Water → 3-{2-[(2-{[3-(Bromomethyl)phenyl]amino}-5-chloropyrimidin-4-yl)amino]ethyl}phenol

HRID 1614947Notes

Reaction equation

HRID 1614947 reaction equation
[Cl:1][C:2]1[C:3]([NH:17][CH2:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([O:26]C)[CH:21]=2)=[N:4][C:5]([NH:8][C:9]2[CH:10]=[C:11]([CH2:15]O)[CH:12]=[CH:13][CH:14]=2)=[N:6][CH:7]=1.B(Br)(Br)[Br:29].O>C(Cl)Cl>[Br:29][CH2:15][C:11]1[CH:10]=[C:9]([NH:8][C:5]2[N:4]=[C:3]([NH:17][CH2:18][CH2:19][C:20]3[CH:21]=[C:22]([OH:26])[CH:23]=[CH:24][CH:25]=3)[C:2]([Cl:1])=[CH:7][N:6]=2)[CH:14]=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 962WaterHCID 25134Boron tribromideHCID 58467923{3-[(5-Chloro-4-{[2-(3-methoxyphenyl)ethyl]amino}pyrimidin-2-yl)amino]phenyl}methanol

Product 1

HCID 584678503-{2-[(2-{[3-(Bromomethyl)phenyl]amino}-5-chloropyrimidin-4-yl)amino]ethyl}phenolYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of {3-[(5-chloro-4-{[2-(3-methoxyphenyl)ethyl]amino}pyrimidin-2-yl)amino]phenyl}methanol (0.30 g, 0.78 mmol) in methylene chloride (5.0 mL) was added slowly a solution of boron tribromide in methylene chloride (2.3 mL, 2.3 mmol, 1.0 M) at 0° C. The mixture was allowed to warm up to rt and stirred overnight. The resultant mixture was cooled in a dry ice bath when water was added. The mixture was allowed to warm up to rt. Both aqueous layer (no product in it) and organic layer (containing small amounts of product, plus byproducts) were checked and discarded. The remaining solid residue was triturated with cold EtOAc and then filtered. The cake was washed with cold EtOAc and then H2O to give the desired product as a white powder (0.30 g, 89%). LCMS for C19H19BrClN4O (M+H)+: m/z=433.0, 435.0, 437.0. 1H NMR (400 MHz, CD3OD): δ 7.94 (s, 1H), 7.60 (s, 1H), 7.40 (m, 2H), 7.32 (m, 1H), 7.05 (m, 1H), 6.60 (m, 3H), 4.54 (s, 2H), 3.76 (t, J=6.4 Hz, 2H), 2.85 (t, J=7.6 Hz, 2H).

Workup

  1. additionwas added
  2. temperatureto warm up to rt
  3. additionBoth aqueous layer (no product in it) and organic layer (containing small amounts of product, plus byproducts)
  4. customThe remaining solid residue was triturated with cold EtOAc
  5. filtrationfiltered
  6. washThe cake was washed with cold EtOAc

Sources & evidence

ORD record
ord-0ff5a4d070634f04b90d80d2a9d7b7d4
Source dataset
uspto-grants-2014_07
Patent number
US08765727B2

Reaction notes

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