DE945447C - Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexane - Google Patents
Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexaneInfo
- Publication number
- DE945447C DE945447C DEC6238A DEC0006238A DE945447C DE 945447 C DE945447 C DE 945447C DE C6238 A DEC6238 A DE C6238A DE C0006238 A DEC0006238 A DE C0006238A DE 945447 C DE945447 C DE 945447C
- Authority
- DE
- Germany
- Prior art keywords
- nitrocyclohexane
- cyclohexylhydroxylamine
- palladium
- parts
- vol
- 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
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 title claims description 12
- GUQRKZPMVLRXLT-UHFFFAOYSA-N n-cyclohexylhydroxylamine Chemical compound ONC1CCCCC1 GUQRKZPMVLRXLT-UHFFFAOYSA-N 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000002574 poison Substances 0.000 claims 1
- 231100000614 poison Toxicity 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- -1 nitrocyclohexane Cyclohexylhydroxylamine Chemical compound 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Cyclohexylhydroxylamin aus Nitrocyclohexan Cyclohexylhydroxylamin besitzt eine besondere Bedeutung, weil es in einfacher Weise durch Oxydation in Cyclohexanonoxim und dieses durch Beclunannsche Umlagerung in Caprolactam übergeführt werden kann. Man hat bereits vorgeschlagen, Nitrocyclohexan mit Reduktionsmitteln, wie Zinn(II)-chlorid in stark salzsaurer Lösung, Natrium und Alkohol, Natriumamalgam, Eisen(II)-hydroxyd, Natriumhydrosulfit, Zink in essigsaurer Lösung oder Zink in Gegenwart von Puffersalzen, zu reduzieren, ohne indessen auf diesen Wegen zu wirklich befriedigenden Verfahren gelangen zu können.Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexane Cyclohexylhydroxylamine is of particular importance because it is easy to use by oxidation in cyclohexanone oxime and this by Beclunann rearrangement in Caprolactam can be transferred. It has already been proposed to use nitrocyclohexane with reducing agents such as tin (II) chloride in a strong hydrochloric acid solution, sodium and alcohol, sodium amalgam, iron (II) hydroxide, sodium hydrosulfite, zinc in acetic acid Solution or zinc in the presence of buffer salts, without, however, reducing these ways to be able to arrive at really satisfactory procedures.
Es ist auch bekannt, daß man Nitrobenzol durch Hydrieren in Gegenwart von Pulladiumkatalysatoren in N-Phenylhydrokylamin überführen kann, wenn man in sehr starker Verdünnung arbeitet und die Hydrierung abbricht, sobald die erforderliche Wasserstoffmenge aufgenommen ist, um die Bildung von Anilin zu verhindern. Bei der Hydrierung von aliphatischen Nitroverbindungen mittels Palladium als Katalysator zu den entsprechenden Hydroxylaminderivaten hat man schon in Gegenwart molarer Mengen schwacher Säuren gearbeitet, wobei diese Säuren mit der basisch wirkenden Hydroxylamingruppe der Reaktionsprodukte unter S alzbildung reagieren und dadurch Folgereaktionen, wie die Bildung von Aminen, vermieden werden.It is also known that nitrobenzene can be obtained by hydrogenation in the presence of pulladium catalysts can be converted into N-phenylhydrokylamine if one in very strong dilution works and the hydrogenation stops as soon as the required Amount of hydrogen is absorbed to prevent the formation of aniline. In the Hydrogenation of aliphatic nitro compounds using palladium as a catalyst the corresponding hydroxylamine derivatives are already available in the presence of molar amounts Weak acids worked, these acids with the basic hydroxylamine group the reaction products react with formation of salts and thus follow-up reactions, such as the formation of amines, can be avoided.
Es wurde nun gefunden, daB man Cyclohexylhydroxylamin vorteilhafter herstellen kann, wenn man Nitrocyclohexan in Gegenwart von Palladium enthaltenden Katalysatoren unter milden Bedingungen, vorzugsweise in Abwesenheit von Säuren, mit Wasserstoff reduziert. Als Katalysatoren eignen sich besonders solche, bei denen das Palladium als Metall auf. einem Trägerstoff niedergeschlagen ist, der zweckmäßig aus Calciumca:rbonat, Aluminiumoxyd oder Bariumsulfat, aber auch aus Aktivkohle besteht. Der Palladiumgehalt des Katalysators kann zwischen 0,05 und- 3%, vorteilhafterweise etwa i %, betragen. Mit Katalysatoren mit höheren Palladiumgehalten bzw. mit solchen, die wirksame ändere Katalysatoren enthalten, entsteht Cyclohexylamin als unerwünschtes Nebenprodukt. Diese hohe Wirksamkeit der zu palladiumreichen bzw. zu wirksamen anderen Palladiumkatalysatoren läßt sich jedoch durch Zusatz von Stoffen, z. B. von Schwermetallen, wie Blei, oder von organischen Verbindungen, wie Chinolin, oder von Salzen von organischen Säuren mit organischen Basen, vermindern. Die Reaktionstemperaturen liegen im allgemeinen zwischen etwa 5 und 2o°. Die jeweils günstigsten Temperaturen hängen von der Art der verwendeten Katalysatoren ab und sind durch Vorversuche zu ermitteln. Sie liegen z. B. bei Verwendung eines Katalysators, der i % Palladium auf Calciumcarbonat enthält, bei-i5 bis 2o° und bei Verwendung eines Katalysators, der i % Palladium auf Aluminiumoxyd. enthält, bei io bis 15°. Bei höheren-Temperaturen tritt die Bildung des unerwünschten Cyclohexylamins immer mehr in den Vordergrund, bei niedrigeren Temperaturen ist die Reaktionsgeschwindigkeit zu gering. Man kann jedoch auch bei höheren Temperaturen, z. B. 3o°, arbeiten, ohne daß sich Cyclohexylumin bildet, wenn man die Hydrierung in schwach saurer Lösung, z. B. in Gegenwart von Essigsäure; durchführt. Bei Benutzung von Essigsäure bleibt das gebildete Cyclohexylhydroxylamin jedoch in Lösung und wird durch Zugabe von Alkali ausgefällt. Der Druck des verwendeten Wasserstoffs . ist von geringem Einfluß auf den Verlauf der Umsetzung. Man' kann sowohl ohne Druck als auch bei erhöhten Drucken von io at und mehr arbeiten. Die Reduktion wird zweckmäßig in ,einem Lösungs- bzw. Suspensionsmittel durchgeführt. Als Lösungs- bzw. Suspensionsmittel eignen sich Methanol, Methanol-Wasser oder Cyclohexan. -Beispiel i In einem mit Kühlvorrichtung versehenen Reaktionsgefäß werden 65 Gewichtsteile Nitrocyclohexan, iSo Gewichtsteile Methanol und 2o Gewichtsteile eines etwa i%igen Palladium-Calciumcarbonat-Katalysä.tors unter ständiger Durchmischung bei einer Temperatur von 20° und einem Überdruck von ioo bis Zoo mm Hg mit Wasserstoff reduziert. Nach etwa 25 Stunden ist die berechnete Menge Wasserstoff aufgenommen und das Cyclohexylhydroxylamin größtenteils ausgefallen. Das Cyclohexylhydroxylamin wird durch Erwärmen in Lösung gebracht und vom Katalysator abfiltriert. Beim Abkühlen des Filtrats fällt der größte Teil des entstandenen Cyclohexylhydroxylamins aus und wird abgesaugt. Durch Eindunsten des Filtrats erhält man eine zweite Fraktion; man saugt sie ab und wäscht die Kristalle mit Petroläther aus. Schmelzpunkt 141 bis 142'; Ausbeute 43,5 Gewichtsteile, entsprechend - 75,51/o der Theorie. Nicht umgesetztes Nitrocyclohexan befindet sich im Filtrat und wird durch Destillation zurückgewonnen. Unter Berücksichtigung des zurückgewonnenen Nitrocyclohexans beträgt die Ausbeute an Cyclohexylhydroxylamin über 8o 0/a; Cyclohexylamin bildet sich nur in Spuren. Beispiel e Man hydriert 65 Teile Nitrocyclohexan, in i5o Teilen Methanol gelöst, in Gegenwart von io Teilen eines i%igen Palladium-Aluminiumoxyd-Katalysators bei 15 bis 2o° und einem Wasserstoffdruck von roo bis Zoo cm Wassersäule. Nach 24 Stunden wird das Reaktionsgemisch, wie im Beispiel i angegeben, aufgearbeitet. Man erhält 33 Teile Cyclohexylhydroxylamin; Ausbeute 75 % (auf den Umsatz bezogen), neben i6 Teilen unverändertem Nitrocyclohexan.It has now been found that cyclohexylhydroxylamine is more advantageous can manufacture if one nitrocyclohexane in the presence of palladium containing catalysts under mild conditions, preferably in the absence of acids, reduced with hydrogen. Particularly suitable catalysts are those in which the palladium appears as a metal. is deposited on a carrier, which is useful from calcium carbonate, aluminum oxide or barium sulfate, but also consists of activated carbon. The palladium content of the catalyst can be between 0.05 and - 3%, advantageously about i%. With catalysts with higher palladium contents Cyclohexylamine is formed with those containing other effective catalysts as an undesirable by-product. This high effectiveness of the palladium-rich or other effective palladium catalysts can, however, be achieved by adding substances z. B. heavy metals such as lead, or organic compounds such as quinoline, or of salts of organic acids with organic bases. The reaction temperatures are generally between about 5 and 20 °. The most favorable temperatures in each case depend on the type of catalysts used and must be carried out through preliminary tests determine. You are z. B. when using a catalyst that contains i% palladium contains calcium carbonate, at -15 to 20 ° and when using a catalyst, the i% palladium on aluminum oxide. contains, at io to 15 °. At higher temperatures the formation of the undesired cyclohexylamine comes more and more to the fore, the reaction rate is too slow at lower temperatures. One can but also at higher temperatures, e.g. B. 3o °, work without cyclohexylumin forms when the hydrogenation is carried out in weakly acidic solution, e.g. B. in the presence of Acetic acid; performs. When using acetic acid, the cyclohexylhydroxylamine formed remains however in solution and is precipitated by the addition of alkali. The pressure of the used Hydrogen. has little impact on the course of implementation. One can work both without pressure and at increased pressures of io at and more. the Reduction is expediently carried out in a solvent or suspension medium. Suitable solvents or suspending agents are methanol, methanol-water or cyclohexane. - Example i 65 parts by weight are added to a reaction vessel provided with a cooling device Nitrocyclohexane, iSo parts by weight of methanol and 2o parts by weight of an approximately i% strength Palladium-calcium carbonate catalyst with constant mixing at a Temperature of 20 ° and an overpressure of 100 to Zoo mm Hg with hydrogen reduced. After about 25 hours, the calculated amount of hydrogen and the cyclohexylhydroxylamine have been absorbed mostly failed. The cyclohexylhydroxylamine is dissolved by heating brought and filtered off from the catalyst. When the filtrate cools, the largest falls Part of the resulting cyclohexylhydroxylamine and is filtered off with suction. By evaporation a second fraction is obtained from the filtrate; they are suctioned off and the crystals are washed with petroleum ether. Melting point 141 to 142 '; Yield 43.5 parts by weight, accordingly - 75.51 / o of theory. Unreacted nitrocyclohexane is in the filtrate and is recovered by distillation. Taking into account the recovered Nitrocyclohexane, the yield of cyclohexylhydroxylamine is over 80 0 / a; Cyclohexylamine only forms in traces. Example e 65 parts of nitrocyclohexane are hydrogenated in Dissolved 150 parts of methanol in the presence of 10 parts of a 1% palladium-aluminum oxide catalyst at 15 to 20 ° and a hydrogen pressure of roo to zoo cm water column. After 24 The reaction mixture is worked up as indicated in Example i for hours. Man receives 33 parts of cyclohexylhydroxylamine; Yield 75% (based on sales), in addition to 16 parts of unchanged nitrocyclohexane.
Beispiel 3 Man hydriert 65 Teile Nitrocyclohexan, gelöst in ioo Teilen Methanol und 4o Teilen Eisessig bei 30° in der im Beispiel 2 angegebenen Weise. Nach 24 Stunden wird das Gemisch durch Zugabe von Natronlauge oder einem anderen alkalisch wirkenden Mittel neutralisiert und das Cyclohexyl= hydroxylamin in bekannter Weise abgetrennt. Man erhält 37 Teile Cyclohexylhydroxylamin neben wenig unverändertem Nitrocyclohexan..Example 3 65 parts of nitrocyclohexane dissolved in 100 parts are hydrogenated Methanol and 40 parts of glacial acetic acid at 30 ° in the manner indicated in Example 2. After 24 hours, the mixture is made by adding sodium hydroxide solution or another alkaline agents neutralized and the cyclohexyl = hydroxylamine in known Way separated. 37 parts of cyclohexylhydroxylamine are obtained in addition to the little unchanged Nitrocyclohexane ..
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC6238A DE945447C (en) | 1952-08-08 | 1952-08-08 | Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC6238A DE945447C (en) | 1952-08-08 | 1952-08-08 | Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE945447C true DE945447C (en) | 1956-07-12 |
Family
ID=7013849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC6238A Expired DE945447C (en) | 1952-08-08 | 1952-08-08 | Process for the preparation of cyclohexylhydroxylamine from nitrocyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE945447C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3119873A (en) * | 1958-10-03 | 1964-01-28 | Inventa Ag | Process for the production of cyclohexanol and cyclohexanone |
| US3393237A (en) * | 1965-09-22 | 1968-07-16 | Abbott Lab | Preparation of cyclohexylhydroxylamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2237365A (en) * | 1938-11-28 | 1941-04-08 | Ig Farbenindustrie Ag | Production of oximes |
| US2423180A (en) * | 1944-03-14 | 1947-07-01 | Union Oil Co | Process for the reduction of nitronaphthenes |
| DE847446C (en) * | 1945-10-18 | 1952-08-25 | Hoffmann La Roche | Process for the production of pentaenes (vitamin A-aether) |
-
1952
- 1952-08-08 DE DEC6238A patent/DE945447C/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2237365A (en) * | 1938-11-28 | 1941-04-08 | Ig Farbenindustrie Ag | Production of oximes |
| US2423180A (en) * | 1944-03-14 | 1947-07-01 | Union Oil Co | Process for the reduction of nitronaphthenes |
| DE847446C (en) * | 1945-10-18 | 1952-08-25 | Hoffmann La Roche | Process for the production of pentaenes (vitamin A-aether) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3119873A (en) * | 1958-10-03 | 1964-01-28 | Inventa Ag | Process for the production of cyclohexanol and cyclohexanone |
| US3393237A (en) * | 1965-09-22 | 1968-07-16 | Abbott Lab | Preparation of cyclohexylhydroxylamine |
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