Water → Methyl 1-amino-4-(4-chlorobenzyl)-2-naphthoate

HRID 1774923Notes

Reaction equation

HRID 1774923 reaction equation
Br.[NH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6](Br)=[CH:5][C:4]=1[C:14]([O:16][CH3:17])=[O:15].[Cl-].[Cl:19][C:20]1[CH:25]=[CH:24][C:23]([CH2:26][Zn+])=[CH:22]N=1.O.Cl[CH2:30]Cl>C1COCC1.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[NH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([CH2:26][C:23]2[CH:22]=[CH:30][C:20]([Cl:19])=[CH:25][CH:24]=2)=[CH:5][C:4]=1[C:14]([O:16][CH3:17])=[O:15]

Participants

7

Reactant 4

HCID 962Water2×HCID 6344DichloromethaneHCID 66979039Methyl 1-amino-4-bromo-2-naphthoate hydrobromideHCID 178478124HCID 178478124, compound

Product 1

HCID 67031942Methyl 1-amino-4-(4-chlorobenzyl)-2-naphthoate

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 1-amino-4-bromo-2-naphthoate hydrobromide (1.94 g, 5.37 mmol) in 10 mL of THF at 0° C. under an atmosphere of nitrogen was added (2-chloro-5-pyridyl)methylzinc chloride (41.6 mL, 0.5 M in THF, 83.2 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.177 g, 0.346 mmol). The reaction was warmed to rt, and after 16 h, treated with water (10 mL). The mixture was diluted dichloromethane and water, and a beige solid was removed via filtration. The filtrate was extracted 2× with dichloromethane and the combined organic fractions were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified via silica gel chromatography, eluting with 0-20% ethyl acetate in hexanes provide methyl 1-amino-4-(4-chlorobenzyl)-2-naphthoate that gave a proton NMR spectra consistent with theory and a mass ion (ES+) of 326.1 for [M+H]+.

Workup

  1. customa beige solid was removed via filtration
  2. extractionThe filtrate was extracted 2× with dichloromethane
  3. dry with materialthe combined organic fractions were dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified via silica gel chromatography
  7. washeluting with 0-20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-b8204c6f227048eab6196bd17f2ef645
Source dataset
uspto-grants-2016_02
Patent number
US09260418B2

Reaction notes

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