Aromatization of unsaturated poly-cyclohexane sulphone

Copolymers of cyclohexene and cyclohexa-1,3-diene with sulphur dioxide have been prepared [poly-1,2-(cyclohexane)sulphone and poly- 1,4-(cyclohexa-2-ene)sulphone, respectively], and a study made of their aromatization. It was found that the latter copolymer only could be partially aromatized by using bromine-sulpholane, sulphur-dimethylformamide or selenium dioxide-decalin. The properties of the polymers are discussed in relation to the proportion of aromatic character. The scope and limitations of introducing aromatic rings into a polymer chain, by an addition polymerization of cyclohexyl derivatives followed by dehydrogenation, are discussed.     

Reaction of tellurium tetrachloride with acetylene

Russian Chemical Bulletin -     

Reaction of tellurium tetrachloride with diallyldimethylsilane

Russian Journal of Organic Chemistry -     

Stannylation of unsaturated carbon-carbon bonds by tin tetrachloride

The reactions of tin tetrachloride and four terminal alkynes (PhCCH, ^tBuCCH, ⁿBuCCH, HOCH₂CCH), norbornene, and norbornadiene in dichloromethane or chloroform solution lead to the formation of stannylation products, which were characterized by ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy. Virtually complete α-regioselectivity was obtained in reaction of all four alkynes without any effect of the relative steric bulk of the substituent R at the triple bond of alkyne RC_βC_αH. The reaction of norbornene and norbornadiene with SnCl₄ is stereoselective, giving an exo stannylation product.     

The reactions of tellurium tetrachloride with aliphatic monoketones

The reactions of 13 aliphatic ketones with tellurium tetrachloride has been studied with proton, carbon-13, and tellurium-125 NMR. Tellurium tetrachloride adds electrophilically to the α-carbon of the enol to form ketonyl tellurium trichlorides. Unsymmetric ketones gave mixtures of isomeric ketonyl tellurium trichlorides. Steric hindrance determines which ketonyl tellurium trichlorides form. Except for the ketonyl tellurium trichloride from 2-butanone, tellurium reacts preferentially with the least substituted α-carbon. Six methyl alkyl ketones also yielded appreciable amounts of diketonyl tellurium dichlorides. In all diketonyl tellurium dichlorides, tellurium is bonded to less hindered methylene carbons.     

Reaction of tellurium tetrachloride with hex-3-yne

Russian Chemical Bulletin -     

Stereoselective addition of tellurium tetrachloride to 4-octyne

Russian Journal of Organic Chemistry - Reaction of tellurium tetrachloride with 4-octyne occurs as an anti-addition and leads to the formation of...     

Regio- and stereoselective addition of tellurium tetrachloride to methyl propargyl ether

Reaction of tellurium tetrachloride with methyl propargyl ether proceeds regio- and stereoselectively to afford a product of anti-addition against the Markovnikoff’s rule in quantitative yield. The obtained compound was reduced by sodium metabisulfite into E,E-bis(3-methoxy-1-chloroprop-1-en-2-yl)ditellane.     

Structure elucidation of a zwitterionic 2-oxazoline obtained by cyclofunctionalization of n-acetyldiallylamine with tellurium tetrachloride

Interaction of tellurium tetrachloride with N-acetyldiallylamine in CH₃CN gave a zwitterionic 2-oxazoline 8a, whose structure was determined by X-ray crystallography. The 2-oxazoline was found to react readily with nucleophilic reagents; water caused cleavage of the oxazoline ring and deacetylation to yield a compound with an intact tetrachlorotellurate(IV) function.     

anti-Markovnikov addition of tellurium tetrachloride to trimethyl ethynyl silane

An investigation of the TeCl₄ interaction with trimethyl ethynyl silane 1 in CHCl₃ has shown that anti-Markovnikov adduct [Z-1-(trimethylsilyl)-2-chlorovinyl]tellurium trichloride is formed as the only product. In time, it is hydrolyzed to give [Z-1-(trimethylsilyl)-2-chlorovinyl]tellurium (hydroxy) dichloride which, in turn, is dehydrated to afford bis[(2-chloro-1-trimethyl-silylvinyl)dichlorotellurium]oxide. These data revealed that the reaction studied was the first example of anti-Markovnikov syn-addition of TeCl₄ to terminal acetylenes. A computed simulation of the TeCl₄ interaction with ethynyl silane 1 in a gas state using PES method did not reveal dominating orientation of the addition but showed the conditions at which anti-Markovnikov addition can occur and which were probably met in carrying out the reaction in CHCl₃.     

Tellurium tetrachloride: Addition to cyclohexene and preparation from tellurium dioxide and trimethylchlorosilane

Tellurium dioxide, trimethylchorosilane, acetyl chloride, or acetyl bromide in glacial acetic acid generated a homogeneous solution. Addition of cyclohexene produced trans-2-halocyclohexyl tellurium trihalides of excellent purity in 70% yield. With dichloromethane or ethanol-free chloroform the same compounds were obtained from heterogeneous reaction mixtures. trans-2-Methoxycyclohexyl tellurium trichloride was obtained quantitatively from tellurium dioxide, trimethylchlorosilane, and cyclohexene in absolute methanol. In the absence of cyclohexene, tellurium tetrachloride was obtained in 91% yield from tellurium dioxide and trimethylchlorosilane in chloroform, and tellurium tetrabromide in 98% yield from tellurium dioxide and acetyl bromide in glacial acetic acid.     

Free-radical addition of carbon tetrachloride and chloroform to unsaturated epoxy compounds

Conclusions The free radical addition of carbon tetrachloride and chloroform to unsaturated epoxy compounds, initiated by benzoyl peroxide, was carried out. nt[mis|Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1642–1644, July, 1970.     

Erratum to: “Stereoselective addition of tellurium tetrachloride to 4-octyne”

Russian Journal of Organic Chemistry -     

One-pot synthesis of aryl butyl tellurides from tellurium tetrachloride and activated aromatics through a solventless step

A solventless preparation of aryl tellurium trichlorides from activated aromatic compounds avoiding the use of hazardous solvents as carbon tetrachloride and chloroform is described. The trichlorides were reduced and alkylated leading to aryl butyl tellurides in a one-pot procedure. Transmetallation of these tellurides with n-butyllithium followed by reaction with benzaldehyde gave the corresponding benzhydrols in good yields.