4-Aminophenol → 4-[(4-Chloro-6-methoxy-1,3,5-triazin-2-yl)amino]phenol

HRID 1499320Notes

Reaction equation

HRID 1499320 reaction equation
Cl[C:2]1[N:7]=[C:6]([Cl:8])[N:5]=[C:4]([O:9][CH3:10])[N:3]=1.[NH2:11][C:12]1[CH:17]=[CH:16][C:15]([OH:18])=[CH:14][CH:13]=1.C([O-])([O-])=O.[Na+].[Na+]>CC(C)=O>[Cl:8][C:6]1[N:5]=[C:4]([O:9][CH3:10])[N:3]=[C:2]([NH:11][C:12]2[CH:17]=[CH:16][C:15]([OH:18])=[CH:14][CH:13]=2)[N:7]=1

Participants

5

Reactant 3

HCID 4034-AminophenolHCID 10340Sodium CarbonateHCID 192672,4-Dichloro-6-methoxy-3,5-triazine

Product 1

HCID 598609844-[(4-Chloro-6-methoxy-1,3,5-triazin-2-yl)amino]phenolYield 76%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A solution of 2,4-dichloro-6-methoxy-1,3,5-triazine (9.00 g, 50.0 mmol) in 100 mL of acetone was cooled to 0° C. and, under stirring, solid 4-amino phenol (5.46 g, 50.0 mmol) was added in small portion, over ca 2 min. The white suspension was then let to warm to room temperature and stirred for further 1 h, while being neutralized with a 2 M aqueous solution of Na2CO3 during the reaction. The mixture was then poured into 500 mL of ice/water and the resulting white precipitate was filtered and dried, to give 9.6 g (38.0 mmol, yield 76%) of 4-[(4-chloro-6-methoxy-1,3,5-triazin-2-yl)amino]phenol that can be used without further purifications. An analytical sample can be obtained by flash chromatography (CC, SiO2, petroleum ether/Et2O 1:1, Rf=: 0.14). The NMR analysis (DMSO d6) reveals the presence, in solution, of 2 rotational isomers (molar ratio 7:3). M.p was 172° C. IR ν(NH) 3476 cm−1. ν(OH) 3269 cm−1. Major isomer: 1H NMR (DMSO d6) δ=3.94 (s, 3H, OCH3); 6.79 (d, J=8.8 Hz, 2H, CH Ar), 7.48 (d, J=8.8 Hz, 2H, CH Ar), 9.40 (s, 1H, OH), 10.46 (s, 1H, NH). 13C NMR (DMSO d6) δ 55.52 (1C, OCH3); 115.46 (2C, CH Ar), 123.91 (2C, CH Ar), 129.49 (1C, C Ar), 154.44 (1C, C Ar), 164.81 (1C, C Ar), 169.57 (1C, C Ar), 171.23 (1C, C Ar). Minor isomer: 1H NMR (DMSO d6) δ 3.96 (s, 3H, OCH3); 6.79 (d, J=8.9 Hz, 2H, CH Ar), 7.39 (d, J=8.9 Hz, 2H, CH Ar), 9.42 (bs, 1H, OH), 10.10.32 (s, 1H, NH). 13C NMR (DMSO d6) δ=55.10 (1C, OCH3); 115.46 (2C, CH Ar), 123.03 (2C, CH Ar), 129.26 (1C, C Ar), 154.76 (1C, C Ar), 165.20 (1C, C Ar), 170.48 (1C, C Ar), 170.64 (1C, C Ar).

Workup

  1. stirringstirred for further 1 h
  2. filtrationthe resulting white precipitate was filtered
  3. customdried

Sources & evidence

ORD record
ord-492db2831ef64cfeb0e25ea1b9fdf695
Source dataset
uspto-grants-2015_12
Patent number
US09200104B2

Reaction notes

Loading…