m-Chloroperbenzoic acid → HCID 178509675, compound

HRID 1962788Notes

Reaction equation

HRID 1962788 reaction equation
[F:1][C:2]([F:7])([F:6])[C:3]([OH:5])=[O:4].[N:8]1[C:13]2[NH:14][CH:15]=[CH:16][C:12]=2[C:11]([C:17]2[CH:18]=[N:19][N:20]([C@@H:22]3[CH2:27][CH2:26][C@H:25]([CH2:28][S:29]([C:31]4[CH:38]=[CH:37][CH:36]=[CH:35][C:32]=4[C:33]#[N:34])=[O:30])[CH2:24][CH2:23]3)[CH:21]=2)=[N:10][CH:9]=1.C1C=C(Cl)C=C(C(OO)=[O:47])C=1.CC#N.O>C(Cl)Cl>[F:1][C:2]([F:7])([F:6])[C:3]([OH:5])=[O:4].[N:8]1[C:13]2[NH:14][CH:15]=[CH:16][C:12]=2[C:11]([C:17]2[CH:18]=[N:19][N:20]([C@@H:22]3[CH2:27][CH2:26][C@H:25]([CH2:28][S:29]([C:31]4[CH:38]=[CH:37][CH:36]=[CH:35][C:32]=4[C:33]#[N:34])(=[O:47])=[O:30])[CH2:24][CH2:23]3)[CH:21]=2)=[N:10][CH:9]=1

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 18373917Acetonitrile--water (1/1)HCID 178509674HCID 178509674, compound

Product 1

HCID 178509675HCID 178509675, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

2-[(cis-4-[4-(7H-Pyrrolo[2,3-d]pyrimidin-4-yl)-1H-pyrazol-1-yl]cyclohexylmethyl)sulfinyl]-benzonitrile (prepared as in Example 687A, 17.2 mg, 0.0000400 mol) (21 mg TFA salt), was dissolved in DCM (10 mL) and cooled to 0° C. To this mixture was added MCPBA (18 mg, 0.0000800 mol). The resulting mixture was stirred for 1 h at 0° C., and then for 16 h at rt. HPLC and LCMS showed 80 area % product, and 3 area % sulfoxide. The MCPBA was removed using a sat'd NaHCO3 wash, and the resulting washed mixture was concentrated by roto-evaporation. The product was isolated by prep HPLCMS using a 19 mm×100 mm C18 column; 23% CH3CN—H2O (0.1% TFA), 1.0 min, to 43% at 6 min; 30 mL/min; detector set at m/z 447 nm; retention time, 5.1 min. The product was isolated from the eluent by freeze-drying. The yield was 5 mg of the TFA salt. 1H NMR (d6-DMSO) δ 12.70 (br s, 1H, NH); 8.83 (s, 1H); 8.82 (s, 1H); 8.41 (s, 1H); 8.21 (dd, 1H); 8.16 (dd, 1H); 8.01 (td, 1H); 7.95 (td, 1H); 7.78 (s, 1H); 7.19 (s, 1H); 4.34 (m, 1H, NCH); 3.62 (d, 2H); 2.28 (m, 1H); 2.10 (m, 2H); 1.90 (m, 2H); 1.72 (m, 4H). MS (ES) 447 (M+1).

Workup

  1. waitfor 16 h at rt
  2. customThe MCPBA was removed
  3. washwash
  4. washthe resulting washed mixture
  5. concentrationwas concentrated by roto-evaporation
  6. customThe product was isolated by prep HPLCMS
  7. customretention time, 5.1 min
  8. customThe product was isolated from the eluent
  9. customby freeze-drying

Sources & evidence

ORD record
ord-bc73b95ec4a7415ebb442d4a9c9532e4
Source dataset
uspto-grants-2013_04
Patent number
US08415362B2

Reaction notes

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