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Methanol → 2-[Bis(tert-butoxycarbonyl)amino)-5-(2'-methylsulfonylphenyl)pyrimidine

HRID 2186220
Notes
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Reaction equation

HRID 2186220 reaction equation
[C:1]([O:5][C:6]([N:8]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[C:9]1[N:14]=[CH:13][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2SC)=[CH:11][N:10]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].O[O:31][S:32]([O-:34])=O.[K+].[CH3:36]O>O>[C:1]([O:5][C:6]([N:8]([C:23]([O:25][C:26]([CH3:27])([CH3:29])[CH3:28])=[O:24])[C:9]1[N:10]=[CH:11][C:12]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[S:32]([CH3:36])(=[O:34])=[O:31])=[CH:13][N:14]=1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 887MethanolHCID 181773202-[Bis(tert-butoxycarbonyl)amino]-5-(2'-methylthiophenyl)pyrimidineHCID 23707502Potassium hydroxy sulfite

Product 1

HCID 181772932-[Bis(tert-butoxycarbonyl)amino)-5-(2'-methylsulfonylphenyl)pyrimidineYield 56%

Reagents, catalysts & solvents 1

HCID 962Water
Solvent
2×

Conditions

Temperature
0 °C

Procedure

2-[Bis(tert-butoxycarbonyl)amino]-5-(2′-methylthiophenyl)pyrimidine (2.13 g, 5.1 mmol) was dissolved in MeOH (20 mL) and cooled to 0° C. In a separate beaker, a solution of Oxone (5.49 g) was generated by dilution to 27 mL with water. A portion of this solution (17 mL, 5.6 mmol) was removed and adjusted to pH 4.2 with sat. Na3PO4 solution (4.7 mL). This mixture was added to the reaction and stirred 23 hours at room temp. The resulting mixture was diluted with water and extracted with CHCl3. The organics were combined, washed with water and brine, dried over Na2SO4, filtered, and evaporated. The crude product was chromatographed on silica gel (50-100% EtOAc/hexanes) to yield the sulfone (1.28 g, 56%). 1H NMR (CDCl3): δ8.81 (s, 2H), 8.28 (dd, 1H, J=7.6, J′=1.4), 7.72 (m, 2H), 7.39 (dd, 1H, J=7.3, J′=1.4), 2.76 (s, 3H), 1.50 (s, 18H).

Workup

  1. additionThis mixture was added to the reaction
  2. extractionextracted with CHCl3
  3. washwashed with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude product was chromatographed on silica gel (50-100% EtOAc/hexanes)

Sources & evidence

ORD record
ord-3c43d7f6bcb8442197a849ed75c8734e
Source dataset
uspto-grants-2002_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06403620B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes