CN109851479A - A kind of chemical synthesis process of antibacterial agent fragrance carvacrol - Google Patents
A kind of chemical synthesis process of antibacterial agent fragrance carvacrol Download PDFInfo
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- CN109851479A CN109851479A CN201910042135.7A CN201910042135A CN109851479A CN 109851479 A CN109851479 A CN 109851479A CN 201910042135 A CN201910042135 A CN 201910042135A CN 109851479 A CN109851479 A CN 109851479A
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Abstract
The present invention relates to a kind of chemical synthesis process of antibacterial agent carvacrol.The synthesis technology selects ortho-methyl phenol and isopropanol is raw material, and with compound methylene chloride, n-hexane (petroleum ether) etc. for reaction dissolvent, by alkylated reaction, liquid-liquid extraction often, is concentrated under reduced pressure, is evaporated under reduced pressure and carvacrol is made.The features such as synthesis technology has simple process, and production cost is low, and yield is high, good quality of product, is easy to the factorial production.
Description
Technical field
The present invention relates to a kind of chemical synthesis process of antibacterial agent fragrance carvacrol.
Background technique
Carvacrol is a kind of phenol compound with bactericidal effect, is primarily present Thymus plant in nature
In essential oil.One of main antimicrobial component in the products such as natural origanum oil, mountain Herba Thymi oil is exactly carvacrol.Since its antibiotic property is wide
Spectrum, safe, residual quantity is extremely low in animal body, is applied to dysentery and anticoccidial of the animals such as treatment chicken, piglet etc..
It is described in U.S. patent Nos US Patent 2286953 using ortho-methyl phenol as raw material, aluminum trichloride (anhydrous)
For catalyst, condensation reaction, the method for preparing carvacrol are carried out with 2 cbloropropane isopropyl chloride.Chinese invention patent CN 1488615A is also situated between
It has continued using ortho-methyl phenol as raw material, aluminum trichloride (anhydrous) is catalyst, carries out condensation reaction with 2 cbloropropane isopropyl chloride and produces carvacrol
Method but the above method there are alkylated material 2 cbloropropane isopropyl chloride toxicity is big, low boiling point is not easy transport storage and price is higher
The defects of.
It has been reported that and uses Zr-Al-SiO2Composite catalyst catalysis isopropanol is reacted with ortho-methyl phenol has synthesized carvacrol
(JournalofChemicalTechnologyandBiotechnology, 2009,84,1499-1508) still this method reaction
Temperature need 180 DEG C, and ultimate yield is lower, only 73%.
The present invention proposes that the chemical synthesis process of carvacrol had both been avoided and makees many of alkylated material using 2 cbloropropane isopropyl chloride
Drawback, improves the safety of production, and overcomes using isopropanol and to need pyroreaction as alkylated material and in equipment, energy consumption
A series of and defects brought by operation etc..
The present invention is mainly characterized by: being used isopropanol to make ortho-methyl phenol alkyl and is combined to carvacrol material with anhydrous trichlorine
Changing aluminium or anhydrous ferric trichloride makes adjacent methyl using methylene chloride or n-hexane (petroleum ether) etc. as reaction dissolvent for catalyst
Phenol and isopropanol are alkylated condensation reaction, after methylene chloride or the extraction of n-hexane (petroleum ether) equal solvent, often,
Rectifying is concentrated under reduced pressure, the high-content carvacrol product for meeting requirement is made.
Summary of the invention
First methylene chloride needed for reaction system or n-hexane (petroleum ether) are added to stirring and refrigerating plant
Reaction kettle in, catalyst aluminum trichloride (anhydrous) or anhydrous ferric trichloride is added, stirring is cooled to 0 DEG C ± 5 DEG C and is slowly added to neighbour
Isopropanol is added dropwise after temperature of reaction system reaches 0 DEG C ± 5 DEG C in methylphenol, and 4h ± lh is reacted at 0 DEG C ± 5 DEG C, terminates
Reaction.At room temperature, to be slowly added to have been loaded with metering for reaction product broken
In the reaction kettle of ice, stirring is then allowed to stand until ice all thawings, oil-yielding stratum is separated, with methylene chloride or n-hexane (stone
Oily ether) again aqueous layer extracted twice, merge the oil reservoir isolated, be concentrated into no methylene chloride or n-hexane under 55 DEG C of -70 DEG C of normal pressures
Until (petroleum ether) solvent steams, carvacrol crude product is obtained, measures its Sheep's-parsley phenol content >=65% with HPLC.Vacuum distillation,
100Pa vacuum degree collects the distillations at 115 DEG C ± 1 DEG C to get faint yellow carvacrol fine work is arrived.
Concrete technology condition of the invention are as follows:
(1) alkylated reaction C7H8O+C3H7OH → C10H14O
The weight of material of o-cresol and isopropanol ratio is 1.3 ± 0.1:1, and catalyst and the weight ratio of o-cresol dosage are
3.3 ± 0.1:1, the weight of the volumetric usage and ortho-methyl phenol of reaction system methylene chloride or n-hexane (petroleum ether)
The ratio between be 5.5 ± 0.5:1,0 DEG C ± 5 DEG C of reaction temperature, reaction time 4h ± lh.
(2) ice solution extracts: end of reaction is at room temperature slowly added into reaction product the reaction for having been loaded with metering trash ice
In kettle, stirring is until ice all melts.The dosage of trash ice is 2-3 times of quantity of solvent, separation oil-yielding stratum, then with reaction dissolvent amount
1/4-1/3 fresh solvent aqueous layer extracted 2-3 times, merge the oil reservoir isolated.
(3) solvent concentration is evaporated off to solvent-free outflow at 55 DEG C -70 DEG C of normal pressure.
(4) it is evaporated under reduced pressure, the fraction at 115 DEG C of 100Pa vacuum degree, collection l DEG C of soil.
Catalyst in the present invention is aluminum trichloride (anhydrous), anhydrous ferric trichloride, and the water phase after liquid-liquid extraction is tri-chlorination
Aluminium or the ferric chloride aqueous solutions solution can the mode Jing Guo thickening recycled.
Using method of the invention, without vacuum distillation, the yield of carvacrol is greater than 70%, and content is greater than 65%.
Detailed description of the invention:
Attached drawing 1 is the chemical synthesis process of antibacterial agent carvacrol of the present invention.
It is an advantage of the invention that alkylated material used in traditional handicraft be low-boiling compound 2 cbloropropane isopropyl chloride, it is toxic and
It is not easy transport storage and price is higher, and alkylated material used in the entire technical process of the present invention overcomes traditional handicraft
Deficiency, accomplished safety, it is environmentally friendly and inexpensive.
Specific embodiment:
Technical process Examples detail is as follows
Embodiment 1
Measure methylene chloride 500L be added 1000L band stirring and cooling device reaction kettle in, addition 300kg catalyst without
Water alchlor, stirring is cooled to -5 DEG C, is slowly added to 100kg o-cresol, after temperature of reaction system reaches -5 DEG C,
72 kg isopropanols are added dropwise, 4h is reacted at -5 DEG C, and reaction was completed.At room temperature reaction product is slowly added to have been loaded with
Ice Xie Zhizhi is stirred in the reaction kettle of the belt stirrer of 1200kg trash ice
Ice all melts, and stands, and separates oil-yielding stratum, washs water layer with 150L methylene chloride every time, altogether twice, merging is isolated
Oil reservoir, be concentrated under 55 DEG C of normal pressures until no dichloromethane solvent steams, obtain 122.2 kilograms of carvacrol crude product, Sheep's-parsley
Phenol content 65.6% (HPLC measurement).Rectification under vacuum 100Pa vacuum degree collects 114 DEG C -116 DEG C of fraction and obtains faint yellow perfume (or spice)
75.6 kilograms of celery phenol, content 98.8%.
Embodiment 2
It measures n-hexane 500L to be added in reaction kettle of the 1000L with stirring and cooling device, 300kg catalyst anhydrous three is added
Aluminium chloride, stirring is cooled to -5 DEG C, is slowly added to 100kg o-cresol, after temperature of reaction system reaches -5 DEG C, is added dropwise
72kg isopropyl is at alcohol, and reaction was completed by reaction 4h at -5 DEG C.Reaction product is slowly added at room temperature to have been loaded with 1200kg
Ice solution is stirred in the reaction kettle of the belt stirrer of trash ice until ice all melts, and standing separates oil-yielding stratum, uses 150L bis- every time
Chloromethanes washs water layer and merges the oil reservoir isolated altogether twice, no n-hexane (petroleum ether) solvent is concentrated under 70 DEG C of normal pressures
Until steaming, 121.6 kilograms of carvacrol crude product are obtained, Sheep's-parsley phenol content 65.4% (HPLC measurement).Rectification under vacuum 100Pa vacuum
The fraction that degree collects 114 DEG C -116 DEG C obtains 74.8 kilograms of faint yellow carvacrol, content 98.6%.
Embodiment 3
It measures methylene chloride 500L to be added in reaction kettle of the 1000L with stirring and cooling device, 300.0kg catalyst is added
Anhydrous ferric trichloride, stirring are cooled to -5 DEG C of and are slowly added to 100kg ortho-methyl phenol, reach -5 DEG C to temperature of reaction system
72kg isopropanol is added dropwise afterwards, 4h is reacted at -5 DEG C, and reaction was completed.At room temperature reaction product is slowly added to have been loaded with
Ice solution is stirred in the reaction kettle of the belt stirrer of 1200kg trash ice until ice all melts, and standing separates oil-yielding stratum, uses every time
150L methylene chloride washs water layer and merges the oil reservoir isolated altogether twice, be concentrated into no dichloromethane solvent under 55 DEG C of normal pressures
Until steaming, 121.4 kilograms of Sheep's-parsley phenol content 65.4% of carvacrol crude product (HPLC measurement) is obtained.Rectification under vacuum 100Pa vacuum degree
It collects 114 DEG C -116 DEG C of fraction and obtains 74.6 kilograms of faint yellow carvacrol, content 98.8%.
Embodiment 4
Measure n-hexane 500L be added 1000L band stirring and cooling device reaction kettle in, addition 300.0kg catalyst without
Aqueous ferric chloride, stirring is cooled to -5 DEG C of and is slowly added to l00kg ortho-methyl phenol, after temperature of reaction system reaches -5 DEG C
72kg isopropanol is added dropwise, 4h is reacted at -5 DEG C, and reaction was completed.At room temperature reaction product is slowly added to have been loaded with
Ice solution is stirred in the reaction kettle of the belt stirrer of 1200kg trash ice until ice all melts, and standing separates oil-yielding stratum, uses every time
150L methylene chloride washs water layer and merges the oil reservoir isolated altogether twice, no n-hexane (petroleum is concentrated under 70 DEG C of normal pressures
Ether) until solvent steams, obtain 122.1 kilograms of Sheep's-parsley phenol content 65.3% of carvacrol crude product (HPLC measurement).Rectification under vacuum
The fraction that 100Pa vacuum degree collects 114 DEG C -116 DEG C obtains 75.2 kilograms of faint yellow carvacrol, content 98.8%.
Claims (4)
1. a kind of preparation method of antibacterial agent fragrance carvacrol, it is characterised in that:
(1) methylene chloride needed for reaction system be added to stirring and refrigerating plant reaction kettle in, be added catalyst without
Water alchlor or anhydrous ferric trichloride, stirring are cooled to 0 DEG C ± 5 DEG C, are slowly added to ortho-methyl phenol and wait for temperature of reaction system
After reaching 0 DEG C ± 5 DEG C, isopropanol is added dropwise, reacts 4h+lh at 0 DEG C ± 5 DEG C, reaction was completed, in the above reaction, adjacent methyl
The weight of material of phenol and isopropanol ratio is 1.3 ± 0.1:1, the weight ratio of catalyst and ortho-methyl phenol dosage is 3.3 ±
0.1:1, reaction system methylene chloride or the ratio between n-hexane (petroleum ether) dosage (volume) and ortho-methyl phenol amount (weight)
For 5.5 ± 0.5:1；
(2) after the reaction was completed at room temperature, reaction product solution is slowly added to measure the stirred autoclave of trash ice
In, it is sufficiently stirred and carries out ice solution, the dosage of trash ice is 2-3 times of quantity of solvent, is then allowed to stand, and separates oil-yielding stratum, then molten with reacting
The fresh solvent aqueous layer extracted of the 1/4-1/3 of dosage 2-3 times, merges the oil reservoir isolated, in distillation still at 55 DEG C normal pressure
Until being concentrated into solvent-free steam, carvacrol crude product is obtained, measures its Sheep's-parsley phenol content >=65% with HPLC；
(3) crude product arrives faint yellow carvacrol through the distillations under 115 ± 1 DEG C of vacuum distillation collection, 100Pa vacuum degree
Fine work content >=98%.
2. the preparation method of the carvacrol according to claim 1, it is characterised in that can be replaced with isopropanol in technique of the invention
Carvacrol material requested is combined to as ortho-methyl phenol alkyl for 2 cbloropropane isopropyl chloride.
3. the preparation method of the carvacrol according to claim 1, it is characterised in that can be used in technique of the invention is anhydrous
Ferric trichloride replaces aluminum trichloride (anhydrous) as catalyst.
4. the preparation method of carvacrol according to claim 1 it is characterized in that condensation temp in technique of the invention by
0 DEG C ± 10 DEG C preferably 0 DEG C ± 5 DEG C.
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Cited By (3)
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| CN112920022A (en) * | 2021-01-11 | 2021-06-08 | 吴樟强 | Method for efficiently preparing carvacrol from o-cresol |
| CN113304743A (en) * | 2021-05-14 | 2021-08-27 | 安徽海华科技集团有限公司 | Method for preparing high-purity carvacrol by using o-cresol |
| CN113896617A (en) * | 2021-10-18 | 2022-01-07 | 安徽海华科技集团有限公司 | Chemical synthesis process of carvacrol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112920022A (en) * | 2021-01-11 | 2021-06-08 | 吴樟强 | Method for efficiently preparing carvacrol from o-cresol |
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| CN113304743A (en) * | 2021-05-14 | 2021-08-27 | 安徽海华科技集团有限公司 | Method for preparing high-purity carvacrol by using o-cresol |
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| CN113896617B (en) * | 2021-10-18 | 2022-04-05 | 安徽海华科技集团有限公司 | Chemical synthesis process of carvacrol |
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