ES2599352T3 - Método para la preparación de ácido betulínico - Google Patents
Método para la preparación de ácido betulínico Download PDFInfo
- Publication number
- ES2599352T3 ES2599352T3 ES12832504.0T ES12832504T ES2599352T3 ES 2599352 T3 ES2599352 T3 ES 2599352T3 ES 12832504 T ES12832504 T ES 12832504T ES 2599352 T3 ES2599352 T3 ES 2599352T3
- Authority
- ES
- Spain
- Prior art keywords
- betulinic acid
- betulin
- preparation
- aldehyde
- toluene
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title abstract 4
- QGJZLNKBHJESQX-UHFFFAOYSA-N 3-Epi-Betulin-Saeure Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C(=C)C)C5C4CCC3C21C QGJZLNKBHJESQX-UHFFFAOYSA-N 0.000 title abstract 3
- CLOUCVRNYSHRCF-UHFFFAOYSA-N 3beta-Hydroxy-20(29)-Lupen-3,27-oic acid Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C(O)=O)CCC5(C)CCC(C(=C)C)C5C4CCC3C21C CLOUCVRNYSHRCF-UHFFFAOYSA-N 0.000 title abstract 3
- DIZWSDNSTNAYHK-XGWVBXMLSA-N Betulinic acid Natural products CC(=C)[C@@H]1C[C@H]([C@H]2CC[C@]3(C)[C@H](CC[C@@H]4[C@@]5(C)CC[C@H](O)C(C)(C)[C@@H]5CC[C@@]34C)[C@@H]12)C(=O)O DIZWSDNSTNAYHK-XGWVBXMLSA-N 0.000 title abstract 3
- QGJZLNKBHJESQX-FZFNOLFKSA-N betulinic acid Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C QGJZLNKBHJESQX-FZFNOLFKSA-N 0.000 title abstract 3
- PZXJOHSZQAEJFE-UHFFFAOYSA-N dihydrobetulinic acid Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C(O)=O)CCC(C(C)C)C5C4CCC3C21C PZXJOHSZQAEJFE-UHFFFAOYSA-N 0.000 title abstract 3
- MQYXUWHLBZFQQO-UHFFFAOYSA-N nepehinol Natural products C1CC(O)C(C)(C)C2CCC3(C)C4(C)CCC5(C)CCC(C(=C)C)C5C4CCC3C21C MQYXUWHLBZFQQO-UHFFFAOYSA-N 0.000 title abstract 3
- JYDNKGUBLIKNAM-UHFFFAOYSA-N Oxyallobutulin Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(CO)CCC(C(=C)C)C5C4CCC3C21C JYDNKGUBLIKNAM-UHFFFAOYSA-N 0.000 abstract description 5
- FVWJYYTZTCVBKE-ROUWMTJPSA-N betulin Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(CO)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FVWJYYTZTCVBKE-ROUWMTJPSA-N 0.000 abstract description 5
- MVIRREHRVZLANQ-UHFFFAOYSA-N betulin Natural products CC(=O)OC1CCC2(C)C(CCC3(C)C2CC=C4C5C(CCC5(CO)CCC34C)C(=C)C)C1(C)C MVIRREHRVZLANQ-UHFFFAOYSA-N 0.000 abstract description 5
- MHAVMNJPXLZEIG-UHFFFAOYSA-N betulinic aldehyde Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(C=O)CCC(C(=C)C)C5C4CCC3C21C MHAVMNJPXLZEIG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- FELCJAPFJOPHSD-ROUWMTJPSA-N Lup-20(29)-en-28-al, 3beta-hydroxy- Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C=O)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FELCJAPFJOPHSD-ROUWMTJPSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- AKUYURNRLXSOLV-AYKZKCBTSA-N Betulinaldehyde Natural products C[C@H]1CC[C@@]2(C)[C@H](CC[C@@]3(C)[C@@H]4CC[C@]5(CC[C@H]([C@H]5[C@@H]4CC[C@@H]23)C(=C)C)C=C)C1(C)C AKUYURNRLXSOLV-AYKZKCBTSA-N 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 6
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 6
- 101100189356 Mus musculus Papolb gene Proteins 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- MHAVMNJPXLZEIG-CNRMHUMKSA-N (1r,3as,5ar,5br,7ar,11ar,11br,13ar,13br)-5a,5b,8,8,11a-pentamethyl-9-oxo-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysene-3a-carbaldehyde Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C=O)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C MHAVMNJPXLZEIG-CNRMHUMKSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Un método para la preparación de ácido betulínico a partir de betulina, caracterizado porque el citado método comprende oxidar betulina a aldehído betulínico con un proceso de oxidación catalizado por un catalizador basado en rutenio (II) o rutenio (VII) en presencia de un oxidante, siendo el oxidante dioxígeno procedente de oxígeno atmosférico, y oxidar el aldehído betulínico a ácido betulínico.
Description
Tabla 1 Oxidación catalítica de betulina a aldehído betulínico de acuerdo con la presente invención (reacción I)
- Ejemplo
- Betulina (mg) Disolvente (ml) Catalizador (mg) Cocatalizador opcional (mg) Temp. (ºC) Presión (bares) Oxidante Tiempo (horas) Conversión (%) Aldehído betilínico (%) Aldehído betulónico (%) Otros (%)
- 1.1
- 220 Tolueno 40 ml RuCl2(PPh3)3 20 mg TEMPO 10 mg 105 1 Balón O2 27 17 15 — 2
- 1.2
- 510 Tolueno 50 ml RuCl2(PPh3)3 41 mg TEMPO 22 mg 100 4 Flujo de aire 20 ml/min 14 55 52 2 2
- 1.3
- 501 Tolueno 50 ml RuCl2(PPh3)3 40 mg TEMPO 20 mg 100 8 Flujo de aire 20 ml/min 14 54 50 2 2
- 1.4
- 503 Tolueno 50 ml RuCl2(PPh3)3 41 mg TEMPO 41 mg 100 8 Flujo de aire 20 ml/min 14 64 59 2 2
- 1.5
- 504 Tolueno 50 ml RuCl2(PPh3)3 81 mg TEMPO 40 mg 100 8 Flujo de aire 20 ml/min 14 74 69 3 2
- 1.6
- 1.500 Tolueno 90 ml RuCl2(PPh3)3 480 mg TEMPO 240 mg 100 8 Flujo de aire 20 ml/min 7 99 80 1 18
- 1.7
- 503 Tolueno 50 ml TPAP 39 mg — 110 1 Flujo de aire 50 ml/min 7 59 38 14 8
- 1.8
- 501 1,2- dicloroetano 50 ml TPAP 40 mg — 80 1 Flujo de aire 50 ml/min 7 43 37 2 4
- Ejemplo
- Betulina (mg) Disolvente (ml) Catalizador (mg) Cocatalizador opcional (mg) Temp. (ºC) Presión (bares) Oxidante Tiempo (horas) Conversión (%) Aldehído betilínico (%) Aldehído betulónico (%) Otros (%)
- 1.9
- 500 Tolueno 50 ml TPAP 40 mg — 110 1 Flujo de aire 50 ml/min 7 48 30 10 8
- 1.10
- 221 DCM 15 ml TPAP 18 mg — 22 1 Balón O2 3 90 60 25 5
- 3.10 *
- 221 DCM 15 ml TPAP 17 mg — 22 1 NMO 204 mg = 3 eq 2,5 >95 — 95 <1
(*) Reacción Ia
Claims (1)
-
imagen1 imagen2
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE1150818A SE537100C2 (sv) | 2011-09-12 | 2011-09-12 | Förfarande för derivatisering av en kemisk komponent i trä |
| SE1150818 | 2011-09-12 | ||
| PCT/IB2012/054632 WO2013038312A1 (en) | 2011-09-12 | 2012-09-07 | Method for preparation of betulinic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2599352T3 true ES2599352T3 (es) | 2017-02-01 |
Family
ID=47882687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES12832504.0T Active ES2599352T3 (es) | 2011-09-12 | 2012-09-07 | Método para la preparación de ácido betulínico |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2755990B8 (es) |
| ES (1) | ES2599352T3 (es) |
| PL (1) | PL2755990T3 (es) |
| SE (1) | SE537100C2 (es) |
| WO (1) | WO2013038312A1 (es) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2565773C1 (ru) * | 2014-10-20 | 2015-10-20 | Федеральное государственное бюджетное учреждение науки Институт органической химии Уфимского научного центра Российской академии наук (ИОХ УНЦ РАН) | Способ получения бетулиновой кислоты |
| WO2016113863A1 (ja) * | 2015-01-14 | 2016-07-21 | 株式会社 東芝 | 非水電解質電池及び電池パック |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2250481A1 (fr) * | 1998-11-02 | 2000-05-02 | Andre Pichette | Procede de preparation de derives du betulinol directement a partir de l'ecorce du bouleau blanc |
| US20030073858A1 (en) * | 2001-01-11 | 2003-04-17 | Krasutsky Pavel A. | Methods for manufacturing betulinic acid |
| CN101302244B (zh) * | 2008-06-06 | 2011-04-13 | 东北林业大学 | 一种桦木酸的生产方法 |
-
2011
- 2011-09-12 SE SE1150818A patent/SE537100C2/sv not_active IP Right Cessation
-
2012
- 2012-09-07 EP EP12832504.0A patent/EP2755990B8/en active Active
- 2012-09-07 PL PL12832504T patent/PL2755990T3/pl unknown
- 2012-09-07 ES ES12832504.0T patent/ES2599352T3/es active Active
- 2012-09-07 WO PCT/IB2012/054632 patent/WO2013038312A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP2755990A1 (en) | 2014-07-23 |
| EP2755990A4 (en) | 2015-03-25 |
| PL2755990T3 (pl) | 2017-01-31 |
| WO2013038312A1 (en) | 2013-03-21 |
| EP2755990B1 (en) | 2016-07-20 |
| EP2755990B8 (en) | 2016-12-21 |
| SE537100C2 (sv) | 2015-01-07 |
| SE1150818A1 (sv) | 2013-03-13 |
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