Trifluoroacetic acid → HCID 86653772, compound

HRID 1528126Notes

Reaction equation

HRID 1528126 reaction equation
[CH3:1][O:2][C:3]1[C:8]([CH3:9])=[C:7]([CH3:10])[C:6]([O:11][CH3:12])=[C:5]([CH3:13])[C:4]=1[CH:14](O)[CH2:15][CH:16]=[CH2:17].C(O)(C(F)(F)F)=O.[SiH](CC)(CC)CC>C(Cl)Cl>[CH2:14]([C:4]1[C:5]([CH3:13])=[C:6]([O:11][CH3:12])[C:7]([CH3:10])=[C:8]([CH3:9])[C:3]=1[O:2][CH3:1])[CH2:15][CH:16]=[CH2:17]

Participants

5

Reactant 3

HCID 6422Trifluoroacetic acidHCID 12052TriethylsilaneHCID 86653771HCID 86653771, compound

Product 1

HCID 86653772HCID 86653772, compoundYield 55.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Crude 1-(2,5-dimethoxy-3,4,6-trimethylphenyl)but-3-en-1-ol (9.8 g) in 10 mL CH2Cl2 was added slowly, dropwise to a rapidly stirred, biphasic solution of TFA (10.5 mL, 153 mmol, 5 equiv.) and Et3SiH (6.3 mL, 1.3 equiv). The exothermic reaction was cooled in a room temperature water bath until addition was complete and the reaction stirred for and additional 2 h at room temperature. The brown solution was concentrated via rotovap, azeotroped 3×50 mL MeOH and 3×50 mL heptane and remainder taken up into 100 mL 5% EtOAc/heptane. The organic layer was washed 1×100 mL water, 1×50 mL saturated aqueous NaCl, filtered to remove particulates and dried over Na2SO4. Flash chromatography yielded 5.08 g of 1-(but-3-enyl)-2,5-dimethoxy-3,4,6-trimethylbenzene as a pale yellow oil which solidified upon standing to an off white wax. 1H NMR (400 MHz, CDCl3) δ=5.93 (m, 1H), 5.08 (m, 1H), 4.99 (m, 1H), 3.68 (s, 3H), 3.65 (s, 3H), 2.70 (m, 2H), 2.24 (m, 5H), 2.18 (s, 6H) ppm.

Workup

  1. customThe exothermic reaction
  2. additionuntil addition
  3. stirringthe reaction stirred for and additional 2 h at room temperature
  4. concentrationThe brown solution was concentrated via rotovap
  5. customazeotroped 3×50 mL MeOH and 3×50 mL heptane and remainder
  6. washThe organic layer was washed 1×100 mL water, 1×50 mL saturated aqueous NaCl
  7. filtrationfiltered
  8. customto remove particulates
  9. dry with materialdried over Na2SO4

Sources & evidence

ORD record
ord-08cdaf30f9f54079b3cfef51f2256fd6
Source dataset
uspto-grants-2015_07
Patent number
US09090576B2

Reaction notes

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