Oxides oxychlorides

The reaction with oxygen converts phosphorus trichloride to phosphorus trichloride oxide (oxychloride), POCI3 the trichloride is able to remove oxygen from some molecules, for example sulphur trioxide... 

Design of Layered Phosphonates Possessing Functionalities for Coordination to Multiply Bonded Bimetallic Cores. Solids shown in Figure 3c can be designed readily with LMPs because their galleries can be modified by pendant functionalities covalently anchored to the layers with the methods introduced by Alberti (25,55) and Dines (54-57). Reaction of organic phosphonic or arsonic acids with M4+ oxides, oxychlorides, and halides yields M(03XR)2 (X = P or As M = Ti, Zr, U, Th, and Ce) layered materials,... 

Ferenc and Bocian [175] studied the thermal properties of 5-chloro-2-methoxybenzoates of lanthanides(III) and divalent transition metal ions, in both air and nitrogen atmospheres. The complexes were obtained as mono-, di-, tetra-and pentahydrates with a metal-to-ligand ratio of 1 3 (in the case of lanthanides(III)) and 1 2 (in the case of d-block elements). The compoxmds showed colours typical for Ln and ions and all of them are polycrystalline compounds. When heated, they dehydrate to form anhydrous salts, which in air are decomposed to the oxides of the respective metals, while in nitrogen to the mixtures of metal oxides, oxychlorides and carbon. 

Aqueous HCl, or any other inorganic acid except HF, carefully added to a solution of Sb salts in OH" precipitates the corresponding oxide, hydrated oxide, oxychloride (SbOCl) etc., often soluble in more acid or concentrated Cl" and so on. The trioxide, Sb203, dissolves in HCl ... 

The oxide dichloride, b.p. 351 K, is separated from the less volatile phosphorus oxychloride by a fractional distillation. 

The preparation of 4-methylcoumarin is an example of the Pechmann reaction, which consists in the interaction of a phenol with a 3-ketonic ester In the presence of a condensing agent (sulphuric acid, aluminium chloride, phosphorus oxychloride or pho.sphoric oxide) ... 

Chloroacetyl chloride is manufactured by reaction of chloroacetic acid with chlorinating agents such as phosphoms oxychloride, phosphoms trichloride, sulfuryl chloride, or phosgene (42—44). Various catalysts have been used to promote the reaction. Chloroacetyl chloride is also produced by chlorination of acetyl chloride (45—47), the oxidation of 1,1-dichloroethene (48,49), and the addition of chlorine to ketene (50,51). Dichloroacetyl and trichloroacetyl chloride are produced by oxidation of trichloroethylene or tetrachloroethylene, respectively. 

This hquid contains 27% chlorine and 12% phosphoms. It is made from ethylene oxide, diethylene glycol, and phosphoms oxychloride (80). It is available ia the United States and Japan from Daihachi. 

Reaction with Meta/ Oxides. The reaction of hydrogen chloride with the transition-metal oxides at elevated temperatures has been studied extensively. Fe202 reacts readily at temperatures as low as 300°C to produce FeCl and water. The heavier transition-metal oxides require a higher reaction temperature, and the primary reaction product is usually the corresponding oxychlorides. Similar reactions are reported for many other metal oxides, such as Sb202, BeO, AI2O2, andTi02, which lead to the formation of relatively volatile chlorides or oxychlorides. 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, aHenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphoms oxychloride [10025-87-3] POCl (H)- Because sulfonic acids are generally not converted directiy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphoms pentachlotide [10026-13-8] and phosphoms pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl haUdes (12,13). The conversion may also be accompHshed by continuous electrolysis of thiols or disulfides in the presence of aqueous HCl [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfutic acid [7789-21-17, or by reaction of the sulfonic acid or sulfonate with fluorosulfutic acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl haUde, can be achieved under oxidative halogenation conditions (15). 

The volatile chlorides ate collected and the unreactedsohds and nonvolatile chlorides ate discarded. Titanium tetrachloride is separated from the other chlorides by double distillation (12). Vanadium oxychloride, VOCl, which has a boiling point close to TiCl, is separated by complexing with mineral oil, reducing with H2S to VOCI2, or complexing with copper. The TiCl is finally oxidized at 985°C to Ti02 and the chlorine gas is recycled (8,11) (see also... 

In the ketone method, the central carbon atom is derived from phosgene (qv). A diarylketone is prepared from phosgene and a tertiary arylamine and then condenses with another mole of a tertiary arylamine (same or different) in the presence of phosphoms oxychloride or zinc chloride. The dye is produced directly without an oxidation step. Thus, ethyl violet [2390-59-2] Cl Basic Violet 4 (15), is prepared from 4,4 -bis(diethylamino)benzophenone with diethylaruline in the presence of phosphoms oxychloride. This reaction is very useful for the preparation of unsymmetrical dyes. Condensation of 4,4 -bis(dimethylamino)benzophenone [90-94-8] (Michler s ketone) with AJ-phenjl-l-naphthylamine gives the Victoria Blue B [2580-56-5] Cl Basic Blue 26, which is used for coloring paper and producing ballpoint pen pastes and inks. 

Zirconium tetrachloride is instantly hydrolyzed in water to zirconium oxide dichloride octahydrate [13520-92-8]. Zirconium tetrachloride exchanges chlorine for 0x0 bonds in the reaction with hydroxylic ligands, forming alkoxides from alcohols (see Alkoxides, METAl). Zirconium tetrachloride combines with many Lewis bases such as dimethyl sulfoxide, phosphoms oxychloride and amines including ammonia, ethers, and ketones. The zirconium organometalLic compounds ate all derived from zirconium tetrachloride. 

Oxide Chlorides. Zirconium oxide dichloride, ZrOCl2 -8H2 0 [13520-92-8] commonly called zirconium oxychloride, is really a hydroxyl chloride, [Zr4(OH)g T6H2 0]Clg T2H2O (189). Zirconium oxychloride is produced commercially by caustic fusion of zircon, followed by water washing to remove sodium siUcate and to hydrolyze the sodium zirconate the wet filter pulp is dissolved in hot hydrochloric acid, and ZrOCl2 -8H2 O is recovered from the solution by crystallization. An aqueous solution is also produced by the dissolution and hydrolysis of zirconium tetrachloride in water, or by the addition of hydrochloric acid to zirconium carbonate. 

Zirconium oxychloride is an important intermediate from which other zirconium chemicals are produced. It readily effloresces, and hydrates with 5—7 H2O are common. The salt caimot be dried to the anhydrous form, and decomposes to hydrogen chloride and zirconium oxide. 

Aqueous solutions of zirconium oxide dinitrate [13826-66-9] (zirconium oxynitrate) and zirconium oxychloride behave very similarly these two compounds have been cocrystallized in soHd solution (202) where ZrO(N03 -5H2 O was the stable hydrate. 

The most common basic sulfate is 5Zr02 ASO 535. [84583-91-5] which is precipitated in good yield when a zirconium oxychloride solution is heated with the stoichiometric amount in sulfate ion. It is used to prepare high purity oxides and ammonium zirconium carbonate. 

Copper(II) oxychloride [1332-65-6], Cu2Cl(OH)2, is found in nature as the green hexagonal paratacamite [12186-OOA] or rhombic atacamite [1306-85-0]. It is usually precipitated by air oxidation of a concentrated sodium chloride solution of copper(I) chloride (13—15). Often the solution is circulated through a packed tower of copper metal, heated to 60—90°C, and aerated. 

Acceleration modifies the surface layer of palladium nuclei, and stannous and stannic hydrous oxides and oxychlorides. Any acid or alkaline solution in which excess tin is appreciably soluble and catalytic palladium nuclei become exposed may be used. The activation or acceleration step is needed to remove excess tin from the catalyzed surface, which would inhibit electroless plating. This step also exposes the active palladium sites and removes loose palladium that can destabilize the bath. Accelerators can be any acidic or alkaline solution that solubilizes excess tin. 

Phosphoms oxychloride reacts with ethylene oxide in the presence of aluminum chloride to give tris-2-chloroethyl phosphate, a valuable plasticizer (75). Phosgene reacts with ethylene oxide and other alkylene oxides to form esters of chlorocarbonic acid (76) (see Carbonic and carbonochloridic esters). 

Treatment of pyridazine 1-oxides with phosphorus oxychloride results in a-chlorination with respect to the N-oxide group, with simultaneous deoxygenation. When the a-position is blocked, substitution occurs at the y-position. 3-Methoxypyridazine 1-oxide, for example, is converted into 6-chloro-3-methoxypyridazine and 3,6-dimethylpyridazine 1-oxide into 4-chloro-3,6-dimethylpyridazine. 

The second most important nucleophilic substitution in pyridazine A-oxides is the replacement of a nitro group. Nitro groups at the 3-, 4-, 5- and 6-position are easily substituted thermally with a chlorine or bromine atom, using acetyl chloride or hydrobromic acid respectively. Phosphorus oxychloride and benzoyl chloride are used less frequently for this purpose. Nitro groups in nitropyridazine A-oxides are easily replaced by alkoxide. The... 

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