Methyl Acrylate → HCID 86746753, compound

HRID 1591062Notes

Reaction equation

HRID 1591062 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C.[OH:27][CH:28]1[CH:32]([CH2:33][O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:31]([O:42][CH2:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH2:30][CH:29]1[N:50]1[CH:55]=[C:54](I)[C:53](=[O:57])[NH:52][C:51]1=[O:58].[C:59]([O:63][CH3:64])(=[O:62])[CH:60]=[CH2:61]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[OH:27][CH:28]1[CH:32]([CH2:33][O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:31]([O:42][CH2:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH2:30][CH:29]1[N:50]1[CH:55]=[C:54]([CH:61]=[CH:60][C:59]([O:63][CH3:64])=[O:62])[C:53](=[O:57])[NH:52][C:51]1=[O:58]

Participants

7

Reactant 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 19007161HCID 19007161, compound

Product 1

HCID 86746753HCID 86746753, compoundYield 35.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent2×

Procedure

A mixture of palladium(II) acetate (0.195 g, 0.871 mmol), triphenylphosphine (0.456 g, 1.74 mmol) and triethylamine (2.56 ml, 0.0183 mol) in dioxane (200 ml, purified on basic alumina and degassed in vacuo) was heated for 10 minutes at 90° under nitrogen. A solution of [1S-(1α,2β,3α,4β)]-1-[2-hydroxy-4-(phenylmethoxy)-3-[(phenylmethoxy)-methyl]cyclopentyl-5-iodo-2,4(1H,3H)-pyrimidine-dione (6.70 g, 0.0122 mol, dried by concentration in vacuo from dry toluene) and methyl acrylate (3.23 ml, 0.0366 mol) in degassed dioxane (20 ml) was added, and the reaction was heated at 90° for 4.5 hours. Celite (5 g) was added, and after stirring at 90° for 15 minutes, the hot slurry was filtered through Celite and washed with chloroform (80 ml). The filtrate and the wash were combined and concentrated in vacuo to a residue, which was dissolved in chloroform (400 ml). The chloroform was washed with water (100 ml), dried (sodium sulfate) and concentrated in vacuo to a residue. Chromatography of the residue on a column of Merck silica gel (800 ml, packed in dichloromethane) by eluting with a gradient of chloroform to 5% ethanol in chloroform gave 2.21 g of desired product as a residue.

Workup

  1. temperaturewas heated for 10 minutes at 90° under nitrogen
  2. temperaturethe reaction was heated at 90° for 4.5 hours
  3. additionCelite (5 g) was added
  4. filtrationthe hot slurry was filtered through Celite
  5. washwashed with chloroform (80 ml)
  6. concentrationconcentrated in vacuo to a residue, which
  7. dissolutionwas dissolved in chloroform (400 ml)
  8. washThe chloroform was washed with water (100 ml)
  9. dry with materialdried (sodium sulfate)
  10. concentrationconcentrated in vacuo to a residue
  11. washChromatography of the residue on a column of Merck silica gel (800 ml, packed in dichloromethane) by eluting with a gradient of chloroform to 5% ethanol in chloroform

Sources & evidence

ORD record
ord-c2c901028a0a46bd9132457072d18b6f
Source dataset
uspto-grants-1993_04
Patent number
US05206244

Reaction notes

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