Nitrogen derivation with

The numerous reactions between nitrogenous derivatives with different states of oxidation are represented in the table (pi 68), which is more difficult to read than the usual summary tables in which there are less troublesome crossings between lines and groups. 

Benzene Derivatives with a Nitrogen Containing Side-Chain... 

Category Ic cyclizations involve formation of the C3-C3a bond and require aniline derivatives with a nitrogen substituent appropriate for such reaction. Some, but not all, such cyclizations also require an o-substituent, frequently halogen. The rctrosynthetic transformations corresponding to the most important of this group of syntheses are shown in Scheme 4.1... 

Substituted ammonium ions derived from nitrogen bases with names ending in -amine receive names formed by changing -amine into -ammonium. When known by a name not ending in -amine, the cation name is formed by adding the ending -ium to the name of the base (eliding the final vowel) e.g., anilinium, hydrazinium, imidazolium, acetonium, dioxanium. 

Structural parameters and interatomic distances derived from electron diffraction (7) (77JST(42)l2i) and X-ray diffraction (8) studies (76AX(B)3178) provide unequivocal evidence that pyrazine is planar with >2a symmetry. There is an increased localization of electron density in the carbon-nitrogen bonds, with carbon-carbon bonds being similar in length to those in benzene. ... 

Amino groups a to nitrogen are hydrolyzed to the corresponding oxo compounds (as in the purines and pteridines) in bo h acid and alkaline conditions. Schiff bases are reduced to benzylamino derivatives with borohydride. 

The fully saturated pyrazolidines have been utilized as models for the study of the nitrogen inversion of hydrazines. For instance, (75), a 2,3-diazabicyclo[2.2.1]heptene derivative, presents a consecutive inversion process at two nitrogen atoms with an activation barrier... 

Mcntasty el al. [35] and others [13, 36] have measured methane uptakes on zeolites. These materials, such as the 4A, 5A and 13X zeolites, have methane uptakes which are lower than would be predicted using the above relationship. This suggests that either the zeolite cavity is more attractive to 77 K nitrogen than a carbon pore, or methane at 298 K, 3.4 MPa, is attracted more to a carbon pore than a zeolite. The latter proposition is supported by the modeling of Cracknel et al. [37, 38], who show that methane densities in silica cavities will be lower than for the equivalent size parallel slit shaped pore of their model carbon. Results reported by Ventura [39] for silica xerogels lead to a similar conclusion. Thus, porous silica adsorbents with equivalent nitrogen derived micropore volumes to carbons adsorb and deliver less methane. For delivery of 150 V./V a silica based adsorbent would requne a micropore volume in excess of 0.70 ml per ml of packed vessel volume. 

Recently Stamhuis et al. (33) have determined the base strengths of morpholine, piperidine, and pyrrolidine enamines of isobutyraldehyde in aqueous solutions by kinetic, potentiometric, and spectroscopic methods at 25° and found that these enamines are 200-1000 times weaker bases than the secondary amines from which they are formed and 30-200 times less basic than the corresponding saturated tertiary enamines. The baseweakening effect has been attributed to the electron-withdrawing inductive effect of the double bond and the overlap of the electron pair on the nitrogen atom with the tt electrons of the double bond. It was pointed out that the kinetic protonation in the hydrolysis of these enamines occurs at the nitrogen atom, whereas the protonation under thermodynamic control takes place at the -carbon atom, which is, however, dependent upon the pH of the solution (84,85). The measurement of base strengths of enamines in chloroform solution show that they are 10-30 times weaker bases than the secondary amines from which they are derived (4,86). 

The formation of vinylogous amides from primary amines and -dicarbonyl compounds gives rise to hydrolyzable amine derivatives with greatly decreased nucleophilicity of the nitrogen function. Thus these derivatives have found some use as protecting groups in peptide syntheses 617-619). 

The course of methylation of all the thio derivatives with diazomethane was then investigated. These mcthylations generally result in mixtures of substances it may be deduced from the products isolated, however, that this reaction proceeds first at the nitrogen atom (in contrast with alkaline methylation) and only then at the sulfur one. The methylation of the 3-methylmercapto derivative to 4-methyl-3-methylmercapto-5-oxo-4,5-dihydro-l,2,4-triazine (95) is of interest in this connection. 

Effect of Some Nitrogen-, Oxygen-, and Sulfur-Containing Groups on the Rate Constants for the Reaction of Chloro-s-triazine Derivatives with Various Nucleophiles... 

Products of cyclization of 5-aminoethylene benzotriazole derivatives with eliminated prototropy of the azole ring can be alkylated on the nitrogen atom of the pyridone and then hydrolyzed to the corresponding acids (76JAP(K)1, 89FA619). The prepared compounds 167-169 and their salts were tested against bacteria (no data) (76JAP(K)1). 

Synthetic and structural chemistry of heme derivatives with nitrogen oxide ligands 99ACR350. 

Amines are organic derivatives of ammonia in the same way that alcohols and ethers are organic derivatives of water. Like ammonia, amines contain a nitrogen atom with a lone pair of electrons, making amines both basic and nucleophilic. We ll soon see, in fact, that most of the chemistry of amines depends on the presence of this lone-pair of electrons. 

Compounds with the classical nonsystematic name diazoamino compound (R-N2NRiR2) and their (logical) derivatives with two or more adjacent nitrogen atoms are considered as substitution products of triazene (NH2 — N=NH), 1-tetrazene, etc. (Rule 942.1). Simple examples are 3-methyltriazene (CH3-NH-N = NH) and 3-methyl-l-tetrazene [NH2-N(CH3)-N = NH]. The classical name is retained only for compounds containing the same group R at each end of an - N=N - NH - group (Rule C-942.2), e. g., A-methyldiazoaminobenzene,... 

Linfield, Jungermann, and Guttmann [181,183,184] extended this reaction to a number of long-chain fatty nitrogen derivatives to form products with surface-active and antibacterial properties, as shown in Eqs. (109) and (110) ... 

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