Hydrochloric Acid → HCID 59445929, compound

HRID 1191573Notes

Reaction equation

HRID 1191573 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][CH:9]=2)=[CH:4][C:3]=1I.C([Mg]Br)(C)C.[B:21](OC)([O:24]C)[O:22]C.Cl>O1CCCC1.C(OCC)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][CH:9]=2)=[CH:4][C:3]=1[B:21]([OH:24])[OH:22]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 59445916HCID 59445916, compoundHCID 178418365HCID 178418365, compound

Product 1

HCID 59445929HCID 59445929, compoundYield 81.9%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-75 °C

Procedure

To a solution of 4-bromo-4′-chloro-3-iodobiphenyl (8.00 g, 20.40 mmol) in a mixed solvent system of anhydrous diethyl ether (80 ml) and anhydrous tetrahydrofuran (80 ml) at −75° C. is added isopropylmagnesium bromide (31.60 ml, 15% in tetrahydrofuran) dropwise, maintaining the temperature of the reaction mixture below −70° C. When the addition is complete the mixture is stirred at −75° C. for an additional 2 hours, then allowed to warm to −25° C. at which point trimethyl borate (3.15 g, 30.60 mmol) is added dropwise. After the addition is complete the reaction is allowed to warm to room temperature and stir overnight, followed by cooling in an ice-bath and acidification with 2M aqueous hydrochloric acid. The crude product is extracted with ethyl acetate (×3), and the organic fractions are combined, washed with brine, then dried over anhydrous magnesium sulfate. The mixture is filtered and the filtrate is evaporated in vacuo to give a solid which is further triturated with hexanes to afford 4-bromo-4′-chlorobiphenyl-3-yl-boronic acid (5.20 g) as a white solid.

Workup

  1. temperaturemaintaining the temperature of the reaction mixture below −70° C
  2. additionWhen the addition
  3. additionis added dropwise
  4. additionAfter the addition
  5. temperatureto warm to room temperature
  6. stirringstir overnight
  7. temperatureby cooling in an ice-bath
  8. extractionThe crude product is extracted with ethyl acetate (×3)
  9. washwashed with brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. filtrationThe mixture is filtered
  12. customthe filtrate is evaporated in vacuo
  13. customto give a solid which
  14. customis further triturated with hexanes

Sources & evidence

ORD record
ord-a3e86482ac58441abec92d2b0ce65ef5
Source dataset
uspto-grants-2014_03
Patent number
US08680012B2

Reaction notes

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