Dimethyl (2-propynyloxy)(1,1,2-trimethylpropyl)-silane → (4-Bromo-2-{3-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-prop-1-ynyl}-5-methyl-phenyl)-carbamic acid methyl ester

HRID 853096Notes

Reaction equation

HRID 853096 reaction equation
[CH3:1][O:2][C:3](=[O:14])[NH:4][C:5]1[CH:10]=[C:9]([CH3:11])[C:8]([Br:12])=[CH:7][C:6]=1I.[CH3:15][Si:16]([CH3:27])([O:23][CH2:24][C:25]#[CH:26])[C:17]([CH3:22])([CH3:21])[CH:18]([CH3:20])[CH3:19]>C(N(CC)CC)C>[CH3:1][O:2][C:3](=[O:14])[NH:4][C:5]1[CH:10]=[C:9]([CH3:11])[C:8]([Br:12])=[CH:7][C:6]=1[C:26]#[C:25][CH2:24][O:23][Si:16]([CH3:27])([CH3:15])[C:17]([CH3:22])([CH3:21])[CH:18]([CH3:20])[CH3:19]

Participants

4

Reactant 2

HCID 18455989Dimethyl (2-propynyloxy)(1,1,2-trimethylpropyl)-silaneHCID 57543475Methyl (4-Bromo-2-iodo-5-methylphenyl)carbamate

Product 1

HCID 68890098(4-Bromo-2-{3-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-prop-1-ynyl}-5-methyl-phenyl)-carbamic acid methyl esterYield 43.6%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

To a solution of 3.70 g (4-bromo-2-iodo-5-methyl-phenyl)-carbamic acid methyl ester and 0.070 g bis-triphenylphosphine palladium dichloride and 0.038 g cuprous iodide in 25 ml triethylamine was added 2.38 g dimethyl (2-propynyloxy)(1,1,2-trimethylpropyl)-silane and the mixture was heated 2 h at reflux. The reaction mixture was partitioned between water and ethyl acetate. The phases were separated and the organic phase was washed with 1N hydrochloric acid, sodium bicarbonate and brine, dried with magnesium sulfate and purified by chromatography on silica gel with hexane:ethyl acetate=4:1 to yield 1.92 g (4-bromo-2-{3-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-prop-1-ynyl}-5-methyl-phenyl)-carbamic acid methyl ester as a light brown oil. MS: M+NH4+=457.0 M+Na+=462.2

Workup

  1. temperaturethe mixture was heated 2 h
  2. temperatureat reflux
  3. customThe reaction mixture was partitioned between water and ethyl acetate
  4. customThe phases were separated
  5. washthe organic phase was washed with 1N hydrochloric acid, sodium bicarbonate and brine
  6. dry with materialdried with magnesium sulfate
  7. custompurified by chromatography on silica gel with hexane

Sources & evidence

ORD record
ord-3822e9602b8a4b2c88b8a9bcde58ab84
Source dataset
uspto-grants-2007_08
Patent number
US07253281B2

Reaction notes

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