ChemicalBook CAS DataBase List 2-AMINO-4,4'-DICHLORODIPHENYL ETHER

2-AMINO-4,4'-DICHLORODIPHENYL ETHER synthesis

4synthesis methods

Product Name:2-AMINO-4,4'-DICHLORODIPHENYL ETHER
CAS Number:121-27-7
Molecular formula:C12H9Cl2NO
Molecular Weight:254.11

4-Chloro-1-(4-chlorophenoxy)-2-nitrobenzene

135-12-6

121-27-7

4,4'-Dichloro-2-nitro-diphenyl ether (12.0 g, 42.2 mmol) was used as a raw material, which was mixed with FeCl3 (702 mg, 4.33 mmol) and activated charcoal (3.70 g) in MeOH (360 mL) and stirred at 50 °C. Hydrazine monohydrate (7.00 mL, 144 mmol) was added slowly over 10 minutes, followed by heating the reaction mixture to reflux and stirring for 1 hour. After completion of the reaction, the mixture was cooled, filtered through diatomaceous earth and the filter cake was washed with MeOH. The filtrate was concentrated under reduced pressure to give an oily residue. This residue was dissolved with EtOAc, and the organic layer was washed sequentially with saturated aqueous NaHCO3 and brine, and then dried with Na2SO4. After filtration to remove the insoluble matter, the filtrate was concentrated under reduced pressure to give 5-chloro-2-(4-chlorophenoxy)-aniline (8) (10.6 g, 99% yield) as a colorless solid with a melting point of 59-61 °C. The product was characterized by 1H NMR (400 MHz, CDCl3), 13C NMR (100 MHz, CDCl3) and LC-MS (ESI) to confirm its structure.

135-12-6
43 suppliers
$144.00/250mg

121-27-7
126 suppliers
$26.00/1g

Yield: 99%

Reaction Conditions:

with iron(III) chloride;hydrazine hydrate in methanol at 50;

Steps:

3 5.1.3. 5-Chloro-2-(4-chlorophenoxy)aniline (8)22
A solution of 7 (12.0 g, 42.2 mmol), FeCl₃ (702 mg, 4.33 mmol), and activated charcoal (3.70 g) in MeOH (360 mL) was stirred at 50 °C, and to the mixture was added hydrazine monohydrate (7.00 mL, 144 mmol) over 10 min, and then stirred under reflux for 1 h. The reaction mixture was cooled down, filtered through Celite, washed with MeOH, and the resulting solution was concentrated under reduced pressure. The residue oil was diluted with EtOAc, and the organic layer was washed with saturated aqueous NaHCO₃, brine, and dried over Na₂SO₄. The insoluble material was filtered off, and the solution was concentrated under reduced pressure to give 8 (10.6 g, 99%) as a colorless solid. Mp 59-61 °C. ¹H NMR (400 MHz, CDCl₃): δ (ppm) 3.85 (br s, 2H), 6.67 (dd, J = 2.6, 8.2, 1H), 6.76 (d, J = 8.2, 1H), 6.80 (d, J = 2.6, 1H), 6.89 (d, J = 8.7, 2H), 7.26 (d, J = 8.7, 2H). ¹³C NMR (100 MHz, CDCl₃): δ (ppm) 116.07, 118.33, 118.42, 121.04, 127.98, 129.76, 130.17, 139.75, 141.32, 155.81. LC-MS (ESI) m/z 254, 256 [M+H]⁺.

References:

Nakao, Akira;Suzuki, Hiroko;Ueno, Hiroaki;Iwasaki, Hiroshi;Setsuta, Tomofumi;Kashima, Akiko;Sunada, Shinji [Bioorganic and Medicinal Chemistry,2015,vol. 23,# 15,p. 4952 - 4969]

89-61-2 Synthesis