Dimethylformamide → HCID 22292431, compound

HRID 966867Notes

Reaction equation

HRID 966867 reaction equation
O=P(Cl)(Cl)Cl.[C:6]([O:9][CH2:10][CH2:11][CH2:12][S:13][C:14]1[S:15][CH:16]=[CH:17][CH:18]=1)(=[O:8])[CH3:7].CN([CH:22]=[O:23])C.C(=O)([O-])[O-].[Na+].[Na+]>ClCCCl>[C:6]([O:9][CH2:10][CH2:11][CH2:12][S:13][C:14]1[S:15][C:16]([CH:22]=[O:23])=[CH:17][CH:18]=1)(=[O:8])[CH3:7]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 24813Phosphorus oxychlorideHCID 22292432HCID 22292432, compound

Product 1

HCID 22292431HCID 22292431, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

POCl3 (3.4 mL, 0.036 mol) was added dropwise to a solution of 61 (4.9 g, 0.023 mol) and dry DMF (3.5 mL, 0.045 mol) in 1,2-dichloroethane (100 mL) at 0° C. The resultant mixture was refluxed for 2 hours, poured into ice water and neutralized by addition of 6 M sodium carbonate. The reaction mixture was extracted with methylene chloride (3×100 mL). The combined extracts were washed with saturated brine, dried (MgSO4). After filtration, methylene chloride was removed using a rotary evaporator. The residue was purified by column chromatography over silica gel, eluting with 10% ethyl acetate in methylene chloride. The product was obtained as orange liquid (4.5 g, 82%). 1H NMR δ: 2 (m, 2 H, CH2—CH2—OCOCH3), 2.03 (s, 3 H, CH3), 3.04 (t, 2 H, J=7.2 Hz, S—CH2), 4.15 (t, 2 H, J=6.2 Hz, CH2—OCOCH3), 7.04 (d, 1 H, J=3.9 Hz, aromatic H), 7.59 (d, 1 H, J=3.9 Hz, aromatic H), 9.75 (s, 1 H, CHO); λmax/nm (εmax/dm3 mol−1cm−1) 339 (14,200); HRMS (EI+) calc. for C10H12O3S2: 244.0231. found 244.0228. The product was used without further purification in preparation of 63.

Workup

  1. extractionThe reaction mixture was extracted with methylene chloride (3×100 mL)
  2. washThe combined extracts were washed with saturated brine
  3. dry with materialdried (MgSO4)
  4. filtrationAfter filtration, methylene chloride
  5. customwas removed
  6. customa rotary evaporator
  7. customThe residue was purified by column chromatography over silica gel
  8. washeluting with 10% ethyl acetate in methylene chloride

Sources & evidence

ORD record
ord-4580f670eadf470c98ac511d9a1f1e09
Source dataset
uspto-grants-2005_10
Patent number
US06953570B2

Reaction notes

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