Ylides, bismuthonium

Bismuthonium Ylides. Prior to 1988 the only bismuthonium yhdes known were (1) and (2). 

Bismuthonium ylides, 4 34 Bismuth(III) oxide, 4 23-24 Bismuth oxide(l l), 4 23 Bismuth oxide(l 2), 4 23 Bismuth oxide(2 4), 4 23 Bismuth oxide(3 5), 4 23 Bismuth oxide(4 9), 4 23 Bismuth oxide halides, 4 23 Bismuth oxides, 4 23-24 Bismuth oxybromide, 4 23 Bismuth oxychloride, 4 23 physical properties of, 4 20t pigment used in makeups, 7 836t Bismuth oxyfluoride, 4 23 Bismuth oxyiodide, 4 23 Bismuth pentafluoride, 4 22 physical properties of, 4 20t Bismuth phosphate, 4 25... 

The reaction of the same bismuthonium ylide with isothiocyanates in the presence of a copper(H) catalyst afforded the sulfur-incorporated spiro-cyclic compound as the main product, in addition to a small amount of carbon-carbon bond formed products (Scheme 12) [28],... 

R = Php-Tol, 4-CIC6H4, hexyl, Ph C02CH2 Scheme 11 Reaction of bismuthonium ylide with alkynes... 

Scheme 12 Reaction of bismuthonium ylide with isothiocyanates...

Lloyd, D., Gosney, I. and Ormiston, R.A. (1987) Arsonium ylides (with some mention also of arsinimines, stibonium and bismuthonium ylides). Chemical Society Reviews, 16, 45-74. 

Until fairly recently relatively little was known about stibonium and bismuthonium ylides, but in the last decade there have been a number of studies of these compounds. 

There are earlier reviews of the chemistry of arsonium , stibonium and bismuthonium ylides. ... 

IX. BISMUTHONIUM YLIDES AND IMINES A. Preparation of Bismuthonium Ylides... 

The first bismuthonium ylide to be prepared and isolated was triphenylbismuthonium tetraphenylcyclopentadienylide, made by thermal decomposition of diazotetraphenylcyc-lopentadiene in the presence of triphenylbismuth . More recently some other bismuthonium ylides (Pli3Bi=CX2, X = RCO or RSO2) have been prepared and isolated by the diazo method, using copper hexafluoroacetylacetonate as catalyst... 

Stabilized bismuthonium ylides have also been made from compounds having reactive methylene groups, CH2CXY, X, Y = RCO or RSO2, either by making their sodium salts and letting the latter react with dichlorotriphenylbismuth, or by reaction with triphenyl-bismuth oxide 1 181. 

Triphenylbismuthonium tetraphenylcyclopentadienylide is stable for some time as a solid but decomposes rapidly in solution it decomposed rapidly when treated with acid or with base. Acyl and sulphonyl bismuthonium ylides are moderately stable, but less so than their arsonium and stibonium analogues some, while stable in solution in inert solvents, decompose when isolation is attempted ... 

The bismuthonium ylides (45, X = CH2,0) react with aryl or alkyl aldehydes to give a variety of products, depending on the ylide, the aldehyde (RCHO) and the conditions. The products include cyclopropane derivatives (46), furan derivatives analogous to 46 but with a furan ring replacing the cyclopropane ring, and in some cases (from 45, X = O and... 

A number of triphenylbismuthonium diacylylides and also the diphenylsulphonylylide undergo transylidation when treated with dimethyl sulphide in the presence of copper(I) chloride in benzene at room temperature, giving the corresponding dimethylsulphonium ylides no such reaction took place with diphenyl sulphide Some of these bismuthonium ylides reacted with triphenylarsine or triphenylphosphine and were converted thereby into arsonium or phosphonium ylides they did not react with triphenylstibine L The conversion of the diacetylylide into the 4,4-dimethyl-2,6-dioxocyclohexylide as mentioned in Section IX.A should also be noted. 

---