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Methyl Acrylate → (E)-3-{1'-tert-butoxycarbonyl-3,4-dihydro-4-oxo-spiro[2H-(1,3)-benzoxazine-2,4'-piperidin]-6-yl}-acrylic acid methyl ester

HRID 518160
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 518160
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]2([NH:18][C:17](=[O:19])[C:16]3[CH:20]=[C:21](Br)[CH:22]=[CH:23][C:15]=3[O:14]2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:25]([O:29][CH3:30])(=[O:28])[CH:26]=[CH2:27]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[CH3:30][O:29][C:25](=[O:28])/[CH:26]=[CH:27]/[C:21]1[CH:22]=[CH:23][C:15]2[O:14][C:11]3([CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]3)[NH:18][C:17](=[O:19])[C:16]=2[CH:20]=1
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Komponenten

6

Edukt 2

HCID 7294Methyl AcrylateHCID 2794762tert-Butyl 6-bromo-4-oxo-3,4-dihydro-1'H-spiro[1,3-benzoxazine-2,4'-piperidine]-1'-carboxylate

Produkt 1

HCID 66932321(E)-3-{1'-tert-butoxycarbonyl-3,4-dihydro-4-oxo-spiro[2H-(1,3)-benzoxazine-2,4'-piperidin]-6-yl}-acrylic acid methyl esterAusbeute 99,6 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 80271Tri-o-tolylphosphineKatalysator2×
HCID 167845palladium(II) acetateKatalysator2×
HCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

6-Bromo-3,4-dihydro-4-oxo-spiro[2H-(1,3)-benzoxazine-2,4′-piperidin]-1′-carboxylic acid tert-butyl ester (5.00 g, 12.6 mmol) was dissolved in hot DMF (15 ml) and then TEA (5.26 ml, 37.8 mmol), tris(o-tolyl)phosphine (153 mg, 0.504 mmol), Pd(OAc)2 (56 mg, 0.25 mmol) and methyl acrylate (3.25 g, 37.8 mmol) were added at RT. The mixture was heated at 100° C. for 6 h under N2 with a further addition of tris(o-tolyl)phosphine (153 mg, 0.504 mmol) and Pd(OAc)2 (56 mg, 0.25 mmol) after three hours) and then partitioned between brine and AcOEt. The organic phase was rinsed with water and brine, dried over Na2SO4 and evaporated. The residue was triturated in AcOEt and petroleum ether to give (E)-3-{1′-tert-butoxycarbonyl-3,4-dihydro-4-oxo-spiro[2H-(1,3)-benzoxazine-2,4′-piperidin]-6-yl}-acrylic acid methyl ester (5.05 g)

Aufarbeitung

  1. customthen partitioned between brine and AcOEt
  2. washThe organic phase was rinsed with water and brine
  3. dry with materialdried over Na2SO4
  4. customevaporated
  5. customThe residue was triturated in AcOEt

Quellen und Nachweise

ORD-Eintrag
ord-be0584b2d179450a844797cf5d2b0314
Quelldatensatz
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09115148B2

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