CH219928A - Process for the preparation of 2,6-dimethyl-undecanol- (10). - Google Patents
Process for the preparation of 2,6-dimethyl-undecanol- (10).Info
- Publication number
- CH219928A CH219928A CH219928DA CH219928A CH 219928 A CH219928 A CH 219928A CH 219928D A CH219928D A CH 219928DA CH 219928 A CH219928 A CH 219928A
- Authority
- CH
- Switzerland
- Prior art keywords
- dimethyl
- undecanol
- alcohol
- preparation
- catalyst
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- GGYKPYDKXLHNTI-UHFFFAOYSA-N 2,6,10,14-tetramethylhexadecane Chemical compound CCC(C)CCCC(C)CCCC(C)CCCC(C)C GGYKPYDKXLHNTI-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YFHFHLSMISYUAQ-UHFFFAOYSA-N farnesane Chemical compound CCC(C)CCCC(C)CCCC(C)C YFHFHLSMISYUAQ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CRDAMVZIKSXKFV-FBXUGWQNSA-N (2-cis,6-cis)-farnesol Chemical compound CC(C)=CCC\C(C)=C/CC\C(C)=C/CO CRDAMVZIKSXKFV-FBXUGWQNSA-N 0.000 description 1
- 239000000260 (2E,6E)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol Substances 0.000 description 1
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 1
- CMOACRYSMHFBHV-UHFFFAOYSA-N CC(=C)C=CC=C(CCCC(CC)C)C Chemical compound CC(=C)C=CC=C(CCCC(CC)C)C CMOACRYSMHFBHV-UHFFFAOYSA-N 0.000 description 1
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 1
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229930002886 farnesol Natural products 0.000 description 1
- 229940043259 farnesol Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CRDAMVZIKSXKFV-UHFFFAOYSA-N trans-Farnesol Natural products CC(C)=CCCC(C)=CCCC(C)=CCO CRDAMVZIKSXKFV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
Description
Verfahren zur Darstellung von 2,6-Dimethyl-undecanol-(10). Wird auf Pseudojonon in Gegenwart eines Fdelmetallkatalysators Wasserstoff einwirken gelassen, so entsteht 2,6-Dimethyl-undecanon- (10) (Hexahydropseudojonon) (Annalen der Chemie, Bd. 475 1929] S. 189).
Es wurde nun gefunden, dass bei der Durch führung der Hydrierung von Pseudojonon in
EMI0001.0011
Gegenwart eines Nickelkatalysators nicht nur die drei Doppelbindungen des Moleküls ab gesättigt werden, sondern zugleich auch die Ketogruppe in die Alkoholgruppe übergeht und sich das bis jetzt unbekannte 2,6-Dimethyl- undecanol-(10) der nachstehenden Formel in nahezu quantitativer Ausbeute bildet:
Die Hydrierbarkeit der drei Doppelbindun gen des Moleküls auch mit Nickel als Kata lysator war zu erwarten, doch stand es keines wegs fest, dass gleichzeitig die Ketogruppe in die Alkoholgruppe verwandelt werden könnte. Der, wie Versuche ergaben, glatte Verlauf der Hydrierung konnte nicht voraus gesehen werden, da aus dem Schrifttum be kannt ist, dass aus Verbindungen der gleichen Körperklasse bei der Hydrierung schon unter gelinden Bedingungen der Sauerstoff gänzlich eliminiert wird. So entsteht z.
B. aus Farnesol (2,6,10-Trimethyl-dodecan-trien(2,6,10)-ol(12) leicht der Kohlenwasserstoff 2,6,10-Trimethyl- dodecan (Annalen der Chemie, Bd. 464 (1928 S. 87), und bei der Hydrierung von Phytol mit Platin als Katalysator bildet sich als Nebenprodukt der Kohlenwasserstoff Phytan (Helvetica Chimica Acta, Bd. 12 [1929] S.916).
Bei der Hydrierung von Pseudojonon ent steht zunächst Hexahydropseudojonon.
Das 2,6-Dimethyl.undecanol-(10) ist eine farblose Flüssigkeit von schwachem Geruch; sein spezifisches C'@ewicht beträgt dijo = 0,8\>9, sein Brechungskoeffizient ist n D = 1,4411. Bei 10 mm Druck siedet der Alkohol zwischen 130-131 . Die neue Verbindung ist in Wasser unlöslich, mit Alkohol und Äther ist sie misch bar. Durch Anwendung der üblichen Methoden lässt sich die Alkoholgruppe substituieren, beispielsweise durch Halogen.
Das 2,6-Dimethy 1-undecanol-(10) soll als Zwischenprodukt für die Herstellung pharma zeutischer Präparate Verwendung finden. <I>Beispiel:</I> 1000 Gewichtsteile Pseudojonon, 250 C1e- wichtsteile Methanol werden mit 50 Gewichts teilen eines hochaktiven Nickelkatalysators in einem Rührautoklav en mit Wasserstoff von 50-100 atü behandelt. Die 'Wasserstoffauf nahme setzt rasch ein und bewirkt eine be trächtliche Temperatursteigerung.
Nach Ab klingen des Temperaturanstieges wird der Autoklav erwärmt und bis zum Stillstand der Wasserstoffaufnahme auf 115-125 ge halten. Hierauf wird erkalten gelassen und der Katalysator durch Filtration abgetrennt. Bei der fraktionierten Destillation des Filtrates erhält man das 2,6-Dimethyl-undeea,nol-(10) in nahezu quantitativer Ausbeute.
Die Hydrierung kann auch ohne Ver dünnungsmittel durchgeführt werden. Als Katalysator lässt sich ein trägerfreies oder auch ein auf Trägern wie Kieselgur oder Aluminiumoxyd niedergeschlagenes Nickel be nützen. Die Temperatur kann innerhalb weiter Grenzen gewühlt werden.
Process for the preparation of 2,6-dimethyl-undecanol- (10). If hydrogen is allowed to act on pseudojonone in the presence of a soft metal catalyst, 2,6-dimethyl-undecanone- (10) (hexahydropseudojonon) is formed (Annalen der Chemie, Vol. 475 1929] p. 189).
It has now been found that when carrying out the hydrogenation of pseudojonon in
EMI0001.0011
The presence of a nickel catalyst not only saturates the three double bonds of the molecule, but at the same time also converts the keto group into the alcohol group and the previously unknown 2,6-dimethyl- undecanol- (10) of the following formula is formed in almost quantitative yield:
It was to be expected that the three double bonds of the molecule could also be hydrogenated with nickel as a catalyst, but it was by no means certain that the keto group could be converted into the alcohol group at the same time. The smooth course of the hydrogenation, as tests have shown, could not be foreseen, since it is known from the literature that oxygen is completely eliminated from compounds of the same body class during hydrogenation even under mild conditions. So z.
B. from farnesol (2,6,10-trimethyl-dodecan-triene (2,6,10) -ol (12) easily the hydrocarbon 2,6,10-trimethyl-dodecane (Annalen der Chemie, Vol. 464 (1928 P. 87), and during the hydrogenation of phytol with platinum as a catalyst, the hydrocarbon phytan is formed as a by-product (Helvetica Chimica Acta, vol. 12 [1929] p.916).
In the hydrogenation of pseudojonon, hexahydropseudojonon is initially formed.
2,6-Dimethyl.undecanol- (10) is a colorless liquid with a faint odor; its specific C '@ e weight is dijo = 0.8 \> 9, its refractive index is n D = 1.4411. At 10 mm pressure the alcohol boils between 130-131. The new compound is insoluble in water, it can be mixed with alcohol and ether. The alcohol group can be substituted by using the usual methods, for example by halogen.
The 2,6-Dimethy 1-undecanol- (10) is to be used as an intermediate for the manufacture of pharmaceutical preparations. <I> Example: </I> 1000 parts by weight of pseudojonone, 250 parts by weight of methanol are treated with 50 parts by weight of a highly active nickel catalyst in a stirred autoclave with hydrogen of 50-100 atmospheres. The 'hydrogen uptake sets in quickly and causes a considerable increase in temperature.
After the temperature rise has subsided, the autoclave is heated and kept at 115-125 until the uptake of hydrogen has stopped. It is then allowed to cool and the catalyst is separated off by filtration. In the fractional distillation of the filtrate, the 2,6-dimethyl-undeea, nol- (10) is obtained in almost quantitative yield.
The hydrogenation can also be carried out without a diluent. A support-free nickel or a nickel deposited on supports such as kieselguhr or aluminum oxide can be used as a catalyst. The temperature can be chosen within wide limits.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH219928T | 1941-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH219928A true CH219928A (en) | 1942-03-15 |
Family
ID=4451403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH219928D CH219928A (en) | 1941-01-13 | 1941-01-13 | Process for the preparation of 2,6-dimethyl-undecanol- (10). |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH219928A (en) |
-
1941
- 1941-01-13 CH CH219928D patent/CH219928A/en unknown
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