Methane, dichloromethoxy- → 7-Fluoro-2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde

HRID 1271690Notes

Reaction equation

HRID 1271690 reaction equation
[F:1][C:2]1[CH:11]=[CH:10][C:5]2[O:6][CH2:7][CH2:8][O:9][C:4]=2[CH:3]=1.NC1C=C[C:16]2[O:17]CCOC=2C=1.COC(Cl)Cl>ClCCl.[Ti](Cl)(Cl)(Cl)Cl>[F:1][C:2]1[C:11]([CH:16]=[O:17])=[CH:10][C:5]2[O:6][CH2:7][CH2:8][O:9][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 21004Methane, dichloromethoxy-HCID 891481,4-Benzodioxan-6-ylamineHCID 124645456-Fluoro-2,3-dihydro-1,4-benzodioxine

Product 1

HCID 146448837-Fluoro-2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of 6-fluoro-2,3-dihydro-benzo[1,4]dioxine (prepared from 6-amino-2,3-dihydro-benzo[1,4]dioxine according to the procedure of V. Daukas, P. Gaidelis, R. Martinkus, S. Urboniene, Chemija, 1999, 10 (1), 59), (154 mg, 1 mmol) in dichloromethane (0.5 ml) was treated with dichloromethyl methyl ether (0.25 ml) at 0° C. under argon. Titanium tetrachloride (0.45 ml) in dichloromethane (0.5 ml) was added over 0.25 hours. The cooling bath was removed and the mixture was stirred at ambient temperature for 1 hour before being quenched with water and extracted with ether. The ether extract was washed with aqueous sodium bicarbonate and brine. Drying and evaporation afforded a brown oil which was purified by chromatography on silica (ethyl acetate/hexane) affording a clear oil (0.12 g).

Workup

  1. customThe cooling bath was removed
  2. custombefore being quenched with water
  3. extractionextracted with ether
  4. extractionThe ether extract
  5. washwas washed with aqueous sodium bicarbonate and brine
  6. customDrying
  7. customevaporation
  8. customafforded a brown oil which
  9. customwas purified by chromatography on silica (ethyl acetate/hexane)

Sources & evidence

ORD record
ord-68e80ed2664c4d6487f1f1d84dcaf99e
Source dataset
uspto-grants-2007_04
Patent number
US07205408B2

Reaction notes

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