Triphenylphosphine → 4-(4-Bromo-3,5-dimethylphenoxy)thiane

HRID 416136Notes

Reaction equation

HRID 416136 reaction equation
[Br:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([OH:9])=[CH:4][C:3]=1[CH3:10].[S:11]1[CH2:16][CH2:15][CH:14](O)[CH2:13][CH2:12]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1>[Br:1][C:2]1[C:7]([CH3:8])=[CH:6][C:5]([O:9][CH:14]2[CH2:15][CH2:16][S:11][CH2:12][CH2:13]2)=[CH:4][C:3]=1[CH3:10]

Participants

6

Reactant 4

HCID 11776Triphenylphosphine2×HCID 819704-Bromo-3,5-dimethylphenolHCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 576296Tetrahydro-2H-thiopyran-4-ol2×

Product 1

HCID 593425534-(4-Bromo-3,5-dimethylphenoxy)thianeYield 86.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-bromo-3,5-dimethylphenol (0.201 g, 1.00 mmol), tetrahydro-2H-thiopyran-4-ol (0.130 g, 1.10 mmol) and triphenylphosphine (0.341 g, 1.30 mmol) in tetrahydrofuran (5 mL) was added diethyl azodicarboxylate (40% solution in toluene, 0.591 mL, 1.30 mmol), and the mixture was stirred at room temperature for 1.5 hr. Tetrahydro-2H-thiopyran-4-ol (0.0591 g, 0.500 mmol), triphenylphosphine (0.157 g, 0.600 mmol) and diethyl azodicarboxylate (40% solution in toluene, 0.272 mL, 0.600 mmol) were added, and the mixture was further stirred for 1.5 hr. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-20:80) to give the title compound (0.261 g, yield 86%) as colorless crystals.

Workup

  1. stirringthe mixture was further stirred for 1.5 hr
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. customthe residue was purified by silica gel column chromatography (ethyl acetate:hexane=0:100-20:80)

Sources & evidence

ORD record
ord-3134f61bedd645d5bd7952aaa17d57a5
Source dataset
uspto-grants-2012_01
Patent number
US08088821B2

Reaction notes

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