Synthesis and properties of acetylenic derivatives

S. F. Vasilevsky Synthesis and properties of acetylenic derivatives of pyrazoles 2002AHC1... 

Vasilevsky, S.F., Tretyakov, E.V. and Elguero, J. (2002) Synthesis and properties of acetylenic derivatives of pyrazoles, in Advances in Heterocyclic Chemistry, vol. 82 (ed. A.R. Katritzky), Elsevier, New York-London, pp. 1-99. 

Acetylenecarboxylic esters, reactions with nitrogen-containing heterocycles, 23, 263 Acetylenic derivatives of pyrazoles, synthesis and properties of, 82, 1 Acetylenic esters, synthesis of heterocycles through nucleophilic additions to, 19,297 Acid-catalyzed polymerization of pyrroles and indoles, 2, 287... 

Synthesis and properties of fluoropyrroles and their analogues 12S2115. Synthesis of pyrroles from acetylene derivatives 13MI21. 

H. Goto, X. Dai, T. Ueoka, K. Akagi, Synthesis and properties of polymers from monosubstituted acetylene derivatives bearing ferroelectric liquid crystalline groups, Macromolecules, 37, 4783-4793 (2004). 

The synthesis and properties of optically active thiet 1,1-dioxides have been reviewed. The generation of sulphenes from p-nitrophenyl sulpho-nates is claimed to have advantages in the preparation of 3-amino-4-arylthiet 1,1-dioxides from acetylenic amines, principally in the avcndance of the presence of triethylamine hydrochloride, which is believed to cause isomerization of the thiet derivative. Several other thiet dioxides have been obtained by reaction of a sulphene with an acetylenic amine. - They are claimed to be anti-inflammatory agents. The formaticm of a thiet 1,1-dioxide from acetylenic sulphine (167) and an enamine has been noted previously. A number of substituted thiet dioxides have been prepared by addition of sulphene to enamines followed by a Cope elimination of the amine. These compounds were tested for analgesic activity but none was found. Thiet 1,1-dioxide (123) is obtained from... 

S. F. Vasilevsky and E. V. Tetryakov (Novosibirsk, Russia), together with J. Elguero (Madrid, Spain), have summarized the synthesis, chemical and spectroscopic properties, and biological activity of acetylenic derivatives of pyrazoles, a field which has shown explosive growth in the past few years. 

Artali, R. et al.. Synthesis, x-ray crystal structure and biological properties of acetylenic flavone derivatives, Farmaco, 58, 875, 2003. 

The state of research on the two classes of acetylenic compounds described in this article, the cyclo[ ]carbons and tetraethynylethene derivatives, differs drastically. The synthesis of bulk quantities of a cyclocarbon remains a fascinating challenge in view of the expected instability of these compounds. These compounds would represent a fourth allotropic form of carbon, in addition to diamond, graphite, and the fullerenes. The full spectral characterization of macroscopic quantities of cyclo-C should provide a unique experimental calibration for the power of theoretical predictions dealing with the electronic and structural properties of conjugated n-chromophores of substantial size and number of heavy atoms. We believe that access to bulk cyclocarbon quantities will eventually be accomplished by controlled thermal or photochemical cycloreversion reactions of structurally defined, stable precursor molecules similar to those described in this review. 

Cycloadditions. The dienophilic properties of ( )-phenyl-sulfonyl-2-trimethylsilylethylene allow the preparation of adducts with reactive dienes such as cyclopentadiene and anthracene. The adducts are smoothly converted to alkenes upon treatment with fluoride ion, establishing the equivalence of the title reagent to acetylene. Alkylation of the a-sulfonyl carbanion can precede the elimination such that synthetic equivalents to HC CH, HC CD, and RC CH are available. The use of this reagent is highlighted by the synthesis of several functionalized dibenzobarrelenes (eq 1). The equivalency to DC CD and RC=CD is illustrated by the preparation of deuterated derivatives. 

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