CN1488615A - Green synthesis process for carvacrol for fodder antibacterial agent - Google Patents
Green synthesis process for carvacrol for fodder antibacterial agent Download PDFInfo
- Publication number
- CN1488615A CN1488615A CNA031567088A CN03156708A CN1488615A CN 1488615 A CN1488615 A CN 1488615A CN A031567088 A CNA031567088 A CN A031567088A CN 03156708 A CN03156708 A CN 03156708A CN 1488615 A CN1488615 A CN 1488615A
- Authority
- CN
- China
- Prior art keywords
- isothymol
- reaction
- solvent
- anhydrous
- catalyzer
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention refers to a chemical synthesis craft of antimicrobial carvacrol for animal. The craft uses O-cresol as materials, uses harmless dichloromethane and n-hexane as reaction solvent, the product is produced through alkylation reaction, extraction, decompression condensing and decompression distillation. The method is simple.
Description
The present invention relates to the chemical synthesis process of a kind of animal with the antiseptic-germicide isothymol.
Isothymol is a kind of phenol compound with germicidal action, mainly exists in the Thymus plants essential oil at occurring in nature.One of main antibiotic composition in natural anti-bacteria agent for feeding wild marjoram oil, the mountain region green pepper wet goods product is exactly an isothymol.Because its germ resistance wide spectrum, safety, residual quantity is extremely low in the animal body, is applied to treating aspects such as the diarrheas of animals such as chicken, piglet and anticoccidial.
Having introduced with the Ortho Cresol among the U.S. patent of invention US Patent 2286953 is raw material, and aluminum trichloride (anhydrous) is a catalyzer, carries out condensation reaction with 2 cbloropropane isopropyl chloride, prepares the method for isothymol.Although this method can obtain the isothymol of higher yields, but the solvent that uses in this method is ethylene dichloride, and the toxicity of ethylene dichloride is very high, be deadly poisonous compound, also be carcinogenic substance simultaneously, not only harmful Working environment, and can bring certain toxic residue to product, make synthetic product must carry out strict making with extra care, just can use.
The objective of the invention is for the protection environment, eliminate the toxic residue material in the chemosynthesis of antiseptic-germicide isothymol, improve security of products.
Principal feature of the present invention is: adopting aluminum trichloride (anhydrous) or iron trichloride is catalyzer, with to the minimum greenization compound methylene dichloride of human body and environmental hazard or normal hexane etc. as reaction solvent, make Ortho Cresol and 2 cbloropropane isopropyl chloride carry out the alkylation condensation reaction, again through after methylene dichloride or the extraction of normal hexane equal solvent, concentrating under reduced pressure makes the isothymol product that content is high and can directly use.
Detailed description of the present invention:
Earlier required methylene chloride of reaction system or normal hexane are joined in the reactor that has whipping appts, add catalyzer aluminum trichloride (anhydrous) or FERRIC CHLORIDE ANHYDROUS, stirring is cooled to-15 ℃ ±-5 ℃, slowly add Ortho Cresol, after the question response system temperature reaches-15 ℃ ±-5 ℃, drip 2 cbloropropane isopropyl chloride, react 4h ± 1h down, finish reaction at-15 ℃ ±-5 ℃.Under the room temperature, in resultant of reaction, slowly add trash ice, stir until ice and all melt.Leave standstill, isolate oil reservoir,, merge isolated oil reservoir, under 35 ℃, 200Pa vacuum tightness, till being concentrated into no methylene dichloride or normal hexane solvent and steaming, obtain the isothymol crude product with methylene dichloride or normal hexane washing water layer twice.Measure its isothymol content 〉=70% with HPLC.Underpressure distillation, the distillations under 40Pa vacuum tightness, 95 ℃ ± 1 ℃ of collection, the 4mm promptly obtains faint yellow isothymol elaboration.
Concrete processing condition of the present invention are:
(1) alkylated reaction: C
7H
8O+C
3H
7Cl → C
10H
14O
Ortho Cresol is 1.25: 1 with the weight of material ratio of 2 cbloropropane isopropyl chloride, the weight ratio of catalyzer and Ortho Cresol consumption is 1.9 ± 0.1: 1, the volume of reaction system methylene chloride or normal hexane consumption and Ortho Cresol amount and weight ratio are 4.9 ± 0.6: 1, temperature of reaction-15 ℃ ±-5 ℃, reaction times 4h ± 1h.
(2) liquid-liquid extraction: at room temperature in resultant of reaction, add trash ice, stir until ice and all melt.The consumption of trash ice is 2～3 times of quantity of solvent, isolates oil reservoir.With fresh reactant solvent wash water layer 2～3 times, merge isolated oil reservoir.The cleaning solvent consumption is 1/4～1/5 of a trash ice amount.
(3) concentrating under reduced pressure: under 35 ℃, be concentrated into solvent-free outflow under the 200Pa vacuum tightness.
(4) underpressure distillation: the cut under 40Pa vacuum tightness, 95 ℃ ± 1 ℃ of collection, the 4mm.
Catalyzer among the present invention is aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, and the water after the liquid-liquid extraction is aluminium salt or iron salt solutions, can it be reclaimed through the mode of thickening.Adopt method of the present invention, without underpressure distillation, the yield of isothymol is greater than 60%, and content is greater than 65%.
Accompanying drawing 1 is the process flow sheet of antiseptic-germicide isothymol of the present invention.
Advantage of the present invention is: the solvent that uses in the traditional handicraft is the deadly poisonous compound dichloroethanes, also is carcinogen simultaneously, Harmful working environment not only, and can bring certain toxic residue to product is so that synthetic product must carry out is strict Refining, just can use. And employed reactant is minimum to human body and environmental hazard in the whole technical process of the present invention, Technical process is simple.
Embodiment 1
Take by weighing methylene dichloride 50L and add in the 100L reactor, add 20.0kg catalyzer aluminum trichloride (anhydrous), stir and be cooled to-10 ℃, slowly add the 10.92kg Ortho Cresol, after the question response system temperature reaches-10 ℃, drip the 8.76kg 2 cbloropropane isopropyl chloride ,-10 ℃ of reaction 4.0h end reactions down.Under the room temperature, in resultant of reaction, slowly add the 100.0kg trash ice, stir until ice and all melt.Leave standstill, isolate oil reservoir, use 20L washed with dichloromethane water layer at every turn, totally twice, merge isolated oil reservoir, till being concentrated into no dichloromethane solvent under 35 ℃, 200Pa vacuum tightness and steaming, obtain 11.2L isothymol crude product.Isothymol content 〉=70% (HPLC mensuration).Underpressure distillation is collected and is obtained faint yellow isothymol 7.6L (cut under 40Pa vacuum tightness, 94 ℃～96 ℃ of collections, the 4mm).
Embodiment 2
Take by weighing normal hexane 50L and add in the 100L reactor, add 20.0kg catalyzer aluminum trichloride (anhydrous), stir and be cooled to-15 ℃, slowly add the 10.92kg Ortho Cresol, after the question response system temperature reaches-15 ℃, drip the 8.76kg 2 cbloropropane isopropyl chloride ,-15 ℃ of reaction 4.0h end reactions down.Under the room temperature, in resultant of reaction, slowly add the 100.0kg trash ice, stir until ice and all melt.Leave standstill, isolate oil reservoir, at every turn with 20L normal hexane washing water layer, totally twice, merge isolated oil reservoir, vacuum concentration obtains 12.0L isothymol crude product till do not have the normal hexane solvent and steam under 35 ℃, 200Pa vacuum tightness.Isothymol content 〉=65% (HPLC mensuration).
Embodiment 3
Take by weighing methylene dichloride 50L and add in the 100L reactor, add 20.0kg catalyzer FERRIC CHLORIDE ANHYDROUS, stir and be cooled to-10 ℃, slowly add the 10.92kg Ortho Cresol, after the question response system temperature reaches-10 ℃, drip the 8.76kg 2 cbloropropane isopropyl chloride ,-10 ℃ of reaction 4.0h end reactions down.Under the room temperature, in resultant of reaction, slowly add the 100.0kg trash ice, stir until ice and all melt.Leave standstill, isolate oil reservoir, use 20L washed with dichloromethane water layer at every turn, totally twice, merge isolated oil reservoir, till being concentrated into no dichloromethane solvent under 35 ℃, 200Pa vacuum tightness and steaming, obtain 10.8L isothymol crude product.Isothymol content 〉=70% (HPLC mensuration).
Embodiment 4
Take by weighing normal hexane 50L and add in the 100L reactor, add 20.0kg catalyzer FERRIC CHLORIDE ANHYDROUS, stir and be cooled to-15 ℃, slowly add the 10.92kg Ortho Cresol, after the question response system temperature reaches-15 ℃, drip the 8.76kg 2 cbloropropane isopropyl chloride ,-15 ℃ of reaction 4.0h end reactions down.Under the room temperature, in resultant of reaction, slowly add the 100.0kg trash ice, stir until ice and all melt.Leave standstill, isolate oil reservoir, at every turn with 20L normal hexane washing water layer, totally twice, merge isolated oil reservoir, till being concentrated into no normal hexane solvent under 35 ℃, 200Pa vacuum tightness and steaming, obtain 11.6L isothymol crude product.Isothymol content 〉=65% (HPLC mensuration).
Annotate: the green synthesis process connotation of indication of the present invention is that the solvent in this reaction system is to animal and human's class toxicity very low and environmentally friendly methylene dichloride and normal hexane, and does not have " three wastes " discharging in the production process of the present invention.
Claims (3)
1. the preparation method of an anti-bacteria agent for feeding isothymol is characterized in that:
(1) the required methylene chloride of reaction system is added in the reactor that has whipping appts, add the catalyzer aluminum trichloride (anhydrous), stirring is cooled to-15 ℃ ±-5 ℃, slowly add Ortho Cresol, after the question response system temperature reaches-15 ℃ ±-5 ℃, drip 2 cbloropropane isopropyl chloride, react 4h ± 1h down at-15 ℃ ±-5 ℃, finish reaction, more than in the reaction, Ortho Cresol is 1.25: 1 with the weight of material ratio of 2 cbloropropane isopropyl chloride, and the weight ratio of catalyzer and Ortho Cresol consumption is 1.9 ± 0.1: 1, and the volume of reaction system methylene chloride or normal hexane consumption and Ortho Cresol amount and weight ratio are 4.9 ± 0.6: 1;
(2) at room temperature, in resultant of reaction, slowly add trash ice, stirring is all melted until ice, and the consumption of trash ice is 2～3 times of quantity of solvent, leaves standstill, isolate oil reservoir, with 1/4～1/5 fresh reactant solvent wash water layer of trash ice amount 2～3 times, merge isolated oil reservoir, be evaporated to till solvent-free the steaming under 35 ℃ of 200Pa vacuum tightnesss, obtain the isothymol crude product, measure its isothymol content 〉=70% with HPLC;
(3) distillations under 95 ℃ ± 1 ℃, 40Pa vacuum tightness, 4mm is collected in underpressure distillation, promptly obtains faint yellow isothymol elaboration.
2. the preparation method of anti-bacteria agent for feeding isothymol according to claim 1 is characterized in that the available normal hexane in the technology of the present invention replaces methylene dichloride as the required solvent of reaction system.
3. the preparation method of anti-bacteria agent for feeding isothymol according to claim 1 is characterized in that the available FERRIC CHLORIDE ANHYDROUS in the technology of the present invention replaces aluminum trichloride (anhydrous) as catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156708 CN1244530C (en) | 2003-09-08 | 2003-09-08 | Green synthesis process for carvacrol for fodder antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03156708 CN1244530C (en) | 2003-09-08 | 2003-09-08 | Green synthesis process for carvacrol for fodder antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488615A true CN1488615A (en) | 2004-04-14 |
| CN1244530C CN1244530C (en) | 2006-03-08 |
Family
ID=34156957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03156708 Expired - Fee Related CN1244530C (en) | 2003-09-08 | 2003-09-08 | Green synthesis process for carvacrol for fodder antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1244530C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475448B (en) * | 2009-01-21 | 2011-08-24 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| WO2017124675A1 (en) * | 2016-01-22 | 2017-07-27 | 淮安万邦香料工业有限公司 | Method for using menthene diol to synthesise carvacrol |
| WO2017124676A1 (en) * | 2016-01-22 | 2017-07-27 | 淮安万邦香料工业有限公司 | Method for synthesizing carvacrol by using limo nene epoxides |
| CN109851479A (en) * | 2019-01-17 | 2019-06-07 | 亿如科技(北京)有限公司 | A kind of chemical synthesis process of antibacterial agent fragrance carvacrol |
| EP3630150A4 (en) * | 2017-05-23 | 2021-04-28 | University of Massachusetts | Purified anthelmintic compositions and related methods |
-
2003
- 2003-09-08 CN CN 03156708 patent/CN1244530C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475448B (en) * | 2009-01-21 | 2011-08-24 | 淮安万邦香料工业有限公司 | Green synthesis of high-content carvacrol capable of replacing natural origanum |
| WO2017124675A1 (en) * | 2016-01-22 | 2017-07-27 | 淮安万邦香料工业有限公司 | Method for using menthene diol to synthesise carvacrol |
| WO2017124676A1 (en) * | 2016-01-22 | 2017-07-27 | 淮安万邦香料工业有限公司 | Method for synthesizing carvacrol by using limo nene epoxides |
| EP3630150A4 (en) * | 2017-05-23 | 2021-04-28 | University of Massachusetts | Purified anthelmintic compositions and related methods |
| US11826389B2 (en) | 2017-05-23 | 2023-11-28 | University Of Massachusetts | Purified anthelmintic compositions and related methods |
| US11844815B2 (en) | 2017-05-23 | 2023-12-19 | University Of Massachusetts | Purified anthelmintic compositions and related methods |
| CN109851479A (en) * | 2019-01-17 | 2019-06-07 | 亿如科技(北京)有限公司 | A kind of chemical synthesis process of antibacterial agent fragrance carvacrol |
| CN109851479B (en) * | 2019-01-17 | 2022-07-05 | 亿如科技(北京)有限公司 | Chemical synthesis process of antibacterial agent spice carvacrol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1244530C (en) | 2006-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2392706T3 (en) | Procedure for obtaining a composition rich in hydroxytyrosol from vegetation water | |
| CN113636919B (en) | Method for synthesizing 3-chloro-5-trifluoromethyl trifluoroacetophenone | |
| CN1488615A (en) | Green synthesis process for carvacrol for fodder antibacterial agent | |
| CN105481657B (en) | The method that carvacrol is synthesized with limonene epoxide | |
| CN101774879A (en) | Method for simultaneously extracting high-purity beta-methylnaphthalene and indole from coal tar | |
| CN101456873A (en) | Agricultural bactericidal agent | |
| CN109851479A (en) | A kind of chemical synthesis process of antibacterial agent fragrance carvacrol | |
| FI68087B (en) | FOERFARANDE FOER AOTERVINNING AV GALLIUM UR SYNNERLIGEN BASISKA LOESNINGAR GENOM VAETSKE / VAETSKE-EXTRACT | |
| CN101955517A (en) | Method for extracting and purifying microcystin | |
| CN107805262B (en) | A kind of production method of chlopyrifos | |
| CA2052812C (en) | Process for acylation or alkylation of aromatic compounds in hydrogen fluoride | |
| PL88944B1 (en) | ||
| CN102766030A (en) | Method for preparing 3-bromine-4-hydroxy benzaldehyde | |
| CN103339097A (en) | Prevention of precipitation from nitrated aromatic crude products | |
| CN1134445C (en) | Method for preparing dibenzyl sorbitol | |
| FR2475576A1 (en) | PROCESS FOR RECOVERING METALS, ESPECIALLY PRECIOUS METALS | |
| CN107522721A (en) | A kind of technique of efficiently purification nimbin raw medicine | |
| CN110256200A (en) | A method of separating and recovering solvent from pharmacy class methanol mixing solvent slop | |
| CN1068106A (en) | The new method synthetic herbicide of monoetherization oxyfluorfen | |
| CN102826977A (en) | Synthesis method and application of 7-methoxy-3,7-dimethyloctyl aldehyde | |
| JPS591433A (en) | Purification of n-methylpyrrolidone | |
| CN101386573A (en) | Method for preparing 1-o-hydroxyphenyl butanone | |
| CN100494150C (en) | Preparation and application of indandione derivative raticide and ammonium or sodium salt thereof | |
| CN105384606A (en) | Method for preparing carvacrol from 2-hydroxy-5-isopropenyl-2-methylcyclohexanone | |
| CN1958481A (en) | Chloroactic acid method for treating wastewater of glycine, and comprehensive utilization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060308 Termination date: 20110908 |