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

HRID 1066030Notes

Reaction equation

HRID 1066030 reaction equation
[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]

Participants

6

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-928d1de6dc6447b089465f4a55cecdc5
Source dataset
uspto-grants-2001_06
Patent number
US06242433B1

Reaction notes

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