Search results for "Acetylene"
showing 10 items of 143 documents
Cycloaddition Reactions with Vinyl Heterocycles
1995
Publisher Summary The Diels-Alder reaction is one of the most common and elegant methods for the construction of six-membered rings. Although the number of Diels-Alder cycloadditions with open-chain and alicyclic dienes is very large, the number of examples with aromatic heterocyclic compounds is relatively small. The introduction of a vinyl group as a substituent onto a heterocycle increases the number of possible reactions. This new possibility, however attractive for synthetic purposes, is successful only with π-excessive five-membered heterocyclic derivatives with a few exceptions. The chapter discusses the reactions of vinyl heterocycles with carbodienophiles. The endocyclic and exo-en…
ChemInform Abstract: Synthesis and Chemical Reactivity of 5-Methoxy-2-vinyl-4-azaindoles.
2010
Abstract 2-Vinyl-4-azaindoles are less reactive with dienophiles than 2-vinylindoles. 5-Methoxy-2-vinyl-4-azaindole 2a and its 1-methyl derivative 2a reacts with N-phenylmaleimide to yield cycloadducts only under vigorous conditions. 2b produces a cycloadduct with dimethyl acetylenedicarboxylate, while 2a yields a Michael-type adduct. Reactions with more reactive dienophiles gave only polymeric products.
ChemInform Abstract: Carbazole Synthesis via an in situ Trapping Strategy with Indolyl Enol Ethers.
2010
Indolyl enol ethers, generated from the alkoxy(indolyl)carbenium tetra- fluoroborates (1) by treatment with sodium hydride, can be trapped with dimethyl acetylenedicarboxylate or N-phenylmaleimide to furnish the se- lectively functionalized carbazoles (3), (4), (5), (9), (10), and (13). In addition, the biaryl derivatives (6) and (11) are produced by a ring- opening reaction of the primarily formed Diels-Alder adduct. In the case of the biaryl derivative (6), an X-ray crystal structure analysis yields valuable information on constitutions and configurations in the biaryl series. The phenomenon of atropisomerism is discussed for this compound
ChemInform Abstract: Reaction of 2,2′-Bis(N-methylindolyl) with Dimethyl Acetylenedicarboxylate and Thermally and Photochemically Induced Cyclization…
2010
2,2′-Bis(N-methylindolyl) 1 reacts with dimethyl acetylenedicarboxylate to furnish the 3-dimethyl maleoyl-substituted 2,2′-bisindolyl 2. Compound 2 cyclizes under aluminum trichloride catalysis according to a polar process to give a cyclopenta[2,1-b:3,4-b′]diindole derivative 4. Reaction of compound 4 with benzyl-amine yields the spiro derivative 5. Photochemically-induced 1,6-electrocyclization of compound 2 gives rise to the indolo[2,3-a]carbazole 6 directly, which is readily transformed to the pyrrolo-annelated carbazole 7 by treatment with benzylamine.
Reaction of 2,2′-bis(N-methylindolyl) with dimethyl acetylenedicarboxylate and thermally- and photochemically-induced cyclizations of the product
1995
2,2′-Bis(N-methylindolyl) 1 reacts with dimethyl acetylenedicarboxylate to furnish the 3-dimethyl maleoyl-substituted 2,2′-bisindolyl 2. Compound 2 cyclizes under aluminum trichloride catalysis according to a polar process to give a cyclopenta[2,1-b:3,4-b′]diindole derivative 4. Reaction of compound 4 with benzyl-amine yields the spiro derivative 5. Photochemically-induced 1,6-electrocyclization of compound 2 gives rise to the indolo[2,3-a]carbazole 6 directly, which is readily transformed to the pyrrolo-annelated carbazole 7 by treatment with benzylamine.
Cycloaddition reactions of 2-vinylthiophen
1985
Abstract Cycloaddition reactions between 2-vinylthiophen and the dienophiles maleic anhydride, dimethyl acetylenedicarboxylate,' methyl propiolate, and methyl acrylate, are reported. Products include simple benzo[b]thiophen carboxylates (6, 13, 17) and reduced derivatives (3, 4, 18). The acetylenic dienophiles also gave a dihydrobenzthienyl-acrylate (16) or -fumarate (11), and the dithienylcyclohexene esters (7) and (14).
The reaction betweentriazolobenzopyridinium and triazolothiazolium ylides with dimethyl acetylenedicarboxylate
1998
Abstract The reaction of some [1,2,3]triazolo[1,5- a ]quinolinium 1,2 , [1,2,3]triazolo[5,1- a ]isoquinolinium 3,4 and [1,2,3]triazolo[5,1- b ]thiazolium 5,6 ylides with dimethyl acetylenedicarboxylate is described. Compounds as dimethyl pyrrolo[1,2- a ]quinoline-1,2-dicarboxylate 19 , dimethyl pyrrolo[2,1- a ]isoquinoline-2,3-dicarboxylate 20 , 1,1-dicyano-2,3-dimethoxycarbonyl-1 H -pyrido[1,2- a ]quinoline 24 , 4,4-dicyano-2,3-dimethoxycarbonyl-4 H -pyrido[2,1- a ]isoquinoline 25 , and 7-methyl-5,6-dimethoxy-carbonylpyrrolo[2,1- a ]thiazole 14b , are formed.
Toward an Understanding of the Molecular Mechanism of the Reaction between 1-Methylpyrrole and Dimethyl Acetylenedicarboxylate. An ab Initio Study
1998
The molecular mechanism for the reaction between 1-methylpyrrole and dimethyl acetylenedicarboxylate (DMAD) has been studied using ab initio methods. Two alternative reaction pathways have been considered, both of which correspond to stepwise processes with initial, rate-determining formation of a common zwitterionic intermediate. This intermediate is formed by nucleophilic attack of the pyrrole ring to the carbon−carbon triple bond of DMAD. Closure of this intermediate (pathway A) affords a [4 + 2] cycloadduct, whereas intramolecular proton transfer (pathway B) affords a Michael adduct. The much larger potential energy barrier of the second step in pathway B relative to pathway A is respon…
Theoretical study on the mechanism of the domino reactions of tertiary α-cyano-enamines and dimethyl acetylenedicarboxylate
2001
Abstract The mechanisms of the domino reaction between dimethyl acetylenedicarboxylate, 1 , and 2-( N , N -dimethylamino)acrylonitrile, 2 , and these in presence of acrylonitrile have been theoretically studied using ab initio methods. These domino reactions comprise several pericyclic-type reactions. The geometrical and electronic analysis of the HF/6-31G ∗ transition structures and intermediates allows characterizing the processes that take place along these domino reactions. B3LYP/6-31G ∗ energetic results are in agreement with the experimental outcomes.
Theoretical Study on the Molecular Mechanism of the Domino Cycloadditions between Dimethyl Acetylenedicarboxylate and Naphthaleno- and Anthracenofura…
2001
AM1, B3LYP/6-31G//AM1, and B3LYP/6-31G computational studies were performed to select the reaction pathway controlling the reactions between dimethyl acetylenedicarboxylate (DMAD) and two furanophanes, naphthalenofuranophane and anthracenofuranophane. For these domino reactions, several pathways have been characterized on the potential energy surface corresponding to two consecutive cycloadditions. The first step corresponds to a [4 + 2] intermolecular cycloaddition of DMAD with the furan ring or with the naphthalene or anthracene ring of both furanophane systems to yield an oxabicyclo[2.2.1]heptadiene or a bicyclo[2.2.2]octadiene intermediate, respectively. The second step corresponds to […