4-Chlorobenzoic Acid → HCID 4674743, compound

HRID 530776Notes

Reaction equation

HRID 530776 reaction equation
[Cl:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=O)=[CH:4][CH:3]=1.C(Cl)(C(Cl)=O)=O.[F:17][C:18]1[CH:24]=[CH:23][C:21]([NH2:22])=[CH:20][C:19]=1[N+:25]([O-:27])=[O:26].CCN(C(C)C)C(C)C>C(Cl)Cl.CN(C=O)C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([NH:22][C:21]2[CH:23]=[CH:24][C:18]([F:17])=[C:19]([N+:25]([O-:27])=[O:26])[CH:20]=2)=[O:8])=[CH:9][CH:10]=1

Participants

7

Reactant 4

HCID 63184-Chlorobenzoic AcidHCID 65578Oxalyl chlorideHCID 677684-Fluoro-3-nitroanilineHCID 81531Diisopropylethylamine

Product 1

HCID 4674743HCID 4674743, compoundYield 39,592.898%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

To the solution of 4-chlorobenzoic acid (19) (9.36 g, 0.06 mmol) in DCM (150 mL) was added (COCl)2 (17.4 mL, 0.3 mol) dropwise and cat. amount of DMF at 0° C. The mixture was stirred at room temperature for 2 h and evaporated. The residue was again dissolved in DCM (150 mL) and added to a mixture of 4-fluoro-3-nitroaniline (6.24 g, 0.04 mol) and DIEA (20.9 mL, 0.12 mol) in CH2Cl2 (100 mL) at 0° C. The mixture was allowed to stir at room temperature overnight. The solvent was removed under vacuo and the residue was washed with sat. NaHCO3 aq. (50 mL) and brine (50 mL). The organic layer was separated, dried and purified by crystallization to give 20 (7 g, 60%).

Workup

  1. customat 0° C
  2. customevaporated
  3. dissolutionThe residue was again dissolved in DCM (150 mL)
  4. stirringto stir at room temperature overnight
  5. customThe solvent was removed under vacuo
  6. washthe residue was washed with sat. NaHCO3 aq. (50 mL) and brine (50 mL)
  7. customThe organic layer was separated
  8. customdried
  9. custompurified by crystallization

Sources & evidence

ORD record
ord-083a6e84eba34249aaf43dc619cf1fa7
Source dataset
uspto-grants-2016_05
Patent number
US09353099B2

Reaction notes

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