1,2,3-Triaminated products

The initial study was performed using various thiols (R SH) as nucleophiles, which afforded 1,2-aminothiol derivatives 98 bearing two adjacent stereogenic centers in one-pot good yield process (up to 72%) with marvelous stereoselectivity (dr up to 96 4, >99% ee) [58a]. Likewise, the subsequent employment of an aza-nucleophile gave access to iyn-diaminated aldehydes 99 and 100, easily converted in 1,2,3-triaminated products or 1,3-diamino alcohols [58b]. In both cases, the mechanistic pathway involves the first soft nucleophile attack to the iminium intermediate A, followed by the addition of a suitable electrophile 96 to the enamine intermediate B, giving the nearly enantiopure products 98-100 (Scheme 2.28). 

The nitrolysis of hexamine can be controlled by changes in conditions to follow either of two paths. Strongly acidic conditions lead to triazine and linear triamine products. With nitric acid and acetic anhydride the dinitrotetraazabicyclo[3.3.1]nonane (328) is produced, and opening of the methylene bridge then gives the tetrazocane (329) and finally, in the presence of ammonium nitrate, HMX or the tetramine (330) (51JA2773). 

Overbased Mo-alkylene earth metal sulfonates 2,6-Di-ferf-butyl-4-methyl phenyl-borate Borated polyhydroxy-alkyl sulfides Borated N-hydrocarbyl alkylene triamines Product of boric acid and cocosyl sarcosene Product of 1,2-hexadecanediol, C15-C19 alcohols and boric acid Zinc salts of partially borated and partially phosphosulfurized penta or dipentaerythritol N-Oleylglycolamide N-Alkoxylakylene diamine diamide N-Cocoformamide... 

The majority of analgesics can be classified as either central or peripheral on the basis of their mode of action. Structural characteristics usually follow the same divisions the former show some relation to the opioids while the latter can be recognized as NSAlD s. The triamino pyridine 17 is an analgesic which does not seem to belong stmcturally to either class. Reaction of substituted pyridine 13 (obtainable from 12 by nitration ) with benzylamine 14 leads to the product from replacement of the methoxyl group (15). The reaction probably proceeds by the addition elimination sequence characteristic of heterocyclic nucleophilic displacements. Reduction of the nitro group with Raney nickel gives triamine 16. Acylation of the product with ethyl chlorofor-mate produces flupirtine (17) [4]. 

Diethylene triamine pentaacetic acid is a chelating agent that sequesters metal ions so they cannot combine with other ingredients in a product. 

Sheratte55 reported the decomposition of polyurethane foams by an initial reaction with ammonia or an amine such as diethylene triamine (at 200°C) or ethanolamine (at 120°C) and reacting the resulting product containing a mixture of polyols, ureas, and amines with an alkylene oxide such as ethylene or propylene oxide at temperatures in the range of 120-140°C to convert the amines to polyols. The polyols obtained could be converted to new rigid foams by reaction with the appropriate diisocyanates. 

Rigid polyurethane foams were prepared at room temperature using eommercial polyols and polymerie 4,4 -diphenyl methane diisoeyanate, and used to study their reeyeling by aminolysis. The reaction products obtained by treatment with diethylene triamine at 180 C were evaluated as hardeners for epoxy resins. The exothermie heats of euring were determined over the temperature range 60-80 C by differential scanning calorimetry. A reaction order of 2.2-2.4 was obtained. 8 refs. 

Photolytic. Irradiation of trifluralin in hexane by laboratory light produced a,a,a-trifluoro-2,6-dinitro-A-propyl-jo-toluidine and a,a,a-trifluoro-2,6-dinitro-p-toluidine. The sunlight irradiation of trifluralin in water yielded a,a,a-trifluoro-A, 7 -dipropyl-5-nitrotoluene-3,4-diamine, a,a,a-trifluoro-A/ ,A/ -dipropyltoluene-3,4,5-triamine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazoline, and 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole. 2-Amino-6-nitro-a,a,a-trifluoro-p-toluidine and 2-ethyl-5-nitro-7-(trifluoromethyl)benzimidazole also were reported as major products under acidic and basic conditions, respectively (Crosby and Leitis, 1973). In a later study, Leitis and Crosby (1974) reported that trifluralin in aqueous solutions was very unstable to sunlight, especially in the presence of methanol. The photodecomposition of trifluralin involved oxidative TV-dealkylation, nitro reduction, and reductive cyclization. The principal photodecomposition products of trifluralin were 2-amino-6-nitro-a,a,a-trifluoro-jo-toluidine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimida-zole 3-oxide, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazole, and two azoxybenzenes. Under alkaline conditions, the principal photodecomposition product was 2-ethyl-7-nitro-5-(trifluoromethyl)-benzimidazole (Leitis and Crosby, 1974). 

The synthetic and industrial importance of this reaction lies in its generality, and the ease with which the amino substituent in the products can be subsequently transformed into other functionalities. Pyridine itself is more difficult to aminate than quinoline or isoquinoline, and it does not react with potassium amide in liquid ammonia even on prolonged treatment. However, pyridine is aminated in good yield by sodamide in toluene, and di- and tri-amination can be achieved with excess sodamide at higher temperatures. The 4-position is substituted last in triamination y-amination is very difficult indeed and only takes place when all a -positions are occupied. 

An impressive solid-phase synthesis of bicyclic guanidines has been communicated, and the approach is outlined in Scheme 20 45,46 iV-acylated dipeptides 18 were reduced to triamines by exhaustive borane reduction, then reacted with thiocarbonyldiimidazole. An intermediate thiocarbonyl was cyclized to the guanidine product in this process. 

Secondly, iron(II) was observed to form octahedral complexes that incorporate the triamine in preference to the monoamine. When complex 16 was mixed with an equimolar amount of triamine in aqueous solution, complex 14 and monoamine were the only products observed (Scheme 1.15). The chelate effect [40] may be understood to drive this substitution The incorporation of one equivalent of triamine results in the liberation of three equivalents of monoamine, which provided the entropic driving force for this reaction. 

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