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

HRID 646910ノート

反応式

HRID 646910 の反応式
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

参加物

8

反応物 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

生成物 1

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

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-1337f10142374f50928affd448b8f8c8
出典データセット
uspto-grants-2010_04
特許番号
US07705042B2

反応ノート

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