Reduction with titanium chloride

Reduction. Triaryknethane dyes are reduced readily to leuco bases with a variety of reagents, including sodium hydrosulfite, 2inc and acid (hydrochloric, acetic), 2inc dust and ammonia, and titanous chloride in concentrated hydrochloric acid. Reduction with titanium trichloride (Knecht method) is used for rapidly assaying triaryknethane dyes. The TiCl titration is carried out to a colorless end point which is usually very sharp (see Titanium COMPOUNDS, inorganic). 

Although primary and secondary nitro compounds may be converted, respectively, to aldehydes and ketones by consecutive treatment with alkalis and sulfuric acid (Nef s reaction) the same products can be obtained by reduction with titanium trichloride (yields 45-90%) [565] or chromous chloride (yields 32-77%) [190]. The reaction seems to proceed through a nitroso rather than an aci-nitro intermediate [565] (Scheme 54, route b). 

The synthesis of unsymmetrical 1,4-diketones results from the conjugate addition of the nitronate anion (as the acyl anion equivalent) to an a,fi-unsaturated ketone [Method (6)].l47a The intermediate nitroketone is converted into the diketone by reduction with titanium(m) chloride at pH 1, or by ozono-lysis of the nitronate anion147b (cf. Section 5.7.7, p. 599). 

Nitrogen-13-labeled ammonia (ty2 = 10 min) is produced by reduction of 13N-labeled nitrates and nitrites that are produced by proton irradiation of water in a cyclotron. The reduction is carried out with titanium chloride in alkaline medium. 13N-NH3 is then distilled and finally trapped in acidic saline solution. Wester et al (1991) has used a pressurized target of aqueous ethanol, in which ethanol acts as a hydroxyl free radical scavenger to improve the... 

Benzyloxyimidazole undergoes useful 2-Uthiations hydrogenolysis produces 2-substituted 1-hydroxy-imidazoles and these, in turn, can be converted into the 2-substituted imidazoles by reduction with titanium(III) chloride. ... 

A. Al-Wehaid and A. Townshend, Spectrophotometric Flow-Injection De-terminaion of Nitrate Based on Reduction with Titanium(III) Chloride. Anal. Chim. Acta, 186 (1986) 289. 

The titanium(IV) chloride adducts of (75) and (79), after reduction with diethylaluminum chloride, catalyzed the dimerization of isoprene and the trimerization of butadiene as effectively as other rf-cyclopentadienyl-based tertiary arsine ligands <84TLl97l). 

Very reactive metals, eg, titanium or 2irconium, which in the Hquid state react with all the refractory materials available to contain them, also require reduction to soHd metal. Titanium is produced by metallothermic reduction of its chloride using Hquid magnesium at 750°C (KroU process). 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

Reduction. Just as aromatic amine oxides are resistant to the foregoing decomposition reactions, they are more resistant than ahphatic amine oxides to reduction. Ahphatic amine oxides are readily reduced to tertiary amines by sulfurous acid at room temperature in contrast, few aromatic amine oxides can be reduced under these conditions. The ahphatic amine oxides can also be reduced by catalytic hydrogenation (27), with 2inc in acid, or with staimous chloride (28). For the aromatic amine oxides, catalytic hydrogenation with Raney nickel is a fairly general means of deoxygenation (29). Iron in acetic acid (30), phosphoms trichloride (31), and titanium trichloride (32) are also widely used systems for deoxygenation of aromatic amine oxides. 

Titanium Sulfates. Solutions of titanous sulfate [10343-61-0] ate readily made by reduction of titanium(IV) sulfate ia sulfuric acid solutioa by electrolytic or chemical means, eg, by reduction with ziac, ziac amalgam, or chromium (IT) chloride. The reaction is the basis of the most used titrimetric procedure for the determination of titanium. Titanous sulfate solutions are violet and, unless protected, can slowly oxidize ia coatact with the atmosphere. If all the titanium has been reduced to the trivalent form and the solution is then evaporated, crystals of an acid sulfate 3 Ti2(S0 2 [10343-61-0] ate produced. This purple salt, stable ia air at aormal temperatures, dissolves ia water to give a stable violet solutioa. Whea heated ia air, it decomposes to Ti02, water, sulfuric acid, and sulfur dioxide. 

An 80% yield of tetraphenylfuran is obtained by treatment of benzoyl chloride with active titanium generated by lithium aluminum hydride reduction of titanium trichloride (Scheme 84e) (8UOC2407). The reaction nroceeds via benzil and tetraphenylbut-2-ene-l,4-dione, both of which are minor products of the reaction. 

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... 

Determination of perchlorate as silver chloride Discussion. Perchlorates are not reduced by iron (II) sulphate solution, sulphurous acid, or by repeated evaporation with concentrated hydrochloric acid reduction occurs, however, with titanium(III) sulphate solution. Ignition of perchlorates with ammonium... 

Titanium tetrachloride is produced on an industrial scale by the chlorination of titanium dioxide-carbon mixtures in reactors lined with silica. During the reactor operation, the lining comes into contact not only with chlorine but also with titanium tetrachloride. There appears to be no attack on silica by either of these as the lining remains intact. However, the use of such a reactor for chlorinating beryllium oxide by the carbon-chlorine reduction chlorination procedure is not possible because the silica lining is attacked in this case. This corrosion of silica can be traced to the attack of beryllium chloride on silica. The interaction of beryllium chloride with silica results in the formation of silicon tetrachloride in accordance with the reaction... 

Titanium dichloride forms a low-melting eutectic with sodium chloride, and so the reaction mass is molten at this temperature. Additional sodium is then added to complete the reduction ... 

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... 

Solutions of low-valence titanium chloride (titanium dichloride) are prepared in situ by reduction of solutions of titanium trichloride in tetrahydrofuran or 1,2-dimethoxyethane with lithium aluminum hydride [204, 205], with lithium or potassium [206], with magnesium [207, 208] or with a zinc-copper couple [209,210]. Such solutions effect hydrogenolysis of halogens [208], deoxygenation of epoxides [204] and reduction of aldehydes and ketones to alkenes [205,... 

Aliphatic and aromatic sulfides undergo desulfurization with Raney nickel [673], with nickel boride [673], with lithium aluminum hydride in the presence of cupric chloride [675], with titanium dichloride [676], and with triethyl phosphite [677]. In saccharides benzylthioethers were not desulfurized but reduced to toluene and mercaptodeoxysugars using sodium in liquid ammonia [678]. This reduction has general application and replaces catalytic hydrogenolysis, which cannot be used [637]. 

Chemical deoxygenation of sulfoxides to sulfides was carried out by refluxing in aqueous-alcoholic solutions with stannous chloride (yields 62-93%) [186 Procedure 36, p. 214), with titanium trichloride (yields 68-91%) [203], by treatment at room temperature with molybdenum trichloride (prepared by reduction of molybdenyl chloride M0OCI3 with zinc dust in tetrahydrofuran) (yields 78-91%) [216], by heating with vanadium dichloride in aqueous tetrahydrofuran at 100° (yields 74-88%) [216], and by refluxing in aqueous methanol with chromium dichloride (yield 24%) [190], A very impressive method is the conversion of dialkyl and diaryl sulfoxides to sulfides by treatment in acetone solutions for a few minutes with 2.4 equivalents of sodium iodide and 1.2-2.6 equivalents of trifluoroacetic anhydride (isolated yields 90-98%) [655]. 

As noted earlier, most classical antidepressant agents consist of propylamine derivatives of tricyclic aromatic compounds. The antidepressant molecule tametraline is thus notable in that it is built on a bicyclic nucleus that directly carries the amine substituent. Reaction of 4-phenyl-l-tetralone (18) (obtainable by Friedel-Crafts cyclization of 4,4-diphenyl butyric acid) with methyl amine in the presence of titanium chloride gives the corresponding Schiff base. Reduction by means of sodium borohydride affords the secondary amine as a mixture of cis (21) and trans (20) isomers. The latter is separated to afford the more active antidepressant of the pair, tametraline (20). 

Magnesium chloride also is a by-product during reduction of titanium(IV) chloride with magnesium metal ... 

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