Fortschritte in der Chemie der Oxazolinone-(5)

Steglich, Wölfgang

doi:10.1007/bfb0050745

Cited by 42 publications

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References 125 publications

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“…(vgl. dazu[6]) durch Nachbargruppenbeteiligung der zweiten Amidfunktion und Abspaltung von Dimethylaminhydrochlorid eine naheliegende Hypothese; beim Arbeiten in nichtnucleophilen Losungsmitteln gelingt es tatsachlich, das postulierte Zwischenprodukt zu isolieren. So wird z.B.…”

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Selektive Umfunktionalisierung der terminalen Amidgruppe offenkettiger Polyamide via 2‐Oxazolin‐5‐one als Zwischenstufen. Vorläufige Mitteilung

Obrecht

Heimgartner

1981

Helvetica Chimica Acta

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Selective Modification of the Terminal Amide Group of Linear Polyamides via 2-0xazolin-5onesas Intermediates SummaryTreatment of aqueous or alcoholic solutions of diamides of type 2 with HC1 leads to the formation of amide-acids and amide-esters of type 3 (Scheme I and Table). It has been shown, that 2-oxazolin-5-ones of type 4 are intermediates of this selective transformation of the disubstituted terminal amide group. The selectivity of the transformation is demonstrated by the reaction sequence shown in These results show the usefulness of the dimethylamide group as a protecting group for carboxylic acids for example in the peptide synthesis.Wie schon vor langerer Zeit berichtet worden ist [I], reagiert 3-Dimethylamino-2,2-dimethy1-2 H-azirin (1) mit Carbonsauren schon unterhalb Raumtemperatur zu Diamiden des Typs 2 (Schemal). Die glatte und nahezu quantitative Bildung von 2 wird via das Primaraddukt a und dessen Umwandlung zum Zwitterion b formuliert.In Zusammenhang mit der Verwendung von Aminoazirinen des Typs 1 als Bausteine fur die Synthese von Heterocyclen (vgl. [2] [3]) stellte sich das Problem, die terminale Amidgruppierung in Molekeln des Typs 2 selektiv in eine Ester-bzw. Thioesterfunktion unter Bildung von 3 uberzufiihren.Beim Einleiten von getrocknetem HC1-Gas in eine athanolische Losung des aus 1 und Benzoesaure erhaltenen N,N-Dimethyl-2-benzoylamino-2-methyl-1)

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Selektive Umfunktionalisierung der terminalen Amidgruppe offenkettiger Polyamide via 2‐Oxazolin‐5‐one als Zwischenstufen. Vorläufige Mitteilung

Obrecht

Heimgartner

1981

Helvetica Chimica Acta

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“…In the course of synthetic approaches to peptide alkaloid derivatives (I), a conjugate addition of a phenol to the isobutylidene-2-oxazolin-5-one (isobutylidene azlactone) 1 was attempted (2). When N-(N'-carbobenzoxyphenylalany1)-tyramine and 1 were allowed to react in acetonitrile solution containing some triethylamine, instead of the desired addition product there was isolated a colorless solid, C,,H,,NO,, m.p.…”

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The Oxygenation of 2-Oxazolin-5-ones: A New Synthesis of Imides

Bisson¹,

Yeats²,

Warnhoff³

1972

Can. J. Chem.

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In the presence of mild base such as triethylamine, the two 4-alkylidene-2-phenyI-2-oxazolin-5-ones, 1 and 8, rapidly absorb oxygen at room temperature with the loss of carbon dioxide and the formation of the imides 4 and 10. The imide probably arises by decomposition of a hydroperoxide resulting from the reaction of oxygen and the anion of the oxazolinone. A hydroperoxide intermediate will also account for the origin of the acidic by-products 6 a and l l a . The 2-methyl-2-oxazolin-5-one 14 did not react with oxygen at room temperature; at 60" some reaction occurred but no imide was formed.Lorsque mis en presence d'une base faible comme la triethylamine, les deux alkylidkne-4 phenyl-2 oxazolin-5-ones, I et 8 absorbent rapidement de I'oxygkne a la temperature ambiante pour ensuite liberer du gaz carbonique et conduire aux imides 4 et 10. La formation d'un imide peut &tre attribuee a la decomposition d'un hydroperoxyde issu de la reaction entre I'oxygtne et I'anion de I'oxazolinone. L'intermediaire hydroperoxyde peut aussi expliquer I'origine des produits secondaires acidiques Q et llcr. La methyl-2-oxazolin-5-one 14 ne reagit pas avec I'oxygine a la temperature ambiante: toutefois a 60" une transformation fut observee mais non la formation d'un imide.

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Organometallic Complexes of Iridium, Palladium, Chromium and Iron from 2-Phenyl-5(4H)-oxazolones − Organometallic Labelled Dipeptides

Bauer

Prem

Polborn

et al. 1998

Eur. J. Inorg. Chem.

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Reactions of 2‐phenyl‐4‐R‐5(4H)‐oxazolones (R = Me, CH2Ph, CHMeEt) with [(η5‐C5Me5)IrCl2]2 afforded the cyclometallated complexes (η5‐C5Me5)(Cl)Ir(L) (1−3) [L = 2‐phenyl‐4‐R‐5(4H)‐oxazolone(C‐o,N)]. 2‐Phenyl‐5(4H)‐oxazolone reacts with [(η5‐C5Me5)IrCl2]2 and palladium(II) acetate to give complexes with a C‐o,N‐bridging oxazolone [(η5‐C5Me5)(Cl)Ir]2(μ‐Cl)(μ‐L‐H+) (4) and Pd3(μ‐ac)5(μ‐L‐H+) (5). 2‐Phenyloxazolone anions were added to the π ligands of [(η5‐C6H7)Fe(CO)3]+ and [(η7‐C7H7)Cr(CO)3]+ to give the adducts 6−11. Dipeptide derivatives 12−18 were obtained by reaction of 1, 2 and by reaction of the adduct 6 from [(η5‐C6H7)Fe(CO)3]+; and the anion of 2‐phenyloxazolone with α‐amino acid esters. These reactions may be used for the labelling of peptides. Saponification of 15−18 yields the organometallic substituted peptide acids 19−22. Their dianions (deprotonation of COOH and peptide amide) were used as ligands towards (Ph3P)2PtCl2 to yield the bimetallic complexes 23−25. The structures of 4, 5, 9 and 10 were determined by X‐ray diffraction.

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Fortschritte in der Chemie der Oxazolinone-(5)

Cited by 42 publications

References 125 publications

Selektive Umfunktionalisierung der terminalen Amidgruppe offenkettiger Polyamide via 2‐Oxazolin‐5‐one als Zwischenstufen. Vorläufige Mitteilung

Selektive Umfunktionalisierung der terminalen Amidgruppe offenkettiger Polyamide via 2‐Oxazolin‐5‐one als Zwischenstufen. Vorläufige Mitteilung

The Oxygenation of 2-Oxazolin-5-ones: A New Synthesis of Imides

Organometallic Complexes of Iridium, Palladium, Chromium and Iron from 2-Phenyl-5(4H)-oxazolones − Organometallic Labelled Dipeptides

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