HCID 58551273, compound → HCID 58551317, compound

HRID 1908184Notes

Reaction equation

HRID 1908184 reaction equation
[C:1]([S:5]([C:8]1[CH:13]=[CH:12][C:11]([C:14]([N:16]2[CH2:21][CH2:20][C:19]3([C:33]4[CH:32]=[N:31][N:30]([CH3:34])[C:29]=4[C:28]4[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=4[O:22]3)[CH2:18][CH2:17]2)=[O:15])=[CH:10][C:9]=1OC)(=[O:7])=[O:6])([CH3:4])([CH3:3])[CH3:2].Br[C:38]1[CH:43]=[CH:42][C:41]([C:44]([N:46]2[CH2:51][CH2:50][C:49]3([C:63]4[CH:62]=[N:61][N:60]([CH3:64])[C:59]=4[C:58]4[CH:57]=[CH:56][CH:55]=[CH:54][C:53]=4[O:52]3)[CH2:48][CH2:47]2)=[O:45])=[CH:40][C:39]=1[CH3:65]>>[C:1]([S:5]([C:8]1[CH:13]=[CH:12][C:11]([C:14]([N:16]2[CH2:17][CH2:18][C:19]3([C:33]4[CH:32]=[N:31][N:30]([CH3:34])[C:29]=4[C:28]4[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=4[O:22]3)[CH2:20][CH2:21]2)=[O:15])=[CH:10][C:9]=1[CH3:38])(=[O:7])=[O:6])([CH3:3])([CH3:2])[CH3:4].[CH2:1]([S:5]([C:38]1[CH:43]=[CH:42][C:41]([C:44]([N:46]2[CH2:51][CH2:50][C:49]3([C:63]4[CH:62]=[N:61][N:60]([CH3:64])[C:59]=4[C:58]4[CH:57]=[CH:56][CH:55]=[CH:54][C:53]=4[O:52]3)[CH2:48][CH2:47]2)=[O:45])=[CH:40][C:39]=1[CH3:65])(=[O:7])=[O:6])[CH3:2]

Participants

4

Reactant 2

HCID 58551273HCID 58551273, compoundHCID 67467105HCID 67467105, compound

Product 2

HCID 58551317HCID 58551317, compoundHCID 67463630HCID 67463630, compound

Procedure

(4-Isopropylsulfanyl-3-methoxy-phenyl)-(1-methylspiro[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone (291 mg, 0.6277 mmol) was dissolved in acetic acid (3 mL) and hydrogen peroxide (200 μL, 6.527 mmol) was added. The reaction mixture was heated at 80° C. for 40 minutes before it was partitioned between ethyl acetate (15 mL) and water (10 mL). The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate and then purified by column chromatography utilizing a gradient of 0-5% methanol in dichloromethane to yield (4-isopropylsulfonyl-3-methoxy-phenyl)-(1-methylspiro[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone (51 mg, 24%) as a white solid. ESI-MS m/z calc. 495.2. found 496.5 (M+1)+. Retention time: 1.52 minutes (3 min run). 1H NMR (400 MHz, DMSO) δ 7.83 (d, J=8.0 Hz, 1H), 7.74 (d, J=7.6 Hz, 1H), 7.45 (s, 1H), 7.34 (s, 1H), 7.29 (t, J=7.8 Hz, 1H), 7.22 (d, J=8.0 Hz, 7.15-7.06 (m, 2H), 4.45-4.31 (m, 1H), 4.10 (s, 3H), 3.97 (s, 3H), 3.68 (septet, J=6.7 Hz, 1H), 3.59-3.22 (m, 3H), 2.10-1.82 (m, 4H), 1.17 (d, J=6.9 Hz, 6H). (4-(tert-Butylsulfonyl)-3-methoxyphenyl)(1-methyl-1H-spiro[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone was also synthesized using the procedures described above. (4-(tert-Butylsulfonyl)-3-methylphenyl)(1-methyl-1H-spiro-[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone and (4-(ethylsulfonyl)-3-methylphenyl)(1-methyl-1H-spiro[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone were synthesized from (4-bromo-3-methylphenyl)(1-methyl-1H-spiro[chromeno[4,3-c]pyrazole-4,4′-piperidine]-1′-yl)methanone using the procedures described above.

Workup

  1. customRetention time: 1.52 minutes (3 min run)

Sources & evidence

ORD record
ord-d1560f212e234e9ab0fadd9ab0b13916
Source dataset
uspto-grants-2013_12
Patent number
US08598164B2

Reaction notes

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