The SPECTRA OF SATURATED AND Α–β UNSATURATED SIX-MEMBERED LACTAMS

Edwards, O. E.; Singh, Tara

doi:10.1139/v54-088

Can. J. Chem.

1954

DOI: 10.1139/v54-088

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The SPECTRA OF SATURATED AND Α–β UNSATURATED SIX-MEMBERED LACTAMS

O. E. Edwards¹,

Tara Singh²

Abstract: The ~~ltraviolet and infrared spectra of some saturated and ur~satr~rated sixmembered lactarns are described, and the unusual features in the 3p and Gp regions discussed. A corllparison is made of these spectra with those previor~sly ascribed to a-p n s a tr a t e d lactams.

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Cited by 27 publications

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“…The C = O stretching vibration in saturated N-alkyl six membered lactams gives rise to an absorption band near 1640 cm.-I (8). T h e position of this band for four pyrrolidoiles is indicated in Table I.…”

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Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Edwards¹,

Chaput²,

Clarke³

et al. 1954

Can. J. Chem.

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Ethyl a-acetosy-2-pyridineacetate ant1 ethyl a-bromo-2-pyridineacetate have been prepared, and the latter converted in three steps to 1,2-dicarbethoxy-3-0x0-octahydropyrrocoline. The main carbonyl hand of simple saturated five membered lactams in the infrared is observed to lie close t o 1700 cm-I.The methyleile group of ethyl 2-pyridineacetate is of comparable activity to that of ethyl acetoacetate. For example, a useful anion can be obtained by reaction with sodiuin or potassiuin (1, 4). Further parallel between the reactivities of the two compouilds has now been found in the ease of bromination and acetoxylation. Like acetoacetic ester (6), 2-pyridineacetic esters react rapidly with a molar equivaleilt of bromine a t 5OC. in carbon disulphide solution to give a-bromo esters, and react a t room temperature with lead tetraacetate in benzene to give the a-acetoxy compound. In contrast, the methylene group of malonic esters does not react a t a useful rate with lead tetraacetate in benzene until the solution is heated to around 100' (6).The synthesis of octahydropyrrocolines with reactive substituents has been achieved by Clemo and co-workers (2, 3, 4) and by Lions and Willison (10). The work of Diels and co-workers (5, and earlier papers) has led to pyrrocolines substituted with carboxyls, which presumably could be reduced to the corresponding octahydro derivatives. By reaction of ethyl a-bromo-2-pyridineacetate with the anion from ethyl malonate, reduction of the product, and cyclization, 1,2-dicarbethoxy-3-0x0-octah~~dropyrrocoline 111 has now been obtained. The malonic hydrogen and carboxyl groups in this compound are of potential value for building additional rings on the five membered ring.The reactions used in preparing and characterizing the various products are shown in the flowsheet. The mixture obtained when the bromo compound reacted with the ~nalonic anion contained some ethyl 1,1,2,2-ethanetetracarboxylate, probably arising from ethyl bromomalonate formed by bromine exchange. This could be partly removed by distillation under high vacuum, but the desired product I could not be distilled without considerable decomposition. By chron~atography on neutral alumina, however, I could be freed from the ethanetetracarboxylic ester, unchanged malonic ester, and colored impurities.I proved to be a very weak base (pKA around 2.4 in 50% aqueous methanol). A somewhat low basicity (PI< 3.6) has been observed for a,a-di-(2-pyridy1)-1 Alanuscript received M a y 7 , 1954.

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mentioning

confidence: 99%

Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Edwards¹,

Chaput²,

Clarke³

et al. 1954

Can. J. Chem.

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Die Basen C₂₁H₂₀N₂O₃ und C₂₁H₂₀N₂O₄ aus Isostrychninsäure; ihre Darstellung, Umsetzungen und Struktur als β‐Methylen‐indolenin‐Derivate

Teuber

Fahrbach

1958

Chem. Ber.

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Durch die Einwirkung von Persäuren oder Kalium‐nitrosodisulfonat auf Isostrychninsäure entstehen neben anderen Produkten die Basen C21H20N2O3 und C21H20N2O4, von denen die letztere phenolischen Charakter besitzt. Beide Basen sind Fünfringlactone und enthalten eine β‐Methylen‐indolenin‐Struktur. Bei der katalytischen Hydrierung gehen sie in Di‐und Tetrahydroderivate über, die vollaromatische Indole sind. In den Lactonbasen sind Ring IV und V des Strychningerüsts unter Öffnung der 7.16‐Bindung zu einem neungliedrigen Ring verschmolzen. – Die Reaktionen der Basen werden beschrieben, ihre Spektren und Bildungsweise diskutiert. Auf die Bedeutung der Indoliden‐methan‐Struktur für die Chemie der Indolalkaloide sowie für präparative Zwecke wird hingewiesen.

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2.2‐Dimethyl‐chinuclidon‐(6), ein mesomeriefreies Säureamid

Pracejus¹

1959

Chem. Ber.

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PRACElUSJahrg. 92 : Reinigung Uber das Kupfersalz ohne Destillation. Ausb. 31 % d. Th. CIS HI&^ (262.3) Ber. C 68.68 H 6.92 Gef. C 69.02 H 7.23 Kupfersalz: Blaue Nadeln aus Athanol, Schmp. 128". [C15H1704]2C~ (586.1) Ber. C 61.47 H 5.85 Gef. C 61.6 H 5.8 b) Umsetzung mit Phosgen 0.05 Mol I gibt man zu einer Lbsung von 10 g Phosgen in 40 ccm Toluol und laDt unter Kiihlung im Kaltegemisch 16 ccm F'yridin zutropfen. Man ruhrt noch 2 Stdn. im Eisbad und gieDt am nachsten Morgen auf Eis/Salzsaure. Nach dem Trocknen uber CaClz treibt man das Toluol i. Vak. ab, preDt den Ruckstand auf Ton und kristallisiert urn. Weitere Reinigung durch Hochvakuumsublimation. Cyclischer Kohlensaureester des C-Phenylacetyl-acetessigesters (Illa): Gelbliche BIattchen aus Benzol, Schmp. 108", Ausb. 29 % d. Th. Cl5Hl405 (274.3) Ber. C 65.58 H 5.15 Gef. C 65.68 H 5.2 Cyclischer Kohlensaureester des Cf a-NaphthyIacetyl/-acetessigesters (IIIb) : Gelbe Nadeln aus Benzol/Petrolather, Schmp. 125", Ausb. 5 1 % d. Th. l m UV-Licht gelbgriine Fluoremru. C19Hl605 (324.3) Ber. C 70.36 H 4.97 Gef. C 70.71 H 5.06 c) Totalhydrolyse: Eine Probe der Verbindung It16 wurde in kalte 2n NaOH eingetragen und nach vollstandiger Losung angesiiuert. Aus der tither. Lbsung des abgeschiedenen 61s fie1 beim Schutteln mit waOr. Kupferacetatlbsung der Kupferkomplex des C-[a-Naphthylacetyll-acetessigesters (I b) aus. Ausb. praktisch quantitat. C-Ij3-Phenyl-propionyll-acetessigester ( I d ) 2.2-Dimethyl-chinuclidon-(6)wird durch eine 12stufige Synthese in racemischer und optisch aktiver Form dargestellt. Dieses ,,Lactam" ist aus sterischen Griinden keiner Saureamidmesomerie fahig. Die sich daraus ergebenden Eigenschaften ~ Basizitat, Reaktivitat und spektrales Verhaltenwerden untersucht und diskutiert. Bicyclische Lactame, deren N-Atom den ,,Kopf" eines niedergliedrigen, symmetrischen Briickenringsystems (z. B. vom Chinuclidin-Typ) bildet, sollten praktisch frei von Saureamidmesomerie sein. Die Orbitale des Carbonyl-x-Elektronenpaares und des einsamen Elektronenpaares am Stickstoff zeigen namlich in solchen Verbindungen wegen der starr pyramidalen Konfiguration des N-Atoms ein Minimum an Uber-1) Vgl. d a m B. M. WEPSTER in ,,W. Klyne und P. B. D. de la Mare, Progress in Stereo-2) Collect. Trav. chim.

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The SPECTRA OF SATURATED AND Α–β UNSATURATED SIX-MEMBERED LACTAMS

Abstract: The ~~ltraviolet and infrared spectra of some saturated and ur~satr~rated sixmembered lactarns are described, and the unusual features in the 3p and Gp regions discussed. A corllparison is made of these spectra with those previor~sly ascribed to a-p n s a tr a t e d lactams.

Cited by 27 publications

References 10 publications

Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Die Basen C₂₁H₂₀N₂O₃ und C₂₁H₂₀N₂O₄ aus Isostrychninsäure; ihre Darstellung, Umsetzungen und Struktur als β‐Methylen‐indolenin‐Derivate

2.2‐Dimethyl‐chinuclidon‐(6), ein mesomeriefreies Säureamid

Contact Info

Product

Resources

About

The SPECTRA OF SATURATED AND Α–β UNSATURATED SIX-MEMBERED LACTAMS

Abstract: The ~~ltraviolet and infrared spectra of some saturated and ur~satr~rated sixmembered lactarns are described, and the unusual features in the 3p and Gp regions discussed. A corllparison is made of these spectra with those previor~sly ascribed to a-p ~~n s a t~~r a t e d lactams.

Cited by 27 publications

References 10 publications

Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Some Reactions of Ethyl 2-Pyridineacetate: 1,2-Dicarbethoxy-3-Oxo-Octahydropyrrocoline

Die Basen C21H20N2O3 und C21H20N2O4 aus Isostrychninsäure; ihre Darstellung, Umsetzungen und Struktur als β‐Methylen‐indolenin‐Derivate

2.2‐Dimethyl‐chinuclidon‐(6), ein mesomeriefreies Säureamid

Contact Info

Product

Resources

About

Abstract: The ~~ltraviolet and infrared spectra of some saturated and ur~satr~rated sixmembered lactarns are described, and the unusual features in the 3p and Gp regions discussed. A corllparison is made of these spectra with those previor~sly ascribed to a-p n s a tr a t e d lactams.

Die Basen C₂₁H₂₀N₂O₃ und C₂₁H₂₀N₂O₄ aus Isostrychninsäure; ihre Darstellung, Umsetzungen und Struktur als β‐Methylen‐indolenin‐Derivate