Abstract
New functionalized carboranyl derivatives of amineboranes and boron analogs of esters are reported. The reaction of 1,12‐(aminopropyl)‐1,12‐dicarbadodecaborane (2), 2‐(aminopropyl)‐1,2‐dicarbadodecaborane (4), 1‐methyl‐2‐(aminopropyl)‐1,2‐dicarbadodecaborane (6), 1‐phenyl‐2‐(aminopropyl)‐1,2‐dicarbadodecaborane (8) with Me~3~NBH~2~X produced novel carboranylamineboranes of the general formula 1,12‐[(CH~2~)~3~NH~2~BH~2~X]~2~‐1,12‐C~2~B~10~H~10~ [X = CN (2a), COOCH~3~ (2b), CONHEt (2c), CONHCH(CH~2~C~6~H~5~)COOCH~3~ (2d), CONHCH(CH~3~)COOCH~3~ (2e), CONHCH[CH(CH~3~)~2~]COOCH~3~ (2f), CONHCH(CH~2~C~6~H~4~OH)COOCH~3~ (2g), 1‐CH~2~NH~2~BH~2~CN (2h)] or 1‐R‐2‐[(CH~2~)~3~NH~2~BH~2~X]‐1,2‐C~2~B~10~H~10~ {R = H, X = CN (4a), COOCH~3~ (4b), CONHEt (4c), COOH (4d); R = CH~3~, X = CN (6a), COOCH~3~ (6b), CONHCH(CH~2~C~6~H~5~)COOCH~3~ (6c), CONHCH(CH~3~)COOCH~3~ (6d), CONHCH[CH(CH~3~)~2~]COOCH~3~ (6e), CONHCH(CH~2~C~6~H~4~OH)COOCH~3~ (6f); R = C~6~H~5~, X = CN (8a), COOCH~3~ (8b), CONHCH(CH~2~C~6~H~5~)COOCH~3~ (8c), CONHCH(CH~3~)COOCH~3~ (8d), CONHCH[CH(CH~3~)~2~]COOCH~3~ (8e), CONHCH(CH~2~C~6~H~4~OH)COOCH~3~ (8f)} by the amine exchange reaction. The reaction of 1‐(aminomethyl)‐1,2‐dicarbadodecaborane with Me~3~NBH~2~X (X = CN) produced 1‐[CH~2~NH~2~BH~2~CN]‐1,2‐C~2~B~10~H~10~ (2h). Compounds 2a, 4a, 6a, and 8a were also synthesized by the reaction of 1,12‐(aminopropyl)‐1,12‐dicarbadodecaborane hydrochloride (1), 2‐(aminopropyl)‐1,2‐dicarbadodecaborane hydrochloride (3), 1‐methyl‐2‐(aminopropyl)‐1,2‐dicarbadodecaborane hydrochloride (5), 1‐phenyl‐2‐(aminopropyl)‐1,2‐dicarbadodecaborane hydrochloride (7) with sodium cyanoborohydride. The reaction of Li~2~[1,2‐CO~2~‐1,2‐C~2~B~10~H~10~] (9) or Li[1‐R‐2‐CO~2~‐1,2‐C~2~B~10~H~10~], R = CH~3~ (10), R = C~6~H~5~ (11), with Me~3~NBH~2~I gave 1,2‐CO~2~BH~2~NMe~3~‐1,2‐C~2~B~10~H~10~ (9a) or 1‐R‐2‐CO~2~BH~2~NMe~3~‐1,2‐C~2~B~10~H~10~, R = CH~3~ (10a), R = C~6~H~5~ (11a), as new boron analogs of esters. All of these compounds were characterized by IR spectroscopy, ^1^H, ^13^C and ^11^B NMR spectroscopy and chemical analyses. Copyright © 2003 John Wiley & Sons, Ltd.