-1.41(m,1H),1.39-1.38(m,2H).13C NMR(150Hz,CDCl3)δ:157.1(q,J＝42Hz),133.3,130.3,114.5(q,J＝285Hz),82.0,50.5,48.1,45.8,42.8,41.7,39.2,28.8.19F NMR(565Hz,CDCl3)δ:(-75.5).
(2) 10.5g tricyclodecenyl trifluoroacetate are dissolved in 100mL methanol and 11.7g K are added2CO3Stirred at room temperature for 2 h. Methanol was concentrated to dryness, 50mL of water was added, dichloromethane (50mL x2) was extracted, the organic phases were combined, washed with dilute hydrochloric acid (1mol/L) to neutrality, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to give 5.8g of tricyclodecenylalcohol as a colorless oil in 94% yield with a GC content of 97.5%.
Product tricyclodecenyl alcohol characterisation:1H NMR(600Hz,CDCl3)δ:5.67-5.65(m,1H),5.43-5.41(m,1H),3.81-3.74(m,1H),2.56-2.49(m,2H),2.45(s,1H),2.02-1.95(m,3H),1.89-1.84(m,1H),1.70-1.65(m,1H),1.38-1.35(m,1H),1.32-1.28(m,2H).13C NMR(150Hz,CDCl3)δ:132.4,131.2,74.7,51.2,48.8,42.9,42.0,41.8,39.2,28.1.
example 2
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 6.3g (0.055mol) of trifluoroacetic acid was slowly added dropwise thereto while controlling the reaction temperature at about 50 ℃. After the dropwise addition, the system was stirred for 5 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 10.2g of tricyclodecenyl trifluoroacetate in 83% yield.
(2) The procedure of example 1 was followed except that 10.2g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol, and 11.5g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.7g tricyclodecenyl alcohol as a colorless oil in 94.4% yield with a GC content of 97.3%.
Example 3
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 8.0g (0.07mol) of trifluoroacetic acid was slowly dropped thereinto, and the reaction temperature was controlled to about 40 ℃. After the dropwise addition, the system was stirred and reacted for 10 min. 30mL of water was added to the reaction system, extraction was performed with dichloromethane (20 mL. times. 2), the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 10.7g of tricyclodecenyl trifluoroacetate in a yield of 87%.
(2) The procedure of example 1 was followed except that 10.7g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol and 12.0g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 6.1g tricyclodecenyl alcohol as a colorless oil in 95.6% yield with 98% GC content.
Example 4
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 11.4g (0.1mol) of trifluoroacetic acid was slowly dropped thereinto, and the reaction temperature was controlled to about 30 ℃. After the dropwise addition, the system was stirred for 5 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 9.8g of tricyclodecenyl trifluoroacetate in a yield of 80%.
(2) The procedure of example 1 was followed except that 9.8g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol and 11.0g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.5g of tricyclodecenyl alcohol as a colorless oil in 93.5% yield with 98.0% GC content.
Example 5
(1) 6.6g (0.05mol) of dicyclopentadiene was charged in a 50mL round-bottomed flask, and 8.6g (0.075mol) of trifluoroacetic acid was slowly added dropwise thereto while controlling the reaction temperature at about 30 ℃. After the dropwise addition, the system was stirred and reacted for 10 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 10.6g of tricyclodecenyl trifluoroacetate in 86% yield.
(2) The procedure of example 1 was followed except that 10.6g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol, and 11.9g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.9g of tricyclodecenyl alcohol as a colorless oil in 94% yield with 98.1% GC content.
Example 6
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 6.8g (0.06mol) of trifluoroacetic acid was slowly dropped thereinto, and the reaction temperature was controlled to about 35 ℃. After the dropwise addition, the system was stirred and reacted for 8 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 10.5g of tricyclodecenyl trifluoroacetate in a yield of 85%.
(2) The procedure of example 1 was followed except that 10.5g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol, and 11.7g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.9g of tricyclodecenyl alcohol as a colorless oil in 95% yield and 97.6% GC content.
Example 7
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 5.7g (0.05mol) of trifluoroacetic acid was slowly dropped thereinto, and the reaction temperature was controlled to about 30 ℃. After the dropwise addition, the system was stirred and reacted for 10 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 9.8g of tricyclodecenyl trifluoroacetate in a yield of 80%.
(2) The procedure of example 1 was followed except that 9.8g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol and 11.0g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.5g of tricyclodecenyl alcohol as a colorless oil in 93.9% yield with 98% GC content.
Example 8
(1) 6.6g (0.05mol) of dicyclopentadiene was put in a 50mL round-bottomed flask, and 10.3g (0.09mol) of trifluoroacetic acid was slowly dropped thereinto, and the reaction temperature was controlled to about 48 ℃. After the dropwise addition, the system was stirred and reacted for 10 min. 30mL of water was added to the reaction system, dichloromethane (20mL x2) was extracted, the organic phases were combined, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to dryness to give a white solid, which was recrystallized from anhydrous ethanol to give 10.1g of tricyclodecenyl trifluoroacetate in a yield of 82%.
(2) The procedure of example 1 was followed except that 10.1g of tricyclodecenyl trifluoroacetate was dissolved in 100mL of methanol, and 11.3g K was added2CO3Stirred at room temperature for 2 h.
Final concentration gave 5.6g tricyclodecenyl alcohol as a colorless oil in 94.6% yield with a GC content of 97%.
Claims (8)
1. A process for preparing tricyclodecenyl alcohol, comprising: adding dicyclopentadiene and trifluoroacetic acid to obtain tricyclodecenyl trifluoroacetate, and hydrolyzing with potassium carbonate to obtain tricyclodecenyl alcohol;
the reaction temperature of the addition reaction is 30-50 ℃; the reaction time of the addition reaction is 5-10 min.
2. The method of claim 1, wherein the dicyclopentadiene to trifluoroacetic acid feed molar ratio is from 1:1 to 2.
3. The method of making tricyclodecenyl alcohol as claimed in claim 1, wherein the addition reaction takes place in a solvent-free state.
4. The method of claim 1, wherein the addition reaction is followed by extraction, washing, drying, and recrystallization to yield tricyclodecenyl trifluoroacetate.
5. The method of claim 1, wherein the hydrolyzing comprises dissolving tricyclodecenyl trifluoroacetate in methanol, adding potassium carbonate and stirring.
6. The method of claim 5, wherein after the hydrolysis is completed, the methanol is concentrated to dryness, and then extracted, washed and dried to obtain tricyclodecenyl alcohol.
7. A tricyclodecenyl trifluoroacetate having the formula:
8. a method of preparing tricyclodecenyl trifluoroacetate according to claim 7, comprising: the dicyclopentadiene and trifluoroacetic acid are subjected to addition reaction to obtain tricyclodecenyl trifluoroacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910241116.7A CN109912410B (en) | 2019-03-28 | 2019-03-28 | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910241116.7A CN109912410B (en) | 2019-03-28 | 2019-03-28 | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912410A CN109912410A (en) | 2019-06-21 |
| CN109912410B true CN109912410B (en) | 2022-02-15 |
Family
ID=66967273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910241116.7A Active CN109912410B (en) | 2019-03-28 | 2019-03-28 | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912410B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133965A (en) * | 1976-09-08 | 1979-01-09 | Hitachi Chemical Company, Ltd. | Process for producing tricyclo(5,2,1,02,6)-3-decene-8 (or 9)-ol |
| US6048664A (en) * | 1999-03-12 | 2000-04-11 | Lucent Technologies, Inc. | Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
| JP2008208062A (en) * | 2007-02-26 | 2008-09-11 | Hitachi Chem Co Ltd | Manufacturing method of tricyclo[5.2.1.02,6]dec-3-en-8 (or 9)-ol |
| CN101679195A (en) * | 2007-06-05 | 2010-03-24 | 美礼联专用化学品公司 | Process for making tricyclodecenyl esters |
| CN102659733A (en) * | 2012-04-18 | 2012-09-12 | 上海应用技术学院 | Preparation method of decahydro-spiro[furan-2(3H),5'-[4,7]methano-5H-indene] |
| CN104829454A (en) * | 2015-03-20 | 2015-08-12 | 安徽华业香料股份有限公司 | Method of synthesizing tricyclodecenyl isobutyrate spice |
| CN107954864A (en) * | 2017-10-23 | 2018-04-24 | 江苏馨瑞香料有限公司 | A kind of preparation method of tricyclodecenyl esters |
-
2019
- 2019-03-28 CN CN201910241116.7A patent/CN109912410B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4133965A (en) * | 1976-09-08 | 1979-01-09 | Hitachi Chemical Company, Ltd. | Process for producing tricyclo(5,2,1,02,6)-3-decene-8 (or 9)-ol |
| US6048664A (en) * | 1999-03-12 | 2000-04-11 | Lucent Technologies, Inc. | Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
| JP2008208062A (en) * | 2007-02-26 | 2008-09-11 | Hitachi Chem Co Ltd | Manufacturing method of tricyclo[5.2.1.02,6]dec-3-en-8 (or 9)-ol |
| CN101679195A (en) * | 2007-06-05 | 2010-03-24 | 美礼联专用化学品公司 | Process for making tricyclodecenyl esters |
| CN102659733A (en) * | 2012-04-18 | 2012-09-12 | 上海应用技术学院 | Preparation method of decahydro-spiro[furan-2(3H),5'-[4,7]methano-5H-indene] |
| CN104829454A (en) * | 2015-03-20 | 2015-08-12 | 安徽华业香料股份有限公司 | Method of synthesizing tricyclodecenyl isobutyrate spice |
| CN107954864A (en) * | 2017-10-23 | 2018-04-24 | 江苏馨瑞香料有限公司 | A kind of preparation method of tricyclodecenyl esters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912410A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108558692B (en) | Preparation method of amide compound | |
| CN107501112A (en) | A kind of Chiral Synthesis of chiral beta amino acids and the synthetic method of medicine intermediate | |
| CN110551133A (en) | Process for preparing tert-butyl-5- (hydroxymethyl) -7-oxa-2-azaspiro [3.5] nonane-2-carboxylic acid ester | |
| CN109912410B (en) | Method for preparing tricyclodecenyl alcohol, reaction intermediate and preparation method thereof | |
| EP2921473B1 (en) | 1-cyan-1-(7-methoxyl-1-naphtyl) methanol ester compound and preparation method and use thereof | |
| CN112225647A (en) | Method for synthesizing 5-bromo-2-methoxyphenol | |
| CN112645833A (en) | Synthesis method of (S) -2, 6-diamino-5-oxohexanoic acid | |
| CN113024489A (en) | Preparation method of oseltamivir synthesis process impurity | |
| CN111548356B (en) | Process for preparing tert-butyl-1, 8-dioxa-4, 11-diazaspiro [5.6] dodecane-11-carboxylic acid ester | |
| CN109836368B (en) | Preparation method of high-purity liraglutide side chain | |
| CN110343056B (en) | Preparation method of N-tert-butyloxycarbonyl-N-methyl-2-amino-4, 4-dimethylpentanoic acid | |
| CN113861034A (en) | Preparation method of 2-fluoro-3-nitrobenzoic acid | |
| CN113831237A (en) | Synthesis method of 9-anthracenecarboxylic acid | |
| CN111574524B (en) | 2- (tert-butoxycarbonyl) -7-oxyylidene-2, 6-diazaspiro [3.4] octane-5-carboxylic acid preparation method | |
| CN114380661B (en) | Synthetic method of (+/-) -lavender alcohol | |
| CN113387844A (en) | Preparation method of azodicarbonic acid dialkyl ester | |
| CN111205251B (en) | Preparation method of chiral ligand (3S,4S) -2, 5-dioxy tetrahydrofuran-3, 4-bis-carbamic acid benzyl ester | |
| CN113024486A (en) | Method for preparing oseltamivir intermediate | |
| CN115819232B (en) | Synthesis method of cycloalkyl acrylate compound | |
| CN115181047B (en) | Preparation method of chiral 3- (dimethylamino) pyrrolidine | |
| CN115322143B (en) | Preparation method of 4-tert-butyl piperidine formate hydrochloride | |
| CN113387874B (en) | Method for synthesizing 6, 6-dialkyl piperidine-2-carboxylic acid compound | |
| US4433163A (en) | Process for the production of 3,3-dimethylglutaric acid or its esters | |
| CN110551129B (en) | Preparation method of 4, 5-dihydro-1H, 3H-pyrrolo [1,2-A ] [1,4] diazepine-2, 4-dicarboxylic acid-2-tert-butyl ester | |
| CN111592451B (en) | Preparation method of 4- (4-phenylbutoxy) benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |