Multinuclear magnetic resonance study of organomercury fulminates. The structure of mercury fulminate in solution

¹H, ¹³C, ¹⁴N and ¹⁹⁹Hg NMR data were obtained for organomercury fulminates, RHgCNO (R ? Me, Ph, CNO). The relatively slow relaxation processes effective for the quadrupolar nitrogen muclei of these compounds allow the detection of ¹⁹⁹Hg? ¹⁴N scalar coupling constants. This feature is ascribed to the presence of low electric field gradients around the ¹⁴N nucleus, owing to the presence of the mercury atom. In mercury fulminate, the ¹⁹⁹Hg nucleus appears to be coupled with two equivalent ¹⁴N nuclei, thus indicating the existence of a covalent structure Hg(CNO)₂ in solution.     

Reaction of trimethyliodosilane with monosubstituted acetylene derivatives

Conclusions The reaction of phenylacetylene and 1-hexyne with Me₃SiI in the presence of Mg at 170–180° gave the corresponding trimethyl(organylethynyl)silanes in 80–95% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, p. 897, April, 1981.     

Direct vinylation of glucose derivatives with acetylene

Vinyl ethers, promising chiral carbohydrate synthons, have been synthesized by the addition of glucose acetals (1,2:5,6-di-O-isopropylidene-α-d-glucofuranose, methyl 4,6-O-benzylidene-α-d-glucopyranoside, 1,2-O-cyclohexylidene-α-d-glucofuranose, methyl α-d-glucopyranoside) to acetylene under atmospheric and elevated pressures in an autoclave in the presence of superbase catalytic systems (KOH-DMSO, t-BuOK-DMSO). The complete vinylation of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose and methyl α-d-glucopyranoside has been realized under elevated pressure of acetylene in the system KOH-THF as well.     

Reactions of acetylene ketones in superacids

Vinyl type cations ArC⁺=CHCOR generated from acetylene ketones ArC≡CCOR in superacids HSO₃F and CF₃SO₃H react with diverse benzene derivatives to form alkenylation products, E-/Z-isomers of diarylpropenone structures Ar(Ar’)C=CHCOR. The alkenylation of aromatic compounds with acetylene ketones in superacids occurs with the primary syn-addition of a hydrogen and an aryl residue to the acetylene bond followed by transformation of the product into anti-isomer under the conditions of the reaction.     

Interaction of trichlorogermane with acetylene and its derivatives

Conclusions In the presence of ether, trichlorogermane reacts with acetylene, forming Cl₃GeCH = CHGeCl₃, while without ether, Cl₃GeCH₂GeCl₃ is exclusively formed.Let us express our gratitude to L. A. Leites, V. A. Petukhov, A. N. Egorochkin, and G. N. Kartsev for taking the IR. Raman, UV, and NMR spectra and the dipole moments.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8 pp. 1515–1518, August, 1964     

Some acetylene derivatives of indoline

Conclusions A method was developed for the synthesis of 1-methyl-5-ethynylindoline and its derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1169–1170, May, 1976.     

Reactions of benzothiazole-2-thione and benzothiazole-2-one with acetylene

Reaction of benzothiazole-2-thione and benzothiazole-2-one with acetylene in the presence of potassium hydroxide or cadmium acetate gives 2-vinylthiobenzothiazole and 3-vinylbenzothiazol-2-one, respectively. Benzothiazole-2-thione is partially convened to benzothiazol-2-one by the action of Cd(OAc)₂. Under vinylation conditions the latter also forms 2-vinylthioaniline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 270–271, February, 1991.     

Reactions of bis(diphenylphosphine)acetylene with metal carbonyl complexes

The reaction of [Co₂(CO)₈] with DPPA at room temperature yields a diphosphine bridged product [Co₄(CO)₁₂(μ-Ph₂-P-C≡C-P-Ph₂)₂] 1. Heating of 1 at 45°C promoted cleavage of the P-C_sp bond with the formation of binuclear, phosphido-bridged σ-π-acetylide isomer complexes [Co₂(CO)₅(μ-PPh₂) (μ-σ-π-C≡C-PPh₂ )] 2a, 2b. Heating (60°C) of the complex [CpFe(CO)₂CH₃] and DPPA affords mono and binuclear acetyl, P-coordinated diphenylphosphinoalkyne metal complexes [CpFe(Ph₂P-C≡C-PPh₂)CO(COCH₃)] 3, [CpFeCO(COCH₃)]₂-μ-(Ph₂P-C≡C-PPh₂) 4.