Ketene Acetals. XXIX. The Mechanism of the Reaction of Ketene Acetal with Various Halides

McElvain, S. M.; McShane, Herbert F.

doi:10.1021/ja01130a057

Cited by 19 publications

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“…Found: C,51.27;,5.90;N,21.32. Ethyl 3-Phenylorthopropionate. This compound was prepared according to the literature (McElvain and McShane, 1952) from ethyl hydrocinnamimidate hydrochloride (9.06 g, 0.043 mol). The crude product (5.36 g) was, however, not fractionated by distillation.…”

Section: Methodsmentioning

confidence: 99%

Aminoacyl derivatives of nucleosides, nucleotides, and polynucleotides. XXII. Substrate specificity of ribosomal peptidyltransferase. Effect of modification in the heterocyclic, carbohydrate and amino acid moiety of 2'(3')-O-L-phenylalanyladenosine

Zemlicka¹,

Chládek²,

Ringer³

et al. 1975

Biochemistry

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The chemical synthesis of 2'(3')-O-L-phenylalanyl derivatives of nebularine (Ld), 6-methoxynebularine (Ih), N6,N6-dimethyladenosine (Lk), 6-methylthionebularine (Lo), 8-bromoadenosine (Lr), tubercidin (Iu), and 3'-O-L-phenylalanyl derivatives of 1-(beta-D-arabinofuranosyl)cytosine (IIIg) and 9-(beta-D-arabinofuranosyl)adenine (IIIl) is described. 2'(3')-O-(3-Phenyl)propionyladenosine (Iv) was obtained by reaction of adenosine with ethyl 3-phenylorthopropionate and subsequent hydrolysis of the orthoester intermediate IV with formic acid. Compounds Id, Ih, Ik, Io, and Iu were active in the release of Ac-Phe from N-Ac-Phe-tRNA-poly(U)-70S ribosome complex: at 0.01 mM the release of Ac-Phe was 50-100% of that of A-Phe. At 1 mM, compounds Ir and IIIg released 30 and 25% of Ac-Phe relative to A-Phe whereas derivatives Iv and IIIl were virtually inactive. The results indicate the following conclusions regarding ribosomal peptidyltransferase activity of 2'(3')-O-aminoacyl nucleosides: (a) the presence of the 2'-hydroxy group in the ribo configuration is more important for a highly active substrate (A-Phe) than for one of moderate activity (C-Phe); (b) the heterocyclic (purine) residue is in the anti conformation although this requirement is not absolute; (c) the presence of the amino group of the aminoacyl moiety is required; (d) acceptor activity is dependent upon the substituent in the position 6 of the purine moiety.

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Section: Methodsmentioning

confidence: 99%

Aminoacyl derivatives of nucleosides, nucleotides, and polynucleotides. XXII. Substrate specificity of ribosomal peptidyltransferase. Effect of modification in the heterocyclic, carbohydrate and amino acid moiety of 2'(3')-O-L-phenylalanyladenosine

Zemlicka¹,

Chládek²,

Ringer³

et al. 1975

Biochemistry

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“…Ethyl DL-Orthophenylalaninate (4a) and 2,5-Dibenzyl-3,6diethoxy-2,5-dihydropyrazine (5). The procedure4 for preparation of amino acid ortho esters was extended to the phenylalanine derivative 4a.…”

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confidence: 99%

“…Further elution with chloroform (100 ml) gave iV-benzyloxycarbonyl-L-phenylalaninol (19,1.53 g, 23%), mp 92-92.5 °C (lit.17 JV-Benzyloxycarbonyl-L-phenylalaninal Dimethyl Acetal (17). Aldehyde 16 (0.4 g, 1.4 mmol) was added portionwise to a mixture of dimethylformamide dimethyl sulfate complex28 (0.31 g, 1.55 mmol) and anhydrous methanol (65 mg, 2 mmol) at room temperature with stirring which then continued for 2.5 h. The mixture was kept overnight, and the crystallized product was washed with petroleum ether and recrystallized from petroleum ether-ether (1:1) to give acetal 17 (0.28 g, 60%): mp 58-60 °C; [a]22D -8.4°(c 1.22, CHC13); ir (KBr) 3350 cm-1 (NH), 1690 (CO, urethane), 1550 (amide II band, urethane); NMR (CDC13) 7.25 and 7.16 (two s, 10, CeHB), 5.00 (s, 2, CH2 of benzyloxycarbonyl), 4.08 (m, 2, CH), 3.41 and 3.35 (two s, 6, OCH3), 2.85 (m, 2, CH2).…”

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confidence: 99%

Some transformations of DL-phenylalanine ortho esters and N-benzyloxycarbonyl-L-phenylalaninal

Zemlicka¹,

Murata²

1976

J. Org. Chem.

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Glycine ortho esters have found a wide use2 in the synthesis of glycyl derivatives of ribonucleosides,2a'b ribonucleotides,20 and ribooligonucleotides.2d_h The application of the ortho ester exchange method which provides the basis of the synthetic approach28 to the above mentioned compounds for amino acids other than glycine has been hampered for a long time by a lack of general method for the preparation of amino acid ortho esters.3

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Die Darstellung einiger Heterocyclen aus Acylketen‐Derivaten (Benzoxazole, Benzothiazole, Benzothiodiazine, Chinazolone). Über Keten‐Derivate, X

Stachel

1963

Archiv der Pharmazie

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Bei der Einwirkung von Ammoniak und seinen Deriva,ten auf Acylketen-acetale (I) entstehen Acylketen-0,N-acetale (111) oder -N,N-acetale *) 3). Die Umsetzung ist verstiindlich durch die Annahme, daD dabei zunachst aus den Komponenten Addukte des Typs I1 entstehen, die aber im allgemeinen nicht faDbar sind und sofort unter Alkoholabspaltung zerfallen. ,OR, 3 R-CO-CH,-C-OR /OR------+ R-CO--CH=C /OR R--CO-CH=C< - OR"R, 'NR, I I1 I11Verwendet man zu dieser Umsetzung Amine, die noch weitere reaktionsfahige Gruppen in geeigneter Stellung im Molekul enthalten, so kann sich an die Acylketen-0,N-acetal-Bildung eine Cyclisierung anschliel3en. Ringschlusse konnen ein-ma1 unter Beteiligung der Carbonylgruppe der Keten-Derivate (I oder 111) verlaufen; Beispiele dafiir wurden in der vorangegangenen Mitt.1) und fruher4) gegeben. Zum andern ist RingschluD unter Erhalt der Carbonylgruppe moglich, so daD man zu cyclischen Acylketen-Derivaten bzw. tautomeren Formen kommt. Dies sol1 im folgenden an einigen Beispielen gezeigt werden. Nach dem einleitend Gesagten war zu erwarten, da13 sich Benzoylketen-acetal (IV) mit o-Aminophenol zunachst zum 0,N-Acetal VI umsetzen wurde. Man erhalt als Reaktionsprodukt eine kristalline Verbindung, die durch ihre geringe Loslichkeit auffallt. Die Analyse zeigt, daD weder die erwartete Verbindung VI noch ihr Cyclisierungsprodukt VII vorliegen kann. Die Ergebnisse entsprechen dagegen der Zusammensetzung der Verbindung V. Es bleibt indes nachzuweisen, daD nicht etwa, VII mit 2 Molekeln ,,Kristall-xthanol" vorliegt. Die neue Verbindung 1aBt sich durch Erhitzen in Eisessig leicht in 2-Phenacylbenzoxazol (VII) iiberfiihren. Die Verbindung ist kurzlich von russischen Autorcn auf anderem Wege erhalten worden ; der im Referat wiedergegebene Schmp. stimmt 1) IX. Mitt.: H.-D. Stachel, Chem. Ber., im Druck. 2, H.-D. Stachel, Chem. Ber. 93, 1059 (1960). 3 ) H.-D. Stach,el, Arch. Pharmaz. 296, im Druck. 4) H.-D. 9tacheZ, Cheni. Ber. 95, 2172 (1962). Archiv 296. Band. Heft 5 22

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Ketene Acetals. XXIX. The Mechanism of the Reaction of Ketene Acetal with Various Halides

Cited by 19 publications

References 0 publications

Aminoacyl derivatives of nucleosides, nucleotides, and polynucleotides. XXII. Substrate specificity of ribosomal peptidyltransferase. Effect of modification in the heterocyclic, carbohydrate and amino acid moiety of 2'(3')-O-L-phenylalanyladenosine

Aminoacyl derivatives of nucleosides, nucleotides, and polynucleotides. XXII. Substrate specificity of ribosomal peptidyltransferase. Effect of modification in the heterocyclic, carbohydrate and amino acid moiety of 2'(3')-O-L-phenylalanyladenosine

Some transformations of DL-phenylalanine ortho esters and N-benzyloxycarbonyl-L-phenylalaninal

Die Darstellung einiger Heterocyclen aus Acylketen‐Derivaten (Benzoxazole, Benzothiazole, Benzothiodiazine, Chinazolone). Über Keten‐Derivate, X

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