1,3-Benzodioxole → HCID 53217346, compound

HRID 1746068Notes

Reaction equation

HRID 1746068 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[O:3][CH2:2]1.C([Li])(CC)C.C(O[B:19]1[O:23][C:22]([CH3:25])([CH3:24])[C:21]([CH3:27])([CH3:26])[O:20]1)(C)C>O1CCCC1>[O:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[C:9]([B:19]3[O:23][C:22]([CH3:25])([CH3:24])[C:21]([CH3:27])([CH3:26])[O:20]3)[C:4]=2[O:3][CH2:2]1

Participants

5

Reactant 3

HCID 92291,3-BenzodioxoleHCID 50177412-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 178418400CID 53628100

Product 1

HCID 53217346HCID 53217346, compoundYield 34.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-108 °C

Procedure

Benzo[d][1,3]dioxole (3.05 g, 25 mmol) was dissolved in tetrahydrofuran (50 mL) and cooled to −108° C. utilizing a tetrahydrofuran/liquid nitrogen bath. sec-Butyllithium (1.4 M in cyclohexane; 19.64 mL, 27.5 mmol) was added dropwise, keeping the temperature below −100° C. The reaction mixture was then stirred at temperatures between −100° C. and −108° C. for 2 h to ensure complete deprotonation. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.65 g, 25.00 mmol) was then added to the reaction mixture dropwise, keeping the temperature below −100° C. The reaction mixture was then allowed to warm to room temperature and partitioned between diethyl ether and water. The organic phase was extracted with water once again and the aqueous phases combined and acidified to pH 4 with HCl. The product was extracted with diethyl ether and the organic phase was dried and concentrated under vacuum. The product was purified by flash chromatography (silica gel) to provide the title compound as a white solid (2.14 g, 34.5%): 1H NMR (300 MHz, CDCl3) δ 7.21 (dd, J=7.6, 1.4 Hz, 1H), 6.90 (dd, J=7.7, 1.5 Hz, 1H), 6.82 (t, J=7.6 Hz, 1H), 6.02 (s, 2H), 1.36 (s, 12H); EIMS m/z 248.

Workup

  1. customthe temperature below −100° C
  2. customthe temperature below −100° C
  3. temperatureto warm to room temperature
  4. custompartitioned between diethyl ether and water
  5. extractionThe organic phase was extracted with water once again
  6. extractionThe product was extracted with diethyl ether
  7. customthe organic phase was dried
  8. concentrationconcentrated under vacuum
  9. customThe product was purified by flash chromatography (silica gel)

Sources & evidence

ORD record
ord-94b0d9ce196c40259209b5af224b92e4
Source dataset
uspto-grants-2015_10
Patent number
US09149038B2

Reaction notes

Loading…