CN103739435B - Method of turpentine heterogeneous preparation of camphene - Google Patents
Method of turpentine heterogeneous preparation of camphene Download PDFInfo
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- CN103739435B CN103739435B CN201310241520.7A CN201310241520A CN103739435B CN 103739435 B CN103739435 B CN 103739435B CN 201310241520 A CN201310241520 A CN 201310241520A CN 103739435 B CN103739435 B CN 103739435B
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- 238000000034 method Methods 0.000 title claims abstract description 16
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 title claims abstract description 5
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 241000779819 Syncarpia glomulifera Species 0.000 title abstract 6
- 239000001739 pinus spp. Substances 0.000 title abstract 6
- 229940036248 turpentine Drugs 0.000 title abstract 6
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 title abstract 3
- 229930006739 camphene Natural products 0.000 title abstract 3
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 6
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 6
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 2
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 2
- MLXXYNMLZFRZOH-UHFFFAOYSA-N Cl(=O)(=O)[O-].C(C)[NH+](CC)CC Chemical compound Cl(=O)(=O)[O-].C(C)[NH+](CC)CC MLXXYNMLZFRZOH-UHFFFAOYSA-N 0.000 claims description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 2
- 229930006722 beta-pinene Natural products 0.000 claims description 2
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 28
- 239000002608 ionic liquid Substances 0.000 description 17
- 230000009466 transformation Effects 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000006317 isomerization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 239000001293 FEMA 3089 Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- 239000004577 thatch Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LQFBACQDOOBRFT-UHFFFAOYSA-N acetic acid;thiocyanic acid Chemical compound SC#N.CC(O)=O LQFBACQDOOBRFT-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OEJNXTAZZBRGDN-UHFFFAOYSA-N toxaphene Chemical compound ClC1C(Cl)C2(Cl)C(CCl)(CCl)C(=C)C1(Cl)C2(Cl)Cl OEJNXTAZZBRGDN-UHFFFAOYSA-N 0.000 description 1
- 238000013316 zoning Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method of turpentine heterogeneous preparation of camphene. The method comprises the following steps: turpentine and catalyst are weighed according to a mol ratio n(turpentine):n(catalyst)=9:1-3, and turpentine and catalyst are added into a reaction vessel simultaneously for 4-8 hours of reaction at 110-140 DEG C. After reaction, the vessel is cooled to room temperature, and a catalyst phase and a product phase are layered, and the catalyst phase and the product phase are respectively recovered. The catalyst is not needed to be treated, and can be recycled directly. According to the process condition, the conversion rate of turpentine is more than 95%, and the selectivity of camphene is more than 60%.
Description
Technical field
The present invention relates to Forest Chemicals preparing technical field, a kind of turps isomery prepares the method for amphene specifically.
Background technology
Amphene is a kind of important organic synthesis raw material, can be used for the fine chemicals such as artificial camphor, spices, agricultural chemicals, thiocyanic acid acetic acid different thatch ester, the different thatch ester of acetic acid, toxaphene.Amphene is the white crystals thing with camphor smell, be present in widely in turps, pitch, Oleum lavandula angustifolia, lemon wet goods natural essential oil, but content is little, is difficult to adopt fractionating process out isolated from essential oil, generally take turps as raw material, isomery preparation under an acidic catalyst.Industrially adopt active earths and titanium to be that amphene is prepared in the isomerization of catalyst turps at present, but this technique is to there is productive rate in varying degrees low, long reaction time, catalyzer is expensive and be difficult to reclaim the shortcomings such as use more.Therefore, developing new class catalyzer is the key promoting that amphene is produced.Ag/NiY molecular sieve (isomerization reaction of Xu Xuetang etc., Ag/NiY molecular sieve catalytic α-pinene. Guangxi Chemical Industry, 2000,29 (4): 7-8), TiO
2/ SO
4 2-solid super-strong acid (Tan Zhixin etc., TiO
2/ SO
4 2-the α-pinene isomerization reaction of catalysis. chemistry of forest product and industry, 1994,14(2): 1-9), using natural clinoptilolite (Wang Yaming etc., the isomerization reaction of using natural clinoptilolite catalysis α-pinene. forest chemical engineering communication, 1997,3 (1): 30-32), rare-earth solid superacid SO
4 2-/ TiO
2-La
2o
3(Chen Huizong etc., rare-earth solid superacid SO
4 2-/ TiO
2-La
2o
3the α-pinene isomerization reaction of catalysis. Jiangxi Normal University's journal (natural science edition), 2001,25 (4): 305-309) etc. catalyzer, be all used to catalyzing turpentine oil isomerization reaction and prepare amphene.Although these solid acid catalysts overcome the some shortcomings of traditional catalyst, but still also exist that relative reactivity is low, the surface easily shortcoming such as the low and strength of acid skewness of carbon distribution, acid site density, thus limit their application.
Ionic liquid (Ionic liquids) has that steam forces down, thermostability is high, character controllable, solvability are good, can not make the advantages such as the designability of catalyst deactivation and structure, is used to many chemical reaction processes as the eco-friendly solvent of a class or catalyzer.The group at present some with catalytic active center is assembled in the structure of ionic liquid by chemical reaction, prepares the focus that functionalized ion liquid becomes research.This mode that active centre group is connected with ionic liquid by the mode of chemical bonding, can realize the separation of ionic liquid well, reclaim and recycle.Therefore, adopting acidic functionalized ionic liquid to replace the solid acid catalyst catalyzing turpentine oil isomery of exploitation at present to prepare amphene, will be the effective ways promoting that amphene is produced.
Summary of the invention
The shortcomings such as to prepare the relative catalyst activity existed in amphene low in order to solve prior art, and product selectivity is low, and aftertreatment is complicated, the present invention proposes a kind of Br nsted-Lewis acidic ion liquid is the method that catalyst turps isomery prepares amphene.The method technique is simple, and catalyst activity is high can be recycled, and the preparation for amphene provides an eco-friendly operational path.
Technical scheme of the present invention is:
The ratio of n (turps): n (catalyzer)=9:1 ~ 3, takes turps and catalyzer, adds reactor simultaneously in molar ratio, at temperature of reaction 110 ~ 140 DEG C, and reaction 4-8 hour.After reaction terminates, be cooled to room temperature, catalyzer phase and the layering of product phase, reclaim catalyzer phase and product phase respectively.Catalyzer without the need to process, direct reuse.
Described turps, its content consisting of α-pinene is 85 ~ 95%, and the content of beta-pinene is 5 ~ 10%, and specific rotation is 0.85 ~ 23.45.
Described catalyzer is Br nsted-Lewis acidic ion liquid (3-sulfonic acid) the propyl group triethyl ammonium chlorate of sulfur acid functionalization, has following structure: [HSO
3– (CH
2)
3– NEt
3] Cl-M, M=ZnCl
2, FeCl
3or CrCl
3one wherein.
The present invention compares existing amphene technology of preparing, and tool has the following advantages:
1, reaction conditions is gentle, easy and simple to handle.
2, reaction product phase and the not miscible and AUTOMATIC ZONING of Br nsted-Lewis acidic ionic liquid catalysts, make product recovery process more easily easy.
3, catalyst B r nsted-Lewis acidic ion liquid stable performance, acid without running off, can be recycled.
4, environmentally friendly technology route is belonged to.
specific implementation method
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
embodiment 1:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-ZnCl
2, at 140 DEG C stirring reaction 4h.After completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 97.00%, and the selectivity of amphene is 66.08%.
embodiment 2:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-ZnCl
2, at 140 DEG C stirring reaction 5h, after completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 98.21%, and the selectivity of amphene is 62.72%.
embodiment 3:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-ZnCl
2, at 140 DEG C stirring reaction 8h, after completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 98.86%, and the selectivity of amphene is 60.75%.
embodiment 4:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-ZnCl
2, at 130 DEG C stirring reaction 4h.After completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 95.70%, and the selectivity of amphene is 63.45%
embodiment 5:
Get 0.02mol turps in reaction flask, add 0.0044mol [HSO
3– (CH
2)
3– NEt
3] Cl-FeCl
3, at 140 DEG C stirring reaction 4h.After completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 96.00%, and the selectivity of amphene is 61.00%.
embodiment 6:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-FeCl
3, at 140 DEG C stirring reaction 5h, after completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 95.75%, and the selectivity of amphene is 63.42%.
embodiment 7:
Get 0.02mol turps in reaction flask, add 0.0022mol [HSO
3– (CH
2)
3– NEt
3] Cl-CrCl
3, at 140 DEG C stirring reaction 4h, after completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 95.21%, and the selectivity of amphene is 61.72%.
embodiment 8:
Get 0.02mol turps in reaction flask, add 0.0044mol [HSO
3– (CH
2)
3– NEt
3] Cl-CrCl
3, at 140 DEG C stirring reaction 4h, after completion of the reaction, be cooled to room temperature, gravity settling, product and ionic liquid layering, separate upper strata product, product used Na successively
2cO
3solution and saturated aqueous common salt washing sample to neutral, then use anhydrous MgSO
4drying, gas chromatographic analysis measures its composition.Gained turps transformation efficiency is 95.70%, and the selectivity of amphene is 60.45%.
embodiment 9-14:
Ionic liquid, with embodiment 1, is just changed into the ionic liquid reclaimed in embodiment 1 by experiment condition and step, carries out repeating reuse experiment for five times, and reuse the results are shown in Table 1.
the repetition reuse result of table 1 ionic liquid
| Reuse number of times | 1 | 2 | 3 | 4 | 5 |
| Transformation efficiency/% | 97.00 | 96.35 | 96.42 | 96.28 | 96.25 |
| Selectivity/% | 66.08 | 65.97 | 66.02 | 65.83 | 65.76 |
Claims (1)
1. a turps isomery prepares the method for amphene, it is characterized in that n (turps) in molar ratio: the ratio of n (catalyzer)=9:1 ~ 3, take turps and catalyzer, wherein the terebinthine content consisting of α-pinene is 85 ~ 95%, the content of beta-pinene is 5 ~ 10%, specific rotation is 0.85 ~ 23.45, catalyzer is Br nsted-Lewis acidic ion liquid (3-sulfonic acid) the propyl group triethyl ammonium chlorate containing sulfonic acid funtionalized, has following structure: [HSO
3– (CH
2)
3– NEt
3] Cl-M, M=ZnCl
2, FeCl
3or CrCl
3one wherein; Add reactor, at temperature of reaction 110 ~ 140 DEG C, reaction 4-8 hour, after reaction terminates, is cooled to room temperature, catalyzer phase and the layering of product phase, reclaims catalyzer phase and product phase respectively simultaneously, catalyzer without the need to processing, direct reuse.
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|---|---|---|---|
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Non-Patent Citations (2)
| Title |
|---|
| "使用优级松节油及湿钛催化剂直接异构制莰烯的探讨";蔡成辉等;《福建林业科技》;19911231;第18卷(第2期);28-30 * |
| "酸性离子液体催化合成乙酸龙脑酯";季开慧等;《林产化学与工业》;20080831;第28卷(第4期);34-38 * |
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