- COORDINATION AND CATALYTIC REACTIONS OF UNSATURATED COMPOUNDS. VIII. HETEROGENEOUS CATALYTIC ACETOXYLATION OF 1-HEXENE AND CYCLOHEXENE
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During the acetoxylation of 1-hexene and cyclohexene in acetic acid in the presence of atmospheric oxygen and intermetallic compounds based on palladium and rhodium the ester groups are introduced into the substrate molecule.In the case of 1-hexene, the monoacetates of 1,2-hexanediol and 3-acetoxy-1-hexene are formed preferentially.The reactivity of the cyclic alkene is more clearly defined than that of the acyclic analog, and the catalyzate contains the cis- and trans-diacetoxy derivatives, 3-acetoxycyclohexene, and the products from ring concentration.The difference in the catalytic activity of the palladium and rhodium intermetallic compounds shows up mainly in the actoxylation of 1-hexene.The ring concentration products are evidently formed in the stages involving the transformation of the actoxonium ion.
- Devekki, A. V.,Yakushkin, M. I.,Egor'kov, A. N.,Belyaeva, N. V.,Mozzhukhina, T. N.,et al.
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p. 1680 - 1684
(2007/10/02)
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- Thallium(I) Carboxylate Modification of the Hunsdiecker Reaction
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Treatment of a thallium(I) carboxylate with 1 molar equivalent of bromine gives the corresponding thallium(III) carboxylate dibromide.High yields of primary alkyl bromides are obtained if the thallium(III) carboxylate dibromide is treated with 0.5 mol equiv. of bromine in refluxing carbon tetrachloride.Pyrolysis of the thallium(III) derivative in the absence of added bromine gives a low yield of the corresponding alkyl bromide.The use of thallium(I) carboxylates for the preparation of alkyl bromides in high yields is limited to the salts of primary carboxylic acids.A simple procedure for the preparation of alkyl bromides from carboxylic acids using thallium(I) carbonate has been developed.
- Cambie, Richard C.,Hayward, Rodney C.,Jurlina, Jeffrey L.,Rutledge, Peter S.,Woodgate, Paul D.
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p. 2608 - 2614
(2007/10/02)
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