Water → HCID 178451224, compound

HRID 2389508Notes

Reaction equation

HRID 2389508 reaction equation
[N+:1]([C:4]1[CH:9]=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[CH:6][C:5]=1[NH:14][CH2:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])([O-])=O.[C:23](N1C=CN=C1)(N1C=CN=C1)=[S:24].O>C1COCC1>[SH:24][C:23]1[N:14]([CH2:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[C:5]2[CH:6]=[CH:7][C:8]([C:10]([F:13])([F:12])[F:11])=[CH:9][C:4]=2[N:1]=1

Participants

5

Reactant 3

HCID 962WaterHCID 802641,1'-ThiocarbonyldiimidazoleHCID 86225047HCID 86225047, compound

Product 1

HCID 178451224HCID 178451224, compoundYield 72.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a test tube equipped with a septum, tert-butyl (2-nitro-4-trifluoromethyl-phenylamino)-acetate (Starting material 5-VIII, 80 mg, 0.25 mmol) is dissolved in dry THF (0.5 ml). Argon is allowed to bubble through this solution for 10 min. Then dry palladium on carbon (10% w/w, 26 mg, 10% mol) is added and the flask is set under H2 atmosphere. The resulting mixture is shaken vigorously at rt overnight. If necessary, another 8% mol of palladium on charcoal 10% w/w is added and the resulting suspension is stirred for another hour under H2 atmosphere. The crude mixture is then filtered over celite to remove any solid particle. The celite is rinsed once with dry THF. To the resulting light yellow solution is added, under argon, 1,1′-thiocarbonyldiimidazole (89 mg, 0.5 mmol, 2 eq.). The resulting orange solution is allowed to stir at rt for 5 h. Water is then added. The yellow solid formed is filtered over a fritted funnel, rinsed thoroughly with water and dried under high vacuum. This yields the title compound (60 mg) in 73% as a yellow solid: tR=1.10 min (LC-3), ESI-MS (pos.): m/z 332.99 [M+H]+, 331.13 [M−H]+; 1H-NMR (DMSO-d6): δ (ppm) 1.41 (s, 9H, tBu), 5.06 (s, 2H, NHCH2CO2), 7.44 (s, 1H, Harom), 7.57 (s, 2H, Harom), 13.25 (br. s, 1H, SH).

Workup

  1. customto bubble through this solution for 10 min
  2. additionThen dry palladium on carbon (10% w/w, 26 mg, 10% mol) is added
  3. additionIf necessary, another 8% mol of palladium on charcoal 10% w/w is added
  4. stirringthe resulting suspension is stirred for another hour under H2 atmosphere
  5. filtrationThe crude mixture is then filtered over celite
  6. customto remove any solid particle
  7. washThe celite is rinsed once with dry THF
  8. additionTo the resulting light yellow solution is added, under argon
  9. stirringto stir at rt for 5 h
  10. customThe yellow solid formed
  11. filtrationis filtered over a fritted funnel
  12. washrinsed thoroughly with water
  13. customdried under high vacuum

Sources & evidence

ORD record
ord-ceab4d520c7f437ebb734af3b33909e9
Source dataset
uspto-grants-2012_09
Patent number
US08273740B2

Reaction notes

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