Pyridine → 2-{[5-(bis{[4-(tert-butyl)phenyl]sulfonyl}amino)-1-{2-([tert-butyl(dimethyl)silyl]oxy}ethyl}4-{4-methylphenyl}-1H-pyrazol-3-yl]oxy}ethyl acetate

HRID 1368652Notes

Reaction equation

HRID 1368652 reaction equation
[C:1]([O:4][CH2:5][CH2:6][O:7][C:8]1[C:12]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)=[C:11]([NH2:20])[N:10]([CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25])[N:9]=1)(=[O:3])[CH3:2].[C:31]([C:35]1[CH:40]=[CH:39][C:38]([S:41](Cl)(=[O:43])=[O:42])=[CH:37][CH:36]=1)([CH3:34])([CH3:33])[CH3:32].[C:45](OCC)(=O)C.[CH3:51][CH2:52][CH2:53][CH2:54][CH2:55][CH3:56].[S:57](Cl)(Cl)(=[O:59])=[O:58].N1[CH:67]=[CH:66][CH:65]=CC=1>CN(C1C=CN=CC=1)C.S([O-])([O-])(=O)=O.[Cu+2]>[C:1]([O:4][CH2:5][CH2:6][O:7][C:8]1[C:12]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)=[C:11]([N:20]([S:57]([C:53]2[CH:52]=[CH:51][C:56]([C:66]([CH3:65])([CH3:67])[CH3:45])=[CH:55][CH:54]=2)(=[O:59])=[O:58])[S:41]([C:38]2[CH:39]=[CH:40][C:35]([C:31]([CH3:34])([CH3:33])[CH3:32])=[CH:36][CH:37]=2)(=[O:43])=[O:42])[N:10]([CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:25])[CH3:26])[N:9]=1)(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 1049PyridineHCID 24648Sulfuryl chlorideHCID 1398824-t-Butylbenzenesulfonyl chlorideHCID 21226206Ethyl acetate hexaneHCID 234003092-{[5-amino-1-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-(4-methylphenyl)-1H-pyrazol-3-yl]oxy}ethyl acetate

Product 1

HCID 222820282-{[5-(bis{[4-(tert-butyl)phenyl]sulfonyl}amino)-1-{2-([tert-butyl(dimethyl)silyl]oxy}ethyl}4-{4-methylphenyl}-1H-pyrazol-3-yl]oxy}ethyl acetate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 24462Copper SulfateCatalyst

Procedure

A solution of 2-{[5-amino-1-(2-{[tert-butyl(dimethyl)silyl]oxy}ethyl)-4-(4-methylphenyl)-1H-pyrazol-3-yl]oxy}ethyl acetate (0.35 g) (Preparation 30), 4-(tert-butyl)phenylsulfonyl chloride (0.25 g) and 4-(N,N-dimethyl)aminopyridine (98 mg) in pyridine (4 ml) was stirred at room temperature overnight. Tlc (30:70 ethyl acetate/hexane) indicated a new less polar product had formed, but the reaction appeared to have proceeded only 50% to completion. A further aliquot of the sulfonyl chloride (0.25 g) was added to the reaction mixture and stifling at room temperature was continued for a further 4 days. Tlc analysis then indicated complete disappearance of the starting materials and a single new product was observed. The reaction mixture was poured into saturated copper (II) sulfate solution (100 ml) and the aqueous mixture was extracted with ether (2×5 ml). The combined ether extracts were washed with saturated copper (II) sulfate solution (30 ml). The organic extract was dried over magnesium sulfate, filtered and concentrated under reduced pressure to leave a yellow/brown gum. The gum was recrystallised from methanol/water to give the title compound as yellow crystals (325 mg).

Workup

  1. customhad formed
  2. customstifling at room temperature
  3. extractionthe aqueous mixture was extracted with ether (2×5 ml)
  4. washThe combined ether extracts were washed with saturated copper (II) sulfate solution (30 ml)
  5. extractionThe organic extract
  6. dry with materialwas dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto leave a yellow/brown gum
  10. customThe gum was recrystallised from methanol/water

Sources & evidence

ORD record
ord-36cad1b90c084206a0b7308298d6099f
Source dataset
uspto-grants-2003_06
Patent number
US06573270B1

Reaction notes

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