The dehydrogenation of methanol to formaldehyde in the absence of oxygen on a silver catalyst has been studied in a pulse system. The results suggest that the reaction is initiated on the surface of the catalyst, and that the formation of formaldehyde proceeds homogeneously in the gas phase. Formaldehyde yields per pass of more than 40% were obtained at 670°C with a contact time of 0.001 sec. J . D. Ulinder and E. L. Tolkfson, Can. J. Chem. Eng. 52. 518 (1974). A . S. Borisoc. V . V. Tsvetkoc and V. D. Yuqorlol~.skii. J. Phys. Chem. (USSR) (Engl. transl.) 50 (8). 1288 (1976). A . J . Dandy, J. Chem. SOC. 5956 (lY63). S. M. Loos and M. V. Poljwkor, Chem. Abstr. 52. 1601Xh (1958). M . V. Polyakoc. N . P. Ecmeneriko and V . V. Sliulj*u. Chem. Abstr. 59, 1516Xe (1963).
289 5-Ethy/-2,4-dipropylhexahydropyrimidine (6b). To a mixture of 2-ethyl-l.3-hexanediamine (9b, 7.5 g) in hexanes (100 9) was added anh. potassium carbonate (3 g) and butanal (3.8 9). The solution was stirred for f h, filtered and the solvent removed under reduced pressure. Distillation afforded 6b (7.5 g) b.p. 118-123°C (15 mm 2.4-Dibutyl-5-propylhexahydropyrimidine (6c). Prepared from 2-propyl-1,3-heptanediamine (9c, 2.2 g) and pentanal (1.2 g) as described above. Distillation afforded 6c (2.4 g), b.p. I 1&120°C (0.05 mm Hg).Hg).
5-(2-Azahexyl)-5-ethyl-2.4.6-tripropylhexahydropyriniidine (7b). Asample (13.6 g) of 5-(2-azahexyl)-5-ethyl-4,6-nonanediamine (80% 10b + 20% Ilb) and butanal (3.9 g) were reacted as described for 6b to yield 7b (12.8), b.p. 129-133OC (0.05 mm Hg).
5-(2-Azaheptyl)-5-propyl-2,4,6-tripropylhexahydropyriniidine (7c).A sample (6 g) of 6-(2-azaheptyl)-6-propyl-5,7-undecanediamine (85% 1Oc + 15% llc) was reacted with pentanal (1.6 g) as described above to afford 7c (3.5 g). B.p. 174-178°C (0.05 mm Hg). Abstract. For the selective gas-phase ammoxidation of toluene on a Bi-Mo-0 catalyst a kinetic model has been developed in which the combustion of ammonia and benzonitrile has been taken into account. The effect of steam has been investigated. Temperature in the 64CL750 K region has hardly any effect on the selectivity to nitrile, which is maximal at 83 %. Values are given for the rate parameters of main and side reactions.
Kinetics of the gas
Während die Titelreaktion im Bereich von 640‐750 Kkeine Abhängigkeit der NH3‐Umsetzung vom O2‐Druck aufweist, wird diese durch zunehmenden Wasserdampfdruck erniedrigt, was auf eine Adsorption von H2O an der Katalysatoroberfläche zurückgeführt wird.
Previous worksup1-6/sup on an initial model system for the synthesis of polyaromatic dyes for potential use in solar energy collection used the Doebner modified Knoevenagel condensation. This project is continuing the work on this approach to establish its viability.
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