DE877303C - Process for the preparation of oximes - Google Patents
Process for the preparation of oximesInfo
- Publication number
- DE877303C DE877303C DEB17437A DEB0017437A DE877303C DE 877303 C DE877303 C DE 877303C DE B17437 A DEB17437 A DE B17437A DE B0017437 A DEB0017437 A DE B0017437A DE 877303 C DE877303 C DE 877303C
- Authority
- DE
- Germany
- Prior art keywords
- oximes
- preparation
- parts
- nitrocyclohexane
- reaction
- 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 5
- 150000002923 oximes Chemical class 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Oximen Es wurde gefunden, daß man Nitroalkane oder Nitrocycloalkane, vorzugsweise Nitrocyclohexan, in technisch einfacher Weise und in guter Ausbeute zu den entsprechenden Oximen umsetzen kann, wenn man sie mit Alkylenoxyden behandelt.Process for the preparation of oximes It has been found that one can use nitroalkanes or nitrocycloalkanes, preferably nitrocyclohexane, in a technically simple manner and can convert them to the corresponding oximes in good yield if they are used with Treated alkylene oxides.
Für das Verfahren geeignete Nitroalkane sind außer Nitrocyclohexan und dessen Substitutionsprodukten z. B. Nitromethan, Nitroäthan und Nitropropan. Geeignete Alkylenoxyde sind vorzugsweise Äthylenoxyd, Propylenoxyd und Butylenoxyd.In addition to nitrocyclohexane, suitable nitroalkanes for the process are and its substitution products e.g. B. nitromethane, nitroethane and nitropropane. Suitable alkylene oxides are preferably ethylene oxide, propylene oxide and butylene oxide.
Die Reaktion wird zweckmäßig in Gegenwart von Katalysatoren ausgeführt, insbesondere von solchen, die in wäßriger Lösung eine alkalische Reaktion zeigen, wie die Hydroxyde, Carbonate, Bicarbonate und Alkoholate des Natriums, Kaliums und Calciums. Auch die Zugabe geringer Salzmengen oder von organischen Basen fördert die Umsetzung. Die günstigsten Reaktionstemperaturen liegen zwischen o und zoo°, doch kann auch bei niedrigerer oder höherer Temperatur gearbeitet werden. Es ist in der Regel zweckmäßig, mindestens zur Vervollständigung der Umsetzung, die Reaktionsmischung vor ihrer Aufarbeitung auf höhere Temperaturen zu erwärmen. Der Zusatz von Lösungsmitteln, wie Methanol, Äthanol, Propanol und Butanol, begünstigt die Umsetzung. Das Verfahren kann bei normalem Druck oder bei erhöhtem Druck kontinuierlich oder diskontinuierlich durchgeführt werden. Die in dem nachstehenden Beispiel angegebenen Teile sind Gewichtsteile.The reaction is expediently carried out in the presence of catalysts, especially those that show an alkaline reaction in aqueous solution, such as the hydroxides, carbonates, bicarbonates and alcoholates of sodium, potassium and Calcium. The addition of small amounts of salt or organic bases is also beneficial the implementation. The most favorable reaction temperatures are between 0 and zoo °, but it is also possible to work at a lower or higher temperature. It is generally expedient, at least to complete the reaction, the reaction mixture to be heated to higher temperatures before working up. The addition of solvents, such as methanol, ethanol, propanol and butanol, favors the implementation. The procedure can be continuous or discontinuous at normal pressure or at elevated pressure be performed. The ones given in the example below Parts are parts by weight.
Beispiel i Teil Natrium wird in 23o Teile Äthylalkohol eingetragen. Nach dem Auflösen des Natriums werden i Teil Kaliumcarbonat und 3o Teile Nitrocyclohexan zugefügt. Dann werden bei o bis 1o° q.o Teile Äthylenoxyd unter Rühren langsam eingeleitet, und hierauf wird i Stunde bei q.0° nachgerührt.Example 1 part of sodium is added to 230 parts of ethyl alcohol. After the sodium has dissolved, 1 part of potassium carbonate and 3o parts of nitrocyclohexane are added added. Then at 0 to 10 ° q.o parts of ethylene oxide are slowly introduced with stirring, and this is followed by stirring at 0 ° for 1 hour.
Nach Beendigung der Umsetzung wird der Alkohol im Vakuum abdestilliert. Dann wird der Rückstand mit verdünnter Salzsäure aufgenommen und die Salzsäurelösung zur Entfernung von geringen Teilen von nicht umgesetztem Nitrocyclohexan zeit Äther ausgeschüttelt. Anschließend neutralisiert man die Salzsäurelösung durch Zugabe von Natronlauge. Hierbei fällt das Cyclohexanonoxim in Form von Kristallen aus, die abgetrennt und aus Ligroin umkristallisiert werden.After the reaction has ended, the alcohol is distilled off in vacuo. Then the residue is taken up with dilute hydrochloric acid and the hydrochloric acid solution to remove small parts of unreacted nitrocyclohexane time ether shaken out. The hydrochloric acid solution is then neutralized by adding of caustic soda. The cyclohexanone oxime precipitates in the form of crystals, which are separated and recrystallized from ligroin.
Man erhält Cyclohexanonöxim in einer Ausbeute von 7o "/o der Theorie, berechnet auf das umgesetzte Nitrocyclohexan. Durch Extraktion der Mutterlaugen mit Äther läßt sich noch weiteres Cyclohexanonoxim erhalten.Cyclohexanone oxime is obtained in a yield of 70 "/ o of theory, calculated on the converted nitrocyclohexane. By extraction of the mother liquors further cyclohexanone oxime can be obtained with ether.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB17437A DE877303C (en) | 1951-11-04 | 1951-11-04 | Process for the preparation of oximes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB17437A DE877303C (en) | 1951-11-04 | 1951-11-04 | Process for the preparation of oximes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE877303C true DE877303C (en) | 1953-05-21 |
Family
ID=6959337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB17437A Expired DE877303C (en) | 1951-11-04 | 1951-11-04 | Process for the preparation of oximes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE877303C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945065A (en) * | 1958-07-30 | 1960-07-12 | Du Pont | Process for the reduction of nitrocy-clohexane to cyclohexanone oxime |
| US3123639A (en) * | 1964-03-03 | Production of beta-hybsoxyalkyl |
-
1951
- 1951-11-04 DE DEB17437A patent/DE877303C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3123639A (en) * | 1964-03-03 | Production of beta-hybsoxyalkyl | ||
| US2945065A (en) * | 1958-07-30 | 1960-07-12 | Du Pont | Process for the reduction of nitrocy-clohexane to cyclohexanone oxime |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE877303C (en) | Process for the preparation of oximes | |
| DE947162C (en) | Process for working up the reaction mixture obtained in the nitration of cyclohexane | |
| DE922649C (en) | Process for working up the reaction mixture obtained in the nitration of cyclohexane | |
| DE1077650B (en) | Process for the preparation of phenylacetaldehyde dialkyl acetals | |
| DE2233489C3 (en) | Process for the preparation of octachlorodipropyl ether | |
| DE590432C (en) | Process for the preparation of addition compounds of hypochlorous or interruptive acid with organic compounds | |
| DE894118C (en) | Process for the preparation of ªªª-diphenyl-ethylamines disubstituted on the nitrogen | |
| DE495020C (en) | Process for the preparation of methylal | |
| DE860637C (en) | Process for the preparation of sulfur-containing cyclic organic compounds | |
| DE529538C (en) | Process for the preparation of aromatic nitro compounds | |
| DE2509481C3 (en) | Process for the preparation of N-acetylsalicylamide | |
| DE748289C (en) | Process for the production of butene- (1) -one- (3) | |
| DE1217947B (en) | Process for the preparation of 2, 3-dichlorobutadiene- (1, 3) | |
| DE3811095C2 (en) | ||
| DE653073C (en) | Process for the preparation of alkylaminoalkyl ethers of apoquinine | |
| DE644647C (en) | Process for the preparation of salts of the ªÏ-methylfonic acids of pyrazolone amines with ring nitrogen bases | |
| DE741320C (en) | Process for the preparation of 2, 4, 6-trimethyl-3-acetylpyridine | |
| AT162164B (en) | Process for the preparation of α, α-di (nitrophenyl) -β, β, β-trichloroethanes. | |
| DE965321C (en) | Process for the production of pure terephthalic acid | |
| DE939811C (en) | Process for the production of ªÏ-caprolactam and its derivatives | |
| CH282274A (en) | Process for the preparation of 2,9-dimethyl-1,10-phenanthroline. | |
| AT141030B (en) | Process for the production of ethyl alcohol. | |
| DE2435821A1 (en) | PROCESS FOR THE RECOVERY OF PROPYLENE OXIDE | |
| DE1136321B (en) | Process for the preparation of 4-cyano-2,2-dimethylbutyraldehyde | |
| DE805400C (en) | Process for the production of dinitrophenyl ethers |