NO752191L - - Google Patents
Info
- Publication number
- NO752191L NO752191L NO752191A NO752191A NO752191L NO 752191 L NO752191 L NO 752191L NO 752191 A NO752191 A NO 752191A NO 752191 A NO752191 A NO 752191A NO 752191 L NO752191 L NO 752191L
- Authority
- NO
- Norway
- Prior art keywords
- stated
- procedure
- stand
- hydrogen atom
- carbon atoms
- Prior art date
Links
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims 1
- 150000008046 alkali metal hydrides Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D461/00—Heterocyclic compounds containing indolo [3,2,1-d,e] pyrido [3,2,1,j] [1,5]-naphthyridine ring systems, e.g. vincamine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Fremgangsmåte for fremstilling 2-hydroksya1kylde soksyvinkaminater.Process for the preparation of 2-hydroxyalkyl-cold soxyvin kaminates.
Description
Foreliggende oppfinnelse vedrorer en fremgangsmåte forThe present invention relates to a method for
fremstilling a<y>2 hydrosy-alkyldesoksyvinkaminater.preparation of a<y>2 hydroxy-alkyldeoxyvincaminates.
I patent nr. (patentansokning 75.0294) er det beskrevetIt is described in patent no. (patent application 75.0294).
estere av 16,17 dihydroappovinkaminsyre (eller desoksyvinkamin-esters of 16,17 dihydroappovincamine acid (or desoxyvincamine-
syre) tilsvarende den folgende formel:acid) corresponding to the following formula:
hvori R står for et mettet eller umettet alifatisk hydrokarbon med rett eller forgrenet kjede, inneholdende 2-6 karbonatomer og som kan bære 1 eller 2<1>substituenter valgt blant gruppen bestående av hydroksyl eller alkoksy med rett eller forgrenet kjede, inneholdende 1-6 karbonatomer, samt deres syreaddisjons- wherein R represents a saturated or unsaturated straight or branched aliphatic hydrocarbon containing 2-6 carbon atoms and which may bear 1 or 2<1>substituents selected from the group consisting of hydroxyl or straight or branched alkoxy containing 1-6 carbon atoms, as well as their acid addition
salter med farmasøytisk tålbare uorganiske eller organiske syrer.salts with pharmaceutically acceptable inorganic or organic acids.
Disse estere fremstilles ved anvendelse av kjente metoder ogThese esters are produced using known methods and
spesielt etter det folgende reaksjonsskjema:especially according to the following reaction scheme:
I formelen (B) står X for hydroksyl eller et halogenatom In formula (B), X stands for hydroxyl or a halogen atom
og R^og R^- representerer:and R^ and R^- represent:
- hver et hydrogenatom .( i dette tilfelle er (B) de hydroappo-vinkaminsyre eller et av dens halogenider )., - eller de representerer samlet en ytterligere binding ( i dette tilfellet er (B) appovinkaminsyre eller et av dens halogenider - each a hydrogen atom .( in this case (B) they are hydroappovincamic acid or one of its halides)., - or they collectively represent an additional bond ( in this case (B) is appovincamic acid or one of its halides
I formelen (C) har R den samme betydning som i formel (A) og M representerer et hydrogenatom eller et alkalimetalLatom. In formula (C), R has the same meaning as in formula (A) and M represents a hydrogen atom or an alkali metal atom.
Når R-j^ og R2hver representerer et hydrogenatom oppnås ■ forbindelsen med formel (A) direkte og i det tilfelle hvor de samlet står for en ytterligere binding medforer fremgangsmåten et siste trinn med When R-j^ and R2 each represent a hydrogen atom, ■ the compound of formula (A) is obtained directly and in the case where they together represent a further bond, the method entails a final step with
en reduksjon av dobbeltbindingen for oppnåelse av forbindelsen (A). a reduction of the double bond to obtain compound (A).
Man kan likeledes reagere et alkalimetallsalt av desoksyvinkaminsyre med en forbindelse XR (X = halogen). One can likewise react an alkali metal salt of deoxyvinicamic acid with a compound XR (X = halogen).
Den foreliggende oppfinnelse vedrorer en ny fremgangsmåte for fremstilling av 2-hydroksy-alkylestere av desoksyvinkaminsure med den generelle formel (I): The present invention relates to a new process for the production of 2-hydroxy alkyl esters of desoxyvinic acid with the general formula (I):
. hvori R^står for lavere alkyl inneholdende 1-4 karbonatomer . in which R^ stands for lower alkyl containing 1-4 carbon atoms
R2og R^står uavhengig av hverandre for et hydrogenatom eller en me tylgruppe. R 2 and R 4 stand independently of each other for a hydrogen atom or a methyl group.
Det særegne ved fremgangsmåten i henhold til oppfinnelsen er at forbindelser med den generelle formel II: The peculiarity of the method according to the invention is that compounds with the general formula II:
hvori R.^ R2 og R^har samme betydning som i den generelle formel I, in which R.sub.2, R.sub.2 and R.sub.2 have the same meaning as in the general formula I,
R^og R^står enten hver for et hydrogenatom eller samlet forR^ and R^ either each stand for a hydrogen atom or together stand for
en ytterligere binding mellom de to karbonatomer som bærer dem hydrogener i sk, kjemisk eller f'katalytisk-. a further bond between the two carbon atoms that carry them hydrogens in sk, chemically or f'catalytic-.
Den kjemiske hydrogenring gjennomfores ved hjelp av ét alkali-hydrid, foretrukket kaliumborhydrid, under omroring i lopet av minst 12 timer i en alkohol som metanol. The chemical hydrogen ring is carried out by means of an alkali hydride, preferably potassium borohydride, with stirring for at least 12 hours in an alcohol such as methanol.
Den katalytiske hydrogenering gjennomfores fortrinnsvis ved hjelp av rodium på aluminiumoksyd, under et trykk på fra 50..:-- 100 kg/cm<2>og en temperatur på fra 80-150°C, i en alkohol som etanol. The catalytic hydrogenation is preferably carried out using rhodium on aluminum oxide, under a pressure of from 50..:-- 100 kg/cm<2> and a temperature of from 80-150°C, in an alcohol such as ethanol.
Fordelen ved den nye metode i henhold til oppfinnelsen liggerThe advantage of the new method according to the invention lies
i de gode utbytter, og den enkle utforelse.in the good yields, and the simple implementation.
Forbindelsene med den generelle formel II er tidligere kjentThe compounds of the general formula II are previously known
og kan fremstilles ved vanlig forestring ved at man omsetter desoksyvinkamiri-syre eller appovinkaminsyre eller et av deres funksjonelle derivater med et ketonderivat tilsvarende formel III: and can be produced by ordinary esterification by reacting desoxyvincamic acid or appovincamic acid or one of their functional derivatives with a ketone derivative corresponding to formula III:
hvori R^, R 2 og R^ har samme betydning som i formelene I og II og X står for en OH-gruppe eller et halogenatom, foretrukket klor. in which R^, R 2 and R^ have the same meaning as in formulas I and II and X stands for an OH group or a halogen atom, preferably chlorine.
Denne reaksjonen gjennomfores foretrukket ved en temperatur på 75-120°C i et ikke-polart løsningsmiddel, som en eter, et hydrokarbon, et klorert hydrokarbon, dimetylformamid etc. This reaction is preferably carried out at a temperature of 75-120°C in a non-polar solvent, such as an ether, a hydrocarbon, a chlorinated hydrocarbon, dimethylformamide, etc.
Det folgende eksempel illustrerer fremgangsmåten i henhold til oppfinnelsen. The following example illustrates the method according to the invention.
EKSEMPEL:EXAMPLE:
Fremstilling av 2-hydroksy-propyldesoksyvinkaminat a - fra 2-propanondesoksyvinkaminat Preparation of 2-hydroxy-propyldesoxyvincaminate a - from 2-propanedesoxyvincaminate
Til en losning av 11 gram (0,02 mol) 2-propanondesoksyvinkaminat To a solution of 11 grams (0.02 mole) of 2-propane deoxyvincaminate
i 100 ml metanol avkjolt til 0°C tilsettes litt etter litt under omroring 3 gram kaliumborhydrid. Omrøringen av reaksjonsblandingen fortsettes over natten, omtrent 3/4 av løsningsmiddelet avdampes og 150 ml vann tilsettes. Blandingen ekstreheres med etylasitat, torres over natriumsulfat og inndampes til torrhet. Det oppnås 5 gram (utbyttet = 45%) av 2-hydroksypropyldesoksyvinkaminat i form av en kromatografisk ren harpiks. 3 grams of potassium borohydride are added little by little while stirring to 100 ml of methanol cooled to 0°C. Stirring of the reaction mixture is continued overnight, approximately 3/4 of the solvent is evaporated and 150 ml of water is added. The mixture is extracted with ethyl acetate, dried over sodium sulphate and evaporated to dryness. 5 grams (yield = 45%) of 2-hydroxypropyldesoxyvincaminate are obtained in the form of a chromatographically pure resin.
b - fra 2-propanonappovinkaminatb - from 2-propanone appovincamine
I en 250 ml autoklav innfores en opplosning av 15 gram (0,0397 mol) 2-propanonappovinkaminat i 150 ml absolutt etanol og 1 gram 5% In a 250 ml autoclave, introduce a solution of 15 grams (0.0397 mol) of 2-propanone appovincamine in 150 ml of absolute ethanol and 1 gram of 5%
Rh på aluminiumoksyd.Rh on aluminum oxide.
Hydrogeneringen gjennomfores under 90 kg/cm trykk ved 80 C i - ■ lopet av 15 timer. Den oppnådde opplosning filtreres og inndampes til torrhet. Det oppnås 12 gram ( utbyttet = 80% ) 2-hydroksypropyldesoksyvinkaminat i form av en harpiks. The hydrogenation is carried out under 90 kg/cm pressure at 80 C over the course of 15 hours. The solution obtained is filtered and evaporated to dryness. 12 grams (yield = 80%) of 2-hydroxypropyldesoxyvincaminate are obtained in the form of a resin.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7421582A FR2275455A1 (en) | 1974-06-21 | 1974-06-21 | D-Hydroxyalkyl desoxyvincaminates - by hydrogenation of 2-oxoalkyl desoxyvincaminates and the corresp. apovincaminates (NO190176) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO752191L true NO752191L (en) | 1975-12-23 |
Family
ID=9140348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO752191A NO752191L (en) | 1974-06-21 | 1975-06-19 |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS532880B2 (en) |
| DK (1) | DK280175A (en) |
| ES (1) | ES438736A1 (en) |
| FI (1) | FI751820A7 (en) |
| FR (1) | FR2275455A1 (en) |
| HU (1) | HU169622B (en) |
| LU (1) | LU72780A1 (en) |
| NO (1) | NO752191L (en) |
| SE (1) | SE7506949L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5413194U (en) * | 1977-06-29 | 1979-01-27 | ||
| DE2952939C2 (en) * | 1978-07-11 | 1986-01-09 | Molins Ltd., London | Packing machine for cigarettes |
| JP2669250B2 (en) * | 1992-02-24 | 1997-10-27 | 東洋製罐株式会社 | Method and apparatus for collecting and supplying cylindrical cans |
| CN114249721B (en) * | 2021-11-29 | 2023-10-17 | 南京中医药大学 | Application of vincamine PEG derivative in preparing medicament for treating diabetic peripheral neuropathy, diabetic foot and pulmonary fibrosis |
| CN114920743B (en) * | 2022-05-09 | 2023-08-04 | 南京中医药大学 | Indole alkaloid and preparation method and application thereof |
-
1974
- 1974-06-21 FR FR7421582A patent/FR2275455A1/en active Granted
-
1975
- 1975-06-17 SE SE7506949A patent/SE7506949L/en not_active Application Discontinuation
- 1975-06-18 FI FI751820A patent/FI751820A7/fi not_active Application Discontinuation
- 1975-06-19 NO NO752191A patent/NO752191L/no unknown
- 1975-06-20 DK DK280175A patent/DK280175A/en unknown
- 1975-06-20 LU LU72780A patent/LU72780A1/xx unknown
- 1975-06-20 HU HUSI1475A patent/HU169622B/hu unknown
- 1975-06-20 ES ES438736A patent/ES438736A1/en not_active Expired
- 1975-06-20 JP JP7541075A patent/JPS532880B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5141398A (en) | 1976-04-07 |
| ES438736A1 (en) | 1977-03-16 |
| FR2275455A1 (en) | 1976-01-16 |
| SE7506949L (en) | 1975-12-22 |
| FI751820A7 (en) | 1975-12-22 |
| FR2275455B1 (en) | 1976-10-22 |
| DK280175A (en) | 1975-12-22 |
| JPS532880B2 (en) | 1978-02-01 |
| LU72780A1 (en) | 1976-11-11 |
| HU169622B (en) | 1976-12-28 |
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