DE1001251B - Process for the production of ethyl acetate from acetaldehyde - Google Patents
Process for the production of ethyl acetate from acetaldehydeInfo
- Publication number
- DE1001251B DE1001251B DEW15568A DEW0015568A DE1001251B DE 1001251 B DE1001251 B DE 1001251B DE W15568 A DEW15568 A DE W15568A DE W0015568 A DEW0015568 A DE W0015568A DE 1001251 B DE1001251 B DE 1001251B
- Authority
- DE
- Germany
- Prior art keywords
- acetaldehyde
- ethyl acetate
- aluminum
- production
- dimethylaniline
- 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims description 39
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 11
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 9
- GURLNXRFQUUOMW-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[AlH3] Chemical compound [Al](Cl)(Cl)Cl.[AlH3] GURLNXRFQUUOMW-UHFFFAOYSA-K 0.000 claims 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 239000000725 suspension Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
Die Herstellung von Essigester aus Acetaldehyd mit Aluminiumäthylat als Katalysator ist schon vielfach bearbeitet worden. Um bei dieser Reaktion gleichbleibende und gute Umsätze zu erzielen, wobei als Umsatz der Quotient aus Gewichtsteilen Aldehyd und Alkoholat bezeichnet wird, muß das Aluminiumäthylat stets die gleiche katalytische Wirksamkeit haben und außerdem der Aldehyd außerordentlich rein sein; Spuren von Wasser oder Säuren im Aldehyd verschlechtern die Umsätze wesentlich. Die Aktivität des Alkoholate ist abhängig von der Qualität des verwendeten Alkohols und Aluminiums.The production of ethyl acetate from acetaldehyde with aluminum ethylate as a catalyst is already common been processed. In order to achieve consistent and good conversions in this reaction, with as Conversion is the quotient of parts by weight of aldehyde and alcoholate, the aluminum ethylate must always have the same catalytic effectiveness and, moreover, the aldehyde be extremely pure; traces of water or acids in the aldehyde worsen the conversions considerably. The activity of the alcoholate is depending on the quality of the alcohol and aluminum used.
Um hohe Umsätze zu erreichen, aktiviert man im allgemeinen das Alkoholat. Zu diesem Zweck sind schon die verschiedenartigsten Stoffe vorgeschlagen worden und werden zum Teil auch in der Praxis verwendet. So ist bekannt, daß durch Metallhalogenide, vor allem Sublimat oder wasserfreie Chloride des Eisens, Aluminiums und Zinks eine Umsatzsteigerung erreicht werden kann. Nach anderen Verfahren setzt man bei der Aluminiumäthylatherstellung elementares Chlor, Brom oder Jod zu. Auch Chlorwasserstoff ist schon als Aktivator vorgeschlagen worden. Als besonders günstig hat sich ein Zinkoxydzusatz erwiesen, wenn man das Aluminiumäthylat vor Verbrauch mehrere Tage lagert und gleichzeitig intensiv rührt. Ein vollständig befriedigendes Ergebnis wurde aber bisher nicht erzielt, wohl vor allem deswegen, weil der Reaktionsmechanismus dieser Essigestersynthese noch nicht einwandfrei geklärt ist.In order to achieve high conversions, the alcoholate is generally activated. For this purpose are already A wide variety of substances have been proposed and some are also used in practice. It is known that metal halides, especially sublimate or anhydrous chlorides of iron, aluminum and zinc an increase in sales can be achieved. Other methods are used elemental chlorine, bromine or iodine added to the production of aluminum ethylate. Hydrogen chloride is also available as Activator has been proposed. The addition of zinc oxide has proven to be particularly beneficial if you use it Aluminum ethylate is stored for several days before consumption and is stirred intensively at the same time. A completely satisfying one The result has not yet been achieved, probably mainly because of the reaction mechanism this ethyl acetate synthesis has not yet been fully clarified.
Es wurde überraschenderweise gefunden, daß die bisher erreichten Umsätze auf einfache Weise ohne nennenswerte Belastung der Wirtschaftlichkeit des Verfahrens erheblich, oft um mehr als das Doppelte, gesteigert werden können. Das Verfahren zur Herstellung von Essigsäureäthylester aus Acetaldehyd in Gegenwart von aluminiumchloridhaltigem Aluminiumäthylat besteht im wesentlichen darin, daß dem Acetaldehyd und bzw. oder dem Aluminiumäthylat geringe Mengen Dimethylanilin, vorzugsweise 0,05 bis 0,1 °/0, bezogen auf Acetaldehyd, zugesetzt werden. Aus der nebenstehenden Tabelle ist auf Grund vergleichender Versuche die außerordentliche Wirksamkeit des Zusatzes von Dimethylanilin zu ersehen.It has surprisingly been found that the conversions achieved so far can be increased considerably, often by more than double, in a simple manner without any significant impact on the economic viability of the process. The process for the production of ethyl acetate from acetaldehyde in the presence of aluminiumchloridhaltigem Aluminiumäthylat consists essentially in the fact that the acetaldehyde and or or the Aluminiumäthylat small amounts dimethylaniline, preferably 0.05 to 0.1 ° / 0, based on acetaldehyde was added. The table opposite shows the extraordinary effectiveness of the addition of dimethylaniline on the basis of comparative tests.
Das Aluminiumäthylat wird als Suspension verwendet, die in der bekannten Weise folgendermaßen hergestellt
wird. Aluminiumspäne werden mit einem Gemisch aus Essigester und Äthylalkohol, das 25 % Alkohol enthält,
durch Kochen unter Rückfluß und Rühren umgesetzt. Zur Vervollständigung der Reaktion wird gegen Ende
derselben Chlor eingeleitet. Anschließend wird von den überschüssigen Aluminiumspänen dekantiert, die Alkoholatsuspension
mit 1 % Zinkoxyd versetzt und zwei Tage bei 50° gerührt. Die gebrauchsfertige Aluminiumäthylat-Verfahren
zur Herstellung
von Essigsäureäthylester aus AcetaldehydThe aluminum ethylate is used as a suspension which is prepared in the known manner as follows. Aluminum shavings are reacted with a mixture of ethyl acetate and ethyl alcohol, which contains 25% alcohol, by boiling under reflux and stirring. To complete the reaction, chlorine is passed in towards the end of the same. The excess aluminum shavings are then decanted, 1% zinc oxide is added to the alcoholate suspension and the mixture is stirred at 50 ° for two days. The ready-to-use aluminum ethylate method of manufacture
of ethyl acetate from acetaldehyde
Anmelder:Applicant:
Wacker-Chemie G.m.b.H.,
München 22, Prinzregentenstr. 22Wacker-Chemie GmbH,
Munich 22, Prinzregentenstr. 22nd
Dr. Alfons Ascherl und Dr. Franz Büttner,Dr. Alfons Ascherl and Dr. Franz Büttner,
Burghausen (Obb.),
sind als Erfinder genannt wordenBurghausen (Obb.),
have been named as inventors
Suspension ist hellgrau und enthält etwa 28 % Aluminiumäthylat und etwa 2 °/0 Aluminiumchlorid.Suspension is light gray and contains about 28% Aluminiumäthylat and about 2 ° / 0 aluminum chloride.
Tabelle
Verwendet wurden jeweils 1000 g Acetaldehyd.Tabel
1000 g of acetaldehyde were used in each case.
a) In einem Rundkolben mit Rührer, Thermometer, Rückflußkühler und Zulaufgefäß für Acetaldehyd werden 90 g Essigester und 26,15 g Aluminiumäthylatsuspension, die, wie oben beschrieben, hergestellt ist, vorgelegt. Unter Rühren und Kühlen läuft Acetaldehyd zu. Die Zulaufgeschwindigkeit wird so eingestellt, daß die Temperatur im Kolben bei 1 bis 3° gehalten werden kann. Sobald die exotherme Reaktion nachläßt, wird der Aldehydzulauf abgestellt. Insgesamt läßt man 981 g Acetaldehyd in 65 Minuten zulaufen. Das Reaktionsgemisch (1085,3 g) bleibt bei Raumtemperatur über Nacht stehen, anschließend wird der Aldehydgehalt mit Hydroxylaminsulfat bestimmt, der 16,5% beträgt; 802 g Acetaldehyd sind somit in Essigester übergeführt.a) In a round bottom flask equipped with a stirrer, thermometer, reflux condenser and feed vessel for acetaldehyde 90 g ethyl acetate and 26.15 g aluminum ethylate suspension, which is prepared as described above, submitted. Acetaldehyde is added with stirring and cooling. The feed rate is adjusted so that the temperature in the flask can be kept at 1 to 3 °. As soon as the If the exothermic reaction subsides, the aldehyde feed is switched off. A total of 981 g of acetaldehyde is left in 65 minutes to run. The reaction mixture (1085.3 g) remains at room temperature overnight, then the aldehyde content is determined with hydroxylamine sulfate, which is 16.5%; 802 g acetaldehyde are thus converted into ethyl acetate.
609 767/422609 767/422
b) Die Umsetzung wird wie bei a) ausgeführt unter Zusatz von 25,4 g Aluminiumäthylat und 0,1 °/0 Dimethylanilin. In 110 Minuten läßt man 1565 g Acetaldehyd zulaufen. Erhalten werden 1679,4 g Rohprodukt, das 8,1 % Aldehyd bzw. 1429 g Essigester enthält, zurückgewonnen werden 139 g Aldehyd.b) The reaction is carried out as in a) with the addition of 25.4 g Aluminiumäthylat and 0.1 ° / 0 dimethylaniline. 1565 g of acetaldehyde are allowed to run in over 110 minutes. 1679.4 g of crude product, which contains 8.1% aldehyde or 1429 g of ethyl acetate, are obtained, and 139 g of aldehyde are recovered.
a) Der Versuch ohne Zusatz von Dimethylanilin wird wie im Beispiel 1 a) ausgeführt, jedoch mit einer weniger aktiven Aluminiumäthylatsuspension. Aus 1000 g Acetaldehyd und 23 g Aluminiumäthylat wurden 432 g Essigester erhalten. 565 g Acetaldehyd wurden unverändert zurückgewonnen.a) The experiment without the addition of dimethylaniline is carried out as in Example 1 a), but with one less active aluminum ethylate suspension. From 1000 g of acetaldehyde and 23 g of aluminum ethylate, 432 g of ethyl acetate were obtained obtain. 565 g of acetaldehyde were recovered unchanged.
b) 23 g der gleichen Aluminiumäthylatsuspension werden mit 91 g Essigester versetzt und 1 g Dimethylanilin zugegeben. In 65 Minuten läßt man 953,4 g Aldehyd zulaufen. Um die Reaktionstemperatur von 2 bis 3° zu halten, muß die Kühlbadtemperatur zu Beginn der Reaktion etwa —28°, am Ende etwa —20° sein. Die Aldehydbestimmung nach 16 Stunden ergibt 74 g = 7 % Acetaldehyd im Reaktionsgemisch. Es sind also 879 g Essigester entstanden.b) 23 g of the same aluminum ethylate suspension 91 g of ethyl acetate are added and 1 g of dimethylaniline is added. 953.4 g of aldehyde are left in 65 minutes run up. In order to keep the reaction temperature from 2 to 3 °, the cooling bath temperature must be at the beginning of the Reaction about -28 °, at the end about -20 °. the Aldehyde determination after 16 hours gives 74 g = 7% acetaldehyde in the reaction mixture. So it's 879 g Ethyl acetate was formed.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW15568A DE1001251B (en) | 1954-12-16 | 1954-12-16 | Process for the production of ethyl acetate from acetaldehyde |
| CH338435D CH338435A (en) | 1954-12-16 | 1955-10-27 | Process for the preparation of ethyl acetate |
| FR1138971D FR1138971A (en) | 1954-12-16 | 1955-12-15 | Process for preparing ethyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEW15568A DE1001251B (en) | 1954-12-16 | 1954-12-16 | Process for the production of ethyl acetate from acetaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1001251B true DE1001251B (en) | 1957-01-24 |
Family
ID=7595542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEW15568A Pending DE1001251B (en) | 1954-12-16 | 1954-12-16 | Process for the production of ethyl acetate from acetaldehyde |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH338435A (en) |
| DE (1) | DE1001251B (en) |
| FR (1) | FR1138971A (en) |
-
1954
- 1954-12-16 DE DEW15568A patent/DE1001251B/en active Pending
-
1955
- 1955-10-27 CH CH338435D patent/CH338435A/en unknown
- 1955-12-15 FR FR1138971D patent/FR1138971A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR1138971A (en) | 1957-06-24 |
| CH338435A (en) | 1959-07-15 |
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