Stibine reactions with

There has been much interest in the reactivity of nitronium salts, for example, toward amides in acetonitrile,the oxidation of alkanes in acetonitrile (via a carbenium ion intermediate),and toward organic sulfides, phosphines, arsines, and stibines. Reaction with diaryl, aryl alkyl, and dialkyl sulfides give sulfoxides, but a few percent of the ring C-nitro products were found for diphenyl sulfide. This is a result of the equilibrium between nitrito onium ions ] X-ONO and nitronium ions This is the first demonstration of the ambident reactivity... 

The aromatic primary and secondary stibines are readily oxidized by air, but they are considerably more stable than their aHphatic counterparts. Diphenylstibine is a powerful reducing agent, reacting with many acids to Hberate hydrogen (79). It has also been used for the selective reduction of aldehydes and ketones to the corresponding alcohols (80). At low temperatures, diphenylstibine undergoes an addition reaction with ketene (81) ... 

The same method may be used for the preparation of tri- -tolyl-stibine. Starting with 282 g. of -bromotoluene (Org. Syn. 6, 21) and proceeding in the same manner as described there was secured 150-157 g. (77 -80 per cent of the theoretical amount) of crude tri-/>-toIyl-stibine. This product purified by recrystallization from methyl alcohol or ether melts at 125-126°. The reaction is somewhat more vigorous in this case and sometimes cooling is necessary at first. 

Organolead derivatives prepared in recent years by one or more of the above reactions are the azides 208>, cyanides 123>, fulminates 45>, arsinates 171), sulfides 104>, alkoxides 242>, peroxides 263>, amines 231>, and phosphines, arsines, and stibines 280-281) The alkoxide 105>, hydride 231> and amine 231> derivatives of organolead undergo reaction with various unsaturated organic compounds to form novel organolead compounds, many of which are not synthesizable by other methods. 

Triphenylstibine Phs Sb and, less freqnently, trialkylstibines or bi- and tridentate stibine ligands, for example, CH2(SbPh2)2 and CH3C(CH2SbPh2)3 are nsed as donor ligands in transition metal complexes. (Cp3)3Sb is exceptional becanse it does not act as a donor but as an electron pair acceptor in the reaction with a carbene (eqnation 5). ... 

The reactivities of alkyl halides are in the sequence RI > RBr > RCl and MeX > EtX > PrX. Benzyl hahde reactions with tin do not require catalysts (equation 2). For less reactive halides, the catalysts and promoters employed include metals (sodium, magnesium, zinc, or copper), Lewis bases (amines, triorganophosphines and -stibines, alcohols, or ethers), iodides, and onium salts (R4MX). The use of tin-sodimn alloys can result in tri- or tetraorganotin products. Electrochemical synthesis has also been reported, e.g. the formation of R2SnX2 from the oxidation of anodic tin by RX in benzene solution and the formation of ILtSn from RI (R = Me or NCCH2CH2) and cathodic tin. 

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