Jan. 20, 1957
A SILICONANALOGOF XANTHENE
20 hr.; maximum pressure attained was 90 p.s.i.g. The vessel was cooled and pressured to 200 p.s.i.g. with purified, dry nitrogen to facilitate removal of the products. The contents of the vessel were then charged to a distillation flask held a t Dry Ice temperature. Distillation of the product under purified nitrogen a t 10 mm. gave 0.51 mole (71 9.) of butyldichloroborane, b. + 4 O (10 mm.), and 0.59 mole (94.5 9 . ) of dibutylchloroborane, b. 54' (10 mm.). Both products are colorless when first distilled and are pyrophoric in air. Both products hydrolyze violently in water. Butylfluoroisopropoxyborane.-Butyldifluoroborane (0.25 mole, 24.6 9.) and 0.25 mole (34.7 g.) of dichlorobutylborane were charged to a stirred flask a t -40". Isopropyl alcohol (0.50 mole, 35 8.) was added dropwise in 30 minutes. Hydrogen chloride was evolved. Distillation gave tw% major fractions: butylfluoroisopropoxyborane, b. 60' (100 mm.), 0.17 mole (24.6 g.), 34%, and butyldiisopropoxyborane, b. 105" (100 mm.), 0.13 mole (24.8 g.), 27y0. The entirepreparation was performed under an atmosphere of purified, dry nitrogen. Anal. Calcd. for C7H16OBF: C, 57.5; H , 11.0; B, 7.41; F, 13.2. Found: C, 58.9; H, 11.7; B, 7.6; F, 12.5; C1, 0.0. Calcd. for C10H2302B: C, 64.5; H, 12.4; B,5.82. Found: C,64.2; H, 12.4; B,6.7; F , 0 . 9 .
[CONTRIBUTION FROM
THE
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Butylcyclohexyloxyfluoroborane.-Butyldichloroborane (0.14 mole, 20 g.), and 0.15 mole (16 g.) of difluorobutylborane were charged to a flask equipped with a stirrer. Cyclohexanol (0.35 mole, 33.5 g.) was added dropwise in 30 minutes a t about -80' and the solution was allowed to come to room temperature. During this time hydrogen chloride was removed with a nitrogen sweep. Calcium carbonate, 2 g., was then added and stirring was continued an additional 2 hr. Distillation gave 0.049 mole (9 9.) of butylcyclohexyloxyfluoroborane, b.p. 60-65' (10 mm.), 21%, and 0.12 mole (30.5 g.) of butyldicyclohexyloxyborane, b.p. 156-160" (1 mm.), 50%. Butylcyclohexyloxyfluoroborane tends to disproportionate t o butyldicyclohexyloxyborane and butyldifluoroborane during distillation. Traces of acid catalyze this disproportionation. The entire preparation was performed under an atmosphere of purified, dry nitrogen. Anal. Calcd. for ClaH200BF: C, 64.5; H , 10.8; F, 10.2; B, 5.81. Found: C, 65.1; €1, 11.4; F, 12.1; B, 4.3; C1,
