Sodium Carbonate → 1-[5-(3,6-Dihydro-2H-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine

HRID 646910노트

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HRID 646910 반응식
CC1(C)COB([C:8]2[CH:9]=[CH:10][C:11]([N+:21]([O-:23])=[O:22])=[C:12]([N:14]3[CH2:19][CH2:18][CH:17]([CH3:20])[CH2:16][CH2:15]3)[CH:13]=2)OC1.[S:25]1[CH2:30][CH:29]=[C:28](OS(C(F)(F)F)(=O)=O)[CH2:27][CH2:26]1.[Li+].[Cl-].C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O>[S:25]1[CH2:26][CH:27]=[C:28]([C:8]2[CH:9]=[CH:10][C:11]([N+:21]([O-:23])=[O:22])=[C:12]([N:14]3[CH2:15][CH2:16][CH:17]([CH3:20])[CH2:18][CH2:19]3)[CH:13]=2)[CH2:29][CH2:30]1

참가 물질

8

반응물 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 226257513,6-Dihydro-2H-thiopyran-4-yl trifluoromethanesulfonateHCID 586384871-[5-(5,5-Dimethyl-[1,3,2]dioxaborinan-2-yl)-2-nitro-phenyl]-4-methyl-piperidine

생성물 1

HCID 586385191-[5-(3,6-Dihydro-2H-thiopyran-4-yl)-2-nitro-phenyl]-4-methyl-piperidine수율 97%

시약·촉매·용매 3

HCID 178418397HCID 178418397, 화합물촉매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

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온도
80 °C

실험 절차

To a mixture of 1-[5-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-2-nitro-phenyl]-4-methyl-piperidine (as prepared in Example 33, step (b), 60 mg, 0.18 mmol), trifluoromethanesulfonic acid 3,6-dihydro-2H-thiopyran-4-yl ester (as prepared in the previous step, 54 mg, 0.22 mmol), Pd(PPh3)4 (31 mg, 0.027 mmol) and LiCl (15 mg, 0.36 mmol) in 1 mL of 1,4-dioxane was added 2.0 M Na2CO3 aq solution (80 μL, 0.16 mmol). The resulting mixture was stirred at 80° C. for 1 h, and then cooled to RT. Treated with 50 mL of EtOAc, the mixture was washed with H2O, brine and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (1% EtOAc/hexane) gave 56 mg (97%) of the title compound as a brown oil: 1H-NMR (CDCl3; 400 MHz): δ 7.77 (d, 1H, J=8.6 Hz), 7.01 (d, 1H, J=1.8 Hz), 6.88 (dd, 1H, J=8.6, 1.8 Hz), 6.24 (m, 1H), 3.34-3.37 (m, 2H), 3.26 (d, 2H, J=12.4 Hz), 2.89 (t, 2H, J=5.7 Hz), 2.82 (td, 2H, J=12.0, 1.6 Hz), 2.64-2.69 (m, 2H), 1.70 (dd, 2H, J=12.4, 2.1 Hz), 1.52 (m, 1H), 1.36-1.47 (m, 2H), 0.99 (d, 3H, J=6.2 Hz). Mass spectrum (ESI, m/z): Calcd. for C17H22N2O2S, 319.1 (M+H), found 319.1.

후처리

  1. temperaturecooled to RT
  2. washthe mixture was washed with H2O, brine
  3. dry with materialdried (Na2SO4)
  4. customRemoval of the solvent under reduced pressure

출처 및 근거

ORD 기록
ord-1337f10142374f50928affd448b8f8c8
출처 데이터셋
uspto-grants-2010_04
특허 번호
US07705042B2

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