Vermischte Notizen über die Aldehyd‐Verbindungen von Oxy‐aminen und über partielle Acylierung dieser Amine

Abstract

Die Substanz wurcle jedoch trotz mehrfacher Variierung der Versuchsbedingungen nur bei diesem einen Versuch in der angegebenen, winzigen Ausbeute erhalten, so dal3 eine Uberfuhrung derselben in die gesuchte (3-p-nlethoxyphenyl-B-oxy-a-aniino-propionsiiure nieht moglich war. 506. Max Bergmann, Reinhold Ulpte und Francisco C ama ch 0 : Vermischte Notieen iiber die Aldehyd-Verbindungen von Oxy-aminen und Gber partielle Acylierung dieser Amine. (Eingegangcn am 15. Juni 1922 ) [,4us d Iiaiscr-~~illiclm-Iiistilulcn fiir I.edcr-Forschung und fiir Fasers tofl-Chemie.]Verbindungen, welche neben Hydroxyl die Aminogruppe enthaltcn, sind in der Natur recht verbreitet. Ihr Auftreten unter den lebenswichtigen Stoffenwir erinnern an das Scrin, Tyrosin, die Qxy-glutaminsBure der Proteine oder an den Amino-Bthylalkohol und das Sphingosinweist auf die Bedeutung einer solchen liombination von bnsischer und alkoholischer Natur hin. Die Methoden fur die experimentelle Bearbeitung derartiger Verbindungstypen sind aber noch recht dcs Ausbaues bedurftig.Wir haben verschieclentlich die A l d e h y d -V e r b i n d u n g e n von Osy-basen mit Nutzen fiir wechselnde Zwecke verwenden konnen, vor allem zur R e i n i g u n g d e r O x y -a m i n e und fur ihre p a r t i e 11 e A c y 1 i e r u n g und teilen hier einige derartigc Beohachtungen mit.3.) M. 23, S17 u. 550 [1904]; Al. 26, 931 u. 936 j 190.51; B. 49, 250 i191GJ; vcrgl. dazu I<. 1IelJ und U i b r i g , B. 45, 1974 [1915].

The Oxazolidines.

“…The observation of M. Bergmann, Ulpts, and Camacho (23) that an aminoalcohol gives with an excess of formaldehyde not the oxazolidine but the X-methyl derivative can be explained in an analogous manner, although the authors assumed that the formation of the oxazolidine is reversed and the aminoalcohol is methylated directly. The same explanation applies to the observation of Heinzelmann, Kolloff, and Hunter (61) that substituted 2-amino-1 -indanols are converted by formaldehyde not into oxazolidines, but directly into the 2V,iV-dimethyl derivatives of the starting materials.…”

“…The condensation with carbonyl compounds takes place with both primary and secondary |3-hydroxyethylamines; obviously, tertiary amines are incapable of entering into reaction. Indeed, the use of formaldehyde has been (23) suggested occasionally as a means of separating tertiary from secondary /3-hydroxyethylamines; only the latter react to form oxazolidines, which are separated.…”

“…It gives a product which may be 3-carbopropoxyoxazolidine (I), although its discoverers had originally assigned to it the formula (II) of N-carbopropoxy-N-methylaminoacetaldehyde. An The comparative ease with which different aminoalcohols and different car- Ci.......... Ethanolamine (7,8,9,10,11,13,14,18,28,35,75,76,85,87,88,89,108) Cl.......... N-Methylethanolamine (14,IS,19,53,74,75) l-Amino-2-propanoI (34) 2-Amino-l-propanol (58) 1-Amino-2,3-propanediol (20,83) 2-Amino-l, 3-propanediol (100) l-Amino-3-chloro-2-hydroxypropane (22,23,103) C........... Diethanolamine (19,56) jV-Ethvlethanolamine (38,66) 2-Amino-2-methvl-l-propanol (58,105) 2-Amino-l-butanol (8, 58, 88s) 2-Amino-2-methvl-l, 3-propanediol Aminotrimethy lolmethane (1,34,59,106) (1, 91, 92, 106) Ci.......... l-Amino-3-methyl-2-butanol…”

Chemoselective Polyamidation of 3,3′-Dihydroxybenzidine

“…The resonance for amide carbonyl of benzanilide (11) is observed at 165.8 ppm. On the other hand, phenyl benzoate (12) shows the resonance of ester carbonyl at 164.9 ppm. Furthermore, the resonance for ester carbonyl of p-nitrophenylester (13) is shifted to upper field compared to that for ester carbonyl of p-methoxyphenylester (14).…”

“…Compound 15 should not be obtained because of intramolecular rearrangement of compound 15 to the more thermodynamically stable isomer, compound 1. 12 Actually, we cannot observe the formation of 15 for all reactions. The basicity of base strongly affected the ratio of products 1 and 4.…”