DE1181698B - Process for the production of methylbutenol by catalytic hydrogenation of methylbutynol - Google Patents
Process for the production of methylbutenol by catalytic hydrogenation of methylbutynolInfo
- Publication number
- DE1181698B DE1181698B DEL41355A DEL0041355A DE1181698B DE 1181698 B DE1181698 B DE 1181698B DE L41355 A DEL41355 A DE L41355A DE L0041355 A DEL0041355 A DE L0041355A DE 1181698 B DE1181698 B DE 1181698B
- Authority
- DE
- Germany
- Prior art keywords
- methylbutynol
- methylbutenol
- hydrogenation
- production
- catalytic hydrogenation
- 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.)
- Pending
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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von Methylbutenol durch katalytische Hydrierung von Methylbutinol 2-Methylbuten-3-ol-2 besitzt erhebliche Bedeutung, da man aus ihm durch einfache Wasserabspaltung Isopren erhalten kann.Process for the production of methylbutenol by catalytic hydrogenation of methylbutynol 2-methylbuten-3-ol-2 is of considerable importance, since one from isoprene can be obtained from it by simply splitting off water.
Die selektive Hydrierung von Acetylenalkoholen der allgemeinen Formel ist bereits bekannt und z. B. in der USA.-Patentschrift 2 516 826 und der britischen Patentschrift 594 459 beschrieben.The selective hydrogenation of acetylene alcohols of the general formula is already known and z. In U.S. Patent 2,516,826 and British Patent 594,459.
Derartige selektive Hydrierungen werden gewöhnlich in Gegenwart von Palladium durchgeführt, das sich als der beste Katalysator für diese Umsetzungen erwiesen hat, doch übersteigt die Ausbeute 'an Alkohol nach den Angaben in den günstigen Beispielen der oben aufgeführten Patentschriften nie 90 bis 94,°/o, während daneben gesättigter Alkohol und etwas Acetylenalkohol gebildet werden.Such selective hydrogenations are usually in the presence of Palladium, which proves to be the best catalyst for these conversions has proven, but the yield of alcohol exceeds the information in the favorable Examples of the patents listed above never 90 to 94,%, while next to it saturated alcohol and some acetylene alcohol are formed.
Auch die Verwendung eines Palladiumkatalysators, der teilweise durch Blei vergiftet ist (L i n d 1 a r, Helv. Chem. Acta, 35, S.446 bis 450, 1952), oder der Zusatz beträchtlicher Mengen von Chinolin (britische Patentschrift 810 913) zu der zu hydrierenden Lösung beeinfiußt die Selektivität der Reaktion nicht merklich und führt nicht immer zu wiederholbaren Ergebnissen, während andererseits bei der Durchführung des Verfahrens, insbesondere zufolge der Möglichkeit einer Vergiftung des Hydriergefäßes, erhebliche Nachteile in Kauf genommen werden müssen.Also the use of a palladium catalyst, which is partly through Lead is poisoned (L i n d 1 a r, Helv. Chem. Acta, 35, pp. 446 to 450, 1952), or the addition of considerable amounts of quinoline (British patent 810 913) to the solution to be hydrogenated does not noticeably affect the selectivity of the reaction and does not always lead to repeatable results, while on the other hand with the Carrying out the procedure, in particular, due to the possibility of poisoning of the hydrogenation vessel, considerable disadvantages have to be accepted.
Eine gewisse Verbesserung bei der Herstellung von Methylbutenol aus Methylbutinol ergab sich bereits durch die Anwendung der an sich bekannten Tatsache. daß bei der Hydrierung von Dreifachbindungen zu Doppelbindungen in Gegenwart von Palladiumkatalysatoren das Trägermaterial für das Palladium eine wichtige Rolle spielt. Aus .früheren Veröffentlichungen war bekannt, daß sich unter anderem Palladium auf Calciumcarbonat als Träger für die partielle Hydrierung einer Dreifachbindung zur Doppelbindung besonders gut eignet.Some improvement in the production of methylbutenol from Methylbutynol already resulted from the application of the known fact. that in the hydrogenation of triple bonds to double bonds in the presence of Palladium catalysts, the support material for the palladium, play an important role plays. From earlier publications it was known that, among other things, palladium on calcium carbonate as a carrier for the partial hydrogenation of a triple bond particularly suitable for double bonds.
Die Anwendung dieser Erkenntnis auf die Herstellung von Methylbutenol aus Methylbutinol setzte allerdings voraus, daß ganz bestimmte Verfahrensbedingungen eingehalten wurden, die sich nicht aus dem Stand der Technik ableiten ließen. Es wurde gefunden, daß sich Ausbeuten von 95% und mehr nur dann erreichen ließen, wenn man bei Normaldruck bei einer Temperatur arbeitete, die möglichst genau in der Mitte zwischen 30 und 40° C liegt. Abweichungen von diesen Grenzwerten nach oben oder unten führten zu Fehlresultaten, die auch durch Druckänderungen nicht vermieden werden konnten.Applying this knowledge to the manufacture of methylbutenol from methylbutynol, however, required very specific process conditions were complied with, which could not be derived from the state of the art. It it was found that yields of 95% and more could only be achieved if one worked at normal pressure at a temperature that was as close as possible in the middle is between 30 and 40 ° C. Deviations from these limit values upwards or below led to incorrect results that could not be avoided by pressure changes could become.
Das erfindungsgemäße Verfahren zur Herstellung von Methylbutenol durch Hydrierung von Methylbutinol in Gegenwart von Palladiumkatalysatoren auf BaS04 oder CaCOg als Träger ist daher dadurch gekennzeichnet, daß man die Hydrierung zwischen 30 und 40° C, vorzugsweise bei 35 ± 1° C, und unter Atmosphärendruck durchführt.The inventive method for the preparation of methylbutenol by Hydrogenation of methylbutynol in the presence of palladium catalysts on BaS04 or CaCOg as a carrier is therefore characterized in that the hydrogenation between 30 and 40 ° C, preferably at 35 ± 1 ° C, and under atmospheric pressure.
Bei Einhaltung dieser Reaktionsbedingungen lassen sich durchwegs Ausbeuten von mindestens 95 bis fast 98 % erreichen, während Abweichungen sofort den Umsetzungsgrad herabdrücken.If these reaction conditions are observed, yields can be achieved throughout of at least 95 to almost 98%, while deviations immediately reach the degree of implementation press down.
Einige Beispiele mögen das erfindungsgemäße Verfahren näher erläutern.A few examples may explain the method according to the invention in more detail.
Beispiel 1 In einem Reaktionsgefäß aus Glas mit 250 cms Fassungsvermögen, das in eine Rüttelvorrichtung gestellt ist und dessen Temperatur mittels eines Thermostaten genau auf 35°C eingeregelt ist, werden 50 cm3 Methylbutinol und 25 mg Pd/CaCOg (5 % Pd) eingebracht.Example 1 In a glass reaction vessel with a capacity of 250 cms, which is placed in a vibrator and its temperature by means of a thermostat is regulated to exactly 35 ° C 50 cm3 methylbutynol and 25 mg Pd / CaCOg (5% Pd) introduced.
Nachdem die Apparatur mit Stickstoff gespült wurde, wird Wasserstoff eingeleitet und mit dem Rütteln begonnen. Nachdem 12,2 NIHz absorbiert wurden, stellt man das Rütteln ein und trennt die Flüssigkeit vom Katalysator. Die mit Hilfe der Gaschromatographie durchgeführte Analyse lieferte folgende Ergebnisse: Methylbutinol . . . . . . . . . 0,40/0 Methylbutenol . . . . . . . . . 96,80/0 Methylbutanol . . . . . . . . . 2,80/0 Beispiel2 Man verfährt wie im Beispiel 1, wobei in das Reaktionsgefäß 50 cm3 Methylbutinol und 26 mg Pd/BaS04 (5 % Pd) eingebracht werden. Nach Aufnahme von 12,25l Wasserstoff wird die Umsetzung abgebrochen.After the apparatus has been purged with nitrogen, it becomes hydrogen initiated and started shaking. After 12.2 NIHz has been absorbed, the one shakes and separates the liquid from the catalyst. The with the help of the Analysis performed by gas chromatography gave the following results: methylbutynol . . . . . . . . . 0.40 / 0 methylbutenol. . . . . . . . . 96.80 / 0 methyl butanol. . . . . . . . . 2.80 / 0 Example 2 The procedure is as in Example 1, except that in the reaction vessel 50 cm3 of methylbutynol and 26 mg of Pd / BaS04 (5% Pd) are introduced. After admission the reaction is terminated by 12.25 l of hydrogen.
Die Analyse des Filtrats ergibt die folgende Zusammensetzung: Methylbutinol . . . . . . . . . 0,5% Methylbutenol . . . . . . . . . 97,0,D/o Methylbutanol . . . . . . . . . 2,5% Beispiel 3 In einen 2-1-Kolben mit mechanischem Rührwerk, der in ein genau auf 35° C gehaltenes Bad getaucht ist, (5 % werden Pd) eingebracht, 1 1 Methylbutinol und es wird und wie 3 im g Pd/CaCO3 Beispiel 1 verfahren. Nachdem 245 1 Hz absorbiert wurden, wird die Umsetzung abgebrochen und die hydrierte Flüssigkeit vom Katalysator getrennt.Analysis of the filtrate gives the following composition: methylbutynol . . . . . . . . . 0.5% methylbutenol. . . . . . . . . 97.0, D / o methyl butanol. . . . . . . . . 2.5% Example 3 In a 2-1 flask with mechanical stirrer, the is immersed in a bath kept exactly at 35 ° C, (5% are Pd), 1 1 methylbutynol and the procedure is as in 3 in g Pd / CaCO3 example 1. After this 245 1 Hz have been absorbed, the reaction is terminated and the hydrogenated liquid separated from the catalyst.
Die Analyse liefert folgendes Ergebnis: Methylbutinol . . . . . . . . . 0,00/0 Methylbutenol . . . . . . . . . 97,71/0 Methylbutanol . . . . . . . . . 2,3,1/0 Alle im Temperaturbereich zwischen 30 und 40° C durchgeführten Versuche ergaben Ausbeuten, die jedenfalls nicht niedriger als 950/9 lagen.The analysis gives the following result: methylbutynol. . . . . . . . . 0.00 / 0 methylbutenol. . . . . . . . . 97.71 / 0 methyl butanol. . . . . . . . . 2,3,1 / 0 All tests carried out in the temperature range between 30 and 40 ° C gave yields which were in any case not lower than 950/9.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT1181698X | 1961-03-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1181698B true DE1181698B (en) | 1964-11-19 |
Family
ID=11432724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEL41355A Pending DE1181698B (en) | 1961-03-01 | 1962-03-01 | Process for the production of methylbutenol by catalytic hydrogenation of methylbutynol |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1181698B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1115238B (en) * | 1957-02-05 | 1961-10-19 | Basf Ag | Process for the partial hydrogenation of acetylene compounds |
| GB888999A (en) * | 1959-07-07 | 1962-02-07 | Distillers Co Yeast Ltd | Selective hydrogenation of acetylenically unsaturated compounds and catalyst therefor |
-
1962
- 1962-03-01 DE DEL41355A patent/DE1181698B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1115238B (en) * | 1957-02-05 | 1961-10-19 | Basf Ag | Process for the partial hydrogenation of acetylene compounds |
| GB888999A (en) * | 1959-07-07 | 1962-02-07 | Distillers Co Yeast Ltd | Selective hydrogenation of acetylenically unsaturated compounds and catalyst therefor |
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