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1.
Kinetic studies of the aminolysis of [methyl(thiomethyl)carbene]pentacarbonyl chromium(0),(CO)5CrC(CH3)(SCH3) (1-Cr(S)) and [methyl(thiomethyl)carbene]pentacarbonyltungsten(0), (CO)5WC(CH3)(SCH3) (1-W(S)), with morpholine, a secondary amine, in 50% acetonitrile-50% H2O (v/v at 25 °C) is reported. The second-order rate constant (kA in m−1 s−1) increases with amine concentration, giving a linear dependence with an intercept on the rate axis and a tendency towards leveling off at higher amine concentration. The reaction was found to undergo general base catalysis. The mechanism proposed is very similar to those for ester reactions, involving a nucleophilic addition of amine to the substrate to yield a zwitterionic tetrahedral intermediate in the first step, followed by deprotonation to form in the second step, which, in the third step, converted to product by H2O and/or conjugate acid of the base (BH+), assisted MeS− expulsion. The reactivity (k1) of 1-W(S) was found to be higher than that of 1-Cr(S), whereas, comparable , water catalyzed and , BH+ catalyzed, leaving group departure were found for both the carbenes complexes. All these observations have been explained successfully. 相似文献
2.
Adam Sokoowski Jan Chlebicki Kazimiera A. Wilk 《Colloids and surfaces. A, Physicochemical and engineering aspects》1993,80(2-3):243-249
The surface tension isotherms for pure oligooxypropylenated piperidine and morpholine at the aqueous solution—air interface were determined and interpreted. The surface excess concentration, Γ, the surface area per molecule, A, and the standard free energy of adsorption, ΔG°, were calculated according to a new empirical adsorption equation. The standard free energy contribution for the oxypropylene group (PO) in morpholine derivatives,ΔG° (PO) = −3.34 kJ mol−1, is substantially lower than that for the PO group located in the piperidine derivatives, i.e. ΔG° (PO)= −3.12 kJ mol−1. 相似文献
3.
S. Vatsala V. Bansal D. K. Tuli M. M. Rai S. K. Jain S. P. Srivastava A. K. Bhatnagar 《Chromatographia》1994,38(7-8):456-460
Summary Hydrazine, an oxygen scavenger in boiler water, was derivatised to the corresponding acetone azine and determined at the ng ml–1 level by gas chromatography. Morpholine, a corrosion inhibitor used in steam boilers, was estimated either directly (if >2.0 g ml–1) or by quantitative preconcentration (0.1 ng – 2.0 g ml–1). To obtain symmetrical peaks for these amines, the column packing was coated with KOH. Use of a nitrogen-specific detector improved accuracy of estimation of hydrazine and morpholine, giving a RSD of 1.9–3.6%. Chromatographic analysis of these amines in boiler feed water and steam condensate samples collected from boilers servicing a petroleum refinery is described. Environmental safety regulations calls for monitoring of hydrazine and the methods developed can easily be adapted for this purpose. 相似文献
4.
An effective route to novel maleimides is described, which involves the reaction of an enamine derived from the addition of a secondary amine to a dialkyl acetylenedicarboxylate with an arylsulfonyl isocyanate. These maleimides in solution indicate dynamic NMR because of restricted rotation around the carbon-nitrogen bond, resulting from conjugation of the side-chain nitrogen with the adjacent α,β-unsaturated ester group. 相似文献
5.
A variety of privileged bis-spirochromanones were synthesized for the first time from 4,6-diacetyl resorcinol in one-pot by carrying out the Kabbe condensation in room temperature ionic liquid [bbim]Br. 相似文献
6.
Mohsen Nikpour Hossein Eshtiagh-Hosseini Masoud Mirzaei Amir Aghaei Kaju Soroush Zarinabadi 《中国化学快报》2010,21(4):501-505
<正>A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]~+ cations andα-Keggin[(PO_4)W_(12)O_(36)]~(3-) polyoxoanion.The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like(2D/∞)[(PO_4)W_(12)O_(36)]~(3-)) which forming via van der Waals interactions along the x axis. 相似文献
7.
Vapor–liquid equilibria (VLE) data at 100 kPa have been determinated for the ternary system cyclohexane + cyclohexene + morpholine and two constituent binary systems cyclohexane + morpholine and cyclohexene + morpholine. The thermodynamic consistency of experimental data has been verified. Both binary systems deviate moderately from ideality without the presence of an azeotrope. The VLE data have been well correlated using local composition models (Wilson, NRTL and UNIQUAC) and have been also predicted with the original UNIFAC. 相似文献
8.
The scope of the palladium-catalyzed carboamination reaction for the synthesis of 2-substituted pyrrolidines, piperidines, and morpholines was investigated. Formation of a 2,4-disubstituted pyrrolidine proceeded in high yield but with a diastereoisomeric ratio of only 2:5, favoring the cis-isomer. The diastereoselectivity is hence significantly smaller than that observed previously in the formation of 2,3- and 2,5-disubstituted pyrrolidines. The yields of substituted piperidines and morpholines were lowered by competing Heck arylation reactions. Both the N-substituent and the choice of phosphine ligand for the palladium-catalyzed reaction were determining for the outcome. 相似文献
9.
XU Liang-zhong ZHU Chong-yi YU Chen-long LI Kai SI Guo-dong 《高等学校化学研究》2005,21(6):673-676
The title compound, 2-( 4-fluorophenyl ) -2-oxo-1-( 1H-1, 2,4-triazol-1-yl ) ethyl morpholine-4-carbodithioate, was synthesized and its structure was confirmed by means of IR, MS, 1 H NMR and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test showed that the synthesized compound possesses some biological activities. 相似文献
10.
Donn G. WishkaDaniel P. Walker 《Tetrahedron letters》2011,52(37):4713-4715
The novel bridged bicyclic morpholinethione (±)-6-oxa-3-azabicyclo[3.1.1]heptan-2-thione (9) has been prepared in six steps. This conformationally restricted morpholinethione was prepared stereoselectively using straightforward chemistry and inexpensive starting materials. The key oxetane ring was formed via an intramolecular alkylation reaction. 相似文献