Реакция #62268

Уравнение реакции

compound 51

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

allyl alcohol

→

product

Выход 72.0%

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

Выход 72.0%

Растворители

MeOH CHCl3

Условия реакции

Обработка

1. 1
   Температураwas heated
2. 2
   Другоеindicated that reaction
3. 3
   ДругоеExcess allyl alcohol was evaporated in vacuo
4. 4
   Другоеto afford the crude compound (52), which
5. 5
   Другоеwas partitioned between NaHCO3 (50 mL) and EtOAc (50 mL)
6. 6
   ПромывкаThe organic layer was washed with water (3×50 mL), brine (3×50 mL)
7. 7
   Сушкаdried (MgSO4)
8. 8
   Концентрированиеconcentrated in vacuo
9. 9
   ДругоеPurification by flash chromatography (CHCl3)

Методика

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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