Dimethylformamide → 3-(1-phenylsulfonyl-4-hex-1-ynyl-1H-pyrazol-3-yl)-pyridine

HRID 2043043Notes

Reaction equation

HRID 2043043 reaction equation
C(N(CC)CC)C.CN(C=O)C.[C:13]1([S:19]([N:22]2[CH:26]=[C:25](I)[C:24]([C:28]3[CH:29]=[N:30][CH:31]=[CH:32][CH:33]=3)=[N:23]2)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[CH:34]#[C:35][CH2:36][CH2:37][CH2:38][CH3:39]>C(OCC)(=O)C.[Cu]I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[C:13]1([S:19]([N:22]2[CH:26]=[C:25]([C:34]#[C:35][CH2:36][CH2:37][CH2:38][CH3:39])[C:24]([C:28]3[CH:29]=[N:30][CH:31]=[CH:32][CH:33]=3)=[N:23]2)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 127321-HexyneHCID 575480663-(1-phenylsulfonyl-4-iodo-1H-pyrazol-3-yl)-pyridine

Product 1

HCID 575480443-(1-phenylsulfonyl-4-hex-1-ynyl-1H-pyrazol-3-yl)-pyridineYield 77%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

To triethyl amine (10 ml) and DMF (4 ml) containing 36B (0.97 g, 2.36 mmol), was added 3 eq of hex-1-yne (0.81 ml). The resulting mixture was stirred for another 2 hours under N2. Successively were added 10 mol % of CuI (45 mg), 5 mol % of PdCl2(PPH3)2 (83 mg) and 18 mol % of PPH3 (111 mg). After the addition, the resulting solution was warmed at 70° C. for 18 hours under N2. After cooling to room temperature, the mixture was diluted with ethyl acetate, washed three times with a saturated NaHCO3 solution, dried (Na2SO4), filtered and concentrated. The resulting residue was purified by flash chromatography (diethyl ether/PE (1/1)) to afford 3-(1-phenylsulfonyl-4-hex-1-ynyl-1H-pyrazol-3-yl)-pyridine (43A) as an oil (0.66 g, 77%). 1H-NMR (400 MHz, CDCl3): δ 9.5-9.2 (bs, 1H), 8.8-8.4 (bs, 1H), 8.34 (bd, J=8 Hz, 1H), 8.21 (s, 1H), 8.08-8.04 (m, 2H), 7.67 (bt, J=7 Hz, 1H), 7.57 (bt, J=7 Hz, 2H), 7.41-7.32 (bs, 1H), 2.42 (t, J=7 Hz, 2H), 1.62-1.53 (m, 2H), 1.49-1.39 (m, 2H), 0.93 (t, J=7 Hz, 3H).

Workup

  1. additionAfter the addition
  2. temperatureAfter cooling to room temperature
  3. washwashed three times with a saturated NaHCO3 solution
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe resulting residue was purified by flash chromatography (diethyl ether/PE (1/1))

Sources & evidence

ORD record
ord-15af3522b00f4a93b3932890463fbfdf
Source dataset
uspto-grants-2013_11
Patent number
US08586606B2

Reaction notes

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