4-(Bis(2-chloroethyl)amino)benzaldehyde → HCID 10451067, Verbindung

HRID 1739710

Reaktionsgleichung

Reaktionsgleichung von HRID 1739710
ClCCN(C1C=CC(C=O)=CC=1)CCCl.[Cl:16][CH2:17][CH2:18][N:19]([C:23]1[CH:30]=[CH:29][C:26]([C:27]#[N:28])=[CH:25][CH:24]=1)[CH2:20][CH2:21][Cl:22].N[C:32]1[C:39]([NH2:40])=[CH:38][CH:37]=[CH:36][C:33]=1[C:34]#[N:35]>CO>[Cl:16][CH2:17][CH2:18][N:19]([C:23]1[CH:24]=[CH:25][C:26]([C:27]2[NH:40][C:39]3[CH:32]=[C:33]([C:34]#[N:35])[CH:36]=[CH:37][C:38]=3[N:28]=2)=[CH:29][CH:30]=1)[CH2:20][CH2:21][Cl:22]

Komponenten

5

Edukt 3

HCID 710184-(Bis(2-chloroethyl)amino)benzaldehydeHCID 153358Benzonitrile, 4-(bis(2-chloroethyl)amino)-HCID 224592032,3-Diaminobenzonitrile

Produkt 1

HCID 10451067HCID 10451067, VerbindungAusbeute 40 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel2×

Versuchsvorschrift

A solution of 4-(N,N-bis(2-chloroethyl)amino)-benzaldehyde (IX, n=0) [Anker, R. M., Cook, A. H., "Quinoxaline cyanines. Part IV. Some halogenated styryl derivatives", J. Chem. Soc., 1944 489-4927] (1.32 g, 5.4 mmol) in MeOH (25 mL) was added to a stirred solution of 2,3-diaminobenzonitrile (X) [Stephens, F. F., Bower, J. D., "The preparation of benzimindazoles and benzoxazoles from Schiff's bases. Part II.", J. Chem. Soc., 1950 1722-1726] (0.72 g, 5.4 mmol) in aqueous MeOH (25 mL), immediately followed by a 0.05M aqueous solution of cupric acetate (1.1 mol equiv.). The suspension was brought briefly to the boil and filtered hot. The precipitate was washed with aqueous MeOH and redissolved in conc. HCl. This acid solution was treated with an aqueous solution of Na2S (1.5 mol equiv.) and the precipitated CuS removed by filtration. The filtrate was then basified with conc. ammonia, diluted with water and repeatedly extracted with EtOAc. The combined organic extracts were dried (Na2SO4), filtered and concentrated, and the residue was chromatographed on SiO2. Elution with CH2Cl2 /EtOAc (3:1) yielded 2-[4-(N,N-bis(2-chloroethyl)amino)phenyl]-5-cyanobenzimidazole (XI, n=0) [compound 7 of Table 1] (0.80 g, 40% yield), mp (EtOAc/petroleum ether) 80° C. (dec.). 1H NMR ((CD3)2CO) δ 8.15 (d, J2',3' =9.0 Hz, 2 H, H-2',H-6'), 7.94 (d, J4,6 =1.5 Hz, 1 H, H-4), 7.69 (d, J6,7 =8.5 Hz, 1 H, H-7), 7.50 (dd, J6,7 =8.5 Hz and J4,6 =1.5 Hz, 1 H, H-6), 6.99 (d, J2',3' =9.0 Hz, 2 H, H-3',H-5'), 3.94 (br t, J=7.5 Hz, 4 H, NCH2CH2Cl), 3.83 (br t, J=7.5 Hz, 4 H, NCH2CH2Cl). 13C NMR δ 155.98, 149.75, 143.08, 140.50, 129.62, 126.31, 120.58, 120.13, 118.40, 116.15, 112.93, 105.47, 53.52, 41.43. Anal. (C18H16Cl2N4) C,H,N,Cl.

Aufarbeitung

  1. filtrationfiltered hot
  2. washThe precipitate was washed with aqueous MeOH
  3. dissolutionredissolved in conc. HCl
  4. customthe precipitated CuS removed by filtration
  5. additiondiluted with water
  6. extractionrepeatedly extracted with EtOAc
  7. dry with materialThe combined organic extracts were dried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customthe residue was chromatographed on SiO2
  11. washElution with CH2Cl2 /EtOAc (3:1)

Quellen und Nachweise

ORD-Eintrag
ord-f935838eaad64a7eb6b792f7049b5c50
Quelldatensatz
uspto-grants-1999_10
Patentnummer
US05968933

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