Lists
Lists
Shafferman, Rodulph (1958) The derivatives of di-n-butylboronous acid. Doctoral thesis, Northern Polytechnic.
Di-n-butylboronous anhydride, (Bun2B)2O, was prepared by the reaction of n-butylmanesium bromide with ether-boron trifluoride and subsequent hydrolysis. Its reactions with alcohols (except tert.-butanol) , water boron halides, and phosphorus pentachloride resulted in boron-oxygen fission. Thus, with alcohols it yielded the appropriate boronites, Bun2 BOR; with water the acid, Bun2 BOH; and the boron and phosphorus halides di-n- butylboxun halides, Bun2 BX. With acetie acid and trifluoroacetic acid carbon-boron fission took place to produce novel compound s of the type (Bu2 BOCOR)2O.
Di-n-butylboron chloride reacted with numerous hydroxy compounds, including alcohols (including tert.butanol), carboxylic acids, water, and ethyl acetoacetate, in each case eliminating hydrogen chloride.
n-Butylboron dichloride was prepared by the reaction of boron trichloride with n-butylboronic anhydride. With water and alcohols it reacted similarly to di-n-butylboron chloride but with pyridine it formed a 1:1 complex whereas di-n-butylboron chloride formed a 2:1 complex.
Di-n-butylbororous esters were readily hydrolysed and their alcoholysis to form esters of higher molecular weights was also studied. The tendency for complex formation between certain nitrogen bases (EtNH2, Et2 NH, Et3N, C5H5N) and n-buty lboronates, and di-n-butylboronites was also studied as part of a programme to determine factors influencing boron-nitrogen coordination.
The reaction of acetic acid and trifluoroacetic acid with phenylboron and n-butoxyboron chlorides proceeded by the elimination of hydrogen chloride. Butoxyboron acetates were not isolated but the diborates [(RCOO)2B]2O, n-butyl borate, and acetic anhydride were obtained. The phenylboron chlorides gave benzene with trifluoroacetic acid and the corresponding carboxylates, CF3COOBPh2 and (CF3COO)2BPh were therefore prepared not fro m the free acid, but from its sodium salt.
The infra-red spectra of the above-mentioned acetates and trifluoroacetates gave valuable information concerning their structures and particularly it has been demonstrated that chelation of the type (figure I) is evident.
 |
View Item |