Chromium reaction

Chromium reaction in an aqueous solution with a base produces a pale blue-violet precipitate having composition Cr(H20)3(0H)3. 

Noteworthy is the fact that these neutral nitrosyls, including the precursor iodide, are chiral by virtue of having four unique ligands bound to chromium. Reaction of bipy or phen with [(jj -C5H5)Cr(NO)2(MeCN)]PF6 at 100 °C results in displacement of MeCN and one NO... 

The reactions of molybdenum and tungsten carbenes M(CO)5 =C(OMe)Me with o,(D-enynes proceed differently to the analogous chromium reactions specifically the tendency for cyclopropanation is greater. It is conceivable that seven coordinate intermediates are intermediates in these processes.294 Photolysis of carbene complexes such as Cr(CO)5 s=C(OEt)R (R = Me, Bu )... 

Chromium dioxide. Cr02 (HjO plus O2 on Cr03 at high temperature). Black solid with the rutile structure forming chromates(IV) in solid stale reactions. Used in magnetic lap>es. 

The reaction provides a valuable method of preparing anhydrous chlorides of metals. It has been used to prepare the anhydrous chlorides of copper(II), zinc, cadmium, chromium(III), iron(III). cobalt(Il) and nickel. 

The reactivity of the transition metals towards other elements varies widely. In theory, the tendency to form other compounds both in the solid state (for example reactions to form cations) should diminish along the series in practice, resistance to reaction with oxygen (due to formation of a surface layer of oxide) causes chromium (for example) to behave abnormally hence regularities in reactivity are not easily observed. It is now appropriate to consider the individual transition metals. 

Anthracene is oxidised by chromium trioxide, Cr04, to anthraquinone. As the reaction is carried out in solution, a solvent is required which will dissolve both the anthracene and the chromium trioxide, and at the same time be... 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

Hydrogenations with coppcr-chromium oxide catalyst are usually carried out in the liquid phase in stainless steel autoclaves at pressures up to 5000-6000 lb. per square inch. A solvent is not usually necessary for hydrogenation of an ester at 250° since the original ester and the alcohol or glycol produced serve as the reaction medium. However, when dealing with small quantities and also at temperatures below 200° a solvent is desirable this may be methyl alcohol, ethyi alcohol, dioxan or methylcyc/ohexane. 

The most abundant natural steroid is cholesterol. It can be obtained in large quantides from wool fat (15%) or from brain or spinal chord tissues of fat stock (2-4%) by extraction with chlorinated hydrocarbons. Its saturated side-chain can be removed by chromium trioxide oxidation, but the yield of such reactions could never be raised above 8% (see page 118f.). 

Step 3 A series of redox reactions converts chromium from the 4+ oxidation state m HCr03 to the 3 + oxidation state... 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

In this titration the analyte is oxidized from Fe + to Fe +, and the titrant is reduced from CryOy to Cr +. Oxidation of Fe + requires only a single electron. Reducing CryOy, in which chromium is in the +6 oxidation state, requires a total of six electrons. Conservation of electrons for the redox reaction, therefore, requires that... 

The atoms in each half-reaction are then balanced. The zinc half-reaction is already balanced in this respect, so we begin by balancing chromium in the dichromate half-reaction. 

Chemical ingenuity in using the properties of the elements and their compounds has allowed analyses to be carried out by processes analogous to the generation of hydrides. Osmium tetroxide is very volatile and can be formed easily by oxidation of osmium compounds. Some metals form volatile acetylacetonates (acac), such as iron, zinc, cobalt, chromium, and manganese (Figure 15.4). Iodides can be oxidized easily to iodine (another volatile element in itself), and carbonates or bicarbonates can be examined as COj after reaction with acid. 

The equilibrium is more favorable to acetone at higher temperatures. At 325°C 97% conversion is theoretically possible. The kinetics of the reaction has been studied (23). A large number of catalysts have been investigated, including copper, silver, platinum, and palladium metals, as well as sulfides of transition metals of groups 4, 5, and 6 of the periodic table. These catalysts are made with inert supports and are used at 400—600°C (24). Lower temperature reactions (315—482°C) have been successhiUy conducted using 2inc oxide-zirconium oxide combinations (25), and combinations of copper-chromium oxide and of copper and silicon dioxide (26). 

Usually, organoboranes are sensitive to oxygen. Simple trialkylboranes are spontaneously flammable in contact with air. Nevertheless, under carefully controlled conditions the reaction of organoboranes with oxygen can be used for the preparation of alcohols or alkyl hydroperoxides (228,229). Aldehydes are produced by oxidation of primary alkylboranes with pyridinium chi orochrom ate (188). Chromic acid at pH < 3 transforms secondary alkyl and cycloalkylboranes into ketones pyridinium chi orochrom ate can also be used (230,231). A convenient procedure for the direct conversion of terminal alkenes into carboxyUc acids employs hydroboration with dibromoborane—dimethyl sulfide and oxidation of the intermediate alkyldibromoborane with chromium trioxide in 90% aqueous acetic acid (232,233). 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Make acid yields coumaUc acid when treated with fuming sulfuric acid (19). Similar treatment of malic acid in the presence of phenol and substituted phenols is a facile method of synthesi2ing coumarins that are substituted in the aromatic nucleus (20,21) (see Coumarin). Similar reactions take place with thiophenol and substituted thiophenols, yielding, among other compounds, a red dye (22) (see Dyes and dye intermediates). Oxidation of an aqueous solution of malic acid with hydrogen peroxide (qv) cataly2ed by ferrous ions yields oxalacetic acid (23). If this oxidation is performed in the presence of chromium, ferric, or titanium ions, or mixtures of these, the product is tartaric acid (24). Chlorals react with malic acid in the presence of sulfuric acid or other acidic catalysts to produce 4-ketodioxolones (25,26). 

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