Phenylacetylene → HCID 13691003, Verbindung

HRID 622135

Reaktionsgleichung

Reaktionsgleichung von HRID 622135
[CH2:1]([N:4]1[CH2:9][CH2:8][N:7]([C:10](=[N:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)[C:11]#[C:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:6][CH2:5]1)[CH:2]=[CH2:3].ClC(Cl)=NC1C=CC(OC)=CC=1.C(N1CCNCC1)C=C.C1(C#C[Li])C=CC=CC=1.C1(C#C)C=CC=CC=1.[C:66]([OH:73])(=[O:72])/[CH:67]=[CH:68]\[C:69]([OH:71])=[O:70]>C(OCC)C.O1CCCC1.C([Li])CCC.CCCCCC.C(Cl)Cl.C(#N)C>[C:66]([OH:73])(=[O:72])/[CH:67]=[CH:68]\[C:69]([OH:71])=[O:70].[C:66]([OH:73])(=[O:72])/[CH:67]=[CH:68]\[C:69]([OH:71])=[O:70].[CH2:1]([N:4]1[CH2:9][CH2:8][N:7]([C:10](=[N:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)[C:11]#[C:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:6][CH2:5]1)[CH:2]=[CH2:3]

Komponenten

13

Edukt 6

HCID 10821PhenylacetyleneHCID 444266Maleic AcidHCID 8064221-AllylpiperazineHCID 13381069(4-Methoxyphenyl)carbonimidoylHCID 13691002HCID 13691002, VerbindungHCID 178506790HCID 178506790, Verbindung

Produkt 1

HCID 13691003HCID 13691003, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 3283Diethyl EtherLösungsmittelHCID 6342AcetonitrileLösungsmittel2×HCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×HCID 8058HexaneLösungsmittelHCID 178418339ButyllithiumLösungsmittel

Reaktionsbedingungen

Temperatur
20 °C

Versuchsvorschrift

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.

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-fdd35117ba814339a44c7e8d5224d812
Quelldatensatz
uspto-grants-1988_09
Patentnummer
US04769366

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