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N-Hydroxyphthalimide → [cis-2-[[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]methyl]-1-(4-methoxyphenyl)-4-oxo-3-azetidinyl]carbamic acid 1,1-dimethylethyl ester

HRID 247640
ノート
印刷プレビュー

反応式

HRID 247640 の反応式
[CH3:1][C:2]([O:5][C:6](=[O:23])[NH:7][C@H:8]1[C:11](=[O:12])[N:10]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=2)[C@H:9]1[CH2:21][OH:22])([CH3:4])[CH3:3].O[N:25]1[C:29](=[O:30])[C:28]2=[CH:31][CH:32]=[CH:33][CH:34]=[C:27]2[C:26]1=[O:35].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>>[CH3:4][C:2]([O:5][C:6](=[O:23])[NH:7][C@H:8]1[C:11](=[O:12])[N:10]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=2)[C@H:9]1[CH2:21][O:22][N:25]1[C:29](=[O:30])[C:28]2[C:27](=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:26]1=[O:35])([CH3:1])[CH3:3]
参加物実験手順後処理出典と根拠反応ノート

参加物

5

反応物 4

HCID 10665N-HydroxyphthalimideHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 13944672cis-2-Hydroxymethyl-1-(4-methoxyphenyl)-4-oxo-3-azetidinyl-carbamic acid 1,1-dimethylethyl ester

生成物 1

HCID 13944674[cis-2-[[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]methyl]-1-(4-methoxyphenyl)-4-oxo-3-azetidinyl]carbamic acid 1,1-dimethylethyl ester
収率 59.4%

実験手順

To a mixture of cis-2-hydroxymethyl-1-(4-methoxyphenyl)-4-oxo-3-azetidinyl-carbamic acid 1,1-dimethylethyl ester (5.8 g, 18 mmol), N-hydroxyphthalimide (3.0 g, 18 mmole) and triphenylphosphine (5.7 g, 22 mmol) was added diethyl azodicarboxylate (3.7 g, 21 mmol). The reaction was allowed to stir at room temperature for 0.5 hours whereby the solvent was removed in vacuo. The reaction mixture was dissolved in methylene chloride and again the solvent evaporated to remove any residual THF. A solid precipitates and is washed with a solution of methylene chloride-diethyl ether (1:1). The filtrate is concentrated and the solid precipitate is again washed with a solution of methylene chloride-diethyl ether (1:1) and combined with the previously recovered material to afford 5.0 g of [cis-2-[[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]methyl]-1-(4-methoxyphenyl)-4-oxo-3-azetidinyl]carbamic acid 1,1-dimethylethyl ester (59%). Another 1.9 g (22.3%) of product could be recovered after concentration of the filtrate followed by flash chromatography (ethyl acetate-hexane, 1:9): mp 188°-189° C.; IR (KBr) 3435, 2980, 1795, 1735, 1710, 1500, 1390, 1370, 1160, and 1130 cm-1 ; NMR(CDCl3) δ 1.48 (9H, s), 3.74 (3H, s), 4.40 (1H, br d, J=12 Hz), 4.52 (1H, m), 4.98 (1H, br d, J=12 Hz), 5.44 (1H, m), 6.22 (1H, d, J-9 Hz, exchangeable), 6.82 (2H, d, J=8 Hz), 7.43 (2H, d, J=8 Hz), 7.78 (4H, m).

後処理

  1. customwas removed in vacuo
  2. dissolutionThe reaction mixture was dissolved in methylene chloride
  3. customagain the solvent evaporated
  4. customto remove any residual THF
  5. customA solid precipitates
  6. washis washed with a solution of methylene chloride-diethyl ether (1:1)
  7. concentrationThe filtrate is concentrated
  8. washthe solid precipitate is again washed with a solution of methylene chloride-diethyl ether (1:1)

出典と根拠

ORDレコード
ord-bccfc8cdb9a44e1aaccc94c472c5df93
出典データセット
uspto-grants-1987_11
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04709025

反応ノート

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