CN105985243A - Novel process for synthesis of borneol ester by esterification of pinene - Google Patents
Novel process for synthesis of borneol ester by esterification of pinene Download PDFInfo
- Publication number
- CN105985243A CN105985243A CN201510055421.9A CN201510055421A CN105985243A CN 105985243 A CN105985243 A CN 105985243A CN 201510055421 A CN201510055421 A CN 201510055421A CN 105985243 A CN105985243 A CN 105985243A
- Authority
- CN
- China
- Prior art keywords
- esterification
- reaction
- oxalic acid
- australene
- time
- 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.)
- Pending
Links
Abstract
The invention relates to a novel process for synthesis of borneol ester by esterification of alpha-pinene, specifically to a novel esterification process combining a feeding manner and a reaction temperature sequence. The process comprises the following steps: dividing the raw material alpha-pinene into two parts, adding one part of the alpha-pinene into an esterification reactor when a reaction starts so as to form a mother liquor, then adding the other part of the alpha-pinene into the esterification reactor step by step when the reaction is conducted for a period of time, dividing a raw material oxalic acid into a plurality of parts, adding one part of the oxalic acid into the esterification reactor when the reaction starts, then successively adding the remaining oxalic acid into the esterification reactor when the reaction is conducted for a certain time, carrying out an esterification reaction in the presence of a catalyst so as to synthesize bornyl oxalate, after the reaction is completed, subjecting a reaction product to water washing, and performing distillation and saponification and hydrolysis so as to obtain borneol.
Description
Technical field
The present invention relates to a kind of new technology with australene low temperature lactate synthesis oxalic acid norbornene ester, particularly to a kind of esterification novel process combining feeding mode and reaction temperature sequence.
Background technology
Preparing Borneolum Syntheticum after oxalic acid norbornene ester saponification, norbornene ester is the intermediate product of synthetic borneol.Borneolum Syntheticum is the hexagonal flake crystalline solid of semi-transparent clear, has the mixing abnormal smells from the patient of similar Camphora and Herba Menthae, is also a kind of important industrial chemicals, spice, Chinese medicine ingredients and food additive, is additionally operable to prepare highclass perfumes, anthelmintic, to anticancer etc..The applicating history of Borneolum Syntheticum is long, is used as perfume or the spice of ink and pharmaceutical from ancient times.Modern age is in addition to Medicine prescriptions, Borneolum Syntheticum is in order to prepare health care medicinal, such as rendan mini-pills, menthocamphorate, medicament for the eyes etc., it is also widely used for cosmetics, article of everyday use, such as indoor fragrance agent, toothpaste, prepared Chinese ink, incense, cleaning agent for mouth cavity, disinfectant etc., in spices and essence is modulated, Borneolum Syntheticum is famous and precious fixastive and the important source material of preparation highclass perfumes, is the perfume material of synthetic perfume manufacture Borneolum Syntheticum esters, is additionally operable to the essence such as seasoning.In addition Borneolum Syntheticum also has removing the necrotic tissue anticorrosion, the effect of repellent insects.Can also be as refrigerant additive in beverage industry.Borneolum Syntheticum to medicine for central nervous system, medicine for cardiovascular system, has the effect promoting that principal agent plays curative effect especially.Compared with natural Broneolum Syntheticum, often containing normal borneol and isoborneol in synthetic Borneolum Syntheticum, when playing medical value, the content of normal borneol is the highest more good.
The method of synthetic borneol ester has a variety of, and including with the Oleum Terebinthinae containing pinene as raw material, and anhydrous oxalic acid, monoxone etc. carry out esterification under different types of catalyst system.It is reported, the most industrialized method is mainly australene and anhydrous oxalic acid through lactate synthesis oxalic acid norbornene ester, saponification prepares the Borneolum Syntheticum of high value further, but in this traditional method, in esterification products, norbornene ester content is low, and immediate cause is that the selectivity of esterification is the highest, causes content of bornyl alcohol in saponification resultant low, the content of normal borneol is the highest, has had a strong impact on the quality of synthetic borneol.
Summary of the invention
Consider the deficiency in existing esterification technique, it is an object of the present invention to provide the new technology of a kind of australene lactate synthesis norbornene ester, improve the content of norbornene ester in esterification products, to improving content of bornyl alcohol and normal borneol proportion in saponification resultant, because the content of Borneolum Syntheticum and normal borneol accounting are determined by esterification process, unrelated with saponification process, thus improve the quality of synthetic borneol.
The synthetic borneol technical process of the present invention comprises the following steps:
A certain amount of australene is divided into two parts, and portion joins in esterifying kettle in time reacting initial, and as mother solution, another part is gradually added in esterifying kettle in time reacting 25～50 min, and the joining day controls in 60～90 min.A certain amount of oxalic acid is divided into some parts, a addition esterifying kettle in time reacting initial, remaining oxalic acid puts into esterifying kettle successively in reaction certain time, esterification is carried out under catalyst boric anhydride and acetic anhydride, control esterification reaction temperature and controlling at 50～75 DEG C, reduce temperature again after reacting a period of time at prior to 55 ~ 75 DEG C to react a period of time at 50 ~ 65 DEG C, total reaction time 3.0～6.0 hours, prepare oxalic acid norbornene ester.Esterification reaction product can be prepared Borneolum Syntheticum after washing, steaming light oil, saponification.
Advantages of the present invention is embodied in:
1. according to the feature of this system reaction very exothermic, anhydrous oxalic acid is put into by esterification reaction process by several times, control reaction rate and exothermic heat of reaction, reactant concentration maintains rational scope, effectively reduce the side reactions such as pinene generation autohemagglutination, improve reaction selectivity, maintenance process is kept the safety in production.
Australene is not disposable addition the most in the esterification reaction, but part is gradually added when esterification is violent, can control esterification heat release, and maintain rational reactant concentration, keep higher reaction selectivity.
The ester content of the thick ester obtained after esterification the most of the present invention can reach 64%～68%, and after saponification, normal borneol content can reach 84%, and relatively traditional handicraft (64%) is greatly improved.
Detailed description of the invention
Embodiment 1
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.6g, promoter acetic anhydride 0.12g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 87min, control cooling water flow and carry out esterification, temperature is 65 DEG C, it is down to 55 DEG C after reaction 25min, esterification is after totally 4.5 hours, system color is the most substantially deepened, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 66.2%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 84.4%.
Embodiment 2
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.6g, promoter acetic anhydride 0.12g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 76min, control cooling water flow and carry out esterification, temperature is reaction 25min at 68 DEG C, after reaction 50min, reaction temperature is reduced to 57 DEG C, after esterification 4.0 hours, system color is the most substantially deepened, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 60.4%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 68.3%.
Embodiment 3
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.6g, promoter acetic anhydride 0.12g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 70min, control cooling water flow and carry out esterification, temperature is reaction 25min at 69 DEG C, after reaction 50min, reaction temperature is reduced to 55 DEG C, after esterification 3.0 hours, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 64.0%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 71.8%.
Embodiment 4
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.8g, promoter acetic anhydride 0.18g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 67min, control cooling water flow and carry out esterification, temperature is after reaction 30min, reaction temperature to be reduced to 57 DEG C at 67 DEG C, after esterification 4.0 hours, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 60.1%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 74.6%.
Embodiment 5
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.6g, promoter acetic anhydride 0.13g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 60min, control cooling water flow and carry out esterification, temperature is after reaction 50min, reaction temperature to be reduced to 55 DEG C at 65 DEG C, after esterification 4.0 hours, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 67.7%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 83.1%.
Embodiment 6
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.6g, promoter acetic anhydride 0.11g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 90min, esterifying kettle is put into during 120min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 90min, control cooling water flow and carry out esterification, temperature is after reaction 50min, reaction temperature to be reduced to 60 DEG C at 65 DEG C, after esterification 5.0 hours, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 53.9%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 61.3%.
Embodiment 7
Take australene 64g and be divided into two parts, a addition esterifying kettle in time reacting initial, major catalyst boric anhydride 0.8g, promoter acetic anhydride 0.15g is in esterifying kettle, warming while stirring is to reaction temperature, take anhydrous oxalic acid 11g again and be divided into five parts, in time reacting initial, 25min, 50min, 140min, esterifying kettle is put into during 220min, another part of australene imports esterifying kettle in reaction 25min by constant-flux pump, controlling flow makes australene add complete at 60min, control cooling water flow and carry out esterification, temperature is after reaction 30min, reaction temperature to be reduced to 55 DEG C at 60 DEG C, after esterification 6.0 hours, stop esterification.Being washed by esterification products, after distillation, take 2g, be accurate to 0.001g, after saponification, titrate with standard sulfuric acid solution, analyzing ester content is 64.0%, after similarity condition saponification, with gas chromatographic analysis content of bornyl alcohol for 73.8%.
The foregoing is only presently preferred embodiments of the present invention, all according to the equal change made in the scope of the invention and modification, all should belong to the coverage of the present invention.
Claims (4)
1. the new technology of a pinene lactate synthesis Borneolum Syntheticum, it is characterised in that: under catalyst existence condition, by the way of feeding mode and reaction temperature combined sequence, australene and anhydrous oxalic acid are carried out low temperature esterification, synthesis of oxalic acid norbornene ester.
The most according to claim 1, the catalyst used includes the combination of boric anhydride and acetic anhydride, and its mass ratio is 3.0:1 ~ 5.5:1.
The most according to claim 1, it is 4.0:1 ~ 7.0:1 that australene and anhydrous oxalic acid add the ratio of gross mass, more preferably 4.0:1 ~ 6.0:1, wherein, australene is divided into two parts, a addition when esterification is initial, forms mother solution, another part is gradually added reactor in time reacting 25～50 min, and the joining day controls in 60～90 min；Anhydrous oxalic acid is divided into some parts, and a addition esterifying kettle in time reacting initial, remaining oxalic acid puts into esterifying kettle successively in reaction certain time.
The most according to claim 1, it is 50～75 DEG C that esterification reaction temperature controls, the mode that reaction temperature point and temperature sequence combine, and reduces temperature again and react a period of time at 50 ~ 65 DEG C at 55 ~ 75 DEG C after reacting a period of time, total reaction time 3.0～6.0 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510055421.9A CN105985243A (en) | 2015-02-04 | 2015-02-04 | Novel process for synthesis of borneol ester by esterification of pinene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510055421.9A CN105985243A (en) | 2015-02-04 | 2015-02-04 | Novel process for synthesis of borneol ester by esterification of pinene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105985243A true CN105985243A (en) | 2016-10-05 |
Family
ID=57036971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510055421.9A Pending CN105985243A (en) | 2015-02-04 | 2015-02-04 | Novel process for synthesis of borneol ester by esterification of pinene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105985243A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409563A (en) * | 2018-02-11 | 2018-08-17 | 广西壮族自治区林业科学研究院 | A kind of method of turpentine oil synthesis of acetic acid pine tar ester |
| CN109970510A (en) * | 2019-05-16 | 2019-07-05 | 梧州黄埔化工药业有限公司 | A kind of method of environmentally protective synthetic borneol |
| CN110015948A (en) * | 2019-05-16 | 2019-07-16 | 梧州黄埔化工药业有限公司 | A method of synthesis high purity borneol |
| CN113683485A (en) * | 2021-08-16 | 2021-11-23 | 湖北武当安泰药业有限公司 | Preparation method of synthetic borneol |
| CN115108907A (en) * | 2022-05-24 | 2022-09-27 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by directly esterifying alpha-pinene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB222141A (en) * | 1923-09-19 | 1925-09-24 | Geza Austerweil | An improved process for the production of terpene alcohols |
| GB306387A (en) * | 1928-02-18 | 1930-01-13 | Ludwig Schmidt | An improved process for obtaining bornyl and isobornyl esters |
| CN103980117A (en) * | 2014-06-04 | 2014-08-13 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing diisoborneol oxalate |
-
2015
- 2015-02-04 CN CN201510055421.9A patent/CN105985243A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB222141A (en) * | 1923-09-19 | 1925-09-24 | Geza Austerweil | An improved process for the production of terpene alcohols |
| GB306387A (en) * | 1928-02-18 | 1930-01-13 | Ludwig Schmidt | An improved process for obtaining bornyl and isobornyl esters |
| CN103980117A (en) * | 2014-06-04 | 2014-08-13 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing diisoborneol oxalate |
Non-Patent Citations (1)
| Title |
|---|
| 伍忠萌: "《林产精细化学品工艺学》", 31 March 2002 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409563A (en) * | 2018-02-11 | 2018-08-17 | 广西壮族自治区林业科学研究院 | A kind of method of turpentine oil synthesis of acetic acid pine tar ester |
| CN108409563B (en) * | 2018-02-11 | 2021-06-18 | 广西壮族自治区林业科学研究院 | Method for synthesizing terpinyl acetate from turpentine |
| CN109970510A (en) * | 2019-05-16 | 2019-07-05 | 梧州黄埔化工药业有限公司 | A kind of method of environmentally protective synthetic borneol |
| CN110015948A (en) * | 2019-05-16 | 2019-07-16 | 梧州黄埔化工药业有限公司 | A method of synthesis high purity borneol |
| CN113683485A (en) * | 2021-08-16 | 2021-11-23 | 湖北武当安泰药业有限公司 | Preparation method of synthetic borneol |
| CN115108907A (en) * | 2022-05-24 | 2022-09-27 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by directly esterifying alpha-pinene |
| CN115108907B (en) * | 2022-05-24 | 2023-05-26 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by direct esterification of alpha-pinene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105985243A (en) | Novel process for synthesis of borneol ester by esterification of pinene | |
| CN101951875B (en) | Physiological coolants based on lactoyl esters of menthyl lactate | |
| CN105585470B (en) | A method of 2- hydroxy-3-methyl -2- cyclopentene-1-ones are prepared by fructose | |
| CN102993004B (en) | The method of phanteine and meraneine/neryl acetate one-step synthesis | |
| CN104004639B (en) | The manufacture method of BAIXIANGGUOCU | |
| CN1843171A (en) | Production method for green vegetable fruit rice noodle | |
| CN109534970A (en) | A kind of preparation method of high-purity natural benzaldehyde | |
| CN101830779B (en) | Method for selectively synthesizing normal borneol | |
| CN101899361A (en) | Single-tower continuous rectification method of eucalyptus oil | |
| CN107892640B (en) | Preparation method for preparing camphene by alpha-pinene isomerization | |
| CN106316839B (en) | A method of by biomass glycerol one-step synthesis method methyl lactate | |
| ATE330922T1 (en) | METHOD FOR PRODUCING PROPANE-1,3-DIOL BY GAS PHASE HYDROGENATION OF .BETA.-PROPIOLACTONE, OLIGOMERS OF .BETA.-PROPIOLACTONE, 3-HYDROXYPROPIONIC ACID ESTERS OR MIXTURES THEREOF | |
| CN102277237A (en) | Preparation method of high-purity glyceride type fish oil | |
| CN107927536B (en) | Health product containing octacosanol | |
| CN102351689A (en) | Preparation technique of p-hydroxy-cinnamic acid | |
| CN104926651B (en) | The preparation method of terpinyl acetate | |
| CN104370977B (en) | Preparation method of 2-O-(2, 3, 4, 6-tetra-O-acetyl-Beta-D-glucopyranosyl)-3-O-benzyl-5, 6-isopropylidene-ascorbic acid | |
| CN106831322A (en) | A kind of production method of α bisabolols | |
| KR20140023874A (en) | Novel carboxylic acid ester compound and production therefor, and perfume composition thereof | |
| CN110078609A (en) | A kind of preparation method preparing C3H6O3 by watermelon ketone | |
| KR20130011364A (en) | Method for producing processed ginseng or processed ginseng extract using subcritical water | |
| CN101503354A (en) | Method for preparing terpinyl acetate | |
| CN110204432A (en) | A kind of application for the method and palmitoleic acid preparing palmitoleic acid using macadamia nut oil | |
| JPH01261346A (en) | Production of 3, 5, 6-trimethyl-4-hydroxy-2- cyclohexene-1-one | |
| US20230404940A1 (en) | Intoxication-reducing supplemental mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161005 |
|
| RJ01 | Rejection of invention patent application after publication |