Peracetic Acid → 1,4-Dimethyl-6-hexadecyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-5-yl acetate

HRID 60401ノート

反応式

HRID 60401 の反応式
Br[C:2]1[C:3]([CH3:28])=[C:4]2[CH2:26][CH2:25][N:24]([CH3:27])[C:5]2=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23].CN(C)CCN(C)C.[Li]CCCC.COB(OC)OC.[C:49]([O:52]O)(=[O:51])[CH3:50].C(N(CC)CC)C.C(OC(=O)C)(=O)C>C1COCC1.CN(C1C=CN=CC=1)C.O>[C:49]([O:52][C:2]1[C:3]([CH3:28])=[C:4]2[CH2:26][CH2:25][N:24]([CH3:27])[C:5]2=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])(=[O:51])[CH3:50]

参加物

11

反応物 7

HCID 6585Peracetic AcidHCID 7918Acetic AnhydrideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 8470Trimethyl borateHCID 8471TriethylamineHCID 716780615-Bromo-1,4-dimethyl-6-hexadecyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridineHCID 178418339Butyllithium

生成物 1

HCID 706839131,4-Dimethyl-6-hexadecyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridin-5-yl acetate

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
0 °C

実験手順

To a solution of 43.5 mg (0.10 mmol) of 5-bromo-1,4-dimethyl-6-hexadecyl-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine in 1 mL of THF was added 14.2 μL (0.10 mmol) of tetramethylethylenediamine (TMEDA) at −20° C. followed by 119 μL (0.19 mmol, 1.6 M in hexanes) of n-BuLi. After 30 min, 23.4 μL (0.21 mmol) of trimethoxy boron was added and the resulting mixture was stirred for another 1 h. To the reaction mixture was added slowly 44.1 μL (0.21 mmol, 32 wt %) of peracetic acid and the solution was then warmed to 0° C. over a period of 30 min. The mixture was diluted by 5 mL of H2O and extracted with three 5-mL portions of EtOAc. The combined organic layer was washed with brine, dried (MgSO4) and the solvent was concentrated under diminished pressure. The resulting oil was dissolved in 2 mL of CH2Cl2 at 0° C., followed by the addition of 79.6 μL (0.57 mmol) of triethylamine, 1.2 mg (0.01 mmol) of DMAP and 27.0 μL (0.29 mmol) of acetic anhydride. The reaction mixture was stirred at room temperature for 1 h and quenched by the addition of 2 mL of sat aq NH4Cl. The solution was then extracted with three 5-mL portions of EtOAc. The combined organic layer was washed with brine, dried (MgSO4) and the solvent was concentrated under diminished pressure. The residue was purified by flash chromatography on a silica gel column (20 1.7 cm). Elution with 100:1 hexanes/ethyl acetate gave 2c as a yellow oil: yield 15.0 mg (37%); silica gel TLC Rf 0.20 (3:7 EtOAt/hexanes); 1H NMR (CDCl3) δ 0.86 (t, 3H, J=6.8 Hz), 1.23-1.28 (m, 28H), 1.60 (quint, 2H, J=7.6 Hz), 1.93 (s, 3H), 2.28 (s, 3H), 2.44 (t, 2H, J=8.0 Hz), 2.82 (t, 2H, J=8.0 Hz), 2.87 (s, 3H) and 3.41 (t, 2H, J=8.0 Hz); 13C NMR (CDCl3) δ 12.9, 14.1, 20.5, 22.7, 24.6, 28.7, 29.4, 29.51, 29.59 29.64, 29.68, 29.68, 29.68, 29.68, 29.68, 29.68, 29.68, 31.9, 32.5, 33.3, 52.8, 120.1, 134.7, 136.5, 149.7, 161.2 and 169.9; mass spectrum, m/z 430.3 (M)+ (theoretical 430.4); mass spectrum (APCI), m/z 431.3637 (M+H)+ (C27H47N2O2 requires 431.3638).

後処理

  1. extractionextracted with three 5-mL portions of EtOAc
  2. washThe combined organic layer was washed with brine
  3. dry with materialdried (MgSO4)
  4. concentrationthe solvent was concentrated under diminished pressure
  5. dissolutionThe resulting oil was dissolved in 2 mL of CH2Cl2 at 0° C.
  6. stirringThe reaction mixture was stirred at room temperature for 1 h
  7. customquenched by the addition of 2 mL of sat aq NH4Cl
  8. extractionThe solution was then extracted with three 5-mL portions of EtOAc
  9. washThe combined organic layer was washed with brine
  10. dry with materialdried (MgSO4)
  11. concentrationthe solvent was concentrated under diminished pressure
  12. customThe residue was purified by flash chromatography on a silica gel column (20 1.7 cm)
  13. washElution with 100:1 hexanes/ethyl acetate

出典と根拠

ORDレコード
ord-e7a6d11f6dc94ab4925a36ebaf718ac5
出典データセット
uspto-grants-2016_09
特許番号
US09440967B2

反応ノート

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