Chloroform, reaction with 1 octene

Chloroform, reaction with 1-octene to give l,l,3-trichloro- -nonane, 45, 104... 

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 fuimel, 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 tc 150°), giving crude l,l,3-trichloro- -nonane (19.4 g.) as a yellow oil, b.p. 60-85° (0.1 mm.), 1.4650. The purity of this... 

Diethylammonium chloride, in reaction of 1-octene with chloroform to give 1,1,3-trichloro-n-nonane, 46, 104... 

Muller and co-workers have demonstrated the potential of coupling several spontaneous chemical steps to biocatalysis in a one-pot domino reaction to form bicyclo[2.2.2]octenes.13 A tyrosinase from mushrooms was immobilized on glass beads with the phenol substrate in a mixture of chloroform and a dienophile under air. Tyrosinase can transform a wide variety of phenols to the corresponding catechol, and the presence of air resulted in spontaneous oxidation to the ortho-quinone (Scheme 21.3). The presence of a dienophile then resulted in a Diels-Alder cycloaddition to form the bicyclo[2.2.2]octene product. Significant yields were achieved with a broad range of phenols and dienophiles. 

To a solution of the iodonium salt (103 mg, 0.19 mmol) in benzene (3 ml) was added triethylamine (22 mg, 0.23 mmol) at room temperature, under nitrogen, and the mixture was stirred for 30 min. The reaction mixture was poured into water and extracted with ether. Drying of the extract and concentration produced an oil which was purified by preparative TLC (hexane-chloroform) to give 3-(phenylsulphonyl)bicyclo[3.3.0]-2-octene (33 mg, 71%) and the accompanying alkyne (8 mg, 18%) as colourless oils. 

Unsaturated AT-chlorosulfonyl-jft-lactams are generally unstable and readily rearrange to the product of formal 1,4-addition. Thus, the reaction of 1,3-cyclohexadiene with CSI at room temperature affords a quantitative yield of adduct 150. Hydrolysis of 150 with benzenethiol in the presence of pyridine gives 151 in 67% yield. When the reaction mixture of CSI and 1,3-cyclohexadiene was refluxed in chloroform, 152 was formed in 90% yield as a viscous oil. Hydrolysis of 152 with aqueous NaOH gave iV-unsubstituted lactams in 35% yield. 2-Azabicyclo[2.2.2]octene (153) can be conveniently prepared by reduction of 152 with LiAlH4 after hydrolysis (equation 81)76. 

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