Extracurricular laboratory: Synthetic route of 16588-26-4

Here is a brief introduction to this compound(16588-26-4)Safety of 3-Bromo-4-chloronitrobenzene, if you want to know about other compounds related to this compound(16588-26-4), you can read my other articles.

In organic chemistry, atoms other than carbon and hydrogen are generally referred to as heteroatoms. The most common heteroatoms are nitrogen, oxygen and sulfur. Now I present to you an article called Synthesis and ultraviolet spectra of nitrodiphenyl-amine disperse dyes. II. Synthesis of some substituted 2- and 4-nitrodiphenylamines, published in 1967, which mentions a compound: 16588-26-4, mainly applied to DIPHENYLAMINES DISPERSE DYE; DYE DIPHENYLAMINES DISPERSE; DISPERSE DYE DIPHENYLAMINES, Safety of 3-Bromo-4-chloronitrobenzene.

The synthesis of some substituted 2- and 4-nitrodiphenylamines, yellow dyes for synthetic fibers, is described. Condensation of 0.02 mole 2,5-Cl2C6H3NO2 with 0.04 mole PhNH2 in 50 ml. boiling EtOH containing 3 g. NaOAc gave 52.8% I (R = NO2, R1 = Cl, R2 = R3 = R4 = H), m. 59-60° (75% aqueous alc.). Other I were prepared similarly (R, R1, R2, R3, R4, % yield, and m.p. given): NO2, Cl, OMe, H, H, 50, 100-1°; NO2, Cl, H, OMe, H, 37, 90°; NO2, Cl, H, H, OMe, 48, 118-19°; NO2, Cl, F, H, H, 21, 113-14°; NO2, Cl, H, F, H, 40, 99-100°; NO2, Cl, H, H, F, 38, 80-1°; NO2, Cl, H, H, SO2Me, 15, 210-11°; CF3, NO2, H, H, H, 71, 63-4°; CF3, NO2, OMe, H, H, 16, 106-7°; CF3, NO2, H, OMe, H, 32, 88°; CF3, NO2, H, H, OMe, 74, 87-8°; CF3, NO2, F, H, H, 30, 60-1°; CF3, NO2, H, F, H, 57, 73-4°; CF3, NO2, H, H, F, 20, 74-5°; MeSO2, NO2, H, H, H, 82, 169-70°; Me, NO2, H, H, H, 23, 133-4°; NO2, Me, H, H, H, 79, 34-5°; NO2, OMe, H, H, H, 23, 44-5°. Fusion of 0.02 mole 3,4-Cl2C6H3NO2 (II) with 0.04 mole PhNH2 gave 31.8% I (R = Cl, R1 = NO2, R2 = R3 = R4 = H), m. 112-13°. Other I (R = Cl, R1 = NO2) were prepared similarly (R2, R3, R4, % yield, and m.p. given): OMe, H, H, 36, 108-9°; H, OMe, H, 25, 122-3°; H, H, OMe, 32, 99-100°; H, H, F, 20, 119-20°. Condensation of 0.02 mole 4,3-Cl(O2N)C6H3SO2NH2 (III) and 0.03 mole PhNH2 by fusing for 6 hrs. at 130° gave 71.8% I (R = NO2, R1 = SO2NH2, R2 = R3 = R4 = H), m. 179-80°. Other I (R = NO2, R1 = SO2NH2) were prepared similarly (R2, R3, R4, % yield, and m.p. given): Me, H, H, 84, 195-6°; H, Me, H, 85, 172-3°; H, H, Me, 90, 196-7°; OMe, H, H, 41, 225-6°; H, OMe, H, 91, 181-2°; H, H, OMe, 89, 226-7°; F, H, H, 61, 206-7°; H, F, H, 77, 195-6°; H, H, F, 80, 234-5°; Cl, H, H, 42, 202-3°; H, Cl, H, 80, 201-2°; H, H, Cl, 80, 241-2°; Br, H, H, 60, 200-1°; H, Br, H, 79, 207-8°; H, H, Br, 84, 235-6°; CF3, H, H, 40, 169-70°; H, CF3, H, 82, 210-11°; H, H, CF3, 29, 260-1°; H, H, SO2Me, 59, 253-4°. Condensation of 4.7 g. 2,5-Cl(O2N)C6H3SO2NH2 (IV) with 0.04 mole PhNH2 in 100 ml. boiling PhNO2 for 24 hrs. gave 68.4% I (R = SO2NH2, R1 = NO2, R2 = R3 = R4 = H), m. 175-6°. Other I (R = SO2NH2, R1 = NO2) were prepared similarly (R2, R3, R4, % yield, and m.p. given): OMe, H, H, 62, 205-8°; H, OMe, H, 59, 172-4°; H, H, OMe, 65, 160°; F, H, H, 60, 182-3°; H, F, H, 68, 173-4°; H, H, F, 71, 162-4°. A mixture of 25 g. 4,3-Cl(O2N)C6H3CO2H and 50 ml. SOCl2 was refluxed for 2 hrs., stripped of excess SOCl2, and treated with excess NH4OH to give 86.4% 4,3-Cl(O2N)C6H3CONH2, m. 154-5° (EtOH), which (0.02 mole) was condensed with 0.04 mole PhNH2 in EtOH containing NaOAc to give 34.4% I (R = NO2, R1 = CONH2, R2 = R3 = R4 = H), m. 194-5°. Other I were prepared similarly (R, R1, R2, R3, R4, % yield, and m.p. given): NO2, CONH2, OMe, H, H, 68, 144-5°; NO2, CONH2, H, OMe, H, 72, 170-1°; NO2, CONH2, H, H, OMe, 68, 220-1°; NO2, CONH2, F, H, H, 60, 169-71°; NO2, CONH2, H, F, H, 67, 191-2°; NO2, CONH2, H, H, F, 78, 207-8°; NO2, CONH2, H, H, SO2Me, 10, 244-5°; CONH2, NO2, H, H, H, 25, 184-5°; CONH2, NO2, OMe, H, H, 59, 215-16°; CONH2, NO2, H, OMe, H, 55, 198-9°; CONH2, NO2, H, H, OMe, 79, 216-17°; CONH2, NO2, F, H, H, 49, 184-5°; CONH2, NO2, H, F, H, 43, 233-4°; CONH2, NO2, H, H, F, 82, 231-2°; CONH2, NO2, H, H, SO2Me, 7, 207-8°. Esterification of 4,3-Cl(O2N)C6H3CO2H gave 4,3-Cl(O2N)C6H3CO2Et, m. 60-1° (EtOH), which was condensed with PhNH2 in boiling EtOH to give 92.8% I (R = NO2, R1 = CO2Et, R2 = R3 = R4 = H), m. 114-15°. Other I were prepared similarly (R, R1, R2, R3, R4, % yield, and m.p. given): NO2, CO2Et, OMe, H, H, 72, 116-18°; NO2, CO2Et, H, OMe, H, 70, 105-6°; NO2, CO2Et, H, H, OMe, 63, 128-9°; NO2, CO2Et, F, H, H, 15, 120-2°; NO2, CO2Et, H, F, H, 69, 79-80°; NO2, CO2Et, H, H, F, 52, 138-9°; NO2, CO2Et, H, H, SO2Me, 13, 149-50°; CO2Et, NO2, H, H, H, 29, 111-12°; CO2Et, NO2, OMe, H, H, 41, 112-13°; CO2Et, NO2, H, OMe, H, 46, 81-2°; CO2Et, NO2, H, H, OMe, 56, 120-2°; CO2Et, NO2, F, H, H, 18, 105°; CO2Et, NO2, H, F, H, 59, 119-20°; CO2Et, NO2, H, H, F, 34, 121-2°; CO2Et, NO2, H, H, SO2Me, 10, 189-90°; NO2, CF3, H, H, H, 63, 84°; NO2, CF3, OMe, H, H, 39, 123-4°; NO2, CF3, H, OMe, H, 81, 67-8°; NO2, CF3, H, H, OMe, 80, 85-6°; NO2, CF3, F, H, H, 76, 77-8°; NO2, CF3, H, F, H, 70, 93°; NO2, CF3, H, H, F, 54, 77-8°; NO2, CF3, H, H, SO2Me, 10, 149-50°. Nitration of p-ClC6H4SO2Me with KNO3 in concentrated H2SO4 at 80-5° for 3 hrs. gave 81.7% 4,3-Cl(O2N)C6H3SO2Me, m. 121-2° (20% aqueous alc.), which was condensed with PhNH2 to give 92% I (R = NO2, R1 = SO2Me, R2 = R3 = R4 = H), m. 130-1°. A solution of 15 g. 0-ClC6H4CN in fuming HNO3 was allowed to warm to room temperature from 0-4° in 1 hr., kept for 1 hr. at room temperature, and mixed with 600 ml. ice-water to give 81.8% 2,5-Cl(O2N)C6H3CN, m. 108° (EtOH), which was condensed with PhNH2 in the presence of NaOAc to give 78% I (R = CN, R1 = NO2, R2 = R3 = R4 = H), m. 159-60°. Similarly prepared was I (R = NO2, R1 = CN, R2 = R3 = R4 = H), m. 121-2°. A suspension of 21.7 g. 4,2-Br(O2N)C6H3NH2 in 85 ml. concentrated HCl at 0-4° was diazotized with NaNO2, stirred 1 hr. at 5°, mixed with 15 g. CuCl2 in 50 ml. concentrated HCl, warmed to 70° in 1 hr., and stirred for 30 min. at 70° and overnight at room temperature to give 50% 5,2-Br(Cl)C6H3NO2, m. 70-1° (20% aqueous alc.), which was condensed with PhNH2 to give 80.5% I (R = NO2, R1 = Br, R2 = R3 = R4 = H), m. 54-6°. Similarly prepared were I (R = Br, R1 = NO2, R2 = R3 = R4 = H), m. 111-12°. I (R = NO2, R1 = F, R2 = R3 = R4 = H), m. 120-1°, and I (R = F, R1 = NO2, R2 = R3 = R4 = H), m. 134°. Nitration of 4-ClC6H4CHO gave 80% 4,3-Cl(O2N)C6H3CHO, m. 65-6° (EtOH), which was condensed with PhNH2 in the presence of NaOAc to give a mixture of I (R = NO2, R1 = CHO, R2 = R3 = R4 = H), m. 147-8°, and 4,3-PhNH(O2N)C6H3CH:NPh, m. 108-9°. Similarly prepared was 2,5-PhNH(O2N)C6H3CHO, m. 182° (by-product and m. 132-3°). Attempted conversion of II with 2-, 3-, or 4-FC6H4NH2 or with 3-MeOC6H4NH2 in refluxing HCONMe2 gave 75-85% 2,4-Cl(O2N)C6H3NMe2, m. 78°. Similarly, III and 2- or 4-F3CC6H4NH2 in HCONMe2 gave 4,3-Me2N(O2N)C6H3SO2NH2, m. 133-4°, while IV with all arylamines in HCONMe2 gave 2,5-Me2N(O2N)C6H3SO2NH2, m. 147-8° (EtOH).

Here is a brief introduction to this compound(16588-26-4)Safety of 3-Bromo-4-chloronitrobenzene, if you want to know about other compounds related to this compound(16588-26-4), you can read my other articles.

Reference:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts