Ethylene Glycol → 2-[(6-Bromo-2-naphthyl)thio]benzonitrile

HRID 735309Notes

Reaction equation

HRID 735309 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([SH:12])[CH:6]=[CH:5]2.I[C:14]1[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=1[C:16]#[N:17].C(=O)([O-])[O-].[K+].[K+].C(O)CO>[Cu]I.O.C(O)(C)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([S:12][C:14]1[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=1[C:16]#[N:17])[CH:6]=[CH:5]2

Participants

8

Reactant 4

HCID 174Ethylene GlycolHCID 11430Potassium CarbonateHCID 27593582-IodobenzonitrileHCID 197648176-Bromonaphthalene-2-thiol

Product 1

HCID 689008402-[(6-Bromo-2-naphthyl)thio]benzonitrile

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolventHCID 3776IsopropanolSolvent

Procedure

A mixture of 6-bromo-2-naphthyl hydrosulfide (Step 2, 2.08 g, 8.7 mmol), 2-iodobenzonitrile (2 g, 8.56 mmol), copper(I) iodide (83 mg, 0.44 mmol) and potassium carbonate (2.4 g, 17.4 mmol) was degassed then isopropyl alcohol (10 mL) and ethylene glycol (0.97 mL, 17.4 mmol) added. The reaction was heated to 80° overnight. The cooled reaction mixture was poured into water and extracted with dichloromethane (x3). The combined organic layers were washed with ammonium chloride solution, water and brine, filtered, dried over MgSO4 and evaporated in vacuo to give 2-[(6-bromo-2-naphthyl)thio]benzonitrile (2.85 g, containing some 2,2′-dithiobis(6-bromonaphthalene)). 2.19 g of this was treated according to the method of Example 2 Step 4 to give 2-[(6-bromo-2-naphthyl)sulfonyl]benzonitrile (1.33 g, 56%). 1H NMR (500 MHz, CDCl3) δ 8.76 (1H, s), 8.41 (1H, d, J=8.0 Hz), 8.07 (1H, s), 7.94-7.79 (5H, m), 7.72-7.68 (2H, m); m/z (ES+) 372, 374 [MH+].

Workup

  1. customwas degassed
  2. temperatureThe reaction was heated to 80° overnight
  3. customThe cooled reaction mixture
  4. extractionextracted with dichloromethane (x3)
  5. washThe combined organic layers were washed with ammonium chloride solution, water and brine
  6. filtrationfiltered
  7. dry with materialdried over MgSO4
  8. customevaporated in vacuo

Sources & evidence

ORD record
ord-c5d2180029084903bd9de41f732af9a8
Source dataset
uspto-grants-2009_09
Patent number
US07592456B2

Reaction notes

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