Suboxides

Carbon suboxide, C3O2, OCCCO. M.p. — 107 C, b.p. 6-8°C. A toxic gas (malonic acid plus P2O5) which polymerizes at room temperature. Reforms malonic acid with water. 

Boutou V, Lebeault M A, Allouohe A R, Bordas C, Paulig F, Viallon J and Chevaleyre J 1998 Struotural transition in barium suboxide olusters Phys. Rev. Lett. 80 2817... 

Liquid carbon suboxide added to a solution of 2-ethylaminothiarole in anhydrous ether at 0°C gives immediate formation of a white precipitate of the mesoionic xanthine (121) (R=H) (130), otherwise prepared by reaction between 2-ethylaminothiazole and phenoxycarbonyl isocyanate (see p. 65 and Ref. 304),... 

Titanium silicalite Titanium silicates Titanium-silicon alloy Titanium slag Titanium suboxides... 

Materials for PC Media. Crystalline alloys of elements from the fifth and sixth main group are preferred (3,103,109—111). As the first PC materials, tellurium suboxides as well as Te/Se or Te films that had been doped with small amounts of other elements like Ge, As, or Sb to shift the crystallization point to >100°C have been described. 

Ketenes and related compounds have been reviewed extensively (1 9). For the synthesis and synthetic uses of conjugated ketenes see Reference 10. Ketenes with three or more cumulated double bonds have been prepared (11,12). The best known is carbon suboxide [504-64-3] 3 2 preparative uses and has been reviewed (13—16). Thioketenes (17,18), ketenimines (19—21), and their dimers show interesting reactivity, but they have not achieved iadustrial importance to date. 

Reactions. Heating an aqueous solution of malonic acid above 70°C results in its decomposition to acetic acid and carbon dioxide. Malonic acid is a useful tool for synthesizing a-unsaturated carboxyUc acids because of its abiUty to undergo decarboxylation and condensation with aldehydes or ketones at the methylene group. Cinnamic acids are formed from the reaction of malonic acid and benzaldehyde derivatives (1). If aUphatic aldehydes are used acryhc acids result (2). Similarly this facile decarboxylation combined with the condensation with an activated double bond yields a-substituted acetic acid derivatives. For example, 4-thiazohdine acetic acids (2) are readily prepared from 2,5-dihydro-l,3-thiazoles (3). A further feature of malonic acid is that it does not form an anhydride when heated with phosphorous pentoxide [1314-56-3] but rather carbon suboxide [504-64-3] [0=C=C=0], a toxic gas that reacts with water to reform malonic acid. 

Berzehus (19) further appHed and amplified the nomenclature introduced by Guyton de Morveau and Lavoisier. It was he who divided the elements into metalloids (nonmetals) and metals according to their electrochemical character, and the compounds of oxygen with positive elements (metals) into suboxides, oxides, and peroxides. His division of the acids according to degree of oxidation has been Httie altered. He introduced the terms anhydride and amphoteric and designated the chlorides in a manner similar to that used for the oxides. 

Lower Oxides. A number of hard, refractory suboxides have been prepared either as by-products of elemental boron production (1) or by the reaction of boron and boric acid at high temperatures and pressures (39). It appears that the various oxides represented as B O, B O, B22O2, and B23O2 may all be the same material ia varying degrees of purity. A representative crystalline substance was determined to be rhombohedral boron suboxide, B12O2, usually mixed with traces of boron or B2O3 (39). A study has been made of the mechanical properties of this material, which exhibits a hardness... 

Use of excess air levels of 5 percent or less has been shown to reduce fuel ash corrosion in furnaces, most likely by stabilizing the vanadium as a refractory suboxide, VO2 or V2O3. Utility plants have had some success using this method to control vanadium ash corrosion. However, practical application of excess air control in refinery and chemical plant operations is difficult, and has not been particularly successful. Problems with particulates, smoke, pollution, and flame control are encountered unless the necessary expensive control systems and operator attention are constantly available. 

Figure 3-14 shows an induction period in the reaction of carbon suboxide (O=C=C=C=0) with triethylamine. This reaction is complex and is not yet... 

Figure 3-14. Absorbance-time plots for the reaction of carbon suboxide and triethylamine in ether solution in the presence of acetic anhydride. The initial C3O2 concentration was 2.03 X I0 - M the amine concentrations were 3 X lO " M, 5 x 10 M, and 7 X lO " M.

In addition to the above oxides M2O, M2O2, M4O6, MO2 and MO3 in which the alkali metal has the constant oxidation state 4-1, rubidium and caesium also form suboxides in which the formal oxidation state of the metal is considerably lower. Some of these intriguing compounds have been known since the turn of the century but only recently have their structures been elucidated by single crystal X-ray analysis. Partial oxidation of Rb at low temperatures gives RbeO which decomposes above —7.3°C to give copper-coloured metallic crystals of Rb902 ... 

Tricarbon dioxide, C3O2, often called carbon suboxide and ponderously referred to in Chemical Abstracts as l,2-propadiene-l,3-dione, is a foul-smelling gas obtained by dehydrating malonic acid, CH2(C02H)2, at... 

Other oxides of phosphorus are less well characterized though the suboxide PO and the peroxide P2O6 seem to be definite compounds. PO was obtained as a brown cathodic deposit when a saturated solution of Et3NHCl in anhydrous POCI3 was electrolysed between Pt electrodes at 0°. Alternatively it can be made by the slow reaction of POBrs with Mg in Et20 under reflux ... 

Silber-oxydul, n. silver suboxide, -ojydver bindung,/. compound of silver oxide specif., argentate. -papier, n. silver paper, silvered paper. 

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