CN101125798A - Method for preparing 3- bornylene - Google Patents
Method for preparing 3- bornylene Download PDFInfo
- Publication number
- CN101125798A CN101125798A CNA200710071154XA CN200710071154A CN101125798A CN 101125798 A CN101125798 A CN 101125798A CN A200710071154X A CNA200710071154X A CN A200710071154XA CN 200710071154 A CN200710071154 A CN 200710071154A CN 101125798 A CN101125798 A CN 101125798A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solvent
- butanone
- borneol
- weight ratio
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of organic chemical industry field, in particular to the preparation method of 3-Campholenyl-2-Butanol. 3-campholenyl-2-Butanol is prepared by three continuous reaction steps: firstly, campholenic aldehyde is used as raw material to do an aldol condensation with butanone; secondly, 3-Subcampholenyl-2-Butanone, fatty alcohols with 2 to 4 carbon atoms, solid base and copper /chromium catalyst are reacted with each other; finally crude 3-Campholenyl-2-Butanol is added with solvent and reductant, and the finished product is prepared. The invention has the advantages of mild reaction condition, safe operation, and complete reaction, easy control of reaction endpoint as well as colorless and good fragrance of obtained sandalwood 210, etc. The invention avoids a technical obstacle of incomplete reaction or over-reduction which is existed in other technologies. The product of the invention can be widely used in makeup essence, soap essence, detergent essence and household essence.
Description
Technical field
The invention belongs to organic chemical industry's synthetic field, specifically be meant the preparation method of a kind of 3-borneol alkenyl-2-butanols.
Technical background
3-borneol alkenyl-2-butanols (3-Campholenyl-2-butanol, CAS accession number 65113-99-7; EINECS accession number 265-453-0) China is called santal 210, another name Sandalore; Sandasweet, also be 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol, it has intensive banksia rose fragrance, fragrance exactly likes natural sandalwood, is a kind of important spices in fine chemistry industry, is widely used in cosmetic essence, soap compound, detergent essence and the household essence.
3-borneol alkenyl-2-butanols is to be raw material with the campholenic aldehyde, carry out getting through catalytic hydrogenation again behind the aldol condensation with butanone (US4052341, CA97198416).
Preparation method in the past, adopt used hydrogen reducing (US4052341) merely more, the difficult control of this method reaction end, the incomplete or overreaction of reaction.Reaction not exclusively then has a large amount of intermediate products (following I and II), contains I and II in the finished product and then can make finished product have coarse banksia rose fragrance; Produce more by product (following III and IV) during overreaction, III and IV do not have the characteristic perfume of santal, so containing sandalwood aroma that III and IV then can cause finished product in the finished product weakens even disappears, though consequently this method has characteristics simple to operate, still prepare the aroma quality instability of product.
Summary of the invention
The present invention is directed to deficiency of the prior art, it is simple to have proposed a kind of technology, the preparation method of the 3-borneol alkenyl-2-butanols of economical and efficient.
The present invention is achieved by following technical proposals:
The preparation method of a kind of 3-borneol alkenyl-2-butanols is characterized in that being undertaken by following step:
(1) campholenic aldehyde is a raw material, carries out aldol condensation with butanone and obtains 3-sub-borneol alkene base-2-butanone; This step is disclosed for having corresponding document now, also is the simple with hydrogen reducing (US4052341) method of present more employing, the difficult control of this method reaction end, the incomplete or overreaction of reaction.But in the present invention, this need at first implement as preliminary program of the present invention, and more main is following step.
(2) Fatty Alcohol(C12-C14 and C12-C18) of 3-sub-borneol alkene base-2-butanone, 2～4 carbon atoms, solid alkali, copper/chrome catalysts mixing are reacted, 3-borneol alkenyl-2-butanone wherein: the weight ratio of solvent is 1: 0.5～2.5, solid alkali: the weight ratio of Cu-Cr catalyst is 1: 100～350, in hydrogen pressure 1～4MPa, 100 ℃～200 ℃ reactions down of temperature, can get 3-borneol alkenyl-2-butanols crude product; As preferably, the Fatty Alcohol(C12-C14 and C12-C18) of wherein said 2～4 carbon atoms is ethanol, Virahol, isopropylcarbinol or sec-butyl alcohol.As preferably, the solid alkali described in the above-mentioned preparation method is NaOH, KOH, K
2CO
3As preferably, 3-borneol alkenyl-2-butanone wherein: the weight ratio of solvent is 1: 1.5; Solid alkali: the weight ratio of Cu-Cr catalyst is 1: 200.
As preferably, reaction stand-by time wherein is to show that by gas-chromatography raw material or intermediate content are less than 5% (weight percent).At this moment, the reaction that realizes substantially is complete.
(3), add solvent ether, reductive agent LiAlH 3-borneol alkenyl-2-butanols crude product
4Or solvent is that toluene, reductive agent are aluminum isopropylate, and perhaps solvent is a Virahol, and reductive agent is NaBH
4, 3-borneol alkenyl-2-butanols crude product wherein: the weight ratio of reductive agent is 1: 0.0004～0.004, reductive agent: the weight ratio of solvent is 1: 50～300, temperature control is between the room temperature to 100 ℃, reaction 2～6h, get final product finished product.As preferably, wherein said 3-borneol alkenyl-2-butanols crude product: the weight ratio of reductive agent is 1: 0.001, reductive agent: the weight ratio of solvent is 1: 150.
As preferably, after the crude product in the above-mentioned steps (2) is stopped reaction, remove solvent and unreacted butanone, and the crude product that obtains through rectification under vacuum.
In order to obtain better product, above-mentioned 3-borneol alkenyl-2-butanols finished product is through neutralization, washing, layered filtration, the finished product that obtains of rectifying again.
Beneficial effect: the present invention adopts campholenic aldehyde to prepare 3-borneol alkenyl-2-butanols, respond mild condition, operational safety, react completely, reaction end is easy to advantages such as the santal controlling, obtain is 210 colourless, fragrance is good, avoided reaction that other technology exists not thoroughly or the technology barrier of over reduction.
Embodiment
The preparation of embodiment 1:3-sub-borneol alkene base-2-butanone
Add 350g (4.86mol) butanone in the reactor, 800ml methyl alcohol, 350ml water and 30gKOH stir adding 200g (1.315mol) campholenic aldehyde down, and temperature of reaction remains on room temperature, drips off the back and continues at room temperature to react 8h, up to reacting completely; Reactant neutralizes with acetate, washes with water to neutrality again.Remove solvent methanol and unreacting material butanone, 90～120 ℃/2.5mmHg fraction is collected in underpressure distillation, gets the 243.8g product, productive rate 90%.
The preparation of embodiment 2:3-borneol alkenyl-2-butanols crude product
Add 200g (0.97mol) 3-sub-borneol alkene base-2-butanone in the autoclave pressure, 160ml Virahol, 0.06gKOH, 20g copper/chrome catalysts, mixture is stirring heating under 1～3MPa hydrogen pressure, and temperature maintenance is reacted to gas-chromatography and shows that raw material or intermediate content are 4.5% between 100 ℃～200 ℃, stopped reaction, remove the solvent Virahol in the reactant, 103 ℃～106 ℃/133Pa fraction is collected in underpressure distillation, get the 185.4g product, productive rate 91%.
The preparation of embodiment 3:3-borneol alkenyl-2-butanols crude product
Add 200g (0.97mol) 3-sub-borneol alkene base-2-butanone in the autoclave pressure, 180ml sec-butyl alcohol, 20g copper/chrome catalysts, 0.06gKOH, mixture is stirring heating under 1～3MPa hydrogen pressure, and temperature maintenance is reacted to gas-chromatography and shows that raw material or intermediate content are 4.3% between 110 ℃～200 ℃, stopped reaction, remove the solvent sec-butyl alcohol in the reactant, 103 ℃～106 ℃/133Pa fraction is collected in underpressure distillation, get the 187g product, productive rate 91.5%.
The preparation of embodiment 4:3-borneol alkenyl-2-butanols finished product
Add 250g3-borneol alkenyl-2-butanols crude product, 5g LiAlH in the three-necked bottle
4, the 500ml anhydrous diethyl ether, temperature control is in 10～30 ℃ of backflow 2h, up to reacting completely; Reactant neutralizes with ethyl acetate, washes with water to neutrality, removes solvent ether, and 105 ℃～107 ℃/266Pa fraction is collected in rectification under vacuum.Get the 239.9g product, productive rate 96%.
The preparation of embodiment 5:3-borneol alkenyl-2-butanols finished product
Add 250g3-borneol alkenyl-2-butanols crude product in the three-necked bottle, the 5g aluminum isopropylate, 500ml toluene, 60～100 ℃ of backflow 6h of temperature control are up to reacting completely; Reactant neutralizes with dilute sulphuric acid, washes with water to neutrality again, removes solvent toluene, and 105 ℃～107 ℃/266Pa fraction is collected in rectification under vacuum, gets the 242.8g product, productive rate 97.1%.
The preparation of embodiment 6:3-borneol alkenyl-2-butanols finished product
Add 250g3-borneol alkenyl-2-butanols crude product, 5gNaBH in the three-necked bottle
4, the 500ml Virahol, 10～60 ℃ of temperature controls, backflow 7h is up to reacting completely; Reactant neutralizes with dilute sulphuric acid, washes with water to neutrality again, removes the Virahol that desolvates, and 105 ℃～107 ℃/266Pa fraction is collected in rectification under vacuum, gets the 237.5g product, productive rate 95%.
Claims (8)
1. the preparation method of 3-borneol alkenyl-2-butanols is characterized in that being undertaken by following step:
(1) campholenic aldehyde is a raw material, carries out aldol condensation with butanone and obtains 3-sub-borneol alkene base-2-butanone;
(2) Fatty Alcohol(C12-C14 and C12-C18) of 3-sub-borneol alkene base-2-butanone, 2～4 carbon atoms, solid alkali, copper/chrome catalysts mixing are reacted, 3-borneol alkenyl-2-butanone wherein: the weight ratio of solvent is 1: 0.5～2.5, solid alkali: the weight ratio of Cu-Cr catalyst is 1: 100～350, in hydrogen pressure 1～4MPa, 100 ℃～200 ℃ reactions down of temperature, can get 3-borneol alkenyl-2-butanols crude product;
(3), add solvent ether, reductive agent LiAlH 3-borneol alkenyl-2-butanols crude product
4Or solvent is that toluene, reductive agent are aluminum isopropylate, and perhaps solvent is a Virahol, and reductive agent is NaBH
4, 3-borneol alkenyl-2-butanols crude product wherein: the weight ratio of reductive agent is 1: 0.0004～0.004, reductive agent: the weight ratio of solvent is 1: 50～300, temperature control is between the room temperature to 100 ℃, reaction 2～6h, get final product finished product.
2. preparation method according to claim 1, the Fatty Alcohol(C12-C14 and C12-C18) that it is characterized in that described 2～4 carbon atoms is ethanol, Virahol, isopropylcarbinol or sec-butyl alcohol.
3. preparation method according to claim 1 is characterized in that described solid alkali is NaOH, KOH, K
2CO
3
4. preparation method according to claim 1, it is characterized in that described 3-borneol alkenyl-2-butanone: the weight ratio of solvent is 1: 1.5; Solid alkali: the weight ratio of Cu-Cr catalyst is 1: 200.
5. preparation method according to claim 1 is characterized in that the reaction stand-by time in the described step (2) is to show that by gas-chromatography raw material or intermediate content are less than 5% (weight percent).
6. preparation method according to claim 1, it is characterized in that crude product in the described step (2) is stopped reaction after, remove solvent and unreacted butanone, and the crude product that obtains through rectification under vacuum.
7. preparation method according to claim 1, it is characterized in that described 3-borneol alkenyl-2-butanols crude product: the weight ratio of reductive agent is 1: 0.001, reductive agent: the weight ratio of solvent is 1: 150.
8. preparation method according to claim 1 is characterized in that described 3-borneol alkenyl-2-butanols finished product is through neutralization, washing, layered filtration, the finished product that obtains of rectifying again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710071154A CN101125798B (en) | 2007-09-14 | 2007-09-14 | Method for preparing 3- bornylene-2-butanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710071154A CN101125798B (en) | 2007-09-14 | 2007-09-14 | Method for preparing 3- bornylene-2-butanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101125798A true CN101125798A (en) | 2008-02-20 |
| CN101125798B CN101125798B (en) | 2010-05-26 |
Family
ID=39093950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710071154A Active CN101125798B (en) | 2007-09-14 | 2007-09-14 | Method for preparing 3- bornylene-2-butanol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101125798B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891594A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Synthesizing method of 2-borneol alkenyl propanol |
| CN103449993A (en) * | 2013-08-22 | 2013-12-18 | 广州百花香料股份有限公司 | Production method of 3-campholenyl-2-butanone |
| US20160207862A1 (en) * | 2013-09-06 | 2016-07-21 | Takasago International Corporation | Fragrance composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4052341A (en) * | 1976-04-29 | 1977-10-04 | Givaudan Corporation | 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol compound and perfume compositions |
-
2007
- 2007-09-14 CN CN200710071154A patent/CN101125798B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891594A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Synthesizing method of 2-borneol alkenyl propanol |
| CN101891594B (en) * | 2010-07-21 | 2013-03-20 | 浙江新化化工股份有限公司 | Synthesizing method of 2-borneol alkenyl propanol |
| CN103449993A (en) * | 2013-08-22 | 2013-12-18 | 广州百花香料股份有限公司 | Production method of 3-campholenyl-2-butanone |
| CN103449993B (en) * | 2013-08-22 | 2015-04-29 | 广州百花香料股份有限公司 | Production method of 3-campholenyl-2-butanone |
| US20160207862A1 (en) * | 2013-09-06 | 2016-07-21 | Takasago International Corporation | Fragrance composition |
| US9643908B2 (en) * | 2013-09-06 | 2017-05-09 | Takasago International Corporation | Fragrance composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101125798B (en) | 2010-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102083776B (en) | Method of producing neopentyl glycol | |
| CN103360215B (en) | The method of a kind of 3-methyl-3-butene-1-alcohol catalysis transposition synthesis prenol in water-organic biphasic system | |
| CN102295531B (en) | Method for preparing citronellol by using hydrogenating citral | |
| CN101125798B (en) | Method for preparing 3- bornylene-2-butanol | |
| CN109622050B (en) | Catalyst and method for preparing nerol and geraniol by using same | |
| CN102625790B (en) | Method for producing alicyclic alcohol | |
| CN104876807A (en) | Synthesis process of hydroxybenzene ether (III) | |
| US9056820B2 (en) | Alicyclic alcohol | |
| CN1984860A (en) | Method for producing a propargyl alcohol and an allyl alcohol | |
| CN101830798A (en) | Preparation method of high-cis vertenex | |
| EP2660232A1 (en) | Novel alicyclic alcohol | |
| PL126971B1 (en) | Method of obtaining cyclohexanon and/or cyclohexanone | |
| CN101891594B (en) | Synthesizing method of 2-borneol alkenyl propanol | |
| WO2013076226A1 (en) | Process for preparing 3-substituted 2-alkenals, in particular prenal | |
| CN100560556C (en) | A kind of synthetic method of cyclohexyloxy allyl acetate | |
| CN113527077A (en) | Method for preparing anisyl propionaldehyde from anisole | |
| CN106631686A (en) | Preparation method of beta-phenethyl alcohol | |
| CN109776281A (en) | A kind of synthetic method of ethyl isobutyl perfume (or spice) phenol | |
| US20100256421A1 (en) | Propanal Production Methods | |
| CN110586062A (en) | Si-Mg-Zr-Zn composite metal oxide catalyst and preparation method and application thereof | |
| CN110240538B (en) | Method for preparing high-carbon branched-chain secondary alcohol | |
| CN114539026B (en) | Method for synthesizing 1, 2-pentanediol by using ethanol and 1, 2-propanediol as raw materials | |
| CN211645082U (en) | Device for preparing cyclohexylmethanol by benzyl alcohol hydrogenation | |
| CN102816071A (en) | Synthesis method of N-ethyl ethylene diamine | |
| CN1660737A (en) | Method for synthesizing 2-olefine-butanol borneolene from olefine aldehyde borneol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: GLEE BIOTECHNOLOGY CO., LTD. Free format text: FORMER NAME: GELIN PERFUME CHEMISTRY CO LTD, HANGZHOU |
|
| CP03 | Change of name, title or address |
Address after: 311604, Zhejiang City, Jiande Province town of plum peak - South Peak High-tech Industrial Park Patentee after: Green Biotechnology Co.,Ltd. Address before: 311600 Hangzhou, Jiande City, Zhejiang Province, Yushan Patentee before: Gelin Perfume Chemistry Co., Ltd., Hangzhou |