CN1026317C - Process for snythetizing borneol by esterification and saponification with solid acid catalyzing a-pinene - Google Patents
Process for snythetizing borneol by esterification and saponification with solid acid catalyzing a-pinene Download PDFInfo
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- CN1026317C CN1026317C CN 92112124 CN92112124A CN1026317C CN 1026317 C CN1026317 C CN 1026317C CN 92112124 CN92112124 CN 92112124 CN 92112124 A CN92112124 A CN 92112124A CN 1026317 C CN1026317 C CN 1026317C
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Abstract
The present invention belongs to a new method for snythetizing borneol. Sn, Zr , Ti, or Al chloride or sulfate as a raw material is hydrolyzed, heated, introduced to 0.5% ferrous sulfate, treated with acid and heated again to prepare a solid acid catalyst GIC-90 suitable for alpha-pinene esterification. The catalyst is safe, stable and tractable for catalyzing temperature programmed esterification between alpha-pinene and C1 to C4 organic acid as well as aromatic carboxylate. An esterification reactant is saponified into borneol with 40 to 45% of product yield and 60 to 75% of pure borneol content.
Description
The invention belongs to the borneolum syntheticum novel method.
Borneol is a kind of famous and precious medicine and spices, and over 100 years, chemists constantly explore various borneolum syntheticum new ways, mainly contain four kinds of synthetic methods
(1): 1, camphor reduction method; 2, the catalytic isomerization method of firpene (comprising esterification-saponification method and organo-magnesium compound decomposition method); 3, the enzyme transforming process of firpene and Terpineol 350; 4, direct hydration method.At present, industrial main employing boric anhydride, acetic anhydride catalysis α-Pai Xi and oxalic acid esterification-saponified method, there is main drawback in this method: the esterification very exothermic, explosive, very dangerous; One time charging capacity is little, and oxalic acid must divide and feed intake for six times, and production efficiency is low; Product yield only about 30% wherein contains positive borneol only 60%; By product is mainly the monoterpene dimer, and utility value is low.Chinese patent CN85102398B provides a kind of direct hydration to prepare the method for borneol, this method reaction safety and steady, positive borneol content height in the product, but this method exists catalyst levels big, and catalyzer and reaction oil separation difficulty and product cost are crossed problems such as height.The purpose of this invention is to provide a kind of new synthesis technique, the production efficiency of borneolum syntheticum is improved, product cost reduces.
The invention process case is as follows:
To obtain hydrous oxide in 100～300 ℃ of thermal treatments 4～8 hours through the muriate or the vitriol hydrolysis of tin, zirconium, titanium, aluminium, the solution impregnation that is made into hydrochloric acid, sulfuric acid or the phosphoric acid of the ferrous sulfate that heavily accounts for hydrous oxide 0.5% and 0.1～0.2N 24 hours, the weight ratio of acid solution and hydrous oxide is 1: 1～1.5, stir into pulpous state 80～100 ℃ of oven dry, in 100～300 ℃ of thermal treatments 24 hours, make the solid acid catalyst that is suitable for the α-Pai Xi esterification again.With industrial α-Pai Xi and organic acid is raw material, use above-mentioned catalyzer, catalyzer and α-Pai Xi weight ratio are 1.5～3: 100, organic acid and α-Pai Xi mol ratio are 0.3～0.6: 1, press temperature program(me): 50 ℃ (2.5～4 hours) → 60 ℃ (0.5～1 hour) → 90 ℃ of (0～1 hour) temperature reactions, reactant is through steaming light oil, and saponification generates borneol, the renewable use of catalyzer.
Borneolum syntheticum novel method provided by the invention, production efficiency height not only, product cost has obvious decline than prior art, and esterification once feeds intake, the reaction stable equilibrium, principal product borneol yield 40～45% contains positive borneol 60～75%.
Example one, GIC-90 Preparation of catalysts
The sulfate liquor of the purified titanium of ilmenite acidolysis gained of learning from else's experience carries out thermal hydrolysis and generates hydrated titanium dioxide, accurately take by weighing 1.0 liters of grams of this hydrated titanium dioxide, in 1000～300 ℃ of thermal treatments 4～8 hours, after being chilled to room temperature, the solution impregnation that is made into 5.0 gram ferrous sulfate and 100 milliliters of 0.1N hydrochloric acid 24 hours is stirred to pulpous state, 80～100 ℃ of oven dry, in 100～300 ℃ of thermal treatments 24 hours, make the GIF-90 catalyzer that is suitable for the α-Pai Xi esterification.After reusing once, by above-mentioned preparation process repetitive operation, catalyzer can return to original activity.
Example two, GIC-90 Preparation of catalysts
Take by weighing the water that obtains through zirconium oxychloride decomposition, washing, drying and contain 1.0 kilograms of zirconium dioxides, in 100～300 ℃ of thermal treatments 4～8 hours, after being chilled to room temperature, the solution impregnation that is made into 5.0g ferrous sulfate and 700 milliliters of 0.1N hydrochloric acid 24 hours, be stirred to pulpous state, 80～100 ℃ of oven dry,, make the GIG-90 catalyzer that is suitable for the reaction of α-Pai Xi ester in 100～300 ℃ of thermal treatments 24 hours.After reusing once, by above-mentioned preparation process repetitive operation, catalyzer can return to original activity.
The esterification of example three, α-Pai Xi and oxalic acid
Control electric-heated thermostatic water bath starting temperature is 50 ℃.In the there-necked flask that agitator, prolong and thermometer are housed, add 30.0 gram GIF-90 type catalyzer successively, 210.0 gram anhydrous oxalic acid and 1000.0 gram α-Pai Xis, feeding intake finishes starts stirring reaction simultaneously, and presses the assigned temperature temperature programming: 50 ℃ (3.5 hours) → 60 ℃ (0.5 hour) → 90 ℃ (0.5 hour).Reaction is told solid catalyst and is waited to reuse after finishing.Reaction solution with 1500 ml waters in 80～90 ℃ give a baby a bath on the third day after its birth time after, the mixture of monoterpene and borneol such as water flowing steam steams by product monoterpene 400.0g, wherein is mainly amphene, kautschin.The residue reaction oil is borneol acetate and a small amount of monoterpene dimer, adds 600.0 gram 30% sodium hydroxide and 300.0 gram clear water, and in 100 ℃ of saponification, the steam of water flowing simultaneously steams borneol, stops distillation after 3.5 hours.54.90 thick borneol of gram that steam and the thick borneol of 32.5 grams that recovery obtains from the by product monoterpene are merged, get the borneol product with 120# gasoline recrystallization secondary, crystalline mother solution is by reclaiming wherein borneol as next recrystallization solvent.Product total yield about 41.0% contains positive borneol about 66%.
Claims (4)
1, a kind of method of borneolum syntheticum, this method comprise the preparation catalyzer and carry out esterification that its step is as follows:
(1) preparation catalyzer
The muriate hydrolysis of zirconium, titanium is obtained hydrous oxide in 100～300 ℃ of thermal treatments 4～8 hours, the solution impregnation that is made into ferrous sulfate and 0.1～0.2N acid 24 hours, the weight ratio of acid solution and hydrous oxide is 1: 1～1.5, in 80～100 ℃ of oven dry, in 100～300 ℃ of thermal treatments 24 hours, make catalyzer.
(2) esterification
With the catalyst levels of preparation in (1) is 1.5～3% and α-Pai Xi and C of α-Pai Xi
1～C
4Organic acid carry out esterification, the temperature program(me) of its reaction is 50 ℃ (2.5～4) hour → 60 ℃ (0.5～1 hour) → 90 ℃ (0～1 hour), organic acid and α-Pai Xi mol ratio are 0.3-0.6: 1.
(3) refining
The esterification liquid of above-mentioned (2) is obtained thick borneol through washing, steaming light oil, saponification and steam distillation, obtain product borneol through 120# gasoline recrystallization, catalyzer is reused once after regeneration can be used.
2,, it is characterized in that the ferrous sulfate consumption is 0.5% of a hydrous oxide weight in the used dipping solution of above-mentioned preparation catalyzer according to the method described in the claim 1.
3,, it is characterized in that the acid in the used dipping solution of above-mentioned preparation catalyzer can be hydrochloric acid, phosphoric acid or sulfuric acid according to the method described in the claim 1.
4, according to the method described in the claim 1, catalyzer and α-Pai Xi weight ratio are 1.5～3: 100 when it is characterized in that esterification, and organic acid and α-Pai Xi mol ratio are 0.3-0.6: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112124 CN1026317C (en) | 1992-10-05 | 1992-10-05 | Process for snythetizing borneol by esterification and saponification with solid acid catalyzing a-pinene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92112124 CN1026317C (en) | 1992-10-05 | 1992-10-05 | Process for snythetizing borneol by esterification and saponification with solid acid catalyzing a-pinene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1074210A CN1074210A (en) | 1993-07-14 |
| CN1026317C true CN1026317C (en) | 1994-10-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92112124 Expired - Fee Related CN1026317C (en) | 1992-10-05 | 1992-10-05 | Process for snythetizing borneol by esterification and saponification with solid acid catalyzing a-pinene |
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| Country | Link |
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| CN (1) | CN1026317C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061901C (en) * | 1997-03-12 | 2001-02-14 | 厦门大学 | Supported solid-acid catalyst for producing butyl acetic ether |
| CN102101824A (en) * | 2010-01-21 | 2011-06-22 | 河北金木药业集团有限公司 | Preparation method of borneol |
| CN102584577B (en) * | 2012-02-07 | 2013-12-18 | 周建华 | Postprocessing method for synthetic borneol |
| CN104030889B (en) * | 2014-06-23 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | A kind of method preparing positive borneol |
| CN110327939B (en) * | 2019-07-02 | 2021-07-27 | 昆明理工大学 | Preparation method and application of esterification-saponification reaction catalyst |
| CN111229255B (en) * | 2020-03-02 | 2023-02-28 | 昆明理工大学 | Application of lanthanum-modified chiral nematic mesoporous silicon catalyst in synthesis of borneol |
| CN112920013B (en) * | 2021-02-05 | 2023-04-07 | 广西壮族自治区林业科学研究院 | Turpentine synthesized fatty acid borneol ester, preparation method and application thereof in preparation of 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 |
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- 1992-10-05 CN CN 92112124 patent/CN1026317C/en not_active Expired - Fee Related
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| CN1074210A (en) | 1993-07-14 |
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