Pyridine → HCID 59128681, compound

HRID 1991103Notes

Reaction equation

HRID 1991103 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5]([C:7]2[C:15]3[C:10](=[N:11][CH:12]=[C:13](B4OC(C)(C)C(C)(C)O4)[CH:14]=3)[N:9]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[CH:8]=2)[CH:4]=[N:3]1.[CH2:33]([SH:36])[CH2:34][CH3:35].N1C=CC=CC=1>CN(C=O)C.CCOC(C)=O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH3:1][N:2]1[CH:6]=[C:5]([C:7]2[C:15]3[C:10](=[N:11][CH:12]=[C:13]([S:36][CH2:33][CH2:34][CH3:35])[CH:14]=3)[N:9]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[CH:8]=2)[CH:4]=[N:3]1

Participants

7

Reactant 3

HCID 1049Pyridine3×HCID 7848Propyl mercaptan3×HCID 59128702HCID 59128702, compound

Product 1

HCID 59128681HCID 59128681, compoundYield 13%

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalyst3×HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 25 (60 mg, 0.132 mmol), n-propanethiol (21.1 mg, 0.264 mmol), copper (II) acetate (36 mg, 0.198 mmol), pyridine (32 μL, 0.396 mmol) and 4A molecular sieves (50 mg) in DMF (1.5 mL) were heated at 110° C. for 25 h. More n-propanethiol (21.1 mg, 0.264 mmol), copper (II) acetate (36 mg, 0.198 mmol) and pyridine (32 μL, 0.396 mmol) were added and heating continued for 20.5 h. More n-propanethiol (21.1 mg, 0.264 mmol), copper (II) acetate (36 mg, 0.198 mmol), pyridine (32 μL, 0.396 mmol) and 4A sieves were added again and the heating continued at 130° C. overnight. The reaction mixture was cooled, diluted with AcOEt, filtered and washed with brine. The aqueous layer was extracted with AcOEt (2×), and the combined organic extracts dried (MgSO4) and concentrated. The residue was purified by preparative LCMS (column LUNA 10 μ C18(2) 00G-4253-V0 250×50 mm) using water—acetonitrile (0.1% AcOH) as eluent (in gradient; flow 80 mL/min) to give 26 as an orange oil (6.7 mg, 13%); 1H NMR (400 MHz, CDCl3) δ-0.056 (s, 9H), 0.93 (t, J=8.3 Hz, 2H), 1.00 (t, J=7.3 Hz, 3H), 1.61 (sextet, J=7.4 Hz, 2H), 2.84 (t, J=7.3 Hz, 2H), 3.57 (t, J=8.3 Hz, 2H), 4.00 (s, 3H), 5.68 (s, 2H), 7.43 (s, 1H), 7.64 (s, 1H), 7.76 (s, 1H), 8.15 (d, J=2.0 Hz, 1H), 8.45 (d, J=2.0 Hz, 1H).

Workup

  1. temperatureheating
  2. waitthe heating continued at 130° C. overnight
  3. temperatureThe reaction mixture was cooled
  4. filtrationfiltered
  5. washwashed with brine
  6. extractionThe aqueous layer was extracted with AcOEt (2×)
  7. dry with materialthe combined organic extracts dried (MgSO4)
  8. concentrationconcentrated
  9. customThe residue was purified by preparative LCMS (column LUNA 10 μ C18(2) 00G-4253-V0 250×50 mm)

Sources & evidence

ORD record
ord-5dfb38c8a1e3416d9d8d4a38feb95d9e
Source dataset
uspto-grants-2010_01
Patent number
US07645769B2

Reaction notes

Loading…