Reference

Alkylamines

Alkylamines. (Daicel Chemical Industries, Ltd., Japan). Jpn. Tokkyo Koho JP 58040941 B4 8 Sep 1983 Showa, 4 pp. (Japanese). (Japan). CODEN: JAXXAD. CLASS: IC: C07C087-02; C07C085-12. APPLICATION: JP 78-84159 10 Jul 1978. DOCUMENT TYPE: Patent CA Section: 45 (Industrial Organic Chemicals, Leather, Fats, and Waxes) Section cross-reference(s): 23 During the manuf. of alkylamines by the redn.Some commonly used reagents like 7664-41-7 and 142-84-7 are used in this experiment. of aliph. nitriles with H, the by-product NH3 is removed by adding water to the reaction mixt. Thus, propionitrile (I) [107-12-0] 0.28, PrNH2 [107-10-8] 0.39, NH3 3.2, H 1.93, and water 0.85 mol/h were passed through a tubular reactor contg. 200 mL Ni catalyst at 150° and cooled at 5° to give a condensate contg. NH3 0.38, PrNH2 0.25, Pr2NH [142-84-7] 0.18, and Pr3N [102-69-2] 0.02 mol/h with complete collection of the by-product NH3 (0.22 mol/h) in the crude liq. When I 0.24, PrNH2 0.1, Pr2NH 0.04, Pr3N 0.05, NH3 1.26, and H 5.46 mols/h were passed through the reactor, only 1.1% NH3 was collected in the crude liq. .

Rate-Determining Step in the Electrogenerated Chemiluminescence from Tertiary Amines with Tris(2,2'-bipyridyl)ruthenium(II)

Rate-Determining Step in the Electrogenerated Chemiluminescence from Tertiary Amines with Tris(2,2'-bipyridyl)ruthenium(II). Wightman, R. Mark; Forry, Samuel P.; Maus, Russell; Badocco, Denis; Pastore, Paolo (Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA). Journal of Physical Chemistry B, 108(50), 19119-19125 (English) 2004 American Chemical Society. CODEN: JPCBFK. ISSN: 1520-6106. DOCUMENT TYPE: Journal CA Section: 72 (Electrochemistry) Section cross-reference(s): 67, 73 The rates and mechanism of coreactant electrogenerated chemiluminescence (ECL) from tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)32+) and the tertiary amines, tripropylamine (TPrA) and trimethylamine (TMeA), in aq. soln. were studied. Transient (0.5 ms) potential steps were used with microelectrodes to study the emission time course under a variety of soln. conditions. With amine concns. that are low with respect to Ru(bpy)32+, the emission rises continually during the transient potential step and decays slowly after its termination. But the emission approaches a plateau during the potential step and is rapidly extinguished afterward with concns. of Ru(bpy)32+ that are much lower than the amine concn. At intermediate pH values, the emission intensity increases approx. linearly with pH. The emission after the potential step is unaffected by the rest potential. To simulate these temporal characteristics by finite difference methods, a mechanism employing 15 discrete chem. and electrochem. steps was employed, using literature-based thermodn. values and electron-transfer rate consts.There are some commonly used reagents with their cas registry numbers 102-69-2 and 103635-04-7 in this article. evaluated from Marcus theory. The rate-limiting step is the deprotonation of the amine radical cation. The simulations required a rate const. for the homogeneous oxidn. of the tertiary amine by electrogenerated Ru(bpy)33+ value much below its Marcusian-calcd. value to match the exptl. data. .