Pyridine → HCID 18787684, compound

HRID 1107646Notes

Reaction equation

HRID 1107646 reaction equation
[F:1][C:2]([F:24])=[CH:3][CH2:4][NH:5][C:6]1[CH:7]=[C:8]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:9]2[C:14]([CH:15]=1)=[CH:13][CH:12]=[CH:11][CH:10]=2.N1C=CC=CC=1.[CH3:31][C:32](OC(C)=O)=[O:33]>O1CCOCC1.CN(C1C=CN=CC=1)C>[F:1][C:2]([F:24])=[CH:3][CH2:4][N:5]([C:6]1[CH:7]=[C:8]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:9]2[C:14]([CH:15]=1)=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:32](=[O:33])[CH3:31]

Participants

6

Reactant 3

HCID 1049PyridineHCID 7918Acetic AnhydrideHCID 18787682HCID 18787682, compound

Product 1

HCID 18787684HCID 18787684, compoundYield 96%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
25 °C

Procedure

A solution of 210 (149 mg, 0.46 mmol) in dioxane (5 mL) under Ar was treated with DMAP (50 mg, 0.40 mmol), pyridine (0.37 mL, 4.6 mmol) and Ac2O (0.2 mL, 2.3 mmol) and stirred at 25° C. for 19 h. The reaction solution was quenched by the addition of 10% aqueous HCl (10 mL) and EtoAc (10 mL). The aqueous layer was removed and extracted with EtOAc (3×5 mL). The organic solutions were combined, washed with saturated aqueous NaCl (15 mL), dried (MgSO4), and concentrated under reduced pressure. Chromatography (SiO2, 15% EtOAc-hexane) afforded 211 (162 mg, 169 mg theoretical, 96%) as a pale yellow oil: 1H NMR (CDCl3, 400 MHz) δ8.33 (dd, 1H, J=1.6, 8.1 Hz, C8-H), 7.77 (dd, 1H, J=1.7, 7.5 Hz, C5-H), 7.52 (m, 5H, C6H5), 7.38 (m, 2H, C6 and C7-H), 7.20 (d, 1H, J=1.6 Hz, C4-H), 6.57 (d, 1H, J=1.6 Hz, C2-H), 5.25 (s, 2H, CH2Ph), 4.43 (dtd, 1H, J=1.9, 7.9, 24.8 Hz, C2'-H), 4.32 (dd, 1H, J=1.6, 1.6 Hz, C1'-H), 4.30 (m, 1H, C1'-H), 1.82 (s, 3H, CH3CO); 13C NMR (CDCl3, 100 MHz) δ170.0, 160.0, 157.1, 155.1, 139.4, 135.9, 133.8, 128.2, 127.7, 127.2, 127.1, 126.9, 125.7, 124.7, 121.9, 118.6, 105.0, 74.9 (dd, J=75.2, 91.6 Hz), 69.8, 41.8 (d, J=28 Hz), 22.0; 19F NMR (CDCl3, 376 MHz) δ-87.0 (d, J=40.0 Hz), -89.1 (dd, J=24.8, 40.0 Hz); IR (film) vmax 2928, 1745, 1660, 1413 cm-1 ; FABHRMS (NBA-NaI) m/z 368.1740 (M+H+, C22H19F2NO requires 368.1470).

Workup

  1. customThe reaction solution was quenched by the addition of 10% aqueous HCl (10 mL) and EtoAc (10 mL)
  2. customThe aqueous layer was removed
  3. extractionextracted with EtOAc (3×5 mL)
  4. washwashed with saturated aqueous NaCl (15 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-57c55e8e2d134b6da9a33bc291fa7868
Source dataset
uspto-grants-2000_05
Patent number
US06060608

Reaction notes

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