Sodium Bicarbonate → 6-fluoro-2,2-dimethyl-4H-1,3-benzodioxine-8-carbaldehyde

HRID 253276Notes

Reaction equation

HRID 253276 reaction equation
[F:1][C:2]1[CH:13]=[C:12]([CH2:14][OH:15])[C:5]2[O:6][C:7]([CH3:11])([CH3:10])[O:8][CH2:9][C:4]=2[CH:3]=1.[O-]Cl.[Na+].C([O-])(O)=O.[Na+]>C(Cl)Cl.O.CC1(C)N([O])C(C)(C)CCC1.[K+].[Br-]>[F:1][C:2]1[CH:13]=[C:12]([CH:14]=[O:15])[C:5]2[O:6][C:7]([CH3:11])([CH3:10])[O:8][CH2:9][C:4]=2[CH:3]=1

Participants

8

Reactant 3

HCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 66890263(6-fluoro-2,2-dimethyl-4H-1,3-benzodioxin-8-yl)methanol2×

Product 1

HCID 860251526-fluoro-2,2-dimethyl-4H-1,3-benzodioxine-8-carbaldehydeYield 146.4%

Reagents, catalysts & solvents 4

HCID 253877Potassium BromideCatalystHCID 2724126TempoCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

The crude (6-fluoro-2,2-dimethyl-4H-1,3-benzodioxin-8-yl)methanol (35.15 g, 166 mmol) was dissolved in biphasic mixture of CH2Cl2 (230 mL) and water (180 mL). The mixture was cooled to 0° C., and TEMPO (519 mg, 3.3 mmol) and KBr (2.0 g, 16.6 mmol) were added. Finally, NaClO (aq) (5%, 500 mL, 332 mmol) saturated with NaHCO3 was added gradually by addition funnel. The mixture was stirred for 15 min after the all the reagents were added. The layers were partitioned, and the aqueous phase was extracted with CH2Cl2. The organic extracts were combined, dried over magnesium sulfate, filtered, and concentrated in vacuo. The resulting solid was triturated sequentially with hexanes and methanol to yield a white crystalline solid. This procedure was repeated two more times on a further 38 g of (6-fluoro-2,2-dimethyl-4H-1,3-benzodioxin-8-yl)methanol (179 mmol). The triturated solids of all three experiments were combined to provide 51.1 g of 6-fluoro-2,2-dimethyl-4H-1,3-benzodioxine-8-carbaldehyde (243 mmol, 70% yield). 1H NMR (400 MHz, CDCl3): δ 10.37 (d, 1H), 7.41 (dd, 1H), 6.96-6.94 (m, 1H), 4.88 (s, 2H), 1.61 (s, 6H).

Workup

  1. additionwere added
  2. customThe layers were partitioned
  3. extractionthe aqueous phase was extracted with CH2Cl2
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting solid was triturated sequentially with hexanes and methanol
  8. customto yield a white crystalline solid

Sources & evidence

ORD record
ord-01a92ddfef2f406fa8c0abe5ad408a30
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

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