Metalation and halogen-metal interconversion reactions of some halogenated phenyl ethers was written by Langham, Wright;Brewster, R. Q.;Gilman, Henry. And the article was included in Journal of the American Chemical Society in 1941.Electric Literature of C8H7ClO3 This article mentions the following:
The reactions of certain halogen derivatives of Ph2O with MeLi, BuLi and PhLi have been studied. When the halogen is I or Br, halogen-metal interconversion is found to be the predominant reaction. IC6H4OPh undergo interconversion more readily than the Br derivatives and the Cl derivatives are essentially not affected. During long periods of reaction or upon refluxing in ether, p-Br and p-Cl derivatives are metalated by MeLi, BuLi and PhLi; under the same conditions the p-I derivative is metalated in reactions with BuLi and PhLi. In general 0.01 mol of the ether was reacted with 0.02 mol of the Li derivative at 26° for 0.25 h. 2-IC6H4OPh with BuLi gives 79%, PhLi 56% (79% at 18-20° for 24 h.), MeLi (0.1 mol) 14% of 2-PhOC6H4CO2H after carbonation of the reaction product. 3-IC6H4OPh with BuLi gives 75% or with 0.1 mol PhLi 37% of 3-PhOC6H4CO2H. 4-IC6H4OPh (I) with BuLi gives 93% or 0.1 mol of PhLi gives 33% of 4-PhOC6H4CO2H; 0.02 mol I and 0.1 mol of BuLi at 20-2° for 26 h. or 0.02 mol I and 0.02 mol of PhLi at 34° for 15 h. give 30 or 32% of 2,5-(PhO)-IC6H3CO2H. 4-IC6H4OC6H4OMe-4 with 0.2 mol BuLi or 0.01 mol of PhLi gives 61 or 47% of 4-(4′-MeOC6H4O)-C6H4CO2H. 2-BrC6H4OPh and BuLi give 65% of 2-PhOC6H4CO2H. 4-BrC6H4OPh with 0.01 mol of BuLi for 0.033 h. or 0.02 mol of PrLi at 26° for 0.083 h. gives 36 or 80% of 4-PhOC6H4CO2H; 0.1 mol of PhLi gives 7% of 2,5-(PhO)BrC6H3CO2H; 0.15 mol ether and 0.8 mol PhLi at 20° for 24 h. or 0.01 mol of ether and 0.01 mol of MeLi for 24 h. at 20° give 35 and 14% of 2,5-(PhO)-BrC6H3CO2H. 3,4-Br(MeO)C6H3OPh gives with BuLi 66% of 2,5-MeO(PhO)C6H3CO2H. 2-ClC6H4OPh does not react with MeLi at 20° after 24 h. 2,5-(PhO)ClC6H3CO2H results in 16, 23, 36 and 14% yields from 0.005, 0.015, 0.02 or 0.01 mol of 4-ClC6H4OPh with 0.008 mol BuLi at 26° in 0.25 h., 0.02 mol BuLi at 34° in 10 h., 0.01 mol of PhLi at 20° in 26 h. or 0.01 mol of MeLi at 20° in 24 h. Many comments are given on the individual experiments p-FC6H4OMe (0.03 mol) and 0.05 mol MeLi (all experiments at 34° for 14 h.) give 17.7% of 2,5-(MeO)FC6H3CO2H and 38.5% unreacted F compound p-ClC6H4OMe (0.03 mol) gives 21.6% of 2,5-(MeO)ClC6H3CO2H and 57% unreacted Cl derivative p-BrC6H4OMe (0.02 mol) and 0.03 mol MeLi give 21.7% of 2,5-(MeO)BrC6H3CO2H; in another experiment there resulted 16% of acid and 50% of unreacted Br compound p-IC6H4OMe (0.03 mol) and 0.05 mol of MeLi give 13.1% of 4-MeOC6H4CO2H and 48.6% of p-MeC6H4OMe; in a 2nd experiment the yields were 5 and 52%, resp. o-ClC6H4OMe does not react with MeLi. o-BrC6H4OMe gives 16.6% of 2-MeOC6H4CO2H and 43.5% of o-MeC6H4OMe. o-IC6H4OMe (0.013 mol) and 0.03 mol of MeLi give 12.5% of 2-MeOC6H4CO2H and 75% of o-MeC6H4OMe. m-BrC6H4OMe (0.02 mol) and 0.03 mol of MeLi give 0.7 g. of an acidic gum, 13% of m-MeC6H4OMe and 0.43 g. of a product b9 79-81°. In the experiment, the researchers used many compounds, for example, 5-Chloro-2-methoxybenzoic acid (cas: 3438-16-2Electric Literature of C8H7ClO3).
5-Chloro-2-methoxybenzoic acid (cas: 3438-16-2) belongs to organic chlorides. Organochlorines are organic compounds having multiple chlorine atoms. They were the first synthetic pesticides that were used in agriculture. They are resistant to most microbial and chemical degradations. Alkanes and aryl alkanes may be chlorinated under free radical conditions, with UV light. However, the extent of chlorination is difficult to control.Electric Literature of C8H7ClO3
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics