CH372296A - Process for the preparation of esters of dihydroxydehydro-ss-carotene - Google Patents
Process for the preparation of esters of dihydroxydehydro-ss-caroteneInfo
- Publication number
- CH372296A CH372296A CH52963A CH5296359A CH372296A CH 372296 A CH372296 A CH 372296A CH 52963 A CH52963 A CH 52963A CH 5296359 A CH5296359 A CH 5296359A CH 372296 A CH372296 A CH 372296A
- Authority
- CH
- Switzerland
- Prior art keywords
- carotene
- dehydro
- acid
- organic
- solvent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 17
- 150000002148 esters Chemical class 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000011648 beta-carotene Substances 0.000 title claims description 3
- 229960002747 betacarotene Drugs 0.000 title claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- USOYOVIXFHOMRI-BMRNFGFJSA-N 1,3,3-trimethyl-2-[(1e,3e,5e,7z,11e,13e,15e,17e)-3,7,12,16-tetramethyl-18-(2,6,6-trimethylcyclohexen-1-yl)octadeca-1,3,5,7,11,13,15,17-octaen-9-ynyl]cyclohexene Chemical compound CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C#C/C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C USOYOVIXFHOMRI-BMRNFGFJSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000012259 ether extract Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000005192 partition Methods 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 238000007127 saponification reaction Methods 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Estern des Dihydroxydehydro-p-carofins
Die Erfindung betrifft ein neues Verfahren zur Herstellung von Estern des 4,4'-Dihydroxy-15,15' dehydro-2S-carotins, welches dadurch gekennzeichnet ist, dass man 15,1 5'-Dehydro-iJ-carotin in Gegenwart einer organischen Säure in einem organischen Lösungsmittel nacheinander mit N-Bromsuccinimid und mit einer tertiären organischen Base behandelt.
Gegebenenfalls wird das veresterte Reaktionsprodukt zu der entsprechenden 4,4'-Dihydroxy-carotinverbin- dung verseift.
Als organische Säure kann man beispielsweise Essigsäure, Propionsäure, Ameisensäure oder Benzoe- säure verwenden. Das als Reaktionsmedium verwendete organische Lösungsmittel ist vorzugsweise ein polares Lösungsmittel, insbesondere ein halogenierter Kohlenwasserstoff, wie z. B. Chloroform, Methylenchlorid, Dichloräthan usw. Es ist zweckmässig, die Reaktion bei tiefer Temperatur, vorzugsweise unter 0 C, verlaufen zu lassen und die tertiäre Base, beispielsweise N-Athyl-morpholin, N-Äthyl- piperidin, Triäthylamin oder Diäthylanilin, zur Neutralisation des entstandenen Bromwasserstoffes und allfälliger überschüssiger organischer Säure nach kurzer Zeit, vorzugsweise etwa eine halbe Minute nach Einsetzen der Reaktion, zuzusetzen.
Falls die gebildeten Ester der 4,4'-Dihydroxy 15,1 5'-dehydro-fl-carotinverbindungen verseift werden, geschieht dies am besten alkalisch, insbesondere mit einer alkoholischen Alkalilauge, z. B. methanolischer Kalilauge, unter schwachem Erwärmen, z. B. auf 50".
Die Verfahrensprodukte können nach an sich bekannten Methoden (Verteilung zwischen Lösungsmitteln, Chromatographie usw.) gereinigt werden.
In dem folgenden Beispiel sind alle Temperaturen in Celsiusgraden angegeben.
Beispiel
Man löst 1 g 15, 15'-Dehydro-ss-carotin in
100 ml reinem Chloroform und 1,5 ml Eisessig.
Dann kühlt man die Lösung auf 180 ab. Unter kräftigem Rühren des Gemisches in einer Stickstoffatmosphäre während 2 Minuten bei 180 wird 0,66 g Bromsuccinimid in einem Mol zugegeben. Unmittelbar anschliessend gibt man 8 ml Diäthylanilin zu und lässt die Temperatur des Reaktionsgemisches innerhalb der nächsten 30 Minuten auf 20 steigen. Das Reaktionsgemisch wird hierauf mit 100 ml Diäthyl äther verdünnt und mit 0, 1n Salzsäure, dann mit Wasser, anschliessend mit 5 5e/aiger Natriumhydrogen- carbonatlösung und erneut mit Wasser gewaschen.
Nach dem Trocknen der Lösung über Natriumsulfat, Filtrieren und Abdampfen des Lösungsmittels wird der Rückstand bei Raumtemperatur in einer Stickstoffatmosphäre mit einer Lösung von 1 g Kaliumhydroxyd in 10 ml Methanol und 50 ml Dimethyl äther gerührt. Das Reaktionsgemisch wird mit Dimethyläther verdünnt und zweimal mit 300 ml Wasser behandelt. Der Ätherextrakt wird mit Natriumsulfat getrocknet und dann eingeengt. Der aus 1,2 g rohem 4,4'-Dihydroxy- 15,1 5'-dehydro-ss-carotin bestehende Rückstand kristallisiert aus Methylenchlorid-Methanol in Form roter Kristalle vom Smp.
149-150 .
PATENTANSPRUCH
Verfahren zur Herstellung von Estern des 4, 4'- Dihydroxy-1 5,1 5'-dehydro-fl-carotins, dadurch gekennzeichnet, dass man 15,15'-Dehydro-1B-carotin in Gegenwart einer organischen Säure in einem organischen Lösungsmittel nacheinander mit N-Bromsuccinimid und mit einer tertiären organischen Base behandelt.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the preparation of esters of dihydroxydehydro-p-carofins
The invention relates to a new process for the preparation of esters of 4,4'-dihydroxy-15,15 'dehydro-2S-carotene, which is characterized in that 15,1 5'-dehydro-iJ-carotene in the presence of an organic Acid treated in an organic solvent successively with N-bromosuccinimide and with a tertiary organic base.
If appropriate, the esterified reaction product is saponified to give the corresponding 4,4'-dihydroxycarotene compound.
Acetic acid, propionic acid, formic acid or benzoic acid, for example, can be used as the organic acid. The organic solvent used as the reaction medium is preferably a polar solvent, in particular a halogenated hydrocarbon, such as. B. chloroform, methylene chloride, dichloroethane, etc. It is advisable to allow the reaction to proceed at low temperature, preferably below 0 C, and to use the tertiary base, for example N-ethyl-morpholine, N-ethyl-piperidine, triethylamine or diethylaniline Neutralization of the resulting hydrogen bromide and any excess organic acid to be added after a short time, preferably about half a minute after the start of the reaction.
If the esters formed of 4,4'-dihydroxy 15,1 5'-dehydro-fl-carotene compounds are saponified, this is best done under alkaline conditions, in particular with an alcoholic alkali solution, e.g. B. methanolic potassium hydroxide, with gentle heating, for. B. to 50 ".
The process products can be purified by methods known per se (partition between solvents, chromatography, etc.).
In the following example, all temperatures are given in degrees Celsius.
example
Dissolve 1 g of 15, 15'-dehydro-ss-carotene in
100 ml of pure chloroform and 1.5 ml of glacial acetic acid.
Then the solution is cooled to 180. While stirring the mixture vigorously in a nitrogen atmosphere for 2 minutes at 180 °, 0.66 g of bromosuccinimide in one mole is added. Immediately thereafter, 8 ml of diethylaniline are added and the temperature of the reaction mixture is allowed to rise to 20 within the next 30 minutes. The reaction mixture is then diluted with 100 ml of diethyl ether and washed with 0.1N hydrochloric acid, then with water, then with 5% sodium hydrogen carbonate solution and again with water.
After drying the solution over sodium sulfate, filtering and evaporating the solvent, the residue is stirred at room temperature in a nitrogen atmosphere with a solution of 1 g of potassium hydroxide in 10 ml of methanol and 50 ml of dimethyl ether. The reaction mixture is diluted with dimethyl ether and treated twice with 300 ml of water. The ether extract is dried with sodium sulfate and then concentrated. The residue consisting of 1.2 g of crude 4,4'-dihydroxy-15,1 5'-dehydro-ss-carotene crystallizes from methylene chloride-methanol in the form of red crystals of mp.
149-150.
PATENT CLAIM
Process for the preparation of esters of 4,4'-dihydroxy-1 5,1 5'-dehydro-fl-carotene, characterized in that 15,15'-dehydro-1B-carotene is added in the presence of an organic acid in an organic solvent treated successively with N-bromosuccinimide and with a tertiary organic base.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH52963A CH372296A (en) | 1959-01-07 | 1959-01-07 | Process for the preparation of esters of dihydroxydehydro-ss-carotene |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH370402T | 1959-01-07 | ||
| CH52963A CH372296A (en) | 1959-01-07 | 1959-01-07 | Process for the preparation of esters of dihydroxydehydro-ss-carotene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH372296A true CH372296A (en) | 1963-10-15 |
Family
ID=25737345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH52963A CH372296A (en) | 1959-01-07 | 1959-01-07 | Process for the preparation of esters of dihydroxydehydro-ss-carotene |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH372296A (en) |
-
1959
- 1959-01-07 CH CH52963A patent/CH372296A/en unknown
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