Picryl Chloride → 2',4',6'-Trinitro-4-methylbiphenyl

Participants

Reaction Steps

4-iodotoluene is reacted with picryl chloride in the presence of copper bronze at 215° C. to yield 2′,4′,6′-trinitro-4-methylbiphenyl (1). C 7 ⁢ H 7 ⁢ I + C 6 ⁢ H 2 ⁢ Cl ⁢ N 3 ⁢   ⁢ O 6 ⁢ → Δ Cu ⁢ C 13 ⁢ H 9 ⁢ I 3 ⁢ N 3 ⁢   ⁢ O 6 2′,4′,6′-trinitro-4-methylbiphenyl (1) is reacted with stannous chloride and hydrochloric acid to yield 2′,4′,6′-triamino-4-methylbiphenyl (2). C 13 ⁢ H 9 ⁢ N 3 ⁢   ⁢ O 6 ⁢ → H ⁢   ⁢ Cl Sn ⁢   ⁢ Cl 2 ⁢ C 13 ⁢ H 15 ⁢ N 3 2′,4′,6′-triamino-4-methylbiphenyl (2) is reacted with sodium nitrite and hydrochloric acid to convert the amino groups to diazonium groups. The diazonium groups react with potassium iodide to yield 2′,4′,6′-triiodo-4-methylbiphenyl (3). C 13 ⁢ H 15 ⁢ N 3 ⁢ → H ⁢   ⁢ Cl Na ⁢   ⁢ N ⁢   ⁢ O 2 ⁢ → K ⁢   ⁢ I ⁢   ⁢ C 13 ⁢ H 9 ⁢ I 3 Aromatic nitration of 2′,4′,6′-triiodo-4-methylbiphenyl (3) is performed with nitric acid and sulfuric acid to yield a mixture of 2′,4′,6′-triiodo-2-nitro-4-methylbiphenyl (4) and 2′,4′,6′-triiodo-3-nitro-4-methylbiphenyl (5). The products are separated using column chromatography. C 13 ⁢ H 9 ⁢ I 3 ⁢ → H 2 ⁢   ⁢ S ⁢   ⁢ O 4 H ⁢   ⁢ N ⁢   ⁢ O 3 ⁢ C 13 ⁢ H 8 ⁢ I 3 ⁢ N ⁢   ⁢ O 2 The methyl group of 2′,4′,6′-triiodo-3-nitro-4-methylbiphenyl (5) is oxidized by potassium permanganate to yield 2′,4′,6′-triiodo-3-nitrobiphenyl-4-carboxylic acid (6). C 13 ⁢ H 8 ⁢ I 3 ⁢ N ⁢   ⁢ O 2 ⁢ → K ⁢   ⁢ Mn ⁢   ⁢ O 4 ⁢ C 13 ⁢ H 6 ⁢ I 3 ⁢ N ⁢   ⁢ O 4 2′,4′,6′-triiodo-3-nitrobiphenyl-4-carboxylic acid (6) is reacted with thionyl chloride to yield 2′,4′,6′-triiodo-3-nitrobiphenyl-4-carbonyl chloride (7). C 13 ⁢ H 6 ⁢ I 3 ⁢ N ⁢   ⁢ O 4 ⁢ → S ⁢   ⁢ O ⁢   ⁢ Cl 2 ⁢ C 13 ⁢ H 5 ⁢ Cl ⁢ I 3 ⁢ N ⁢   ⁢ O 3 The hydroxyl groups of D-Glucosamine (8) are protected by reaction with acetic anhydride in the presence of pyridine to yield 1,3,4,6-tetra-O-acetyl-D-glucosamine (9). C 6 ⁢ H 13 ⁢ N ⁢   ⁢ O 5 ⁢ → C 5 ⁢   ⁢ H 5 ⁢ N C 4 ⁢   ⁢ H 6 ⁢   ⁢ O 3 ⁢ C 14 ⁢ H 21 ⁢ N ⁢   ⁢ O 9 1,3,4,6-tetra-O-acetyl-D-glucosamine (9) is reacted with 2′,4′,6′-triiodo-3-nitrobiphenyl-4-carbonyl chloride (7) to yield 2-nitro-4-(2′,4′,6′-triiodophenyl)-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (10). C14H21NO9+C13H5ClI3NO3→C27H25I3N2O12 2-nitro-4-(2′,4′,6′-triiodophenyl)-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (10) is treated with stannous chloride in the presence of hydrochloric acid to yield 2-amino-4-(2′,4′,6′-triiodophenyl)-benzoyl-D-glucosamine (11). C 27 ⁢ H 25 ⁢ I 3 ⁢ N 2 ⁢   ⁢ O 12 ⁢ → Sn ⁢   ⁢ Cl 2 ,   ⁢ H ⁢   ⁢ Cl ⁢ C 19 ⁢ H 19 ⁢ I 3 ⁢ N 2 ⁢   ⁢ O 6

Provenance & Evidence