Isopropyl Acetate → Methyl 5-nitro-2-(2,6-dimethoxyphenyl)-benzoate

HRID 1059120Notes

Reaction equation

HRID 1059120 reaction equation
Br[C:2]1[C:7]([O:8][CH3:9])=[CH:6][CH:5]=[CH:4][C:3]=1[O:10][CH3:11].IC1C(OC)=CC=CC=1OC.COC1C=CC=C(OC)C=1.Br[C:34]1[CH:43]=[CH:42][C:41]([N+:44]([O-:46])=[O:45])=[CH:40][C:35]=1[C:36]([O:38][CH3:39])=[O:37].IC1C=CC([N+]([O-])=O)=CC=1C(OC)=O.[N+](C1C=CC(OS(C(F)(F)F)(=O)=O)=C(C=1)C(OC)=O)([O-])=O.C(OC(=O)C)(C)C>[Cl-].[Cl-].[Zn+2]>[CH3:11][O:10][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([O:8][CH3:9])[C:2]=1[C:34]1[C:35]([C:36]([O:38][CH3:39])=[O:37])=[CH:40][C:41]([N+:44]([O-:46])=[O:45])=[CH:42][CH:43]=1

Participants

9

Reactant 7

HCID 7915Isopropyl AcetateHCID 90251,3-DimethoxybenzeneHCID 245494Methyl 2-Bromo-5-nitrobenzoateHCID 6122962-Bromo-1,3-dimethoxybenzeneHCID 113914072-Iodo-1,3-dimethoxybenzeneHCID 11415548Methyl 2-iodo-5-nitrobenzoateHCID 18755364Methyl 5-nitro-2-{[(trifluoromethyl)sulfonyl]oxy}benzoate

Product 1

HCID 11001627Methyl 5-nitro-2-(2,6-dimethoxyphenyl)-benzoate

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst2×

Procedure

The process comprising treating 2-bromo-1,3-dimethoxybenzene, 2-iodo-1,3-dimethoxybenzene or 1,3-dimethoxybenzene with an organolithium reagent in a first solvent at a temperature of about −5° C. to about 15° C., preferably about 0° C. to about 5° C., after complete addition of the organolithium reagent, the temperature is allowed to warm to ambient temperature and the reaction mixture is stirred for about 1 to 4 hours, preferably about 2 hours, recooling the reaction mixture to about 0° C. and then adding ZnCl2 while maintaining the temperature between −5° C. and 15° C., preferably about −5° C. to about 5° C., after complete addition of ZnCl2 allowing the temperature to warm to ambient temperature and allowing the reaction mixture to stir for about 1 to 4 hours, preferably about 2 hours, recooling the reaction mixture to about 0° C. and adding methyl 2-bromo-5-nitrobenzoate, methyl 2-iodo-5-nitrobenzoate or methyl 5-nitro-2-{[(trifluoromethyl)sulfonyl]oxy}benzoate followed by addition of first transition metal catalyst and maintaining the reaction temperature between about 10° C. and about 55° C., preferably between about 20° C. and about 45° C., about 30 minutes after complete addition of first transition metal catalyst adding isopropylacetate and stirring for about 20 to about 90 minutes and then filtering to provide methyl 2′,6′-dimethoxy-4-nitro-1,1′-biphenyl-2-carboxylate;

Workup

  1. customto about 0° C.
  2. temperatureto warm to ambient temperature
  3. stirringto stir for about 1 to 4 hours, preferably about 2 hours
  4. customto about 0° C.
  5. temperaturemaintaining the reaction temperature between about 10° C. and about 55° C., preferably between about 20° C. and about 45° C., about 30 minutes
  6. stirringstirring for about 20 to about 90 minutes
  7. filtrationfiltering

Sources & evidence

ORD record
ord-11ead8a64682451f9e68f85d429b48ec
Source dataset
uspto-grants-2003_02
Patent number
US06518430B1

Reaction notes

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