Potassium Hydroxide → 3-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridine

HRID 660167Notes

Reaction equation

HRID 660167 reaction equation
[C:1]1([S:7]([N:10]2[CH:14]=[C:13]([CH:15]=[CH:16][CH2:17][CH2:18][CH2:19][CH3:20])[C:12]([C:21]3[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=3)=[N:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[K+].NN.O>C(O)COCCO>[CH:15]([C:13]1[C:12]([C:21]2[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=2)=[N:11][NH:10][CH:14]=1)=[CH:16][CH2:17][CH2:18][CH2:19][CH3:20].[C:1]1([S:7]([N:10]2[CH:14]=[C:13]([CH:15]=[CH:16][CH2:17][CH2:18][CH2:19][CH3:20])[C:12]([C:21]3[CH:22]=[N:23][CH:24]=[CH:25][CH:26]=3)=[N:11]2)(=[O:8])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 14797Potassium HydroxideHCID 24654Hydrazine hydrate (1:1)HCID 672844273-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridine

Product 2

HCID 672844273-(1-phenylsulfonyl-4-hex-1-enyl-1H-pyrazol-3-yl)-pyridineHCID 178442469HCID 178442469, compound

Reagents, catalysts & solvents 1

HCID 8117Diethylene GlycolSolvent

Procedure

Compound 46A (0.34 g, 0.97 mmol), 0.7 g of KOH and 1 ml of NH2NH2.H2O were combined in diethylene glycol (10 ml) and warmed to reflux for 1 hour under N2. The mixture was cooled, concentrated and redissolved in MeOH. Filtration over 25 g of SCX-2 (MeOH followed by 1 N NH3/MeOH) and subsequent purification by flash chromatography (ethyl acetate) afforded 3-(4-hex-1-enyl-1H-pyrazol-3-yl)-pyridine (the deprotected analog of 46A). Yield 0.18 g (86%). (TLC diethyl ether Rf 0.18). 3-(4-Hex-1-enyl-1H-pyrazol-3-yl)-pyridine was converted to the title compound 47A, using the methodology described for the conversion of 21 A to 22A (see Scheme 3). Yield: 50% (amorphous). LCMS (method A); Rt: 2.30 min, ([M+H]+=246). 1H-NMR (400 MHz, CDCl3): δ 7.59 (s, 1H), 6.22 (bd, J=16 Hz, 1H), 6.03-5.98 (bs, 1H), 5.98-5.88 (m, 1H), 3.26-3.21 (m, 2H), 2.63 (bt, J=7 Hz, 2H), 2.44 (s, 3H), 2.43-2.36 (m, 2H), 2.19-2.11 (m, 2H), 1.46-1.29 (m, 4H), 0.91 (t, J=7 Hz, 3H).

Workup

  1. temperaturewarmed
  2. temperatureto reflux for 1 hour under N2
  3. temperatureThe mixture was cooled
  4. concentrationconcentrated
  5. dissolutionredissolved in MeOH
  6. filtrationFiltration
  7. customover 25 g of SCX-2 (MeOH followed by 1 N NH3/MeOH) and subsequent purification by flash chromatography (ethyl acetate)

Sources & evidence

ORD record
ord-d9597efcb52a4c168eb36486c0305c8f
Source dataset
uspto-grants-2011_12
Patent number
US08084473B2

Reaction notes

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