CN1013439B - Preparation of camphor by resin catalized direct hydration of camphene - Google Patents
Preparation of camphor by resin catalized direct hydration of campheneInfo
- Publication number
- CN1013439B CN1013439B CN 85104105 CN85104105A CN1013439B CN 1013439 B CN1013439 B CN 1013439B CN 85104105 CN85104105 CN 85104105 CN 85104105 A CN85104105 A CN 85104105A CN 1013439 B CN1013439 B CN 1013439B
- Authority
- CN
- China
- Prior art keywords
- camphor
- camphene
- amphene
- hydration
- resin
- 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.)
- Expired
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the preparation of camphor by the direct hydration of camphene catalyzed by resin, which belongs to a synthesis method of camphor. Macroporous styrene type strong acid cation exchange resin is used for catalyzing the direct hydration of camphene to obtain borneolum, and in the presence of copper as a catalyst, borneolum is heated and dehydrogenated to prepare camphor. The proportion of camphene to water to solvent as materials for preparing borneolum by the hydration of camphene is 1: 0.2 to 3: 1 to 7.5, reaction temperature is from 40 to 80 DEG C, and the space velocity of the materials is from 0.05 to 1.5/h. Byproducts are produced by the hydration reaction, one of the byproducts can be converted into the raw material camphene under the action of ZnCl2 or NaHSO4, and the produced camphene can be used for hydration to prepare borneolum.
Description
The invention belongs to composition method of camphor.
General artificial camphor is all made by amphene, adopts Ti Senkefa
(1)Synthetic route:
The shortcoming of this operational path is: 1. operational path is long, 2. expends industrial chemicals such as a large amount of Glacial acetic acid and caustic soda, 3. causes the environmental pollution of serious equipment corrosion.
Main points of the present invention are that macropore styrene type strong-acid cation-exchange resin camphene catalyzed by nanometer solid superacid direct hydration obtains isocamphol, and then the heating dehydrogenation makes camphor in the presence of the copper catalyst, and its reaction formula is:
During amphene direct hydration synthetizing isoborneol, material proportion is an amphene: water: solvent=1: 0.2～3: 1～7.5.Temperature of reaction is 40～80 ℃, and the material air speed is 0.05～1.5 o'clock
-1Adopt this law to shorten technical process, removed important industrial chemicals such as Glacial acetic acid and caustic soda from; Equipment corrosion and environmental pollution have been prevented.This law amphene transformation efficiency reaches 42.5%, and the content of isocamphol reaches 6.07% in the hydration reaction liquid.When resin catalysis amphene direct hydration obtains isocamphol, still have by product to produce, wherein a kind of by product is at ZnCl
2Or NaHSO
4It is material camphene more than 90% that effect can change into down content, can be used for the hydration synthetizing isoborneol after the recovery again, thereby has not only reduced raw material consumption and cost, and improved the quality of product camphor.
Example 1:
With DOO1-CC resin 125 grams, use 800ml1NH
2SO
4Drip washing is washed till neutrality with pure water again, puts into the 500ml there-necked flask.Take by weighing Virahol 44 gram again, amphene 20 grams, the trimethyl carbinol 66 grams are poured in the there-necked flask after miscible, are heated to 55 ℃, under agitation react 20 hours, and sampling analysis, isocamphol content are 4.77%, and the amphene transformation efficiency is 41%.
Example 2:
Measure DOO1-CC resin 690ml, the diameter 25mm that packs in the high 1600mm glass column, uses 1NH
2SO
4Drip washing uses pure water drip washing to neutral, standby again.
With amphene 360 grams, water 216 grams, sec-butyl alcohol 648 grams, Virahol 864 grams are miscible, pour in the constant temperature header tank that is communicated with resin column, be heated to 60 ℃, open the joint door of post lower end, the flow velocity that the mixed solution that makes header tank divides with 1～1.5ml/ is got effluent liquid analysis through resin column, isocamphol content is 5.9%, and the amphene transformation efficiency is 33%.
Example 3:
With the resin column in the example 2 and other same devices, the feed liquid proportioning is amphene 350 grams, water 490 grams, Virahol 630 grams, n-propyl alcohol 350 grams react by the method in the example 2, get reception liquid and analyze, isocamphol content is 6.1%, and the amphene transformation efficiency is 33%.
Example 4:
With isocamphol 500 grams, dimethylbenzene 133 grams add in the 1000ml there-necked flask, are warming up to 164 ℃, divide water outlet from water trap, add ventilation breather 5 grams then, in 160 ℃ of reactions 6 hours, heat up and steam dimethylbenzene, are cooled to 164 ℃ again, add NaHSO
40.5 gram, water 0.3 gram reacts half an hour again, adds the CaO5 gram then, load onto a meter lattice fractional column on there-necked flask, the distillation that heats up when column top temperature reaches 205 ℃, stops distillation, then there-necked flask is connected with sublimation chamber, heating sublimation can get smart camphor 193 grams, and purity is 99.4%.
Example 5:
Isocamphol 1500 grams, dimethylbenzene 605 grams are added in the 3000ml there-necked flask, under agitation reflux, and from water trap, moisture is gone out, be cooled to 168 ℃, add ventilation breather 15 grams, temperature rising reflux is 5 hours again, load onto fractional column then, steam dimethylbenzene, be cooled to 152 ℃ again, add 22 gram ZnCl
2With 4 gram water, react 2 hours, add again 15 gram CaO will and in liquid steam in another there-necked flask, load onto fractional column, steam the fractions before 205 ℃, is communicated with sublimation chamber then, distil, get smart camphor 893 and restrain.
Claims (3)
1, a kind of method by amphene system camphor, it is characterized in that with large hole cation exchanger resin being that the hydration of catalyst amphene makes isocamphol, the reaction mass proportioning is an amphene: water: solvent=1: (0.2-3): (1-7.5), solvent can be used n-propyl alcohol and the mixture of Virahol (1: 1.8) or the mixture of the Virahol and the trimethyl carbinol (1: 3.3), temperature of reaction is 20-80 ℃, when the material air speed is 0.05-1.5
-1, the isocamphol that makes is just obtained camphor after dehydrogenation.
2, by the described method of claim 1, it is characterized in that the used resin of catalysis is the macropore strong acid cation exchange resin by amphene system camphor.
3, by the described method by amphene system camphor of claim 1, a kind of by product that produces when it is characterized in that the amphene synthetizing isoborneol is converted into material camphene under zinc dichloride or sodium pyrosulfate effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104105 CN1013439B (en) | 1985-05-29 | 1985-05-29 | Preparation of camphor by resin catalized direct hydration of camphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104105 CN1013439B (en) | 1985-05-29 | 1985-05-29 | Preparation of camphor by resin catalized direct hydration of camphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104105A CN85104105A (en) | 1986-11-26 |
| CN1013439B true CN1013439B (en) | 1991-08-07 |
Family
ID=4793636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104105 Expired CN1013439B (en) | 1985-05-29 | 1985-05-29 | Preparation of camphor by resin catalized direct hydration of camphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1013439B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704705B (en) * | 2009-05-08 | 2012-12-26 | 兰福光 | Method for converting isobornyl isopropyl ether |
| CN101973851B (en) * | 2010-10-27 | 2013-04-10 | 上海华谊（集团）公司 | Method for synthesizing isoborneol by using hydration of camphene |
| CN102344343A (en) * | 2011-08-18 | 2012-02-08 | 福建青松股份有限公司 | Method for producing high-purity isoborneol |
| CN104151142A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Preparation method of isoborneol |
| CN105152883A (en) * | 2015-09-07 | 2015-12-16 | 广西梧州通轩林产化学有限公司 | Method for preparing camphor by using camphene as raw material |
| CN105130768B (en) * | 2015-09-07 | 2017-08-25 | 广西梧州通轩林产化学有限公司 | The method that camphor is prepared by raw material of amphene |
| CN110194717B (en) * | 2019-04-29 | 2022-03-04 | 宁夏万香源生物科技有限公司 | Method for producing camphorquinone by using by-product generated in camphor synthesis process as raw material |
-
1985
- 1985-05-29 CN CN 85104105 patent/CN1013439B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104105A (en) | 1986-11-26 |
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