Process for producing chlorinated hydrocarbons in the presence of a polyvalent bismuth compound
The preparation of chlorinated hydrocarbons by reacting a chlorinated alkane substrate, such as 1,1,1,3-tetrachloropropane, with a source of chlorine, such as chlorine (Cl 2 ), in the presence of a polyvalent bismuth compound, such as triphenyl bismuth and/or triphenyl bismuth dichloride, is described. With the method of the present invention, the chlorinated alkane product has covalently bonded thereto at least one more chlorine group than the chlorinated alkane substrate, and the chlorinated alkane substrate and the chlorinated alkane product each have a carbon backbone structure that is in each case the same.
1. A method of preparing a chlorinated alkane product comprising,
reacting a chlorinated alkane substrate with a source of chlorine in the presence a polyvalent bismuth compound, thereby forming a product comprising said chlorinated alkane product,
wherein said chlorinated alkane product has covalently bonded thereto at least one more chlorine group than said chlorinated alkane substrate, and
said chlorinated alkane substrate and said chlorinated alkane product each have a carbon backbone structure that is in each case the same.
2. The method of claim 1 , wherein said source of chlorine is selected from chlorine (Cl 2 ), sulfuryl chloride, and combinations thereof.
3. The method of claim 1 , wherein said polyvalent bismuth compound is selected from the group consisting of a pentavalent bismuth compound, a trivalent bismuth compound, and combinations thereof.
4. The method of claim 3 , wherein said pentavalent bismuth compound comprises one or more pentavalent bismuth compounds represented by the following Formula (I),
Bi(R 1 ) a (Cl) b (I)
wherein the sum of a and b is 5, provided that b is 2, 3, or 4, and
R 1 independently for each a is selected from the group consisting of linear or branched alkyl, cyclic alkyl, and aryl.
5. The method of claim 3 , wherein said trivalent bismuth compound comprises one or more trivalent bismuth compounds represented by the following Formula (II),
Bi(R 2 ) c (Cl) d (II)
wherein the sum of c and d is 3, and
R 2 independently for each c is selected from the group consisting of linear or branched alkyl, cyclic alkyl, and aryl.
6. The method of claim 5 , wherein the sum of c and d is 3, c is from 1 to 3, and d is from 0 to 2.
7. The method of claim 3 , wherein
said pentavalent bismuth compound comprises triphenyl bismuth dichloride, and
said trivalent bismuth compound comprises triphenyl bismuth.
8. The method of claim 1 , wherein said polyvalent bismuth compound is supported on a solid support.
9. The method of claim 8 , wherein said solid support is selected from the group consisting of silica supports, alumina supports, zeolite supports, and combinations of two or more thereof.
10. The method of claim 1 , wherein said polyvalent bismuth compound is present in a catalytic amount.
11. The method of claim 1 , wherein said method is performed as a batch method, a continuous method, and combinations thereof.
12. The method of claim 1 , wherein
said chlorinated alkane substrate is 1,1,1,3-tetrachloropropane, and
said chlorinated alkane product is 1,1,1,2,3-pentachloropropane.
13. The method of claim 12 , wherein said source of chlorine is chlorine (Cl 2 ), and reacting 1,1,1,3-tetrachloropropane with said source of chlorine is conducted with a mole ratio of chlorine (Cl 2 ) to 1,1,1,3-tetrachloropropane of 0.2:1 to 1.5:1.
14. The method of claim 12 , wherein reacting 1,1,1,3-tetrachloropropane with said source of chlorine in the presence of said polyvalent bismuth compound is conducted at a temperature of at least 40° C., and a pressure of at least 1 psia.
15. The method of claim 14 , wherein said temperature is from 40° C. to 200° C., and said pressure is from 1 psia to 500 psia.
16. The method of claim 12 , wherein said 1,1,1,3-tetrachloropropane is formed from reacting carbon tetrachloride with ethylene in the presence of an iron chloride, iron metal, and a trialkylphosphate.