Reaktion #62268

Reaktionsgleichung

compound 51

4-(4-hydroxymethyl-2-methoxy-5-nitrophenoxy)butyric acid

allyl alcohol

→

product

Ausbeute 72.0%

4-(4-hydroxymethyl-2-methoxy-5-nitrophenoxy)butyric acid allyl ester

Ausbeute 72.0%

Lösungsmittel

MeOH CHCl3

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturwas heated
2. 2
   Sonstigeindicated that reaction
3. 3
   SonstigeExcess allyl alcohol was evaporated in vacuo
4. 4
   Sonstigeto afford the crude compound (52), which
5. 5
   Sonstigewas partitioned between NaHCO3 (50 mL) and EtOAc (50 mL)
6. 6
   WaschenThe organic layer was washed with water (3×50 mL), brine (3×50 mL)
7. 7
   Trocknendried (MgSO4)
8. 8
   Einengenconcentrated in vacuo
9. 9
   SonstigePurification by flash chromatography (CHCl3)

Vorschrift

A mixture of compound 51 (7.00 g 24.50 mmol), allyl alcohol (80 mL) and p-tosic acid (742 mg, 3.90 mmol) was heated at reflux under a N2 atmosphere for 4 hOURS, at which time TLC (2% MeOH/CHCl3) indicated that reaction had gone to completion. Excess allyl alcohol was evaporated in vacuo to afford the crude compound (52), which was partitioned between NaHCO3 (50 mL) and EtOAc (50 mL). The organic layer was washed with water (3×50 mL), brine (3×50 mL) and then dried (MgSO4), and concentrated in vacuo. Purification by flash chromatography (CHCl3) yielded the product as an orange-brown solid (5.78 g, 72%). MP=73-75° C. 1H NMR (250 MHz, CDCl3) δ 7.70 (s, 1H), 7.16 (s, 1H), 6.00-5.84 (m, 1H), 5.36-5.21 (m, 2H), 4.94 (d, J=6.3 Hz), 4.62-4.59 (m, 2H), 4.13 (t, J=6.2 Hz, 2H), 3.97 (s, 3H), 2.67-2.56 (m, 3H), 2.20 (pent, J=6.7 Hz, 2H). 13C NMR 5173.1 (C12), 154.7 (Cquat.), 147.3 (Cquat.), 139.6 (Cquat.), 133.2 (Cquat.), 132.4 (C14), 118.7 (C15), 111.1 (C6), 109.9 (C3), 68.6 (C9), 65.6 (C13), 62.7 (C1), 56.7 (C8), 30.9 (C11), 24.6 (C10). IR (cm−1) 3329.4, 3100.0, 2972.1, 1734.5, 1647.9, 1577.4, 1508.1, 1281.5, 932.8, 884.0, 815.8, 758.2, 662.2. MS (M+ —OH) 308. Anal. Calcd for C16H19NO7: C, 55.38; H, 5.89; N, 4.31. Found: C, 52.41; H, 5.86; N, 4.67.

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