Phenol → 4,4-Dimethylchroman

HRID 1193618

Reaction equation

HRID 1193618 reaction equation
[C:1]1([OH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.P([O-])([O-])(O[CH2:11][C:12](C1C=CC=CC=1)([C:16]1C=CC=CC=1)[C:13](C)=[CH2:14])=O>C(=S)=S>[CH3:11][C:12]1([CH3:16])[C:6]2[C:1](=[CH:2][CH:3]=[CH:4][CH:5]=2)[O:7][CH2:14][CH2:13]1

Participants

4

Reactant 2

HCID 996PhenolHCID 131715882Diphenyl-3-methyl-3-buten-1-yl phosphate

Product 1

HCID 3167634,4-Dimethylchroman

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Conditions

Temperature
0 °C

Procedure

To a dry, ice-cooled flask containing 34.95 g (0.134 mol) of stannic chloride was added quickly under argon 63.0 g (0.669 mol) of phenol. The mixture was stirred at 0° C. for 0.5 hour and then treated with 43.0 g (0.135 mol) of diphenyl-3-methyl-3-buten-1-yl phosphate (from Example 7), followed by a 5 ml carbon disulfide rinse. The mixture was stirred at room temperature for 21 hours and then quenched by pouring onto 700 g ice and 1 litre of 1.5N NaOH. The mixture was extracted with 1×600 ml and 2×300 ml ether. The combined ether fractions were washed with 2N NaOH, saturated NaCl and dried (MgSO4). Solvent was removed in vacuo and the residue purified by flash chromatography (silica; 2% ether in hexane) to give the title compound as a colorless oil. PMR (CDCl3)67: 1.34 6HCA1°80-1°85 2HA mCA 4°15-4°20 2HA mcA 6°80 1Ha ddA J~8.1 Hz, 1.5 Hz), (1H, td, J~8.1Hz, 5.1 Hz), 7.07 (1H, td, J~8.1 Hz, 1.5 Hz), 7.26 (1H, dd, J~8.1 Hz, 1.5 Hz).

Workup

  1. temperatureTo a dry, ice-cooled flask
  2. washrinse
  3. stirringThe mixture was stirred at room temperature for 21 hours
  4. customquenched
  5. additionby pouring onto 700 g ice and 1 litre of 1.5N NaOH
  6. extractionThe mixture was extracted with 1×600 ml and 2×300 ml ether
  7. washThe combined ether fractions were washed with 2N NaOH, saturated NaCl
  8. dry with materialdried (MgSO4)
  9. customSolvent was removed in vacuo
  10. customthe residue purified by flash chromatography (silica; 2% ether in hexane)

Sources & evidence

ORD record
ord-6cebab08b7034572a3e528b6ce5c70c5
Source dataset
uspto-grants-1989_03
Patent number
US04810804

Linked notes

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