Ethylenediaminetetraacetic Acid → Carbonylbis[3-(2-pyridyl)benzene]

HRID 2117821Notes

Reaction equation

HRID 2117821 reaction equation
[C:1]([Li])([CH3:4])([CH3:3])C.Br[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=1.Br[C:14]1[CH:15]=[C:16]([CH:26]=[CH:27][CH:28]=1)[C:17]([C:19]1[CH:24]=[CH:23][CH:22]=[C:21](Br)[CH:20]=1)=[O:18].[CH2:29](N(CC(O)=O)CC(O)=O)[CH2:30][N:31](CC(O)=O)CC(O)=O>[Cl-].[Zn+2].[Cl-].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.O1CCCC1.CCCCC>[C:17]([C:19]1[CH:24]=[CH:23][CH:22]=[C:21]([C:4]2[CH:1]=[CH:3][CH:29]=[CH:30][N:31]=2)[CH:20]=1)([C:16]1[CH:26]=[CH:27][CH:28]=[C:14]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=2)[CH:15]=1)=[O:18]

Participants

9

Reactant 4

HCID 6049Ethylenediaminetetraacetic AcidHCID 79732-BromopyridineHCID 12731928Bis(3-bromophenyl)methanoneHCID 178418306HCID 178418306, compound

Product 1

HCID 23135812Carbonylbis[3-(2-pyridyl)benzene]Yield 75.8%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-70 °C

Procedure

In a nitrogen atmosphere, a n-pentane solution of t-butyllithium (17.8 ml, 1.60M, 28.5 mmol) was dropwise added to tetrahydrofuran cooled to −70° C., then a tetrahydrofuran (5 ml) solution of 2-bromopyridine (1.2 ml, 12.9 mmol) was added thereto while 15 minutes, after a dropwise, the mixture was stirred at −70° C. for 30 minutes. Then, a tetrahydrofuran solution of zinc chloride (31.8 ml, 0.50 M, 15.9 mmol) was added to the mixture while 10 minutes. Thereafter, the temperature of the reaction mixture was allowed to warm to room temperature while 1 hour, tetrakis(triphenylphosphine)palladium (203 mg) and 3,3′-dibromobenzophenone (2.0 g, 5.88 mmol) were successively added thereto, the reaction mixture was stirred under reflux for 18 hours. After the reaction mixture was allowed to cool, then the mixture was poured into a mixture of ethylenediaminetetraacetic acid (7.0 g)/an aqueous saturated sodium hydrogen carbonate solution (210 ml), an organic layer was separated, furthermore an aqueous layer was extracted with toluene. The organic layer was combined, and the solvent was distilled off, and the residue was purified by silica gel column chromatography and recrystallization, thereby obtaining 1.5 g of carbonylbis[3-(2-pyridyl)benzene as white powder. Yield: 75.8%.

Workup

  1. temperatureto warm to room temperature while 1 hour
  2. stirringthe reaction mixture was stirred
  3. temperatureunder reflux for 18 hours
  4. temperatureto cool
  5. customan organic layer was separated
  6. extractionfurthermore an aqueous layer was extracted with toluene
  7. distillationthe solvent was distilled off
  8. customthe residue was purified by silica gel column chromatography and recrystallization

Sources & evidence

ORD record
ord-617ddd39ded6445d8b1148585546c17e
Source dataset
uspto-grants-2008_10
Patent number
US07442797B2

Reaction notes

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