반응 #3194

반응 방정식

1,2-Dihydroxy-4,5-dinitrobenzene

1-chloro-2,3-dihydroxypropane

potassium hydroxide

→

light yellow fluffy solid

수율 67.9%

1,2-Bis(2,3-dihydroxypropyloxy)-4,5-dinitrobenzene

수율 67.9%

용매

1-butanol

반응 조건

후처리

1. 1
   농축The resulting mixture was concentrated under reduced pressure
2. 2
   기타the dark residue was partitioned between 100 mL of THF and 100 mL of brine/50 mL water solution in a 500 mL separatory funnel
3. 3
   기타to separate
4. 4
   추출the aqueous phase was extracted with THF (2×100 mL)
5. 5
   세척The combined THF extracts were washed with brine (2×50 mL)
6. 6
   건조dried over MgSO4
7. 7
   농축concentrated to an oily residue
8. 8
   workup.ADDITIONHere, CH2Cl2 was added very carefully
9. 9
   기타precipitation of the crude product
10. 10
    여과the suspension was filtered with a medium glass fritted funnel
11. 11
    기타air dried for several minutes
12. 12
    온도80 mL of diethyl ether at reflux
13. 13
    여과hot filtered
14. 14
    기타to remove some impurities
15. 15
    workup.DISSOLUTIONThe crude product was dissolved in a mixture of acetone and methanol (sonication may be required)
16. 16
    workup.ADDITION6 grams of deactivated silica gel was added to the orange solution
17. 17
    농축The slurry was concentrated to dryness
18. 18
    기타the orange solid was dried in vacuo for one hour
19. 19
    세척The column was eluted
20. 20
    온도with increasing concentration of methanol (0-10%)
21. 21
    기타After a bright yellow impurity (monoalkylated product) was removed a colorless product
22. 22
    세척to elute (using 8-10% methanol in CHCl3 eluents)
23. 23
    세척Conversely, on TLC the product will elute faster than the bright yellow monoalkylated product
24. 24
    기타The purified dialkylated tetrahydroxy product can be recrystallized from acetone/diethyl ether

실험 절차

8C, FIG. 8. 1,2-Dihydroxy-4,5-dinitrobenzene 8B (5.0 g, 22 mmol) and 1-chloro-2,3-dihydroxypropane (12.1 g, 110 mmol) were refluxed for 48 hours in a solution of potassium hydroxide (4.4 g) in 1-butanol (100 mL) under a nitrogen atmosphere. The resulting mixture was concentrated under reduced pressure, and the dark residue was partitioned between 100 mL of THF and 100 mL of brine/50 mL water solution in a 500 mL separatory funnel. The mixture was allowed to separate and the aqueous phase was extracted with THF (2×100 mL). The combined THF extracts were washed with brine (2×50 mL), dried over MgSO4 and concentrated to an oily residue. Here, CH2Cl2 was added very carefully to insure precipitation of the crude product. After stirring for 15 minutes, the suspension was filtered with a medium glass fritted funnel and air dried for several minutes. The orange solid was taken up in 120 mL of CHCl3 and 80 mL of diethyl ether at reflux and hot filtered to remove some impurities. The crude product was dissolved in a mixture of acetone and methanol (sonication may be required), then 6 grams of deactivated silica gel was added to the orange solution. The slurry was concentrated to dryness and the orange solid was dried in vacuo for one hour. The orange solid was loaded on a packed deactivated silica gel column. The column was eluted starting with neat CHCl3 followed by CHCl3 with increasing concentration of methanol (0-10%). After a bright yellow impurity (monoalkylated product) was removed a colorless product began to elute (using 8-10% methanol in CHCl3 eluents). Conversely, on TLC the product will elute faster than the bright yellow monoalkylated product. The purified dialkylated tetrahydroxy product can be recrystallized from acetone/diethyl ether to yield 2.60 grams (30%) of a light yellow fluffy solid. 1H NMR (d6 -acetone): δ2.95 (bs, 4H, OH), 3.69 (d, 4H, OCH2CH(OH)CH2OH), 4.06 (p, 2H, OCH2CH(OH)CH2 OH), 4.24-4.35 (m, 4H, OCH2CH(OH)CH2OH), 7.72 (s, 2H, Ar--H); 13C NMR (d6 -acetone): δ63.55, 70.89, 72.53, 109.99, 137.22, 152.77. CI MS 349.

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