A solution of
0.54 g. (2 mmoles) of ferric chloride hexahydrate and
0.33 g. (3 mmoles) of diethylammonium chloride (Note
1) in
5 g. of methanol is added to a solution of
11.2 g. (0.1 mole) of 1-octene (Note
2) and
0.42 g. (2 mmoles) of benzoin (Note
3) in
36 g. (0.3 mole) of chloroform (Note
4). The resulting homogeneous mixture is introduced into a
Carius tube of about 100-ml. capacity. Air is displaced by dropping a few pieces of dry ice into the tube (Note
5). The tube is sealed (Note
6), heated to 130°, kept at that temperature for 15 hours, cooled to room temperature (Note
7), and opened. The contents of the tube are transferred to a
separatory funnel, and the tube is rinsed with about
10 ml. of chloroform. The reaction mixture is washed with 40 ml. of water. The aqueous solution is extracted with
10 ml. of chloroform, and the extract is added to the original
chloroform layer. Solvent is distilled at atmospheric pressure (bath temperature up to 130°). The distillation flask is allowed to cool, and distillation is continued at 25 mm. (bath temperature up to 120°) (Note
8). The flask is cooled again, and distillation is continued to dryness at 0.1 mm. (bath temperature up to 150°), giving crude
1,1,3-trichloro-n-nonane (
19.4 g.) as a yellow oil, b.p.
60–85° (0.1 mm.),
n25D 1.4650. The purity of this product is 95% (Note
9), and the actual yield is
80%. Fractionation of this material through a
13-in. Vigreux column gives
15 g. (
64%) of pure, colorless
1,1,3-trichloro-n-nonane, b.p.
61–62° (0.1 mm.),
n25D 1.4640 (Note
10) and (Note
11).