CN1049842A - Synthetic method of isoborneol by catalyzing camphenic water with resin - Google Patents
Synthetic method of isoborneol by catalyzing camphenic water with resin Download PDFInfo
- Publication number
- CN1049842A CN1049842A CN 90104209 CN90104209A CN1049842A CN 1049842 A CN1049842 A CN 1049842A CN 90104209 CN90104209 CN 90104209 CN 90104209 A CN90104209 A CN 90104209A CN 1049842 A CN1049842 A CN 1049842A
- Authority
- CN
- China
- Prior art keywords
- amphene
- reaction
- solvent
- hydration
- loop reactor
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Though resin catalysis amphene hydration synthetizing isoborneol has the patent report, but the result is undesirable, the present invention's continuous separation loop reactor that designs for the amphene hydration reaction specially, select for use acetone-diketoalcohol-mesityl oxide and their mixed solvent to carry out this reaction industrial amphene transformation efficiency can be reached more than 95%, the isocamphol productive rate can be higher than 85%.
Description
The present invention relates to the method for amphene hydration system camphor.
Though at present with the existing patent report of the exchange resin catalyzed amphene direct hydration of macropore strong acid cation synthetizing isoborneol.[CN 85104105A] [IN 154,860. indian patent C.A105227075P].But its result is also undesirable.The transformation efficiency of amphene is about 40% in the method hydration reaction of patent (1), though unreacted amphene can continue to use after separating, has increased equipment and energy consumption.The transformation efficiency of the method amphene that patent (2) is introduced can reach 92%, but contains the camphene hydrate up to 22% in the hydrated product, and isocamphol content is 70% and employed solvent dioxane, costs an arm and a leg, and is unfavorable to suitability for industrialized production.
The present invention on custom-designed continuous separation loop reactor, uses appropriate solvent to carry out the amphene hydration with strong acid cation exchange resin catalyst, has obtained comparatively ideal result.The transformation efficiency of industry amphene can be higher than 95%, and the productive rate of isocamphol can reach more than 85%.
Embodiment of the present invention are as follows:
One, resin catalyst selects for use
Can select the catalyzer of various storng-acid cation exchange resins for use as the amphene hydration, preferably select the macropore strong acid cation exchange resin for use, resin dispatches from the factory and is generally the sodium type, uses conventional acid treatment solution before using and changes over Hydrogen, as be that Hydrogen then can directly use when dispatching from the factory.
Two, continuous separation loop reactor
The continuous recirculation reactor of amphene hydration reaction as shown in drawings
1, well heater 2, thermowell 3, thermometer 4, bottle for material
5, return line 6, catalyzer 7, fixed bed reaction post 8, fractional column
9, prolong 10, thermometer 11, condenser
In fixed bed reaction post (7), add resin catalyst, industrial amphene, water and the solvent that adding prepares by a certain percentage in bottle for material (4), startup well heater (1), be heated to certain temperature, gaseous phase materials carries out appropriate separation through fractional column (8) when material seethes with excitement, be condensed into liquid at condenser (9) and (11), carry out returning bottle for material by return line after the hydration reaction through the fixed bed reaction post, circulating reaction like this, last amphene transformation efficiency can reach more than 95%, and the overall yield of isocamphol is higher than 85%.A small amount of by product is arranged in addition, and camphene hydrate and 3-baras camphor produce.
Three, solvent
Add appropriate solvent fast reaction speed greatly in the amphene hydration reaction, these solvents can be used acetone, butanone, dioxane, diacetone alcohol, mesityl oxide etc.
The present invention uses acetone, diacetone alcohol, mesityl oxide and composition thereof, the consumption of solvent is that the 0.5-5 of amphene weight doubly all can, be preferably between 0.65-1.5 times and (when using acetone, but generate mesityl oxide) because acetone condensation under resin catalysis is diacetone alcohol and partial dehydration as solvent.So solvent promptly becomes mixed solvent behind the reaction certain hour, this mixed solvent can use repeatedly, only needs suitably to replenish acetone when partial loss.
Embodiment one
In embodiment two described reactors, operate.In reaction column, add 7400 type macropore strong acid cation exchange resins (Shanghai Resin Factory's productions), 75 grams (dry weight) and in bottle for material, adds industrial amphene 150 grams, deionized water 100 gram acetone 150 grams, material seethes with excitement and begins to react when adding thermal material to 65 ℃.React after 100 hours, industrial amphene transformation efficiency is 82%.It is isocamphol 76.8%, camphene hydrate 19.7%, fenchol 3.6% that product is formed (disregarding water and solvent).React after 200 hours, industrial amphene transformation efficiency is 91%, and the isocamphol productive rate reaches 80%, and camphene hydrate is 8.8%.
Embodiment two
In embodiment two described reactors, operate.In reaction column, add dry hydrogen type macropore strong acid cation exchange resin (Chemical Plant of Nankai Univ.'s production) 75 grams, in bottle for material, add industrial amphene 150 grams, deionized water 100 grams, diacetone alcohol 70 grams, acetone 75 grams, material boiling beginning reaction when adding thermal material to 89 ℃.React after 50 hours, industrial amphene transformation efficiency reaches 95.2%, and the productive rate of isocamphol is 73%, and camphene hydrate is 16.9%; React after 80 hours, industrial amphene transformation efficiency reaches 98.1%, the isocamphol productive rate is 85.1%, and camphene hydrate is 8.8%.
Embodiment three
Repeat embodiment (two) operations, solvent changes dioxane 150 grams, all the other all same embodiment (two) into.React after 50 hours, industrial amphene transformation efficiency is 97.5%, and the productive rate of isocamphol is 85.4%, and camphene hydrate is 6.5%.
Claims (3)
1, a kind of method of amphene hydration synthetizing isoborneol is used the exchange resin catalyzed amphene hydration of macropore strong acid cation, it is characterized by catalytic hydration and is reflected at use solvent accelerated reaction in the continuous separation loop reactor, and this method comprises the steps:
(1) Preparation of Catalyst
Select for use macropore strong acid ion exchange resin to make catalyzer, make Hydrogen with common acid treatment method.
(2) amphene hydration reaction
With industrial amphene is raw material, adds resin catalyst and solvent and carry out the catalytic hydration reaction in continuous separation loop reactor.
2, according to the method described in the claim 1, the operation that it is characterized by described continuous separation loop reactor is to add catalyzer in reaction column (7), in bottle for material (4), add a certain proportion of industrial amphene and solvent, be heated to the material boiling with well heater (1), gas phase is separated through fractional column (8), is condensed into liquid and carries out hydration reaction in condenser, passes through return line, return bottle for material, so circulating reaction.
3, according to the method described in the claim 1, it is characterized by described solvent can be acetone, diacetone alcohol, mesityl oxide and their mixture, and solvent load can be 0.5-5 a times of amphene weight, especially can be 0.65-1.5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104209 CN1024464C (en) | 1990-06-05 | 1990-06-05 | Synthetic method of isoborneol by catalyzing camphenic water with resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90104209 CN1024464C (en) | 1990-06-05 | 1990-06-05 | Synthetic method of isoborneol by catalyzing camphenic water with resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1049842A true CN1049842A (en) | 1991-03-13 |
| CN1024464C CN1024464C (en) | 1994-05-11 |
Family
ID=4878446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90104209 Expired - Fee Related CN1024464C (en) | 1990-06-05 | 1990-06-05 | Synthetic method of isoborneol by catalyzing camphenic water with resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024464C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064662C (en) * | 1998-05-06 | 2001-04-18 | 中国科学院广州化学研究所 | Method of directly preparing terpene hydrate alcohol by terpene |
| CN101372453B (en) * | 2008-09-03 | 2011-05-11 | 华东理工大学 | Improved process for preparing isobornyl acetate |
| CN102746121A (en) * | 2011-04-20 | 2012-10-24 | 江苏天士力帝益药业有限公司 | Refining method of high purity borneol |
| CN101723807B (en) * | 2009-12-14 | 2012-10-24 | 上海应用技术学院 | Preparation method of borneol |
| RU2490248C2 (en) * | 2009-01-28 | 2013-08-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Method of obtaining exo-2-norborneol and its derivatives |
| CN104151142A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Preparation method of isoborneol |
-
1990
- 1990-06-05 CN CN 90104209 patent/CN1024464C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064662C (en) * | 1998-05-06 | 2001-04-18 | 中国科学院广州化学研究所 | Method of directly preparing terpene hydrate alcohol by terpene |
| CN101372453B (en) * | 2008-09-03 | 2011-05-11 | 华东理工大学 | Improved process for preparing isobornyl acetate |
| RU2490248C2 (en) * | 2009-01-28 | 2013-08-20 | Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран | Method of obtaining exo-2-norborneol and its derivatives |
| CN101723807B (en) * | 2009-12-14 | 2012-10-24 | 上海应用技术学院 | Preparation method of borneol |
| CN102746121A (en) * | 2011-04-20 | 2012-10-24 | 江苏天士力帝益药业有限公司 | Refining method of high purity borneol |
| CN102746121B (en) * | 2011-04-20 | 2015-03-25 | 江苏天士力帝益药业有限公司 | Refining method of high purity borneol |
| CN104151142A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Preparation method of isoborneol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024464C (en) | 1994-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW499420B (en) | Catalytic processes for the preparation of acetic esters | |
| CN103896740A (en) | Method for producing methyl phenol | |
| CN111875479B (en) | Application of acidic ionic liquid in high-selectivity synthesis of borneol | |
| CN111187148B (en) | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one | |
| CN103420792A (en) | Combined production method of isopropanol and methyl isobutyl ketone | |
| CN102000559A (en) | Method for preparing dimethoxymethane by adopting supported niobium oxide catalyst | |
| US4359587A (en) | Method for preparing carbonyl compounds | |
| CN1024464C (en) | Synthetic method of isoborneol by catalyzing camphenic water with resin | |
| CN101759530B (en) | A kind of preparation method of dihydroxy-benzene | |
| CN100553779C (en) | A kind of unsaturated aldehyde hydrogen transfer reduction prepares the recovery method of pure Al catalysts in the unsaturated alcohol reaction | |
| CN103130768A (en) | Preparation method of compound with 1,3-dioxane structure | |
| CN111514925B (en) | Catalyst for co-production of methyl acetate and acetone from dimethyl ether, preparation method and application thereof | |
| CN110563692A (en) | Method for preparing galaxolide musk by using superfine aluminum trichloride as catalyst | |
| CN111875493B (en) | Method for synthesizing borneol by using imidazole acidic ionic liquid | |
| CN103420786B (en) | The method of coproducing methyl isobutyl ketone and methyl isobutyl carbinol | |
| CN110327971B (en) | Preparation method and application of acidic ionic liquid catalyst | |
| JPS63255242A (en) | Production of asymmetric aliphatic ketone | |
| CN1681751A (en) | Method for extending catalyst life in processes for preparing vinyl aromatic hydrocarbons | |
| CN111039754A (en) | Method for producing ethylene glycol from formaldehyde | |
| CN114539033B (en) | Method for simultaneously producing p-tert-butylphenol and m-tert-butylphenol | |
| CN112851496A (en) | Preparation method of p-toluic acid | |
| CN114478606A (en) | Synthetic method of tributyl borate | |
| CN107602516B (en) | Method for synthesizing delta-cyclopentanolide under catalysis of amino acid ionic liquid | |
| CN1013439B (en) | Preparation of camphor by resin catalized direct hydration of camphene | |
| CN115850035B (en) | Spice synthesized from 1, 8-terpene diol and process thereof |
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 | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |