Triphenylphosphine → 4-(3,5-Dimethyl-benzylsulfanyl)-nitrobenzene

HRID 855993Notes

Reaction equation

HRID 855993 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([SH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[CH3:11][C:12]1[CH:13]=[C:14]([CH:17]=[C:18]([CH3:20])[CH:19]=1)[CH2:15]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1.C(OCC)(=O)C>[CH3:11][C:12]1[CH:19]=[C:18]([CH:17]=[C:14]([CH3:15])[CH:13]=1)[CH2:20][S:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 158094-NitrobenzenethiolHCID 337063,5-Dimethylbenzyl alcoholHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 694205454-(3,5-Dimethyl-benzylsulfanyl)-nitrobenzeneYield 50%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 4-nitrothiophenol (0.400 g, 2.57 mmol), 3,5-dimethylbenzyl alcohol (0.38 ml, 2.57 mmol) and triphenylphosphine (0.743 g, 2.84 mmol) in 10 ml anhydrous tetrahydrofuran was added diethyl azodicarboxylate (0.446 ml, 2.84 mmol). The reaction mixture was stirred overnight at room temperature under nitrogen. It was then diluted with 90 ml ethyl acetate and the resulting solution was washed sequentially with 70 ml saturated aqueous sodium bicarbonate solution, 70 ml water and 70 ml brine, dried (anhydrous sodium sulfate) and concentrated under reduced pressure. The solid residue was triturated with 95:5 hexane/ethyl acetate (20 ml) and filtered. The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography (silica gel, 15 g), eluting with 95:5 hexane/ethyl acetate to yield title compound as a yellow solid (0.35 g, 50% yield). 1H NMR (400 MHz, CD3Cl): δ2.30 (s, 6H), 4.18 (s, 2H), 6.92 (s, 1H), 7.0 (s, 2H), 7.33 (d, 2H), 8.10 (d, 2H).

Workup

  1. washthe resulting solution was washed sequentially with 70 ml saturated aqueous sodium bicarbonate solution, 70 ml water and 70 ml brine
  2. dry with materialdried (anhydrous sodium sulfate)
  3. concentrationconcentrated under reduced pressure
  4. customThe solid residue was triturated with 95:5 hexane/ethyl acetate (20 ml)
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated under reduced pressure
  7. customthe residue was purified by column chromatography (silica gel, 15 g)
  8. washeluting with 95:5 hexane/ethyl acetate

Sources & evidence

ORD record
ord-e0d9570265fa4b15a7bd50bb9b2f9895
Source dataset
uspto-grants-2007_08
Patent number
US07262318B2

Reaction notes

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