GB669574A - A process for the production of 1(p-hydroxyphenyl)-1-hydroxy-2-(aralkyl-amino)-propanes - Google Patents
A process for the production of 1(p-hydroxyphenyl)-1-hydroxy-2-(aralkyl-amino)-propanesInfo
- Publication number
- GB669574A GB669574A GB9141/49A GB914149A GB669574A GB 669574 A GB669574 A GB 669574A GB 9141/49 A GB9141/49 A GB 9141/49A GB 914149 A GB914149 A GB 914149A GB 669574 A GB669574 A GB 669574A
- Authority
- GB
- United Kingdom
- Prior art keywords
- chme
- benzyl
- group
- toluene
- sulphonyl
- 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
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
- C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
- C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
Abstract
Aminopropanols of the formula <FORM:0669574/IV (b)/1> (where R is an aliphatic hydrocarbon residue of 2-5 carbon atoms) are prepared by the following methods: (1) hydrogenating the ketone <FORM:0669574/IV (b)/2> or a salt thereof (R1=H or group split off during hydrogenation, e.g. benzyl) with a noble metal or nickel catalyst; in the latter case, when using a salt, 1 mol. of alkali is added either initially or after 1 mol. of hydrogen has been taken up (by elimination of R1); (2) decomposing the derivative <FORM:0669574/IV (b)/3> by hydrogenation with palladium or heating with mineral acid (when R2=benzyl) or saponification (when R2=residue of a carboxylic or sulphonic acid); (3) reacting an aralkylamine with HO-C6H4-CO.CO.CH3 (or a benzyl ether or carboxylic or sulphonic ester thereof) to give a Schiff's base or aldehyde ammonia; the product is then hydrogenated with a noble metal or nickel catalyst whereby C=N and C=O bonds are reduced and the benzyloxy group if present is converted to a hydroxy group; where an ester was used as starting material, final hydrolysis gives the free p-hydroxy group; (4) an aralkyl or aralkenyl aldehyde or ketone is condensed with <FORM:0669574/IV (b)/4> (or the corresponding R2O- compound) with simultaneous or subsequent reduction; the residue R2 if present is then eliminated as in (2); (5) suspending <FORM:0669574/IV (b)/5> in an organic solvent in which it is sparingly soluble and hydrogenating it together with an aldehyde or ketone R5-CO-R4-C6H5, where R4 and R5 are aliphatic hydrocarbon residues or R5 may be hydrogen, and the sum of the carbon atoms in R4 and R5 is 1-4. In method (1) the reduction and splitting off of R1 may occur simultaneously or successively in either order, depending on the reaction conditions. Suitable solvents for method (5) are methanol, ethanol and isopropanol, with or without water. The products may be obtained as mixtures of stereoisomers which may be separated; hydrochlorides and hydrobromides are described. Examples are given of all 5 methods, the group R in the products being -CHMe-, -CH2-CH2-, -CHMe-CH2-, -CH2-CH2-CH2-, -CHMe-CH2-CH2-, -CH2-CH2-CH2-CH2- and -CHMe-CH2-CH2-CH2-. The acyl group R2 is preferably toluene p-sulphonyl. The starting materials for method (2) are obtained by method (1), or else by the Meerwein-Ponndorf reduction with aluminium isopropylate, e.g. the following (a) R2=benzyl, R=-CHMe-CH2-CH2-, (b) R2=toluene p-sulphonyl, R=-CHMe-CH2-CH2, and (c) R2=toluene p-sulphonyl, R= -CH2-CH2-CH2-. Aralkylaminopropanones (p) R2O-C6H4-CO-CHMe-NH-R-C6H5, where R and R2 are as above, are made by reacting NH2-R-C6H5 with R2O-C6H4-CO-CHMe-Hal (especially Br), e.g. the compounds (1) R2= benzyl, R=-CH2-CH2-CH2-, the benzyl group being subsequently split off with hydrogen, (2) R2=H, R=-CH2-CH2-CH2-, (3) R2=benzyl, R=-CHMe-CH2-CH2-, the benzyl group being subsequently split off with hydrogen, (4) R2=H, R=-CHMe-CH2-CH2-, (5) R2=toluene p-sulphonyl, R= -CHMe-CH2-CH2-, the tosyl group being subsequently split off with alcohol, and (5) R2=toluene p - sulphonyl, R=-CH2-CH2-CH2-. p-Hydroxypropiophenone derivatives are made as follows: (1) the ketone is converted into its acetate, toluene p-sulphonate and benzyl ether, all three being then brominated. The acetyl-bromo-compound is treated with strong ammonia to give p-hydroxy-a -aminopropiophenone which is catalytically reduced to the corresponding carbinol; (2) the ketone or its benzyl ether or esters as in (1) is treated with nitrous acid or a nitrous ester to form the isonitroso derivative. This is then catalytically reduced to 1-(p-hydroxyphenyl)-2-amino-1-propanol or the corresponding ether or ester.ALSO:A hydrogenation catalyst comprises freshly prepared palladium chloride solution to which charcoal has been added.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9141/49A GB669574A (en) | 1949-04-04 | 1949-04-04 | A process for the production of 1(p-hydroxyphenyl)-1-hydroxy-2-(aralkyl-amino)-propanes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9141/49A GB669574A (en) | 1949-04-04 | 1949-04-04 | A process for the production of 1(p-hydroxyphenyl)-1-hydroxy-2-(aralkyl-amino)-propanes |
Publications (1)
Publication Number | Publication Date |
---|---|
GB669574A true GB669574A (en) | 1952-04-02 |
Family
ID=9866156
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9141/49A Expired GB669574A (en) | 1949-04-04 | 1949-04-04 | A process for the production of 1(p-hydroxyphenyl)-1-hydroxy-2-(aralkyl-amino)-propanes |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB669574A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2661373A (en) * | 1953-03-02 | 1953-12-01 | Kulz Ida | Certain amino alcohols and ketones |
US3278601A (en) * | 1960-12-19 | 1966-10-11 | Philips Corp | Aralkylamines and methods of preparation thereof |
-
1949
- 1949-04-04 GB GB9141/49A patent/GB669574A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2661373A (en) * | 1953-03-02 | 1953-12-01 | Kulz Ida | Certain amino alcohols and ketones |
US3278601A (en) * | 1960-12-19 | 1966-10-11 | Philips Corp | Aralkylamines and methods of preparation thereof |
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