Methane → (3-hydroxyphenyl)boronic Acid

HRID 496117Notes

Reaction equation

HRID 496117 reaction equation
S(O)(O)(=O)=O.N[C:7]1[CH:8]=[C:9]([B:13]([OH:15])[OH:14])[CH:10]=[CH:11][CH:12]=1.NC1C=C(B(O)[OH:24])C=CC=1.OS(O)(=O)=O.N([O-])=O.[Na+].C>O>[OH:24][C:7]1[CH:8]=[C:9]([B:13]([OH:15])[OH:14])[CH:10]=[CH:11][CH:12]=1

Participants

6

Reactant 4

HCID 297MethaneHCID 1118Sulfuric Acid2×HCID 162111393-Aminophenylboronic Acid HemisulfateHCID 23668193Sodium Nitrite

Product 1

HCID 2734359(3-hydroxyphenyl)boronic AcidYield 94%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Procedure

A stirred solution of 3-aminophenylboronic acid hemisulfate (6.2 g; 33.3 mmol) and 50% H2SO4 (3.7 ml; 33.3 mmol) in H2O (100 ml) at −2° C. was solution of NaNO2 (2.5 g; 36.3 mmol) in H2O (20 ml) over 1 h. The reaction mixture was slowly added to a stirred solution of conc. H2SO4 (25 ml) in H2O (20 ml) at reflux. After complete addition, the reaction mixture was refluxed for 30 min., cooled, added activated charcoal, heated to reflux, cooled and filtered through celite. The filtrate was saturated with NaCl (s), filtered and extracted with Et2O (5×100 ml). The combined organic fractions were dried (Na2SO4) and evaporated to dryness to give 4.3 g (94%) product.

Workup

  1. customat −2° C.
  2. customover 1 h
  3. temperatureat reflux
  4. additionAfter complete addition
  5. temperaturethe reaction mixture was refluxed for 30 min.
  6. temperaturecooled
  7. additionadded
  8. temperatureheated
  9. temperatureto reflux
  10. temperaturecooled
  11. filtrationfiltered through celite
  12. filtrationfiltered
  13. extractionextracted with Et2O (5×100 ml)
  14. dry with materialThe combined organic fractions were dried (Na2SO4)
  15. customevaporated to dryness

Sources & evidence

ORD record
ord-d07dcf20e2ac45de86bf1d6b8bf223c5
Source dataset
uspto-grants-2005_09
Patent number
US06943159B1

Reaction notes

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