DE442413C - Process for the preparation of aliphatic secondary amino alcohols - Google Patents
Process for the preparation of aliphatic secondary amino alcoholsInfo
- Publication number
- DE442413C DE442413C DEC36437D DEC0036437D DE442413C DE 442413 C DE442413 C DE 442413C DE C36437 D DEC36437 D DE C36437D DE C0036437 D DEC0036437 D DE C0036437D DE 442413 C DE442413 C DE 442413C
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- amino alcohols
- secondary amino
- aliphatic secondary
- water
- 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
- C07C215/04—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 saturated
- C07C215/06—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 saturated and acyclic
- C07C215/08—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 saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
Description
Verfahren zur Darstellung von aliphatischen sekundären Aminoalkoholen. Zur Darstellung von sekundären Aminoalkoholen stehen verschiedene Verfahren zur Verfügung, z. B. der Austausch des Halogens in Äthylenhalogenhydrin durch Monoalkylderivate, sowie die Aufspaltung von Äthylenoxyd durch Ammoniakderivate. Beide Verfahren haben den Nachteil, daß gleichzeitig dreifach und zweifach substituierte Amine entstehen. Irn Falle der Verwendung von Äthylenoxyd und Methylamin erhält man bei der Aufarbeitung des Reaktionsgemisches trotz Anwendung eines großen Methylaminüberschusses neben Monoäthylolmethylamin in der Hauptsache Bisäthylolniethylamin.Process for the preparation of aliphatic secondary amino alcohols. Various methods are available for the preparation of secondary amino alcohols Available, e.g. B. the replacement of the halogen in ethylene halohydrin by monoalkyl derivatives, as well as the splitting of ethylene oxide by ammonia derivatives. Both procedures have the disadvantage that triply and doubly substituted amines are formed at the same time. In the case of the use of ethylene oxide and methylamine, one obtains in the work-up of the reaction mixture despite the use of a large excess of methylamine Monoäthylolmethylamin mainly bisäthylolniethylamin.
Auch der Weg, das A-Oxazolidon durch Alkali aufzuspalten, der bei arornatischen Aminen gute Ergebnisse zeitigt, versagt in der aliphatischen Reihe, da gänzlicher Zerfall des Moleküls eintritt. Es wurde nun gefunden, daß die Behandlung der N-substituierten Urethane der allgemeinen Formel: R.NH-CO.O.CH,.CH,.CI (R=Alk-yl oder Aralkyl) mit Alkalien in überraschend guten Ausbeuten zu den gewünschten Aminoalkoholen führt. Dies ist um so überraschender, als man als Zwischenprodukt der Reaktion das erwähnte /,t-Oxazolidon annehmen muß, gemäß der folgenden Gleichung: Beispiel i.Also the way, the A-oxazolidone splitting by alkali, which produces good results with aromatic amines, fails in the aliphatic series because the molecule breaks down completely. It has now been found that the treatment of the N-substituted urethanes of the general formula: R.NH-CO.O.CH, .CH, .CI (R = alk-yl or aralkyl) with alkalis gives the desired yields in surprisingly good yields Amino alcohols leads. This is all the more surprising since one must assume the mentioned /, t-oxazolidone as an intermediate product of the reaction, according to the following equation: Example i.
i Mol. Methylcarbamidsäure-ß-chloräthylester (erhalten durch Umsetzen von Chlorarneisensäure-ß-chloräthylester in benzolischer Methylaminlösung, unter 15 mm Druck bei iio bis 112' siedend) wird mit 4 M01. Natronlauge in möglichst konzentrierter Lösung vereinigt. Nach kurzer Zeit tritt unter lebhafter Erwärmung eine Reaktion ein, die durch Ste - hen über Nacht oder zweistündiges Erhitzen auf etwa go0 beendet wird. Das entstandene Monoäthyloln-iethylamin wird von dem gebildeten Natriunicarbonat und Natrii -imchlorid durch Destillation befreit und gegebenenfalls nochmal fraktioniert. -Die Verbindung ist in Wasser, Alkohol und Äther leicht löslich und siedet bei 1590 unter 750 mm Druck. Das Pikrat hat einen Schmelzpunkt von 148 bis 15o0. Die Ausbeute beträgt 6o bis 8o Prozent.1 mol. Methylcarbamic acid ß-chloroethyl ester (obtained by reacting chloroarneic acid ß-chloroethyl ester in benzene methylamine solution, boiling under 15 mm pressure at 10 to 112 ') is mixed with 4 M01. Sodium hydroxide solution combined in a solution that is as concentrated as possible. After a short time a reaction occurs with vigorous warming caused by Ste - hen is completed overnight or two-hour heating to about GO0. The resulting monoethylolnethylamine is freed from the sodium bicarbonate and sodium chloride formed by distillation and, if necessary, fractionated again. -The compound is easily soluble in water, alcohol and ether and boils at 1590 under 750 mm pressure. The picrate has a melting point of 148 to 150. The yield is 6o to 8o percent.
B e i s p i e 1 - :2.B ice p y 1 -:. 2
8 g Äthylcarbamidsäure-ß-chloräthylester (farbloses, wasserunlösliches, dickes 01, das bei iio bis iii0 unter 12 mm Druck siedet und in analoger Weise wie der Ausgangsstoff nach Beispiel i dargestellt wird) löst man mit 6,5 g Natriumhydroxyd in 8 g Wasser und 5 g Alkohol. Man erhält etwa 4 g Äthylaminoäthanol vom Siedepunkt 169 bis 170. Das Pikrat schmilzt bei 12,5 bis 1261 (vgl. Berichte, Band 31 [1898] Seite 1074). 8 g Äthylcarbamidsäure-ß-chloräthylester (colorless, water-insoluble, fat 01, which boils at iio to iii0 under 12 mm pressure and is shown i in an analogous manner to the starting material of Example) is dissolved with 6.5 g of sodium hydroxide in 8 g of water and 5 g of alcohol. About 4 g of ethylaminoethanol with a boiling point of 169 to 170 are obtained. The picrate melts at 12.5 to 1261 (cf. Reports, Volume 31 [1898], page 1074).
Beispiel 3. Isoamylcarbamidsäure - ß - chloräthylester (KP", io6', analog dem Äthylhornologen hergestellt, im Aussehen und Verhalten diesem ähnlich) wird mit Alkali in Gegenwart von Wasser und Alkohol zerlegt und liefert Isoamylaminoäthanol vom KP" io5 bis io6'. Sein Pikrat schmilzt bei 94 bis 95' (vgl-Annalen, Band 315, Seite 1:21).Example 3. Isoamylcarbamic acid - ß - chloroethyl ester (KP ", io6 ', produced analogously to the ethyl hornologue, similar in appearance and behavior to this) is decomposed with alkali in the presence of water and alcohol and gives isoamylaminoethanol from KP" io5 to io6'. His picrate melts at 94 to 95 ' (see Annalen, Volume 315, page 1:21).
Beispiel 4.Example 4.
Ausgehend vom Benzylearbamidsäure-ßchloräthylester (KP.,s 105', KP,5 218 bis :2201) erhält man bei analoger Behandlung das Benzylaminoäthanol vom KP" 148 bis 149', KP"o 1050. Das wasserfreie Pikrat schmilzt bei 134 bis 1351, das Pikrat mit i Mol. Kristallwasser bei io4 bis io6'.Starting from benzylearbamic acid ßchlorethylester (KP., S 105 ', KP, 5 218 to: 2201) an analogous treatment gives the benzylaminoethanol from KP " 148 to 149 ', KP "o 1050. The anhydrous picrate melts at 134 to 1351, the picrate with i mole of water of crystallization at io4 to io6 '.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC36437D DE442413C (en) | 1925-03-25 | 1925-03-25 | Process for the preparation of aliphatic secondary amino alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC36437D DE442413C (en) | 1925-03-25 | 1925-03-25 | Process for the preparation of aliphatic secondary amino alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE442413C true DE442413C (en) | 1927-03-30 |
Family
ID=7022275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC36437D Expired DE442413C (en) | 1925-03-25 | 1925-03-25 | Process for the preparation of aliphatic secondary amino alcohols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE442413C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2617825A (en) * | 1948-06-04 | 1952-11-11 | Givaudan Corp | Process for preparation of salts of 1-amino-2-haloethanes |
| US3168525A (en) * | 1960-04-25 | 1965-02-02 | S B Penick And Company | Process for making oxazolidones |
| US3215690A (en) * | 1963-04-23 | 1965-11-02 | Ralph G Haber | Process for the production of derivatives of oxazolidones and oxazinones |
| US4272455A (en) * | 1979-12-26 | 1981-06-09 | The Dow Chemical Company | Production of monoalkyleneglycols, monoalkanolamines and alkylenediamine |
-
1925
- 1925-03-25 DE DEC36437D patent/DE442413C/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2617825A (en) * | 1948-06-04 | 1952-11-11 | Givaudan Corp | Process for preparation of salts of 1-amino-2-haloethanes |
| US3168525A (en) * | 1960-04-25 | 1965-02-02 | S B Penick And Company | Process for making oxazolidones |
| US3215690A (en) * | 1963-04-23 | 1965-11-02 | Ralph G Haber | Process for the production of derivatives of oxazolidones and oxazinones |
| US4272455A (en) * | 1979-12-26 | 1981-06-09 | The Dow Chemical Company | Production of monoalkyleneglycols, monoalkanolamines and alkylenediamine |
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