CN1049210C - 制备β-石竹烯醇的方法 - Google Patents
制备β-石竹烯醇的方法 Download PDFInfo
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- CN1049210C CN1049210C CN93111516A CN93111516A CN1049210C CN 1049210 C CN1049210 C CN 1049210C CN 93111516 A CN93111516 A CN 93111516A CN 93111516 A CN93111516 A CN 93111516A CN 1049210 C CN1049210 C CN 1049210C
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- 238000000034 method Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229930004725 sesquiterpene Natural products 0.000 claims abstract description 6
- 150000004354 sesquiterpene derivatives Chemical class 0.000 claims abstract description 6
- CQUAYTJDLQBXCQ-NHYWBVRUSA-N (-)-isolongifolene Chemical compound C([C@@H](C1)C2(C)C)C[C@]31C2=CCCC3(C)C CQUAYTJDLQBXCQ-NHYWBVRUSA-N 0.000 claims abstract description 5
- 235000011609 Pinus massoniana Nutrition 0.000 claims abstract description 5
- 241000018650 Pinus massoniana Species 0.000 claims abstract description 5
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- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019687 Lamb Nutrition 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 abstract 1
- 235000011613 Pinus brutia Nutrition 0.000 abstract 1
- 241000018646 Pinus brutia Species 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 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 16
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 8
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- HICYDYJTCDBHMZ-UHFFFAOYSA-N (+)-alpha-Longipinen Natural products C12C3C(C)=CCC1C3(C)CCCC2(C)C HICYDYJTCDBHMZ-UHFFFAOYSA-N 0.000 description 1
- HICYDYJTCDBHMZ-COMQUAJESA-N (+)-alpha-longipinene Chemical compound CC1(C)CCC[C@]2(C)[C@]3([H])[C@@]1([H])[C@@]2([H])CC=C3C HICYDYJTCDBHMZ-COMQUAJESA-N 0.000 description 1
- WCEIQUQVIOGRBF-ZYBGGCANSA-N (3ar,4r,8as)-1,5,5,8a-tetramethyldecahydro-1,2,4-(methanetriyl)azulene Chemical compound CC1(C)CCC[C@]2(C)C3(C)C4[C@H]1[C@H]2CC43 WCEIQUQVIOGRBF-ZYBGGCANSA-N 0.000 description 1
- 229930192694 Caryophyllenol Natural products 0.000 description 1
- 235000008495 Chrysanthemum leucanthemum Nutrition 0.000 description 1
- 244000192528 Chrysanthemum parthenium Species 0.000 description 1
- 235000000604 Chrysanthemum parthenium Nutrition 0.000 description 1
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 description 1
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 241001643642 Viticis Species 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010634 clove oil Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000008384 feverfew Nutrition 0.000 description 1
- 238000001911 insensitive nuclei enhancement by polarisation transfer Methods 0.000 description 1
- WCEIQUQVIOGRBF-UHFFFAOYSA-N longicyclene Natural products CC1(C)CCCC2(C)C3(C)C4C1C2CC43 WCEIQUQVIOGRBF-UHFFFAOYSA-N 0.000 description 1
- 229930004728 longipinene Natural products 0.000 description 1
- 238000000968 medical method and process Methods 0.000 description 1
- 239000001683 mentha spicata herb oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 235000019721 spearmint oil Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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Abstract
本发明公开了一种制备β-石竹烯醇的方法，它是利用中国马尾松松脂组分中110-120℃/6mmHg倍半萜烯馏份。用硫酸作催化剂进行异构反应，在制备异长叶烯的过程中，将釜底中的残渣用来进行分离、重结晶、精制等步骤来制取β-石竹烯醇。
Description
本发明涉及制备β-石竹烯醇的一种方法。
β-石竹烯醇是一种重要的三环倍半萜醇，可广泛应用于香料及医药制造工业。目前，制备β-石竹烯醇的方法是由β-石竹烯经水合反应来制备的。日本专利JP[01,268,657]就是利用薄荷油中的β-石竹烯来制备β-石竹烯醇的。另外，可从丁子香(Cloveoil)、苦配巴油(Copalhaoil)、熏衣草油(Larcnderoil)及中国菊科植物的艾叶油、牡荆油中进行分离获取少量的β-石竹烯来制备β-石竹烯醇。
中国马尾松松脂倍半萜烯组分中含有长叶烯、β-石竹烯、长叶环烯、长叶蒎烯，其中β-石竹烯含量13～17％，但因其化学结构同其它组分相近，沸点相差在2℃以内，所以，工业上进行分离来得到β-石竹烯，是很难实施这一操作的。
本发明的目的是为了提供一种利用中国马尾松松脂倍半萜组份中所含的β-石竹烯，不需要通过分离来制备β-石竹烯醇的方法。
本发明是这样实现的，以中国马尾松松脂组分中110～120℃/6mmHg倍半萜烯馏份，用硫酸作催化剂进行异构反应来制备异长叶烯，在精馏异长叶烯操作完成后，釜底中存有15％以上的残渣，通常此残渣被作为工业废渣丢弃或处理烧掉。本发明是将此残渣进行分离，重结晶、精制等步骤制得β-石竹烯醇，这已通过结构及反应历程的研究，认定是组分中的β-石竹烯，在催化剂硫酸存在下，经重排、跨环、水合反应而生成。用该方法制备β-石竹烯醇，具有工艺简单、产品质量高等优点，是制备β-石竹烯醇新方法。
实施例一
分离
称取精馏异长叶烯釜底中残渣1245g装入2000ml三口瓶中，加热至160℃～220℃，在10mmHg下真空蒸馏，收集150℃～200℃馏份，将得到的蒸馏液放置，待结晶析出后，在布氏漏斗中抽滤得879.3g β-石竹烯醇结晶物m.p＝62.8℃(温度计未校正)。
实施例二
重结晶
称取例一中β-石竹烯醇结晶物500g加入500ml正己烷，在水浴50℃条件下溶解，热保温过滤，滤液放置结晶，待结晶析出后过滤得440g β-石竹烯醇m.p＝94.2～94.8℃(温度计未校正)光谱测定数据；
(1)MS：(m/e)M+222，207，204，189，179，108，81(基峰)。
(2)IR：(Cm-1)3400(S，OH)，2950(S，CH2)，1160(m，CH2)，1330，1100，1059，1019(S，C_OH)。
(3)｀HNMR：(δppm)0.882(3H，s，CH3)，1.005(6H，S，CH3×2)，1.457～1.888(14H，m，CH2×7)，1.479(IH，m，OH，加重水后消失)，2.080～2.193(2H，m，CH×2)。
(4)13CNMR：(极化转移方法INEPT，δppm)70.9(C)，48.8(CH2)，44.9(CH)，39.8(CH)，38.7(CH2)，37.5(CH2)，36.8(CH2)，34.9(C)，34.8(C)，34.6(CH2)，33.3(CH3)，30.5(CH3)，22.0(CH2)，20.9(CH2)。
(5)13CNMR：(偏共振方法OFR，δppm)，70.9(S)，48.8(t)，44.9(d)，39.8(d)，38.7(t)，37.5(t)，36.8(t)，34.9(s)，34.8(s)，34.6(t)，33.3(q)，30.5(q)，22.0(t)，20.9(t)，20.9(q)。
(6)13CNMR：(反转门去偶定量方法IGD、δppm)，70.9(lc)，48.8(lc)，44.9(lc)，39.8(lc)，38.7(lc)，37.5(lc)，36.8(lc)34.9(lc)，34.8(lc)，34.6(lc)，33.3(lc)30.5(lc)，22.0(lc)，20.9(2c).
实施例三
精制
称取重结晶后得到的β-石竹烯醇200g，加入装有回流装置的容器中，加入400ml无水乙醇，再加入10g针剂木质活性炭，在水浴上加热回流10分钟，然后热保温过滤，将滤液放置结晶，当结晶析出后过滤，真空干燥，得180gβ-石竹烯醇测定旋光值[α]20＝-7.5℃(C＝10乙醇)。
Claims (1)
1.一种制备β-石竹烯醇的方法，包括使用以中国马尾松松脂组分中110℃～120℃/6mmHg倍半萜烯馏份为原料，用硫酸作催化剂进行异构反应，待反应完成后，经水洗、精馏，先得到异长叶烯，而后在160℃～220℃/10mmHg下真空蒸馏，取150℃～200℃馏份，该馏份结晶析出物为β-石竹烯醇粗制品，将此粗制品用正己烷在水浴50℃条件下溶解，重结晶提纯，最后用无水乙醇溶解后加入针剂木质活性炭，在水浴上加热回流10分钟，然后保温过滤，将滤液放置结晶，当结晶析出后过滤，真空干燥得到精制的β-石竹烯醇。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111516A CN1049210C (zh) | 1993-05-26 | 1993-05-26 | 制备β-石竹烯醇的方法 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93111516A CN1049210C (zh) | 1993-05-26 | 1993-05-26 | 制备β-石竹烯醇的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1095704A CN1095704A (zh) | 1994-11-30 |
| CN1049210C true CN1049210C (zh) | 2000-02-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93111516A Expired - Fee Related CN1049210C (zh) | 1993-05-26 | 1993-05-26 | 制备β-石竹烯醇的方法 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314645C (zh) * | 2004-03-02 | 2007-05-09 | 南京大学 | 一种生产β－石竹烯醇的方法 |
| CN106083517A (zh) * | 2016-06-28 | 2016-11-09 | 广西梧松林化集团有限公司 | 高纯度长叶烯的制备方法 |
| CN110923254B (zh) * | 2019-12-09 | 2021-04-16 | 中国林业科学研究院亚热带林业研究所 | 马尾松长叶烯合成酶基因和产品及用途 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229599A (en) * | 1978-09-29 | 1980-10-21 | International Flavors & Fragrances Inc. | Preparation of a caryophyllene alcohol mixture |
| US4267076A (en) * | 1978-09-29 | 1981-05-12 | International Flavors & Fragrances Inc. | Preparation of a caryophyllene alcohol mixture in perfume compositions |
-
1993
- 1993-05-26 CN CN93111516A patent/CN1049210C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229599A (en) * | 1978-09-29 | 1980-10-21 | International Flavors & Fragrances Inc. | Preparation of a caryophyllene alcohol mixture |
| US4267076A (en) * | 1978-09-29 | 1981-05-12 | International Flavors & Fragrances Inc. | Preparation of a caryophyllene alcohol mixture in perfume compositions |
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| Publication number | Publication date |
|---|---|
| CN1095704A (zh) | 1994-11-30 |
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