Tertiary aliphatic amines

The results of catalysis with primary and secondary amines indicate that ruthenium carbonyl forms active catalysts in aqueous ethylenediamines, diethanolamine, pyrrolidine and piperidine solutions. No detectable amounts of hydrogen are formed with aromatic and unsaturated primary and secondary amines under the present WGS conditions. Tertiary amines were found not to initiate catalyst systems as active as those produced by the best primary and secondary amines. Aliphatic tertiary amines exhibited only weak activity. 

Nitrous acid does not react with aliphatic tertiary amines, such as triethyl-amine, (CaHj)aN, nor does it usually react with aromatic tertiary amines such as triphenylamine, (CaHj)aN, which contain three aryl groups. 

Aliphatic tertiary amines have been prepared by the desulfurization of thenyl-dialkylamines obtained from the Leuckart reaction with 2-... 

The reaction may be accelerated by using an aliphatic tertiary amine catalyst, usually within the range of 0.2 to 2j0% based on the total weight of the reactants. A stirred, jacketed re-... 

The well-known photopolymerization of acrylic monomers usually involves a charge transfer system with carbonyl compound as an acceptor and aliphatic tertiary amine, triethylamine (TEA), as a donor. Instead of tertiary amine such as TEA or DMT, Li et al. [89] investigated the photopolymerization of AN in the presence of benzophenone (BP) and aniline (A) or N-methylaniline (NMA) and found that the BP-A or BP-NMA system will give a higher rate of polymerization than that of the well-known system BP-TEA. Still, we know that secondary aromatic amine would be deprotonated of the H-atom mostly on the N-atom so we proposed the mechanism as follows ... 

The electron transfer step is typically fast and efficient. Griller et a/.292 measured absolute rate constants for decay of benzophenone triplet in the presence of aliphatic tertiary amines in benzene as solvent. Values lie in die range 3-4x109 M 1 s 1 and quantum yields are close to unity. 

Pappalardo, J.A. The Acyclic Aliphatic Tertiary Amines Macmillan NY, 1965, p. 14. 

Certain quaternary ammonium salts will alkylate [Co (DMG)2py] . The addition of PhCH2NMc3 I to a solution of the complex in methanol gives the PhCH2Co complex in 45% yield. The reaction works more slowly with dimethylpiperidinium iodide to give the CH3—Co complex 15). There is no alkylation with tertiary amines alone 164), but in the presence of equimolar amounts of dimethylacetylenedicarboxylate certain aliphatic tertiary amines can alkylate [Co (DMG)2py] in methanol solution. The reaction also produces the enamine derivative of a maleic ester, and the mechanism appears to involve addition of the amine to the triple bond to form an ammonium salt, which can then attack the Co(I) derivative (75). 

The reaction of 1,4-disubstituted tetrazoliums (149) with aliphatic tertiary amines such as triethylamine leads via deprotonation to 150 followed by ring opening to form a carbodiimide (74) with the loss of nitrogen (Scheme 20).237,238 Under the same conditions, 1,4,5-trisubstituted... 

Primary amine-containing polymeric particles are available from a number of manufacturers and have either aliphatic or aryl amine groups on their surface. Occasionally, a particle type may have secondary or tertiary amines present, but these should be avoided for covalent coupling, as primary amines typically give better reaction yields than secondary amines and tertiary amines are unreactive. 

This kinetic feature is observed by using primary and secondary amines, both aromatic and aliphatic. Tertiary amines263 (and other substances unable to produce substitution products such as 2-hydroxypyridine264) may act as a catalyst in apolar solvents, in a series of runs carried out without changing the initial concentration value of substrate and of amines, it was found that the addition of tertiary amines enhances kabs values. 

Olefin 6. Tertiary/secondary amine-aliphatic carbon... 

Quinine has two potentially basic centres, a cyclic tertiary amine at a ring junction, and one in a quinoline ring system. pAfa 8.5 is reasonably basic, and this is most likely from the aliphatic tertiary amine. We need to convince ourselves that the quinoline nitrogen is less basic. This is true. As far as reactivity is concerned, a quinoline ring system behaves as two separate parts, either pyridine or benzene, depending upon the reagent. Thus, quinoline has pATa very similar to that of pyridine, i.e. around 5. 

Electrochemical oxidation of aliphatic tertiary amines in acetonitrile together with compounds having weakly acidic hydrogens, such as dimethyl malonate, leads to addition of the malonate anion to the immonium cation intermediate. 2,4,6-Collidine is added to combine with protons, which are released during reaction [90],... 

M. Miocque u. J.P. Duclos, Chim. Ther. 4, 363-380 (1969) , Halogenated Aliphatic Tertiary Amines in Organic Synthesis". 

A large cationic radius generally increases the nucleophilic reactivity of the anion in an ion pair. A small cationic radius results in stronger electrostatic attraction and lesser reactivity of the anion. Catalysts with the active site separated from the polymer backbone by an aliphatic chain have higher activity than those prepared by quatemi-zation of a chloromethylpolystyrene with a tertiary amine or tertiary phosphine, leaving only one carbon atom between the active site and the aromatic ring. 

A number of other heterocycllcs have been similarly studied and shown by H nmr, to produce quaternary ammonium salts with living polyTHF.2- Moreover, their rates of reaction are a direct function of their basicities, the following order of reactivities being observed ethyl pyridine > pyridine > isoquinoline > quinoline > acridine. Aliphatic tertiary amines also react in the same way the order of reactivities was found to be triethylame > tributylamlne > dlethylanillne. In all cases studied, the quaternary ammonium salt once formed did not exchange with any excess oxonium lone. 

TMA is a volatile aliphatic tertiary amine with a pungent odour resembling rotting fish (Fig. 7.4.1). TMA has a 100-fold greater olfactory potency than its N-oxide. The reported threshold odour for TMA is 0.9 ppm. Exposure to concentrations above 20 ppm gives moderate irritation of the respiratory system and the eyes. Dermal contact with a concentrated aqueous solution may cause severe burns [4]. Oral ingestion of 15 mg TMA hydrochloride/kg body weight induces nausea and ichthyo-hydrosis [9]. 

For reviews of this reaction, sec Gibson, in Patai, Ref. 355, pp. 45-55 Spiallcr Pappalardo The Acyclic Aliphatic Tertiary Amines Macmillan New York. 1965, pp. 14-29. 

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