Reaction of dithiomalonic acid dianilide with substituted acetylenic ketones

The reaction of dithiomalonic acid dianilide with 1-benzoyl(2-thienyl, 2-furoyl)-2-phenylacetylenes in glacial acetic acid in the presence of equimolar amount of perchloric acid under heating (90–115°C) was used to prepare 6-anilino-2-(acylmethyl)-2-phenyl-4-(phenylimino)-4H-1,3-dithiinium perchlorates in good yields.     

Reaction of methyl propiolate with thiosemicarbazones

Methyl propiolate reacts with thiosemicarbazones in methanol in the presence of triethylamine to give 2-benzylidene(thenylidene, or furfurlidene)azino-3H-1,3-thiazin-4-ones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 123–125, January, 1988.     

The reaction of methyl propiolate with 2-aminopyridines

The structure (III) reported by Lappin (2) for the diadducts formed by the reaction of methyl propiolate with 2-aminopyridines has been found to be incorrect. The correct structure (IV) has been proven by spectral studies and cyclisation to compound VII. In two cases new compounds having structures of the type (III) have been isolated. N.M.R. data are reported for all products.     

Reaction of acylacetylenes and methyl propiolate with N,N′-bis(dithiocarboxy)piperazine

The reaction of N,N-bis(dithiocarboxy)piperazine with acetylenic ketones and methyl propiolate gave N,N-bis(acylvinyldithiocarbo)- and N,N -bis(methoxy-carbonylvinyldithiocarbo)piperazines. Heating the compounds obtained with perchloric acid leads to intramolecular cyclization with the formation of N,N -bis[2-acyl(methoxycarbonyl)methyl-1,3-dithietanium]piperazine perchlorates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2637–2640, November, 1990.     

Heterocyclic N-Glycosides. VI. The reaction of glycosyl azides with propiolic acid and methyl propiolate

The synthesis of a series of N-glycosyl-v-triazoles has been accomplished by the 1,3-dipolar cycloaddition of several glycosyl azides to methyl propiolate and propiolic acid. In most of the cases the two isomeric v-triazoles were obtained. Structural and anomeric configuration assignments for the N-glycosides obtained were made on the basis of NMR data. None of the compounds possessed appreciable biological activity against HeLa cells in culture and mouse Sarcoma 180.     

Reaction of methyl ester of n-methylimidoacetic acid with chloral

Russian Chemical Bulletin -     

Reaction of trifluororacemic acid methyl ester with 1,3-dienes

The reaction of trifluororacemic acid with 1,3-dienes affords Diels-Alder reaction products in a high yield and with a high degree of specificity. Catalysis by SnCl₄ changes the course of the reaction of the ester with isoprene, affording an ene reaction product.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 141–145. January, 1991.     

Reaction of 2-thiopyrrolidones with monochloroacetic acid and its methyl ester

Calculations of the electronic structure of 5-alkyl-2-thiopyrrolidones and their oxygen analogs were carried out by the MO LCAO method in the CNDO/2 approximation. The obtained data were used to discuss the reactivity of the investigated compounds in the alkylation of monochloroacetic acid, leading, in the case of 2-thiopyrrolidones, to the formation of the corresponding thiazolinones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1690–1692, December, 1986.     

Arylazide cycloaddition to methyl propiolate: DFT-based quantitative prediction of regioselectivity

Several 1(4-substituted)phenyl-4- or 5-methoxycarbonyl-1,2,3-triazoles have been synthesized by 1,3-dipolar cycloaddition of the corresponding arylazides to methyl propiolate in carbon tetrachloride. The regioselectivity of these reactions cannot be rationalized on the basis of the electronic demands of the reactants or frontier molecular-orbital theory. Therefore, we applied to this problem a quantitative formulation of the HSAB principle to this problem developed within density functional theory. Global and local reactivity indices were computed at B3LYP/6-311+G(d,p) level both in vacuo and in carbon tetrachloride (by the COSMO approach). The direction of charge transfer upon reactive encounter has been determined and the computed regioselectivity has been shown to be in good agreement with the experimental results. The relationship between computed and experimental data and how it is affected by the solvent have been discussed.     

Reaction of para-substituted aromatic acids with methyl thiocyanate in trifluoroacetic acid

We have investigated the reactions of aromatic carboxylic acids (p-XC₆H₄COOH, in which X=F, Cl, Br, I, NO₂, CH₃, H, OCH₃) with methyl thiocyanate in trifluoroacetic acid. It was shown that the starting acids are converted to S-methyl benzothioates [p-XC₆H₄COSCH₃ (40–70%)] and the nitrile of the acid [p-XC₆H₄CN (20–50%)]. In addition to starting acid, in the reaction mixtures products of the reaction of CF₃COOH with methyl thiocyanate were identified.Institute of Oil and Gas Problems, Russian Academy of Sciences, I. M. Gubkin State Academy of Oil and Gas, 117917 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 412–416, February, 1992.     

Reaction of ADP with amino acid methyl esters mediated by trimethylsilyl chloride

Reaction of ADP with amino acid methyl esters mediated by trimethylsilyl chloride in pyridine produced adenosine 5'-phosphoramidates in good yields under mild conditions, it is interesting that nucleophilic attack of amino acid methyl esters only occurred on alpha-phosphorus of ADP.     

A 2-iridafuran from reaction between a 1-iridaindene and methyl propiolate

The coordinatively unsaturated 1-iridaindene, Ir[C₈H₅(Ph-3)]Cl(PPh₃)₂ has a labile chloride ligand and is easily converted to the corresponding iodide, Ir[C₈H₅(Ph-3)]I(PPh₃)₂ (1) by reaction with NaI. When Ir[C₈H₅(Ph-3)]I(PPh₃)₂ (1) is treated with methyl propiolate a reactive five-coordinate complex with both a diphenylvinyl ligand from ring-opening of the 1-iridaindene, and a 3-methoxy-3-oxoprop-1-ynyl ligand from deprotonation of methyl propiolate, is first produced. Reaction of this complex with aqueous HCl generates the 2-iridafuran, Ir[OC₃H(CHCPh₂-3)(OMe-5)]ClI(PPh₃)₂ (2) probably from initial protonation at the β-carbon of the 3-methoxy-3-oxoprop-1-ynyl ligand to form a vinylidene ligand and subsequent migration of the diphenylvinyl ligand to the α-carbon of this ligand accompanied by oxygen coordination to iridium. Similar treatment of 1 with methyl propiolate followed by aqueous HI gives the corresponding complex, Ir[OC₃H(CHCPh₂-3)(OMe-5)]I₂(PPh₃)₂ (3). The X-ray crystal structures of 2 and 3 together with NMR spectroscopic data confirm the 2-metallafuran structures of these complexes.     

Reaction of aryl chromium carbene complexes with ethyl propiolate a versatile vinyl ether formation

Arylmethoxychromium-carbene complexes reacted with ethyl propiolate in the presence of alcohol to form and yields of aryl vinyl ether derivatives of malonate.