4-Formylphenylboronic Acid → 7-[(2,4-Dichloro-5-methoxyphenyl)amino]-3-(4-formylphenyl)thieno[3,2-b]pyridine-6-carbonitrile

HRID 1178683Notes

Reaction equation

HRID 1178683 reaction equation
Br[C:2]1[C:6]2=[N:7][CH:8]=[C:9]([C:22]#[N:23])[C:10]([NH:11][C:12]3[CH:17]=[C:16]([O:18][CH3:19])[C:15]([Cl:20])=[CH:14][C:13]=3[Cl:21])=[C:5]2[S:4][CH:3]=1.[CH:24]([C:26]1[CH:31]=[CH:30][C:29](B(O)O)=[CH:28][CH:27]=1)=[O:25]>COCCOC.C(=O)(O)[O-].[Na+]>[Cl:21][C:13]1[CH:14]=[C:15]([Cl:20])[C:16]([O:18][CH3:19])=[CH:17][C:12]=1[NH:11][C:10]1[C:9]([C:22]#[N:23])=[CH:8][N:7]=[C:6]2[C:2]([C:29]3[CH:30]=[CH:31][C:26]([CH:24]=[O:25])=[CH:27][CH:28]=3)=[CH:3][S:4][C:5]=12

Participants

5

Reactant 2

HCID 5910734-Formylphenylboronic AcidHCID 113962683-Bromo-7-[(2,4-dichloro-5-methoxyphenyl)amino]thieno[3,2-b]pyridine-6-carbonitrile

Product 1

HCID 117513977-[(2,4-Dichloro-5-methoxyphenyl)amino]-3-(4-formylphenyl)thieno[3,2-b]pyridine-6-carbonitrileYield 61.7%

Reagents, catalysts & solvents 2

HCID 80711,2-DimethoxyethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

A mixture of 3-bromo-7-[(2,4-dichloro-5-methoxyphenyl)amino]thieno[3,2-b]pyridine-6-carbonitrile (1.67 g, 3.89 mmol), 4-formylphenyl boronic acid (1.17 g, 7.78 mmol), and tetrakis(triphenylphosphine)pallidium (225 mg, 0.20 mmol) in 50 mL of ethylene glycol dimethyl ether and 42 mL of saturated aqueous sodium bicarbonate is heated at reflux for 2 hours and then cooled to room temperature. The precipitate is collected by filtration washing with ethyl acetate and diethyl ether to provide 1.09 g of 7-[(2,4-dichloro-5-methoxyphenyl)amino]-3-(4-formylphenyl)thieno[3,2-b]pyridine-6-carbonitrile as a tan solid, mp 268° C. dec; 1H NMR (DMSO-d6) δ 3.87 (s, 3H), 7.44 (s, 1H), 7.79 (s, 1H), 8.01 (d, J=8 Hz, 2H), 8.23 (d, J=8 Hz, 2H), 8.55 (s, 1H), 8.73 (s, 1H), 9.86 (s, 1H), 10.05 (s, 1H); MS 454.0, 456.0 (M+H)+; HRMS found: 454.01716 (M+H)+.

Workup

  1. temperatureis heated
  2. temperatureat reflux for 2 hours
  3. filtrationThe precipitate is collected by filtration
  4. washwashing with ethyl acetate and diethyl ether

Sources & evidence

ORD record
ord-159712cdce714ebca497416ad1ce0474
Source dataset
uspto-grants-2007_10
Patent number
US07276519B2

Reaction notes

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