反応 #1328404

反応方程式

Epichlorohydrin

potassium hydroxide

sodium sulfate

→

glycidyl ether

収率 65.0%

反応条件

後処理

1. 1
   その他equipped with a reflux condenser
2. 2
   温度with prior cooling of the reaction mixture to 20–25° C
3. 3
   その他After the termination of the reaction
4. 4
   ろ過the unreacted solids were filtered off
5. 5
   抽出The filtrate was extracted with diethyl ether
6. 6
   洗浄washed with distilled water until the washed water
7. 7
   乾燥The organic layer was dried over anhydrous magnesium sulfate
8. 8
   workup.ADDITIONtreated with activated charcoal
9. 9
   ろ過filtered
10. 10
    その他The solvents were removed
11. 11
    workup.ADDITIONa mixture of acetone and hexane in a ratio of 1:4 by volume as the eluant
12. 12
    workup.ADDITIONFractions containing the product
13. 13
    その他were collected
14. 14
    その他the solvents were evaporated
15. 15
    その他to yield an oily residue that
16. 16
    その他was crystallized from a mixture of acetone and 2-propanol in a ratio of 3:1 by volume
17. 17
    ろ過The crystals were filtered off
18. 18
    洗浄washed with 2-propanol

実験手順

Epichlorohydrin (160 ml, 2 mol, from Aldrich, Milwaukee, Wis.) and 4-diethylaminosalicylaldehyde 9-fluorenone azine (50 g, 0.14 mol, prepared as described above) were added to a 250 ml 3-neck round bottom flask equipped with a reflux condenser, a thermometer, and a mechanical stirrer. The reaction mixture was stirred vigorously at 35–40° C. for 7 hours. During this time, 26.8 g (0.4 mol) of powdered 85% potassium hydroxide and 6.8 g (0.05 mol) of anhydrous sodium sulfate (Na2SO4) were added in three portions with prior cooling of the reaction mixture to 20–25° C. After the termination of the reaction, the mixture was cooled to room temperature, and the unreacted solids were filtered off. The filtrate was extracted with diethyl ether and washed with distilled water until the washed water had a neutral pH. The organic layer was dried over anhydrous magnesium sulfate, treated with activated charcoal, and filtered. The solvents were removed and the residue was subjected to column chromatography (silica gel, grade 62, 60–200 mesh, 150 Å, Aldrich) using a mixture of acetone and hexane in a ratio of 1:4 by volume as the eluant. Fractions containing the product were collected, and the solvents were evaporated to yield an oily residue that was crystallized from a mixture of acetone and 2-propanol in a ratio of 3:1 by volume. The crystals were filtered off and washed with 2-propanol to yield 35 g (65%) of glycidyl ether of 4-diethylaminosalicylaldehyde 9-fluorenone azine. The melting point was found to be 135.5–136.6° C. The 1H NMR spectrum (100 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 9.1 (s, 1H, CH═N); 8.8 (m, 1H, Ar); 8.2 (d, 1H, 6-H of 1,2,4-subst. Ph); 8.1–7.2 (m, 7H, Ar); 6.5 (d, 1H, 5-H of 1,2,4-subst. Ph); 6.2 (s, 1H, 3-H of 1,2,4-subst. Ph); 4.5–4.2 (dd, 1H, one of OCH2); 4.2–4.0 (dd, 1H, one of OCH2); 3.6–3.3 (m, 5H, CH2N, CH); 3.0 (m, 1H, one of CH2 of oxirane); 2.8 (dd, 1H, one of CH2 of oxirane); and 1.2 (t, 6H, CH3). An elemental analysis yielded the following results in weight percent: C, 76.08; H, 6.31; N, 9.77, which compared with calculated values for C27H27N3O2 in weight percent: C, 76.21; H, 6.40; N, 9.87.

出典