Viscosity of binary mixtures. IV. Triethylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities and densities of seven binary mixtures of n-hexane, n-octane, isooctane, n-propylamine, n-butylamine, n-hexylamine, and n-octylamine with triethylamine have been measured at 303.15 and 313.15 K. Deviations of viscosities from a linear dependence on the mole fraction and values of excess Gibbs energy of activation G ^*E of viscous flow are attributable to the H-bonding and to the size of the alkylamine and alkane molecules.     

Study of viscosity of mono-, di-, and trialkylamines

Viscosities of several mono-, di-, and trialkylamines have been measured in the temperature range 298 to 333 K. It is observed that viscosities are highly dependent on shape, size, and association through H-bond or through dipole. Following the transition state theory, energy, Gibbs free energy, and entropy of activation of viscous flow have been calculated. The values of expansion energy for these liquids have also been calculated using free volume theory, and subsequently amines have been classified as volume-restrained or energy-restrained liquids. The group contribution method of Van Velzen, Cardozo, and Langenkamp for estimating viscosity has been examined with the present and literature data, and the new group contribution increments N _i and B _i for amines have been evaluated.     

Viscosity of binary mixtures. I. mono-, di-, and tri-n-butyl and -n-octylamine with cyclohexane

Viscosities for six binary mixtures of n-butylamine, di-n-butylamine, tri-n-butylamine, n-octylamine, di-n-octylamine, and tri-n-octylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspendedlevel viscometer. Deviations of viscosities from a rectilinear dependence on mole fraction are attributed to H-bonding and to the size of alkylamine compounds. The application of the Eyring's theory of activation energy is examined. The free volume theory of Prigogine-Flory-Patterson (PFP) and the experimental excess enthalpy have been used to estimate excess viscosity ln = (ln / ₁ ⁰ – x ₂ ln ₂ ⁰ / ₁ ⁰ ) and corresponding free volume, enthalpy, and entropy contributions for five binary mixtures of tri-n-alkylamine: triethyl, tripropyl, tributyl, trihexyl, and trioctylamine with cyclohexane. A comparison of experimental and theoretical excess viscosities indicates a failure of the PFP theory when two components of the mixture differ considerably in size. The size difference contribution to excess viscosity is related to (V ₂ ^*1/2 – V ₁ ^*1/2 ), where V ₁ ^* and V ₂ ^* are hard-core volumes of two components of the mixture.     

合成胺的工业化过程

回顾了最近十几年中甲胺、C2～C5的烷基胺、环已胺的合成工艺，重点讨论了技术的发展。研究过的新技术包括沸石催化的甲胺合成，异丁烯直接胺化制叔丁胺，以及催化精馏制丁胺和环已胺。还讨论了过程发展的方向。     

Characterization of H-FER and H-TON using temperature-programmed desorption of alkylamines

Simultaneous temperature-programmed desorption (TPD) and thermogravimetric analysis (TGA) measurements were performed with n-propylamine and isopropylamine in H-FER and H-TON in order to test whether the Brønsted-acid sites associated with the 10-ring, straight channels in H-FER could be distinguished from the acid sites in the side cavities. In H-TON, the saturation uptakes were identical for both amines, as were the acid-site densities determined from the amounts of amine which reacted to olefin and ammonia products above 600 K. By contrast, the saturation uptake for isopropylamine in H-FER was much lower than the uptake of n-propylamine and the site density determined from the amounts which react were also significantly lower. It is argued that the n-propylamine results for H-FER provide a measure of the total Brønsted-acid-site density, while the isopropylamine results provide a measure of the site density in the 10-ring channels.     

Viscosity of biniary mixtures. III. Tri-n-butylamine with alkanes and monoalkylamines at 303.15 and 313.15 K

Viscosities of seven binary systems of n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-hexane, n-octane, and isoctane (2,2,4-trimethylpentane) with tributylamine have been measured at 303.15 and 313.15 K with an Ubbelohde suspended-level viscometer. Based on Eyring's theory, values of excess Gibbs energy of activation G ^*E of viscous flow have been calculated. Deviations of viscosities from linear dependence on the mole fraction and values of G ^*E are attributed to the H-bonding and to the size of alkylamine and alkane molecules. The free volume theory of Prigogine-Flory-Patterson in combination with work by Bloomfield-Dewan has been used to estimate the excess viscosity ln and the terms corresponding to enthalpy, entropy, and free volume contributions for the present binary mixtures.     

Iminium cations as intermediates in the hydrodenitrogenation of alkylamines over sulfided NiMo/γ-Al2O3

The mechanism of the hydrodenitrogenation of the mixed dialkyl- and trialkylamines C₁NHC₆ and C₁N(C₆)₂ was studied over sulfided NiMo/γ-Al₂O₃ at 280 °C and 3 MPa. C₁NHC₆ reacted by disproportionation to C₁N(C₆)₂ as well as C₆N(C₁)₂ and by substitution by H₂S to methylamine and hexanethiol as well as hexylamine and methanethiol. C₁N(C₆)₂ reacted by substitution with H₂S to C₁NHC₆ and C₆NHC₆ and methane- and hexanethiol. The probability of breaking the C₁N bond was only slightly smaller than of breaking the C₆N bond in C₁N(C₆)₂. In the reaction of an equimolar mixture of C₅NHC₅ and C₁N(C₆)₂ both C₁N(C₅)₂ and C₆N(C₅)₂ were formed. The transfer of the methyl group in these reactions cannot be explained by imine and enamine intermediates, only iminium cation intermediates can explain all the products in the hydrodenitrogenation of monoalkyl-, dialkyl- and trialkylamines.     

Synthesis of Sulfated Sodium Salts of 1-Alkylamino-3-alkyloxy-2-propanols and N,N-Di-(2-hydroxy-3-alkyloxy propyl) Alkylamines as Potential Surfactants

1-Alkylamino-3-alkyloxy-2-propanols, V (a–g) and N,N-di-(2-hydroxy-3-alkyloxy propyl) alkylamines, VI (a–g) were prepared with the same chain length both for alkyl amino and alkyloxy groups by condensation of alkyl glycidyl ethers with long chain alkylamines by employing thermal and microwave-assisted methods. All the products were characterized by ¹H-NMR, IR and fast atom bombardment mass spectrometry studies. These compounds were further sulfated and evaluated as their sodium salts for surfactant properties namely surface tension, critical micelle concentration, emulsifying property, wetting, foaming power and calcium tolerance. Sulfated 1-dodecylamino-3-dodecyloxy-2-propanol, VII c and sulfated N,N-di-(2-hydroxy-3-dodecyloxy propyl) dodecylamine, VIII c were found to exhibit superior surfactant properties among the respective series of monomers and dimers.

Viscosity of binary mixtures. II. n-butyl,n-hexyl,n-octyl,n-decyl,and n-dodecylamine with benzene and n-hexyl,n-decyl,and n-dodecylamine with cyclohexane

Viscosities of eight binary systems of n-butylamine, n-hexylamine, n-octylamine, n-decylamine, and n-dodecylamine with benzene and n-hexylamine, n-decylamine, and n-dodecylamine with cyclohexane have been measured at 303.15 K with an Ubbelohde suspended level viscometer. Based on Eyring's theory, values of excess Gibbs energy of activation G ^*E of viscous flow have been calculated. Deviations of viscosities from linear dependence on the mole fraction and values of G ^*E are attributed to H-bonding and to the size of alkylamine molecules. The free volume theory of Prigogine-Flory-Patterson in combination with the work of Bloomfield-Dewan has been used to estimate the excess viscosity In and the terms corresponding to enthalpy, entropy, and free volume contributions for 10 binary mixtures containing n-butyl, n-hexyl, n-octyl, n-decyl, and n-dodecylamine with benzene and cyclohexane.     

Solvent-free synthesis of 1-[3-alkyl-4-methyl-2-thioxo-2,3-dihydrothiazole-5-yl]-ethanones in a multicomponent reaction

A simple and efficient one-pot synthesis of 1-[3-alkyl-4-methyl-2-thioxo-2,3-dihydrothiazole-5-yl]-ethanones from the reaction of primary alkylamines and carbon disulfide in the presence of 3-chloro acetylacetone is described. This protocol has several advantages such as lack of need for a solvent and catalyst, high yields, mild conditions and short reaction times.