Hydrochloric Acid → 2-Hydroxy-3'-carboethoxy-(1,1'-biphenyl)-6-carboxylic acid, ethyl ester

HRID 275173Notes

Reaction equation

HRID 275173 reaction equation
C[O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:4]=1[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:15]=1.CB(Br)C.C([O-])(O)=O.[Na+].Cl>ClCCCl>[OH:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:4]=1[C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:15]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 123224Dimethylboronbromide2×HCID 516892Sodium BicarbonateHCID 867484752-Methoxy-3'-carboethoxy-[1,1'-biphenyl]-6-carboxylic acid, ethyl ester

Product 1

HCID 867484762-Hydroxy-3'-carboethoxy-(1,1'-biphenyl)-6-carboxylic acid, ethyl esterYield 71.2%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

Diester 6a (0.968 g., 2.95 mmol, 1 equiv.) is dissolved under argon in 9.8 mL of 1,2-dichloroethane. Dimethylboron bromide (1.16 mL, 11.9 mmol, 4.03 equiv. ) is added, the flask is sealed and the mixture allowed to stir for 21 hours at ambient temperature. Another 1.16 mL of dimethylboron bromide is added, and the mixture stirred, sealed under argon, for 3 days. The flask is cooled to 0° C., and 20 mL of saturated NaHCO3 is added with caution. The mixture is poured into 1N HCl, and extracted thrice with EtOAc. The combined extracts are washed with brine, dried (MgSO4), and evaporated. Chromatography using 10% EtOAc/hexane yields 2-hydroxy-3'-carboethoxy-(1,1'-biphenyl)-6-carboxylic acid, ethyl ester (7a) (0.659 g., 2.10 mmol, 71%) as a yellow oil: UVmax (CHCl3) 242 nm (ε=10155), 296 nm (ε=4591 ); 1H NMR (300 MHz, CDCl3) δ 8.09 (dd, J=2, 8 Hz, 1H, ArH), 7.96 (dd, J=2, 2 Hz, 1H, ArH), 7.57-7.45 (m, 3H, ArH), 7.33 (dd, J=8, 8 Hz, 1H, ArH), 7.14 (dd, J=2, 8 Hz, 1H, ArH), 4.98 (br, 1H, OH), 4.35 (q, J=7 Hz, 2H, CO2CH2), 3.99 (q, J=7 Hz, 2H, CO2CH2), 1.36 (t, J=7 Hz, 3H, CH2CH3), 0.95 (t, J=7 Hz, 3H, CH2CH3); 13C NMR (75 MHz, CDCl3) δ 167.18 (C=O), 166.13 (C=O), 153.18, 135.46, 134.13, 131.76, 131.25, 130.67, 129.42, 129.16, 129.03, 127.32, 122.42, 119.19, 61.21, 60.85, 14.30, 13.70; IR (film) 3406, 2982, 1718, 1296, 1236, 758 cm-1 ; MS (DCI) m/e 315 (MH+), 269 (M--C2H5O). HRMS Calcd for C18H18O5Na: 337.1052. Found: 337.1044.

Workup

  1. customthe flask is sealed
  2. stirringthe mixture stirred
  3. customsealed under argon, for 3 days
  4. temperatureThe flask is cooled to 0° C.
  5. extractionextracted thrice with EtOAc
  6. washThe combined extracts are washed with brine
  7. dry with materialdried (MgSO4)
  8. customevaporated

Sources & evidence

ORD record
ord-e1abd0355b044ce3ade7c0e8cdb3ca0f
Source dataset
uspto-grants-1995_02
Patent number
US05391817

Reaction notes

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