Substitutions amines, 1,1

Reduction of Nitro Substituents. These reactions are very common in anaerobic environments and result in amine-substituted pesticides anaerobic bacteria capable of reducing nitrate to ammonia appear to be primarily responsible. All nitro-substituted pesticides appear to be susceptible to this transformation, eg, methyl parathion (7) (eq. 9), triduralin, and pendimethalin. 

Monochloramine is also used in organic synthesis for preparation of amines, substituted hydrazines, etc. For example, reaction of NH2CI with 3-azabicyclo [3.3.0]octane [5661-03-0] yields A/-amino-3-azabicyclo[3.3.0]octane [54528-00-6] a pharmaceutical intermediate (38). 

The range of nueleophiles whieh have been observed to partieipate in nueleophilie aromatie substitution is similar to that for S[, 2 reactions and includes alkoxides, phenoxides, sulftdes, fluoride ion, and amines. Substitutions by earbanions are somewhat less common. This may be because there are frequently complications resulting from eleetron-transfer proeesses with nitroaromatics. Solvent effects on nucleophilic aromatic substitutions are similar to those discussed for S 2 reactions. Dipolar... 

Another interesting fact to be noted is that the bicyclic enamine (87) and its pyrrolidine analogue failed to undergo reduction with 98% formic acid, whereas the pyrrolidine enamine of 2-bicyclo[2.2.1]hepten-5-carboxalde-hyde (94), which exists largely in the transoid form (49), was readily reduced to (95). However, the saturated amine-substituted norbornane can be obtained directly from norbornanone under the more vigorous conditions of the Leuckart reaction (49a). 

Reactions of Enamine Salts with OrganometalUc Compounds Organolithium and organomagnesium compounds react with enamine salts to give amines substituted on the ix-carbon atoms. The treatment of. -dehydroquinolizidinium perchlorate (163) with alkylmagnesium halides gives 9-alkylated quinolizidines (164) (252,256). Formation of... 

Palladium, (diammine)bis(thiocyanato)-isomerism, 1, 185 Palladium, dichlorobis(amine)-substitution reactions stereochemistry, 1, 318 Palladium, dichlorobis(pyridine)-substitution reactions, 1, 314 Palladium, dinitritobis(triisopropylphosphine)-substitution reactions, I, 314 Palladium, ethylene-synthesis... 

With regard to the promoting effect of Ag+ in bromine/amine substitution reactions, one must address the problem of the complexation of Ag+ by amines in organic solvents (F. Pulidori, M. Remelli, F. D Angeli, P. Marchetti, work in progress). 

Polyhedral oligomeric silsesquioxane (POSS) has been extensively studied as starting substrate to construct nanocomposites with precise control of nanoarchitecture and properties. Octahedral derivatives are the most representative ones of this family. It was reported that the HRP-catalyzed conjugation of catechin on amine-substituted octahedral silsesquioxane amplified the beneficial physiological property of flavonoids. The POSS-catechin conjugate exhibited great... 

Experimental screening established that compound 42 shown in Fig. 8.11 disrupts ZipA-FtsZ protein-protein interaction. However, previous studies suggested potential issues with toxicity associated with this class of compounds. Additionally such amine-substituted pyridyl-pyrimidines are heavily patented in the context of kinase inhibition. Both of these factors limit the scope of the subsequent lead optimization process, to transform this compound into a viable drug. Knowledge that compound 42 was a micromolar inhibitor of ZipA-FtsZ was exploited by searching for molecules that were similar in shape. 

A series of 4-arylpyrimidines that arc amine substituted at pyrimidine C-2 was prepared. FK360 was most effective from this group on both arachidonate-induced cerebral oedema in rats and as an in vitro inhibitor of lipid peroxidation. The authors link effects of FK360 to the arachidonic acid cascade (Kuno et al., 1992). This is an unusual structure. 

In compounds (333) and (336) the amines substitute one of the dithiophosphate ligands to form a NiN4S2 core with the second dithiophosphate ligand serving as a counterion. Coordination number 5 is rare, but is found for complex (345) where one of thiophosphates switched to a monodentate coordination,879 and in compound (346) where only one additional phosphine adduct coordinates to Ni.880... 

The condensation of activated thiols onto adjacent nitriles is a common method for the preparation of amine-substituted thiophenes. A three component condensation was utilized to prepare a-aminothiophene 11 <00TL1597>. An alternate method for preparing amino-substituted thiophenes involved the treatment of ketene S,JV-acetal 12 with an activated carbonyl compound 13 which gave thiophene 14 <00JOC3690>. This type of reaction has also been utilized to prepare building blocks for the synthesis of fused thiophenes <00JHC363>. 

A series of polyether macrocycles [59]—[66] (Fig. 33) that contain a coordinated reducible, redox-active 16-electron molybdenum nitrosyl (Mo(NO)(3+ group have been prepared (Al-Obaidi et al, 1986 Beer et al., 1987). Compounds [59]—[63] were synthesized from the reactions between [Mo(NO)LX2] (L = tris(3,5-dimethylpyrazolyl)hydroborate X = Cl or I ) and the appropriate amine substituted benzo-crown ether. Compounds... 

Abstract Starting with tetracyanodibenzo(l,4,7,10-tetrathia-(12-crown-4)) (1) and 4-nitro-l,2-dicyanobenzene (2), nitro-substituted dimeric phthalocyanine (3) was synthesized. In the second step, using hydrazine hydrate as a reductant, amine-substituted dimeric phthalocyanine (4) was synthesized from nitro-substituted dimeric phthalocyanine. Stractmres of all synthesized compounds were determined by elemental analyses, UV/vis, H-NMR and IR spectroscopy. 

The IR spectra of both 3 and 4 taken with the KBr pellets. The stretching peaks at 2983, 2858 cm confirmed the presence of -CH respectively for compounds 3and 4. The stretching peaks at around 1523-1344 cm in the spectrum of 3 indicated the presence of a -NO group that disappeared in case of the amine-substituted pc 4. The presence of-NH - in the stracture of 4 was observed at 3447-3417 cm". The C-S-C ether chain was characterized by the an absorption at 1,090 cm for all dimeric compounds. 

According to experiments (Jonsson et al. 1996), the deprotonation of (Et2NH)+ takes place at the nitrogen rather than at the a-carbon. However, Costentin and Saveant (2004) showed that if a stabilized carboradical can be produced, some intramolecular reorganization takes place and a proton leaves the carbon, not the nitrogen. The formation of the amine-substituted allyl radical is just the case +NH2-CH2=CH-CH2H H+ -f NH2CH2=CH-CH2 . 

Pechmann and Nold utilized the reaction of diazomethane with phenyl isothiocyanate for one of the earliest syntheses of a 1,2,3-thiadiazole <84CHEC-I(6)447>. This method continues to be used <82MI 407-0l> for the synthesis of 5-amine substituted 1,2,3-thiadiazoles (34), and 4,5-disubstituted... 

The alternative regiochemical disposition of the diazo and tether of indole 260 failed to deliver any product upon addition of catalyst. Friedrichsen and co-workers (136) also applied this method to amine substituted tethers to generate polyaza-cyclic compounds (Scheme 4.70). The presence of the amino substituted furan subsequent to diazo-decomposition made it possible to cleave the ether bridge through the facility of the amino group formed to produce adduct 263. 

Various aromatic secondary amines, substituted phenols, and pyrazoli-dones (3) that function as traps for the propagating peroxy radicals gave dead-stop induction periods when used at a concentration of 50 p.p.m. An indication of the ease of oxidation of chloroprene is that 50 p.p.m. of 2,6-di-ferf-butyl-4-methylphenol gave an induction period of only 15 minutes, while the same concentration of antioxidant prevented n-hexadecane from oxidizing for 2 hours at 160°C. 

Anhydro sugars react similarly with amines substituted anilines lead to N-aryl-/3-D-glycosylamine derivatives.221... 

Fig. 10.2. Reaction protocol for the transformation of alcohols to amines via mesylation and amine substitution, as shown in PGVL Flub.

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