Triethylamine → 2-Chloro-4-trimethylsilanylethynyl-benzoic acid methyl ester

HRID 1877423Notes

Reaction equation

HRID 1877423 reaction equation
[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7](Br)=[CH:6][C:5]=1[Cl:11].C(N(CC)CC)C.[C:20]([Si:22]([CH3:25])([CH3:24])[CH3:23])#[CH:21]>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.[Cu]I>[CH3:1][O:2][C:3](=[O:12])[C:4]1[CH:9]=[CH:8][C:7]([C:21]#[C:20][Si:22]([CH3:25])([CH3:24])[CH3:23])=[CH:6][C:5]=1[Cl:11]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 22058730Methyl 4-Bromo-2-chlorobenzoate

Product 1

HCID 673682802-Chloro-4-trimethylsilanylethynyl-benzoic acid methyl ester

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
70 °C

Procedure

To a degassed solution of 4-bromo-2-chloro-benzoic acid methyl ester (3.0 g, 12.0 mmol, 1.0 equiv; [CAS RN 185312-82-7]) in triethylamine (24.3 g, 33.5 mL, 240.5 mmol, 20.0 equiv; [CAS RN 121-44-8]) under Ar was added ethynyl-trimethyl-silane (1.24 g, 1.78 mL, 12.63 mmol, 1.05 equiv; [CAS RN 1066-54-2]), tetrakis(triphenylphosphine)palladium(0) (0.70 g, 0.60 mmol, 0.05 equiv; [CAS RN 14221-01-3]) and copper(I) iodide (0.23 g, 1.20 mmol, 0.1 equiv; [CAS RN 7681-65-4]) and the reaction mixture heated to 70° C. for 18 h. The crude reaction was filtered over Celite®, a sat. solution of NaCl (50 mL) added and extracted with ethyl acetate (3×50 mL). The combined organic phases were dried over Na2SO4 and the product used in the consecutive step without any further purification. Yield: 4.52 g (99%) of the title compound in ca. 70% purity as a slightly brown oil. MS (ISN): 267.0 [M+H]+.

Workup

  1. customThe crude reaction
  2. filtrationwas filtered over Celite®
  3. additiona sat. solution of NaCl (50 mL) added
  4. extractionextracted with ethyl acetate (3×50 mL)
  5. dry with materialThe combined organic phases were dried over Na2SO4
  6. customthe product used in the consecutive step without any further purification

Sources & evidence

ORD record
ord-a998a754ebc441ed934a84cc973d3448
Source dataset
uspto-grants-2012_11
Patent number
US08309734B2

Reaction notes

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