Trichloride preparation

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]. 

After stirring until the lutetium salt is well mixed, the extraction of a sample of 1 litre of solution is taken from the tank. To this volume of solution is added 20 pg of lutetium hexahydrate trichloride prepared from the pure isotope l76Lu (176LuC13.6H20 has for mass 390.4 g mol-1 l76Lu — 175.94gmol ) is added to this solution. 

Preparation of 4-cyanophenylzinc bromide by transmetallation and its reaction with phosphorus trichloride preparation of tris (4-cyanophenyl)phosphine-borane complex8... 

Another method of nitrogen trichloride preparation was published by Balard, who proved that nitrogen trichloride can be obtained when a solution of hypochlorous acid comes into contact with aqueous ammonia or anmumium salts... 

Boron trichloride, BCI3. Colourless mobile liquid, m.p. — 107°C, b.p. 12-5°C. Obtained directly from the elements or by heating B2O3 with pels in a sealed tube. The product may be purified by distillation in vacuo. It is extremely readily hydrolysed by water to boric acid. TetrachJoroborates containing the BCJ4 " ion are prepared by addition of BCI3 to metal chlorides. 

Vanadium oxide trichloride, VOCI3, vanadyl chloride. Readily prepared yellow liquid, b.p. 127 C, formed CK plus heated V2OS plus C. Readily hydrolysed by water. 

Boron forms a whole series of hydrides. The simplest of these is diborane, BjH. It may be prepared by the reduction of boron trichloride in ether by lithium aluminium hydride. This is a general method for the preparation of non-metallic hydrides. 

Both boron and aluminium chlorides can be prepared by the direct combination of the elements. Boron trichloride can also be prepared by passing chlorine gas over a strongly heated mixture of boron trioxide and carbon. Like boron trifluoride, this is a covalent compound and a gas at ordinary temperature and pressure (boiling point 285 K). It reacts vigorously with water, the mechanism probably involving initial co-ordination of a water molecule (p, 152). and hydrochloric acid is obtained ... 

Boron nitride can be prepared by allowing ammonia to react with boron trichloride. The first product is boron amide which decomposes on heating to give the nitride ... 

Pure phosphine can be prepared by the reduction of a solution of phosphorus trichloride in dry ether with lithium aluminium hydride ... 

Antimony forms both a + 3 and a + 5 oxide. The + 3 oxide can be prepared by the direct combination of the elements or by the action of moderately concentrated nitric acid on antimony. It is an amphoteric oxide dissolving in alkalis to give antimonates(III) (for example sodium antimonite , NaSb02), and in some acids to form salts, for example with concentrated hydrochloric acid the trichloride, SbCl3, is formed. 

Phosphonic acid, H3PO3, often called just phosphorous acid , is prepared by the hydrolysis of phosphorus trichloride a stream of air containing phosphorus trichloride vapour is passed into ice-cold water, and crystals of the solid acid separate ... 

Nitrogen trifluoride and trichloride can both be prepared as pure substances by the action of excess halogen on ammonia, a copper catalyst being necessary for the formation of nitrogen trifluoride. 

Phosphorus pentachloride is prepared by the action of chlorine on phosphorus trichloride. To push the equilibrium over to the right, the temperature must be kept low and excess chlorine must be present. Hence the liquid phosphorus trichloride is run dropwise into a flask cooled in ice through which a steady stream of dry chlorine is passed the solid pentachloride deposits at the bottom of the flask. 

Arsenic forms a volatile trifluoride, ASF3, and a fairly volatile trichloride, ASCI3, which fumes in air. The latter is prepared by passing dry hydrogen chloride over arsenic(lll) oxide at 500 K ... 

The following preparation of triethyl phosphite illustrates the interaction of phosphorus trichloride and ethanol in the presence of dimethylaniline the preparation of di-isopropyl hydrogen phosphite illustrates that of phosphorus trichloride and isopropanol in the absence of a tertiary amine. 

Boron exists naturally as 19.78% lOB isotope and 80.22% IIB isotope. High-purity crystalline boron may be prepared by the vapor phase reduction of boron trichloride or tribromide with hydrogen on electrically heated filaments. The impure or amorphous, boron, a brownish-black powder, can be obtained by heating the trioxide with magnesium powder. 

The element was first prepared by Klemm and bonner in 1937 by reducing ytterbium trichloride with potassium. Their metal was mixed, however, with KCl. Daane, Dennison, and Spedding prepared a much purer from in 1953 from which the chemical and physical properties of the element could be determined. 

Titanium trifluoride is prepared by dissolving titanium metal in hydrofluoric acid (1,2) or by passing anhydrous hydrogen fluoride over titanium trihydrate at 700°C or over heated titanium powder (3). Reaction of titanium trichloride and anhydrous hydrogen fluoride at room temperature yields a cmde product that can be purified by sublimation under high vacuum at 930—950°C. 

Organophosphorus Derivatives. Neopentyl glycol treated with pyridine and phosphorus trichloride in anhydrous dioxane yields the cycHc hydrogen phosphite, 5,5-dimethyl-l,3-dioxaphosphorinane 2-oxide (2) (32,33). Compounds of this type maybe useful as flameproofing plasticizers, stabilizers, synthetic lubricants, oil additives, pesticides, or intermediates for the preparation of other organophosphoms compounds (see Flame retardants Phosphorus compounds). 

Hafnium Boride. Hafnium diboride [12007-23-7] HfB2, is a gray crystalline soHd. It is usually prepared by the reaction of hafnium oxide with carbon and either boron oxide or boron carbide, but it can also be prepared from mixtures of hafnium tetrachloride, boron trichloride, and hydrogen above 2000°C, or by direct synthesis from the elements. Hafnium diboride is attacked by hydrofluoric acid but is resistant to nearly all other reagents at room temperature. Hafnium dodecaboride [32342-52-2] has been prepared by direct synthesis from the elements (56). 

Iodine trichloride [865-44-17, ICl, mol wt 233.39, 54.40% I, is a yellow or brownish powder. It is pungent and has a very irritating odor. It decomposes at 77°C iato ICl and CI2. It is prepared by adding finely powdered iodine to an excess of Hquid chlorine. It is used as a chlorinating and oxidising agent (120). 

In analogy to the situation for bipyridine, the blue tris(l,10-phenanthroline)iron(3+) ion [1347949-7], [Fe(phen)2], must be obtained by oxidation of the corresponding iron(II) ion. [Fe(phen)2] has an absorption maximum at 590 nm, an absorptivity of 600 (Mem), and a formation constant of 10 . In solutions of pH > 4, this species is reduced to the iron(II) complex. The reduction is instantaneous in alkaline solution. At pH < 2, protons compete with iron(III) for the phenanthroline nitrogens and coordination is incomplete. [Fe(phen)2] is used most often in solution as an oxidant, but the trichloride [40273-22-1] and the triperchlorate monohydrate [20774-81-6] salts have been prepared. 

Diketene is used to C-acetoacetylate aromatic compounds in the presence of aluminum trichloride [7446-70-0]. Benzene [71-43-2] and diketene react to produce acetoacet5lben2ene [93-91-4]. Pyrrole [109-97-7] and diketene react to produce 2-acetoacet5lpyrrole [22441-25-4]. The C-acetoacetyl derivatives of active methylene compounds such as cyanoacetates, malonodinitrile [109-77-3] and Meldmm s acid [2033-24-1], and olefins can be prepared using diketene. 

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