DE870852C - Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcohols - Google Patents
Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcoholsInfo
- Publication number
- DE870852C DE870852C DEF5353A DEF0005353A DE870852C DE 870852 C DE870852 C DE 870852C DE F5353 A DEF5353 A DE F5353A DE F0005353 A DEF0005353 A DE F0005353A DE 870852 C DE870852 C DE 870852C
- Authority
- DE
- Germany
- Prior art keywords
- halophenols
- catalytic hydrogenation
- cycloaliphatic alcohols
- corresponding cycloaliphatic
- catalysts
- 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.)
- Expired
Links
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
- C07C29/19—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 in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/08—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur katalytischen Hydrierung von Halogenphenolen zu den entsprechenden cycloaliphatischen Alkoholen Es ist bekannt, Halogenphenole mit Hilfe von gebräuchlichen Hydrierungskatalysatoren, wie Nickel, Kobalt oder Kupfer, in Gegenwart von Alkali mit Wasserstoff zu den entsprechenden halogenfreien Phenolen zu hydrieren. Es ist ferner bekannt, Phenole in Form der Alkaliphenolate in wässeriger oder alkoholischer Lösung mit Hilfe der obengenannten Katalysatoren in die entsprechenden cycloaliphatischen Alkohole überzuf'ü'hren. Bisher ist es jedoch nicht gelungen, Halogenphenole in einem Arbeitsgang zu den vorerwähnten halogenfreien Alkoholen zu hydrieren.Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcohols It is known to use halophenols of common hydrogenation catalysts, such as nickel, cobalt or copper, in Presence of alkali with hydrogen to the corresponding halogen-free phenols to hydrate. It is also known to use phenols in the form of the alkali metal phenolates in aqueous or alcoholic solution with the aid of the above-mentioned catalysts in the corresponding transferring cycloaliphatic alcohols. So far, however, it has not been possible Halophenols in one operation to the aforementioned halogen-free alcohols to hydrate.
Es wurde nun gefunden, daB diese Hydrierung in alkalischer Lösung in technisch einfacher Weise durchführbar ist, wenn man als Katalysatoren hochaktive Kontakte verwendet. Der glatte Verlauf dieser Hydrierung ist um so überraschender, als nicht vorherzusehen war, daß die bekanntlich sehr empfindlichen hochaktiven Katalysatoren unter den vorliegenden Hydrierungs'bedingungen beständig sind.It has now been found that this hydrogenation takes place in an alkaline solution can be carried out in a technically simple manner if the catalysts are highly active Contacts used. The smooth course of this hydrogenation is all the more surprising, than could not have been foreseen that the, as is well known, very sensitive, highly active ones Catalysts are stable under the present hydrogenation conditions.
Als 'hochaktive Hydrierungskatalysatoren bewähren sich für diese Zwecke z. B. Raney-Nickel und auf Aktivkohle niedergeschlagenes feinverteiltes Palladium sowie namentlich Nickelkatalysatoren, die neben Chromoxyd noch ein anderes Metalloxyd, wie Aluminium-, Thorium- oder Magnesiumoxyd, enthalten. und insbesondere solche Katalysatoren dieser Art mit einem Gehalt an etwa 5 bis 25 % Chromoxyd und etwa 5 bis etwa 18 %. oder genannten anderen Metalloxyde.As' highly active hydrogenation catalysts have proven themselves for these purposes z. B. Raney nickel and finely divided palladium deposited on activated carbon as well as especially nickel catalysts, which in addition to chromium oxide also contain another metal oxide, such as aluminum, thorium or magnesium oxide. and especially those Catalysts of this type with a content of about 5 to 25% chromium oxide and about 5 to about 18%. or other metal oxides mentioned.
Das vorliegende Verfahren wird vorzugsweise bei Wasserstoffdrücken über etwa 5o, atü, insbesondere bei Drücken von etwa ioo bis etwa Zoo atü, und Temperaturen oberhalb ioo°, ins-'besondere zwischen etwa i5o° bis etwa 2oo°, durchgeführt.The present process is preferably carried out at hydrogen pressures above about 5o atm, especially at pressures from about 100 to about zoo atm, and temperatures above 100 °, in particular between about 150 ° to about 200 °.
In der Regel ist es zweckmäßig, die Hydrierung in Gegenwart eines geringen AIkaliüberschusses, so z. B. von 2o bis 25 %, berechnet auf den Halogengehalt des Phenols,durchzuführen.As a rule, it is advantageous to carry out the hydrogenation in the presence of a small excess of alkali, e.g. B. from 2o to 25%, calculated on the halogen content of phenol.
Unter .den Halogenphenolen, die nach dem vorliegenden Verfahren zu Iden entsprechenden halogenfreien cyeloaliphatischen Alkoholen hydriert werden können, seien z. B. .genannt o-, m-, p-Chlorphenol, o-, m-, p-Chlorkresol, o-, Tn-, p-Chloräthylphenol, o-, m-, p-Chlorbutylphenol, 2-Chlor-a-naphthol, 4-Chlor-a-naphthol, i-Chlor-,B-nap'hthol und 3-Chlorf-napht'hol. Beispiel i Zur katalytischen Hydrierung von p-C'hlor-mkresol wird ein wie folgt hergestellter Katalysator benutzt: EineLösüng von 34o Gewichtsteilen Nickelnitrat, goGewichtsteilen Aluminiumnitrat und i55Gewichtsteilen Chromnitrat in 5oo Teilen Wasser wird bei 9o° mit einer 5%igen Natronlauge in geringem Überschuß versetzt, der gut ausgewaschene Hydroxydniederschlag abgesaugt, getrocknet und bei 25o bis 300° im Wasserstoffstrom reduziert.Among. The halophenols, which according to the present process to Iden appropriate halogen-free cyeloaliphatic alcohols can be hydrogenated, be z. B. called o-, m-, p-chlorophenol, o-, m-, p-chlorocresol, o-, Tn-, p-chloroethylphenol, o-, m-, p-chlorobutylphenol, 2-chloro-a-naphthol, 4-chloro-a-naphthol, i-chloro-, B-nap'hthol and 3-chloro-naphthol. Example i For the catalytic hydrogenation of p-chloro-mcresol a catalyst prepared as follows is used: A solution of 34o parts by weight Nickel nitrate, parts by weight of aluminum nitrate and 55 parts by weight of chromium nitrate in 500 parts of water is at 90 ° with a 5% sodium hydroxide solution in a slight excess added, the well washed out hydroxide precipitate sucked off, dried and with Reduced from 25o to 300 ° in the hydrogen stream.
2o -g des erhaltenen Katalysators werden zu einer Lösung von 5oo g p-Chlor-m-kresol in 288 g einer 5oo/oigen wässerigen Lösung von Natriumhydroxyd gegeben. Dann wird diese Lösung bei 2oo° und einem Druck von 200 .atü 240 Minuten mit Wasserstoff behandelt.2o -g of the catalyst obtained become a solution of 5oo g p-chloro-m-cresol in 288 g of a 500% aqueous solution of sodium hydroxide given. Then this solution is at 2oo ° and a pressure of 200 .atü 240 minutes treated with hydrogen.
DasReaktionsprodukt wird nac h,demAbfiltrieren des Kontaktes angesäuert, dann wird die ölige Schicht nach der Abtrennung von der wässerigen Schicht :destilliert. Man erhält 3709 Methylcyclohexanol (=,92,5o/0 :der Theorie). Beispiel e 5oo g des bei der Herstellung von p-Chlor-mkresol durch Chlorieren eines technischen Kresolgemisches anfallenden Vorlaufs mit einem Chlorgehalt von i i,8 % werden nn 168 g einer 5o%igen wässerigen Natronlauge gelöst und nach Zusatz von 25 g ides im Beispiel i benutzten Chrom- und Aluminiumoxyd enthaltenden Nickelkatalysators bei 2oo° und einem Wasserstoffdruck von Zoo atü i2o Minuten hydriert. Die Aufarbeitung des Reäkt'ionsgemisches wird in ,der gleichen Weise wie im Beispiel i vorgenommen. Man erhält 338 g Methylcyclohexanol (= 85 0/0 ;der Theorie). Außerdem fallen 44g Kresol und i i g eines harzartigen Rückstandes an.The reaction product is acidified after filtering off the contact, then the oily layer is distilled after separation from the aqueous layer. 3709 methylcyclohexanol are obtained (= .92.5o / 0: of theory). Example e 500 g of the first runnings with a chlorine content of 1.8% in the production of p-chloro-mcresol by chlorinating a technical cresol mixture are dissolved in 168 g of a 50% strength aqueous sodium hydroxide solution and, after addition of 25 g of ides in example i used nickel catalyst containing chromium and aluminum oxide hydrogenated at 2oo ° and a hydrogen pressure of zoo atü 12o minutes. The work-up of the reaction mixture is carried out in the same way as in Example i. 338 g of methylcyclohexanol (= 85%; theoretical) are obtained. In addition, 44 g of cresol and iig of a resinous residue are obtained.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF5353A DE870852C (en) | 1951-01-03 | 1951-01-03 | Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcohols |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEF5353A DE870852C (en) | 1951-01-03 | 1951-01-03 | Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcohols |
Publications (1)
Publication Number | Publication Date |
---|---|
DE870852C true DE870852C (en) | 1953-03-16 |
Family
ID=7084543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEF5353A Expired DE870852C (en) | 1951-01-03 | 1951-01-03 | Process for the catalytic hydrogenation of halophenols to the corresponding cycloaliphatic alcohols |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE870852C (en) |
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1951
- 1951-01-03 DE DEF5353A patent/DE870852C/en not_active Expired
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