Germyl peroxides

A new method for synthesis of dialkyl peroxides is based on the novel peroxide transfer reaction between Ge or Sn peroxides and alkyl triflates. Mixed diaUcyl peroxides are obtained from the reaction of bis(butyltin)germyl peroxide with alkyl triflates. 

The germanium peroxides are stable up to about 70 °C for short periods, but some decomposition apparently occurs during distillation above this temperature. All peroxides are readily hydrolyzed to give germyl hydroperoxide. 

Bis[triethylsilyl(-germyl, -stannyl)] tellurium compounds and acyl peroxides formed acyloxytriethylsilanes (-germanes and -stannanes)3. 

Freshly prepared lithium wire, and selenium and tellurium powders were used as supplied. Germyl fluoride may be prepared from germyl iodide11 and lead(II) fluoride.12 Chlorotrimethylsilane is distilled through traps at -45° (chlorobenzene-liquid N2 slush), -78° (methanol-dry ice slush), and -196° (liquid N2) the fraction retained in the trap at -78° is the desired purified chlorotrimethylsilane. Peroxide-free diethyl ether was distilled in a vacuum system from fresh Li[AlH4] and stored in vacuo. Caution. The use of Li[AlHA] for drying ethers can lead to explosions 3 Commercial dry NH3 (10-15 mL portion) was further dried by condensation onto Na pellets (about 1 g) in an ampul (about 50 mL) held at -78° on the vacuum line. After 30 minutes the dried NH3 was pumped from the ampul and degassed in a trap held at -196° before use. 

Evidence for optically active germyl radicals has also been reported. The optically active hydrogermane 7 reacted with CC14 at 80°C in the presence of dibenzoyl peroxide to yield the chlorogermane 8 with substantial retention of configuration (eq. [4]) (21). 

Oxygen reacts with BSD as well as with bis(trimethylgermyl)diazene even at - 78°C to form nitrogen and the bis(trimethylmetal)peroxide (28, 50) [Eq. (57)]. Silylated and germylated alkyldiazenes react with oxygen at 0°C to form peroxides (29). Trimethylsilylphenyldiazene, Me3Si—N=N—Ph,... 

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