Borane adducts of triethylamine, diniethylaminc, and diethylamine were halogenated using free halogens or hydrogen halides, and the proton nmr spectra of these sininc-haloborane adducts were obtained. The resonances of these adducts and of the haloborane adducts of triethylamine showed a shift to lower field with increased size of halogen or with increased number of halogens on boron. This shift to lower field had been previously attributed to inductive effects, but in this work it was shown that the shift to lower field was due to steric interaction between halogens on boron and alkvl groups on nitrogen. Proton mmr spectra for diethylamine-haloboranes were complex and showed patterns attributable to non-equivalent methylene protons. Computer analyses of the spectra allowed assignments consisted with preferred rotational configuration. . The reactions between the secondary amine, dimethylaiaine, and three boron triflouride were examined in detail- diethylamine and boron trifluoride Borane reacted to produce the 1:1 adduct, diethylamine-boron trifluoride. Diethylamine reacted with boron trichloride or boron tribromide Lo produce mLxtiires of both the 1:1 adduct and bis-(diethylamine)-dihaloboronium tetrahaloborate salts. In order to obtain pure 1:1 adduct, it vas necessary to take advantage of the low solubility of the boronium salts in methylene chloride or to directly halogenate dimethvlamine-borane. During the reaction of N-deuterodimethylamine-borane with chlorine, considerable exchange of hydrogen for deuterium on nitrogen occurred. An extensive investigaition of the halogenation reactions of N-deuterodimethylaniineborane indicated that the exchange occured only via the loss of deuterium chloride from a molecule activated as a result of halogenation

William Howard Myers