Radical addition of 2-trichloromethyl-1,3-dioxolane to vinyltrimethylsilane

Conclusion The addition of 2-trichloromethyl-l,3-dioxolane to vinyltrimethylsilane upon initiation by a system consisting of Fe(CO)₅ and a nucleophilic cocatalyst proceeds to cleavage of a C-Cl bond in the trichloromethyl group with the formation of an adduct containing the dioxolanyl ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2351–2353, October, 1986.     

2-Nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines: Synthesis and structure

A reaction of 1-bromo-3,3,3-trichloro-1-nitropropene with pyrocatechol, o-aminophenol, and their substituted derivatives led to 2-nitromethyl-2-trichloromethyl-1,3-benzodioxoles and 2-nitromethyl-2-trichloromethyl-1,3-benzoxazolines. The structure of the compounds synthesized was established by IR, ¹H and ¹³C NMR spectroscopy with HMQC and HMBC ¹H—¹³C experiments, and X-ray diffraction analysis.     

Reaction of hexamethyldisiloxane with 2-ethoxy-1,3-dioxolane

The reaction of hexamethyldisiloxane with 2-ethoxy-1,3-dioxolane is described. It is shown that cleavage of the endo- and exocyclic carbon-oxygen bonds of the ortho ester occurs under mild conditions (16–20C) in the presence of acidic catalysts with the formation of 2-(trimethylsiloxy)ethyl formate, the subsequent transformation of which leads to ethyl formate, trimethylethoxysilane, and 1,2-bis(trimethylsiloxy)ethane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1607–1611, December, 1989.     

Synthesis of 1,3-dioxolane derivatives

Chloral cyanomethylhemiacetal is converted to 2-trichloromethyl-4-imino-1,3-dioxolane under the influence of hydrogen chloride or pyridine. Acetone cyanohydrin reacts with chloral to give 2-trichloromethyl-4-imino-5,5-dimethyl-1,3-dioxolane, the hydrochloride of which in water gives 2-trichloromethyl-4-oxo-5,5-dimethyl-1,3-dioxolane.     

Cationic copolymerization of 2-vinyl-1,3-dioxane with styrene and 1,3-dioxolane

Copolymerization of 2-vinyl-1,3-dioxane with styrene and 1,3-dioxolane was carried out in methylene chloride at 0°C with triethyloxonium tetrafluoroborate as an initiator. Random copolymers were obtained from both of these monomer pairs, but attempted copolymerization of 2-vinyl-1,3-dioxane with 3,3-bis(chloromethyl)oxetane under similar conditions resulted in the homopolymer of the latter monomer. There were three structural units of 2-vinyl-1,3-dioxane in these copolymers as in its homopolymer: the “ester” unit, which was formed by vinyl addition with hydride shift followed by ring-opening rearrangement, the “vinyl” unit produced by ring-opening reaction, and the unit with a pendant 1,3-dioxane ring formed by simple vinyl addition. The fractions of the ester and vinyl units to the total 2-vinyl-1,3-dioxane units in the copolymer of 2-vinyl-1,3-dioxane with styrene decreased with decreasing 2-vinyl-1,3-dioxane content. On the contrary, the fraction of the vinyl unit in the copolymer of 2-vinyl-1,3-dioxane with 1,3-dioxolane increased slightly with decreasing 2-vinyl-1,3-dioxane content, while that of the ester unit decreased. The reactivities of the propagating species are discussed on the basis of these results.     

Speeds of sound and isentropic compressibil- ities of cyclohexane+1,3-dioxolane+2-butanol and n-hexane+1,3-dioxolane+2-butanol

Speeds of sound of the ternary mixtures cyclohexane+1,3-dioxolane+2-butanol and n-hexane+1,3-dioxolane+2-butanol have been measured at the temperatures of 298.15 and 313.15 K. Isentropic compressibilities and excess isentropic compressibilities have been calculated from experimental data. We have also compared the experimental isentropic compressibilities with calculated values from the free length theory and the collision factor theory. Experimental results show positive values of excess isentropic compressibilities in almost the whole composition range for the ternary mixture containing cyclohexane, meanwhile they are negative for the mixture containing n-hexane. Such different behaviour of these systems is related to the large free volume shown by n-hexane. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation of the transformations of 2-trichloromethyl-4-methylene-1,3-dioxolanes

The reactions of 2-trichloromethyl-4-methylene-1,3-dioxolanes with electrophilic and nucleophilic reagents were studied. The conditions that make it possible to carry out the reaction selectively at the double bond with retention of the acetal structure were found. New types of cyclic chloroacetals were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 601–605, May, 1972.     

Radical reactions of vinyltrimethylsilane with 2-methyl-1,3-dioxolane

Conclusions Vinyltrimethylsilane in radical reactions with a cyclic acetal gives 2- and 4-substituted 1,3-dioxolanes together with telomers of linear structure. Increasing the concentration of the monomer and reducing the reaction temperature favors an increase in the proportion of cyclic telomers.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1616–1620, July, 1986.     

Vibrational Satellites and Pseudorotation in 2-Methyl-1,3-dioxolane

Vibrational satellites caused by pseudorotation are identified in the microwave spectrum of 2-methyl-1,3-dioxolane. The rotational constants of the satellites are determined up to state v = 6. Splittings between lower pseudorotational energy levels are determined by measuring the relative intensities of rotational transitions. An attempt is made to determine the form of the pseudorotation function of the molecule using the obtained data.     

Some transformations of 2-methyl-2-allyl-4-methylol-1,3-dioxolane

Conclusions A study was made of the reaction of 2-methyl-2-allyl-4-methylol-1,3-dioxolane with mercaptans, alcohols, halogens and hydrogen halides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1541–1542, July, 1971.     

Cationic copolymerization of 2-methylene-5,5-dimethyl-1,3-dioxane with 2-methylene-1,3-dioxolane and 2-methylene-1,3-dioxane

Copolymers of the cyclic ketene acetals, 2-methylene-5,5-dimethyl-1,3-dioxane, 3 , (M₁) with 2-methylene-1,3-dioxolane, 4 , (M₂) or 2-methylene-1,3-dioxane, 5 , (M₂), were synthesized by cationic copolymerization. An experimental method was designed to study the reactivity of these very reactive and extremely acid sensitive cyclic ketene acetal monomers. The reactivity ratios, calculated using a computer program based on a nonlinear minimization algorithm, were r₁ = 6.36 and r₂ = 1.25 for the copolymerization of 3 with 4 , and r₁ = 1.56 and r₂ = 1.42 for the copolymerization of 3 with 5. FTIR and ¹H-NMR spectra when combined with the values of r₁ and r₂ showed that these copolymers were formed by a cationic 1,2-polymerization (ring-retained) route. Furthermore the tendency existed to form very short blocks of M₁ or M₂ within the copolymers. Cationic copolymerization of cyclic ketene acetals have the potential to be used for synthesis of novel polymers. © 1996 John Wiley & Sons, Inc.     

Homolytic addition of 2-ethoxy-1,3-dioxolane to 1-decene

Conclusions The radical addition of 2-ethoxy-1,3-dioxolane to 1-decene leads mainly to the formation of 2- and 4-decyl-2-ethoxy-1,3-dioxolane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2051–2053, September, 1985.     

Radical telomerization of 3,3,3-trifluoropropene with 2-methyl-1,3-dioxolane

The telomerization of 3,3,3-trifluoropropene with 2-methyl-1,3-dioxolane gives predominantly cyclic telomers as shown by¹³C NMR and gas chromatography-mass spectrometry. This reaction is accompanied by the rearrangement of transient free radical intermediates via 1,5-H-migration.Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2768–2772, December, 1992.     

Cationic ring-opening polymerization of 2-isopropenyl-4-methylene-1,3-dioxolane

Preparation and cationic ring-opening polymerization of 2-isopropenyl-4-methylene-1,3-dioxolane ( VI ) was performed. Unsaturated cyclic acetal VI was prepared by dehydrochlorination of 2-isopropenyl-4-chloromethyl-1,3-dioxolane, which was easily obtained from methacrolein and epichlorohydrin, with sodium methoxide at ambient temperature. The cationic polymerization of VI with BF₃OEt₂ or CF₃SO₃H at ?78°C afforded only crosslinked polymers, whereas the polymerization by CH₃SO₃H gave soluble poly(keto-ether) which consisted of units VII containing an isopropenyl group in the side chain and units VIII containing a carbon-carbon double bond in the main chain. The reaction of VI with ethanethiol in the presence of protic acid was also carried out as a model reaction of the polymerization. The reaction initiated by the addition of proton to the 4-methylene group of VI , and quantitative ring-opening isomerization followed by the addition of ethanethiol afforded acyclic ketone IX and X . On the basis of the model reaction, the polymerization mechanism is also discussed. © 1993 John Wiley & Sons, Inc.