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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
ノート
印刷プレビュー

反応式

HRID 518160 の反応式
[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
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 2

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

生成物 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 ester収率 99.6%

試薬・触媒・溶媒 3

HCID 80271Tri-o-tolylphosphine触媒2 回
HCID 167845
palladium(II) acetate
触媒
2 回
HCID 6228Dimethylformamide溶媒

実験手順

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)

後処理

  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

出典と根拠

ORDレコード
ord-be0584b2d179450a844797cf5d2b0314
出典データセット
uspto-grants-2015_08
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09115148B2

反応ノート

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