Reaktionsgleichung
[C:1]([C:3]1[CH:10]=[CH:9][C:6]([CH:7]=O)=[CH:5][CH:4]=1)#[N:2].[CH3:11][NH:12][C:13]([NH:15][CH3:16])=[O:14].[C:17]1([P:23](OC2C=CC=CC=2)[O:24]C2C=CC=CC=2)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.CCOCC>C1(C)C=CC=CC=1>[C:1]([C:3]1[CH:10]=[CH:9][C:6]([CH:7]2[N:15]([CH3:16])[C:13](=[O:14])[N:12]([CH3:11])[P:23]2(=[O:24])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[CH:5][CH:4]=1)#[N:2]Komponenten
Versuchsvorschrift
A mixture of 0.12 mole each of 4-cyanobenzaldehyde, 1,3-dimethylurea, and diphenyl phenylphosphonite in 150ml of toluene is warmed at reflux (112°) for 3.5 hr and then stripped to 120°/10mm, leaving a viscous, light yellow oil having 31P nmr peaks at -31.2 and -25.7 ppm (~2:1 areas). Dilution of the oil with ether results in separation of a solid from which two isomers are isolated by fractional crystallization. Isomer I: mp 176°-179°; 31P nmr (CDCl3) -30.6 ppm; 1H nmr δ7.3 (m, 9, aryl), 5.1 (d, 1, J = 22Hz, PCH), 3.0 (s, 3, NCH3), 2.95 (d, 3, J = 8Hz, PNCH3). Isomer II: mp 180°-182.5°; 31P nmr -26.7 ppm; 1H nmr δ7.8 (m, 9, aryl), 4.7 (d, 1, J = 7Hz, PCH), 2.9 (s, 3, NCH3), 2.9 (d, 3, J = 8Hz, PNCH3). There is a sharp depression of the mixed melting point of I and II.
Aufarbeitung
- temperatureis warmed
- temperatureat reflux (112°) for 3.5 hr
- customstripped to 120°
- customleaving a viscous, light yellow oil
- customare isolated by fractional crystallization
Quellen und Nachweise
- ORD-Eintrag
- ord-6247d99495c14c89b6c9f649a4e50a3e
- Quelldatensatz
- uspto-grants-1976_06
- Patentnummer
- US03965127
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