تفاعل #62268

معادلة التفاعل

compound 51

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

allyl alcohol

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product

المردود 72.0%

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

المردود 72.0%

المذيبات

MeOH CHCl3

ظروف التفاعل

المعالجة

1. 1
   درجة الحرارةwas heated
2. 2
   أخرىindicated that reaction
3. 3
   أخرىExcess allyl alcohol was evaporated in vacuo
4. 4
   أخرىto afford the crude compound (52), which
5. 5
   أخرىwas partitioned between NaHCO3 (50 mL) and EtOAc (50 mL)
6. 6
   غسيلThe organic layer was washed with water (3×50 mL), brine (3×50 mL)
7. 7
   تجفيفdried (MgSO4)
8. 8
   تركيزconcentrated in vacuo
9. 9
   أخرىPurification by flash chromatography (CHCl3)

الإجراء التجريبي

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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