3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (/) in the cyclotetrasiloxanes _mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of _mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from _mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings D₃, ₂D₂, ₃D, and ₄. The reactivity of the siloxane links rises in the sequence (CH₃)₂Si-O-Si(CH₃)₂ < (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ <(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) . Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.For part I, see [3].     

2-Diphenylphosphinoyloxybenzaldehyde 4-Nitrophenyl-, 4-Phenyl-1-phthalazinyl-, and Aroylhydrazones and Thiosemicarbazone

Condensation of aryl- and aroylhydrazines and thiosemicarbazide with 2-diphenylphosphinoyloxybenzaldehyde results in formation of the corresponding hydrazones and thiosemicarbazone. The products give rise to conformational equilibrium between rotational and Z,E isomers, which is strongly displaced toward the E,E',Z' isomer and is determined by the nature of substituent in the hydrazine fragment.     

The catalytic reactions of triethyl- and triethoxy-silane with unsaturated sulphides

The hydrosilylation of mono- and di-alkenyl sulphides of the type RS(CH₂)_nCH=CH₂ (R = C₂H₅, CH₂=CH, CH₂=CHCH₂, C₃H₇, n = 0, 1 and 4) by triethyl- and triethoxy-silane, catalyzed by H₂PtCl₆·6 H₂O, (Ph₃P)₃RhCl and (PhCN)₂PdCl₂·Ph₃P, has been studied. The addition of hydrosilane to the double bond of alkenyl sulphide leads to a mixture of two isomeric monoadducts. The hydrosilane can cleave the C---S bond of the initial sulphides giving the corresponding derivatives of thiosilanes, X₃SiS(CH₂)_nCH=CH₂ (X = C₂H₅, C₂H₅O). Hydrosilylation of alkenyl sulphides is accompanied by some side reactions such as dehydrocondensation, reduction and polymerization. The effect of the catalyst nature, the structure of hydrosilane and alkenyl sulphide on the reaction route has been investigated.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

The lipids of microalgae II. Lipids of the dry biomass ofMonochrysis lutheri

Institute of the Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 899–900, November–December, 1993.     

Copper precipitation from sulfate solutions with calcium carbonates

Mechanism of interaction of copper sulfate with natural calcium carbonates, responsible for low residual copper concentrations in solutions and for the behavior of open and closed systems in storage is considered.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.     

Effect of Additions of Silica Gel and Certain Salts of Inorganic Acids on Corrosion Resistance of Cement Stone

Effect of additions of silica gel, certain salts on the rheological parameters of cement mortarand corrosion resistance of cement stone was considered.     

2,3-Diphenylthiazolo[3,2-a]pyrimidinium salts

The corresponding 2,3-diphenyl[3,2-a]pyrimidinium salts were obtained by the condensation of 4,5-diphenyl-2-aminothiazole perchlorate with -diketones, -chlorovinyl ketones, -chlorovinyl aldehydes, and 1,1,3,3-tetraethoxypropane. The PMR spectra were used to prove the structures of the compounds obtained, particularly to select the structures of the isomeric salts obtained in the condensation with unsymmetrical -diketones, -chlorovinyl ketones, and -chlorovinyl aldehydes. As a rule, the latter give one isomer — the -unsubstituted (relative to the bridge nitrogen atom) derivative.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 629–631, May, 1972.