Tributylphosphine → 4-[1-(3,4-Dimethoxyphenoxy)-3-butenyl]benzonitrile

HRID 1374089Notes

Reaction equation

HRID 1374089 reaction equation
[OH:1][CH:2]([C:6]1[CH:13]=[CH:12][C:9]([C:10]#[N:11])=[CH:8][CH:7]=1)[CH2:3][CH:4]=[CH2:5].[CH3:14][O:15][C:16]1[CH:17]=[C:18](O)[CH:19]=[CH:20][C:21]=1[O:22][CH3:23].C(P(CCCC)CCCC)CCC.N(C(N1CCCCC1)=O)=NC(N1CCCCC1)=O>C1(C)C=CC=CC=1>[CH3:14][O:15][C:16]1[CH:17]=[C:18]([CH:19]=[CH:20][C:21]=1[O:22][CH3:23])[O:1][CH:2]([C:6]1[CH:7]=[CH:8][C:9]([C:10]#[N:11])=[CH:12][CH:13]=1)[CH2:3][CH:4]=[CH2:5]

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 162513,4-DimethoxyphenolHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 110193454-(1-Hydroxy-3-butenyl)benzonitrile

Product 1

HCID 218676894-[1-(3,4-Dimethoxyphenoxy)-3-butenyl]benzonitrileYield 68.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A cooled (0° C.) mixture of 4-(1-hydroxy-3-butenyl)benzonitrile (14.6 g, 84.3 mmol) and 3,4-dimethoxyphenol (19.5 g, 125.4 mmol) in toluene (500 mL) was treated with tributylphosphine (32.14 mL of 97% purity, 25.6 g, 126.4 mmol), followed by 1,1′-(azodicarbonyl)dipiperidine (31.8 g, 126.4 mmol). After addition was complete, the reaction mixture thickened and the temperature rose to 15° C. Additional toluene was added (500 mL), and the mixture stirred at rt overnight. The precipitate of tributylphosphine oxide was then removed by filtration and the filtrate concentrated in vacuo to give 65.8 g of crude product. This was purified by chromatography on silica gel, eluting with toluene: methanol (98:2), to yield 17.9 g of the sub-title compound.

Workup

  1. temperatureA cooled
  2. additionAfter addition
  3. customrose to 15° C
  4. customThe precipitate of tributylphosphine oxide was then removed by filtration
  5. concentrationthe filtrate concentrated in vacuo
  6. customto give 65.8 g of crude product
  7. customThis was purified by chromatography on silica gel
  8. washeluting with toluene: methanol (98:2)

Sources & evidence

ORD record
ord-b0e44235920c43048eb0efb61bf23362
Source dataset
uspto-grants-2007_01
Patent number
US07164017B2

Reaction notes

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