N-Hydroxyphthalimide → (E,E,E)-N-(3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenyloxy)phthalimide

HRID 1066030ノート

反応式

HRID 1066030 の反応式
[OH:1][N:2]1[C:6](=[O:7])[C:5]2=[CH:8][CH:9]=[CH:10][CH:11]=[C:4]2[C:3]1=[O:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.[CH2:44]([CH2:54][C:55](=[CH:57][CH2:58][CH2:59]/[C:60](=[CH:62]/[CH2:63]O)/[CH3:61])[CH3:56])/[CH:45]=[C:46](/[CH2:48][CH2:49][CH:50]=[C:51]([CH3:53])[CH3:52])\[CH3:47]>C1COCC1>[CH3:61]/[C:60](/[CH2:59][CH2:58]/[CH:57]=[C:55](\[CH3:56])/[CH2:54][CH2:44]/[CH:45]=[C:46](\[CH3:47])/[CH2:48][CH2:49][CH:50]=[C:51]([CH3:53])[CH3:52])=[CH:62]\[CH2:63][O:1][N:2]1[C:3](=[O:12])[C:4]2=[CH:11][CH:10]=[CH:9][CH:8]=[C:5]2[C:6]1=[O:7]

参加物

6

反応物 4

HCID 10665N-HydroxyphthalimideHCID 11776Triphenylphosphine2 回HCID 5462977Diethyl azodicarboxylate2 回HCID 865915033,7,11,15-Tetramethyl-2,6,10,14-hexadecatetraen-1-ol

生成物 1

HCID 15524010(E,E,E)-N-(3,7,11,15-tetramethyl-2,6,10,14-hexadecatetraenyloxy)phthalimide収率 88%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of N-hydroxyphthalimide (1.12 g, 6.88 mmol), triphenylphosphine (1.81 g, 6.88 mmol) and diethylazodicarboxylate (1.19 mL, 7.57 mmol) in anhydrous THF (60 mL) was treated with geranylgeraniol (2.0 g, 6.88 mmol) and the resulting mixture was stirred for 18 h at rt. After addition of triphenylphosphine (0.905 g, 3.44 mmol) and diethylazodicarboxylate (0.595 mL, 3.78 mmol), the mixture was stirred at rt for another 24 h. The solvent was evaporated and the residue was purified on 230-400 mesh silica gel (Macherey-Nagel Silica Gel 60 Art. Nr. 81538) eluting with CH2Cl2-hexane (6:4) and collecting 10 mL fractions. The appropriate fractions were combined and evaporated to give the intermediate 20 (2.63 g, 88%) as a white solid: mp 40-41° C.; 1H-NMR (CDCl3, 80 Mhz) δ 1.58 (s, 9H, 3×CH3), 1.67 (s, 3H, CH3), 1.71 (s, 3H, CH3), 2.03 (m, 12H, 6×CH2), 4.71 (d, 2H, J=7.2 Hz, CH2), 5.07 (br, 3H, 3×CH), 5.52 (t, 1H, J=7.2 Hz, CH), 7.73 (m, 4H, Ar); Anal. Calcd for C28H37NO3 (MW 435.3); C, 77.26; H, 8.50; N, 3.22. Found: C, 77.38; H, 8.38; N, 3.04.

後処理

  1. stirringthe mixture was stirred at rt for another 24 h
  2. customThe solvent was evaporated
  3. customthe residue was purified on 230-400 mesh silica gel (Macherey-Nagel Silica Gel 60 Art. Nr. 81538)
  4. washeluting with CH2Cl2-hexane (6:4)
  5. customcollecting 10 mL fractions
  6. customevaporated

出典と根拠

ORDレコード
ord-928d1de6dc6447b089465f4a55cecdc5
出典データセット
uspto-grants-2001_06
特許番号
US06242433B1

反応ノート

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