CHEMISTRY OF POLYVALENT METAL HALIDES. Technical Progress Report, March 1, 1960 to February 28, 1961
In order to determine the effect of bulky groups on the diborane structure, the hydroboration reaction of highly substituted olefins was studied. The hydroboration of 2methyl-2-butane yielded bis-3-methyl-2-butylborane in 99% yield. Molecular weight determinations and infrared spectra identified the compound as a dimer having unusual physical properties. The dimer reacted with diborane to form the unsymmetrical dimer, 1,1-(3-methyl-2-butyl diborane. Other borane dimers reacted in a similar manner. The hydroboration of cyclohexene and 1-methylcyclohexene in stoichiometric ratios yielded the tetra-alkyldiboranes in quantitative yields. The reactions of the terminal olefins with diborane in THF yielded mixtures of R/sub 2/BH and R/sub 3/B only when the olefin was added to the THF: BH/sub 3/ solutions. The system gallium chloride in toluene, was investigated at O deg C, and a complex having the composition C/sub 6/H/sub 5/CH/ sub 3/: Ga/sub 2/Cl/sub 6/ which was completely miscible with toluene was found. A comparison was made of the ability of hydro gen chloride to dissolve in pure toluene and in a solution of gallium chloride in toluene between the temperatures of -78.5 and O deg C. The rate of chlorine exchange, using Cl/sup 3//sup 6/, between gallium chloride and methyl chloride was measured at -36 deg C. The rate of methylation of toluene was found to be a function of toluene concentration. The rate and isomer distribution in the gallium bromide catalyzed ethylation of the halobenzenes in ethylene dichloride solution was investigated. The relative rate and isomer distributions in the bromination of alkylbenzenes in 85% acetic acid were determined. Experiments are in progress to measure the heats of reaction of boron Lewis acids with various Lewis bases. The borohydride reduction of some phenyl substituted ketones is also being investigated. (M.C.G.)
- Research Organization:
- Purdue Univ., Lafayette, Ind.
- DOE Contract Number:
- AT(11-1)-170
- NSA Number:
- NSA-15-022190
- OSTI ID:
- 4047509
- Report Number(s):
- TID-12991
- Resource Relation:
- Other Information: Orig. Receipt Date: 31-DEC-61
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ACETIC ACID
ACIDS
ALKENES
ALKYL RADICALS
BENZENE
BINDING ENERGY
BORON
BORON HYDRIDES
BUTANE
BUTYL RADICALS
COMPLEXES
CYCLOALKENES
DISTRIBUTION
ELECTRON PAIRS
GALLIUM CHLORIDES
HALIDES
HYDROGEN CHLORIDES
INFRARED RADIATION
ISOMERS
KETONES
LEWIS BASES
METALS
METHYL RADICALS
MOLECULES
QUANTITATIVE ANALYSIS
REDUCTION
SPECTRA
TEMPERATURE
TOLUENE
WEIGHT