DE962787C - Process for the production of oxygen-containing offshoots of butane - Google Patents
Process for the production of oxygen-containing offshoots of butaneInfo
- Publication number
- DE962787C DE962787C DEC6395A DEC0006395A DE962787C DE 962787 C DE962787 C DE 962787C DE C6395 A DEC6395 A DE C6395A DE C0006395 A DEC0006395 A DE C0006395A DE 962787 C DE962787 C DE 962787C
- Authority
- DE
- Germany
- Prior art keywords
- ketobutyraldehyde
- dimethylacetal
- butane
- methoxybutanol
- oxygen
- 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
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/175—Saturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
-
- 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
-
- 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
- C07C45/67—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 isomerisation; by change of size of the carbon skeleton
- C07C45/673—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 isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
Description
Verfahren zur Herstellung sauerstoffhaltiger Abkömmlinge des Butans Es ist bekannt, daß man Acetale bei Temperaturen oberhalb I50" auf katalytischem Wege unter Abspaltung der Acetalgruppen hydrieren kann. Man hat auch schon vorgeschlagen, auf diesem Wege aus Alkoxyacetalen mehrwertige äther herzustellen und so z. B. aus I, I, 3-Trimethoxybutan I, 3-Dimethoxybutan gewonnen. Nach den Angaben der USA.-Patentschrift 2 590 598 ist es zweckmäßig, bei diesen Verfahren hohe Drücke und Temperaturen zwischen I75 und 2200 anzuwenden, da andernfalls die Reaktion nur sehr langsam verläuft. Es mußte daher unzweckmäßig und nicht vorteilhaft erscheinen, Acetale unter gewöhnlichem oder erhöhtem Druck bei Temperaturen unterhalb von I500 einer Behandlung mit Wasserstoff zu unterwerfen.Process for the production of oxygen-containing derivatives of butane It it is known that acetals are catalytic at temperatures above 150 " can hydrogenate with elimination of the acetal groups. It has also been suggested in this way to produce polyvalent ethers from alkoxyacetals and so z. B. off I, I, 3-trimethoxybutane I, 3-dimethoxybutane obtained. According to the USA patent specification 2,590,598 it is advisable to use high pressures and temperatures between I75 and 2200 should be used, otherwise the reaction will be very slow. It must therefore appear inconvenient and unfavorable, acetals among the ordinary or elevated pressure at temperatures below 1500, treatment with hydrogen to subjugate.
Es wurde nun indessen gefunden, daß man für das Lösungsmittel- und Zwischenproduktengebiet wertvolle sauerstoffhaltige Abkömmlinge des Butans aus Acetalen des 3-Ketobutyraldehyds erhält, wenn man Acetale des 3-Ketobutyraldehyds bei gewöhnlichem oder erhöhtem Druck und bei Temperaturen bis zu etwa I50" in Gegenwart von schwermetallhaltigen Katalysatoren mit Wasserstoff behandelt. Als Ausgangsmaterial sind beispielsweise folgende Verbindungen geeignet: 3-Ketobutyraldehyd-I-dialkylacetale oder -I-glykolacetale. It has now been found, however, that for the solvent and Intermediate product area valuable oxygen-containing derivatives of butane from acetals of 3-ketobutyraldehyde is obtained when acetals of 3-ketobutyraldehyde are used with ordinary or elevated pressure and at temperatures up to about 150 "in the presence of heavy metals Catalysts treated with hydrogen. As a starting material are for example the following compounds are suitable: 3-ketobutyraldehyde-I-dialkyl acetals or -I-glycol acetals.
Als Katalysatoren geeignet sind alle üblichen schwermetallhaltigen Hydrierungskatalysatoren, z. B. All customary heavy metal-containing catalysts are suitable as catalysts Hydrogenation catalysts, e.g. B.
Nickel, Kupfer, Chrom auf Kieselgel, Kupfer, Chrom auf Kieselgel, Raney-Nickel oder Kupferchromit nach Adkins, wobei die Reaktionstemperaturen zwischen Raumtemperatur bis etwa 150° betragen und die Drücke zwischen I und 300 at und höher schwanken können.Nickel, copper, chromium on silica gel, copper, chromium on silica gel, Raney nickel or copper chromite Adkins, with the reaction temperatures between room temperature and about 150 ° and the pressures between I and 300 at and higher.
Die Art der entstehenden Verbindungen sei am Beispiel des 3-Ketobutyraldehyd-I-dimethylacetals erläutert, wobei nur die wihtigsten Reaktionsprodukte berücksichtigt sind. The nature of the compounds formed is the example of 3-ketobutyraldehyde-I-dimethylacetals explained, whereby only the most important reaction products are taken into account.
Bei niedrigen und mittleren Hydriertemperaturen werden Hydrierungsgemische erhalten, die je nach den angewendeten Reaktionsbedingungen neben Acetaldoldimethylacetal überwiegend I-Methoxybutanon-(3) und I-Methoxybutanol-(3) in wechselnden Mengenverhältnissen enthalten. Durch geeignete Wahl der Reaktionsbedingungen (Temperatur, Druck, Art des Katalysators) kann der Anteil jedes einzelnen der erwähnten Stoffe auf ein Maximum gebracht werden. At low and medium hydrogenation temperatures, hydrogenation mixtures are used obtained, depending on the reaction conditions used, in addition to acetaldol dimethylacetal predominantly I-methoxybutanone- (3) and I-methoxybutanol- (3) in varying proportions contain. By suitable choice of the reaction conditions (temperature, pressure, type of the catalyst) the proportion of each of the substances mentioned can be maximized to be brought.
Acetaldoldimethylacetal wird aus 3-Ketobutyraldehyd-I-dimethylacetal durch Reduktion der Ketogruppe erhalten und war bei Hydriertemperaturen unterhalb 150° auf Grund des Bekannten als ausschließliches Produkt oder zumindest als Hauptprodukt zu erwarten.Acetaldol dimethyl acetal is obtained from 3-ketobutyraldehyde-I-dimethyl acetal by reducing the keto group and was to be expected as the exclusive product or at least as the main product at hydrogenation temperatures below 150 ° based on what is known.
Überraschenderweise entstehen bei Temperaturen unterhalb I50° jedoch in beträchtlichen Mengen 1-Methoxybutanon-(3) und I-Methoxybutanol- (3), wobei I-Methoxybutan-(I)-on-(3) als Zwischenstufe angenommen wird: Über Acetaldoldimethylacetal kann daneben Butyraldehyd-dimethylacetal gebildet werden.Surprisingly, however, considerable amounts of 1-methoxybutanone- (3) and I-methoxybutanol- (3) are formed at temperatures below 150 °, with I-methoxybutan- (I) -one- (3) being assumed as an intermediate: Butyraldehyde dimethyl acetal can also be formed via acetaldol dimethyl acetal.
Beispiel I 3-Ketobutyraldehyd-I-dimethylacetal wird in einem Hydrierofen von IOO cm3 Reaktionsraum mit fest eingebautem Katalysator bei 300 at H2-Druck einer kontinuierlichen Hydrierung unterworfen. Der Substanzdurchlauf beträgt 20 g 3-Ketobutyradlehyd-I-diinethylacetal je Stunde, und es werden stündlich Iool Abgas abgelassen. Über einem 15 01o Nickel, 5% Kupfer, 1% Chrom und 79 01o Kieselgel enthaltenden Kontakt entstehen aus 264 g 3-Ketobutyraldehyddimethylacetal bei einer Hydriertemperatur von 80° I90 g I-Methoxybutanol-(3). Die Ausbeute von I-Methoxybutanol-(3) beträgt 91% der Theorie. Example I 3-Ketobutyraldehyde-I-dimethylacetal is made in a hydrogenation furnace of 100 cm3 reaction space with a permanently installed catalyst at 300 at H2 pressure one subjected to continuous hydrogenation. The substance flow is 20 g of 3-ketobutyradlehyd-I-diyne ethyl acetal per hour, and Iool exhaust gas is discharged every hour. Over a 15 01o nickel, Contact containing 5% copper, 1% chromium and 79 01o silica gel is formed from 264 g of 3-ketobutyraldehyde dimethyl acetal at a hydrogenation temperature of 80 ° I90 g of I-methoxybutanol- (3). The yield of I-methoxybutanol- (3) is 91% of theory.
Kp.760 145°, D420 0,9129; nD20 1,4143.B.p. 760 145 °, D420 0.9129; nD20 1.4143.
Beispiel 2 3-Ketobutyraldehyd-I-dimethylacetal wird in einem gleichen Hydrierofen wie im Beispiel I und in gleicher Weise hydriert. An einem Katalysator, der aus 20% Kupfer, 1% Chrom und 79 01o Kieselgel besteht, werden bei einer Hydriertemperatur von 600 aus 264 g 3-Ketobutyraldehyd-I-dimethylacetal I77 g I-Methoxybutanol-(3) erhalten. Die Ausbeute an I-Methoxybutanol-(3) beträgt 85 01o der Theorie. Example 2 3-Ketobutyraldehyde-I-dimethylacetal is used in a same Hydrogenation furnace as in Example I and hydrogenated in the same way. On a catalyst which consists of 20% copper, 1% chromium and 79 01o silica gel, are at a hydrogenation temperature of 600 from 264 g of 3-ketobutyraldehyde-I-dimethylacetal I77 g of I-methoxybutanol- (3) obtain. The yield of I-methoxybutanol- (3) is 85,010 of theory.
Kp.760 I45°, DT 0,9120; nD20 1,4143.Bp 760 145 °, DT 0.9120; nD20 1.4143.
Beispiel 3 3-Ketobutyraldehyd-I-dimethylacetal wird, wie im Beispiel 2 angegeben, hydriert. Bei einer Hydriertemperatur von I40° entstehen aus 264 g 3-Ketobutyraldehyd-I-dimethylacetal I34 g Acetaldoldimethylacetal, 25 g I-Methoxybutanol-(3), 25 g Methylbutyläther und 5 g Butyraldehyd-dimethylacetal. Example 3 3-Ketobutyraldehyde-I-dimethylacetal is, as in the example 2 indicated, hydrogenated. At a hydrogenation temperature of 140 °, 264 g are formed 3-ketobutyraldehyde-I-dimethylacetal I34 g acetaldol dimethylacetal, 25 g I-methoxybutanol- (3), 25 g of methyl butyl ether and 5 g of butyraldehyde dimethylacetal.
Die Ausbeute an Acetaldoldimethylacetal beträgt 5001o der Theorie. Kp.20 86°, DlqB 0,9894; nD20 I,4200.The yield of acetaldol dimethylacetal is 50010 of theory. Bp 20-86 °, DlqB 0.9894; nD20 I, 4200.
Beispiel 4 528 g 3-Ketobutyraldehyd-I-dimethylacetal werden mit I5 g Raney-Nickel im I-I-Autoklav bei 1000. und I50 at H2 hydriert. Neben 50 g I-Methoxybutanon-(3) entstehen 355 g I-Methoxybutanol-(3). Die Ausbeute an 1-Methoxybutanol-(3) beträgt 85 01o der Theorie. Example 4 528 g of 3-ketobutyraldehyde-I-dimethylacetal are mixed with I5 g Raney nickel hydrogenated in the I-I autoclave at 1000 and 150 at H2. In addition to 50 g of I-methoxybutanone- (3) 355 g of I-methoxybutanol- (3) are produced. The yield of 1-methoxybutanol- (3) is 85 01o of theory.
Kp.760 145°, DT 0,9129; nD20 1,4143.Bp 760 145 °, DT 0.9129; nD20 1.4143.
Beispiel 5 660 g 3-Ketobutyraldehyd-I-dimethylacetal werden mit 33 g Kupferchromitkontakt im 2-I-Autoklav bei 1000 und I50 at hydriert. Neben einer kleinen Menge I-Methoxybutanon-(3) werden etwa 280 g I-Methoxy- butanol-(3) und gog Acetaldoldimethylacetal erhalten. Example 5 660 g of 3-ketobutyraldehyde-I-dimethylacetal are mixed with 33 g of copper chromite contact hydrogenated in a 2 l autoclave at 1000 and 150 atm. In addition to a small amount of I-methoxybutanone- (3) about 280 g of I-methoxy- butanol- (3) and gog acetaldol dimethyl acetal was obtained.
Beispiel 6 3-Ketobutyraldehyd-I-dimethylacetal wird in einem 2-I-Hydrierofen, gefüllt mit I400 cm3 des im Beispiel I genannten Katalysators, einer drucklosen Hydrierung unterworfen, wobei 50 l/Std. H2 als Frischgas eingefahren werden, während das Kreisgas auf I500 l/Std. gehalten wird und pro Stunde 50 g 3-Ketobutyraldehyd-I-dimethylacetal durch einen Verdampfer über den Kontakt geleitet werden. Bei einer Hydriertemperatur von 1000 entstehen aus 583 g 3-Ketobutyraldehyd-I-dimethylacetal 3Io g I-Methoxybutanol-(3) und IOI g Acetaldoldimethylacetal. Die Ausbeute an f-Methoxybutanol-(3) beträgt 67 0/o der Theorie. Example 6 3-Ketobutyraldehyde-I-dimethylacetal is in a 2-I hydrogenation furnace, filled with 1400 cm3 of the catalyst mentioned in Example I, a pressureless one Subjected to hydrogenation, with 50 l / h. H2 can be run in as fresh gas while the cycle gas to I500 l / h. is held and 50 g of 3-ketobutyraldehyde-I-dimethylacetal per hour be passed through an evaporator over the contact. At a hydrogenation temperature out of 1000 result from 583 g of 3-ketobutyraldehyde-I-dimethylacetal 3Io g of I-methoxybutanol- (3) and IOI g of acetaldol dimethylacetal. The yield of f-methoxybutanol- (3) is 67 0 / o of theory.
Beispiel 7 3-Ketobutyraldehyd-I-dimethylacetal wird in gleicher Weise wie im Beispiel 6, jedoch bei 60° hydriert. Dabei entstehen aus 583 g 3-Ketobutyraldehyd-I-dimethylacetal I32 g I-Methoxybutanol-(3) und 264 g Acetaldoldimethylacetal. Example 7 3-Ketobutyraldehyde-I-dimethylacetal is prepared in the same way as in Example 6, but hydrogenated at 60 °. This results in 583 g of 3-ketobutyraldehyde-I-dimethylacetal I32 g of I-methoxybutanol- (3) and 264 g of acetaldol dimethylacetal.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC6395A DE962787C (en) | 1952-09-13 | 1952-09-13 | Process for the production of oxygen-containing offshoots of butane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC6395A DE962787C (en) | 1952-09-13 | 1952-09-13 | Process for the production of oxygen-containing offshoots of butane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE962787C true DE962787C (en) | 1957-04-25 |
Family
ID=7013895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC6395A Expired DE962787C (en) | 1952-09-13 | 1952-09-13 | Process for the production of oxygen-containing offshoots of butane |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE962787C (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR903035A (en) * | 1942-12-01 | 1945-09-21 | Ig Farbenindustrie Ag | Process for preparing monoethers of 1, 3-butylene glycol |
| US2425042A (en) * | 1943-12-01 | 1947-08-05 | Carbide & Carbon Chem Corp | Glycol diethers |
| US2564760A (en) * | 1951-08-21 | Process fob making alkoxyacetals | ||
| US2590598A (en) * | 1948-12-07 | 1952-03-25 | Gen Aniline & Film Corp | Polyethers and process of preparing the same |
-
1952
- 1952-09-13 DE DEC6395A patent/DE962787C/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2564760A (en) * | 1951-08-21 | Process fob making alkoxyacetals | ||
| FR903035A (en) * | 1942-12-01 | 1945-09-21 | Ig Farbenindustrie Ag | Process for preparing monoethers of 1, 3-butylene glycol |
| US2425042A (en) * | 1943-12-01 | 1947-08-05 | Carbide & Carbon Chem Corp | Glycol diethers |
| US2590598A (en) * | 1948-12-07 | 1952-03-25 | Gen Aniline & Film Corp | Polyethers and process of preparing the same |
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