Germanium alkylation

There are two main subclasses ofhydroperoxid.es organic (alkyl) hydroperoxides, ie, ROOH, and organomineral hydroperoxides, ie, Q(OOH), where Q is sihcon (43), germanium, tin, or antimony. The alkyl group in ROOH can be primary, secondary, or tertiary. Except for ethylbenzene hydroperoxide, only alkyl hydroperoxides are commercially important. 

Many organic peroxides of metals have been hydrolyzed to alkyl hydroperoxides. The alkylperoxy derivatives of aluminum, antimony, arsenic, boron, cadmium, germanium, lead, magnesium, phosphoms, silicon, tin, and zinc yield alkyl hydroperoxides upon hydrolysis (10,33,60,61). 

Basic hydrolysis of secondary alkyl-substituted siUcon and germanium peroxides results in oxygen—oxygen bond cleavage. 

The reduction of alkyl-substituted siUcon and tin peroxides with sodium sulfite and triphenylphosphine has been reported (33,93). Alkyl-substituted aluminum, boron, cadmium, germanium, siUcon, and tin peroxides undergo oxygen-to-metal rearrangements (33,43,94), eg, equations 22 and 23. 

DiaLkyl peroxides may be prepared by reaction of alcohols or alkyl trifluoromethanesulfonates with organomineral peroxides of siUcon, tin, and germanium (44,108), where Q = Sn and Ge ... 

Diarylamines can be A/-alkylated with anhydrides and acyl haUdes or A/-alkylated with alkyl haUdes, alkyl sulfates, and tri- / -alkylphosphites. Diphenylamine derivatives of alkyl—aryl gaUium, germanium, phosphoms, and siUcon are known (17), eg, pentaphenylgermanamine [64653-46-9]. 

Unsolvated organomagnesium compounds have been recommended for the synthesis of organometallic derivatives of mercury, boron, aluminum, silicon, germanium, tin, phosphorus, arsenic, and antimony6-8 and have been used in procedures for the alkylation of aromatic rings and for the production of various polymerization catalysts.4 9... 

Studies of metal alkyls and aryls deal largely with arsenic, germanium and antimony, although some work has also been done on tellurium, mercury, thallium, bismuth and lead. The major contributions can be neatly divided into four periods early studies by Maddock, Sutin and H 1155).56).57) studies by the Polish >- >- and the Strasbourg >- 2).79) groups, work by Riedel and and most recently a series... 

Both alkyl and aryl metals have been studied, but not a very wide range of compounds. Several studies of triphenylarsene and triphenylstibine have been done. Methyl and ethyl compounds of arsenic, germanium, mercury, bismuth, and lead essentially complete the list. In virtually all cases the results have been clouded by difficulties in effecting chemical separation without altering the product distribution. The results do, nonetheless, lead to valid and important conclusions. 

Synthesis of Alkyl,aryl-Substituted Germanium-Containing Heavy Ketones... 

Aminolysis of the corresponding halides is the preferred method for the synthesis of dialkylamino derivatives of boron,1 silicon,2 germanium,3 phosphorus,4 arsenic,5 and sulfur.6 (Dialkylamino) chlorosilanes are prepared stepwise by the reaction of silicon tetrachloride with dialkylamines. This method may be utilized equally well for the conversion of alkyl- or aryl-substituted halides [e.g., (CH3) SiCl4. ] or of oxide and sulfide halides (e.g., POCl3 or PSC13) to the corresponding dialkylamino compounds. 

FIGURE 2. Enthalpies of formation of gaseous germanium tetra-alkyls versus the enthalpies of formation of the corresponding hydrocarbons. The point Me (cal c.) is for the calculated values of A//y"(CH4) and A//y"(GeMe4). See text... 

A plot of A7/y°(SnR4, g) against A///TRII, g), where R is alkyl, is presented in Figure 3 where the enthalpy-of-formation values used are both experimentally determined (Table 3) and calculated. The calculated values are for tetramethyl and tetraethyl tin and methane. As stated above, the enthalpy-of-formation values for tetraethyl tin may be incorrect. That the calculated value for tetraethyl tin results in a better linear fit with tetrapropyl and tetrabutyl tin is further confirmation of this supposition. And, as discussed for the alkyl germaniums, the methyl deviations of methane and tetramethyl tin are too different for their measured values to fit a linear relationship such as equation 7. 

The isotropic germanium hyperfine coupling appears to be smaller for the triaryl radicals as compared with the trialkyl radicals. Since the hyperfine coupling to the germanium atom should increase markedly with increased s-character of the orbital containing the unpaired electron, this observation would imply that the aryl-substituted radicals are somewhat more planar than their alkyl-substituted analogues. 

An important method of alkylation or arylation comparable to the Wiirtz reaction uses germanium tetraiodide31 ... 

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