GB774345A - Improvements in or relating to reductive n-alkylation process - Google Patents
Improvements in or relating to reductive n-alkylation processInfo
- Publication number
- GB774345A GB774345A GB18595/55A GB1859555A GB774345A GB 774345 A GB774345 A GB 774345A GB 18595/55 A GB18595/55 A GB 18595/55A GB 1859555 A GB1859555 A GB 1859555A GB 774345 A GB774345 A GB 774345A
- Authority
- GB
- United Kingdom
- Prior art keywords
- amino
- compounds
- alcohol
- ketone
- reductive alkylation
- 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
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
In a process for the reductive alkylation of an aromatic compound containing at least one amino or nitro group in the presence of hydrogen with a ketone, during which an alcohol is inherently formed, the effluent products of the reductive alkylation comprising an alcohol fraction contaminated with an amino compound or compounds are separated, substantially all the amino compounds are removed from the separated alcohol fraction, and the purified alcohol is dehydrogenated to a ketone which is recycled to the reductive alkylation. The process of the invention is particularly applicable to the production of N:N1-di-sec.-alkyl-p-phenylene diamines, several of which are specified. Specified aromatic compounds containing amino and/or nitro groups are aniline, phenylene diamines, nitrobenzene, dinitrobenzenes, nitroanilines, diaminonitrobenzenes, o - nitro - p - phenylene diamine, dinitroanilines, a - or b -amino- or -nitro-naphthalenes and amino and/or nitro substituted anthracene and phenanthrene compounds. The amino and/or nitro compounds may also contain other substituents such as alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxy, hydroxy, sulphonic acid and halogen. Specified ketones are dialkyl ketones having C1-C20 groups. Specified catalysts for the reductive alkylation are nickel, nickel-kieselguhr composites, nickel or copper or molybdenum sulphides, platinum and palladium, the preferred catalyst being a mixture of copper oxide, chromium oxide and barium oxide. The product of the reductive alkylation comprises hydrogen, the N-alkyl aromatic amine, water, unreacted ketone and the secondary alcohol containing amino-compounds. The N-alkylamino-product and unreacted ketone are separated, the ketone being recycled. The alcohol is freed from water (e.g. by azeotropic distillation) and then may be freed from amino compounds by solvent extraction, preferential adsorption on a solid adsorbent, or by azeotropic distillation, but fractionation is preferred. In the reductive alkylation of p-nitroaniline with methyl ethyl ketone, for example, the sec.-butyl alcohol formed is contaminated with mono- and di-sec.-butyl amines and possibly with minor amounts of cyclohexylamine and other amines. Specified catalysts for the dehydrogenation are zinc oxide, copper and copper oxide but brass catalysts are preferred. A Figure (not shown) is given illustrating in a flow diagram a continuous process of the invention. In examples: (1) p-nitroaniline is reacted with hydrogen and an excess of methyl ethyl ketone at elevated temperature and pressure and in the presence of a mixture of barium oxide, chromium oxide and copper oxide as catalyst, N : N1-di-sec.-butyl-p-phenylene diamine is separated from the reaction products, hydrogen and unreacted ketone are recycled, the sec.-butyl alcohol formed is freed from amino compounds by fractionation, dehydrogenated by passing over a heated brass catalyst and the resultant methyl ethyl ketone is recycled; (2) the dehydrogenation of sec.-butyl alcohol recovered from a reductive alkylation is compared when using purified and unpurified material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB18595/55A GB774345A (en) | 1955-06-28 | 1955-06-28 | Improvements in or relating to reductive n-alkylation process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB18595/55A GB774345A (en) | 1955-06-28 | 1955-06-28 | Improvements in or relating to reductive n-alkylation process |
Publications (1)
Publication Number | Publication Date |
---|---|
GB774345A true GB774345A (en) | 1957-05-08 |
Family
ID=22138018
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB18595/55A Expired GB774345A (en) | 1955-06-28 | 1955-06-28 | Improvements in or relating to reductive n-alkylation process |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB774345A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2446809A1 (en) * | 1979-01-22 | 1980-08-14 | Uop Inc | (N,N')-Di:alkyl-phenylene-di:amine prepn. - by reductive alkylation of nitroaniline and ketone in ether solvent |
RU2632880C1 (en) * | 2016-09-12 | 2017-10-11 | Общество с ограниченной ответственностью "ИФОТОП" | Method of producing n-methyl-para-phenetidine |
-
1955
- 1955-06-28 GB GB18595/55A patent/GB774345A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2446809A1 (en) * | 1979-01-22 | 1980-08-14 | Uop Inc | (N,N')-Di:alkyl-phenylene-di:amine prepn. - by reductive alkylation of nitroaniline and ketone in ether solvent |
RU2632880C1 (en) * | 2016-09-12 | 2017-10-11 | Общество с ограниченной ответственностью "ИФОТОП" | Method of producing n-methyl-para-phenetidine |
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