Search results for "Intramolecular reaction"
showing 10 items of 23 documents
Ab initio molecular dynamics study of overtone excitations in formic acid and its water complex
2018
In this article, we present results from ab initio molecular dynamics simulation of overtone excitation in formic acid monomer and its water complex in the gas phase. For the monomer, a conformation change is observed employing both OH and CH vibrational excitations, which supports experimental findings. In the formic acid–water complex, interconversion also takes place, but it proceeds via hydrogen exchange rather than via intramolecular reaction. Simulations raise a question on effect of quantum and matrix effects to the results. Also, a brief test of different computation methods was done on the system. peerReviewed
Photochemie elektronenreicher 1,3‐Distyrylbenzole
1988
Die 1,3-Distyrylbenzole 3 mit bis zu sieben Alkoxygruppen werden der oxidativen Photocyclisierung unterworfen. Bei der Bildung der Produkte 6, 7 und 8 konnen als Konkurrenz- bzw. Folgeprozesse die Abspaltung von Methanol (3bb 7bb, 3bf 7bf) und die Chinonoxidation (3cf 8) auftreten. Die eigensensiblisierte Erzeugung von Singulettsauerstoff kann bei 6bf zur Endoperoxidbildung fuhren (6bf 11). Photochemistry of Electron-Rich 1,3-Distyrylbenzenes The 1,3-distyrylbenzenes 3, containing up to seven alkoxy groups, are subjected to the oxidative photocyclization. Elimination of methanol (3bb 7bb, 3bf 7bf) and quinone oxidation can occur as competitive or consecutive reactons in the formation of the…
Heterocyclic photorearrangements. Photoinduced rearrangement of 3-styryl-1,2,4-oxadiazoles
1990
The photochemical behaviour of 3-styryl-5-phenyl-(5-methyl)-1,2,4-oxadiazoles in methanol at 254 nm has been investigated. A photoinduced rearrangement to the quinoline system has been pointed out and explained as proceeding through an initial photolysis of the ring ON bond, followed by a six membered ring closure reaction involving the styryl moiety.
Diels-Alder Reactions of (1H-Indol-3-yl)-enacetamides and -endiacetamides: A Selective Access to Acetylamino-Functionalized [b]Annelated Indoles and …
1991
Diels-Alder reactions of the (1H-indol-3-yl)-enacetamides and -endiacetamides 1a–d with some carbodieno-philes and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione give rise to the novel amino-functionalized carbazole; 4–6 and 8 (Scheme 3). Ethenetetracarbonitrile reacts with 1b to furnish the Michael-type adduct 7 (Scheme 3). Structural aspects of the starting materials 1, which exhibit above all 3-vinyl-1H-indole reactivity, are discussed with regard to the prediction of a Diels-Alder process.
Polycondensed nitrogen heterocycles. Part 23. Pyrrolo[3,2-c]cinnolines by a japp-klingemann type reaction
1990
Pyrrolo[3,2-c]cinnoline derivatives were obtained by an unusual Japp-Klingemann reaction involving an intramolecular azadehalogenation on the pyrrole nucleus. Such an azadehalogenation represents the first example of Japp-Klingemann reaction in which the extrusion of positive chlorine ion is verified.
A Synthetic Model for the [4+2] Cycloaddition in the Biosynthesis of the Brevianamides, Paraherquamides, and Related Compounds
2000
Abstract The reactivity of model systems for the proposed [4+2] cycloaddition in the biosynthesis of the brevianamides, paraherquamides, and marcfortines is explored. The model for the intermolecular reaction reveals that the cycloaddition takes place under mild conditions only if activated, very reactive dienophiles are used. When relatively unreactive dienophiles such as cyclopentene and cyclohexene are used, harsh reaction conditions and/or a Lewis acid catalyst are necessary for the reaction. In contrast, the model for the intramolecular reaction demonstrates that the cycloaddition takes place within a few hours at room temperature, even in the absence of a Lewis acid catalyst. Conclusi…
Polyhydroxylated indolizidine alkaloids-synthesis of dideoxycastanospermine
2009
The key transformation developed in this work is the anti-Kishi selective dihydroxylation, which proceeds by way of intramolecular participation of the nitrogen protecting group to furnish the desired stereochemistry required for castanospermine like structures. In this paper, we completed a first syn-thesis of a novel dideoxycastanospermine 6. Peer reviewed
Ring size control in diorganotin sulphides by intramolecular SnN coordination
1992
Abstract The synthesis of intramolecularly coordinated organotin sulphides, [(Me2N CH2CH2CH2)2SnS]n (1) and [Me2NCH2CH2CH2Sn(Ph)S]n (2), is described. Compounds 1 and 2 are dimers in chloroform solution (n = 2). Compound 1 forms a centrosymmetric dimer with a planar rectangular Sn2S2 four-membered ring in its centre. The tin atoms show a distorted trans-cis-cis octahedral coordination by 2C, 2N and 2S. The tin-nitrogen distances are 2.810(3) and 3.158(5) A. Compound 1 can be regarded as a model substance for nucleophilic attack at penta-coordinate tin centres. Although the degree of intramolecular coordination of nitrogen to tin is temperature dependent, the four-membered Sn2Sn2 ring remain…
Attempted synthesis of spongidines by a radical cascade terminating onto a pyridine ring.
2007
Mn(III)-based oxidative free-radical cyclization of an unsaturated beta-keto ester containing a pyridine ring as radical trap has been studied. This intramolecular reaction of nucleophilic carbon-centered radicals with the pyridine ring leads to the stereospecific construction of a tetracyclic compound in which five chiral centers are created in one pot. This synthetic approach represents the first attempt to prepare the anti-inflammatory pyridinium alkaloids spongidine A, B, and D.
Die intramolekulare, radikalische kopf-schwanzbzw. Kopf-Kopf-addition von Phenylen-, Naphthylen- und Biphenylenbis(methacrylat)en
1977
1,2-, 1,3- und 1,4-Phenylenbis(methacrylat) (1a), (1b) und (1c), 2,3- und 1,6-Naphthylenbis(methacrylat) (2a) und (2b) sowie 2,2′-Biphenylenbis(methacrylat) (3) wurden nach einer bekannten Vorschrift dargestellt. Setzt man stark verdunnte Losungen dieser phenolischen Bisester in siedendem Benzol einem grosen Uberschus an 2-Cyano-2-propylradikalen R. (aus AIBN) aus, so entstehen neben wenigen olig-viskosen Produkten hauptsachlich kristallisierbare Verbindungen. Sie entstanden aus der intramolekularen Addition der zwei Methacrylatgruppen und Anlagerung von zwei Radikalen R · je Molekel. 1c gab nur eine derartige Verbindung, die nach den Elementaranlysen, der rel. mol. Masse, spektroskopischen…