Cellulose solutions in dipolar aprotic solvents

Preparation conditions and properties of cellulose solutions in DMAA containing 7–8% lithium chloride are considered. Investigation of the optical anisotropy and structure of cellulose solutions in this solvent confirms that the LS state is attained with an increase in the concentration of cellulose. On the basis of these cellulose solutions, fibers not ranking below viscose fibers in mechanical properties are prepared. The use of a mixed solution of 95% cellulose and 5% poly(amidobenzimidazole) in DMAA containing 7% lithium chloride makes it possible to prepare films and fibers whose strength is more than two times greater than the strength of cellulose hydrate fibers. The deformation-driven orientation and supramolecular structure of fibers and films are studied by spectroscopy and small-angle scattering of polarized light.     

Method for synthesis of alkyl vinyl sulfides by the direct vinylation of thiols in aprotic dipolar solvents

Conclusions A method was developed for the synthesis of vinyl alkyl sulfides by the nucleophilic addition of thiols to acetylene in aprotic dipolar solvents, like hexamethylphosphoric triamide and dimethyl sulfoxide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 956–957, April, 1972.     

Behaviour of aminoacids and aliphatic aldehydes in dipolar aprotic solvents: Formation of oxazolidinones—behaviour of aminoacids and aliphatic aldehydes in dipolar aprotic solvents

Reactions of aliphatic branched aldehydes with proline in dimethyl sulfoxide or acetonitrile solution afford oxazolidin-5-ones with high diastereoselection. Linear aldehydes afford aldolic/crotonic condensation products; with short reaction times, the presence of Oxazolidinones can be detected in the pmr spectra. Acyclic aminoacids and branched aldehydes yield a reaction mixture the pmr and ir spectra of which give evidence for iminic-oxazolidinone equilibria. The structure of (2R,5S)-2-trichloromethyl-1-aza-3-oxabiciclo-[3.3.0]octan-4-one has been confirmed by X-ray diffraction analysis.     

Kinetics of reaction of copper with substituted benzyl chlorides in dipolar aprotic solvents

The reaction of copper with benzyl chlorides in dipolar aprotic solvents has been investigated. The kinetic and thermodynamic parameters of the reaction of copper with benzyl chloride in dimethyl sulfoxide, dimethylacetamide, and hexamethylphosphoramide have been obtained. Hammett plots of log (k/k°) versus the substituent constant σ gave good correlation. The structure of the organic group has little effect on the rate of reaction of benzyl chloride with copper. The kinetic and thermodynamic parameters were correlated with donor number of solvent (DN). The ratio k_RBr/k_RCl and Hammett ρ values provide evidence in favor of the halogen atom transfer mechanism. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 547–555, 2007     

Solute-solvent interactions. VII. Proton magnetic resonance and infrared study of ion solvation in dipolar aprotic solvents

The solvation of a variety of ions by the dipolar aprotic solvents acetonitrile, sulfolane, and dimethylsulfoxide was studied through the influence of salts on the proton magnetic resonance chemical shifts of the solvents. In the case of acetonitrile the results were supplemented with infrared measurements, which showed that in general anions affect only the C–H and cations both the C–C and particularly the CN stretching frequencies of acetonitrile. The results are discussed in conjunction with transport and other data already in the literature. Current views on the structure of these solvents are summarized.From the Ph.D. thesis of this author, University of Pittsburgh, 1972.     

Ion-pair effects on the electroreduction and electrochromic properties of ortho-chloranil in dipolar aprotic solvents

The use of ortho-chloranil (o-CA) as an electrochromic material requires three conditions to operate properly: (1) the reversibility of the electronic transfer of the reaction

; (2) the formation of a visible-light absorbing charge-transfer complex between o-Ca⁻ and the counterion M⁺, and (3) the use of an insoluble salt o-CA⁻M⁺ as a film adherent to the electrode surface. The behavior of the redox o-CA/o-CA⁻ couple has been investigated in different solvents and in the presence of several alkaline and alkaline earth cations (M^z+). The reversibility of the electron transfer and the formation of an adhesive salt layer on the electrode are strongly related to the counter ion M^z+. The ion-pair formation depends on the solvent and particularly on its weak electron donor character. The best electrochromic properties of o-CA were obtained in 0.1 M NaClO₄ acetonitrile solutions.     

Cationic polyelectrolytes. IV. Kinetic study of the reaction of acrylic polymers containing tertiary amine groups with halogenated compounds in dipolar aprotic solvents

The reaction kinetics of halogenated compounds with tertiary amine groups attached at an acrylic macromolecular chain have ben studied. Three acrylic polymers were used. Two of them have mainly a structural unit of N, N-dimethylaminopropylacrylamide and the third is poly(N,N-dimethylaminoethylmethacrylate). Dimethylformamide, dimethylacetamide, and dimethylsulfoxide (DMSO) were used as dipolar aprotic solvents. Benzyl chloride and allyl chloride were considered as halogenated compounds with increased reactivity. The reaction kinetics depend on the polymer and halogenated-compound structures as well as the nature of the solvent. In the most of the cases the reactions carried out on polymers are accompanied by self-accelerating processes, with the exception of DMSO, which obviously has normal second-order kinetics. The reaction of polymers containing units of N,N-dimethylaminopropylacrylamide are compared with one having a low molecular weight, for instance N,N′-bis(3-dimethylaminopropyl)glutaramide.     

The kinetics of reaction of copper with substituted benzyl bromides in dipolar aprotic solvents

The reaction of copper with benzyl bromides in dipolar aprotic solvents has been studied. There are no linear or other simple relations between ε, 1/ε, Y, P, n, and the rate of reaction. The activity of the solvent is determined by donor number (DN) in reaction under consideration. The kinetic and thermodynamic parameters of the reaction of copper with benzyl bromide in dimethyl sulfoxide (DMSO) have been clarified. Hammett plots of log (k/k°) vs. the substituent constant σ gave good correlations (ρ = 0.18, S_ρ = 0.02, r = 0.961 in dimethyl sulfoxide and ρ = 0.21, S_ρ = 0.02, r = 0.947 in dimethylacetamide (DMAA)). The structure of the organic group has little effect on the rate of reaction of benzyl bromide with copper. The Hammett ρ value also depends on DN. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 496–501, 2005     

Extraction of eleutherococcus by aprotic solvents

V. V. Kuibyshev Tomsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 143–144, January–February, 1989.     

Electrochemical studies of sulfonates in non-aqueous solvents: Part III. Trifluoromethanesulfonic acid as a strong acid in dipolar aprotic solvents and acetic acid

Dissociation of trifluoromethanesulfonic acid in non-aqueous solvents has been investigated mainly by conductometry and compared with that of p-toluenesulfonic, methanesulfonic, fluorosulfuric and perchloric acids. The solvents used are dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyronitrile, propylene carbonate, acetonitrile, nitromethane, methyl isobutyl ketone and acetic acid. Trifluoromethanesulfonic acid is completely dissociated in rather basic solvents such as dimethyl sulfoxide, dimethylacetamide and dimethylformamide, while it is associated to some extent in the other solvents, especially in methyl isobutyl ketone and acetic acid. The strength of trifluoromethanesulfonic acid is almost the same as that of perchloric acid in all the solvents. Dissociation constants of the other acids are also obtained.     

An efficient synthesis of tertiary amines from nitriles in aprotic solvents

Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.     

Solvatochromic equilibria of cobalt(II) chloride in binary mixtures of dipolar aprotic solvents with water

The visible absorption spectra of CoCl₂ in binary mixtures of acetone, dmf, dma and dmso with H₂O show the existence of configuration equilibria between tetrahedral (T) and octahedral (O) species. Linear correlations between the values of log K (K = [O]/[T]) and the mole fraction of H₂O, _w, have been observed in all the systems under study; their slopes decrease linearly with an increase of the donor number, DN, of the organic component of the mixture. The formation of octahedral species is enthalpy favoured but entropy disfavoured. It was found that both H and S values change linearly with _w and the slopes of these relationships depend clearly on the DN values.     

Spectrophotometric study of dehalogenation of benzyl halides with nickel in aprotic dipolar solvents in the presence of oxygen

Oxidative dissolution of nickel in the benzyl halogenide – dipolar aprotic solvent system in the presence of air oxygen proceeds with the formation of benzaldehyde, benzyl alcohol, 1,2-diphenylethane, and trace amounts of 4,4'-ditolyl. Spectrophotometry studies have revealed that the oxidation products are formed in the solution rather than at the nickel surface. It has been shown that the oxygen adsorbed at the nickel surface practically does not pass into the solution.