反应详情

温度

20 °C

3-(4-Allyl-1-piperazinyl)-3-(4-methoxyphenylimino)-1-phenyl-1-propyne can be prepared in the following manner: to a solution of N-(dichloromethylene)-p-anisidine (59 g) in ethyl ether (600 cc), a solution of 1-allylpiperazine (72 g) in tetrahydrofuran (450 cc) is added at a temperature of about 20° C. and in the course of 20 minutes, and stirring is continued for a further 30 minutes at a temperature of about 20° C. The precipitate which is formed is separated by filtration. The solution thereby obtained is added in the course of 3 minutes, at a temperature of about -65° C., to a solution of phenylethynyllithium in tetrahydrofuran (600 cc), obtained by reacting phenylacetylene (30.6 g) dissolved in tetrahydrofuran (600 cc) with a 1.6M solution (187 cc) of n-butyllithium in hexane at a temperature of about 20° C. The reaction mixture is allowed to warm up to a temperature of about 20° C. and then poured onto crushed ice (500 g). The aqueous phase is decanted and washed with ethyl ether (3×500 cc). The ether fractions are combined, washed with distilled water (250 cc), dried over anhydrous magnesium sulphate, filtered and then evaporated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C. The residue obtained is dissolved in methylene chloride (200 cc) and the solution is poured into silica (2 kg) contained in a column 8 cm in diameter. Elution is performed with mixtures of methylene chloride and ethyl acetate (4×1 liter containing, respectively, 10%, 20%, 30% and 40% of ethyl acetate); the corresponding eluates are rejected. Elution is then performed with a mixture of methylene chloride and ethyl acetate (50:50 by volume) (3 liters); the corresponding eluate is evaporated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C. The residue obtained is dissolved in boiling acetonitrile (175 cc); maleic acid (35 g) dissolved in boiling acetonitrile (350 cc) is added to the solution. After the mixture is cooled to a temperature of about 20° C., the precipitate formed is separated by filtration. After recrystallization in acetonitrile (550 cc), 3-(4-allyl-1-piperazinyl)-3-(4-methoxyphenylimino)-1-phenyl-1-propyne dimaleate (58.3 g), m.p. 180° C., is thereby obtained.

1. customThe precipitate which is formed
2. customis separated by filtration
3. customThe solution thereby obtained
4. customobtained
5. additionpoured
6. customThe aqueous phase is decanted
7. washwashed with ethyl ether (3×500 cc)
8. washwashed with distilled water (250 cc)
9. dry with materialdried over anhydrous magnesium sulphate
10. filtrationfiltered
11. customevaporated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
12. customThe residue obtained
13. additionthe solution is poured into silica (2 kg)
14. washElution
15. additioncontaining
16. washElution
17. additionis then performed with a mixture of methylene chloride and ethyl acetate (50:50 by volume) (3 liters)
18. customthe corresponding eluate is evaporated to dryness under reduced pressure (20 mm Hg; 2.7 kPa) at 40° C
19. customThe residue obtained
20. dissolutionis dissolved
21. additionis added to the solution
22. temperatureAfter the mixture is cooled to a temperature of about 20° C.
23. customthe precipitate formed
24. customis separated by filtration
25. customAfter recrystallization in acetonitrile (550 cc)