Nitrogen, reactive classes

Many compounds have been reported in the literature to be chemical antiozonants, and nearly all contain nitrogen. Compound classes include derivatives of 2,2,4-trimethyl-l, 2-dihydroquinoline, N-substituted ureas or thioureas, substituted pyrroles, and nickel or zinc dithiocarbamate salts. The most effective antiozonants, however, are derivatives of p-phenylenediamine (p-PDA). The commercial materials are grouped into three classes N,N -dialkyl-p-PDAs, Nalkyl-N -ary 1-p-PDAs, and NX-diary 1-p-PI) As. The NX-dialkyl-p-PDAs (where the alkyl group may be 1-methylheptyl, l-ethyl-3-methylpentyl, 1,4-dimethylpentyl, or cyclohexyl) are the most effective in terms of their reactivity to ozone. These derivatives increase the critical stress required for the initiation of crack growth, and they also reduce the rate of crack growth significantly. The sec-alkyl group is most active, for reasons that are not yet completely clear. The drawbacks of these derivatives are ... 

Dialkoxycarbenes, such as dimethoxycarbene I, constitute a very reactive class of compounds that were initially difficult to handle [2,3]. Fortunately, a convenient, efficient, and safe procedure was developed by Warkentin and coworkers [4]. The protocol generates dimethoxycarbene, together with acetone and nitrogen, by thermolysis of the corresponding 2,2-dimethoxy-5,5-dimethyl-2,5-dihydro-l,3,4-oxadiazole 1 (Scheme 5.3). 

The principal reactions of this class of compounds are summarized in Scheme 172. In most of these reactions the reactive nucleophilic center is the terminal NHj group, although the other exocyclic nitrogen may also be involved, as shown by acetylation, which yields 284 and 285. However, the structure of compound 281 is not the one proposed in a recent report (1582) that attributes the attack to the other exocyclic nitrogen. The formation of osazones (287) from sugars, 2-hydrazinothiazoles, and hydrazine has been reported (525, 531). 

Imino-4-thiazolines are far more basic than their isomeric 2-aminothiazoles (see Table VI-1). They react with most electrophDic centers through the exocyclic nitrogen and are easily acylated (37, 477, 706) and sulfonated (652). The reaction of 2-imino-3-methyi-4-thiazoline (378) with a-chloracetic anhydride yields 379 (Scheme 217) (707). This exclusive reactivity of the exocyclic nitrogen precludes the direct synthesis of endocyclic quaternary salts of 2-imino-4-thiazolines. although this class of compounds was prepared recently according to Scheme 218 (493). 

In the preceding parts of Section 4.04.2.1.3 the electrophilic attack on pyrazolic nitrogen with the concomitant formation of different classes of N—R bond has been examined N—H (iv, v), N—metal (vi), N—C(sp ) (vii, viii, xi), N—C(sp ) (be, x, xi), N—SO2R (x), N—halogen (xii), N—O (xiii) and N—-N (xiv). In this last part the reaction with other Lewis acids leading to the formation of pyrazole N—metalloid bonds will be discussed, and the study of their reactivity will be dealt with in Section 4.04.2.3.lO(viii). 

The first compound of this class with inhibitory activity on the enzyme and on acid secretion was the 2-(pyridylmethyl)sulfinylbenzimidazole, timopra-zole, and the fust pump inhibitor used clinically was omeprazole, 2-[[3,5-dimethyl-4-methoxypyridin-2-yl] methylsulfinyl]-5-methoxy- lH-benzimidazole. Omeprazole is an acid-activated prodrug. Omeprazole and the other PPIs are accumulated in the acidic space of the parietal cell due to the pKa of the pyridine nitrogen and these are converted due to protonation of the benzimidazole nitrogen first to a thiol-reactive cationic sulfenic acid and then dehydrated to form the sulfenamide (Fig. 1). These thiophilic cations then bind to luminally... 

Nitro compounds are versatile precursors for diverse functionalities. Their conversion into carbonyl compounds by the Nef reaction and into amines by reduction are the most widely used processes in organic synthesis using nitro compounds. In addition, dehydration of primary nitro compounds leads to nitrile oxides, a class of reactive 1,3-dipolar reagents. Nitro compounds are also good precursors for various nitrogen derivatives such as nitriles, oximes, hydroxylamines, and imines. These transformations of nitro compounds are well established and are used routinely in organic synthesis. 

Diazaphospholes constitute the most widely investigated class of heterophospholes, the 67t-aromatic phosphorus heterocycles [1,2]. Diazaphospholes are unique in the manner that the five-membered ring incorporates one phosphorus atom. First diazaphosphole representative, i.e. 2//-[l,2,3 diazaphospholc was obtained as early as 1967 [3] and until 1980s the interest of organophosphorus chemists remained in the development of different synthetic routes and in investigating their varied reactivity due to the structural diversity within the class [4], On the basis of the relative positions of the three heteroatoms in the five-membered ring, six monocyclic diazaphosphole systems (A-F) are possible and all of them have been reported (Structure 1). 

This chapter provides an update of Chapter 8.33 in CHEC-II(1996) <1996CHEC-II(8)863>. The work carried out on the bicyclic ring systems with ring junction P, As, Sb, or Bi has focused primarily on phosphorus. Very little work has been done on the other heteroatoms and as such the synthesis and reactivity of these compounds have been reviewed as one section, Section 12.12.7. Most of the compounds in this class contain more than one heteroatom, the additional atoms usually being oxygen and nitrogen. 

The third class of metal catalysts includes nickel and cobalt complexes of Schiff bases and nitrogen macrocyclic ligands, which can form on electroreduction cobalt(I) and nickel(I) reactive intermediates for the activation of organic halides. 

The NO + 03 chemiluminescent reaction [Reactions (1-3)] is utilized in two commercially available GC detectors, the TEA detector, manufactured by Thermal Electric Corporation (Saddle Brook, NJ), and two nitrogen-selective detectors, manufactured by Thermal Electric Corporation and Antek Instruments, respectively. The TEA detector provides a highly sensitive and selective means of analyzing samples for A-nitrosamines, many of which are known carcinogens. These compounds can be found in such diverse matrices as foods, cosmetics, tobacco products, and environmental samples of soil and water. The TEA detector can also be used to quantify nitroaromatics. This class of compounds includes many explosives and various reactive intermediates used in the chemical industry [121]. Several nitroaromatics are known carcinogens, and are found as environmental contaminants. They have been repeatedly identified in organic aerosol particles, formed from the reaction of polycyclic aromatic hydrocarbons with atmospheric nitric acid at the particle surface [122-124], The TEA detector is extremely selective, which aids analyses in complex matrices, but also severely limits the number of potential applications for the detector [125-127],... 

Kirby s configurationally rigid l-azaadamantan-2-one 1 is the extreme of this class.21 23,25 The nitrogen properties of this lactam are clearly amine-like while the carbonyl is ketonic in all respects. Twisted amides undergo rapid hydrolysis or reduction and exhibit enhanced reactivity. 

Carbenes are both reactive intermediates and ligands in catalysis. They occur as intermediates in the alkene metathesis reaction (Chapter 16) and the cyclopropanation of alkenes. As intermediates they carry hydrogen and carbon substituents and belong therefore to the class of Schrock carbenes. As ligands they contain nitrogen substituents and are clearly Fischer carbenes. They have received a great deal of attention in the last decade as ligands in catalytic metal complexes [58], but the structural motive was already explored in the early seventies [59],... 

Reactivities of different compounds vary greatly within each class and require different mechanistic pathways among classes. For example, nitrogen compound reactivities line up in the following order [63] ... 

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