Phenylsilane → Methyl 4-([2,3']bipyridinyl-6-ylaminomethyl)-benzoate

HRID 852902

Reaction equation

HRID 852902 reaction equation
[N:1]1[C:6]([NH2:7])=[CH:5][CH:4]=[CH:3][C:2]=1[C:8]1[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=1.[CH:14]([C:16]1[CH:25]=[CH:24][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][CH:17]=1)=O.C1([SiH3])C=CC=CC=1>C1COCC1.C([Sn](Cl)(Cl)CCCC)CCC>[N:1]1[C:6]([NH:7][CH2:14][C:16]2[CH:25]=[CH:24][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][CH:17]=2)=[CH:5][CH:4]=[CH:3][C:2]=1[C:8]1[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=1

Participants

6

Reactant 3

HCID 12752PhenylsilaneHCID 15294Methyl 4-FormylbenzoateHCID 11586359[2,3'-Bipyridin]-6-amine

Product 1

HCID 58930610Methyl 4-([2,3']bipyridinyl-6-ylaminomethyl)-benzoateYield 98.3%

Reagents, catalysts & solvents 2

HCID 12688Dibutyltin dichlorideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred suspension of a mixture of 11 (3.00 g, 17.52 mmol), methyl 4-formylbenzoate (4.62 g, 28.11 mmol, 1.5-2.0 equiv.) and dibutyl tin dichloride 160 mg, 0.53 mmol) in anhydrous THF (15 mL) at room temperature was added phenylsilane (2.34 mL, 19.28 mmol) in three portions over two days. After stirring for 2 to 7 days the reaction mixture was filtered, filtrate was concentrated and purified by flash chromatography on silica gel (MeOH/CH2Cl2, 2/98→10/90) to afford the title compound 12 (5.50 g, 17.22 mmol, 98% yield) as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) δ (ppm): 9.11 (dd, J=2.3, 0.7 Hz, 1H), 8.55 (dd, J=4.7, 1.8 Hz, 1H), 8.29-8.24 (m, 1H), 7.93 (d, J=8.4 Hz, 2H), 7.57-7.40 (m, 5H), 7.18 (d, J=7.2 Hz, 1H), 6.59 (d, J=8.2 Hz 1H), 4.69 (d, J=6.1 Hz, 2H), 3.85 (s, 3H).

Workup

  1. filtrationwas filtered
  2. concentrationfiltrate was concentrated
  3. custompurified by flash chromatography on silica gel (MeOH/CH2Cl2, 2/98→10/90)

Sources & evidence

ORD record
ord-cdbb4155d2954433adc05ef0eed4ec93
Source dataset
uspto-grants-2007_08
Patent number
US07253204B2

Linked notes

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