Ethanol → 3,5-Dichlorobenzene-1,2-diamine

3,5-Dichloro-1,2-diaminobenzene was prepared using an adaptation of the method of Bellamy, et al. (Bellamy, F. D. et al., Tetrahedron Lett. 25:839 (1984)). A mixture of 2,4-dichloro-6-nitroaniline (1.00 g, 4.8 mmol) and SnCl2 ·2H2O (5.41 g, 24.1 mmol) dissolved in 10 mL ethyl acetate and 5 mL absolute ethanol under N2 was heated at 70° C. for 1 h. All the starting material had reacted as evidenced by TLC (silica gel, 3:1 hexanes:ethyl acetate). The reaction was allowed to cool to room temperature and poured into 40 mL crushed ice. Sufficient sat'd NaHCO3 solution was added (foaming!) to bring the pH to 5. The orange oil/thick white emulsion was extracted with 3×25 mL ethyl acetate and the combined organic extracts washed with sat'd NaCl solution. The organic phase was dried (MgSO4), vacuum filtered and the solvent rotary evaporated to yield a pale orange oil which crystallized on standing to yield 789 mg (93%). 1H NMR (CDCl3) δ3.69 (br s, 4H, 2(NH2)); 6.61 (s, 1H, H-6); 6.82 (s, 1H, H-4).

1. customAll the starting material had reacted
2. additionpoured into 40 mL
3. customcrushed ice
4. additionwas added (foaming!)
5. extractionThe orange oil/thick white emulsion was extracted with 3×25 mL ethyl acetate
6. washthe combined organic extracts washed with sat'd NaCl solution
7. dry with materialThe organic phase was dried (MgSO4), vacuum
8. filtrationfiltered
9. customthe solvent rotary evaporated
10. customto yield a pale orange oil which
11. customcrystallized
12. customto yield 789 mg (93%)

ORDレコード

ord-7ea7bc9cafbc43b4af76ae429420262d

出典データセット

uspto-grants-1997_04

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US05622952