Ethanol → Ruthenium bis(2,2'-bipyridine) (2,2'-bipyridine-4,4'-dicarboxylic acid) bis(hexafluorophosphate)

反応式

OC[C:3]1([CH2:15][OH:16])[CH:8]=[CH:7][N:6]=[C:5]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[CH2:4]1.[OH2:17].[OH2:18].[Ru+2:19].[N:20]1[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1.[F:32][P-:33]([F:38])([F:37])([F:36])([F:35])[F:34].[NH4+].[CH2:40]([OH:42])C>>[F:32][P-:33]([F:38])([F:37])([F:36])([F:35])[F:34].[F:32][P-:33]([F:38])([F:37])([F:36])([F:35])[F:34].[N:10]1[CH:11]=[CH:12][C:13]([C:40]([OH:42])=[O:17])=[CH:14][C:9]=1[C:5]1[CH:4]=[C:3]([C:15]([OH:16])=[O:18])[CH:8]=[CH:7][N:6]=1.[N:20]1[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1.[N:6]1[CH:7]=[CH:8][CH:3]=[CH:4][C:5]=1[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=1.[Ru+2:19]

参加物

反応物 4

HCID 702Ethanol

HCID 9793912Ammonium hexafluorophosphate

HCID 701425084,4-Di(hydroxymethyl)-2,2'-bipyridine

HCID 131720582HCID 131720582、化合物

生成物 1

HCID 15381271Ruthenium bis(2,2'-bipyridine) (2,2'-bipyridine-4,4'-dicarboxylic acid) bis(hexafluorophosphate)

実験手順

4,4'-Diethoxycarbonyl-2,2'-bipyridine was prepared from 2,2-bipyridine-4,'dicarboxylic acid by the method of Sprintschink et al. (J. Amer. Chem. Soc. 99, 4947 (1977)). The diethyl ester (100 mg) was dissolved in anhydrous diethyl ether (35 ml). Lithium aluminum hydride (100 mg) was added, and following a 30 minute incubation diethyl ether (35 ml) and ice cold deionized water (100 ml) were added. The solution was mixed throughly and the ether layer collected. The aqueous phase was extracted twice more with ether (70 ml). The combined ether extracts were dried over anhydrous sodium sulfate and filtered. The solvent was removed on a rotary evaporator to give the desired product (43 mg). This 43 mg of 4,4-Di(hydroxymethyl)-2,2'-bipyridine and 120 mg of cisdichloro his (2,2'-bipyridine) ruthenium (II) dihydrate were added to ethanol (25 ml), and the solution was refluxed for 14 hours. After the solution had cooled, 50 ul of solution of ammonium hexafluorophosphate (1 gm in 1 ml of water) was added, the resultant crystalline solid was collected, washed with a small volume of ethanol and dried to give 138 mg of the hexafluorophosphate salt of the 4,4-dihydroxymethyl complex. This complex (6 mg) was added to thionyl chloride (5 ml), and the solution was refluxed for 6 hours. The thionyl chloride was removed by distillation, and the solid residue was dissolved in a dioxane-water (1:1) mixture (500 ul). This solution containing 4,4'-(dichloromethyl)-2,2'-bipyridyl, bis(2,2'bipyridyl) ruthenium (II) was used for labeling of antibody.