Thionyl Chloride → 4H-1,3-Benzodioxin, 6-(chloromethyl)-2,2,4,4-tetrafluoro-

HRID 1505113Notes

Reaction equation

HRID 1505113 reaction equation
[F:1][C:2]1([F:16])[O:7][C:6]([F:9])([F:8])[C:5]2[CH:10]=[C:11]([CH2:14]O)[CH:12]=[CH:13][C:4]=2[O:3]1.S(Cl)([Cl:19])=O>>[Cl:19][CH2:14][C:11]1[CH:12]=[CH:13][C:4]2[O:3][C:2]([F:16])([F:1])[O:7][C:6]([F:9])([F:8])[C:5]=2[CH:10]=1

Participants

3

Reactant 2

HCID 24386Thionyl ChlorideHCID 591662914H-1,3-Benzodioxin-6-methanol, 2,2,4,4-tetrafluoro-

Product 1

HCID 591658634H-1,3-Benzodioxin, 6-(chloromethyl)-2,2,4,4-tetrafluoro-

Procedure

A mixture of (2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxin-6-yl)-methanol (6.5 g) in thionyl chloride (75 mL) was heated at reflux overnight. The resulting mixture was concentrated under vacuum. The residue was basified with aqueous saturated NaHCO3. The aqueous layer was extracted with dichloromethane (50 mL×3). The combined organic layers were dried over Na2SO4, filtrated, and concentrated under reduced pressure to give 6-chloromethyl-2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine (6.2 g), which was used directly in the next step. 1H NMR (CDCl3, 300 MHz) δ 7.65 (s, 1 H), 7.61 (dd, J=2.1, 8.7 Hz, 1 H), 7.15 (d, J=8.4 Hz, 1 H), 4.60 (s, 2 H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. concentrationThe resulting mixture was concentrated under vacuum
  4. extractionThe aqueous layer was extracted with dichloromethane (50 mL×3)
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. filtrationfiltrated
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-bf5137a7ae6e458c9f02815b9b956192
Source dataset
uspto-grants-2015_12
Patent number
US09216969B2

Reaction notes

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