The process of synthesis of 1, 7-dichloroheptene-3 and 1, 9-dichlorononene-4 by the selective dehydrochlorination reaction of secondary chlorine of 1, 4, 7-trichloroheptane and 1, 4, 9-trichlorononane was investigated. As the fixed catalyst for vapor phase dehydrochlorination reaction of these trichlorides, pumice, granulated activated carbon and those containing various metal chlorides were investigated. The result indicated that the catalyst of granulated activated carbon containing 10% barium chloride was found to be best. Studies on reaction temperatures, flow rate of carrier gas and rate of feeding of raw material indicated that the best condition was found to be 3.44 l of caltalyst, the feeding rate of raw material at 1 kg/hr, the flow rate of nitrogen gas at 120 l/hr at 200°C with space velocity of 0.24 l/hr, and this gave 1, 7-dichloroheptene-3 with 87% yield at 93-95% conversion (93% yield from converted raw material). However, there was a small amount of 1-chloroheptadiene-4, 6 (4-5%) and 1, 4-dichloroheptene-6 (0.7%) as the by-products due to excessive dehydrochlorination. There was no formation of 1, 7-dichloroheptene-3 by the reaction of hydrated lime or sodium hydroxide with 1, 4, 7-trichloroheptane. However, heating of 1, 4, 7-trichloroheptane and 1, 4, 9-trichlorononane in liquid phase without catalyst at 220-260°C or heating in vacuo at 115-120°C in the presence of zinc chloride gave 1, 7-dichloroheptene-3 and1, 9-dichlorononene-4, respectively, but the velocity of dehydrochlorination reaction was much slower than that of using vapor phase reaction under fixed catalyst. Therefore this method is not practical. Dehydrochlorination reaction of 1, 4, 7-trichloroheptane and 1, 4, 9-trichlorononane in liquid phase without catalyst proceeded the first order reactiion. Apparent activation energy of the former was 22.7 kcal/mol and that of latter was 31.4 kcal/mol.
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