Here are some fragments from:
HJ Roth, A Brandau.
Ueber die Aminolyse von Styroloxyd: Darstellung von Phenylaminoaethanolen. Archiv der Pharmazie 292 (1959) 761-777.
The
uebertranssetzung is by SWiM. He picked some interesting notes from the article, i.e. this is NOT the complete text.
1908 - M Tiffeneau and E Fourneau report quantitive conversion of styreneoxide with dimethylamine to 1-phenyl-2-dimethylamino-ethanol [2].
1945 - W S Emerson obtained the same product by reacting styreneoxyde with NH3, but in 18% yield. Better yields were obtained (up to 80%) when working with primary and secondary amines to obtain the N-substituted compounds [3].
1950 - W B Wheatley used iPr-amine and obtained 1-phenyl-2-isopropylamino-ethanol in a 71% yield [4].
1951 - W Beck converted methyl benzylamine to 1-phenyl-2-methylbenzylamino-ethanol with 83% yield [5].
1952 - C L Browne and R E Lutz converted styreneoxyde with benzylamine and obtained two isomeres [6].
1954 - J A Castro converted styreneoxyde with NH3 and reports two isomeres as well: 1-phenyl-2-amino-1-ethanol and 1-phenyl-1-amino-2-ethanol (3.6:1 ratio) [7].
1956 - U Hoffman, H H Kuhn and H Brugger describe in a patent (Anmeinung D 19814
) the synthesis of several aminoalcohols from styreneoxyde using NH3.
1957 - W Ziegenbein and W Franke obtained 1-phenyl-2-N-ethanol-1-lactame by reacting styreneoxyde with lactame [9].
When the aminolysis is applied by reacting styreneoxyde with hexamethylenetetramine (HMTA) and with purine bases, only 1-phenyl-2-amino-1-ethanol derivatives are formed. When NH3 ir benzylamine are used, isomeres are detected:
Ph-CH---CH2 + HN---R --- 1 ---> Ph---CH---CH2---NR2
\ / | |
O R OH
--- 2 ---> Ph---CH---CH2---OH
|
NR2
We are interested to know if the aminolysis of styreneoxydes always yields two isomeres. We tested a large number of amines to form our conclusion:
1. NH3
2. primary amines: MeNH2, EtNH2, ethanolamine, gamma-methoxypropylamine, benzylamine, alfa-phenylethylamine, 1-phenyl-2-amine-ethanol, aniline, p-toluidine.
3. secondary amines: Me2NH, Et2NH, diethanolamine, pyrrolidine, piperidine, morpholine, piperazine, 1-ephedrine.
4. tertiary amines: Me3N, Et3N, triethanolamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, HMTA.
5. acidic amides: acetamide, benzamide.
6. N-substituted acidic amides: methylacetamide, ethylacetamide, methylbenzamide, ethylbenzamide.
7. dicarbonic acid imides: succinimide, phtalimide.
8. purine: theobromine, theophylline.
-R = Ph-CH-CH2-
|
OH
Am ratio St:Am solvent product yield
NH3 6:1 H2O/EtOH R-NH2 28.5%
also 7.3% of the isomere
NH3 3:1 " R-NH2 3.7%
also 11.2% R2NH and 59.5% R3N
MeNH2 1:3 H2O/MeOH R-NHMe 7.3%
MeNH2 2:1 " R-NHMe 82.0%
EtNH2 1:3 EtOH/H2O R-NHEt 36.0%
EtNH2 2:1 " R-NHEt 9.6%
also 78.5% R2-NHEt
Me2NH 1:1 EtOH R-NMe2 82.0%
Et2NH 1:1 EtOH R-NEt2 80.0%
HMTA 1:1 chloroform R-NH2 29.0%
also 0.54% of an intermediary product.
Reaction details not given; the text contains some further data on temperature and reaction times.
References:
2. M Tiffeneau, E Fourneau. C R 146 (1908) 697
3. W S Emerson. J Am Chem Soc 67 (1945) 516
4. W B Wheatley e.a. J Am Chem Soc 72 (1950) 1658
5. W Beck e.a. J Org Chem 16 (1951) 1434
6. C L Browne, R E Lutz. J Org Chem 17 (1952) 1187
7. J A Castro e.a. J Org Chem 19 (1954) 1444
Note: 1-phenyl-2-amino-1-ethanol. Waaw... must give you an enourmous psychedelic high... Obviously, SWiM is looking a bit further than that . Aminolysis of phenylpropenyl oxides? Styrene analogues that can be converted to PEAs?
Ave Hive, synthetisandi te salutant!