DE874916C - Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1) - Google Patents
Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1)Info
- Publication number
- DE874916C DE874916C DESCH106A DESC000106A DE874916C DE 874916 C DE874916 C DE 874916C DE SCH106 A DESCH106 A DE SCH106A DE SC000106 A DESC000106 A DE SC000106A DE 874916 C DE874916 C DE 874916C
- Authority
- DE
- Germany
- Prior art keywords
- diphenyl
- normal
- diastereomeric
- substituted
- propanolen
- 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
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/22—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated
- C07C215/28—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
- C07C215/30—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton
- C07C215/32—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings containing hydroxy groups and carbon atoms of six-membered aromatic rings bound to the same carbon atom of the carbon skeleton containing hydroxy groups and carbon atoms of two six-membered aromatic rings bound to the same carbon atom of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von diastereomeren N-substituierten 1, 3-Diphenyl-3-amino-propanolen-(1) Durch reduzierende Aufspaltung des 3, 5-Diphenyldihydroisoxazols kann man die beiden diastereomeren Normal- und Isoformen des primären i, 3-Diphenyl-3-amino-propanols-(i) erhalten. Aus dem Gemisch der beiden Diastereomeren läßt sich die Normalform des i, 3-Diphenyl-3-amino-propanols-(i) über die Benzylidenv erbindung in guten Ausbeuten sterisch rein darstellen.Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1) By reducing splitting of the 3, 5-diphenyldihydroisoxazole, one can do the two diastereomeric normal and isoforms of primary i, 3-diphenyl-3-aminopropanols- (i) obtain. The normal form of can be obtained from the mixture of the two diastereomers i, 3-Diphenyl-3-aminopropanols- (i) via the benzylidene compound in good yields represent sterically pure.
Damit ist auch die Herstellung von bisher nicht bekannten N-substituierten sterisch reinen Normal-und Isoformen des i, 3-Diphenyl-3-amino-propanols-(i) möglich geworden.This also enables the production of previously unknown N-substituted sterically pure normal and isoforms of 1,3-diphenyl-3-aminopropanols- (i) possible become.
Es zeigte sich nämlich, daß die Alkylierung der Normalform des i, 3-Diphenyl-3-amino-propanols- (i) durch Umsetzung mit Carbonylv erbindungen bei gleichzeitiger katalytischer Hydrierung in guter Ausbeute zu N-alkylierten normal-i, 3-Diphenyl-3-aminopropanolen-(i) führt, die gegebenenfalls über die Chlorverbindung in die N-Substitutionsprodukte des iso-i, 3-Diphenyl-3-amino-propanols-(i) umgelagert werden können.It was shown that the alkylation of the normal form of the i, 3-Diphenyl-3-aminopropanols- (i) by reaction with carbonyl compounds simultaneous catalytic hydrogenation in good yield to N-alkylated normal-i, 3-Diphenyl-3-aminopropanolen- (i) leads, optionally via the chlorine compound rearranged into the N-substitution products of iso-i, 3-diphenyl-3-aminopropanols- (i) can be.
Auf diese Weise konnte z. B. durch Alkylierung der Normalform des i, 3-Diphenyl-3-amino-propanols- (i) mittels Isobutyraldehyd das normal-i, 3-Diphenyl-3-isobutylamino-propanol-(i) in guter Ausbeute erhalten werden. Durch Chlorierung mit P C1, und anschließende Verseifung wurde diese Substanz in iso-i, 3-Diphenyl-3-isobutyla.mino-propanol-(i) umgelagert.In this way, z. B. by alkylation of the normal form of the i, 3-diphenyl-3-aminopropanol- (i) using isobutyraldehyde, the normal-i, 3-diphenyl-3-isobutylamino-propanol- (i) can be obtained in good yield. This substance was rearranged into iso-1,3-diphenyl-3-isobutyla.mino-propanol- (i) by chlorination with P C1 and subsequent saponification.
Beispiel i ii,5 g normal-i, 3-Diphenyl-3-amino-propanol-(i) vorn Fp. = 124 bis i25° wurden in 250 ccm Methanol gelöst und nach Zugabe von 3,1 ccm Cyclohexan in Gegenwart von =o g Platin-Bariumsulfat-Katalysator (1 g Pt) bei 14 ätü und Zimmertemperatur hydriert. Nach beendeter Hydrierung wurde vom Katalysator abfiltriert und die Lösung angesäuert und im Vakuum zur Trockne gedampft. Der Rückstand wurde aus Methanol-Äther umkristallisiert. Das Hydrochlorid desnormal-z, 3-Diphenyl-3-cyclohexylamino-propanols-(i) zeigte einen Fp. = 2o6 bis 207°. Die freie Base wurde mit Ammoniakwasser gefällt und zeigte nach dem Umlösen aus Ligroin einen Fp. =122 bis 12g.°. Beispiel e 11,5 g normal-i, 3-Diphenyl-3-amino-propanol-(i) wurden in 2,50 ccm Methanol gelöst und nach Zusatz von 4 ccm Aceton in Gegenwart von =o g Platin-Bariumsulfat-Katalysator (i g Pt) bei 3,4 atü und Zimmertemperatur hydriert. Die vom Katalysator befreite Lösung wurde angesäuert und das Lösungsmittel im Vakuum abgedampft. Das Hydrochlorid des normal-1, 3-Diphen5T1-3-isopropylamino-propanols-(i) zeigte aus Alkohol-Äther einen Fp. _ =8i bis 183°. Die Ausbeute betrug 9,5 g. Die freie Base zeigte nach dem Umlösen aus Ligroin einen Fp. = 96 bis 97°.Example i ii, 5 g of normal-1,3-diphenyl-3-aminopropanol- (i) with melting point = 124 to 125 ° were dissolved in 250 cc of methanol and, after addition of 3.1 cc of cyclohexane in the presence of = The above-mentioned platinum barium sulfate catalyst (1 g Pt) is hydrogenated at 14 oat and room temperature. When the hydrogenation had ended, the catalyst was filtered off and the solution acidified and evaporated to dryness in vacuo. The residue was recrystallized from methanol-ether. The hydrochloride desnormal-z, 3-diphenyl-3-cyclohexylamino-propanols- (i) had a melting point = 206 to 207 °. The free base was precipitated with ammonia water and, after redissolving from ligroin, had a melting point = 122 to 12 g. °. Example e 11.5 g of normal-i, 3-diphenyl-3-aminopropanol- (i) were dissolved in 2.50 cc of methanol and, after addition of 4 cc of acetone, in the presence of the above-mentioned platinum-barium sulfate catalyst (ig Pt) hydrogenated at 3.4 atmospheres and room temperature. The solution, freed from the catalyst, was acidified and the solvent was evaporated off in vacuo. The hydrochloride of normal-1,3-diphen5T1-3-isopropylamino-propanols- (i) had a melting point of 8 ° to 183 ° from alcohol-ether. The yield was 9.5 g. After redissolving from ligroin, the free base had a melting point = 96 ° to 97 °.
Beispiel 3 11,5 g- normal-i, 3-Diphenyl-3-amilio-propanol-(i) wurden in 25o ccm Methanol und 4,5 g Isobutyraldehyd gelöst und in Gegenwart von =o g Platin-Bariumsulfat-Katalysator (i g Pt) bei 3,4 atü und Zimmertemperatur hydriert. Die vorn- Katalysator befreite Lösung wurde angesäuert und das Lösungsmittel im Vakuum abgedampft. Das Hydrochlorid des normal-i, 3-Diphenyl-3-isobutylamino-propanols-(i) zeigte aus Alkohol-Äther einen Fp. = 205 bis 207°. j Die Ausbeute betrug 12 g.Example 3 11.5 g normal-i, 3-diphenyl-3-amilio-propanol- (i) were dissolved in 250 cc of methanol and 4.5 g of isobutyraldehyde and in the presence of the above-mentioned platinum-barium sulfate catalyst (ig Pt ) hydrogenated at 3.4 atmospheres and room temperature. The solution freed from the catalyst was acidified and the solvent was evaporated in vacuo. The hydrochloride of normal-i, 3-diphenyl-3-isobutylamino-propanols- (i) had a melting point = 205 ° to 207 ° from alcohol-ether. j The yield was 12 g.
Beispiel 4 5 g normal-i, 3-Diphenyl-3-benzalamino-propanol-(i) wurden in 300 ccm Methanol gelöst und in Gegenwart von =o g Platin-Bariumsulfat-Katalysator (i g Pt) bei 3,4 atü und Zimmertemperatur hydriert. Es wurde vom Katalysator abfiltriert, das Lösungsmittel bis auf 50 ccm im Vakuum abdestilliert, filtriert und durch Zugabe von :11 Wasser die Base gefällt. Das normal-_, 3-Dipheny1-3-benzylamino-propanol- (i.) zeigte nach dem Umlösen aus Ligroin einen Fp. = 112 bis i13°. -Das Hydrochlorid zeigte nach dem Umlösen aus Alkohol-Äther einen Fp. = 178 bis 179°.Example 4 5 g of normal-i, 3-diphenyl-3-benzalaminopropanol- (i) were dissolved in 300 cc of methanol and hydrogenated in the presence of the above-mentioned platinum-barium sulfate catalyst (ig Pt) at 3.4 atmospheres and room temperature . The catalyst was filtered off, the solvent was distilled off to 50 ccm in vacuo, filtered and the base was precipitated by adding: 11% of water. The normal-_, 3-Dipheny1-3-benzylamino-propanol- (i.) Showed after dissolving from ligroin a melting point = 112 to 13 °. After dissolving from alcohol-ether, the hydrochloride had a melting point = 178 ° to 179 °.
Beispiel 5 . =o g normal-i, 3-Diphenyl-3-isobutylamino-propanol-(i)-Hydrochlorid (dargestellt nach Beispie13) wurden allmählich in einer Suspension von =o g P C15 in =o ccm Chloroform- eingetragen. Nach 30 Minuten wurden noch weitere 4 ccm Chloroform und i g P C15 zugegeben. Nach einiger Zeit wurden Zoo ccm Äther hinzugefügt, worauf das 1, 3-Diphenyl-3-isobütylamino - i-chlor - propan - hydrochlorid ausfiel. Fp. = 187,5 bis 189°.Example 5. = above normal-i, 3-diphenyl-3-isobutylamino-propanol- (i) -hydrochloride (shown according to Example 13) were gradually added to a suspension of = above P C15 in = 0 ccm of chloroform. After 30 minutes, a further 4 cc of chloroform and ig P C15 were added. After a while, zoo cc of ether were added, whereupon the 1,3-diphenyl-3-isobutylamino-i-chloro-propane-hydrochloride precipitated. Mp = 187.5-189 °.
6 g 1, 3-Diphenyl-3-isobutylamino-i-chlor-propanhydrochlorid wurden in =5o ccm Wasser suspendiert und im Bombenrohr 7 Stunden auf =2o" erhitzt. Es wurde wie üblich aufgearbeitet, wobei nach dem Umlösen aus Alkohol-Äther das Hydrochlorid des iso-1, 3-Diphenyl-3-isopropylamino-propanols-(i) vom Fp. = 196 bis 197° erhalten wurde.6 g of 1,3-diphenyl-3-isobutylamino-i-chloro-propane hydrochloride were suspended in = 5o ccm of water and heated in a sealed tube to = 2o "for 7 hours. It was Worked up as usual, with the hydrochloride after dissolving from alcohol-ether of iso-1,3-diphenyl-3-isopropylamino-propanols- (i) with a melting point of 196 ° to 197 ° became.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH106A DE874916C (en) | 1949-10-15 | 1949-10-15 | Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH106A DE874916C (en) | 1949-10-15 | 1949-10-15 | Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE874916C true DE874916C (en) | 1953-04-27 |
Family
ID=7422237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DESCH106A Expired DE874916C (en) | 1949-10-15 | 1949-10-15 | Process for the preparation of diastereomeric N-substituted 1, 3-diphenyl-3-amino-propanolen- (1) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE874916C (en) |
-
1949
- 1949-10-15 DE DESCH106A patent/DE874916C/en not_active Expired
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