Secondary Aromatic Amines Research Articles

Molecular-Radical Catalysis of the Chain Reaction of Quinone Imine with Hydroquinone under the Action of Aromatic Amines

Secondary aromatic amines are catalysts of the chain reaction (v = 103 units) of N-phenyl-1,4-benzoquinone monoimine with 2,5-di-tert-butyl-1,4-hydroquinone. A complex mechanism of amine catalysis reveals that the rate of the chain reaction may increase, decrease, or remain unchanged in the presence of these compounds. In that case the product composition does not change, and amines are not consumed. The effects of temperature and the nature of para substituents (six species) on the activity of aromatic amines as catalysts were studied. A mechanism was proposed for the catalytic reaction; it implies the coupled occurrence of chain and catalytic processes. An expression for the rate of the catalytic reaction was obtained. The rate constants of individual steps with the participation of a catalyst and its radicals were calculated using the method of crossing parabolas. With the use of these data, a theoretical calculation of the dependence of the reaction rate on catalyst concentration was performed; the results were in good agreement with experimental data. The mechanism of the catalytic reaction was discussed; the similarities and distinctions between this mechanism and the mechanisms of other coupled chain reactions were demonstrated.

A NEW PROTOCOL FOR THE PREPARATION OF AMINALS FROM AROMATIC ALDEHYDES AND THEIR FACILE CONVERSION TO PHOSPHONATES

A new and fast method for the preparation of aminals is reported from the reaction of aromatic aldehydes and secondary amines in the presence of potassium carbonate in high yields. The aminal can be converted to the corresponding iminum salt in reaction with acetyl chloride very easily and in very short time with high yield. Addition of trialkylphosphite, as one possible nucleophile, to the prepared iminium salt produces the α-amino phosphonate in very high yield.

Dicationic [(BINAP)Pd(solvent)2]2+[TfO-]2: Enantioselective Hydroamination Catalyst for Alkenoyl-N-oxazolidinones.

Dicationic (BINAP)palladium(II) complex induced high enantioselectiviies in the addition of primary (and secondary) aromatic amines to α, β-unsaturated oxazolidinones (up to 93% ee).

A Simple Protocol for Direct Reductive Amination of Aldehydes and Ketones Using Potassium Formate and Catalytic Palladium Acetate.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Pd×Et3B‐Catalyzed Alkylation of Amines with Allylic Alcohols.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Utilization of Folin-Ciocalteu phenol reagent for the detection of certain nitrogen compounds.

To determine in more detail the reaction of Folin-Ciocalteu phenol reagent with nitrogen compounds, a number of hydroxylamine-related compounds and a large number of guanidine-containing compounds were tested. In general, guanidine compounds did not react strongly unless they were hydroxyamino or hydrazino derivatives. The non-hydroxyamino paralytic shellfish poison saxitoxin, however, reacted to a significant extent. This may be due to the presence of a five-membered ring structure and its analogy to 2-aminopurines, which react strongly. A number of simpler amines were also tested. Tertiary aliphatic amines, but not primary, secondary, or quaternary amines, reacted strongly with the reagent. Primary, secondary, and tertiary aromatic amines all reacted strongly with the reagent. Reactivity was extended to pyrroles and indole derivatives but not to imidazole and benzimidazole derivatives. Defining the reactivity of Folin-Ciocalteau phenol reagent with nitrogen compounds extends the usefulness of the reagent for the detection and determination of certain nitrogen compounds in basic extracts by colorimetric means and by thin-layer chromatography.

Parallel Synthesis of New β-Amino Esters via Conjugate Nucleophilic Additions­

The Michael addition of secondary cyclic aromatic and nonaromatic amines to methyl 2-{[(tert-butoxycarbonyl)amino]methyl}acrylate afforded substituted β [2] -amino esters in good to excellent yields.

A Simple Protocol for Direct Reductive Amination of Aldehydes and Ketones Using Potassium Formate and Catalytic Palladium Acetate

A method for direct reductive amination of aldehydes and ketones, including α,β-unsaturated carbonyl compounds, has been developed, which requires potassium formate as reductant and palladium acetate as catalyst. Suitable amines include both primary and secondary aliphatic and aromatic amines.

Pd.Et3B-catalyzed alkylation of amines with allylic alcohols.

A combination of catalytic amounts of Pd (0.05 mmol) and Et3B (0.3 mmol) promotes allylic alkylation of primary and secondary aromatic and aliphatic amines (1.0 mmol) by the direct use of allylic alcohols, providing tertiary amines in excellent yields under mild conditions (room temperature approximately 50 degrees C).

Electrochemical copolymerization and characterization of aniline and isoprene in aqueous p‐toluene sulfonic acid solution

AbstractUniform and adherent copolymer coating of poly(aniline‐co‐isoprene) was successfully formed on low‐carbon‐steel electrodes by potentiostatic electropolymerization. Electropolymerization was performed by using aqueous p‐toluene sulfonic acid solution as electrolyte. Applied potential and feed ratios of monomers (aniline and isoprene) were systematically varied and the reactions were done under aqueous conditions. The copolymer coatings were characterized by infrared spectroscopy and the formation of copolymer was confirmed by the presence of aliphatic secondary amine, aromatic secondary amine, and aliphatic CH stretch groups. The electronic structure of the copolymers was further investigated by using UV/Vis absorption spectroscopy. The electrochemistry of the formation of copolymers was studied by using cyclic voltammetry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 184–192, 2002; DOI 10.1002/app.10298

An Efficient Method for the Preparation of Vicinal Tertiary Diamines by Reductive Coupling of Aminoacetals Mediated by Low Valent Titanium Iodide Species

Abstract Aminoacetals, easily prepared by condensation of aromatic aldehydes, secondary amines and alcohols, are reductively coupled by using low valent titanium iodide species to afford the corresponding coupling products, vicinal tertiary diamines, in good to high yields under mild reaction conditions.

The synthesis of three novel pendant armed macrocyclic ligands. The X-ray crystal structure of a cadmium complex derived from the first oxaazamacrocycle bearing two alkylated aromatic amine functions

Three new macrocyclic ligands derived from 2,6-pyridinedicarbaldehyde have been prepared by N-alkylation of a secondary aliphatic amine and two secondary phenylic amines of the oxaazamacrocycle precursor (L) with p-nitrobenzylbromide and bromoacetonitrile. The trialkylated ligand 2 is the first example of a macrocyclic ligand bearing pendant arms on secondary aromatic amine nitrogens. Complexation reactions of macrocycles 2 and 3 with different hydrated metal salts were carried out in order to investigate the complexation capability of these new pendant arm macrocyclic ligands. The X-ray crystal structures of ligands 1 and 3 and of the cadmium complex of 2 have been obtained.

1‐Trifluoromethyl Epoxy Ethers. Effect of Hexafluoro‐2‐propanol on Reactions with Secondary Aromatic Amines: Synthesis of 3‐Trifluoromethyl Indole Derivatives.

ChemInformVolume 32, Issue 29 p. 47-47 Preparative Organic Chemistry 1-Trifluoromethyl Epoxy Ethers. Effect of Hexafluoro-2-propanol on Reactions with Secondary Aromatic Amines: Synthesis of 3-Trifluoromethyl Indole Derivatives. Isabelle Rodrigues, Isabelle Rodrigues Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this authorDaniele Bennet-Delpon, Daniele Bennet-Delpon Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this authorJean-Pierre Begue, Jean-Pierre Begue Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this author Isabelle Rodrigues, Isabelle Rodrigues Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this authorDaniele Bennet-Delpon, Daniele Bennet-Delpon Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this authorJean-Pierre Begue, Jean-Pierre Begue Fac. Pharm., BIOCIS, F-92296 Chatenay-Malabry, Fr.Search for more papers by this author First published: 25 May 2010 https://doi.org/10.1002/chin.200129047Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume32, Issue29July 17, 2001Pages 47-47 RelatedInformation

Exopolysaccharides of Xanthomonas pathovar strains that infect rice and wheat crops.

In order to understand the mode of action of the taxonomically related pathogens Xanthomonas campestris pv. translucens, Xanthomonas oryzae pv. oryzae, and Xanthomonas oryzae pv. oryzicola, which attack wheat and rice crops, we examined the compositional differences of their exopolysaccharides (EPSs). Maximum production of polysaccharide in shake cultures of these pathogens was observed between 24 and 72 h. X. campestris pv. translucens, the leaf streak pathogen of wheat, produced a higher amount of polysaccharide (46.97 microg/ml) at 72 h compared to X. oryzae pv. oryzae (42.02 microg/ml), the bacterial blight pathogen of rice, and X. oryzae pv. oryzicola (41.91 microg/ml), the bacterial leaf streak pathogen of rice. Infrared (FTIR) spectra suggested that the polysaccharides of all three Xanthomonas pathovar strains have an -OH group with intermolecular hydrogen bonding, a C-H group of methyl alkanes, an aldehyde (RCHO) group, a C=C or C=O group, and a C-O group. FTIR spectra also revealed the presence of an acid anhydride group in X. oryzae pv. oryzae, a secondary aromatic or aliphatic amine group in X. campestris pv. translucens, and a primary aromatic or aliphatic amine group in X. oryzae pv. oryzae and X. oryzae pv. oryzicola. Nuclear magnetic resonance (NMR) spectra revealed the presence of unsubstituted sugars, an acetyl amine of hexose or pentose, and a beta-anomeric carbon of hexose or pentose in the polysaccharides of all bacteria. NMR spectra also identified the alpha-anomeric carbon of hexose or pentose in all strains, and a branching at the fourth carbon of the sugar only in X. campestris pv. translucens; the presence of an uronic acid molecule (acid anhydride group) in X. oryzae pv. oryzae; and a deoxy sugar, rhamnose, in X. oryzae pv. oryzicola.

Chemiluminescence of polyamides III. Luminescence accompanying thermooxidation of lactam-based polyamides stabilized by antioxidants

Chemiluminescence accompanying oxidation of lactam-based polyamides stabilized with phenols and secondary aromatic amines as well as with a hindered nitroxy radical was measured. The yields of chemiluminescence per mol of oxygen absorbed were found to be higher for oxidation of polyamide in the presence of antioxidants than in their absence depending on the content of amino and carboxylic end-groups. Because antioxidants react with peroxy radicals by several consecutive inhibition reactions with different yields of chemiluminescence, the intensity of chemiluminiscence also depends on the rate of initiation of the oxidation. The relation between the intensity of chemiluminescence and the rate of oxygen consumption during oxidation of stabilized polyamides differed profoundly for various polyamides depending on their end-group content, on the concentration of antioxidant and also on the conditions of oxidation, especially on the rate of initiation determining the rate of antioxidant consumption. Redox inhibition reactions were found to be the predominant source of chemiluminescence accompanying the oxidation of N-alkylamides in the presence of antioxidants.

1-Trifluoromethyl epoxy ethers. Effect of hexafluoro-2-propanol on reactions with secondary aromatic amines: synthesis of 3-trifluoromethyl indole derivatives.

Trifluoromethyl epoxy ethers 1 and 2 reacted with aromatic amines in hexafluoro-2-propanol at room temperature providing trifluoromethyl indolinols 3 and 4 in excellent isolated yields. 3-Trifluoromethyl indoles 9 and 10 could be prepared by treatment of indolinols with SOCl(2).

Synthesis and in-vitro evaluation of novel low molecular weight thiocarbamates as inhibitors of human leukocyte elastase.

A series of novel low molecular weight thiocarbamate esters (1e-6e) were synthesized and evaluated as inhibitors of human leukocyte elastase (HLE). The thiocarbamate esters studied consist of a substituted primary or secondary aliphatic or aromatic amine and a 1-phenyl-1H-tetrazole-5-thiol (Table I). The HLE catalyzed hydrolysis of N-methoxysuccinyl- L-Ala-L-Ala-L-Pro-L-Val-p-nitroanilide substrate was utilized as the measure of inhibition. N-n-butyl, 1-phenyl-1H-tetrazole-5-thiocarbamate (1e) exhibited the highest inhibitory activity (k(obs) /[I] = 2.1 x 10(5) M(-1). min(-1) ) and N-allyl, 1-phenyl-1H-tetrazole-5-thiocarbamate (2e) (K(obs) /[I] = 6.1 x 10(4) M(-1). min(-1) ) exhibited the second highest inhibitory activity of all the thiocarbamates. The aromatic N-phenyl, 1-phenyl-1H-tetrazole-5-thiocarbamate (4e) showed the lowest inhibitory activity (K(obs) /[I] = 1.9 x 10(2) M(-1). min(-1) ) among the N-monosubstituted derivatives, similar to that of N-ethyl-N-n-butyl, 1-phenyl-1H-tetrazole-5-thiocarbamate (5e) (K(obs) /[I] = 1.8 x 10(2) M(-1).min(-1) ). The N-isopropyl, 1-phenyl-1H-tetrazole-5-thiocarbamate (3e) (K(obs) /[I] = 3.3 x 10(3) M(-1).min(-1) ) was about 10 fold more active than (4e) and N, N-diisopropyl, 1-phenyl-1H-tetrazole- 5-thiocarbamate (6e) showed no inhibitory activity against HLE. In the present work less than 3% of HLE specific activity was regained after 24 hours incubation with each of the tested N-monosubstituted thiocarbamates (1e-4e). The time-dependent inhibition of HLE by the thiocarbamate compounds (1e-5e) seems to involve the interaction and possible chemical modification of one enzyme residue. Straight chain nonpolar aliphatic substituents on the nitrogen of the thiocarbamate functionality may be essential for high inhibitory activity. As the degree of substitution (branching) on the nitrogen of the thiocarbamate functionality increases the inhibitory activity of the compounds decreases. The time-dependent inhibition of HLE and the slow deacylation rates by the N-monosubstituted thiocarbamates are consistent with irreversible inhibition.

Assessment of potential mutagenic activities of a novel benzothiazole MAO-A inhibitor E2011 using Salmonellatyphimurium YG1029

The potential initiation activities of a novel monoamine oxidase type-A (MAO-A) inhibitor E2011, which induced preneoplastic foci in the rat liver, were investigated by comparing the mutagenic activity of E2011, 6-aminobenzothiazole (6-ABT, a structural scaffold of E2011) and its derivatives, which are suggested primary reactive metabolites for E2011-induced hepatotoxicity in the rats in vivo, in the Ames assay system employing two Salmonella tester strains, TA100 and YG1029, a bacterial O-acetyltransferase-overproducing strain of TA100. E2011, a tertiary amine, showed no mutagenic activity both in the Salmonella typhimurium TA100 and YG1029 with and without S9 mix. On the other hand, a secondary aromatic amine ER-174238-00, a typical decarbonated metabolite of E2011, showed weak but significant mutagenicity in YG1029 in the presence of S9 mix, and a primary aromatic amine ER-174237-00, an N-dealkylated derivative of ER-174238-00, exhibited S9-dependent potent mutagenicity in YG1029. Thus, it appears that primary and secondary amino moieties of benzothiazole derivatives at C 6-position are the specific structures contributing to their mutagenic activity. In addition, the alkyl group at C 2-position of E2011, ER-174237-00 and ER-174238-00 is suggested to intensify the mutagenic activity, since the mutagenicity of ER-174237-00 is approximately two-fold higher than that of 6-ABT, which has hydrogen at C 2-position in the place of the alkyl group. These results strongly suggest that E2011 has potential initiation activities in the rat liver in vivo after undergoing decarbonation, one of the metabolic pathways, at the carbonyl moiety of oxazolidinone ring to form mutagenic amine(s).

ChemInform Abstract: Copper-Catalyzed N-Arylation of Amines with Hypervalent Iodonium Salts.

The copper-catalyzed N-arylation of amines with hypervalent iodonium compounds with secondary aliphatic amines, aromatic amines, azoles and amides was accomplished with catalytic CuI (10 mol%) or Cu(acac)2 (5 mol%) in the presence of Na2CO3 or K2CO3 as a base in CH2Cl2 or toluene under mild conditions.

Catalytic oxidative carbonylation of aliphatic secondary amines to tetrasubstituted ureas

Secondary amines can be catalytically carbonylated to symmetrical tetrasubstituted ureas using W(CO) 6 as the catalyst, I 2 as the oxidant, and CO as the carbonyl source. Preparation of the corresponding tetrasubstituted ureas from the aliphatic secondary amines HNR 2 (R=C 2H 5, n-Bu, i-Pr, PhCH 2) and HNRR′ (R,R′=(CH 2) 4; (CH 2) 5; PhCH 2, CH 3) was achieved in moderate yields. Aromatic secondary amines are unreactive.