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A very simple and effective method for the generation of aromatic amine radical cations, which involves mixing of the aromatic amine with a equiv of Cu[(Cl[O.sub.4]).sub.2] in acetonitrile solution is presented. The reaction could be used for synthetic application by taking N,N-dimethylaninline (DMA) and N,N-diethylaniline (DEA) as examples.

The components of the nitrogen chemical shift (CS) tensor of a series of para substituted N-N-dimethylaniline derivatives were examined through measurement of (Super 15)N NMR spectra of powdered samples and through quantum chemical calculations on the isolated molecules. The methodology has proved the feasibility of performing N cross-polarization experiments on nonspinning powder samples at natural isotopic abundance.

The dependence of the activation parameters on both substituents and solvents in selected S(sub N)2 reactions is calculated by using the DFT method with a moderate basis set. The measured and calculated activation parameters show considerable deviations for reactions of ions and for any reaction in protic solvents.

The proline-catalyzed direct asymmetric Mannich reaction between cyclohexanone, formaldehyde, and various anilines is thermally accelerated. With only 0.5 mol % of catalyst, Mannich products with up to 98% ee are obtained after a short period of time in reactions performed under microwave irradiation.

Chiral nitroanilines containing 1,2- or 1,3-diol functionalities is synthesized by nucleophilic aromatic substitution of fluoronitroanilines with 1-aminopropane-2,3-diols and 2-aminopropane-1,3-diol in the melt. The results reveal that the functionalization of the amino nitrogen of p-nitroaniline derivatives with polar groups, which are not in direct n-pi conjugation with the aromatic system, also affects the solvatochromism of the pull-push system in a complex fashion.

A conjugated donor-acceptor-donor molecule incorporating a central moiety of naphthyridine and two terminal moieties of di(hydroxyethyl)aniline connected by ethynyl bridges shows two-stage color changes on binding with mercury(II) ion in Me2SO/H2O solution with a bathochromic shift from 450 to 498 nm, and then an extraordinarily large hypsochromic shift to 378 nm. The designed sensor shows high selectivity toward mercury(II) ion over other competing metal ions.

The reactivity of the phthalimide-N-oxyl radical (PINO) toward the NO-methyl C-H bond of a number of 4-X-substituted N,N-dimethylanilines is investigated. It is found that the PINO is very reactive toward the methyl C-H bond of N,N-dimethylanilines promoting the oxidative N-demethylation of the substrate.

A facile parallel synthesis of polysubstituted 2,6-dicyanoanilines through microwave-promoted three-component reaction of aldehydes, ketones, and propanedinitrile in solution and also on polymer support is developed. The screening for optical properties identified two new compounds with high fluorescence quantum yields.

A study conducted shows how the presence of aromatic substituents OH, CH2OH, CO2H, and CONH2 modifies the relative methylation rate of amines, plausibly by altering the adsorption of these substrates within the pores of the zeolite used. The study demonstrates that several factors could account for the trend of reactivity shown by the amines in their mono-N-methylation with dimethyl carbonate (DMC) and methyl ethyl carbonate (MEC).

A new method is developed for the synthesis of 2-substituted tetrahydroquinolines via the Pd(0)-catalyzed intramolecular hydroamination of anilino-alkynes. This method is implemented for the synthesis of alkaloids such as (_)-angustureine and (_)-galipinine and also for natural products containing tetrahydroquinoline moiety.

InBr3 has promoted the dimerization of 2-ethynylaniline derivatives containing an unsubstituted terminal carbon leading to the production of polysubstituted quinoline derivatives in good yield. This is the first direct synthesis of a quinoline skeleton via a dimerization of identical molecules.

The first photoreactive analogue of 2-amino-[2-(4-octylphenyl)ethyl]-1,3-propanediol (1), a immunosuppressant that traps T cells in lymph nodes were synthesized in 9 steps and 34% overall yield. The key steps were the generation f a quaternary center via alkylation of iodine 8 with lithium salt of 2-nitropropane-1,3-diol acetonide and the selective diazotization of diamine.

A new and efficient method for the selective synthesis of secondary alkyl anilines and heterocyclic anilines including tetrahydroquinolines, benzazepines and benzoxazines in good yield by a BF3-Et2O/BH3 reductive rearrangement of O-silylated oximes is described. The bulk of the substitutents on the silicon atom, the size of the aliphatic ring and the presence of alkoxy substituents on the aryl group all play an important role in the aniline.

Aldimines, generated in situ by the reaction of primary amines or anilines with aldehydes, undergo smooth reaction with various 1,1-cyclopropanediesters in the presence of catalytic Yb(OTf)3. The products are pyrrolidines in which the major diastereomer bears a cis relationship between substituents at the 2- and 5-positions.

The reaction processes of a chiral substrate were examined by monitoring its stereochemical courses to understand the detailed mechanism of tandem iminium cyclization and Smiles rearrangement. The tandem reaction conditions for both the processes are supported by the results of a competition experiment in which the addition of 1 equiv of p-methoxyaniline in the rearrangement step led to a significant amount of anilinyl-exchanged rearrangement product.

L/D-Ala-OMe was introduced into aniline oligomers to induce chirality organization of the [pi]-conjugated aniline oligomer moieties to design aniline oligomers bearing amino acid moieties. The intramolecular hydrogen bonds formed in the amino acid moieties was observed to play an important role towards the regulating the aniline oligomer moieties conformationally.

The practical synthesis of structurally diverse, sterically hindered N-arylpiperazines from 2,2 -(4-nitrophenylsulfonylazanediyl) bis(ethane-2,1-diyl) bis(4-nitrobenzenesulfonate) and substituted anilines is obtained by using microwave irradiation in acetonitrile followed by deprotection with PhSH.

The ability of ortho-alkynylanilines to react with aldehydes and amines in HFIP in the absence of any catalysts is demonstrated. The reaction yields trans-2,3-disubstituted 2,3-dihydro-4-iminoquinolines in a complete trans-selective manner via the three-component alkyne-imine metathesis.

Heats of formation of organic compounds are obtained by adding a constant for a functional group to the heat of formation of its hydrocarbon precursor obtained by counting hydrogens, where a single molecule is used for obtaining the contribution of each functional group. The method is limited to compounds that are not subject to strain or effects of conjugation and the experimental heat of formation of the hydrocarbon precursor is used in these cases.

The intramolecular cyclocarbonylation of substituted 2-(2-iodophenoxy)anilines is catalyzed by Pd[I.sub.2] and 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phospha-adamantane (Cytop 292). A series of substituted dibenzo[b,f][1,4]oxazepin-11 (10H)-ones are prepared under mild reaction conditions.

The CuX (X = I, Br, Cl, CN)-mediated cyclization-halogenation and cyclization-cyanation reactions of [beta]-hydroxyalkynes and o-alkynylphenol and 'aniline derivatives have given rise to 3-halo- and 3-cyanofuro[3,2-b]pyrroles, 3-iodo-, 3-bromo-, and 3-cyanobenzofurans and 3-cyanoindoles.

Heterogeneous catalyzed carbonylation reactions are carried out by using the association of Pd/C and microwave dielectric heating. Pd/C is also used in microwave-assisted cyclocarbonylation of o-iodoaniline with acyl chlorides to produce benzoxazinones.

Carbohydrate oxime formation is catalyzed with up to 20-fold increases in overall reaction rate at 100 mM aniline. The application of the method has provided access to complex glycoconjugates.

The reaction of the benzotriazole N-oxyl radical (BTNO) with a series of 4-X-N,N-dimethylanilines (X = CN, C[F.sub.3], C[O.sub.2]C[H.sub.2]C[H.sub.3], C[H.sub.3], O[C.sub.6][H.sub.5], OC[H.sub.3]) is examined in C[H.sub.3]CN. The results are interpreted based on the electron-transfer mechanism from the N,N-dimethylanilines to the BTNO radical followed by deprotonation of the anilinium radical cation (ET-PT mechanism).

The application of the photo-[S.sub.N]1 reaction on some 4-chloroanilines was explored under solar irradiation with an objective to obtain a convenient metal-free arylation method. The photoarylation process improved by considering more environmentally friendly (co)solvents including water was found to have low impact on the environment and could be considered as serious competitor of metal-catalyzed arylations.

The introduction of ring strain in the dienophile, as with moderately strained bicycle[2.2.1]heptenes (norbornene), has enabled three-component Povarov reaction with in situ formed N-arylimines under Lewis acid catalyzed conditions (B[F.sub.3].O[Et.sub.2]). The preference for the formation of exo-exo diastereomic adducts is seen in most cases, but the formation of exo-endo adducts is observed for reactions of ortho- or meta-substituted anilines.

A simple synthesis of xanthenes and acridines based on a cascade nucleophilic addition-cyclic Michael addition process of arynes and phenols/anilines substituted with [alpha],[beta]-unsaturated groups at the ortho positions is described. The reaction could also be successfully adapted for the synthesis of 9-spiro-xanthene and acridine derivatives with potential biochemical interest.

3-Sulfenyl- and 3-selenylindoles are prepared by a two-step process involving the palladium/copper-catalyzed crossing coupling of N,N-dialkyl-ortho-iodoanilines and terminal alkynes and subsequent electrophilic cyclization of the resulting N,N-dialkyl-ortho-(1-alkynyl)anilines with arylsulfenyl chlorides or arylselenyl chlorides. The presence of a stoichiometric amount of n-[Bu.sub.4]NI is very important for the success of the electrophilic cyclization.

The reaction of 1,4-a ddition of anilines onto Michael acceptors which proceeds easily in specific polar protic solvents, without any promoting agent is described. The selectivity of the reaction could be fined tuned as per the solvent and the electrophile used.

The reaction of the N-(tert-butoxycarbonyl)-2-(1-ethoxycarbonyloxymethylallenyl) aniline with [K.sub.2]C[O.sub.3] or [Pd.sub.2][(dba).sub.3] in refluxing toluene was used to develop conditions for the preparation of the reactive N-(tert-butoxycarbonyl)indolo-2,3-quinodimethane intermediate. The obtained N-(tert-butoxycarbonyl)indolo-2,3-quinodimethane was captured by several alkenyl and alkynyl dienophiles to provide the corresponding tetrahydro- and dihydrocarbazole derivatives.

The reaction between the benzohydroxamate anion (BH[O.sup.-]) and bis(2,4-dinitrophenyl) phosphate (BDNPP) is examined kinetically and the products are characterized by mass and NMR spectroscopy. The studies have shown that the benzohydroxamate anion is considered a self-destructive molecular scissor since it has reacted and has lost its nucleophilic ability.

The scope of Pd-catalyzed synthesis of N-Boc-protected anilines from aryl bromides and tert-butyl carbamate is described. This process is conducted at room temperature by using a combination of [Pd.sub.2][dba.sub.3].CH[Cl.sub.3] and a monodentate ligand, tert-butyl X-Phos.

A scale-up of diazaindoline is achieved in four stages and the key step has involved rapid reductive amination aldehyde with aniline by sodium triacetoxyborohydride (STAB-H) and TFA followed by ring closure of intermediate amine to diazaindoline in the same place. These reaction conditions are applied for facile reductive aminations with anilines and the spectra data have shown the tris(trifluoroacetoxy)borohydride anion as the active reducing agent.

A new class of discotics derived from tris(N-salicyclideneaniline)s are prepared and their thermal and photophysical properties are examined. These systems with outer 1,3,4-oxadiazole wings are present in an inseparable mixture of two keto-enamine tautomeric forms with [C.sub.3h] and [C.sub.s] rotational symmetries and they self-assemble into fluid columnar phase over a wide thermal range.

A method is described for the one-step C-ureidoalkylation of phenol, anisole, or aniline rings furnishing ArC[H.sub.2]NHCONHR (Ar = benzyl) products. With phenol ring systems, higher yields are obtained when the reaction is worked up with an acidic ethanethiol addition to cleave any O-ureidoalkylation products that has formed during the reaction.

A one-pot synthesis is described for [alpha]-carbolines via a palladium-catalyzed aryl amination followed by intramolecular arylation. 2,3-Dichloro- and 2,3-dibromopyridines have reacted with anilines to obtain various substituted [alpha]-carbolines.

The development of a novel tandem reaction to obtain diverse Z-[beta]-(N-indolyl)-[alpha],[beta]-unsaturated esters from readily available [beta]-keto esters and o-alkynyl anilines is reported. The reaction includes the intermolecular [beta]-enamino ester formation and intramolecular cyclization catalyzed by In[Br.sub.3].

A synthetic route is described for bisanilino-1H-pyrrolo[2,3-d]pyrimidines, wherein the C(6)-chloride reactivity is enhanced via reversible acid-catalyzed internal activation of the pyrimidine ring by a C(1')-carboxamide moiety. The selective nucleophilic displacements at C(6) and C(1') has constituted a one-pot tandem protocol for the rapid assembly of bisanilino-1H-pyrrolo[2,3-d]pyrimidines.

The stereocontrol steps of the (S)-proline catalyzed Mannich reaction of cyclohexanone, formaldehyde, and aniline using dimethyl sulfoxide(DMSO) as a solvent is examined. This study has shown that syn- enamine is formed directly via direct proton transfer of the iminium ion, while anti- enamine, which is the starting conformation of the major S-intermediate, is formed through C-N bond rotation of syn- enamine.

An experimental approach is designed for determining the fraction of free amine base in nonaqueous solvents and the mechanistic details are determined for the reaction of phthalic anhydride with aniline in glacial acetic acid solution. An optimum condition is determined for maximum yield of product N-phenylphthalamic acid.

The synthesis of three organic sensitizers containing amorphous N,N-bis-dimethylfluoren-2-yl)aniline unit bridged by p-phenylene vinylene unit is reported. The power conversion efficiency of the DSSCs based on the three sensitizers is shown to be sensitive to the conjugation length of bridged phenylene vinylene groups.

A new approach for a facile and versatile synthesis of functionalized quinolines from 3-formylchromone and substituted anilines is discussed. The methodology is shown to be extremely useful for the synthesis of diverse sets of functional drug-like quinolines.

The utility of pyrrole 2-carboxylic acid as an effective ligand for the Cu-catalyzed monoarylation of anilines with aryl iodides and bromides is reported. The reaction conditions tolerated variety of useful functional groups to yield moderate to good amount of diaryl amine products.

The development of a new atom-economical In[(OTf).sub.3]-catalyzed synthesis of ring-condensed heteroaromatic compounds via a domino intramolecular nucleophilic attack/intermolecular cycloaddition/dehydration reaction is reported. The synthesis used readily available ortho-alkynylanilines and ortho-alkynylbenzaldehydes as starting materials.

A five-step synthesis of 1,8-bis(3-tert-butyl-9-acridyl)naphthalene N,N'-dioxide from 3-tert-butylaniline and 2-chlorobenzoic acid is reported. The findings help to develop a fluorescence ligand displacement assay that facilitates accurate measurements of both the total amount and the enantiomeric excess of several amino alcohols at micromolar concentrations.

An indium-catalyzed intramolecular cyclization of a 2-ethynylaniline having an alkyl or aryl group with the terminal alkyne, which selectively produced a variety of polyfunctionalized indole derivatives in moderate to excellent yields is reported. The findings reveal that indium-promoted reactions could be used for the intramolecular cyclization of other arylalkyne substrates having a carboxylic acid and an amide group.

A kinetic study of the N-demethylation reaction of a number of 4-X-substituted-N,N-dimethylanilines (where X = OMe, OPh, C[H.sub.3], H) promoted by 2,2-diphenyl-1-picrylhydrazyl radical (dpph*) in MeCN is reported. The reaction obtained provides insight into the single-step hydrogen transfer mechanism from the N-C-H bond to dpph* which might take the form a concerted proton-electron transfer (CPET).

The development of a one-pot procedure for the synthesis of substituted 2,6-dicyanoanilines starting from readily available ynones and malononitrile is reported. The synthesis provides a new one-pot pathway for regioselective formation of polysubstituted benzenes.

The development of a new one-pot, two-step procedure for amination/Diels-Alder reaction sequence from furans to anilines is reported. The first selective synthesis of stable oxabicyclic structures in Diels-Alder reactions were also reported which involved aminofuraldehydes as dienophiles.

The cross-coupling of aryl tosylates with amines and anilines is achieved by using a Ni-based catalyst system from the combination of Ni(II)-([sigma]-aryl) complexes/N-heterocyclic carbenes (NHCs). The limitations and scope of this reaction are discussed.