Aminoalkohole, XXIII. Die Reaktion alicyclischer 1.2‐Aminoalkohole mit Oxalsäureestern

Drefahl, Günther; Hartmann, M.; Skurk, Axel

doi:10.1002/cber.19660990413

Chem. Ber.

1966

DOI: 10.1002/cber.19660990413

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Aminoalkohole, XXIII. Die Reaktion alicyclischer 1.2‐Aminoalkohole mit Oxalsäureestern

Günther Drefahl¹,

M. Hartmann²,

Axel Skurk³

Abstract: Die zu Oxamiden, Oxamidsaureestern und Morpholin-dionem(2.3) fuhrenden Reaktionen einiger diastereomerer 2-Amino-cycloalkanole und ihrer N-Methylderivate mit Oxalsaureestern werden beschrieben.Bei der Umsetzung von trans-2-Amino-cyclohexanol mit aquivalenten Mengen Oxalsaure-diathylester erhielten Ried und Draisbachz) N.N'-Bis-[trans-2-hydroxy-cyclohexyll-oxamid (7b). Fiihrt man die Reaktion mit iiberschiissigem Oxalester durch, so bildet sich statt dessen der Oxamidsiiureester Zb, der erwartungsgemaB im IR-Sp… Show more

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Cited by 4 publications

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“…I Ioctadiene-exo-4-syn-8-diol. In accord with these assignments only intractable mixtures were obtained when 2a was treated with either phosgene or diethyl oxalate (12 …”

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confidence: 79%

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Dobson¹,

Davis²,

Hartung³

1968

Can. J. Chem.

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Treatment of the SJJII-epoxyaniide 3 with either aninioniuni hydroxide or sodium hydride gives 10,lldihydro-miti-1 l-hydroxy-lO,5-(iniinometl1ano)-5H-dibenzo[a,cl]cyclol1epten-l3-one (In). This compound is rcadily converted to the SJ~II-epimer l c by oxidation to 10 and subsequent hydrogenation. The ketone l b reacts with Grignard reagents to give the tertiary alcohols lk,l which undergo hydrogenolysis to give the 11-substituted lactains lq,r. Reduction of the lactams with lithiuiii aluniinium hydride gives the corresponding aniines.Canadian Journal of Chemistry, 46, 3391 (1968) We have recently described the preparation of a number of l0,ll-dihydro-l0,5-(epoxymethano)-5H-dibenzo[a,d]cyclohepten-13-ones (1, 2). The present paper outlines a general route to 11-substituted-l0,ll-dihydro-l0,5-(iminometha110)-5H-dibenzo[a,d]cycloheptene derivatives 1 and 2. A different approach has been used by other workers (3-6) to prepare other derivatives and the ring system has been shown to occur naturally in the alkaloids amurensine, amurensinine, and roemfrine (7,8).We have previously found that the synepoxyamide 3 reacts with secondary amines to give anti-1 1-dialkylaminolactones. In attempts to prepare the unsubstituted anti-11-aminolactone 4a both the syn-epoxyamide 3 and the broinolactone 40 were treated with ammonium hydroxide at 140". The product, obtained in 70% yield in both cases, was not the expected lactone but the anti-1 1-hydroxylactam la. Oxidation of l a gave the ketolactam 10 which regenerated l a upon reduction with sodium borohydride. In contrast, catalytic hydrogenation of 10 gave a mixture of 20 % l a and 80 "/,f the syn-hydroxylactam Ic. This hydrogenation parallels that of the ketolactone 4c which gives the syn-hydroxylactone 4d as the major product (2). Reduction of the two epimers l a and l c with lithium aluminium hydride in dimethoxyethane gave the epimeric aminoalcohols 2a and 2c respectively. Other solvents (see Experimental) were markedly inferior for these reductions in accordance with experience in the preparation of 8-hydroxy-5-phenylbenzomorphan derivatives (9). The infrared (i.r.) hydroxyl absorptions of 2a and 2c were concentration-dependent, and concentration-independent respectively, indicating that 2a was the anti-epimer and that 2c was the syn-epimer (10). These assignments were confirmed by the reaction of the syn-aminoalcohol 2c with phosgene. The product was the cyclic carbamate 5, the structure of which was fully supported by its analytical and spectral properties. The geometry of 2a and 2c, as shown by inspection of molecular models, indicates that only 2c can form 5. Cristol and Bly (1 1) have cited an analogous cyclic carbonate formation as a structure proof of dibenzobicyclo [3.2. I Ioctadiene-exo-4-syn-8-diol. In accord with these assignments only intractable mixtures were obtained when 2a was treated with either phosgene or diethyl oxalate (12). Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.245.55.244 on 05/10/18For personal use only.

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“…I Ioctadiene-exo-4-syn-8-diol. In accord with these assignments only intractable mixtures were obtained when 2a was treated with either phosgene or diethyl oxalate (12 …”

mentioning

confidence: 79%

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Dobson¹,

Davis²,

Hartung³

1968

Can. J. Chem.

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“…Complete hydrolysis of the oxamide (-3) occurred on reaction with alkali. Under acetylating conditions only ring fission took place to give N-oxalyl derivatives (11,13,14,(16)(17)(18)(19).…”

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confidence: 99%

Di‐ und Polyaminozucker, XXIV¹⁾ Synthese und Reaktionen der 2,3‐Diamino‐2,3‐didesoxy‐2,3‐N‐oxalyl‐D‐glucose

1981

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Bei der Umsetzung von Benzyl-2,3-diamino-4,6-O-benzyliden-2,3-didesoxy-a-~glucopyranosid (3) mit Oxalstiure-diethylester entstand das cyclische 2,3-0xamid 4, aus dern sich durch Entblockierung die Titelverbindung 9 herstellen lie8. Durch alkalische Hydrolyse konnte der Oxalylrest leicht vollstandig entfernt werden (-3). wahrend unter verschiedenen Acetylierungsbedingungen Ringspaltung zu N-Oxalylderivaten (11, 13, 14, 16-19) erfolgte. Di-and Polyamino Sugars, XXIV') Synthesis and Reactions of 2.3-Diamino-2,3-dideoxy-2,3-N-oxaiyi-wgiucoseUmsetzungen von 3 mit Oxalylchlorid oder Malonylchlorid in hoher Verdilnnung analog der Darstellung von makrocyclischen Diamiden6) schlugen fehl. Bei der Reaktion von 3 in reinem Chem. Ber. 114(1981) 0 Verlag Chemie, GmbH, D-6940 Weinheim, 1981 oo09-2940/81/0404-1306 f 02.50/0 Diund Polyaminozucker. XXlV 1307 Oxalstiure-diethylester bei Raumtemp. bildete sich Uber mehrere im Chromatogramm sichtbare Zwischenprodukte eine dlhnnschichtchromatographisch fast einheitliche Verbindung, die sich aber auch bei schonendster Aufarbeitung weitgehend zersetzte. Nach spektroskopischen Daten konnte es sich nicht urn ein cyclibiertes Produkt handeln. OCH? NHAc NHZ 3 I 2 / I W NHR R: COCHzCOOCzH, 5 I -Das gesuchte Cyclisierungsprodukt 4 entstand in geringer Menge bei kurzzeitigem ErwLrmen') von 3 in Oxalsilure-diethylester, in hoher Ausbeute bei Verwendung von Dimethyl formamid als LOsungsmittel unter Zusatz von katalytischen Mengen Kaliumferf-butylat '.'). Die spektroskopischen Eigenschaften dieser Substanz entsprachen den fiir das cydische Oxamid 4 erwarteten. Das IR-Spektrum zeigte die Amid I-Bande gegenilber offenkettigen SLureamiden zu hoheren Wellenzahlen verschoben in ubereinstimmung mit Literat~rangaben~). Im Massenspektrum erschien der Molekiilpeak in ubereinstimmung mit der erwarteten Molmasse bei m/e = 410. Die Bildung eines dimeren Produkte~'-'~) war demnach ausgeschlossen. Das 'H-NMR-Spektrum zeigte das 1-H-Signal bei 6 = 5.09. Wilhrend in [DJDMSO keine Aufspaltung dieses Signals zu beobachten war, betrug die Kopplungskonstante in (D,]Pyridin 3 Hz. Auf Grund dieser geringen Kopplung wurde auf eine cis-axiaVLquatoriale Konfiguration zwischen 2-H und 1-H geschlossen, da durch den 4.6-Benzylidenrest eine Umlagerung in die 'C4-Konformation auszuschlieaen war. Demzufolge m a t e sich das neue Ringsystem in ei-Chem. Ber. 114(1981)

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Aminoalkohole, XXIV. Notiz über 4‐Methyl‐ und 4‐Cyclohexyl‐morpholin‐dion‐(2.3)

Drefahl¹,

Hartmann²,

Skurk³

1966

Chem. Ber.

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Aminoalkohole, XXIII. Die Reaktion alicyclischer 1.2‐Aminoalkohole mit Oxalsäureestern

Cited by 4 publications

References 3 publications

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Di‐ und Polyaminozucker, XXIV¹⁾ Synthese und Reaktionen der 2,3‐Diamino‐2,3‐didesoxy‐2,3‐N‐oxalyl‐D‐glucose

Aminoalkohole, XXIV. Notiz über 4‐Methyl‐ und 4‐Cyclohexyl‐morpholin‐dion‐(2.3)

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Aminoalkohole, XXIII. Die Reaktion alicyclischer 1.2‐Aminoalkohole mit Oxalsäureestern

Cited by 4 publications

References 3 publications

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Transannular reactions in the dibenzo[a,d]cycloheptene series. III. Preparation of 11-substituted-10,11-dihydro-10,5-(iminomethano)-5H-dibenzo[a,d]cycloheptenes

Di‐ und Polyaminozucker, XXIV1) Synthese und Reaktionen der 2,3‐Diamino‐2,3‐didesoxy‐2,3‐N‐oxalyl‐D‐glucose

Aminoalkohole, XXIV. Notiz über 4‐Methyl‐ und 4‐Cyclohexyl‐morpholin‐dion‐(2.3)

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Di‐ und Polyaminozucker, XXIV¹⁾ Synthese und Reaktionen der 2,3‐Diamino‐2,3‐didesoxy‐2,3‐N‐oxalyl‐D‐glucose