2,4-Dichlorobenzylidenemalononitrile → 2-Aminomethyl-1-(2,4-dichloro-phenyl)-10H-9-oxa-4-aza-phenanthren-3-ylamine

HRID 392184

Reaktionsgleichung

Reaktionsgleichung von HRID 392184
[Cl:1][C:2]1[CH:13]=[C:12]([Cl:14])[CH:11]=[CH:10][C:3]=1[CH:4]=[C:5]([C:8]#[N:9])[C:6]#[N:7].[O:15]1[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:18](=O)[CH2:17][CH2:16]1.C([O-])(=O)C.[NH4+:30]>C1(C)C=CC=CC=1>[NH2:9][CH2:8][C:5]1[C:6]([NH2:30])=[N:7][C:18]2[C:19]3[C:24](=[CH:23][CH:22]=[CH:21][CH:20]=3)[O:15][CH2:16][C:17]=2[C:4]=1[C:3]1[CH:10]=[CH:11][C:12]([Cl:14])=[CH:13][C:2]=1[Cl:1]

Komponenten

5

Edukt 3

HCID 180892,4-DichlorobenzylidenemalononitrileHCID 68110ChromanoneHCID 517165Ammonium Acetate

Produkt 1

HCID 101725512-Aminomethyl-1-(2,4-dichloro-phenyl)-10H-9-oxa-4-aza-phenanthren-3-ylamineAusbeute 7,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
118 °C

Versuchsvorschrift

2-(2,4-dichloro-benzylidene)-malononitrile (95 mg, 0.4 mmol), chroman-4-one (59 mg, 0.4 mmol), ammonium acetate (78 mg, 1.2 mmol), and toluene (4 ml) were placed in a reaction vial and shaken overnight at 118° C. Upon cooling and filtration, the solution was evaporated in a vacuum zentrifuge (45° C.) and the residue was purified by automated, preparative HPLC (YMC CombiPrep C18 column 50×20 mm, solvent gradient 5-95% CH3CN in 0.1% TFA (aq) over 6.0 min, λ=230 nm, flow rate 40 ml/min). The obtained solid (28 mg) was dissolved in THF (1 ml) and added, under an atmosphere of Argon, to a cooled (0° C.) suspension of 100 mg of Lithium aluminum hydride in 1 ml THF in a reaction vial. The reaction mixture was shaken first for 2 h at r.t. and subsequently for 4 h at 40° C. Upon cooling, water was added carefully and the mixture was filtered. The filtrate was evaporated in a vacuum zentrifuge (45° C.). Purification of the re-dissolved (DMF, 1 ml) residue by automated, preparative HPLC (YMC CombiPrep C18 column 50×20 mm, solvent gradient 5-95% CH3CN in 0.1% TFA(aq) over 6.0 min, λ=230 nm, flow rate 40 ml/min) gave 11 mg (7%) of the title compound, MS: m/e=371.9 (M+H+), as a solid.

Aufarbeitung

  1. temperatureUpon cooling
  2. filtrationfiltration
  3. customthe solution was evaporated in a vacuum zentrifuge (45° C.)
  4. customthe residue was purified by automated, preparative HPLC (YMC CombiPrep C18 column 50×20 mm, solvent gradient 5-95% CH3CN in 0.1% TFA (aq) over 6.0 min, λ=230 nm, flow rate 40 ml/min)
  5. dissolutionThe obtained solid (28 mg) was dissolved in THF (1 ml)
  6. additionadded, under an atmosphere of Argon
  7. temperatureto a cooled
  8. addition(0° C.) suspension of 100 mg of Lithium aluminum hydride in 1 ml THF in a reaction vial
  9. stirringThe reaction mixture was shaken first for 2 h at r.t. and subsequently for 4 h at 40° C
  10. temperatureUpon cooling
  11. additionwater was added carefully
  12. filtrationthe mixture was filtered
  13. customThe filtrate was evaporated in a vacuum zentrifuge (45° C.)
  14. customPurification of the
  15. dissolutionre-dissolved (DMF, 1 ml) residue by automated, preparative HPLC (YMC CombiPrep C18 column 50×20 mm, solvent gradient 5-95% CH3CN in 0.1% TFA(aq) over 6.0 min, λ=230 nm, flow rate 40 ml/min)

Quellen und Nachweise

ORD-Eintrag
ord-9c795eebabe74ca6852ff04bce4d7979
Quelldatensatz
uspto-grants-2004_10
Patentnummer
US06800650B2

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