Ammonium Chloride → N4-(5-Chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-N1-(2-dimethylaminoethyl)-5-methoxy-N1-methylbenzene-1,2,4-triamine

HRID 1842696Notes

Reaction equation

HRID 1842696 reaction equation
[NH4+].[Cl-].[Cl:3][C:4]1[C:5]([C:29]2[CH:30]=[N:31][N:32]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=23)=[N:6][C:7]([NH:10][C:11]2[CH:16]=[C:15]([N+:17]([O-])=O)[C:14]([N:20]([CH2:22][CH2:23][N:24]([CH3:26])[CH3:25])[CH3:21])=[CH:13][C:12]=2[O:27][CH3:28])=[N:8][CH:9]=1>O.C(O)C.[Fe]>[Cl:3][C:4]1[C:5]([C:29]2[CH:30]=[N:31][N:32]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=23)=[N:6][C:7]([NH:10][C:11]2[CH:16]=[C:15]([NH2:17])[C:14]([N:20]([CH2:22][CH2:23][N:24]([CH3:25])[CH3:26])[CH3:21])=[CH:13][C:12]=2[O:27][CH3:28])=[N:8][CH:9]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 71270273N-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-N'-(2-dimethylaminoethyl)-2-methoxy-N'-methyl-5-nitrobenzene-1,4-diamine2×

Product 1

HCID 86677330N4-(5-Chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-N1-(2-dimethylaminoethyl)-5-methoxy-N1-methylbenzene-1,2,4-triamineYield 94%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
105 °C

Procedure

A solution of NH4Cl (45 mg, 0.85 mmol) in water (10 mL) was added in one portion to a stirred mixture of N-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-N′-(2-dimethylaminoethyl)-2-methoxy-N′-methyl-5-nitrobenzene-1,4-diamine (Intermediate 34, 600 mg, 1.21 mmol) and iron (405 mg, 7.24 mmol) in ethanol (30 mL). The resulting mixture was stirred at 105° C. for 3 h. The mixture was then concentrated in vacuo and the resulting residue was mixed with DMF (10 mL) and purified by ion exchange chromatography, using an SCX column. The desired product was eluted from the column using 0.35M methanolic ammonia in CH2Cl2 and pure fractions were concentrated in vacuo to give the title compound (530 mg, 94%) as a brown gum; 1H NMR: 2.16 (6H, d), 2.38 (2H, t), 2.66 (3H, d), 2.92 (2H, t), 3.66 (3H, s), 4.60 (2H, s), 6.78 (1H, s), 6.92 (1H, s), 7.12 (1H, t), 7.27-7.4 (1H, m), 8.38 (1H, s), 8.43 (1H, d), 8.49 (1H, s), 8.83 (1H, d), 8.95 (1H, s); m/z: ES+ MH+ 467.

Workup

  1. concentrationThe mixture was then concentrated in vacuo
  2. additionthe resulting residue was mixed with DMF (10 mL)
  3. custompurified by ion exchange chromatography
  4. washThe desired product was eluted from the column
  5. concentrationwere concentrated in vacuo

Sources & evidence

ORD record
ord-29057b6da99344c9a37b7ae3ce834155
Source dataset
uspto-grants-2015_02
Patent number
US08946235B2

Reaction notes

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