CN1560004A - Process for producing beta-pink caryophyllenol - Google Patents
Process for producing beta-pink caryophyllenol Download PDFInfo
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- CN1560004A CN1560004A CNA200410014199XA CN200410014199A CN1560004A CN 1560004 A CN1560004 A CN 1560004A CN A200410014199X A CNA200410014199X A CN A200410014199XA CN 200410014199 A CN200410014199 A CN 200410014199A CN 1560004 A CN1560004 A CN 1560004A
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- bed reactor
- caryophyllenol
- acid catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 229930192694 Caryophyllenol Natural products 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011973 solid acid Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 claims abstract description 4
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001953 recrystallisation Methods 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- 239000003039 volatile agent Substances 0.000 claims description 11
- 230000008030 elimination Effects 0.000 claims description 8
- 238000003379 elimination reaction Methods 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000005243 fluidization Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000011964 heteropoly acid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
- 238000001914 filtration Methods 0.000 abstract description 14
- 241000779819 Syncarpia glomulifera Species 0.000 abstract description 13
- 239000001739 pinus spp. Substances 0.000 abstract description 13
- 229940036248 turpentine Drugs 0.000 abstract description 13
- 239000012043 crude product Substances 0.000 abstract description 11
- 239000003814 drug Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000002778 food additive Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 24
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 12
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 235000004357 Mentha x piperita Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- 244000246386 Mentha pulegium Species 0.000 description 2
- 235000016257 Mentha pulegium Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000001050 hortel pimenta Nutrition 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000002808 molecular sieve 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
- 230000009466 transformation Effects 0.000 description 2
- FUQAYSQLAOJBBC-PAPYEOQZSA-N β-caryophyllene alcohol Chemical compound C1C[C@](C2)(C)CCC[C@]2(O)[C@H]2CC(C)(C)[C@@H]21 FUQAYSQLAOJBBC-PAPYEOQZSA-N 0.000 description 2
- CQUAYTJDLQBXCQ-NHYWBVRUSA-N (-)-isolongifolene Chemical compound C([C@@H](C1)C2(C)C)C[C@]31C2=CCCC3(C)C CQUAYTJDLQBXCQ-NHYWBVRUSA-N 0.000 description 1
- MIOPJNTWMNEORI-XVKPBYJWSA-N (R)-camphorsulfonic acid Chemical compound C1C[C@]2(CS(O)(=O)=O)C(=O)C[C@H]1C2(C)C MIOPJNTWMNEORI-XVKPBYJWSA-N 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 239000001242 FEMA 4410 Substances 0.000 description 1
- 240000007707 Mentha arvensis Species 0.000 description 1
- 235000018978 Mentha arvensis Nutrition 0.000 description 1
- 235000016278 Mentha canadensis Nutrition 0.000 description 1
- 241001479543 Mentha x piperita Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- FUQAYSQLAOJBBC-MYZSUADSSA-N beta-Caryophyllene alcohol Natural products O[C@@]12[C@H]3[C@@H](C(C)(C)C3)CC[C@@](C)(C1)CCC2 FUQAYSQLAOJBBC-MYZSUADSSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001771 mentha piperita Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is a method of producing beta-carypophyllene alcohol, adding water to soak solid acid catalyst for 1-2 hours, filtering out excessive water, blending turpentine heavy fraction (heavy turpentine, containing 5-98% beta-carypophyllene alcohol) 100 mass shares with the solid acid catalyst 11-21 mass shares to react for 0.5-6 hours, filtering out the catalyst, making reduced pressure distillation on the reacting mixture to collect 90-110 deg.C/5mmHg fore-fractions like longifolene, etc, and collecting 140-160 deg.C/5mmHg fraction, being the crude product of beta-carypophyllene alcohol. It uses solvent to recrystallize the crude product so as to obtain refined product of beta-carypophyllene alcohol. The conversion of beta-carypophyllene alcohol is up to 90%-98%, the reacting conditions are moderate, the product has high selectivity, it is easy to producing operation, has fewer side-reactions, and creates a good basis for the next step of separating and purifying. The above catalyst can be repeatedly used and without harmful trace components to the final product-food additive or drug.
Description
Technical field
The present invention relates to a kind of preparation technology of tricyclic sesquiterpene alcohol, specifically, relate to the production technique of β-caryophyllenol.
Background technology
β-caryophyllenol (β-caryophyllene alcohol.CAS 472-97-9) is natural to be present in the high boiling fraction of asia peppermint (Mentha arvensis) oil or green pepper peppermint (Mentha piperita) oil.It is used by U.S. FDA (21CFR121.1164) approval as foodstuff additive.In addition, because of it has stronger physiologically active, be expected to become that a kind of antiasthmatic effect is lasting, toxicity is low newly relievings asthma, cough suppressing medicine.Therefore, the preparation technology of β-caryophyllenol is subjected to extensive attention.Present preparation method is to be raw material with β-caryophyllene; under acid catalysis, carry out hydration reaction; as use sulfuric acid; chloracetic acid, tosic acid, macroporous absorption storng-acid cation exchange resin, molecular sieve etc. are made catalyzer and are reacted in different solvents; but all fail to obtain satisfied result (referring to Cao Yurong etc., " SCI " Vol.20, No.7; pp1086-1087,1999).Do in order to obtain optically active β-caryophyllenol with β-caryophyllene respectively with having optically active D-and L-camphorsulfonic acid in addition, perhaps from the residue of Isolongifolene, separate obtaining the higher β-caryophyllenol of purity.Above preparation method has insoluble defective: 1. catalyzer of Shi Yonging and solvent can cause to a certain degree pollution to the finished product and environment, and 2. the reaction product complexity is difficult to separate purification, and 3. its preparation condition is difficult to carry out suitability for industrialized production.Because must guarantee its sanitary index and the purity of regulation as foodstuff additive and medicament production.So, seek one can reach foodstuff additive and drug use requirement and preparation technology that be environmental friendliness and cleaning again most crucial.
Summary of the invention
The purpose of this invention is to provide and a kind ofly be divided into raw material, the method for the production high-purity beta-caryophyllenol of environmentally friendly, cleaning with the turps double distilled.
Technical scheme of the present invention is as follows:
Method one:
A kind of method of producing β-caryophyllenol, it is made up of the following step:
Step 1, solid acid catalyst was soaked 1-2 hour the elimination excessive water;
Step 2, with 100 parts of (quality, down with) turps last running (heavy turpentine wherein contains β-caryophyllene 5-98%) and 10-100 part solid acid catalyst at 5-100 ℃ of stirring reaction 0.5-6 hour, the elimination catalyzer;
Step 3, with the reaction mixture underpressure distillation, collect 90-110 ℃/5mmHg front-end volatiles longifolene after, collect 110-160 ℃/5mmHg cut, be the thick product of product β-caryophyllenol;
Step 4, with the thick product of β-caryophyllenol innoxious solvent recrystallization, elaboration β-caryophyllenol.
In the step 2 of aforesaid method, described solid catalyst can be macroporous absorption storng-acid cation exchange resin, solid heteropoly acid or SO
4 2-Promotes oxidn thing solid super-strong acid, preferably macroporous absorption storng-acid cation exchange resin.
In the step 4 of aforesaid method, the used solvent of recrystallization can be an alkane solvent, as normal heptane, sherwood oil, industrial naptha or ethanol etc.
Above-mentioned production method also can be implemented with fixed-bed reactor, and promptly method two adopts the following step:
Step 1, solid acid catalyst was soaked 1-2 hour, the elimination excessive water is packed solid acid catalyst into and is with in the fixed-bed reactor of heating jacket, and the temperature of control fixed-bed reactor is 10-100 ℃;
Step 2, turps last running is heated to the temperature of fixed-bed reactor, turps last running was constantly imported the fixed-bed reactor circulating reaction 0.5-6 hour with volume pump;
Step 3 and step 4 are with the step 3 and the step 4 of method one.
Above-mentioned production method also can be implemented with fluidized-bed reactor, and promptly method three adopts the following step:
Step 1, solid acid catalyst was soaked 1-2 hour, the elimination excessive water is packed solid acid catalyst into and is with in the fluidized-bed reactor of heating jacket, and the temperature of controlling flow fluidized bed reactor is 10-100 ℃;
Step 2, turps last running is heated to the temperature of fluidized-bed reactor, with topping-up pump with turps last running constantly from the bottom inlet flow fluidized bed reactor of fluidized-bed reactor, regulate input pressure, make beds form fluidization, reaction mass overflows from bed top, formation circulates, and reacts 0.5-6 hour
Step 3 and step 4 are with the step 3 and the step 4 of method one.
Above-mentioned production method also can adopt fixed-bed reactor continuous production mode to implement, and promptly method four adopts the following step:
Step 1, with the step 1 of method two,
Step 2, turps last running is heated to the temperature of fixed-bed reactor, is 100: 10～100 constantly to add fixed-bed reactor with turps last running and water by the ratio of amount of substance with volume pump, the volume of fixed-bed reactor should make reactant stop in fixed-bed reactor 0.5-6 hour
Step 3 and step 4 are with the step 3 and the step 4 of method one.
Preparation technology of the present invention uses turps last running (heavy turpentine, wherein contain β-caryophyllene 5%-98%) be raw material, selecting solid acid for use is catalyzer, pass through hydration process, reacted 0.5 ~ 6 hour down at 10～100 ℃, generate β-caryophyllenol, isolate unreacted 90～110 ℃/5mmHg front-end volatiles longifolene by underpressure distillation again, isolate 110～160 ℃/5mmHg cut again, be product β-caryophyllenol.Crude product is obtained β-caryophyllenol with normal heptane or other nontoxic solvent (as: sherwood oil, industrial naptha, ethanol etc.) recrystallization.Transformation efficiency is up to 90 %～98% of β-caryophyllenol.Preparation technology's catalyzer of the present invention uses solid acid, carry out fixed bed reaction or other heterogeneous reaction as an acidic catalysts such as macroporous absorption storng-acid cation exchange resin, zeolite, molecular sieve, heteropolyacid, super acids, make among the preparation technology reaction product and catalyst separating easy, technological process is simple.In the reaction product no acidic by product produce or acidic substance residual, need not to neutralize, operation such as washing.Preparation technology of the present invention can select batch reactor for use, and fixed-bed reactor and fluidized-bed reactor also can carry out serialization production, the reaction conditions gentleness, selectivity of product and transformation efficiency height are easy to production operation, side reaction is less, has created good basis for next step separates to purify.The catalyzer that production method of the present invention is selected for use can use repeatedly, and it can not given, and the finished product---foodstuff additive or medicine bring harmful microcomponent, meet hygienic requirements.The present invention uses the fractionating method of continuous rectification, fractionates out β-caryophyllenol, through recrystallization, directly obtains final qualified product.The raw material heavy turpentine that preparation technology of the present invention uses is a natural product, wide material sources, dimensions of market abundance.
Embodiment 1.
Get heavy turpentine (GC analyzes and contains β-caryophyllene 15%) 50g, macroporous absorption storng-acid cation exchange resin (D720 type, Tianjin Chemical Plant of Nankai Univ. produces, handle through the water logging bubble) 10g, in the 250ml there-necked flask, heated and stirred was reacted 4 hours down at 40 ℃, with the reaction mixture vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 140～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 7g, press 1/0.5～2.0 (w/w) heating for dissolving with normal heptane, heat filtering, place crystallization, after to be crystallized the separating out, filter needle-like white crystals 4g, with with the quadrat method recrystallization, get β-caryophyllenol needle crystal thing 4g after the drying, surveying m.p. is 94.1～94.7 ℃, [α]
20 λ=-1.08 (dehydrated alcohol, c=10), IR, it is consistent with literature value that MS measures the gained result.
Embodiment 2.
Get heavy turpentine (GC analyzes and contains β-caryophyllene 46%) 250g, in the 500ml there-necked flask, with agitator, well heater preheating, get macroporous absorption storng-acid cation exchange resin (D720 type, Tianjin Chemical Plant of Nankai Univ. produces, and handles through the water logging bubble) 200g, in the fixed-bed reactor of the strap clamp of packing into cover heating, with constant flow pump reaction mass is conveyed into the fixed-bed reactor top that catalyzer is housed, material preheating temperature and jacket temperature all are controlled at 80 ℃.Flow through time of bed of control reaction mixture is about 20 minutes, simultaneously will be from fixed-bed reactor effusive reaction mixture vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 108g, 50 ℃ of dissolvings, heat filtering is placed crystallization with the 120g sherwood oil.After to be crystallized the separating out, filter, recrystallization once gets needle-like white crystals thing 97g after filtration, the drying again, and surveying m.p. is 94.2～94.6 ℃.
Embodiment 3.
Get half refining heavy turpentine (GC analyzes and contains β-caryophyllene 25%) 700g, water 70g, in the 1000ml there-necked flask, heating under agitation is preheated to 60 ℃, get macroporous absorption storng-acid cation exchange resin (D720 type, Tianjin Chemical Plant of Nankai Univ. produces, and handles through the water logging bubble) 150g packs in the reactor of strap clamp cover heating, and reactor is heated to 60 ℃.Reaction mass is conveyed into circularly the fixed-bed reactor that catalyzer is housed with constant flow pump, react after 3 hours, with the reaction mixture vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 148g, use the 200g normal heptane 40 ℃ of dissolvings, heat filtering is placed crystallization.After to be crystallized the separating out, filter, recrystallization once gets needle-like white crystals thing 123g after filtration, the drying again, and surveying m.p. is 94.1～94.5 ℃.
Embodiment 4.
Get half refining heavy turpentine (GC analyzes and contains β-caryophyllene 42%) 1200g, water 20g, in the 3000ml there-necked flask, stirring heating constant temperature to 40 ℃ is got SO
4 2-Promotes oxidn thing solid super acid catalyst SO
4 2-/ ZrO
2(press document Arata K.Solid superacid.Advances in Catalysis, 1990,37:165; Davis B H, Keogh R A, Sarinivasan R, Sulfated zirconia as a hydrocarbonconversion catalyst.Catal Today, 1994,20:219 preparation.Handling through water logging bubble) 200g packs in the reactor of strap clamp cover heating, and reactor is heated to 40 ℃.Import reaction mass with constant flow pump, react after 3 hours, with the reaction mixture vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 428g, use the 500g normal heptane after 60 ℃ of dissolvings, heat filtering is placed crystallization.After to be crystallized the separating out, filter, recrystallization once gets needle-like white crystals thing 389g after filtration, the drying again, and measuring m.p. is 94.0～94.6 ℃.
Embodiment 5.
Get half refining heavy turpentine (GC analyzes and contains β-caryophyllene 70%) 2000g, in the 3000ml there-necked flask, stirring heating constant temperature to 80 ℃, (chemical reagent factory of Beijing Xinhua produces to get heteropolyacid catalyst 12 phospho-wolframic acids, handling through water logging bubble) 220g packs in the reactor of strap clamp cover heating, and reactor is heated to 80 ℃.Import reaction mass with constant flow pump, react after 3 hours, with the reaction mixture vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 1260g, use the 1500g industrial naptha after 50 ℃ of dissolvings, heat filtering is placed crystallization.After to be crystallized the separating out, filter, recrystallization once gets needle-like white crystals thing 1080g after filtration, the drying again, and surveying m.p. is 94.2～94.6 ℃.
Embodiment 6.
Get refining heavy turpentine (GC analyzes and contains β-caryophyllene 98%) 500g, in the 1000ml there-necked flask, under agitation be heated to 60 ℃, get macroporous absorption storng-acid cation exchange resin (CD-550 Hydrogen, Zhengguang Resin Co., Ltd. produces, and handles through the water logging bubble) 70g packs in the reactor of strap clamp cover heating.With topping-up pump reactant is imported from reactor bottom, regulated its transfer pressure and make beds form fluidization, regulate flow reaction mass is overflowed from bed top, formation circulates.Jacket temperature is controlled at 60 ℃, react after 1.5 hours,, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier the reaction product vacuum fractionation, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, β-caryophyllenol crude product 452g, with the 450g normal heptane after 70 ℃ of dissolvings, place under the heat filtering, room temperature, after waiting to separate out crystallization, filter, recrystallization once filters, dry product 426g again, surveys m.p.94.0～94.6 ℃.
Embodiment 7.
Get heavy turpentine (GC analyzes and contains β-caryophyllene 15%) 1000g, in the 2000ml there-necked flask, under agitation be heated to 100 ℃, get macroporous absorption storng-acid cation exchange resin (D720 type, Tianjin Chemical Plant of Nankai Univ. produces, handling through water logging bubble) 400g packs in the reactor of strap clamp cover heating, and jacket temperature is controlled at 100 ℃.With topping-up pump reaction mass is imported from reactor bottom, regulated its transfer pressure and make beds form fluidization, regulate flow reaction mass is overflowed from bed top, and to make the duration of contact of itself and beds be about 30 minutes.From the effusive liquid phase in bed top through vacuum fractionation, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, β-caryophyllenol crude product 120g, with the mother liquor of 200g recrystallization use in embodiment 6 after 50 ℃ of dissolvings, place under the heat filtering, room temperature, after waiting to separate out crystallization, filter, with 150g sherwood oil recrystallization once, filter, dry product 105g, survey m.p.94.1～94.6 ℃.
Embodiment 8.
Get heavy turpentine (GC analyzes and contains β-caryophyllene 7%) 1800g, in the 3000ml there-necked flask, heated constant temperature to 30 ℃ under agitation, get macroporous absorption storng-acid cation exchange resin (D720 type, Tianjin Chemical Plant of Nankai Univ. produces, handling through water logging bubble) 200g packs in the reactor of strap clamp cover heating, and reactor is heated to 30 ℃.With topping-up pump reactant is imported from reactor bottom, regulated its transfer pressure and make beds form fluidization, regulate flow reaction mass is overflowed from bed top, formation circulates.React after 6 hours,, fractionate out 90～110 ℃/5mmHg front-end volatiles earlier the reactant vacuum fractionation, tell 110～160 ℃/5mmHg of product cut β-caryophyllenol again, get β-caryophyllenol crude product 98g, use the 250g normal heptane after 60 ℃ of dissolvings, heat filtering is placed crystallization.After to be crystallized the separating out, filter, again recrystallization once, filter, after the drying needle-like white crystals thing 82g, survey m.p.94.2～94.8 ℃.
Claims (7)
1. method of producing β-caryophyllenol is characterized in that it is made up of the following step:
Step 1, solid acid catalyst was soaked 1-2 hour, the elimination excessive water,
Step 2, with the turps last running of 100 parts of quality and 11-21 part quality solid acid catalyst at 10-100 ℃ of stirring reaction 0.5-6 hour, the elimination catalyzer,
Step 3, with the reaction mixture underpressure distillation, collect material such as 90-110 ℃/5mmHg front-end volatiles longifolene after, regather 140-160 ℃/5mmHg cut, be the thick product of product β-caryophyllenol,
Step 4, with the thick product solvent recrystallization of β-caryophyllenol, elaboration β-caryophyllenol.
2. method according to claim 1 is characterized in that: in the step 2, described solid acid catalyst is macroporous absorption storng-acid cation exchange resin, heteropolyacid or SO
4 2-Promotes oxidn thing solid super-strong acid.
3. method according to claim 2 is characterized in that: solid acid catalyst is the macroporous absorption storng-acid cation exchange resin.
4. method according to claim 1 is characterized in that: in the step 4, the used solvent of recrystallization is alkane solvent or ethanol.
5. method of producing β-caryophyllenol is characterized in that it is made up of the following step:
Step 1, solid acid catalyst was soaked 1-2 hour, the elimination excessive water is packed solid acid catalyst into and is with in the fixed-bed reactor of heating jacket, and the temperature of control fixed-bed reactor is 10-100 ℃;
Step 2, turps last running is heated to the temperature of fixed-bed reactor, fixed-bed reactor reaction 0.5-6 hour is constantly imported in turps last running with volume pump;
Step 3 and step 4 are with the step 3 and the step 4 of claim 1.
6. method of producing β-caryophyllenol is characterized in that it is made up of the following step:
Step 1, solid acid catalyst was soaked 1-2 hour, the elimination excessive water is packed solid acid catalyst into and is with in the fluidized-bed reactor of heating jacket, and the temperature of controlling flow fluidized bed reactor is 10-100 ℃,
Step 2, turps last running is heated to the temperature of fluidized-bed reactor, with topping-up pump with turps last running constantly from the bottom inlet flow fluidized bed reactor of fluidized-bed reactor, regulate input pressure, make beds form fluidization, reaction mass overflows from bed top, formation circulates, and reacts 0.5-6 hour
Step 3 and step 4 are with the step 3 and the step 4 of claim 1.
7. method of producing β-caryophyllenol is characterized in that it is made up of the following step:
Step 1, with the step 1 of claim 5,
Step 2, turps last running is heated to the temperature of fixed-bed reactor, is 1 with turps double distilled and water by the ratio of amount of substance with volume pump: 1.2-3.0 constantly adds fixed-bed reactor, the volume of fixed-bed reactor stopped reactant 0.5-6 hour in fixed-bed reactor
Step 3 and step 4 are with the step 3 and the step 4 of claim 1.
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| CN110615737A (en) * | 2019-10-15 | 2019-12-27 | 重庆医药高等专科学校 | Beta-caryophyllenol derivative and preparation method and preparation device thereof |
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| CN1049210C (en) * | 1993-05-26 | 2000-02-09 | 中国林业科学研究院林产化学工业研究所 | Method for prepn. of Beta-caryophyllenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110615737A (en) * | 2019-10-15 | 2019-12-27 | 重庆医药高等专科学校 | Beta-caryophyllenol derivative and preparation method and preparation device thereof |
| CN111892500A (en) * | 2019-10-15 | 2020-11-06 | 重庆医药高等专科学校 | Preparation method and preparation device of beta-caryophyllenol derivative |
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