CN109970510A - A kind of method of environmentally protective synthetic borneol - Google Patents
A kind of method of environmentally protective synthetic borneol Download PDFInfo
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- CN109970510A CN109970510A CN201910409892.3A CN201910409892A CN109970510A CN 109970510 A CN109970510 A CN 109970510A CN 201910409892 A CN201910409892 A CN 201910409892A CN 109970510 A CN109970510 A CN 109970510A
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- borneol
- reaction
- australene
- environmentally protective
- esterification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of environmentally protective synthetic borneol, it is related to borneol synthesis field, it is short to be intended to provide a kind of reaction time, reagent is reused, environmentally protective borneol synthetic method, the synthetic method includes the steps that australene and anhydrous oxalic acid are carried out to esterification under the action of catalyst to be obtained oxalic acid borneol acetate and oxalic acid borneol acetate progress saponification is obtained thick borneol, the esterification includes three stages of reaction: the reaction temperature of first stage is 45~65 DEG C, reaction time is 2~8h, the reaction temperature of second stage is 65~75 DEG C, reaction time is 1~3h, the reaction temperature of phase III is 75~88 DEG C, reaction time is 1~2h, it is stood after the esterification, by recycling precipitate, that is, reusable.The borneol that the present invention synthesizes is used for antibacterial, anti-inflammatory drug.
Description
Technical field
The present invention relates to the preparations of borneol, more specifically to a kind of method of environmentally protective synthetic borneol.
Background technique
Borneol, alias: borneol, kapur, brain, borneol, piece brain, borneol brain, plum blossom brain, natural borneol, old Borneolum, plum
Piece.Main component is the crystallization obtained in the resin and volatile oil of kapur, is close to pure d-Bomeol.The tree of kapur
Containing there are many ter penoids in rouge and volatile oil.In addition to borneol, still containing the sequiterpenes such as Humuleno, beta-elemene, carypohyllene, neat pier
The triterpenoids such as tartaric acid, alphitolic acid, asiatic acid, dipterocarpol, dryobalanone, erythrodiol.
Borneol has the function of antibacterial, anti-inflammatory.Experiment in vitro shows: the borneol (0.5%) of higher concentration has bacteriostasis,
And rat egg white pedal swelling can be significantly inhibited, its swollen process scorching to the exudation of liquid and tissue edema etc. has inhibition to make
With.And natural borneol resource is very limited, it is expensive, is much unable to satisfy the increasingly increased needs of the mankind, synthetic borneol
Identical with the bacteriostasis of natural borneol, replacing natural borneol with synthetic borneol is the inexorable trend of development.
Yang Yiwen etc. discloses solid super-strong acid SO4 2-/Al2O3The method for being catalyzed australene borneolum syntheticum, although positive borneol
Content is higher, but the preparation process of its catalyst is relatively complicated, needs that catalysis can just be made by 40 to 50 hours
Agent, complex procedures expend a large amount of human and material resources.
A large amount of waste water, waste residue can be inevitably generated when existing method synthetic borneol, reactant cannot reuse, and
It is longer between hair is seasonable.Therefore, a kind of method for developing synthetic borneol for meeting environmentally protective theory is vital.
Summary of the invention
The object of the present invention is to provide a kind of method of environmentally protective synthetic borneol, the reaction time is short, low manufacture cost,
Discharge without a large amount of waste water and dregs.
The purpose of the present invention is achieved through the following technical solutions: a kind of method of environmentally protective synthetic borneol, including
Australene is carried out esterification with anhydrous oxalic acid under the action of catalyst to obtain oxalic acid borneol acetate and carry out oxalic acid borneol acetate
Saponification obtains the step of thick borneol, and the esterification includes three stages of reaction: the reaction temperature of first stage is 45
~65 DEG C, the reaction time be 2~8h, the reaction temperature of second stage is 65~75 DEG C, the reaction time is 1~3h, phase III
Reaction temperature be 75~88 DEG C, the reaction time is 1~2h, in temperature-rise period, heating is no more than 1 DEG C per minute；The esterification
It is filtered after reaction, by recycling precipitate, that is, reusable.
Further, the step of recycling precipitate are as follows: it is after esterification, interior temperature is cooling, with pump by liquid
It is delivered in settling box, stands 1~12 hour；Then the liquid of settling box is delivered in washing tube with pump, precipitating is expected back
Receipts.
Further, after esterification, interior temperature is cooled to 45 DEG C or less.
Further, when sediment being reused, settling box first is added in 1.5~2.0% australene, stirring makes to sink
Sediment and australene in the bucket of shallow lake are tuned into paste, and after larger shot-like particle, the australene for adding 3~5% enters settling box,
Continue to stir, after so that paste and australene is mixed into liquid condition, be added in reaction pot immediately；Then remaining australene is added
Alkene pours the sediment of remaining in reaction pot through settling box together.
Further, australene is the product that be fractionated through vacuum decompression of turpentine oil in the esterification, content greater than etc.
In 85%.
Further, the quality that feeds intake of the catalyst is the 2~3% of australene quality.
Further, the catalyst is the mixture of hydrated titanium dioxide or hydrated titanium dioxide and acetic anhydride.
Compared with prior art, the device have the advantages that are as follows:
1. the method for environmentally protective synthetic borneol of the invention, esterification is i.e. repeatable by recycling precipitate after the completion
It uses, post-processing is simple, and using the precipitating material of recycling, as raw material, the reaction was continued, content and the first set reaction phase of obtained normal borneol
Than being basically unchanged, the discharge without a large amount of waste water, waste residue meets the theory of environmentally protective synthesis.
2. the method for environmentally protective synthetic borneol of the invention, esterification are not isothermal reactions, it is divided into three temperature
Stage is reacted, and the reaction time is short.Each elementary reaction is steady, mild, no very exothermic and slug, explosion phenomenon.Upper one
Before the reaction in stage terminates, interior temperature heats up naturally with exothermic heat of reaction does not need cooling control heating process, saves the reaction time, ester
Change reaction to be no more than 7 hours.
3. the method for environmentally protective synthetic borneol of the invention, using product of the turpentine oil after vacuum decompression is fractionated,
Anhydrous oxalic acid and hydrated titanium dioxide are that raw material instead of expensive firpene in the prior art greatly reduces borneol
The cost of material of synthesis.
Specific embodiment
With reference to embodiment, technical solution of the present invention is described in further detail, but do not constituted pair
Any restrictions of the invention.
Embodiment 1
300Kg australene is put into reaction pot, stirring is started.Inside and outside temperature is balanced, interior temperature control system is thrown at 40 DEG C or less
Material.82Kg anhydrous oxalic acid, 12Kg hydrated titanium dioxide are put into reaction pot after 20 mesh net filtration of funnel.It is hydrated titanium dioxide
Titanium is before use, drying time 2~5 hours at being put into 140~150 DEG C of baking oven for aqueous hydrated titanium dioxide.After drying
Hydrated titanium dioxide water content is 6~13%.First stage reaction temperature is 65 DEG C, and the reaction time is 2 hours；Second stage is anti-
Answering temperature is 70 DEG C, and the reaction time is 2 hours, and phase III reaction temperature is 75 DEG C, is reacted 2 hours.After esterification,
Interior temperature is cooled to 45 DEG C hereinafter, liquid is delivered in settling box with pump, standing 3~5 hours；Then use pump by settling box
Liquid is delivered in washing tube, by precipitating material recycling.1.5 times of weight of water will be added in liquid, and is passed directly into steaming in pot
Vapour is heated to 100 DEG C, starts stirring 30 minutes, stops stirring, stands 1 hour.Light oil is distilled off in oil reservoir, obtains oxalic acid dragon
Brain ester.The sodium hydroxide solution for adding 33% carries out saponification, realizes saponification distillation, saponification distillation using saponification boiler
Borneol, yield 48% are collected in the temperature control of pot after the completion of 95~103 DEG C, saponification.It is measured through HPLC, wherein positive ice
Piece content is 79%.
Continue on for after precipitating material recycling raw materials used when borneol synthetic reaction are as follows: 300Kg australene, 77Kg are without water plant
Acid, 7.4Kg hydrated titanium dioxide and 45Kg sediment.
5Kg australene first is released from australene measuring tank and enters settling box, is then stirred with wood pulp, and it is heavy in settling box to make
Starch and australene are tuned into paste, after larger shot-like particle, then release 10Kg australene from measuring tank and enter settling box, continue to stir
It mixes, allows in bucket after paste and australene are mixed into liquid condition, rapidly join in reaction pot.Stirring is started, inside and outside temperature is balanced
Degree, interior temperature control system feed intake at 40 DEG C or less, and australene remaining in measuring tank through settling box, together by the sediment of remaining
It pours in reaction pot.
77Kg anhydrous oxalic acid, 7.4Kg hydrated titanium dioxide are put into reaction pot after 20 mesh net filtration of funnel.It feeds intake
When observation at any time in warm situation of change if heating rate is fast (1min heats up 1 DEG C or more) stop charging immediately, and open cooling water
Cooling control is carried out, can just continue to feed intake when interior temperature drops to 40 DEG C or less.Then esterification, first stage reaction temperature are carried out
Degree is 65 DEG C, and the reaction time is 2 hours；Second stage reaction temperature is 70 DEG C, and the reaction time is 2 hours, phase III reaction
Temperature is 75 DEG C, is reacted 2 hours.After the reaction was completed, catalyst is recovered by filtration, will be added 1.5 times of weight of water in filtrate, and
It is passed directly into pot and is steam heated to 100 DEG C, start stirring 30 minutes, stop stirring, stand 1 hour.Oil reservoir is distilled off
Light oil obtains oxalic acid borneol acetate.The sodium hydroxide solution for adding 33% carries out saponification, realizes soap using saponification boiler
Change distillation, borneol, yield 40% are collected in the temperature control for being saponified boiler after the completion of 95~103 DEG C, saponification.Through
HPLC measurement, wherein normal borneol content is 78%.
By embodiment 1 it is found that under same experiment condition, using the precipitating material being recovered by filtration after esterification as raw material
The reaction was continued, although yield is declined slightly, the content of normal borneol is basically unchanged the recycling, it can be achieved that reactant, process
In will not discharge a large amount of waste water, waste residue, meet environmentally protective synthesis theory.
Above embodiments are some embodiments of the invention, are not restricted to the present invention.Those skilled in the art are come
It says, the several improvements and modifications made without departing from the principle of the present invention also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of method of environmentally protective synthetic borneol, including australene and anhydrous oxalic acid are subjected to ester under the action of catalyst
Change reaction to obtain oxalic acid borneol acetate and oxalic acid borneol acetate is carried out saponification and purifies the step of obtaining thick borneol, the esterification
Reaction includes three stages of reaction: the reaction temperature of first stage is 45~65 DEG C, the reaction time is 2~8h, second stage
Reaction temperature is 65~75 DEG C, the reaction time is 1~3h, the reaction temperature of phase III is 75~88 DEG C, the reaction time be 1~
2h, it is characterised in that: stood after the esterification, by recycling precipitate, that is, reusable.
2. the method for environmentally protective synthetic borneol according to claim 1, it is characterised in that: the recycling precipitate
Step are as follows: it is after esterification, interior temperature is cooling, liquid is delivered in settling box with pump, stands 1~12 hour；Then
The liquid of settling box is delivered in washing tube with pump, by precipitating material recycling.
3. the method for environmentally protective synthetic borneol according to claim 2, it is characterised in that: terminate in esterification
Afterwards, interior temperature is cooled to 45 DEG C or less.
4. the method for environmentally protective synthetic borneol according to claim 1 or 2 or 3, it is characterised in that: by sediment weight
Again in use, settling box first is added in 1.5~2.0% australene, stirring is tuned into the sediment in settling box with australene
Paste, after larger shot-like particle, the australene for adding 3~5% enters settling box, continues to stir, makes paste and australene
After being mixed into liquid condition, it is added in reaction pot immediately；Then remaining australene is added through settling box, by the sediment of remaining
It pours in reaction pot together.
5. the method for environmentally protective synthetic borneol according to claim 4, it is characterised in that: α-in the esterification
Firpene is the product that turpentine oil is fractionated through vacuum decompression, and content is more than or equal to 85%.
6. the method for environmentally protective synthetic borneol according to claim 5, it is characterised in that: the catalyst feeds intake
Quality is the 2~3% of australene quality.
7. the method for environmentally protective synthetic borneol according to claim 1 or 6, it is characterised in that: the catalyst is
The mixture of hydrated titanium dioxide or hydrated titanium dioxide and acetic anhydride.
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| CN201910409892.3A CN109970510A (en) | 2019-05-16 | 2019-05-16 | A kind of method of environmentally protective synthetic borneol |
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| CN201910409892.3A CN109970510A (en) | 2019-05-16 | 2019-05-16 | A kind of method of environmentally protective synthetic borneol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115770623A (en) * | 2022-12-09 | 2023-03-10 | 梧州黄埔化工药业有限公司 | Preparation method of ion exchange membrane for camphor esterification reaction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153764A (en) * | 1996-01-02 | 1997-07-09 | 唐松柏 | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst |
| CN101318880A (en) * | 2008-07-23 | 2008-12-10 | 嘉兴学院 | A green synthesis process of borneol |
| CN101830779A (en) * | 2010-05-18 | 2010-09-15 | 嘉兴学院 | Method for selectively synthesizing normal borneol |
| CN102101824A (en) * | 2010-01-21 | 2011-06-22 | 河北金木药业集团有限公司 | Preparation method of borneol |
| CN102241567A (en) * | 2011-04-29 | 2011-11-16 | 南宁辰康生物科技有限公司 | One-step method for synthesizing fenchol with turpentine |
| CN105985243A (en) * | 2015-02-04 | 2016-10-05 | 华东理工大学 | Novel process for synthesis of borneol ester by esterification of pinene |
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2019
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|---|---|---|---|---|
| CN1153764A (en) * | 1996-01-02 | 1997-07-09 | 唐松柏 | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst |
| CN101318880A (en) * | 2008-07-23 | 2008-12-10 | 嘉兴学院 | A green synthesis process of borneol |
| CN102101824A (en) * | 2010-01-21 | 2011-06-22 | 河北金木药业集团有限公司 | Preparation method of borneol |
| CN101830779A (en) * | 2010-05-18 | 2010-09-15 | 嘉兴学院 | Method for selectively synthesizing normal borneol |
| CN102241567A (en) * | 2011-04-29 | 2011-11-16 | 南宁辰康生物科技有限公司 | One-step method for synthesizing fenchol with turpentine |
| CN105985243A (en) * | 2015-02-04 | 2016-10-05 | 华东理工大学 | Novel process for synthesis of borneol ester by esterification of pinene |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115770623A (en) * | 2022-12-09 | 2023-03-10 | 梧州黄埔化工药业有限公司 | Preparation method of ion exchange membrane for camphor esterification reaction |
| CN115770623B (en) * | 2022-12-09 | 2024-03-29 | 梧州黄埔化工药业有限公司 | Preparation method of ion exchange membrane for camphoresterification reaction |
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Application publication date: 20190705 |