SOME NEW HYDROXY-URETHANS AND CHROMO-ISOMERIC SILVER SALTS OF THEIR ACYL DERIVATIVES. III<sup>1</sup>

Oesper, Ralph E.; Broker, Walter

doi:10.1021/ja01687a027

J. Am. Chem. Soc.

1925

DOI: 10.1021/ja01687a027

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SOME NEW HYDROXY-URETHANS AND CHROMO-ISOMERIC SILVER SALTS OF THEIR ACYL DERIVATIVES. III¹

Ralph E. Oesper¹,

Walter Broker²

Abstract: In our hands Bertram's procedure for the preparation of esters of aconityl anil26 did not lead to the isolation of the products sought. However, when, after esterification is complete, the alcohol is distilled in a vacuum at a low temperature, and the residue washed first with a little ether and then with water, recrystallization of the residue from benzene gives a pure product. A comparison of the methyl and ethyl esters made in this way with our products established their identity.

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Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Chapuis

Laumer

Marty

1997

Helvetica Chimica Acta

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Comparative semi‐empirical PM3 and ab initio STO 3‐21G calculations on bornanesultam‐derived dienophiles containing the structural moiety SO2NC(O)X(α) = Y(β) suggest that, among the conformers of low energy, the thermodynamically less stable SO2/C(O)‐syn,C(O)/X=Y‐s‐cis conformation is also reactive in terms of LUMO level and atomic coefficients. Furthermore, the X(α), Y(β) LUMO atomic coefficients are nonequivalent with respect to both X(α)‐re and X(α)‐si faces, and thus have, depending on the conformation, a matching or mismatching stereoelectronic influence with the co‐operative steric effect. This dissymmetry is believed to result from the generalized anemone effect of the N lone pair, itself anomerically stabilized and directed, in the absence of crucial steric interactions, by the pseudo‐axial anti‐periplanar SO bond. Five N‐acyl‐substituted bornanesultams arc discussed ((–)‐1a: N‐acryloyl, XCH, YCH2; (–)‐1b; N‐crotonoyl, XCH, YCHMe; (–)‐1c: N‐N′‐fumaroyl, XCH, YCH(C(O)‐bornanesultam); 2a: N‐glyoxyloyl, XCH, YO; 2b: N‐acylnitroso, XN, YO). In this context, differences with toluenesultams 3 are pointed out. A previous report on N‐(acylnitroso)‐bornanesultam 2b is revisited, and the diastereoselectivity observed is shown to result from thermodynamic control.

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Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Chapuis

Laumer

Marty

1997

Helvetica Chimica Acta

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Studien Zum Ablauf Der Substitution XII. Umlagerung Und Thermischer Zerfall Acylierter Hydroxylamine

Horner

Steppan

1957

Justus Liebigs Ann. Chem.

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Eingegangen am 22. Februar 1957 0,N-Diacyl-N-aryl-hydroxylamine lagern sich im Temperaturbereich um 1 SO", abhangig von der Polaritat des Acylrestes und des Reaktionsmediums, mit Ausbeuten bis zu 100 in 0,N-diacylierte o-Aminophenole um. Bei 180-190" zerfallen die 0,N-Diacyl-N-aryl-hydroxylamine zu 20-30 radikalisch.Die Bildung der isolierten Sekundarprodukte wird durch Annahme einer primaren Homolyse der N-0-Bindung leicht verstandlich. Mit der Vorstellung eines radikalischen Primaraktes steht auch die Initiator-Eigenschaft der zerfal-Ienden 0,N-Diacyl-N-aryl-hydroxylamine bei der Polymerisation von Acrylnitril in u bereinstimmung. -Derivate des Hydroxylamins konnen in maRigen Ausbeuten durch Einwirkung tert. Phosphine desoxydiert werden.In Fortsetzung friiherer Untersuchungen iiber Dibenzoylperoxyd 3) und Azodiben -zoyl4) befaBt sich die vorliegende Arbeit mit der Chemie acylierter Hydroxylarnine. Diese Verbindungstypen besitzen als gemeinsames Merkmal energiereiche Bindungen :Auch die Stammverbindungen (H202 und NH20H) teilen eine Reihe von Eigenschaften: Sie konnen z. B. als Oxydations-und Reduktionsmittel wirken und, in Kombination mit geeigneten Elektronenspendern, in Radikale gespalten werden. Das chemische Verhalten der Diacylperoxyde wird durch die Neigung der O-O-Bindung zur Homolyse bestimmt 5). Nur in besonderen Fallen und in stark polaren Medien kann dieser Bereich auch heterolytisch verandert werden 6 ) . Die bei den 1) XI. Mitteilung: Liebigs Ann. Chem. 602, 135 (1957). 1957 Urnlagerung und thermischer Zerfall acylierter Hydroxylamine 25 Diacylperoxyden durch geeignete Substituenten (OCH3 und NO2 in 4bzw. #-Stellung des Benzolkerns) in der 0-0-Briicke erzeugte Polaritat ist bei N-aryl-bzw. alkyl-substituierten 0,N-Diacyl-hydroxylarninen (auch bei gleichem Acylrest) ein Charakteristikum der N-0-Bindung. Daher wird das chemische Geschehen bei einer Reihe diacylierter Hydroxylamine durch polar zu deutende Reaktionsablaufe beherrscht und homolytische Veranderungen tretenzumindest im Temperaturgebiet urn 150" -in den Hintergrund. ZERSETZUNG VON O,N-DIACYL-N-PHENYL-HYDROXYLAMINEN R'CON(R)OCO"' 1M TEMPERATURBEREICH UM 150' Uber die therniische Zersetzung von N-Alkyl-bzw. Aryl-diacyl-hydroxylarninen finden sich in der Literatur nur sparliche Angaben. E. BAMBERGER, K. BLASKOPF und A. LANDAU 7) berichten, daB 0,N-Dibenzoyl-N-phenyl-hydroxylamin (I) bei starkem Erhitzen lebhaft verpufft. E. MULLER und E. LINDEMANN s) stellen dagegen fest, dal3 I bei mehrstundigem Kochen in Xylol bzw. Cum01 unverandert bleibt. J. SCHEI-BER und P. BRANDT 9 ) machen in einer FuBnote auf die Dissertation von W WORT-MANN (Leipzig 1903) aufmerksam, in welcher die Umlagerung von 0,N-Dibenzoyl-N-(cr-naphty1)-hydroxylamin (X) in O,N-Dibenzoyl-[l-arnino-naphthol-(2)] (XI) beschrieben wird. Ein Reagenzglas-Versuch lehrt folgendes: 0,N-Dibenzoyl-N-phenyl-hydroxylatnin (1) verandert sich ab 130" merklich und bildet bei 150" eine rote Schmelze, welche noch erhebliche Mengen eines hoher schmelzenden Stoffes enthalt. Bei 200" verpufft I heft...

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Total Synthesis of Petrobactin and Its Homologues as Potential Growth Stimuli for Marinobacter hydrocarbonoclasticus, an Oil-Degrading Bacteria

Wang

et al. 2004

J. Org. Chem.

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A modular synthesis was developed to access petrobactin, a catechol-containing siderophore isolated from Marinobacter hydrocarbonoclasticus. A range of petrobactin homologues with differing dihydroxybenzamide motifs and in one case an increased number of carbons in the polyamine backbone were also synthesized. As such, these systems represent new isomeric probes to study iron transport properties in M. hydrocarbonoclasticus. The synthesis of petrobactin and its homologues and the first biological study of how these agents influence the growth of Mycobacterhydrocarbonoclasticus are reported. New synthetic methods were developed to overcome issues (imide formation) encountered in earlier syntheses. Both the (1)H and (13)C NMR of petrobactin were consistent with the recently revised structure showing that petrobactin in fact contains a 3,4-dihydroxybenzene motif rather than a 2,3-dihydroxybenzene motif. The preliminary biological studies suggested that using the native petrobactin 1b for M. hydrocarbonoclasticus-specific growth stimulation may be a poor strategy for oil-spill cleanup.

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SOME NEW HYDROXY-URETHANS AND CHROMO-ISOMERIC SILVER SALTS OF THEIR ACYL DERIVATIVES. III¹

Cited by 4 publications

References 0 publications

Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Studien Zum Ablauf Der Substitution XII. Umlagerung Und Thermischer Zerfall Acylierter Hydroxylamine

Total Synthesis of Petrobactin and Its Homologues as Potential Growth Stimuli for Marinobacter hydrocarbonoclasticus, an Oil-Degrading Bacteria

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SOME NEW HYDROXY-URETHANS AND CHROMO-ISOMERIC SILVER SALTS OF THEIR ACYL DERIVATIVES. III1

Cited by 4 publications

References 0 publications

Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Origin of diastereoselectivity in the thermal [4+2] cycloadditions of dienophiles derived from Oppolzer's sultams: Steric vs. Stereoelectronic Influences

Studien Zum Ablauf Der Substitution XII. Umlagerung Und Thermischer Zerfall Acylierter Hydroxylamine

Total Synthesis of Petrobactin and Its Homologues as Potential Growth Stimuli for Marinobacter hydrocarbonoclasticus, an Oil-Degrading Bacteria

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SOME NEW HYDROXY-URETHANS AND CHROMO-ISOMERIC SILVER SALTS OF THEIR ACYL DERIVATIVES. III¹