Methanol → 5,8-Dihydro-5,8-epoxynaphtho[2,3-d]-1,3-dioxole

HRID 28788

反応式

HRID 28788 の反応式
[O:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[Li][CH2:7][CH2:8][CH2:9][CH3:10].[CH3:11][OH:12].[OH2:13].[C:14]1([CH3:20])C=CC=CC=1>>[O:1]1[CH:5]2[CH:14]=[CH:20][CH:2]1[C:3]1[C:4]2=[CH:10][C:9]2[O:12][CH2:11][O:13][C:8]=2[CH:7]=1

参加物

6

反応物 5

HCID 887MethanolHCID 962WaterHCID 1140TolueneHCID 8029FuranHCID 178418339Butyllithium

生成物 1

HCID 147704315,8-Dihydro-5,8-epoxynaphtho[2,3-d]-1,3-dioxole収率 54%

反応条件

温度
-78 °C

実験手順

To 3,4-dibromobenzo-1,3-dioxolane (1.54 g, 5.50 mmol) and furan (4 g, 58.8 mmol) in PhMe (55 mL) at −78° C. was added BuLi (2.2 mL, 2.5M in hexanes, 5.5 mmol) dropwise. The reaction was stirred for two hours at −78° C. and the allowed to warm to rt. After 3 hours, MeOH (2 mL) was added and the reaction mixture was poured into water. The organic layer was separated and the aqueous layer was extracted three times with Et2O. The combined organic layers were washed with brine, dried over MgSO4, and concentrated. Recrystallization from hexanes gave 25 (560 mg, 54%) as white crystals). Rf=0.47 on silica gel (30% ethyl acetate:hexanes); mp 111-112° C. (Et2O); IR (KBr, cm−1) 2895, 1455, 1292, 1138, 1038, 1014, 848; 1H NMR (400 MHz, CDCl3) δ 7.02 (2H, dd, J=0.9, 0.9 Hz), 6.82 (2H, s), 5.92 (1H, d, J=1.5 Hz), 5.87 (1H, d, J=1.5 Hz), 5.62 (2H, s); 13C NMR (400 MHz, CDCl3) δ 144.3, 143.3, 103.9, 101.1, 82.4. HRMS calcd for C11H02 (M+): 188.0473. Found: 188.0463.

後処理

  1. temperatureto warm to rt
  2. waitAfter 3 hours
  3. customThe organic layer was separated
  4. extractionthe aqueous layer was extracted three times with Et2O
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customRecrystallization from hexanes

出典と根拠

ORDレコード
ord-447854b9ddb2429c8ad5ae9ef463a310
出典データセット
uspto-grants-2008_09
特許番号
US07420003B2

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