Aluminum peroxides

Carbon dioxide is a colorless and odorless gas. It has a molecular weight of 44.01 and specific gravity of 1.101 at — 37°C. It is incompatible with metals (e.g., aluminum peroxide, sodium peroxide, lithium peroxide, sodium, sodium carbide, titanium, and sodium-potassium alloy). 

Lewinski and coworkers recently used this reaction sequence and achieved full characterization of the aluminum-peroxide complex by X-ray single-crystal analysis (Scheme 6.143) [183]. The structure is consistent wifh a mixture of tetra- and hexacoordination and wifh solution spectroscopic data. Unlike fhe usual instabihty of alkylperoxide complexes of aluminum, this peroxo complex is relatively stable, partly because of the hexacoordination also because of fhe steric bulk of fhe t-Bu groups attached to oxygen atoms. 

CHEMICAL PROPERTIES Polymerizes incompatible with copper, aluminum, peroxides, iron, steel and oxidizing agents attacks iron and steel in presence of water FP (-78°C, -112°F) LFL (3.6%) UFL (33.0%) AT (472°C). 

Incompatibilities and Reactivities Anhydrous chlorides of iron, tin, and aluminum peroxides of iron and aluminum alkali metal hydroxides iron strong acids, caustics peroxides [Note Polymerization may occur due to high temperatures or contamination with alkalis, aqueous acids, amines acidic alcohols ] ... 

Incompatibilities and Reactivities Copper, oxidizers, aluminum, peroxides, iron, steel [Note Polymerizes in air. sunlight, or heat unless stabilized by inhibitors such as phenol. Attacks iron steel in presence of moisture.]... 

NaCl, sodium chloride, binary salt, varying Ca3(P04)2, calcium phosphate, oxysalt oxidizer AljlOjlj, aluminum peroxide, peroxide RH, CL, RO CuBtj, copper 11, bromide, binary salt, varying KOH, potassium hydroxide, hydroxide RH, CL LijO, lithium oxide, metal oxide RH, CL Mg(C10)2, magnesium hypochlorite, oxysalt, oxidizer Hg02, mercury II, peroxide, peroxide RH, CL, RO NaF, sodium fluoride, binary salt, varying... 

Destruction of the masking ligand by chemical reaction may be possible, as in the oxidation of EDTA in acid solutions by permanganate or another strong oxidizing agent. Hydrogen peroxide and Cu(II) ion destroy the tartrate complex of aluminum. 

Ethyl ether Eiquid air, chlorine, chromium(VI) oxide, lithium aluminum hydride, ozone, perchloric acid, peroxides... 

Lead dioxide Aluminum carbide, hydrogen peroxide, hydrogen sulfide, hydroxylamine, ni-troalkanes, nitrogen compounds, nonmetal halides, peroxoformic acid, phosphorus, phosphorus trichloride, potassium, sulfur, sulfur dioxide, sulfides, tungsten, zirconium... 

Manganese dioxide Aluminum, hydrogen sulfide, oxidants, potassium azide, hydrogen peroxide, peroxosulfuric acid, sodium peroxide... 

The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

Many organic peroxides of metals have been hydrolyzed to alkyl hydroperoxides. The alkylperoxy derivatives of aluminum, antimony, arsenic, boron, cadmium, germanium, lead, magnesium, phosphoms, silicon, tin, and zinc yield alkyl hydroperoxides upon hydrolysis (10,33,60,61). 

The reduction of alkyl-substituted siUcon and tin peroxides with sodium sulfite and triphenylphosphine has been reported (33,93). Alkyl-substituted aluminum, boron, cadmium, germanium, siUcon, and tin peroxides undergo oxygen-to-metal rearrangements (33,43,94), eg, equations 22 and 23. 

Cyclic Peroxides. CycHc diperoxides (4) and triperoxides (5) are soHds and the low molecular weight compounds are shock-sensitive and explosive (151). The melting points of some characteristic compounds of this type are given in Table 5. They can be reduced to carbonyl compounds and alcohols with zinc and alkaH, zinc and acetic acid, aluminum amalgam, Grignard reagents, and warm acidified iodides (44,122). They are more difficult to analyze by titration with acidified iodides than the acycHc peroxides and have been sucessfuUy analyzed by gas chromatography (112). 

Diacyl peroxides have been reduced with a variety of reduciag agents, eg, lithium aluminum hydride, sulfides, phosphites, phosphines, and haUde ions (187). Hahdes yield carboxyUc acid salts (RO) gives acid anhydrides. With iodide ion and certain trivalent phosphoms compounds, the reductions are sufftcientiy quantitative for analytical purposes. 

Ferrovanadium can also be prepared by the thermite reaction, in which vanadium and iron oxides are co-reduced by aluminum granules in a magnesite-lined steel vessel or in a water-cooled copper cmcible (11) (see Aluminumand aluminum alloys). The reaction is initiated by a barium peroxide—aluminum ignition charge. This method is also used to prepare vanadium—aluminum master alloys for the titanium industry. 

When dry and in contact with metals, vinyl chloride does not decompose below 450°C. However, if water is present, vinyl chloride can corrode iron, steel, and aluminum because of the presence of trace amounts of HCl. This HCl may result from the hydrolysis of the peroxide formed between oxygen and vinyl chloride. 

In the petroleum (qv) industry hydrogen bromide can serve as an alkylation catalyst. It is claimed as a catalyst in the controlled oxidation of aHphatic and ahcycHc hydrocarbons to ketones, acids, and peroxides (7,8). AppHcations of HBr with NH Br (9) or with H2S and HCl (10) as promoters for the dehydrogenation of butene to butadiene have been described, and either HBr or HCl can be used in the vapor-phase ortho methylation of phenol with methanol over alumina (11). Various patents dealing with catalytic activity of HCl also cover the use of HBr. An important reaction of HBr in organic syntheses is the replacement of aHphatic chlorine by bromine in the presence of an aluminum catalyst (12). Small quantities of hydrobromic acid are employed in analytical chemistry. 

Chromium oxide is mixed with aluminum powder, placed in a refractory-lined vessel, and ignited with barium peroxide and magnesium powder. The reaction is exothermic and self-sustaining. Chromium metal of 97—99% purity is obtained, the chief impurities being aluminum, iron, and silicon (Table 4). Commercial chromium metal may also be produced from the oxide by reduction with silicon in an electric-arc furnace. 

When heated in the presence of a carboxyHc acid, cinnamyl alcohol is converted to the corresponding ester. Oxidation to cinnamaldehyde is readily accompHshed under Oppenauer conditions with furfural as a hydrogen acceptor in the presence of aluminum isopropoxide (44). Cinnamic acid is produced directly with strong oxidants such as chromic acid and nickel peroxide. The use of t-butyl hydroperoxide with vanadium pentoxide catalysis offers a selective method for epoxidation of the olefinic double bond of cinnamyl alcohol (45). 

I08J (in a different form than for aluminum adherends) but Pasa Jell 107, Turco 5578 and alkaline peroxide [80] etches are also popular. 

Since aluminum is not attacked by hydrogen sulfide (HjS) solutions, it is used widely as a material in refineries for the handling of hydrocarbons made from sour crudes. In the strongly oxidizing conditions of manufacturing hydrogen peroxide, aluminum is one of the few materials that does not undergo decomposition. 

Aluminum chlorate Ammonium chromate Benzoyl peroxide, dry... 

The stereochemical course of reduction of imonium salts by Grignard reagents was found to depend on the structure of the reagent 714). Hydro-boration of enamines and oxidation with hydrogen peroxide led to amino-alcohols (7/5). While aluminum hydrogen dichloride reacted with enamines to yield mostly saturated amines and some olefins on hydrolysis, aluminum hydride gave predominantly the unsaturated products 716). 

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