Methyl Acrylate → Methyl 3-(2-acetyl-4-benzyloxy-6-nitrophenyl)acrylate

HRID 1372904Notes

Reaction equation

HRID 1372904 reaction equation
C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.F[B-](F)(F)F.C1(C(N)C2CCCCC2)CCCCC1.[C:33]([O:37][CH3:38])(=[O:36])[CH:34]=[CH2:35].FC(F)(F)S(O[C:45]1[C:50]([N+:51]([O-:53])=[O:52])=[CH:49][C:48]([O:54][CH2:55][C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)=[CH:47][C:46]=1[C:62](=[O:64])[CH3:63])(=O)=O>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.O1CCOCC1.CCOCC.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:62]([C:46]1[CH:47]=[C:48]([O:54][CH2:55][C:56]2[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=2)[CH:49]=[C:50]([N+:51]([O-:53])=[O:52])[C:45]=1[CH:35]=[CH:34][C:33]([O:37][CH3:38])=[O:36])(=[O:64])[CH3:63]

Participants

9

Reactant 4

HCID 7294Methyl AcrylateHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 10774245alpha-CyclohexylcyclohexanemethanamineHCID 210728242-Acetyl-4-benzyloxy-6-nitrophenyl trifluoromethanesulfonate

Product 1

HCID 66751245Methyl 3-(2-acetyl-4-benzyloxy-6-nitrophenyl)acrylate

Reagents, catalysts & solvents 4

HCID 67553Tetrabutylammonium IodideCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

100 g of molecular sieve (4 Å), tris(dibenzylideneacetone)dipalladium (5.88 g, 6.42 mmol), tri-tert-butylphosphonium-tetrafluoroborate (3.50 g, 12.06 mmol), dicyclohexylmethylamine (81.2 mL, 0.371 mol), dried tetrabutylammonium iodide (105.8 g, 0.286 mol) and methyl acrylate (32.6 mL, 0.362 mol) are added to a solution of 2-acetyl-4-benzyloxy-6-nitro-phenyl trifluoromethanesulphonate (100.0 g, 0.238 mol) in dioxane (360 mL) under a nitrogen atmosphere. The reaction mixture is stirred for 2 hours at 80° C., diluted with ether (2 L) and combined with 500 g silica gel. The suspension is stirred for 10 min., filtered and the silica gel is washed several times with ether (4×600 mL). The combined organic phases are washed with 1 M aqueous hydrochloric acid (300 mL), sodium bicarbonate solution and sodium chloride solution, dried with sodium sulphate and evaporated down. The oily crude product is recrystallised from hot ethanol (0.75 L). The precipitate is filtered off, washed with ethanol (2×50 mL) and dried at 40 ° C.

Workup

  1. stirringThe suspension is stirred for 10 min.
  2. filtrationfiltered
  3. washthe silica gel is washed several times with ether (4×600 mL)
  4. washThe combined organic phases are washed with 1 M aqueous hydrochloric acid (300 mL), sodium bicarbonate solution and sodium chloride solution
  5. dry with materialdried with sodium sulphate
  6. customevaporated down
  7. customThe oily crude product is recrystallised from hot ethanol (0.75 L)
  8. filtrationThe precipitate is filtered off
  9. washwashed with ethanol (2×50 mL)
  10. customdried at 40 ° C.

Sources & evidence

ORD record
ord-3ec0eca1a5424dc0aa51efd88b3725fa
Source dataset
uspto-grants-2007_01
Patent number
US07160882B2

Reaction notes

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