1.1.1- Trihalides ketones

The reduction of alkyl tellurium trihalides is a convenient method for the preparation of the corresponding dialkyl ditellurium when the trihalides can be obtained by reactions other than the halogenolysis of the dialkyl ditellurium. Addition of tellurium tetrachloride to olefins and condensation with ketones produces alkyl tellurium trichlorides. Sodium sulfide nonahydrate4 and sodium or potassium disulfite5 8 were used as reducing agents. 

Tris(organoamino)boranes have been utilized to prepare, in reasonable yields,4,5 mono- and dihalo(organoamino)boranes which are often difficult to obtain by direct amination of the boron trihalides. Carboxylic acids, 1,3-diketones, ketones, and /3-ketoesters have been converted into carboxamides, enamino-ketones, enamines, and j -enamino-amides, respectively, by reaction with an appropriate tris(organoamino)borane under very mild conditions.6 Sulfenamides (R2NSC6H5) have also been prepared in high yield from selected tris(organoamino)boranes and sulfenic esters under relatively mild conditions.7... 

Zinc di-isobutyl is a liquid, B.pt. 165° to IGT Tl., less readily oxidised than zinc dipropyl. It reacts vigorously with trihalides of phosphorus and arsenic, yielding corresponding phosphines and arsines. With acetaldehyde it forms principally ethyl alcohol, but also a little isobutyl alcohol, and with isovaleryl chloride it gives di-isobutyl ketone. ... 

Reaction with Allylic Halides, Alcohols, and their Derivatives. Allylation of allyl and propargyl trimethylsilyl ethers as well as benzyl and propargylic alcohol derivatives proceeds in the presence of a catalytic amount of Lewis acids, such as ZnC, TMS(OTf), and B(C6F5)3. Direct substitutions of the hydroxyl group of allylic, ben-zylic, and propargylic alcohols are catalyzed by HN(S02F)2, a rhenium-oxo complex, and InCls (eq 27). A combination of chlorodimethylsilane and allyltrimethylsilane effectively promotes the deoxygenative allylation of aromatic ketones in the presence of a catalytic amount of an indium compound, such as indium trihalide or metallic indium (eq 28). Allylation of cyclic allylic acetates with allyltrimethylsilane can be catalyzed by molecular iodine. ... 

Many organic compounds are also prepared by hydrolysis of the appropriate halides. Alcohols can be prepared by hydrolysis of alkyl halides (though yields are often poor due to the formation of considerable amounts of olefins and polyolefins) phenols are prepared from aryl halides under pressure, in the presence of concentrated base (Samuel and Scheinmann, private communication), aromatic aldehydes and ketones from gem-dihalides (Doering and Dorfman, 1953), and aromatic acids from trihalides (Ponticorvo and Rittenberg, 1954). 

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