Toluene → 7-(3-(Chlorodimethylsilyl)propoxy)-4-methyl-2H-chromen-2-one

HRID 2073589

Reaction equation

HRID 2073589 reaction equation
[CH2:1]([O:4][CH2:5][CH:6]=[CH2:7])[CH:2]=[CH2:3].COC1C=C[C:13]2[CH:16]=[CH:17][C:18]([O:20][C:12]=2[CH:11]=1)=[O:19].[CH3:21][SiH:22]([CH3:24])[Cl:23].[C:25]1(C)C=CC=CC=1>>[Cl:23][Si:22]([CH3:24])([CH3:21])[CH2:3][CH2:2][CH2:1][O:4][C:5]1[CH:11]=[C:12]2[C:13]([C:16]([CH3:25])=[CH:17][C:18](=[O:19])[O:20]2)=[CH:7][CH:6]=1

Participants

5

Reactant 4

HCID 1140TolueneHCID 10748MethylumbelliferoneHCID 11194Diallyl etherHCID 66108Chlorodimethylsilane2×

Product 1

HCID 217155697-(3-(Chlorodimethylsilyl)propoxy)-4-methyl-2H-chromen-2-one

Conditions

Temperature
110 °C

Procedure

A 1 L 3-necked flask fitted with condenser, thermometer and addition funnel was charged with 87 g (0.4 mol) of the allyl ether of methylumbelliferone formed by Step 1 and 200 ml toluene. While stirring the contents, 15 ml dimethylchlorosilane and 0.5 ml H2PtCl6 were added. With warming of the reaction mixture by an IR lamp, the reaction initiated at 70 degrees C. and quickly rose to 105 degrees C. with reflux. The addition of 40 additional grams of dimethylchlorosilane (0.5 mol total) was adjusted to produce gentle reflux (30 minutes), followed by stirring at 110 degrees C. for 1 hour. The reaction mixture was cooled to room temperature, and the toluene was removed under reduced pressure. The last traces of solvent were removed under high vacuum. The residue (120 g) was dissolved in 1200 ml of acetonitrile for storage and handling. The substitution of DMSO for THF as the solvent in Step 1 eliminated the need for pressure in Step 2 and made the second step generally run cleaner.

Workup

  1. customA 1 L 3-necked flask fitted with condenser
  2. additionthermometer and addition funnel
  3. additionwere added
  4. temperatureWith warming of the reaction mixture by an IR lamp
  5. custominitiated at 70 degrees C
  6. customquickly rose to 105 degrees C
  7. temperaturewith reflux
  8. customto produce gentle
  9. temperaturereflux (30 minutes)
  10. temperatureThe reaction mixture was cooled to room temperature
  11. customthe toluene was removed under reduced pressure
  12. customThe last traces of solvent were removed under high vacuum
  13. dissolutionThe residue (120 g) was dissolved in 1200 ml of acetonitrile for storage and handling

Sources & evidence

ORD record
ord-47c08a553c754525aee74e65b212226e
Source dataset
uspto-grants-1990_04
Patent number
US04918200

Linked notes

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