Nitrogen competition

Pong, P., Foin, T. C., and Zedler, J. B. (1994b). A simulation model oflagoon algae based on nitrogen competition and internal storage. Ecol. Monogr. 64, 225-247. 

The first quantitative studies of the nitration of quinoline, isoquinoline, and cinnoline were made by Dewar and Maitlis, who measured isomer proportions and also, by competition, the relative rates of nitration of quinoline and isoquinoline (1 24-5). Subsequently, extensive kinetic studies were reported for all three of these heterocycles and their methyl quaternary derivatives (table 10.3). The usual criteria established that over the range 77-99 % sulphuric acid at 25 °C quinoline reacts as its cation (i), and the same is true for isoquinoline in 71-84% sulphuric acid at 25 °C and 67-73 % sulphuric acid at 80 °C ( 8.2 tables 8.1, 8.3). Cinnoline reacts as the 2-cinnolinium cation (nia) in 76-83% sulphuric acid at 80 °C (see table 8.1). All of these cations are strongly deactivated. Approximate partial rate factors of /j = 9-ox io and /g = i-o X io have been estimated for isoquinolinium. The unproto-nated nitrogen atom of the 2-cinnolinium (ina) and 2-methylcinno-linium (iiiA) cations causes them to react 287 and 200 more slowly than the related 2-isoquinolinium (iia) and 2-methylisoquinolinium (iii)... 

A low calorific value gas, which includes nitrogen from air, could be produced for boiler or turbine use in electric power production, or an intermediate calorific value gas containing no nitrogen for an industrial fuel gas, or synthesis gas for chemical and methane production could be provided. This approach which has been studied in Russia, Europe, Japan, and the United States, is stiU noncommercial in part because it is not economically competitive. 

The competitive attack at either oxygen or nitrogen by nucleophiles was the subject of a recent investigation (8IJOC6IO). Whereas triphenylphosphine reacted with oxaziridine (88)... 

Radical and ionic nitrations are often competitive pathways in strong nitrating acid rmxtures. The predominant reaction pathway is determined by the composition of the nitrating medium. Oxides of nitrogen in the nitrating medium add to... 

The MS2N2 complexes and their selenium analogues are readily protonated at the nitrogen attached to the metal (Eq. 7.5). Competitive studies show that the selenium complex is a stronger base than its sulfur analogue. 

A fundamental problem in the alkylation of enamines, which is inherent in the bidentate system, is the competition between the desired carbon alkylation and attack at the nitrogen. With unactivated alkyl halides (3,267), this becomes especially serious with the enamines derived fromcycloheptan-one, cyclooctanone, cyclononanone, and enamines derived from aldehydes. Increasing amounts of carbon alkylation are found with the more reactive allyl and benzyl halides (268-273). However, with allyl halides one also observes increasing amounts of dialkylation of enamines. 

On the basis of the dissociation constant values, it seems sensible to conclude that, in these moderately basic carbinolamines, the hydrogen atom of the hydroxyl group is suflQciently acid to be eliminated under the influence of an alkali and by its transfer to the nitrogen atom of the mesomeric anion, the formation of the amino-aldehyde form may result. Instead of the amino-aldehyde, however, the corresponding bimolecular ether (15a-c) can be obtained. " It can be concluded that the formation of the bimolecular ether (S l or 8 2 mechanism) and the formation of the amino-aldehyde (B-SeI or B-Se2 mechanism) are competitive reactions. It seems probable that where the first reaction can occur the latter one is pushed into the background. The triple tautomeric system postulated by Gadamer... 

It was known that the K+ -competitive imidazopyridine compound, SCH28080, inhibits acid secretion. Then, many reversible inhibitors were developed. These contain protonatable nitrogens but have a variety of core structures such as imidazopyiidines, piperidinopyr-idines, substituted 4-phenylaminoquinolines, pyrrolo [3,2-c]quinolines, guanidinothiazoles, and 2,4-diamino-pyrimidine derivatives. Several reversible inhibitors have been in clinical trials. 

The reversibility of aromatic diazotization in methanol may indicate that the intermediate corresponding to the diazohydroxide (3.9 in Scheme 3-36), i. e., the (Z)-or (is)-diazomethyl ether (Ar — N2 — OCH3), may be the cause of the reversibility. In contrast to the diazohydroxide this compound cannot be stabilized by deprotonation. It can be protonated and then dissociates into a diazonium ion and a methanol molecule. This reaction is relatively slow (Masoud and Ishak, 1988) and therefore the reverse reaction of the diazomethyl ether to the amine may be competitive. Similarly the reversibility of heteroaromatic amine diazotizations with a ring nitrogen in the a-position may be due to the stabilization of the intermediate (Z)-diazohydroxide, hydrogen-bonded to that ring nitrogen (Butler, 1975). However, this explanation is not yet supported by experimental data. 

Zollinger and coworkers (Nakazumi et al., 1983) therefore supposed that the diazonium ion and the crown ether are in a rapid equilibrium with two complexes as in Scheme 11-2. One of these is the charge-transfer complex (CT), whose stability is based on the interaction between the acceptor (ArNj) and donor components (Crown). The acceptor center of the diazonium ion is either the (3-nitrogen atom or the combined 7r-electron system of the aryl part and the diazonio group, while the donor centers are one or more of the ether oxygen atoms. The other partner in the equilibrium is the insertion complex (IC), as shown in structure 11.5. Scheme 11-2 is intended to leave the question open as to whether the CT and IC complexes are formed competitively or consecutively from the components. ... 

In the synthesis of N heterocycles, this technique also overcomes competitive retro Michael addition that lowers the yield of 1,4-adduct in the Michael addition of amines to nitro olefins. Thus, a toluene solution of nitro olefin 159 was treated with allylamine 160, EtgN, and TMSCI under nitrogen at ambient tern-... 

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