Triphenylarsine oxide

Triphenylarsine oxide transfers its oxygen to triphenylphosphine in dichloromethane at 105 °C. 

Hendrickson and co-workers reported that triphenylarsine reacts with DMAD to give tetramethyl l,l,l-triphenylarsole-2,3,4,5-tetracarboxylate (503). However, it was subsequently shown by the same workers that the product formed in this reaction is the adduct 505, not 503 (Scheme 79). Recently, Ciganek has shown that triphenylarsine oxide reacts with DMAD to give the same adduct (505) (Scheme 80). He has further suggested that the formation of 505 in the reaction of triphenylarsine may proceed through a zwitterionic intermediate (504), which reacts with water to give triphenylarsine oxide... 

Isocyanates 345 react with phenanthrenequinone 346 and triphenylarsine oxide to give photochromic oxazines 347 (Equation 48) <1993PS(81)37>. The isocyanate can be replaced by a phosphinimine and the phenanthrene structure can also be replaced by the corresponding phenanthroline (Equation 49) <2003WO42195>. The /ra r-fused tetrahydrooxazine 349 was prepared from epoxide 348 and 2-aminoethyl sulfate (ethanolamine 0-sulfonic acid) (Equation 50) <1987AP625>. 

Triphenylarsine oxide is partly converted to the dihydroxide when heated with water. However, it is not hygroscopic under ordinary conditions. ... 

The flask containing the residual yellow oil is fitted with a water trap and condenser, and 120 ml. of benzene is added. The water is then removed by azeotropic distillation (Note 4). When the removal of water is complete, the triphenylarsine oxide is crystallized by cooling the flask in an ice bath for 1.5-2 hours. The light-brown crystals are collected on a Buchner funnel and washed on the funnel with 25 ml. of cold benzene. The crude product weighs 97-98.5 g. (91-93%) and melts at 186-188°. The crude product is transferred to a porcelain dish and triturated with 50 ml. of benzene, collected on a Buchner funnel, pressed as dry as possible, and washed with 25 ml. of cold benzene. After drying in the air, the triphenylarsine oxide amounts to 89-92 g. (84-87%) of white crystals, melting at 189°. 

C. Tetraphenylarsonium chloride hydrochloride. In a 2-1. round-bottomed three-necked flask fitted with a condenser, a mercury-sealed mechanical Hershberg stirrer, and a dropping funnel is placed 40 g. (0.124 mole) of triphenylarsine oxide dissolved in 1 1. of hot benzene. To this solution there is added with vigorous stirring a solution of phenylmagnesium bromide which is prepared from 34.6 g. (0.22 mole) of bromobenzene, 6.0 g. (0.25 gram atom) of magnesium, and 200 ml. of dry ether. A brown viscous solid separates. The mixture is stirred for 15 minutes and then stirred and heated under reflux on a steam bath for 30 minutes. The solvent is removed by decantation, and the viscous solid is washed with 500 ml. of benzene. The addition product is... 

Triphenylarsine oxide has been prepared by the action of sodium hydroxide on triphenylarsine dibromide/ by the action of potassium permanganate on triphenylarsine, and by the action of hydrogen peroxide on triphenylarsine. The method described here is essentially that of Vaughan and Tarbell. ... 

Abbreviations 4-pic, 4-methylpyridine PNO, pyridine /V-oxide pip, piperidine PhjAsO, triphenylarsine oxide DPM, 2,2,6,6-tetramethylheptane-3,5-dione. 

A facile method for the preparation of a variety of stabilized arsonium ylides in good yield has been developed by the action of active methylene compounds with tertiary arsine oxide or tertiary arsine dihalide. Thus triphenyl-arsine dihalides react with a number of active methylene compounds in the presence of a tertiary amine to afford arsonium ylides (6) (40). The reaction of triphenylarsine oxide with active methylene compounds in the presence of either acetic anhydride or triethylamine-phos-phorus pentoxide gave rise to arsonium ylides (6) (32, 36. 65, 67). 

The reaction of triphenylarsine oxide with strongly acidic methylene compounds in acetic anhydride affords acetylated ylides (7) (32, 67), e.g.,... 

It is necessary that the methylene reactant be a fairly strong carbon acid less acidic compounds such as phenylacetonitrile, acetophenone, or fluorene do not react under these conditions (52). Sulfoxides also condense readily with reactive methylene compounds in the presence of di-cyclohexylcarbodiimide (16) but triphenylarsine oxide did not form ylides under identical conditions. Triphenylarsine sulfide did not react with methylene compounds under any of the above conditions (32). 

In the reversible Wittig reaction, triphenylarsine oxide reacted with electron-deficient acetylene derivatives to form stable ylides. Thus triphenylarsine oxide reacted readily with methyl propiolate, ethyl phenylpropiolate, dimethyl acetylenedicarboxylate, and hexafluoro-2-butyne as well as dicyanoacetylene to give arsonium ylides (12). The reaction temperatures required ranged from -70°C in the case of dicyanoacetylene to 130°C in the case of ethyl phenylpropiolate (15). 

Huang et ol. (48) found that the carbomethoxymethylene triphenylar-sorane reacted with ketones as well as with aldehydes to give various unsaturated esters in good yield. The by-product, triphenylarsine oxide, can be removed by washing with dilute hydrochloric acid. A comparison... 

Fluorenylidene-(9)- (51, 55), carboalkoxymethylene- (28, 29, 48), acetylmethylene- (28, 29, 50), substituted benzoylmethylene- (28, 29, 56, 94) as well as Cv-nitrobenzylidene)- (58, 59, 97) -triphenylarsorane reacted with a variety of aromatic aldehydes to give corresponding olefins and triphenylarsine oxide. 

Cyclopentadiene triphenylarsorane reacted withp-nitrobenzaldehyde in chloroform to give triphenylarsine (10% yield), triphenylarsine oxide (80% yield), and two other unidentified products (24). The corresponding 2,3,4-triphenyl- or tetraphenylcyclopentadienylide under similar conditions afforded triphenylarsine oxide and the corresponding substituted fulvene (25, 68). 

Semistabilized ylides such as benzylidene- (55) or methylene- (59) triphenylarsorane reacted with carbonyl compounds in ether to give olefins as well as oxiranes. For example, reaction of methylene triphenylarsorane with benzophenone gave, besides triphenylarsine oxide... 

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