3- Diisopropylamino

Techert S, Zachariasse KA (2004) Structure determination of the intramolecular charge transfer state in crystalline 4-(diisopropylamino)benzonitrile from picoseconds X-ray diffraction. J Am Chem Soc 126 5593-5600... 

N,N-Dimethylacetamide dimethylacetal 4-Diisopropylamino-2-phenyl-2-pyridin-2-yl-butyramide Lithium aluminum hydride... 

Hydrogenation of 4-diisopropylamino-2-phenyl-2-pyridin-2-yl-butyramide over platinum oxide catalyst reduced the pyridine ring to a piperidine to give 4-diisopropylamino-2-phenyl-2-piperidin-2-yl-butyramide as a white solid, MP 107°-108°C. Structure was confirmed by proton, carbon-13-NMR spectra and by elemental analysis. 

A vigorously stirred suspension of 0.2 to 1 mole of sodium amide in 200 ml of xylene, in which 0.1 moles of 4-diisopropylamino-2,2-diphenyl-butyronitrile were dissolved, was boiled for about twelve hours. After this the excess of sodium amide was decomposed with water and the xylene layer was separated, washed with water and extracted with dilute hydrochloric acid. This acidic extract was made strongly alkaline with a concentrated aqueous sodium hydroxide solution and the separated base was extracted with ether. After drying, the ether evaporated and the l,l-diphenyl-3-diisopropylamino-propane was distilled in vacuum. The oil obtained can be dissolved in ether and after introduction of hydrochloric acid gas the hydrochloric acid addition salt precipitates. It shows a melting point of 171°C. 

The acid extract is made alkaline and extracted with toluene. The toluene solution is washed with water and dried and the solvent is evaporated. Distillation of the residue gives 4-diisopropylamino-2-phenyl-2-(2-pyridyl)-butyronitrile boiling at about 145°-160°C at 0.3 mm pressure. 

A solution of 27.2 parts of 4-diisopropylamino-2-phenyl-2-(2-pyridyl)butyronitrile in 200 parts of concentrated sulfuric acid is heated on a steam bath for 4 hours and then poured onto ice. The resultant mixture is alkalized with 10 N sodium hydroxide, and the pH is adjusted to 6 by the addition of acetic acid. The solution is washed once with benzene before it is alkalized again with 10 N sodium hydroxide solution. The resultant mixture is extracted with benzene, and the solvent is evaporated from the benzene extract. The resultant residue is dissolved in ethanol and the alcohol solution is treated with charcoal and filtered. Evaporation of the solvent leaves a residue which is recrystallized from hexane to give 4-diisopropylamino-2-phenyl-2-(2-pyridyl)butyramide melting at about 94.5-95°C. It may be converted to the phosphate with phosphoric acid. 

Ausnahmen sind die Synthesen des 4-Diisopropylamino-2,3-dimethyl-1 -phenyl-5-py-razolon aus Aceton und 4-Amino-2,3-dimethyl-l-phenyl-5-pyrazolon14 und die von N,N-Dialkyl-anilinen durch reduktive Aminierung von Alkanonen in Form ihrer Acetale mit Anilinen13 (vgl. S. 452). So erhalt man z.B. N,N-Diisopropyl-anilin aus 2,2-Dimethoxy-propan und Anilin iiber Palladium/Kohle (5%) (120 bar/50°) zu 56% d.Th. Mit zunehmender Kettenlange der Acetale sind die Reaktionsbedingungen auf 135-155° und 100 bar zu steigern15. 

By reaction with acid, the /+-diisopropylamino-2,2-dlphenylbutyronltrile (III) is partially hydrolyzed to 4-diisopropylamino-2,2-diphenylbutyramide (IV) v/hich is purified by recrystallization. 

Methyl 4-diisopropylamino-5-oxo-6-phenyl-2,5-dihydro-l,2,3-triazine-2-carboxylate CH2CI2 402 (3.86) 1979CB1535... 

---