MD4209C1 - Способ получения склареолоксида - Google Patents
Способ получения склареолоксида Download PDFInfo
- Publication number
- MD4209C1 MD4209C1 MDA20120036A MD20120036A MD4209C1 MD 4209 C1 MD4209 C1 MD 4209C1 MD A20120036 A MDA20120036 A MD A20120036A MD 20120036 A MD20120036 A MD 20120036A MD 4209 C1 MD4209 C1 MD 4209C1
- Authority
- MD
- Moldova
- Prior art keywords
- sclareol
- sclareoloxide
- acetone
- extraction
- product
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- LAEIZWJAQRGPDA-CIRFHOKZSA-N (4ar,6as,10as,10br)-3,4a,7,7,10a-pentamethyl-1,5,6,6a,8,9,10,10b-octahydrobenzo[f]chromene Chemical compound CC1(C)CCC[C@]2(C)[C@H]3CC=C(C)O[C@]3(C)CC[C@H]21 LAEIZWJAQRGPDA-CIRFHOKZSA-N 0.000 title claims abstract description 15
- XVULBTBTFGYVRC-HHUCQEJWSA-N sclareol Chemical compound CC1(C)CCC[C@]2(C)[C@@H](CC[C@](O)(C)C=C)[C@](C)(O)CC[C@H]21 XVULBTBTFGYVRC-HHUCQEJWSA-N 0.000 claims abstract description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- XVULBTBTFGYVRC-UHFFFAOYSA-N Episclareol Natural products CC1(C)CCCC2(C)C(CCC(O)(C)C=C)C(C)(O)CCC21 XVULBTBTFGYVRC-UHFFFAOYSA-N 0.000 claims abstract description 14
- LAEIZWJAQRGPDA-UHFFFAOYSA-N Manoyloxid Natural products CC1(C)CCCC2(C)C3CC=C(C)OC3(C)CCC21 LAEIZWJAQRGPDA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006385 ozonation reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PNZVFASWDSMJER-UHFFFAOYSA-N acetic acid;lead Chemical compound [Pb].CC(O)=O PNZVFASWDSMJER-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 244000182022 Salvia sclarea Species 0.000 abstract description 3
- 235000002911 Salvia sclarea Nutrition 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000003205 fragrance Substances 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 2
- 239000000341 volatile oil Substances 0.000 abstract description 2
- 238000005899 aromatization reaction Methods 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 150000004141 diterpene derivatives Chemical class 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000005949 ozonolysis reaction Methods 0.000 abstract 1
- 238000011403 purification operation Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000002020 sage Nutrition 0.000 abstract 1
- 239000011877 solvent mixture Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 peroxide compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Изобретение относится к способу получения склареолоксида (1) - соединение используемое в качестве ингредиента различных ароматических композиций, а также интермедиата в синтезе других ценных одорантов терпеновой структуры.В качестве исходного сырья используется склареол (2) - легкодоступный дитерпеноид лабдановой структуры из отходов производства эфирного масла шалфея (Salvia sclarea L.).Способ включает только одну операцию окислительного расщепления боковой цепи склареола при обработке озоном в присутствии каталитического со-окислителя - диацетата свинца, в гомогенной смеси ацетон-вода при температуре -20°С...+15°С. Выделение продукта реакции включает отгонку ацетона, экстракцию полученной суспензии подходящим органическим растворителем и его последующее удаление отгонкой при пониженном давлении. Продукты превращения катализатора могут быть легко выделены для последующего рециклирования из оставшейся после экстракции водной фазы.Полученный таким образом сырой склареолоксид имеет чистоту не менее 97% и может быть использован без дополнительной очистки.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MDA20120036A MD4209C1 (ru) | 2012-03-30 | 2012-03-30 | Способ получения склареолоксида |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MDA20120036A MD4209C1 (ru) | 2012-03-30 | 2012-03-30 | Способ получения склареолоксида |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MD4209B1 MD4209B1 (en) | 2013-03-31 |
| MD4209C1 true MD4209C1 (ru) | 2013-10-31 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MDA20120036A MD4209C1 (ru) | 2012-03-30 | 2012-03-30 | Способ получения склареолоксида |
Country Status (1)
| Country | Link |
|---|---|
| MD (1) | MD4209C1 (ru) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB589650A (ru) * | 1947-12-29 | 1947-06-26 | ||
| US5247100A (en) * | 1989-12-21 | 1993-09-21 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of sclareolide |
| MD217C2 (ru) * | 1992-07-15 | 1995-08-31 | Институт Химии Академии Наук Молдовы | Композиция для ароматизации курительного табака |
| EP0822191A1 (en) * | 1996-08-02 | 1998-02-04 | Quest International B.V. | Preparation of intermediates for norlabdane oxide |
| US5821375A (en) * | 1996-08-02 | 1998-10-13 | Quest International B.V. | Preparation of norlabdane oxide |
| US6380404B1 (en) * | 1999-04-16 | 2002-04-30 | Quest International B.V. | Preparation of norlabdane oxide |
| MD2253C2 (ru) * | 2003-02-03 | 2004-03-31 | "Тутун-Стс" С.А. | Табачный ароматизирующий продукт для курения, способ его получения, ароматическая композиция (варианты), способ получения композиций для табачных изделий (варианты) |
| MD2349C2 (ru) * | 2003-02-03 | 2004-07-31 | "Тутун-Стс" С.А. | Композиция для ароматизации табачной смеси и способ получения ароматизированной табачной смеси |
| US7335796B2 (en) * | 2005-04-05 | 2008-02-26 | Symrise Gmbh & Co., Kg | Process for the preparation of ketones by ozonolysis |
| US20080319232A1 (en) * | 2005-09-28 | 2008-12-25 | Symrise Gmbh & Co. Kg | Synthesis of Aldehydes by Ozonolysis of Secondary Allyl |
-
2012
- 2012-03-30 MD MDA20120036A patent/MD4209C1/ru not_active IP Right Cessation
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB589650A (ru) * | 1947-12-29 | 1947-06-26 | ||
| US5247100A (en) * | 1989-12-21 | 1993-09-21 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of sclareolide |
| MD217C2 (ru) * | 1992-07-15 | 1995-08-31 | Институт Химии Академии Наук Молдовы | Композиция для ароматизации курительного табака |
| EP0822191A1 (en) * | 1996-08-02 | 1998-02-04 | Quest International B.V. | Preparation of intermediates for norlabdane oxide |
| US5821375A (en) * | 1996-08-02 | 1998-10-13 | Quest International B.V. | Preparation of norlabdane oxide |
| US6380404B1 (en) * | 1999-04-16 | 2002-04-30 | Quest International B.V. | Preparation of norlabdane oxide |
| MD2253C2 (ru) * | 2003-02-03 | 2004-03-31 | "Тутун-Стс" С.А. | Табачный ароматизирующий продукт для курения, способ его получения, ароматическая композиция (варианты), способ получения композиций для табачных изделий (варианты) |
| MD2349C2 (ru) * | 2003-02-03 | 2004-07-31 | "Тутун-Стс" С.А. | Композиция для ароматизации табачной смеси и способ получения ароматизированной табачной смеси |
| US7335796B2 (en) * | 2005-04-05 | 2008-02-26 | Symrise Gmbh & Co., Kg | Process for the preparation of ketones by ozonolysis |
| US20080319232A1 (en) * | 2005-09-28 | 2008-12-25 | Symrise Gmbh & Co. Kg | Synthesis of Aldehydes by Ozonolysis of Secondary Allyl |
Non-Patent Citations (8)
| Title |
|---|
| Alvarez-Manzaneda E.J., Chahboun R., Cano M.J., Cabrera Torres E., Alvarez E., Alvarez-Manzaneda R., Haidoura A., Ramos Lopez J.M. O3/Pb(OAc)4: a new and efficient system for the oxidative cleavage of allyl alcohols. Tetrahedron Letters, 2006, 47, 6619-6622 * |
| Castro Juan M., Salido Sofia, Altarejos Joachin, Nogueras Manuel and Sanches Adolfo. 8a,13-Epoxy-14,15-dinorlabd-12-ene (Sclareol Oxide) [(+)-(4aR,6aS,10aS,10bR)-3,4a,7,7,10a-Pentamethyl-4a,5,6,6a,7,8,9,10,10a,10b-decahydro-1H-benzo[f]chromene]. Molbank 2003 M304, Published 8 March 2003. Regăsit în Internet la 2013.01.01, url: http://www.mdpi.org/molbank/molbank2003/m0304.htm vezi documentul integral * |
| Enrique & Chahboun, Rachid & Alvarez, Esteban & Fernández, Antonio & Alvarez-Manzaneda, Ramón & Haidour, Ali & Ramos, Jose Miguel & Akhaouzan, Ali. (Published online 2011-11-09). First enantiospecific synthesis of marine sesquiterpene quinol akaol A. Chemical communications (Cambridge, England), . PMID: 22073392; doi: 10.1039/c1cc14608d. Regăsit la 2013.01.01, url: http://www.biomedsearch.com/nih/First-enantiospecific-synthesis-marine-sesquiterpene/22073392.html sau http://www.ncbi.nlm.nih.gov/pubmed/22073392Alvarez-Manzaneda, * |
| Frija Luis M.T., Frade Raquel F.M. and Afonso Carlos F.M. Isolation, Chemical, and Biotransformation Routes of Labdane-type Diterpenes. Chem. Reviews. dx.doi.org/10.1021-crl 00258k/ Regăsit în Internet la 2013.01.01, url: http://www.scribd.com/doc/97013211/cr100258k * |
| Marjon G. Bolster, Ben J.M. Jansen and Aede de Groot. The synthesis of (-) Ambrox starting from labdanolic acid. Tetrahedron 57(2001), 5657-5662 vezi pag. 5660, coloniţa dreapta, metodica 3.1.5 * |
| Ruzicka L., Seidel C.F., Engel L.L. Zur kenntnis der diterpene. Oxydation des sclareols mit kaliumpermanganat. Helv.Chim.Acta., 1942, 621 * |
| Schiaffo C.E., Dussault P.H. Ozonolysis in Solvent/Water Mixtures: Direct Conversion of Alkenes to Aldehydes and Ketones. J. Org. Chem., 2008, 73, 4688-4690 * |
| Влад П.Ф., Колца М.Н. Синтез и применение душистых веществ из лабдановых дитерпеноидов, Кишинев, Штиинца, 1988, с. 182 vezi pag. 102 * |
Also Published As
| Publication number | Publication date |
|---|---|
| MD4209B1 (en) | 2013-03-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FG4A | Patent for invention issued | ||
| KA4A | Patent for invention lapsed due to non-payment of fees (with right of restoration) | ||
| MM4A | Patent for invention definitely lapsed due to non-payment of fees |