Titanium chloride, reduction with hydrogen

Octanal has been prepared by the reduction of caprylonitrile with hydrogen chloride and stannous chloride,2 by the passage of a mixture of caprylic acid and formic acid over titanium dioxide3 or manganous oxide,4 by dehydrogenation of 1-octanol over copper,6 and by oxidation of 1-octanol.6... 

Titanium (IV) iodide may be prepared by a variety of methods. High-temperature methods include reaction of titanium metal with iodine vapor,1-3 titanium carbide with iodine,4 titanium(IV) oxide with aluminum (III) iodide,5 and titanium (IV) chloride with a mixture of hydrogen and iodine. At lower temperatures, titanium (IV) iodide has been obtained by the combination of titanium and iodine in refluxing carbon tetrachloride7 and in hot benzene or carbon disulfide 8 a titanium-aluminum alloy may be used in place of titanium metal.9 It has been reported that iodine combines directly with titanium at room temperature if the metal is prepared by sodium reduction of titanium (IV) chloride and is heated to a high temperature before iodine is... 

Reduction of l,2,4-triazin-3-ones (84) with Raney nickel, zinc and acetic acid, lithium aluminum hydride, sodium borohydride, titanium(III) chloride, p-toluenethiol, hydrogen and a palladium catalyst, or electrochemically, produces 4,5-dihydro-l,2,4-triazin-3-ones (268) (78HC(33)189, p. 246, 80JHC1237), which may be further reduced to 1,4,5,6-tetrahydro-l,2,4-triazin-3-ones (269). l,2,4-Triazin-3-ones (84) with hydriodic acid and phosphorus yielded imidazoles (05LA(339)243). 3-Alkoxy-l,2,4-triazines (126) and sodium borohydride gave the 2,5-dihydro derivatives (270) (80JOC4594). 

Chemical reduction [with aqueous titanium(III) chloride in dilute acetic acid] or catalytic reduction (in the presence of 10% palladium-on-charcoal by transfer hydrogenation from cyclohexene or with hydrogen) of 3-nitro-4//-pyrido[l,2-a]pyrimidin-4-ones 176 (R = H, 8-Me, 8-OMe, 7-C1) gave 3-amino-4//-pyrido[l,2-a]pyrimidin-4-ones [90JCR(S)308]. Chemical and catalytic reduction of 3,8-dinitro-9-hydroxy-4//-pyrido[l,2-a]pyrimidin-4-one yielded an unstable product. 

Titanium cesium alum, 6 50 Titanium (II) chloride from disproportionation of titanium (III) chloride, 6 56, 61 Titanium(III) chloride, 6 52, 57 Titanium (IV) chloride, reduction of, with hydrogen, 6 52, 57 Titanium complex compounds, cations, with acetylacetone, [Ti-(C.H. hTiCl, and [Ti(C6H7-0,),]FeCl , 2 119, 120 Titanium(IV) oxide, extraction of, from ilmenite, 5 79, 81 to titanium powder with calcium, 6 47... 

The reduction of quinoxaline derivatives or quaternized quinoxalines by titanium(lll) chloride leads to di- or tetrahydro compounds. Several reductions of quinoxalines to 1,2,3,4-tetrahy-droquinoxalines with hydrogen and a metal catalyst at room temperatures and pressure not exceeding 3 atmospheres have been described, the yields of which are sometimes strongly solvent dependent. At higher temperatures and pressures decahydroquinoxalines may be reaction products. ... 

The sodium reduction of titanium tetrachloride was actually carried out as early as 1939 in Germany, and about 670 kg was produced by the Deutsche Gold and Silber Scheideanstalt, during the 1939-45 war. The process, now obsolete, involved reduction in a molten bath of 50 per cent sodium chloride and 50 per cent potassium chloride at 800°C in an atmos phere of hydrogen. The reactors consisted of expendable welded sheet-iron cylindrical vessels, 50 cm diameter by 70 cm deep and 2 mm thick. These rested loosely in a stout iron crucible, fitted into a gas-fired furnace. A portable stirrer was used to agitate the reactor contents. Approximately 20 kg batches of titanium were reduced by distilling 85 kg of titanium tetrachloride at a controlled rate into a melt of 15 kg sodium chloride and 15 kg of potassium chloride, covered with a layer of 46 kg of molten sodium. The titanium sank to the bottom of the molten salts, and at the end of the reaction was recovered from the crushed solidified melt by leaching with dilute hydrochloric acid, in a ceramic-lined vessel. It was finally washed in water and dried at a moderate temperature. The same plant was also used for the production of zirconium metal by the sodium reduction of potassium fluorozirconate (KaZrF ]. 

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