CN105693471A - Preparation method of thymol crystals - Google Patents
Preparation method of thymol crystals Download PDFInfo
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- CN105693471A CN105693471A CN201610040090.6A CN201610040090A CN105693471A CN 105693471 A CN105693471 A CN 105693471A CN 201610040090 A CN201610040090 A CN 201610040090A CN 105693471 A CN105693471 A CN 105693471A
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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
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a preparation method of thymol crystals, which comprises the following steps: after mixing eucalyptus oil and silica gel, performing a cyclization reaction until by sampling inspection, a refraction coefficient of a sample at a temperature of 20 DEG C is 1.4720 to 1.4723 and the sample has fragrance of isopulegol, and discharging to obtain the isopulegol; and after gasifying the isopulegol, performing a dehydrogenation reaction at a temperature of 200 to 300 DEG C by a copper-nickel catalyst to obtain liquid thymol crystals of which a refraction coefficient at a temperature of 20 DEG C is 1.4850 to 1.5100. Compared with the prior art, the preparation method has the following beneficial effect that the thymol crystals, which are prepared by the method, overcome the harsh high-temperature and high-pressure conditions of a conventional friedel-crafts alkylation reaction, are mild in reaction temperature, use the recyclable catalyst and are environmental-friendly, are high in purity, and are kept stable in gloss, unchanged in odor and slightly reduced in content in the storage period.
Description
Technical field
The preparation method that the present invention relates to a kind of thymol, belongs to technical field of medicine synthesis。
Background technology
Thymol, also known as thymol (1963 editions Chinese Pharmacopoeias), thymol, thymol, chemistry 2-isopropyl-5-methylphenol by name, the bactericidal action of thymol is stronger than phenol, and toxicity is low, oral cavity pharyngolaryngeal mucosa there are sterilization, fungicidal action, there are anticorrosion, local anesthetic action in dental caries chamber, for oral cavity, the disinfection of throat, tinea, actinomycosis and otitis。Tra cheo-oesophageal voice can be promoted, be conducive to the secretion of tracheal mucus, easily play phlegm-dispelling functions, then added with bactericidal action, therefore can be used for treating tracheitis, pertussis etc.。Having very strong acaricidal action, 1% solution mortality rate half an hour 100%, the solution 24h of 0.03% kills 100%。Also can be used as ascarifuge agent。Thymol 0.05～0.2% solution has and stronger kills protoscolex effect, can reach 100% effect killing protoscolex in 5～10min, and effect is reliable rapidly, and toxicity is little。
At present, the natural origin of thymol is in labiate Herba thymi vulgaris ThymusserpyllumL. grass, Herba thymi vulgaris T.vulgarisL. herb, Adeps Bovis seu Bubali OriganumvulgareL. herb, Herba Dracocephali DracocephalummoldavicumL. herb, samphire thick fruit celery Trachyspermumammi (L.) Sprague seed。The thymol yield extracted from plant is low, and cost is high, and ambient pressure is big, therefore musk ambrette grass phenol has certain technical advantage, there is the wide market space。
Abroad, synthetic method is mainly fourier alkylated reaction and prepares, and adopting the material containing isopropyl such as metacresol and chloropropane, propylene or isopropanol is raw material, carry out under elevated pressure conditions, easily producing isomer and many induced by alkyl hydroxybenzene etc., the later stage separates complexity, relatively costly。
For solving these problems, application number be 200810219106.5 Chinese patent in refer to the preparation method of a kind of thymol。This method uses metacresol and isopropanol to be raw material, reacts, with γ-Al in fixed bed reactors2O3As catalyst, at reaction temperature 200～350 DEG C, prepare thymol。The abundant raw material source of this technique is extensive, but yield is relatively low 40%, and later-period purification process is indefinite, and impurity is in confused situation。
Chinese patent 104177233A, namely " synthetic method of a kind of thymol " discloses a kind of with menthol for raw material, obtains menthol gas through gasification, under the conveying of carrier gas, with activated carbon supported Ni/Na2SiO3Catalyst generation dehydrogenation reaction, the method that namely condensed, purification obtains thymol。Catalyst used in the method is expensive, and later-period purification treatment process is complicated。
Summary of the invention
The purpose of invention is in that, a kind of a kind of method providing continuous catalysis musk ambrette grass phenol, it is provided that reproducible catalyst, compared to existing patented technology, this law technique exploitativeness is strong, also overcomes prior art method defect in technique and environmental protection accordingly simultaneously。
The present invention is achieved by the following technical solutions: first passes through sedimentation and prepares reproducible catalyst, then passes through rectification and adds dehydrogenation reaction two step and prepare thymol。This law passes through reacting by heating substrate essence isopulegol so that it is being certainly advanced in reactor, with copper-nickel catalyst generation catalytic reaction, continuous feed, by product decrease temperature crystalline, centrifugal drying is prepared into thymol。Reaction substrate essence isopulegol charging rate is 1～10kg/min, and temperature of reactor controls at 200～300 DEG C。
The preparation method that the invention provides a kind of thymol, comprises the steps:
After eucalyptus citriodora oil is mixed with silica gel, carry out cyclization to sampling Detection sample refraction coefficient at 20 DEG C be 1.4720～1.4723 and described sample there is the fragrance of isopulegol, discharging, obtain isopulegol；
After being gasified by described isopulegol, at 200～300 DEG C, carry out dehydrogenation reaction by copper-nickel catalyst, obtain the liquid thymol that the refraction coefficient at 20 DEG C is 1.4850～1.5100。
Silica gel belongs to acidic catalyst, it is possible to choose other acidic catalysts, but later separation is complicated, it is necessary to acid-alkali accommodation。Silica gel consumption is not enough, and the response time extends, and will result in and occurs the by-product of aldol reaction to increase, cause later step yield to reduce under reaction temperature。
In copper-nickel catalyst, activity unit is copper and nickel element, and alkaline components can reduce the dehydration of dehydrogenation reaction, it is to avoid catalyst toxicity is poisoning, and then avoids the reduction of catalysis activity。
Preferably, the preparation method of the copper-nickel catalyst comprises the steps:
Adding copper sulfate and nickel sulfate in first part of purified water, stirring and dissolving is complete, obtains copper sulfate and nickel sulfate mixed aqueous solution；
Second part of purified water adds kieselguhr at 30～60 DEG C, adds sodium carbonate after stirring, after described sodium carbonate all dissolves, add described copper sulfate and nickel sulfate mixed aqueous solution, react；Selecting 30～60 DEG C, will promote the inorganic reaction process of catalyst, the diffusion of stimulating activity elemental copper and nickel drops in neutral temperature, is conducive to it to deposit on diatomite particle。
Reaction scheme is:
After adding water in the reaction product, add and include potassium carbonate and magnesian pasty liquid, after stirring, dry, obtain the copper-nickel catalyst。
Preferably, the temperature of described cyclization is 140～200 DEG C。
Preferably, the weight ratio of described eucalyptus citriodora oil and silica gel is (30～100): (0.5～3)。
Preferably, the step that thymol is carried out to be purified also is included: be specially coarse crystallization, recrystallization and drying。
Preferably, the weight ratio of described copper sulfate, nickel sulfate and first part of purified water is 1:(1～2): (1～3)。
Preferably, the weight ratio of described kieselguhr, sodium carbonate and second part of purified water is (0.5～2): (1～2.5): (16～23)。If this ratio is too high, alkaline components is very few, and the sulfate ion that copper and nickel element combine cannot be replaced, if this ratio is too low, then alkaline components is too much, and will cause catalyst is target product dehydration, and under high temperature, dehydration makes catalysqt deactivation。
Preferably, described in include in potassium carbonate and magnesian pasty liquid, potassium carbonate and magnesian weight ratio are (0.01～5): (0.01～1.00)。
Preferably, the step that isopulegol is purified also is included: be specially fractional distillation。
More specifically, the operation of each step is as follows:
Step one: eucalyptus citriodora oil is mixed with the silica gel (consumption of silica gel is about the 2～3% of eucalyptus citriodora oil weight) being crushed between 60～90 orders, react 7～9 hours between 150～170 DEG C, until sampling Detection to reactant liquor sample refraction coefficient at 20 DEG C be 1.4720～1.4723 and sample there is the fragrance of isopulegol, discharging；The above-mentioned product of rectification, removes front-end volatiles and tails, obtains essence isopulegol；
Silica gel is crushed to certain fineness, is conducive to the dehydration condensation of target component in eucalyptus citriodora oil。
Step 2: step one gained essence isopulegol is passed through heating and gasifying, gas carries out dehydrogenation reaction by catalyst at 200～300 DEG C, detection product index of refraction, collect the product that refraction coefficient is 1.4850～1.5100 at 20 DEG C, by decrease temperature crystalline, centrifugal drying is prepared into thymol。
Compared with prior art, the present invention has following beneficial effect:
1, the thymol good stability prepared by this method, purity is high, keeps color stability within storage period, and abnormal smells from the patient is constant, and content is unaffected；
2, the inventive method is easy, it is adaptable to industrial-scale production；
3, the renewable use of catalyst that the method adopts, long service life；
4, the device that the method adopts is original creation design, continuous feed, sustained response；
Thymol consersion unit is made up of two parts, respectively reaction tube and economizer bank, and economizer bank, by adding isopulegol raw material at the bottom of pipe, passes through heating and gasifying；Reaction tube is made up of size two pipe, and the cavity between two pipes inserts copper-nickel catalyst, and gasified raw material connects in entrance cavity by pipeline, controls to ensure that catalytic reaction carries out by temperature, connect thymol product bottom reaction tube in cavity；
5, the method later-period purification processes simple, decrease temperature crystalline；
6, the eucalyptus citriodora oil that this method adopts, extracts from south China or even Southeast Asia all over raw lemon scented gum, and raw material easily obtains, with low cost。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail。Following example will assist in those skilled in the art and are further appreciated by the present invention, but do not limit the present invention in any form。It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement。These broadly fall into protection scope of the present invention。
Embodiment 1
The present embodiment relates to the preparation of a kind of thymol, specifically includes following steps:
One, the preparation of catalyst
(1) weigh copper sulfate and nickel sulfate, add purified water, copper sulfate: nickel sulfate: water weight ratio is 1:(1～2): (4～6), stirring and dissolving is complete；
(2) measure 16～23 parts of purified water and pour in a mixing bowl, heating；Stirring is lower adds 0.5～2 part of kieselguhr；It is gradually added sodium carbonate 1～2.5 part under stirring again, treats that it all dissolves；Continue to add copper sulfate under stirring and nickel sulfate mixed aqueous solution completes reaction。
(3) a collection of moist catalysis prepared by (1)-(2) is incorporated to together, add about 1L water and stir into pasty state, add by 0.1～0.7 part of potassium carbonate wiring solution-forming and the pasty liquid that is made into by 0.01～1.00 part of magnesium oxide again, being sufficiently stirred for 7～10 hours, product is placed in oven for drying。
Two, thymol (thymol can be obtained by GC-MS test) preparation process
(1) cyclisation: 600～1000Kg eucalyptus citriodora oil adds in reaction pot after mixing homogeneously with silica gel 10～45Kg and is stirred。Open reacting by heating, withdrawing fluid is discharged, reheating allows temperature continue to rise to reaction temperature 140～200 DEG C, after reacting 8～14 hours, refraction index (20 DEG C) is surveyed in sampling, refraction index (20 DEG C) is stable 1.4710～1.4730 and when having the peculiar fragrance of thick isopulegol, cooling down。Treat that kettle temperature declines and stop stirring, collect supernatant after feed clarification and carry out fractional distillation。
(2) fractional distillation: the feed liquid clarified is put into fractional distillation pot。Open cold condenser and cooler water intaking valve also open heat(ing) coil air bleeding valve, after condensed water in vomit pipe, close air bleeding valve, then proceed to start to steam essence isopulegol after one hour with vacuum pump infinite reflux。
Process conditions and parameter: controlling reflux ratio is: 26:4～20:10；Product index of refraction is 1.4715～1.4730。
(3) after dehydrogenation: a, catalyst have aoxidized, to already oxidised copper-nickel catalyst, at 200～450 DEG C, hydrogenation converts to goes back native copper, reduced nickel。
B, essence isopulegol feed in raw material, during reaction tube constant temperature also by economizer bank constant temperature in 230～280 DEG C, open inlet valve, feed in raw material toward in reaction tube by the charging quantity specified。Collect the thymol oozed after reinforced, survey refraction index (20 DEG C)。General refraction index (20 DEG C) maintains between 1.4850～1.5100。
(4) purification
Obtain thymol crude product through coarse crystallization, recrystallization, drying, by detecting condensation point in this process, liquid thymol reaches more than 1.4850 by testing its refraction coefficient, primary crystal condensation point is 46～48 DEG C, after recrystallization, condensation point is more than 48.5 DEG C, dried condensation point is more than 49 DEG C, after obtaining thymol finished product, packs。
Embodiment 2
The present embodiment relates to the preparation of a kind of thymol, specifically includes following steps:
One, the preparation of catalyst
(1) weigh copper sulfate and nickel sulfate, add purified water, copper sulfate: nickel sulfate: water weight ratio is 1:1.5:5, and stirring and dissolving is complete；
(2) measure 16～23 parts of purified water and pour in a mixing bowl, heating；Stirring is lower adds 0.5～2 part of kieselguhr；It is gradually added sodium carbonate 1～2.5 part under stirring again, treats that it all dissolves；Continue to add copper sulfate under stirring and nickel sulfate mixed aqueous solution completes reaction。
(3) a collection of moist catalysis prepared by (1)-(2) is incorporated to together, add about 1L water and stir into pasty state, add by 0.1～0.7 part of potassium carbonate wiring solution-forming and the pasty liquid that is made into by 0.01～1.00 part of magnesium oxide again, being sufficiently stirred for 7～10 hours, product is placed in oven for drying。
Two, thymol preparation process
(1) cyclisation: 600～1000Kg eucalyptus citriodora oil adds in reaction pot after mixing homogeneously with silica gel 10～45Kg and is stirred。Open reacting by heating, withdrawing fluid is discharged, reheating allows temperature continue to rise to reaction temperature 140～200 DEG C, after reacting 8～14 hours, refraction index (20 DEG C) is surveyed in sampling, refraction index (20 DEG C) is stable 1.4710～1.4730 and when having the peculiar fragrance of thick isopulegol, cooling down。Treat that kettle temperature declines and stop stirring, collect supernatant after feed clarification and carry out fractional distillation。
(2) fractional distillation: the feed liquid clarified is put into fractional distillation pot。Open cold condenser and cooler water intaking valve also open heat(ing) coil air bleeding valve, after condensed water in vomit pipe, close air bleeding valve, then proceed to start to steam essence isopulegol after one hour with vacuum pump infinite reflux。
Process conditions and parameter: namely the reflux ratio controlling distillation operation steams product: return product is 20:10 (reflux ratio) 1.4715-1.4730。
(3) after dehydrogenation: a, catalyst have aoxidized, to already oxidised copper-nickel catalyst, at 200～450 DEG C, hydrogenation converts to goes back native copper, reduced nickel。
B, essence isopulegol feed in raw material, during reaction tube constant temperature also by economizer bank constant temperature in 230～280 DEG C, open inlet valve, feed in raw material toward in reaction tube by the charging quantity specified。Collect the thymol oozed after reinforced, survey refraction index (20 DEG C)。General refraction index (20 DEG C) maintains between 1.4850～1.5100。
(4) purification
Obtain thymol crude product through coarse crystallization, recrystallization, drying, after obtaining thymol finished product, pack。
In sum, the present invention has following beneficial effect:
1, the thymol good stability prepared by this method, purity is high, keeps color stability within storage period, and abnormal smells from the patient is constant, and content is unaffected；
2, the inventive method is easy, it is adaptable to industrial-scale production；
3, the renewable use of catalyst that the method adopts, long service life；
4, the device that the method adopts is original creation design, continuous feed, sustained response；
Thymol consersion unit is made up of two parts, respectively reaction tube and economizer bank, and economizer bank, by adding isopulegol raw material at the bottom of pipe, passes through heating and gasifying；Reaction tube is made up of size two pipe, and the cavity between two pipes inserts copper-nickel catalyst, and gasified raw material connects in entrance cavity by pipeline, controls to ensure that catalytic reaction carries out by temperature, connect thymol product bottom reaction tube in cavity；
5, the method later-period purification processes simple, decrease temperature crystalline；
6, the eucalyptus citriodora oil that this method adopts, extracts from south China or even Southeast Asia all over raw lemon scented gum, and raw material easily obtains, with low cost。
Above specific embodiments of the invention are described。It is to be appreciated that the invention is not limited in above-mentioned particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, and this has no effect on the flesh and blood of the present invention。
Claims (9)
1. the preparation method of a thymol, it is characterised in that comprise the steps:
After eucalyptus citriodora oil is mixed with silica gel, carry out cyclization to sampling Detection sample refraction coefficient at 20 DEG C be 1.4720～1.4723 and described sample there is the fragrance of isopulegol, discharging, obtain isopulegol；
After being gasified by described isopulegol, at 200～300 DEG C, carry out dehydrogenation reaction by copper-nickel catalyst, obtain the liquid thymol that the refraction coefficient at 20 DEG C is 1.4850～1.5100。
2. the preparation method of thymol as claimed in claim 1, it is characterised in that the preparation method of the copper-nickel catalyst comprises the steps:
Adding copper sulfate and nickel sulfate in first part of purified water, stirring and dissolving is complete, obtains copper sulfate and nickel sulfate mixed aqueous solution；
Second part of purified water adds kieselguhr at 30～60 DEG C, adds sodium carbonate after stirring, after described sodium carbonate all dissolves, add described copper sulfate and nickel sulfate mixed aqueous solution, react；
After adding water in the reaction product, add and include potassium carbonate and magnesian pasty liquid, after stirring, dry, obtain the copper-nickel catalyst。
3. the preparation method of thymol as claimed in claim 1, it is characterised in that the temperature of described cyclization is 140～200 DEG C。
4. the preparation method of thymol as claimed in claim 1, it is characterised in that the weight ratio of described eucalyptus citriodora oil and silica gel is (30～100): (0.5～3)。
5. the preparation method of thymol as claimed in claim 1, it is characterised in that also include the step that thymol is carried out to be purified: be specially coarse crystallization, recrystallization and drying。
6. the preparation method of thymol as claimed in claim 2, it is characterised in that the weight ratio of described copper sulfate, nickel sulfate and first part of purified water is 1:(1～2): (1～3)。
7. the preparation method of thymol as claimed in claim 2, it is characterised in that the weight ratio of described kieselguhr, sodium carbonate and second part of purified water is (0.5～2): (1～2.5): (16～23)。
8. the preparation method of thymol as claimed in claim 2, it is characterised in that described in include in potassium carbonate and magnesian pasty liquid, potassium carbonate and magnesian weight ratio are (0.01～5): (0.01～1.00)。
9. the preparation method of thymol as claimed in claim 1, it is characterised in that also include the step that isopulegol is purified: be specially fractional distillation。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177233A (en) * | 2014-09-10 | 2014-12-03 | 湖南湘易康制药有限公司 | Thymol synthesis method |
| CN104744219A (en) * | 2015-04-22 | 2015-07-01 | 江苏理工学院 | Preparation method of thymol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177233A (en) * | 2014-09-10 | 2014-12-03 | 湖南湘易康制药有限公司 | Thymol synthesis method |
| CN104744219A (en) * | 2015-04-22 | 2015-07-01 | 江苏理工学院 | Preparation method of thymol |
Non-Patent Citations (2)
| Title |
|---|
| 杨泽榆等: "麝香草酚的合成", 《催化学报》 * |
| 陈保乃: "柠檬桉叶油合成麝香草酚的研究", 《生物质化学工程》 * |
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