Amines tripropylamine

Furin et al. [90] have conducted the electrochemical fluorination of a series of amines, tripropylamine, tributylamine and triamylamine, and a series of enamines formed by the reaction of hexafluoropropene, its dimers and trimers with the secondary amines dipropylamine, dibutylamine and dial-lylamine. As well as the anticipated saturated perfluoroanalogues of the starting materials by-products resulting from structural breakdown were also produced. 

Similarly,both Meinert and Gambaretto, with their respective co-workers [80, 172, 175], have invoked this mechanism to explain the formation of partially fluorinated products in ECF reactions of the amines, tripropylamine, AT-methyl-morpholine, and a series of a,co-dimorpholino- and dipiperidino-alkanes. The selective order in which the hydrogens were substituted in these molecules was said to be consistent with that expected for the mechanism in that carbon atoms nearest to oxygen (in the morpholine rings), where the electron density is greatest, were the first to react, and those nearest to the quaternised nitrogen the last, not in a random order as might be expected in a radical mechanism. 

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Particularly, diisopropylamine and dibutylamine showed high o/t/io-selectivity. Addition of tertiary amines, such as triethylamine, tripropylamine, and tripentylamine was ineffective in the"ortAo-selectivity. In this system A-bromoamine never generates. 

In reactions between Lewis acids and bases such as amines and boranes or boron halides, bulky substituents on one or both species can affect the stability of the acid-base adduct. Perhaps the most straightforward type of effect is simple steric hindrance between substituents on the nitrogen atom and similar large substituents on the boron atom. Figure 9.3 is a diagrammatic sketch of the adduct between molecules of tripropylamine and triethylborane. This phenomenon is known as front or F-... 

The heat of solution of tripropylamine and of dipropylamine in HF was determined by using the same cell with some slight modifications. Instead of using the sample capsule, the amine was introduced in the empty lower trough which was then closed with a Teflon sphere. Afterwards, the HF was poured into the volume above the sphere. A thin Voltalef grease layer on the sphere ensured a tight seal. 

The preparation of tertiary amines by reductive alkylation of ammonia appears to find only limited application. Triethylamine and tripropylamine were prepared by hydrogenation of acetaldehyde and propionaldehyde, respectively, in the presence of ammonia over platinum catalyst.38 A high yield (84.1% by GC) of trinonylamine was... 

Leland and Powell [53] also studied ECL obtained from reaction of [(bpy)3Ru] + with tripropylamine. There is an inverse relationship between the first ionization potential of the amine and ECL intensity and therefore [(bpy)3Ru] + ECL intensity can be ordered as follows tertiary > secondary > primary. 

Anodic oxidation of primary and tertiary [193] aliphatic amines in acetonitrile containing a small amount of residual water produced several compounds, including aldehydes. Tripropylamine is oxidized according to Eq. (51) ... 

Catalytic transalkylation reactions of tertiary amines have been described with Os3(CO)12 (398-400), Ru3(CO),2 (398-401), Ir4(CO)12 (398), and Os3(CO)10S (402). In the catalytic alkyl exchange between triethylamine and tripropylamine... 

Die anodische Oxidation sek. Amine an eincr Silber-Anode liefert neben Nitrilen und Al-koholen etwas Aldehyd141. Arbeitet man an einer Platin- und besonders an einer Gra-phit-Elektrode, sind die Ausbeuten hoher142 (z.B. 25% Propanal aus Dipropylamin). Fiir die Bildung eines Aldehyds ist die Anwesenheit von Wasser erforderlich. Bei Zusatz von Dideuterooxid entsteht aus Tripropylamin 2-Deutero-propanal (zum Mechanismus s.Lit.142, keine Ausbeuteangabe). 

Tert. Amine werden an Platin- bzw. Graphit-Elektroden in mittleren Ausbeuten zu Alde-hyden oxidiert173 (an Silber-Anoden erhalt man niedrigere Ausbeuten). Die Anwesenheit von Wasser ist zur Bildung der Aldehyde erforderlieh. Auf diese Weise erhalt man u. a. aus Tripropylamin.48% Propanal (Aeetonitril/10% Wasser 1,4 V) bzw. aus Tribenzylamin 36% Benzaldehyd (Aeetonitril 1,3 V)173. 

However, tertiary amines catalyse the dimerization of ketenes, so that only those with little tendency to dimerize can be obtained by this route. Diphenyl-ketene is formed almost quantitatively by removing hydrogen chloride from diphenylacetyl chloride with tripropylamine.171... 

The chemiluminescence intensity from the reaction of amines with tris(2,2 -bipyridyl)ruthenium(III) is generally in the order tertiary > secondary > primary, but no definitive mechanisms have been elucidated. Derivatives of tris(2,2 -bipyridyl)ruthenium(II) have been introduced as labels for immunoassay or DNA probes (e.g., (13)). The use of chemiluminescent labels is clearly advantageous due to their nonradio-active nature and they can be quantified at sub-pi-comolar levels via oxidation in the presence of tripropylamine. 

Ruthenium complexes need a strong reductant or oxidant for chemiluminescent reactions of type (b) and (c) above. These reactive compounds are usually radicals derived from simple organic compounds such as amines, amino acids, the reduced form of )S-nicotinamide adenine dinucleotide (NADH), and some antibiotics. Analytical procedures have been developed for some of these compounds on this basis, e.g., for tripropylamine, which gives a detection limit of 2 X 10 moll. ... 

TMA= trimethylamine, TEtA= triethylamine, TPA = tripropylamine, TBA= tributylamine, THA= trihexyl amine, and TOA= trioctylamine. 

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