3-Methoxypropyne → HCID 178494848, compound

HRID 1978932Notes

Reaction equation

HRID 1978932 reaction equation
[Cl:1][C:2]1[CH:22]=[CH:21][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:11]([OH:20])=[C:12]3[CH:18]=[C:17](I)[S:16][C:13]3=[N:14][CH:15]=2)=[O:9])=[CH:4][CH:3]=1.[CH3:23][O:24][CH2:25][C:26]#[CH:27]>C(NCC)C.[Cu](I)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[CH:22]=[CH:21][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:11]([OH:20])=[C:12]3[CH:18]=[C:17]([C:27]#[C:26][CH2:25][O:24][CH3:23])[S:16][C:13]3=[N:14][CH:15]=2)=[O:9])=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 693933-MethoxypropyneHCID 178522942HCID 178522942, compound

Product 1

HCID 178494848HCID 178494848, compoundYield 30%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8021DiethylamineSolvent

Procedure

To a suspension of N-(4-chlorobenzyl)-4-hydroxy-2-iodothieno[2,3-b]pyridine-5-carboxamide (Example No. 2) (1.00 g) in diethylamine (28 mL) is added copper iodide (0.128 g), and Pd(PPh3)2Cl2 (0.079 g) followed by addition of propargyl methyl ether (0.27 mL). The reaction is stirred at rt for 18 h. The reaction mixture is partitioned between H2O (100 mL) and CH2Cl2 (100 mL). The organic layer is removed, and the aqueous layer is extracted with CH2Cl2 (3×100 mL). Combined organic layers are washed with a saturated aqueous NH4Cl solution (200 mL), dried with MgSO4, filtered, and concentrated in vacuo. The resulting brown oil is purified via column chromatography (CH2Cl2:CH3OH; 98:2). The resulting impure material is re-purified via column chromatography (heptane:2-propanol, 10:1; CH2Cl2:CH3OH, 98:2). Fractions homogeneous by TLC are combined and concentrated in vacuo to yield to yield 0.260 g (30%) of the title compound as an off-white solid.

Workup

  1. customThe reaction mixture is partitioned between H2O (100 mL) and CH2Cl2 (100 mL)
  2. customThe organic layer is removed
  3. extractionthe aqueous layer is extracted with CH2Cl2 (3×100 mL)
  4. washCombined organic layers are washed with a saturated aqueous NH4Cl solution (200 mL)
  5. dry with materialdried with MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe resulting brown oil is purified via column chromatography (CH2Cl2:CH3OH; 98:2)
  9. customThe resulting impure material is re-purified via column chromatography (heptane:2-propanol, 10:1; CH2Cl2:CH3OH, 98:2)
  10. concentrationconcentrated in vacuo
  11. customto yield

Sources & evidence

ORD record
ord-8b64b1d002844fc9b387733960b065da
Source dataset
uspto-grants-2001_05
Patent number
US06239142B1

Reaction notes

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