A Detailed procedure for the preparation of Butadiyne

Butadiyne, HC≡CC≡CH, can be obtained in yields up to ～90% by adding 1,4-dichloro-2-butyne, CICH₂C≡CCH₂CI at ～70°C to a mixture of concentrated aqueous potassium hydroxide and dimethylsulfoxide.     

Addition Reaction of Bis（diphenylphosphinyl） Butadiyne with Methylcyclopentadiene

Bis(diphenylphosphinyl)butadiyne reacted with methylcyclopentadiene at room tem- perature and four isomeric products were obtained. Crystal structures of isomers 1 and 3 have been determined. Crystal data for compound 1 C40H36O2P2·2CHCl3: monoclinic, space group C12/c1 with a = 17.983(2), b = 11.8723(12), c = 20.081(2) , β = 111.218(3)°, V = 3996.5(8) 3, Z = 4, Mr = 849.36, Dc = 1.412 g/cm3, F(000) = 1752, μ = 0.546 mm-1, the final R = 0.0351 and wR = 0.0951 for 3965 observed reflections (I > 2σ(I)); and those for compound 3 C40H36O2P2·H2O: triclinic, space group P1 with a = 10.4144(15), b = 13.0558(18), c = 13.742(2) , α = 70.453(8), β = 75.382(8), γ = 72.312(8)°, V = 1653.7(4) 3, Z = 2, Mr = 628.64, Dc = 1.262 g/cm3, F(000) = 664, μ = 0.169 mm-1, the final R = 0.0593 and wR = 0.1296 for 4891 observed reflections (I > 2σ(I)). The structures of the other two isomers are identified via IR, 1H NMR and MS spectra.     

Intramolecular Cyclization of Butadiyne Functionalized Ligands coordinated to Triosmium‐Carbonyl Cluster

Reactions between diynes and [Os₃(CO)₁₁(CH₃CN)] in the presence of water give rise to the formation of intriguing hydride triosmium clusters [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐RC₂COHC≡CR}] ( 1a – 1c ) under mild conditions in high yields. When these allylic alcohol compounds 1a – 1c are dissolved in dry polar and donor solvents, an intramolecular cyclization process takes place to give [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐RC₂CH=COCR}] ( 2a – 2c ) in quantitative yield. The utilization of [Os₃(CO)₁₁(CH₃CN)] as starting material together with the addition of water can replace the inconvenient use of [Os₃(μ‐H)₂(CO)₁₀]. This method of synthesis provides a facile pathway for diyne cyclizations and has a clear advantage over those described to date in the literature. Additionally, the analogous cyclized mixed‐metal complex [Os₃(μ‐H)(CO)₉{μ₃,η¹:η³:η¹‐FcC₂CH=COCFc}] ( 2d ) (Fc = ferrocenyl), was synthesized in order to carry out a comparative electrochemical study with the related compounds [Os₃(CO)₁₁(μ₃‐FcC₄Fc)] ( I ) and [Os₃(CO)₁₀(μ₃‐FcC₄Fc)] ( II ), which were previously reported by R. D. Adams.     

Generation of benzocyclobutadiene derivatives from zirconaindene derivatives

Zirconaindene derivatives produced benzocyclobutadiene derivatives in situ in the presence of CuCl and 1,4-naphthoquinone, which afforded their dimers, 6a,10b-dihydrobenzo[a]biphenylenes and dibenzosemibullvalenes or dibenzo[a,e]cycloctenes.     

Cubane derivatives

Efficient method for the synthesis of cubane-1,4-dicarboxylic and 4-bromocubane-1-carboxylic acid N-(morpholinomethyl)amides has been elaborated. For Part 8, see Ref. 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 396–398, February, 2008.     

Cubane derivatives

An efficient procedure was developed for the preparation of 1,4-cubanedicarboxylic acid dihydrazide (1). Its reactions with acetic anhydride, aromatic aldehydes, and acetylacetone were studied.     

Indole derivatives

The reaction of gramine methiodide with the sodium or potassium derivatives of -oxo sulfoxides leads to the formation of skatyl-substituted sulfoxides. When the latter are cleaved with amalgamated aluminum, skatyl-substituted ketones are obtained.For Communication V, see [4].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1069–1070, August, 1970.     

Indole derivatives

5-Substituted (butyl, phenyl)-5-skatyl(5-methoxyskatyl)barbituric acids were obtained by alkylation of the corresponding barbituric acids with gramine and 5-methoxygramine in dimethylformamide and dimethyl sulfoxide. 5,5-Dialkylation products were obtained in the alkylation of barbituric and thiobarbituric acids with gramine.     

Morpholine derivatives

The β-oxide ring of 3-alkyl-3-(N-morpholinomethyl)oxacyclobutanes is opened to give methiodides or hydrohalide salts, respectively, of 2-alkyl-2-(N-morpholinomethyl)-3-halopropanol when they are heated with methyl iodide in methanol under pressure or heated with hydrohalic acids. When two morpholinomethyl groups are present in the 3 position of the oxacyclobutane ring, it is not opened.     

Tetrazole derivatives

A series of 5-aryl-3-phenyl-1-(tetrazol-5-yl)formazans has been obtained by the azo coupling reaction. In an aqueous alkaline medium they are oxidized to tetrazolium salts with a betaine structure. Information is given on the electronic spectra of the formazans and the tetrazolium salts and the acidic properties and complex-forming capacity of the formazans.For Communication VII, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1570–1573, November 1973.     

Cubane derivatives

New esters of 1,4-cubanedicarboxylic acid, 1,4-(ROCO)₂C₈H₆ (R=Et (3a), Pr (3b), CMe₃ (3c), C₆H₁₃ (3d), CH₂CF₃ (3e), or CH(CF₃)₂ (3f) were synthesized. The structures of esters3a, 3b, 3e, and3f were established by X-ray diffraction analysis. The cubane framework of compound3b is somewhat distorted, whereas the C−C bond lengths and bond angles in the other compounds remain virtually ideal. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 457–462, March, 1998.     

Indole derivatives

The influence of dehydrogenating dehydrating (deaminating) additives on the composition and yield on the products of the cyclization of N-(-hydroxyethyl)aniline and N,N-diphenylethylenediamine has been studied. The closure of the indole and pyrrole rings takes place through the dehydration and deamination, respectively, of the starting material on oxide catalysts. A reaction scheme explaining the formation of all the products observed has been suggested.For Communication L see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 766–769, June, 1970.     

Indole derivatives

The Fischer cyclization of arylhydrazones of 4-thiepanone leads to 1, 3, 6H, 4, 5-dihydrothiepino[4, 3-c]indoles, while the cyclization of arylhydrazones of the S, S-dioxide of 4-thiepanone forms 6H-1, 2, 4, 5-tetrahydrothiepino[5, 4-c]indole.For communication XXIV, see [1].     

Indole derivatives

The synthesis of-glycerides of 3-indolyl carboxylic acids has been effected by the reaction of 3-indolyl carboxylic acids with benzylideneglycerol in the presence of dicyclohexylcarbodiimide with the subsequent elimination of the benzylidene group by hydrogenolysis. The- and-glycerides have been separated by paper chromatography.For communication XXX, see [1].     

Azaindole derivatives

A comparative study of the dehydrogenation of azaindoles by chemical (under the action of quinones) and electrochemical (anode polarography at a rotating platinum disc electrode) methods has been made. The influence of substituents in positions 1 and 6 of the azaindole molecule on the ease of oxidation of the compounds has been investigated. The results are discussed using the method of correlation equations.For part XXVII, see [16].     

Indole derivatives

A new heterocyclic system — 12H-6,7-dihydrobenz[2,3]oxepmo[4,5-b] indole — and a number of its substituted derivatives were synthesized by Fischer cyclization of 5-homochromanone arylhydrazones.See [1] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 65–67, January, 1971.