Allyltributylstannane → 4-Allylnaphthalene-1-carboxylic acid methyl ester

HRID 1814374Notes

Reaction equation

HRID 1814374 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8](Br)=[CH:7][CH:6]=1)=[O:4].[CH2:16]([Sn](CCCC)(CCCC)CCCC)[CH:17]=[CH2:18]>C1(C)C=CC=CC=1.CCOCC.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>[CH3:1][O:2][C:3]([C:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:8]([CH2:18][CH:17]=[CH2:16])=[CH:7][CH:6]=1)=[O:4]

Participants

6

Reactant 2

HCID 90628AllyltributylstannaneHCID 22711886Methyl 4-bromo-1-naphthoate

Product 1

HCID 696928344-Allylnaphthalene-1-carboxylic acid methyl esterYield 89%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 4-bromo-naphthalene-1-carboxylic acid methyl ester (2.0 g, 7.9 mmol) in toluene (20 mL) was added allyltributyltin (2.7 mL), tetrakis(triphenylphosphine)palladium(0) (183 mg, 0.16 mmol) and 2 crystals of BHT. The system was purged under vacuum and nitrogen and allowed to heat to 120° C. under N2 for 4 h. TLC analysis (silica, 1:1 ethyl acetate-hexanes) showed the reaction to be completed with only one new fluorescent spot present. The mixture was diluted with ether, washed with H2O, 10% HCl, and then saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (SiO2, 9:1 hexanes-ether) to give (1.6 g, 89%) 4-allylnaphthalene-1-carboxylic acid methyl ester as a colorless liquid. MS m/z 227.1 (M+1). 1H NMR (400 mHz) CDCl3 8.95(d 1H), 8.11(d, 1H), 8.08(d, 1H), 7.58(m, 2H), 7.37(d, 1H), 6.09(m, 1H), 5.11(m, 2H), 3.99(s, 3H), 3.88(d, 2H).

Workup

  1. customThe system was purged under vacuum and nitrogen
  2. customthe reaction
  3. washwashed with H2O, 10% HCl
  4. dry with materialsaturated sodium bicarbonate, dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by flash chromatography (SiO2, 9:1 hexanes-ether)

Sources & evidence

ORD record
ord-26d834d3d340400aba3e64ce00786ee8
Source dataset
uspto-grants-2005_04
Patent number
US06875765B2

Reaction notes

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