Sodium Carbonate → Methyl 6-(4-hydroxyphenyl)-1-naphthoate

HRID 1693642Notes

Reaction equation

HRID 1693642 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[C:13]([C:17]([O:19][CH3:20])=[O:18])=[CH:12][CH:11]=[CH:10]2)(=O)=O.C(=O)([O-])[O-].[Na+].[Na+].[OH:29][C:30]1[CH:35]=[CH:34][C:33](B(O)O)=[CH:32][CH:31]=1>COCCOC.C(OCC)(=O)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:29][C:30]1[CH:35]=[CH:34][C:33]([C:7]2[CH:8]=[C:9]3[C:14](=[CH:15][CH:16]=2)[C:13]([C:17]([O:19][CH3:20])=[O:18])=[CH:12][CH:11]=[CH:10]3)=[CH:32][CH:31]=1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 27343604-Hydroxyphenylboronic acidHCID 22622428Methyl 6-(((trifluoromethyl)sulfonyl)oxy)-1-naphthoate

Product 1

HCID 59264867Methyl 6-(4-hydroxyphenyl)-1-naphthoateYield 88.3%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of methyl 6-{[(trifluoromethyl)sulfonyl]oxy}-1-naphthoate (271 g, 0.81 mol) (from multiple batches), tetrakis(triphenylphosphine)palladium (0) (37.4 g, 0.032 mol), 2 M sodium carbonate solution (1.3 L) and 4-hydroxyphenyl boronic acid (134 g, 0.97 mol) in ethylene glycol dimethyl ether (1.5 L) was heated at 80° C. for 1.5 h. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (2 L) and water (2 L). The ethyl acetate layer was dried over anhydrous sodium sulfate, filtered and concentrated to a dark semisolid residue. The crude material was purified by crystallization from dichloromethane-heptane to give 199 g of the product as a tan solid. 1H NMR (DMSO-d6): 9.64 (s, 1H), 8.76 (d, J=9 Hz, 1H), 8.21 (m, 2H), 8.07 (d, J=7 Hz, 1H), 7.93 (m, 1H), 7.66 (d, J=9 Hz, 2H), 7.58 (t, J=8 Hz, 1H), 6.89 (d, J=9 Hz, 2H), 3.93 (s, 3H).

Workup

  1. dry with materialThe ethyl acetate layer was dried over anhydrous sodium sulfate
  2. filtrationfiltered
  3. concentrationconcentrated to a dark semisolid residue
  4. customThe crude material was purified by crystallization from dichloromethane-heptane

Sources & evidence

ORD record
ord-075ee4175ec54ae883d7acf76535eb46
Source dataset
uspto-grants-2012_04
Patent number
US08158665B2

Reaction notes

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