Propargyl alcohol → 3,5-Bis-[(3-hydroxyprop-1-ynyl)]-1-(tert-butyldiphenylsilanyloxymethyl)benzene

HRID 2212320Notes

Reaction equation

HRID 2212320 reaction equation
[CH2:1]([OH:4])[C:2]#[CH:3].[C:5]([Si:9]([O:22][CH2:23][C:24]1[CH:29]=[C:28](Br)[CH:27]=[C:26](Br)[CH:25]=1)([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([CH3:8])([CH3:7])[CH3:6]>C(N(CC)CC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:4][CH2:1][C:2]#[C:3][C:26]1[CH:25]=[C:24]([CH2:23][O:22][Si:9]([C:5]([CH3:7])([CH3:6])[CH3:8])([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:29]=[C:28]([C:3]#[C:2][CH2:1][OH:4])[CH:27]=1

Participants

5

Reactant 2

HCID 7859Propargyl alcoholHCID 21964571tert-Butyl-(3,5-dibromobenzyloxy)diphenylsilane

Product 1

HCID 219645693,5-Bis-[(3-hydroxyprop-1-ynyl)]-1-(tert-butyldiphenylsilanyloxymethyl)benzeneYield 88.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

Pd(Ph3P)4 (520 mg), CuBrSMe2 (200 mg) and propargyl alcohol (3.08 ml, 35.1 mmol) are added successively to a solution of tert-butyl-(3,5-dibrombenzyloxy)diphenylsilane (A1, 5.0 g, 9.9 mmol) in triethylamine (50 ml), and the mixture is stirred at RT for 10 min and then under reflux at 80° C. for 2.5 h. After cooling, the reaction mixture is filtered off with suction through kieselguhr, and the filter cake is washed with ethyl acetate (20 ml). The organic phase is concentrated under reduced pressure. Further purification is carried out by chromatography [toluene/acetone (8:2)] on a silica gel column. This gives the title compound (4.0 g) as a colorless solid. TLC, silica gel (glass plates), [toluene/acetone (8:2)], Rf=0.48.

Workup

  1. temperatureunder reflux at 80° C. for 2.5 h
  2. temperatureAfter cooling
  3. filtrationthe reaction mixture is filtered off with suction through kieselguhr
  4. washthe filter cake is washed with ethyl acetate (20 ml)
  5. concentrationThe organic phase is concentrated under reduced pressure
  6. customFurther purification

Sources & evidence

ORD record
ord-0134b684204a4aad852425e5d6d6003f
Source dataset
uspto-grants-2006_09
Patent number
US07101911B2

Reaction notes

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