Oxalyl chloride → HCID 14807709, compound

HRID 1505262Notes

Reaction equation

HRID 1505262 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[C:7]2[C:12]([OH:14])=[O:13].C(Cl)(=O)C(Cl)=O.[CH3:21][C:22]([CH3:25])([O-])[CH3:23].[K+]>ClCCl.CN(C)C=O.O1CCCC1>[C:22]([O:13][C:12]([C:7]1[C:8]2[C:3](=[C:2]([Br:1])[CH:11]=[CH:10][CH:9]=2)[CH:4]=[CH:5][CH:6]=1)=[O:14])([CH3:25])([CH3:23])[CH3:21]

Participants

7

Reactant 3

HCID 65578Oxalyl chlorideHCID 6976055-Bromonaphthalene-1-carboxylic acidHCID 23665647Potassium tert-butoxide

Product 1

HCID 14807709HCID 14807709, compoundYield 90.8%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of 5-bromo-1-naphtoic acid (Example 9.1) (10.8 g) in dichloromethane (93 ml) containing 3 drops of dimethylformamide was added oxalyl chloride (4 ml) and the reaction mixture stirred at ambient temperature for 6 hours. The solution was concentrated to afford a white solid which was re-dissolved in tetrahydrofuran. The solution was cooled to 2° C. and a solution of potassium tert-butoxide (7.2 g) in tetrahydrofuran (148 ml) was added dropwise and the reaction mixture stirred at ambient temperature for 3 hours. The solution was poured onto ice and extracted with ethyl acetate. The combined organic extracts were washed with water, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate) to give 5-bromo-1-naphtoic acid tert-butyl ester (12 g). 1H-NMR (CDCl3, 400 MHz): 8.82 (d, 1H), 8.46 (d, 1H), 8.11 (d, 1H), 7.72 (d, 1H), 7.60 (m, 1H), 7.40 (m, 1H), 1.70 (s, 9H).

Workup

  1. concentrationThe solution was concentrated
  2. customto afford a white solid which
  3. temperatureThe solution was cooled to 2° C.
  4. stirringthe reaction mixture stirred at ambient temperature for 3 hours
  5. additionThe solution was poured onto ice
  6. extractionextracted with ethyl acetate
  7. washThe combined organic extracts were washed with water
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-60f20f0e9c994a9f8833e6abd2d08406
Source dataset
uspto-grants-2015_12
Patent number
US09216973B2

Reaction notes

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