반응 #1328404

반응 방정식

Epichlorohydrin

potassium hydroxide

sodium sulfate

→

glycidyl ether

수율 65.0%

반응 조건

후처리

1. 1
   기타equipped with a reflux condenser
2. 2
   온도with prior cooling of the reaction mixture to 20–25° C
3. 3
   기타After the termination of the reaction
4. 4
   여과the unreacted solids were filtered off
5. 5
   추출The filtrate was extracted with diethyl ether
6. 6
   세척washed with distilled water until the washed water
7. 7
   건조The organic layer was dried over anhydrous magnesium sulfate
8. 8
   workup.ADDITIONtreated with activated charcoal
9. 9
   여과filtered
10. 10
    기타The 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
    기타were collected
14. 14
    기타the solvents were evaporated
15. 15
    기타to yield an oily residue that
16. 16
    기타was crystallized from a mixture of acetone and 2-propanol in a ratio of 3:1 by volume
17. 17
    여과The crystals were filtered off
18. 18
    세척washed with 2-propanol

실험 절차

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.

출처