Dimethylformamide → HCID 59409719, compound

HRID 1892080Notes

Reaction equation

HRID 1892080 reaction equation
Br[C:2]1[CH:3]=[C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[S:5][CH:6]=1.CN(C=O)C.[CH:17]#[C:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23].C(N(CC)CC)C>[Cu]I.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.C(OC)(C)(C)C>[C:17]([C:2]1[CH:3]=[C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[S:5][CH:6]=1)#[C:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 123501-HeptyneHCID 10847330Ethyl 4-bromothiophene-2-carboxylate

Product 1

HCID 59409719HCID 59409719, compoundYield 98%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
65 °C

Procedure

A reaction mixture of compound 1015 (5.64 g, 24.0 mmol), DMF (50 mL), copper (I) iodide (1.37 g, 7.2 mmol), 1-heptyne (9.42 mL, 72.0 mmol), triethylamine (6.70 mL, 48.0 mmol) and tetrakis(triphenylphosphine)palladium(0) (2.77 g, 2.4 mmol) was stirred at 65° C. for 2 hours and then cooled to room temperature. Methyl tert-butyl ether (300 mL) was added to the reaction mixture and the precipitation was removed by filtration. The clear organic solution was washed with saturated sodium chloride, dried over magnesium sulfate and concentrated under vacuum. The crude brown oil was purified with flash silica gel chromatogram (with 0%→5% EtOAc in hexane) to afford ethyl 4-(hept-1-ynyl)thiophene-2-carboxylate (1016, 5.89 g) as a brown oil. 1H NMR (300 MHz, δ, CDCl3) 0.89 (t, 3H). 1.28-1.45 (m, 7H), 1.52-1.62 (m, 2H), 2.36 (t, 12.4 Hz, 2H), 4.33 (q, 2H), 7.48 (s, 1H), 7.72 (s, 1H).

Workup

  1. temperaturecooled to room temperature
  2. customthe precipitation
  3. customwas removed by filtration
  4. washThe clear organic solution was washed with saturated sodium chloride
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under vacuum
  7. customThe crude brown oil was purified with flash silica gel chromatogram (with 0%→5% EtOAc in hexane)

Sources & evidence

ORD record
ord-8dad396f3ce54dedb821e8934b0d99ba
Source dataset
uspto-grants-2013_08
Patent number
US08507647B2

Reaction notes

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