DE810026C - Process for the preparation of Acidylcarbonsaeurenitrilen and their derivatives - Google Patents
Process for the preparation of Acidylcarbonsaeurenitrilen and their derivativesInfo
- Publication number
- DE810026C DE810026C DEP18177D DEP0018177D DE810026C DE 810026 C DE810026 C DE 810026C DE P18177 D DEP18177 D DE P18177D DE P0018177 D DEP0018177 D DE P0018177D DE 810026 C DE810026 C DE 810026C
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- derivatives
- hydrogen cyanide
- preparation
- mixture
- 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
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 lactic acid nitrile Chemical class 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Acidylcarbonsäurenitrilen und deren Derivaten Es ist bekannt, Propannitril-2-acetoxy in der Weise herzustellen, daß man zuerst Acetaldehyd mit Cyanwasserstoff umsetzt und dann das erhaltene Mllchsäurenitril acetyliert.Process for the preparation of acidylcarboxylic acid nitriles and their Derivatives It is known that propanenitrile-2-acetoxy can be prepared in such a way that acetaldehyde is first reacted with hydrogen cyanide and then the resulting lactic acid nitrile acetylated.
Es wurde überraschenderweise gefunden, daß sich diese Umsetzung auf erheblich einfachere und wirtschaftlichere `reise in einem Arbeitsgang ausführen läßt und auch bei anderen Aldehyden, ferner auch bei Ketonen anwendbar ist. Das Verfahren zur Herstellung von Acidylcarbonsäurenitrilen und deren Derivaten besteht im wesentlichen darin, daß ein Gemisch von Aldehyden oder Ketonen, Cyanwasserstoff und acidylierend wirkenden Ve'fbindungen umgesetzt wird, wobei in einem Zuge die Acidylcarbonsäurenitrile entstehen. Diese werden in bekannter Weise weiterverarbeitet, z. B. durch Verseifen oder durch Abspaltung von Säure zu den entsprechenden ungesättigten Carbonsäurenitrilen. Man kann hierzu das Umsetzungsgemisch ohne weiteres verarbeiten oder die Nebenprodukte vorher abtrennen, wenn sie stören. Es ist zweckmäßig, daß bei der Umsetzung gemäß der Erfindung Katalysatoren zugegen sind, z. B. geringe Mengen einer basisch reagierenden Verbindung, z. B. Natriumacetat, Alkalialkoholate, Ammoniumsalze oder organische Basen, z. B. Pyridin, Piperidin, Amine u. dgl. Man kann auch von Verbindungen ausgehen, die mehrere Aldehyd- und bzw. oder Ketogruppen besitzen. Der Cyanwasserstoff kann als solcher verwendet oder im Umsetzungsgemisch erzeugt werden, z. B. aus Cyaniden und Säure. Die Anwendung von Überdruck kann sich als zweckmäßig erweisen. Im einfachsten Ausführungsfalle läßt man ein Gemisch aus Acet- oder Butyraldehyd oder einem Keton, z. B. Aceton, ferner Cyanwasserstoff, Essigsäureanhydrid sowie geringen Mengen Pyridin oder Piperidin unter Rühren aufeinander einwirken, wobei die Wärme abgeführt wird, so daß die Temperatur zweckmäßig nicht über 50' steigt.It has surprisingly been found that this reaction can be carried out in a considerably simpler and more economical way in one operation and can also be used with other aldehydes and also with ketones. The process for the preparation of acidylcarboxylic acid nitriles and their derivatives consists essentially in converting a mixture of aldehydes or ketones, hydrogen cyanide and acidylating compounds, the acidyl carboxylic acid nitriles being formed in one go. These are further processed in a known manner, e.g. B. by saponification or by splitting off acid to give the corresponding unsaturated carboxylic acid nitriles. For this purpose, the reaction mixture can easily be processed or the by-products can be separated off beforehand if they interfere. It is advantageous that catalysts are present in the reaction according to the invention, e.g. B. small amounts of a basic compound, e.g. B. sodium acetate, alkali metal alcoholates, ammonium salts or organic bases, e.g. B. pyridine, piperidine, amines and the like. You can also start from compounds which have several aldehyde and / or keto groups. The hydrogen cyanide can be used as such or generated in the reaction mixture, e.g. B. from cyanides and acid. The use of positive pressure may prove useful. In the simplest embodiment, a mixture of acetaldehyde or butyraldehyde or a ketone, e.g. B. acetone, also hydrogen cyanide, acetic anhydride and small amounts of pyridine or piperidine act on each other with stirring, the heat being dissipated so that the temperature does not expediently rise above 50 ' .
Die Umsetzung geht glatt vor sich, und es entsteht in hoher Ausbeute das entsprechende acidylierte Carbonsäurenitril, das z. B. zweckmäßig nach Abtrennung der Essigsäure durch Leiten der Dämpfe bei 55o bis 6oo ° über erhitzte Flächen in das ungesättigte Nitril, z. B. Acrylsäurenitril, übergeführt werden kann. Beispiel i Ein Gemisch aus i Mol Acetaldehyd, i Mol Essigsäureanhydrid, i,i bis 1,2 Mol Cyanwasserstoff und o,ooi bis 0,002 Mol Pyridin oder Piperidin oder o,o2 Mol Natriumcyanid erwärmt sich innerhalb 2o bis 30 Minuten auf 35 bis 40' und wird durch Kühlen auf dieser Temperatur gehalten, wobei zweckmäßig gerührt wird. Wenn die Temperatur fällt, ist die Umsetzung beendet. Die erhaltene wasserhelle Flüssigkeit besteht fast vollständig aus i Mol Essigsäure und i Mol Propannitril-2-acetoxy, Kp."o =i68 bis 17o° bzw. Kp.ll = 65 bis 66'. The reaction goes smoothly, and the corresponding acidylated carboxylic acid nitrile is formed in high yield. B. expedient after separation of the acetic acid by passing the vapors at 55o to 600 ° over heated surfaces in the unsaturated nitrile, z. B. acrylonitrile, can be converted. Example i A mixture of 1 mole of acetaldehyde, 1 mole of acetic anhydride, 1, 1 to 1.2 moles of hydrogen cyanide and o, ooi to 0.002 mol of pyridine or piperidine or o, o2 mol of sodium cyanide heats up to 35 to 40 minutes within 20 to 30 minutes and is kept at this temperature by cooling, with appropriate stirring. When the temperature falls, the reaction is over. The water-white liquid obtained consists almost entirely of 1 mole of acetic acid and 1 mole of propanenitrile-2-acetoxy, b.p. "o = 168 to 170 ° or b.p. II = 65 to 66".
Das Nitril kann verdampft und durch Leiten über erhitzte Flächen bei 55o bis 6oo ° in Acrylsäurenitril und Essigsäure gespalten werden. Beispiel 2 Ein Gemisch aus i Mol Butyraldehyd, i Mol Essigsäureanhydrid, i,o bis 1,2 Mol Cyanwasserstoff und o,ooi bis o,oo2 Mol Piperidin oder Pyridin wird unter Rühren langsam auf etwa 8o' erwärmt, bis die Umsetzung beendet ist. Die erhaltene Lösung enthält in hoher Ausbeute Pentannitril-2-acetoxy, Kp.lo = 83 bis 85', welches zu dem entsprechenden Amin hydriert werden kann.The nitrile can evaporate and split into acrylonitrile and acetic acid by passing it over heated surfaces at 55o to 600o. EXAMPLE 2 A mixture of 1 mole of butyraldehyde, 1 mole of acetic anhydride, 1.0 to 1.2 mol of hydrogen cyanide and 0.010 to 0.02 mol of piperidine or pyridine is slowly heated to about 80 ° with stirring until the reaction has ended. The solution obtained contains pentanenitrile-2-acetoxy in high yield, boiling point lo = 83 to 85 ', which can be hydrogenated to the corresponding amine.
Beispiel 3 Ein Gemisch aus i,2 Mol Aceton und i Mol Essigsäureanhydrid wird allmählich mit 1,2 Mol Kalium-oder Natriumcyanid versetzt. Wenn die Umsetzung zu heftig wird, muß gekühlt werden. Aus der erhaltenen Reaktionslösung kann das Methylpropannitril-2-acetoxy in etwa 75°/aiger Ausbeute gewonnen werden.Example 3 A mixture of 1.2 moles of acetone and 1 mole of acetic anhydride 1.2 mol of potassium or sodium cyanide are gradually added. When the implementation becomes too violent, must be cooled. From the reaction solution obtained, this can Methylpropanenitrile-2-acetoxy can be obtained in about 75% yield.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP18177D DE810026C (en) | 1948-10-14 | 1948-10-14 | Process for the preparation of Acidylcarbonsaeurenitrilen and their derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP18177D DE810026C (en) | 1948-10-14 | 1948-10-14 | Process for the preparation of Acidylcarbonsaeurenitrilen and their derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE810026C true DE810026C (en) | 1951-08-06 |
Family
ID=7366883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP18177D Expired DE810026C (en) | 1948-10-14 | 1948-10-14 | Process for the preparation of Acidylcarbonsaeurenitrilen and their derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE810026C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019227A1 (en) * | 1979-05-17 | 1980-11-26 | Hoechst Aktiengesellschaft | Process for the preparation of acylated cyanohydrines of aldehydes |
-
1948
- 1948-10-14 DE DEP18177D patent/DE810026C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019227A1 (en) * | 1979-05-17 | 1980-11-26 | Hoechst Aktiengesellschaft | Process for the preparation of acylated cyanohydrines of aldehydes |
| US4336206A (en) | 1979-05-17 | 1982-06-22 | Hoechst Aktiengesellschaft | Process for the manufacture of cyanohydrin acylates of aldehydes |
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