HCID 67413926, compound → HCID 136073174, compound

HRID 1481529Notes

Reaction equation

HRID 1481529 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]([F:17])([F:16])[F:15])[N:5]=[C:4]([NH:18][C:19]([C:21]2[N:22]([CH3:31])[N:23]=[C:24]([C:27]([CH3:30])([CH3:29])[CH3:28])[C:25]=2[Cl:26])=O)[C:3]=1[N+:32]([O-])=O>CC(O)=O.CCOC(C)=O.[Fe]>[C:27]([C:24]1[C:25]([Cl:26])=[C:21]([C:19]2[NH:32][C:3]3[C:4](=[N:5][C:6]([C:8]4[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=4[C:14]([F:17])([F:16])[F:15])=[N:7][C:2]=3[CH3:1])[N:18]=2)[N:22]([CH3:31])[N:23]=1)([CH3:28])([CH3:30])[CH3:29]

Participants

5

Reactant 1

HCID 67413926HCID 67413926, compound

Product 1

HCID 136073174HCID 136073174, compound

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A solution of 5-tert-butyl-4-chloro-2-methyl-2H-pyrazole-3-carboxylic acid [6-methyl-5-nitro-2-(2-trifluoromethyl-phenyl)-pyrimidin-4-yl]-amide (138 mg, 0.278 mmol, prepared as described in STEP A above) in AcOH (10 mL) was treated with iron powder (77.5 mg, 1.39 mmol), and the mixture was heated to 100° C. for 4 h. The cooled mixture was diluted with EtOAc (50 mL) and washed with saturated aqueous NaHCO3 (50 mL). The aqueous layer was extracted again with EtOAc (50 mL). The combined organic extracts were dried over MgSO4 and concentrated in vacuo. The residue was purified on a 24-g SEPRA Si 50 SPE column (Flow rate=20 mL/min; Eluent=EtOAc-hexanes, 1:9 for 15 min, then 1:9 to 2:3 over 40 min) to yield 8-(5-tert-butyl-4-chloro-2-methyl-2H-pyrazol-3-yl)-6-methyl-2-(2-trifluoromethyl-phenyl)-7H-purine as a white solid. 1H-NMR (400 MHz, CDCl3) δ: 10.66 (br. s., 1H), 7.82 (d, J=7.6 Hz, 1H), 7.72-7.77 (m, 1H), 7.66 (t, J=7.5 Hz, 1H), 7.54-7.62 (m, 1H), 4.40 (s, 3H), 2.95 (s, 3H), 1.45 (s, 9H). Mass Spectrum (LCMS, ESI pos.): Calculated for C21H20N6ClF3: 449.1 (M+H). Measured: 449.1.

Workup

  1. washwashed with saturated aqueous NaHCO3 (50 mL)
  2. extractionThe aqueous layer was extracted again with EtOAc (50 mL)
  3. dry with materialThe combined organic extracts were dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified on a 24-g SEPRA Si 50 SPE column (Flow rate=20 mL/min

Sources & evidence

ORD record
ord-cfb04b9aea224259a4600585e7950ef6
Source dataset
uspto-grants-2016_08
Patent number
US09409915B2

Reaction notes

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