Iodine → 4,4'-Bis(2-phenylethenyl)-2,2'-bipyridine

HRID 1855682Notes

Reaction equation

HRID 1855682 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8]2[CH:13]=[C:12]([CH3:14])[CH:11]=[CH:10][N:9]=2)[CH:3]=1.C([C:17]1[CH:26]=[CH:25][C:20]([C:21](OC)=O)=[CH:19][CH:18]=1)=O.[C:27]([O-])(=O)[CH3:28].[K+].II>C(OC(=O)C)(=O)C.CO>[C:27]1([CH:28]=[CH:1][C:2]2[CH:7]=[CH:6][N:5]=[C:4]([C:8]3[CH:13]=[C:12]([CH:14]=[CH:21][C:20]4[CH:19]=[CH:18][CH:17]=[CH:26][CH:25]=4)[CH:11]=[CH:10][N:9]=3)[CH:3]=2)[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=1

Participants

7

Reactant 4

HCID 807IodineHCID 143384,4'-Dimethyl-2,2'-bipyridine3×HCID 15294Methyl 4-Formylbenzoate2×HCID 517044Potassium Acetate

Product 1

HCID 541483854,4'-Bis(2-phenylethenyl)-2,2'-bipyridine

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 7918Acetic AnhydrideSolvent

Procedure

4,4′-Dimethyl-2,2′-bipyridine and methyl 4-formylbenzoate were purchased from Aldrich and Fluka respectively. 4,4′-Di(phenylethenyl)-2,2′-bipyridine 3 was prepared by hydrolysis of the styryl ester 2, which was synthesized from 4,4′-Dimethyl-2,2′-bipyridine 1 by a modified version of the previously described procedure (see Klein et al., 2005 below) as follows: 4,4′-Dimethyl-2,2′-bipyridine (11.054 g, 0.06 mol) and methyl 4-formylbenzoate (29.549 g, 0.18 mol) were dispersed in acetic anhydride (16 mL) then dry potassium acetate (5.889, 0.06 mol) and iodine (50 mg, 2×10−4 mol) were added. The resulting mixture was heated under reflux for 48 h. After cooling, methanol (200 mL) was added and the resulting fine off-white crystals were filtered off. The solid was stirred for 5 minutes with boiling methoxyethanol (400 mL), the mixture allowed to cool to RT, and the crystalline product filtered off and dried to give pure styryl ester (19.449 g, 72%). The compound gave spectroscopic data identical to that previously reported. 4,4′-Dicarboxy(phenylethenyl)-2,2′-bipyridine 3 was then obtained in quantitative yield from the styryl ester according to the literature procedure. (Engineering of a Novel Ruthenium Sensitizer and its Application in Dye-Sensitized Solar Cells for Conversion of Sunlight into Electricity, C. Klein, Md. K. Nazeeruddin P. Liska, Davide Di Censo, N. Hirata, E. Palomares, J. R. Durrant and M. Grätzel, Inorg. Chem. 44, 178-180, 2005).

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureunder reflux for 48 h
  3. temperatureAfter cooling
  4. filtrationthe resulting fine off-white crystals were filtered off
  5. filtrationthe crystalline product filtered off
  6. customdried

Sources & evidence

ORD record
ord-f7b5bfa66c3640ffb2791e183dd17779
Source dataset
uspto-grants-2015_02
Patent number
US08962977B2

Reaction notes

Loading…