Trimethylsilylacetylene → HCID 58368507, compound

HRID 1192715Notes

Reaction equation

HRID 1192715 reaction equation
[Cl:1][C:2]1[C:3](I)=[CH:4][C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[CH3:14][Si:15]([C:18]#[CH:19])([CH3:17])[CH3:16]>C(N(CC)CC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[C:3]([C:19]#[C:18][Si:15]([CH3:17])([CH3:16])[CH3:14])=[CH:4][C:5]([OH:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

6

Reactant 2

HCID 66111TrimethylsilylacetyleneHCID 58368557HCID 58368557, compound

Product 1

HCID 58368507HCID 58368507, compoundYield 104.5%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
65 °C

Procedure

A solution of methyl 5-chloro-2-hydroxy-4-iodobenzoate (690 g, 2.2 mol), copper (I) iodide (4.2 g, 22 mmol) in triethylamine (5.6 L) was degassed with nitrogen for 5-10 minutes, treated with bis(triphenylphosphine)palladium(II) chloride (16 g, 22 mmol) and (trimethylsilyl)acetylene (470 mL, 3.3 mol), degassed with nitrogen for 2 minutes, and heated at 65° C. The heat was removed and the reaction temperature increased from 65 to 85° C. by itself. The temperature was dropped to 75° C. after 30 minutes with stirring. The reaction was cooled to room temperature, filtered over a pad of celite and rinsed with ethyl acetate (3 L). The filtrate was concentrated and dried on a high vacuum pump for 72 hours to give the desired product (650 g, quantitative) as a yellow solid. HPLC 91.3% pure @ 220 nm. LCMS for C13H16ClO3Si (M+H)+: m/z=283.1; Found: 282.8; 1H NMR (400 MHz, DMSO-d6): δ 10.5 (br s, 1 H), 7.76 (s, 1 H), 7.13 (s, 1 H), 3.85 (s, 3 H), 0.24 (s, 9 H).

Workup

  1. customdegassed with nitrogen for 2 minutes
  2. customThe heat was removed
  3. temperaturethe reaction temperature increased from 65 to 85° C. by itself
  4. additionThe temperature was dropped to 75° C. after 30 minutes
  5. temperatureThe reaction was cooled to room temperature
  6. filtrationfiltered over a pad of celite
  7. washrinsed with ethyl acetate (3 L)
  8. concentrationThe filtrate was concentrated
  9. customdried on a high vacuum pump for 72 hours

Sources & evidence

ORD record
ord-72427388c9af458e84f18a3b35b5dbf7
Source dataset
uspto-grants-2014_03
Patent number
US08680108B2

Reaction notes

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