Hydrochloric Acid → HCID 59609876, compound

HRID 1943550Notes

Reaction equation

HRID 1943550 reaction equation
[CH2:1]([O:5][CH:6]1[CH2:11][CH2:10][C:9]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[C:13]=2[F:19])=[CH:8][CH2:7]1)[CH2:2][CH2:3][CH3:4].C([Li])(CC)C.[B:25](OC)([O:28]C)[O:26]C.Cl>C(OCC)(=O)C.C1COCC1.C1CCCCC1.CCCCCC>[CH2:1]([O:5][CH:6]1[CH2:11][CH2:10][C:9]([C:12]2[CH:17]=[CH:16][C:15]([B:25]([OH:28])[OH:26])=[C:14]([F:18])[C:13]=2[F:19])=[CH:8][CH2:7]1)[CH2:2][CH2:3][CH3:4]

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 19107881HCID 19107881, compoundHCID 178418400CID 53628100

Product 1

HCID 59609876HCID 59609876, compoundYield 83.5%

Reagents, catalysts & solvents 4

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8078CyclohexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

4-Butoxy-(2,3-difluorophenyl)cyclohexene (24) (11.0 g) and THF (200 ml) were put in a reaction vessel under a nitrogen atmosphere, and cooled to −74° C. sec-Butyllithium (1.00 M, in a n-hexane and cyclohexane solution; 50.0 ml) was added dropwise thereto in the temperature range of −74° C. to −70° C., and the mixture was stirred for another 2 hours. Then, trimethyl borate (5.2 g) in a THF (50 ml) solution was added dropwise thereto in the temperature range of −74° C. to −65° C., and the stirring was continued for another 8 hours while the mixture was allowed to return to 25° C. Then, the reaction mixture was poured into a vessel containing 1N-hydrochloric acid (100 ml) and ice-water (500 ml), and mixed. Then, ethyl acetate (300 ml) was added thereto and the mixture was allowed to be separated into organic and aqueous phases, and extraction into an organic phase was carried out. The obtained organic layer was fractionated, washed sequentially with water, a saturated aqueous solution of sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, giving 10.7 g of 4-(4-butoxycyclohexenyl)-2,3-difluorophenylboronic acid (25). The yield based on the compound (24) was 83.6%.

Workup

  1. addition50.0 ml) was added dropwise
  2. waitin the temperature range of −74° C. to −65° C., and the stirring was continued for another 8 hours while the mixture
  3. customto return to 25° C
  4. additionThen, the reaction mixture was poured into a vessel
  5. additionmixed
  6. customto be separated into organic and
  7. extractionaqueous phases, and extraction into an organic phase
  8. washwashed sequentially with water
  9. dry with materiala saturated aqueous solution of sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate
  10. distillationThen, the solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-64bba129f6a74e03a92eae41582a61f1
Source dataset
uspto-grants-2013_03
Patent number
US08394294B2

Reaction notes

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