Dimethylformamide → 197915-37-0

HRID 1003898Notes

Reaction equation

HRID 1003898 reaction equation
[OH:1][C:2]1[CH2:3][C:4]([CH2:15][CH2:16][C:17]2[CH:22]=[CH:21][C:20]([NH:23]C(=O)C)=[CH:19][CH:18]=2)([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[O:5][C:6](=[O:8])[CH:7]=1.[C:27]([C:31]1[CH:36]=[C:35]([CH2:37][OH:38])[C:34]([CH3:39])=[CH:33][C:32]=1[S:40]S(C1C=CC(C)=CC=1)(=O)=O)([CH3:30])([CH3:29])[CH3:28].C([O-])([O-])=O.[K+].[K+].CN(C=O)C>CCOC(C)=O.C(O)(=O)C>[NH2:23][C:20]1[CH:21]=[CH:22][C:17]([CH2:16][CH2:15][C:4]2([C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=3)[O:5][C:6](=[O:8])[C:7]([S:40][C:32]3[CH:33]=[C:34]([CH3:39])[C:35]([CH2:37][OH:38])=[CH:36][C:31]=3[C:27]([CH3:30])([CH3:29])[CH3:28])=[C:2]([OH:1])[CH2:3]2)=[CH:18][CH:19]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 10499026S-[2-Tert-butyl-4-(hydroxymethyl)-5-methylphenyl] 4-methylbenzenesulfonothioateHCID 54682268HCID 54682268, compound

Product 1

HCID 54682309197915-37-0

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolvent

Procedure

The title compound was prepared as described in General Method 9 using 0.23 g (0.65 mmol) of N-{4-[2-(4-hydroxy-6-oxo-2-phenyl-3,6-dihydro-2H-pyran-2-yl)-ethyl]-phenyl}-acetamide (prepared in Example RR), 0.33 g (0.90 mmol) of toluene-4-thiosulfonic acid S-(2-tert-butyl-4-hydroxymethyl-5-methyl-phenyl) ester (prepared in Example FFF), 0.54 g (3.9 mmol) of K2CO3, and 5 mL of DMF. The solution was stirred overnight at room temperature and then poured into glacial acetic acid (5 mL) and EtOAc (20 mL). After standard work-up, the residue was triturated with Et2O, and the solids were filtered. The penultimate intermediate was dissolved in H2 0 (30 mL), 50% NaOH (4 mL), and MeOH (5 mL) and was refluxed for 18 hours. The mixture was cooled to room temperature, concentrated, and suspended in phosphate buffer (pH 7.5). Acidification to pH 6.8 with phosphoric acid was followed by extraction with CH2Cl2. The combined extracts were washed with brine, dried (MgSO4), and concentrated to give the title compound, m.p. 218-221° C. 1H NMR (DMSO-d6) δ 1.44 (s, 9 H), 1.76 (s, 3 H), 2.05-2.22 (m, 3 H), 2.40 (m, 1 H), 3.40 (m, partially obscured by H2O, 2 H), 4.32 (s, 2 H), 4.90 (br s, 1 H), 6.17 (s, 1 H), 6.47 (d, 2 H), 6.75 (d, 2 H), 7.21 (s, 1 H), 7.38-7.43 (m, 5 H).

Workup

  1. customThe title compound was prepared
  2. customAfter standard work-up, the residue was triturated with Et2O
  3. filtrationthe solids were filtered
  4. dissolutionThe penultimate intermediate was dissolved in H2 0 (30 mL)
  5. temperature50% NaOH (4 mL), and MeOH (5 mL) and was refluxed for 18 hours
  6. temperatureThe mixture was cooled to room temperature
  7. concentrationconcentrated
  8. extractionAcidification to pH 6.8 with phosphoric acid was followed by extraction with CH2Cl2
  9. washThe combined extracts were washed with brine
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-1d8ee35f94c1488699e9c3918e2568f0
Source dataset
uspto-grants-2000_04
Patent number
US06046355

Reaction notes

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