Triphenylphosphine → 2-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic acid 2-trimethylsilanyl-ethyl Ester

HRID 272150

Reaktionsgleichung

Reaktionsgleichung von HRID 272150
[CH3:1][O:2][P:3]([CH2:7][CH:8]=[CH:9][CH2:10][CH:11]([CH2:15][C:16]([CH3:33])=[CH:17][CH2:18][C:19]1[C:20]([OH:32])=[C:21]2[C:25](=[C:26]([CH3:30])[C:27]=1[O:28][CH3:29])[CH2:24][O:23][C:22]2=[O:31])[C:12]([OH:14])=[O:13])([O:5][CH3:6])=[O:4].[CH3:34][Si:35]([CH:38](O)[CH3:39])([CH3:37])[CH3:36].C1(P([C:54]2[CH:59]=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[CH3:34][Si:35]([CH3:37])([CH3:36])[CH2:38][CH2:39][O:13][C:12](=[O:14])[CH:11]([CH2:10][CH:9]=[CH:8][CH2:7][P:3]([O:5][CH3:6])([O:2][CH3:1])=[O:4])[CH2:15][C:16]([CH3:33])=[CH:17][CH2:18][C:19]1[C:20]([O:32][CH2:54][CH2:59][Si:35]([CH3:37])([CH3:36])[CH3:34])=[C:21]2[C:25](=[C:26]([CH3:30])[C:27]=1[O:28][CH3:29])[CH2:24][O:23][C:22]2=[O:31]

Komponenten

6

Edukt 4

HCID 11776Triphenylphosphine2×HCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 124478981-(Trimethylsilyl)ethanol2×HCID 765461892-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic Acid

Produkt 1

HCID 765461912-[4-(Dimethoxy-phosphoryl)-but-2-enyl]-6-[6-methoxy-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro-isobenzofuran-5-yl]-4-methyl-hex-4-enoic acid 2-trimethylsilanyl-ethyl EsterAusbeute 85 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

A solution of 2-[4-(dimethoxy-phosphoryl)-but-2-enyl]-6-(4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-yl)-4-methyl-hex-4-enoic acid (160 mg, 0.332 mmol) and trimethylsilylethanol (160 mg, 1.36 mmol) in THF (8.00 mL) was stirred with triphenylphosphine (345 mg, 1.33 mmol). To this solution was added diethyl azodicarboxylate (230 μL, 1.33 mmol) at 0° C. The mixture was allowed to warm to room temperature and stirred for 16 hours. Additional triphenylphosphine (180 mg, 0.692 mmol), trimethylsilylethanol (160 mg, 1.36 mmol), and diethyl azodicarboxylate (115 μL, 0.665 mmol) were added and the reaction mixture was stirred for another 1 day at room temperature. The reaction was worked up by removing the solvents in vacuo and purifying the residue by silica gel chromatography to provide 192 mg (85%) of the product as a clear oil. 1H NMR (300 MHz, CDCl3) δ 0.03 (s, 9H), 0.05 (s, 9H), 0.93-0.96 (m, 2H), 1.20-1.29 (m, 2H), 1.78 (s, 3H), 2.01-2.32 (m, 4H), 2.17 (s, 3H), 2.51 (d, 1H, J=22 Hz), 2.58 (d, 1H, J=22 Hz), 2.50-2.60 (m, 1H), 3.37 (d, 2H, J=7 Hz), 3.72 (d, 6H, J=11 Hz), 3.76 (s, 3H), 4.08 (appt t, 2H, J=8 Hz), 4.30 (appt t, 2H, J=8 Hz), 5.12 (s, 2H), 5.15-5.25 (m, 1H), 5.36-5.63 (m, 2H) ppm; 31P (121.4 MHz, CDCl3) δ 29.3 ppm; MS (m/z) 705.3 [M+Na]+.

Aufarbeitung

  1. stirringthe reaction mixture was stirred for another 1 day at room temperature
  2. customby removing the solvents in vacuo
  3. custompurifying the residue by silica gel chromatography

Quellen und Nachweise

ORD-Eintrag
ord-9c0d8f1114954a13b26c8b65171f09a3
Quelldatensatz
uspto-grants-2008_11
Patentnummer
US07452901B2

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