Rearrangement of polybromoalkyl radical with 1,5- and 1,6-migration of hydrogen in the reduction of 1,1,1,3-tetrabromoheptane (in Russian)
The work reported here was directed at a study of the reduction of 1,1,1,3-tetrabromoheptane (I) (TBH) under the action of a system including Fe(CO)/sub 5/ plus Et/sub 3/SiH or i-PrOH as hydrogen donors, together with an examination of the possibility that there may be rearrangement of the intermediate radicals. In the case of Et/sub 3/SiH + Fe(CO)/sub 5/ at 100/sup 0/C, 1,1,3-tetrabromoheptane (II) was formed in quantitative yield from tetrabromoheptane. In the absence of Fe(CO)/sub 5/, or when this was replaced by benzoyl peroxide (BPO), there was little or no reaction. Further reduction of an actual sample of (II) under identical conditions was not observed. In the case of i-PrOH at a ratio i-PrOH:(I) = 3:1 in the presence of Fe(CO)/sub 5/ at 100/sub 0/C there was little or no reaction. Heating to 130/sup 0/C led to the formation of the reduction product (II) in 22-46% yield and, in addition, a mixture of approximately equal quantities of 1,1,3,5-tetrabromoheptane (III) and the 1,13,6-isomer (IV) with an overall yield of up to 30%. With i-PrOH:(I) = 8:1, (II) was formed in 64% yield and the isomeric products (III) and (IV) in 15% yield.
- Research Organization:
- A.N. Nesmeyanov Institute of Organometallic Chemistry, Moscow, USSR
- OSTI ID:
- 6476225
- Journal Information:
- Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States), Vol. 35:2; Other Information: Translated from Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, 35: No. 4, 376-378(Feb 1986)
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
REDUCTION
BROMINATED ALIPHATIC HYDROCARBONS
CARBONYLS
CATALYTIC EFFECTS
IRON COMPOUNDS
ALKYL RADICALS
CARBON 13
CHEMICAL REACTION YIELD
CHEMICAL SHIFT
CONFORMATIONAL CHANGES
HEPTANE
HYDROGEN TRANSFER
ISOMERIZATION
MOLECULAR STRUCTURE
NMR SPECTRA
PROPANOLS
SILANES
STRUCTURAL CHEMICAL ANALYSIS
ALCOHOLS
CARBON ISOTOPES
CHEMICAL REACTIONS
EVEN-ODD NUCLEI
HALOGENATED ALIPHATIC HYDROCARBONS
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
ISOTOPES
LIGHT NUCLEI
NUCLEI
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SILICON COMPOUNDS
RADICALS
SILICON COMPOUNDS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
YIELDS
400201* - Chemical & Physicochemical Properties