Sodium Carbonate → 7-(2,4-dichlorophenyl)-N,N-diethylpyrazolo[1,5-a]pyridin-3-amine

HRID 859133Notes

Reaction equation

HRID 859133 reaction equation
[CH2:1]([N:3]([CH2:14][CH3:15])[C:4]1[CH:5]=[N:6][N:7]2[C:12](I)=[CH:11][CH:10]=[CH:9][C:8]=12)[CH3:2].[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:18]=1B(O)O.C([O-])([O-])=O.[Na+].[Na+]>COCCOC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:16][C:17]1[CH:22]=[C:21]([Cl:23])[CH:20]=[CH:19][C:18]=1[C:12]1[N:7]2[N:6]=[CH:5][C:4]([N:3]([CH2:14][CH3:15])[CH2:1][CH3:2])=[C:8]2[CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 2734659(2,4-Dichlorophenyl)boronic acid2×HCID 858677663-Diethylamino-7-iodopyrazolo[1,5-a]pyridine

Product 1

HCID 99276397-(2,4-dichlorophenyl)-N,N-diethylpyrazolo[1,5-a]pyridin-3-amineYield 80.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 3-diethylamino-7-iodopyrazolo[1,5-a]pyridine (0.20 g, 0.63 mmol) and Pd(PPh3)4 (0.037 g, 0.03 mmol) in DME (5.0 mL) was stirred at room temperature for 10 minutes then treated with 2,4-dichlorophenylboronic acid (0.19 g, 1.27 mmol) and 2M Na2CO3 (3.0 mL). The reaction was heated at 80° C. for 16 hours and cooled down to room temperature. Additional Pd(PPh3)4 (0.037 mg, 0.03 mmol) and 2,4-dichlorophenylboronic acid (0.19 g, 1.27 mmol) were added and heating was continued at 80° C. for 2 hours. The reaction was partitioned between ethyl acetate and water. The aqueous layer was extracted with ethyl acetate (2×). The combined organic solutions was washed with brine, dried over MgSO4, and concentrated in vacuo to dryness. The residue was subjected to column chromatography (5% ethyl acetate/hexane) to give 0.17 g (79%) of a light yellow oil as the title compound: 1H NMR (400 MHz, CDCl3) δ 7.81 (s, 1H), 7.66–7.63 (m, 2H), 7.50 (d, J=8.2 Hz, 1H), 7.44 (d, J=8.2 Hz, 1H), 7.14–7.09 (m, 1H), 6.71 (d, J=6.7 Hz, 1H), 3.15 (q, J=7.1 Hz, 4H), 1.09 (t, J=7.1 Hz, 6H); IR (diffuse reflectance) 2968, 2935, 2814, 1487, 1461, 1377, 1334, 1314, 1149, 1096, 921, 881, 867, 827, 791 cm−1; MS (EI) m/z 333 (M+); Anal. Calcd for C17H17Cl2N3: C, 61.09; H, 5.13; N, 12.57. Found: C, 60.97; H, 5.02; N, 12.54.

Workup

  1. temperaturecooled down to room temperature
  2. temperatureheating
  3. customThe reaction was partitioned between ethyl acetate and water
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×)
  5. washThe combined organic solutions was washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo to dryness

Sources & evidence

ORD record
ord-fe52f60a08cf40d9a13dc9a2e8a3f738
Source dataset
uspto-grants-2006_12
Patent number
US07151109B2

Reaction notes

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