Dichloromethane → HCID 178419376, compound

HRID 2267202Notes

Reaction equation

HRID 2267202 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[N:3]=1.[C-:9]1(B(O)O)[CH:13]=[CH:12][CH:11]=[CH:10]1.[CH-:17]1[CH:21]=[CH:20][CH:19]=[CH:18]1.[Fe+2:22].C(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CO.O>[Br:8][C:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C-:9]2[CH:13]=[CH:12][CH:11]=[CH:10]2)[N:3]=1.[CH-:17]1[CH:21]=[CH:20][CH:19]=[CH:18]1.[Fe+2:22]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 122742,6-DibromopyridineHCID 1539836212152-94-2

Product 1

HCID 178419376HCID 178419376, compound

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
60 °C

Procedure

See Scheme 3. Toluene (15 mL) was added to 2,6-dibromopyridine (0.341 g, 1.44 mmol, purchased from Sigma-Aldrich) and ferrocenylboronic acid (0.321 g, 1.40 mmol, purchased from Sigma-Aldrich) to form an orange suspension. A suspension of (dppf)PdCl2.CH2Cl2 (0.047 g, 0.058 mmol, purchased from Strem) (dppf=1,1′-bis(diphenylphosphino)ferrocene) in toluene (5 mL) was then added followed by a 1 M solution of Na2CO3 (10 mL, 10 mmol) in 4:1 water:methanol. The biphasic mixture was heated to 60° C. for 23 hours. At this time 1H NMR spectroscopic analysis indicated approximately 45% conversion to the desired product. The organic layer was separated, washed with a little water and then brine. The organics were then dried over MgSO4 and filtered. Removal of the volatiles afforded an orange residue. The remaining 2,6-dibromopyridine was removed by sublimation at 45° C./ca. 100 mTorr over 2 hours. The crude was purified on an Al2O3 column using 4% ethyl acetate in hexane as the elutant. The product was still contaminated with some 2,6-diferrocenylpyridine. Pure 2-bromo-6-ferrocenylpyridine was isolated by crystallization from hexamethyldisiloxane. Yield: 0.058 g (12%). 1H NMR(C6D6): δ 6.87 (1H, d), 6.79 (1H, d), 6.64 (1H, t), 4.83 (2H, m), 4.11 (2H, m), 3.83 (5H, s).

Workup

  1. customto form an orange suspension

Sources & evidence

ORD record
ord-d04643089b304e1b8119916b6a23a94a
Source dataset
uspto-grants-2010_12
Patent number
US07858817B2

Reaction notes

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