cas 2217-07-4, N,N-DI-N-PROPYLANILINE | Articles data

Articles about 2217-07-4Total 44 be found

Article title
Article abstract
Author
Journal number and time
Download

Nickel-catalysed amination of aryl chlorides using a dihydroimidazoline carbene ligand
A new arylamination protocol has been developed using a catalyst combination prepared from Ni(acac)2 associated to a sterically hindered dihydroimidazoline carbene ligand. A high efficiency was attained using, in most cases, only 2 mol% Ni/carbene clusters.
Gradel, Benot,Brenner, Eric,Schneider, Rapha?l,Fort, Yves
p. 5689 - 5692
(2001)
Read Online

Preparation method of N-alkylated derivative of primary amine compound
The invention relates to a preparation method of an N-alkylated derivative of a primary amine compound. The method comprises the following steps: uniformly mixing a primary amine compound, an alcohol compound and a catalyst in a reactor, and heating to react for a period of time to generate an N-alkylated substituted tertiary amine compound; wherein the catalyst is a copper-cobalt bimetallic catalyst, and the carrier of the catalyst is Al2O3. According to the method, alcohol is adopted as an alkylating reagent and is low in price and easy to obtain, a byproduct is water, no pollution is caused to the environment, and the overall reaction atom economy is high; the catalyst is simple in preparation method, low in cost, high in reaction activity and good in structural stability; meanwhile, by using the copper-cobalt bimetallic catalyst, the use of strong base additives can be avoided, and the requirement on reaction equipment is low; and the reaction post-treatment is convenient, and the catalyst can be recycled and is environment-friendly.
-
Paragraph 0021; 0055

(2021/07/09)

Heterogeneous Ru/TiO2for hydroaminomethylation of olefins: multicomponent synthesis of amines
Synthesizing aminesviathe hydroaminomethylation (HAM) reaction of olefins, a multicomponent reaction, has been regarded as one of the most attractive methods compared with the traditional methods considering the atom economy and environmental friendliness. However, the use of homogeneous catalysts, complex ligands containing diphosphine or nitrogen, and base or acid additives has severely hampered the utilization of these methods. Herein, an efficient heterogeneous Ru/TiO2-catalyzed HAM reaction of olefins is developed without any additives. Various amines, including secondary and tertiary amines, can be successfully obtained from olefins including aromatic and aliphatic olefins. Systematic studies demonstrate the lower electron density of Ruδ+and the higher number of acid sites of Ru/TiO2, leading to the high HAM reaction activity of olefins. Most importantly, nitrobenzene derivatives can also be transformed to the corresponding products over Ru/TiO2in excellent yields.
An, Jinghua,Gao, Zhuyan,Wang, Yehong,Zhang, Zhixin,Zhang, Jian,Li, Lu,Tang, Bo,Wang, Feng
supporting information
p. 2722 - 2728
(2021/04/21)

Reductive Alkylation of Amines with Carboxylic Ortho Esters
We have demonstrated for the first time that carboxylic ortho esters could be used as an alkylating agent in the reductive alkylation of amines. A variety of amines, including amino acid esters, were alkylated affording mono-alkylated products with high selectivity in practical to high yields using standard heterogeneous catalysts. By applying acyclic ortho esters alkylation was completed at room temperature. (Figure presented.).
Kadyrov, Renat,Moebus, Konrad
supporting information
p. 3352 - 3357
(2020/07/04)

3-hydroxy flavone compound and application thereof
The invention belongs to the technical field of biological fluorescence analysis, and particularly relates to a 3-hydroxy flavone compound and an application thereof. The compound is particularly a 4-n,n-dialkylamino-3-hydroxy flavone compound, and when the compound is used as a fluorescent dye, the lipid droplet targeting property is better, and a cytoskeleton is hardly colored. When conjugated structures such as a benzene ring and the like are added to the left side of a molecule of the compound, the emission wavelength of the molecule can be greatly prolonged, and fluorescence crossing of the molecule from yellow to red is realized. The compound can be applied to the aspects of dynamic lipid droplet imaging in cells, lipid droplet growth process imaging, adipose tissue imaging, even simultaneous imaging of intramuscular fat and intermuscular fat in skeletal muscle tissues, and the like, and has important application values in the fields of fluorescent dyes, biological fluorescent labels and the like.
-
Paragraph 0043; 0047-0053

(2019/11/28)

Colloidal and Nanosized Catalysts in Organic Synthesis: XXIII. Reductive Amination of Carbonyl Compounds Catalyzed by Nickel Nanoparticles in a Plug-Flow Reactor
Reductive amination of aldehydes and ketones with primary and secondary amines under catalysis with nickel nanoparticles supported on zeolite X, MgO, or activated carbon in the gas phase or in the gas-liquid system in a plug-flow reactor proceeds at atmospheric pressure of hydrogen with the formation of secondary or tertiary amines in high yield.
Mokhov, V. M.,Nebykov, D. N.,Paputina, A. N.,Popov, Yu. V.,Shishkin, E. V.
p. 2333 - 2340
(2020/02/25)

Plasma-Made (Ni0.5Cu0.5)Fe2O4 Nanoparticles for Alcohol Amination under Microwave Heating
Amine N-alkylation is a process involved in the production of a wide range of chemicals. Here we describe the synthesis of well-defined (Ni0.5Cu0.5)Fe2O4 magnetic nanoparticles by plasma induction, and their successful application to amine N-alkylation using alcohols as coupling agents through a borrowing hydrogen pathway. Plasma induction allows precise morphology and size control over nanoparticle synthesis, while allowing the one-pot production of decagram quantities of material. Up to date, such nanoparticles have never been applied for organic reactions. By coupling high-end characterization techniques with catalytic optimization, we showed that small Cu(0) satellite nanoparticles played an essential role in alcohol oxidation, whereas both Ni and Cu were required for the last step of the reaction. Using elemental mapping, we demonstrated that catalyst deactivation occurred through a leaching/re-deposition mechanism of Cu and Ni. The reactions were conducted under microwave conditions, which exerted a positive effect on catalytic activity. Finally, the catalyst was active at low metal loadings (2 mol%) even on the gram-scale, and affording unprecedented TON for this reaction catalyzed by Ni/Cu bimetallic systems (19).
Li, Alain You,Dumaresq, Nicolas,Segalla, Andréanne,Braidy, Nadi,Moores, Audrey
p. 3959 - 3972
(2019/08/12)

Nano CoCuFe2O4-catalyzed coupling reaction of arylboronic acid with amines and thiols: An atom-economic and ligand-free route to access unsymmetrical amines and sulfides
An efficient protocol was developed for the nano CoCuFe2O4-catalyzed C-N and C-S bond formation. By this catalytic system, both amine and sulfide-based structural motifs were formed efficiently in aryl halide-free route. The amination reaction of phenyl boronic acid with various types of amines was conducted under ligand-free conditions, in ethanol as a green solvent at 60°C. Unsymmetrical diaryl/aryl alkyl sulfide synthesis via the coupling reaction of arylboronic acids with thiols was also conducted. The nano cobalt-copper ferrite was used as a heterogenous efficient, inexpensive, magnetically separable and recyclable catalyst that can be used for several cycles.
Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh,Gholamtajari, Milad
(2018/10/20)

Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts
With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.
Zhang, Zhiang,Wu, Xunshen,Han, Jianwei,Wu, Wenjun,Wang, Limin
supporting information
p. 1737 - 1741
(2018/04/02)

Efficient synthesis of tertiary amine by direct N-alkylation of secondary amine with carboxylic acid using Ni (0) encat catalyst
In this article, direct N-alkylation of secondary amines with carboxylic acid is described. Readily available diversified carboxylic acid has been explored on variant secondary amines using encapsulated Nickel as catalyst and inexpensive sodium borohydrid
Quadri, Syed Aziz Imam,Das, Tonmoy C.,Jadhav, Shivaji,Farooqui, Mazahar
p. 267 - 277
(2018/01/08)

N-Alkylation of Aniline and Its Derivatives by Alcohols in the Presence of Copper Compounds
N-Alkyl- and N,N-dialkyl-substituted anilines were obtained in the reaction of aniline and its derivatives with primary and secondary alcohols in the presence of catalysts CuCl2·2H2O, CuBr2 and halomethanes as promoters.
Bayguzina,Musina, Ch. F.,Khusnutdinov
p. 1652 - 1659
(2019/02/12)

Heterogeneous catalytic synthesis of quinoline compounds from aniline and C1-C4 alcohols over zeolite-based catalysts
The synthesis of quinolines from aniline and a C1-C4 alcohol was conducted under gas-phase reaction conditions over a series of zeolite-based catalysts. The texture and acid properties of catalysts were characterized by XRD, FT-IR, BET and NH3-TPD techniques. It was found that the total yield of quinolines was positively related to the relative content of Lewis acid sites of the catalyst. Among others, the ZnCl2/Ni-USY-acid catalyst possessed the best performance. Over this catalyst, the reactions of aniline and most of the alcohols provided a 42.3-79.7% total yield of quinolones under mild conditions, however, those of aniline and methanol, ethanol and iso-propanol predominantly led to N-alkylanilines. Furthermore, the reaction pathways for synthesizing quinolines via aniline reacting with polyhydric alcohols or monohydric alcohols was proposed in our work.
Huang, Chen,Li, An,Chao, Zi-Sheng
p. 48275 - 48285
(2017/10/31)

Synthesis of quinolines from aniline and propanol over modified USY zeolite: Catalytic performance and mechanism evaluated by: In situ Fourier transform infrared spectroscopy
The reaction of aniline and propanol to quinolines was conducted in a fixed-bed flow-type reactor, using a series of modified USY zeolite catalysts. The structural, textural and acidic properties of the catalyst were characterized by XRD, N2-physisorption, 27Al MAS NMR, NH3-TPD and pyridine-FTIR, while the mechanism for the reaction of aniline and propanol was investigated by in situ FTIR. It was identified that the reaction of aniline and propanol generated predominantly quinolines, including 2-ethyl-3-methylquinoline and other alkyl quinoline, N-alkyl aniline and other byproducts. Among others, the ZnCl2/Ni-USY catalyst exhibited the best performance, providing a 96.4% conversion of aniline and a 78.3% total yield of quinolines with 81.2% total selectivity to quinolines and 60.1% selectivity to 2-ethyl-3-methylquinoline at 683 K. This was attributed to the larger concentration ratio of Lewis acid sites to Bronsted acid sites over the ZnCl2/Ni-USY catalyst, relative to other catalysts. There were predominantly two possible routes for the formation of quinolines, which required predominantly Lewis acid sites and Bronsted acid sites, respectively. In both the routes, N-phenylpropan-1-imine was proposed as the key intermediate. Relative to that based on Bronsted acid sites, the route based on Lewis acid sites appeared to contribute much more in the generation of quinolines from the reaction of aniline and propanol.
Huang, Chen,Li, An,Li, Li-Jun,Chao, Zi-Sheng
p. 24950 - 24962
(2017/07/10)

Monocarboxylate transporter 1 inhibitors as potential anticancer agents
Potent monocarboxylate transporter 1 inhibitors (MCT1) have been developed based on α-cyano-4-hydroxycinnamic acid template. Structure-activity relationship studies demonstrate that the introduction of p-N, N-dialkyl/diaryl, and o-methoxy groups into cyanocinnamic acid has maximal MCT1 inhibitory activity. Systemic toxicity studies in healthy ICR mice with few potent MCT1 inhibitors indicate normal body weight gains in treated animals. In vivo tumor growth inhibition studies in colorectal adenocarcinoma (WiDr cell line) in nude mice xenograft models establish that compound 27 exhibits single agent activity in inhibiting the tumor growth.
Gurrapu, Shirisha,Jonnalagadda, Sravan K.,Alam, Mohammad A.,Nelson, Grady L.,Sneve, Mary G.,Drewes, Lester R.,Mereddy, Venkatram R.
supporting information
p. 558 - 561
(2015/05/27)

Enhanced Reactivity of Aerobic Diimide Olefin Hydrogenation with Arylboronic Compounds: An Efficient One-Pot Reduction/Oxidation Protocol
A catalyst-free and efficient method for simultaneous olefin hydrogenation and oxidation of arylboronate esters to phenols with hydrazine hydrate and molecular oxygen is presented. The process is based on the utilization of a readily available Lewis acidic arylboron compound, which evades common problems associated with the catalyst-free aerobic hydrogenation of olefins with diimide. Using an operationally simple procedure, the protocol smoothly delivers phenol derivatives and various alkanes in excellent yields with remarkable functional group compatibility. The method allows the reaction to be scaled up to 1 g of the starting materials.
Santra, Surojit,Guin, Joyram
supporting information
p. 7253 - 7257
(2015/11/25)

Catalytic N-Alkylation of Amines Using Carboxylic Acids and Molecular Hydrogen
A convenient, practical and green N-alkylation of amines has been accomplished by applying readily available carboxylic acids in the presence of molecular hydrogen. Applying an in situ formed ruthenium/triphos complex and an organic acid as cocatalyst, a broad range of alkylated secondary and tertiary amines are obtained in good to excellent yields. This novel method is also successfully applied for the synthesis of unsymmetrically substituted N-methyl/alkyl anilines through a direct three-component coupling reaction of the corresponding amines, carboxylic acids, and CO2 as a C1 source.
Sorribes, Iván,Cabrero-Antonino, Jose R.,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
p. 13580 - 13587
(2015/11/10)

Direct N-alkylation of aromatic amines using a microflow reactor: Enhancement of selectivity and reactivity
A simple and highly atom-economical method for the direct N-alkylation of aromatic amines by using a microflow reactor was developed to overcome the problem of over-alkylation. In the developed method, high-yield conversion (up to 100%) was achieved in a relatively short reaction time. The ratio of mono- to di-benzylated products (3.57:1) was higher than that achieved with batch reactions conducted in a 1 L scale flask (0.87:1). The structural features of the microflow reactor meant that short-chain alkyl halides could be converted into products with high reactivity and selectivity under superheating conditions, although their boiling point was much lower than the reaction temperature. This method was successfully applied to the synthesis of a range of secondary amines including an intermediate of indobufen synthesis.
Choi, Yong-Sung,Kim, Yoon-Jung,Shen, Liu-Lan,Lee, Yong Sup,Jeong, Jin-Hyun
supporting information
p. 970 - 974
(2015/04/27)

Relationship between molecular stacking and optical properties of 9,10-bis((4-N,N-dialkylamino)styryl) anthracene crystals: The cooperation of excitonic and dipolar coupling
Five 9,10-bis((4-N,N-dialkylamino)styryl) anthracene derivatives (DSA-C1-DSA-C7) with different length alkyl chains were synthesized. They showed the same color in dilute solutions but different colors in crystals. The absorption, photoluminescence, and fluorescence decay indicate that there exist both excitonic and dipolar coupling in crystals of DSA-C1-DSA-C7. X-ray crystallographic analysis revealed that all the crystals belong to the triclinic space group P1 with one molecule per unit cell and that the molecules in every crystal have the identical orientation. This offers ideal samples to investigate the impact of the molecular stacking on the optical properties of the crystals. For the first time, the cooperation of excitonic and dipolar coupling has been comprehensively studied, and the contribution to the spectral shift from the excitonic and dipolar couplings quantitatively obtained. The experiments of amplified spontaneous emission (ASE) together with measurements of the quantum efficiency further confirmed this interpretation. The results suggest that the excitonic and dipolar couplings between the adjacent molecules are both important and jointly induce the spectral shifts of the crystals.
Li, Feng,Gao, Na,Xu, Hai,Liu, Wei,Shang, Hui,Yang, Wenjun,Zhang, Ming
supporting information
p. 9991 - 9997
(2014/08/18)

Direct catalytic N-alkylation of amines with carboxylic acids
A straightforward process for the N-alkylation of amines has been developed applying readily available carboxylic acids and silanes as the hydride source. Complementary to known reductive aminations, effective C-N bond construction proceeds under mild conditions and allows obtaining a broad range of alkylated secondary and tertiary amines, including fluoroalkyl-substituted anilines as well as the bioactive compound Cinacalcet HCl.
Sorribes, Iván,Junge, Kathrin,Beller, Matthias
p. 14314 - 14319
(2014/12/10)

Solvent-free Buchwald-Hartwig reaction of aryl and heteroaryl halides with secondary amines
A highly efficient solvent-free protocol for the Buchwald-Hartwig amination of (hetero)aryl halides by secondary amines was developed. The reaction is mediated by a Pd(OAc)2/RuPhos catalytic system in air. Various (hetero)aryl halides were coupled with diaryl, alkyl-aryl, and dialkylamines in good to excellent yields (51 examples, 50-99% yield). Copyright
Topchiy, Maxim A.,Asachenko, Andrey F.,Nechaev, Mikhail S.
p. 3319 - 3322
(2014/06/09)

A mild and catalyst-free aromatization using dihydroxylcyclohexanone derivatives as phenyl sources: A new approach to anilines
A new and efficient protocol for the preparation of N-substituted anilines via an aromatization reaction was developed. 3,5-Dihydroxylcyclohexanone derivatives were used as the sources of the phenyl group and reacted smoothly with primary or secondary amines under mild conditions in the absence of metal catalyst and strong base. A variety of N-substituted anilines were prepared by this method with excellent yields up to 99%. The results indicate that this reaction begins with a nucleophilic addition.
Luo, Jun,Ji, Enwei,Ye, Jingyuan,Wu, Runze,Qiu, Lei
p. 4505 - 4508
(2013/08/23)

Direct base-assisted C-N bond formation between aryl halides and aliphatic tertiary amines under transition-metal-free conditions
Direct base-mediated amination of aryl halides with aliphatic tertiary amines via an aryne intermediate was developed under transition-metal-free conditions. This operationally simple C-N bond-coupling protocol could tolerate a variety of functionalized aryl halides as well as several aliphatic tertiary amines. Moreover, this environmentally benign process provides a new strategy for direct C-N bond formation.
Fang, Yang,Zheng, Yueqin,Wang, Zhiyong
supporting information; experimental part
p. 1495 - 1498
(2012/04/17)

Titania-supported iridium subnanoclusters as an efficient heterogeneous catalyst for direct synthesis of quinolines from nitroarenes and aliphatic alcohols
A versatile heterogeneous catalyst consisting of sub-nanosized iridium clusters deposited on titania (Ir/TiO2-NCs) promotes the direct tandem synthesis of quinoline derivatives from readily available nitroarenes and aliphatic alcohols under mild and additive-free conditions (see scheme). The process tolerates the presence of various reactive functional groups and is highly selective.
He, Lin,Wang, Jian-Qiang,Gong, Ya,Liu, Yong-Mei,Cao, Yong,He, He-Yong,Fan, Kang-Nian
supporting information; experimental part
p. 10216 - 10220
(2011/11/13)

Synthesis of a sensitive and selective potassium-sensing fluoroionophore
"Chemical Equation Presented" An efficient synthesis is reported that delivers in 5 steps and 52% overall yield a new structurally simplified fluorescent K+ sensor with improved K+ sensitivity and selectivity over existing K+ sensors. The synthesis procedure utilizes a new template-directed oxidative C-N bond-forming macrocyclization reaction and reports new approaches to Pd(O), Sandmeyer-like and metal-free aminoarylations, as well as organotitanium additions to vinylogous sulfonates.
Carpenter, Richard D.,Verkman
supporting information; experimental part
p. 1160 - 1163
(2010/05/18)

Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles
(Chemical Equation Presented) A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.
Nacario, Ruel,Kotakonda, Shailaja,Fouchard, David M. D.,Tillekeratne, L. M. Viranga,Hudson, Richard A.
p. 471 - 474
(2007/10/03)

Iron-catalyzed transformations of 2-chloro-1,6-heptadienes
(Phosphane)iron complexes in the presence of excess trialkylaluminium reagents catalyze various transformations of 2-chloro-α,ω-dienes, depending on their structure. Most notably, in the cases of simple 2-chloro-1,6-heptadienes, cyclization with transfer of the alkyl group (Me and Et) from the corresponding trialkylaluminium compound was observed to give 2-alkyl-1-methylidenecyclopentanes. Reaction with 2-chloro-1,7-octadiene afforded the product of reductive dehalogenation. In the case of 2-chloro-4-aza-1,6-heptadiene a partial or complete hydrogenation of the double bonds was observed depending on the amount of trialkylaluminum reagent used. Interestingly, allyl(2-chloroallyl)malonate underwent C-C bond cleavage with the loss of an allyl group to give (2-chloroallyl)malonate. In the presence of ruthenium catalysts only reductive dehalogenation was observed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Necas, David,Kotora, Martin,Cisarova, Ivana
p. 1280 - 1285
(2007/10/03)

Aromatization of enamines promoted by a catalytic amount of Pd/C. Synthesis of aromatic amines
(Matrix presented) Aromatic amines were obtained efficiently from enamines by using a catalytic amount of Pd/C in the presence of nitrobenzene and 4 A molecular sieves in refluxing toluene.
Cossy, Janine,Belotti, Damien
p. 2557 - 2559
(2007/10/03)

Ruthenium-catalysed selective N-monoalkylation of anilines with tetraalkyl-ammonium halides
Anilines react with an array of tetraalkylammonium halides in the presence of a catalytic amount of a ruthenium catalyst together with SnCl2·2H2O in dioxane at 180°C to afford selectively N-monoalkylanilines in good yields.
Chan Sik Cho,Joon Seok Kim,Hun Seol Kim,Kim,Sang Chul Shim
p. 3791 - 3797
(2007/10/03)

A novel strategy for N-alkylation of primary amines+
N-alkylation of primary amines has been carried out with alkylbromide using commercial Me2SO and K2CO3 as a base. This process offers a method of selection for obtaining either mono or dialkyl amines.
Srivastava, Sanjay K.,Chauhan, Prem Man Singh,Bhaduri, Amiya P.
p. 2085 - 2091
(2007/10/03)

Nickel-catalysed couplings of aryl chlorides with secondary amines and piperazines
The reaction of aryl chlorides with secondary amines or piperazines in the presence of an in situ generated liganded nickel catalyst gives arylamines in good yields. Our process provides a mild, convenient and cheap method of arylamination starting from readily available substrates.
Brenner, Eric,Schneider, Raphael,Fort, Yves
p. 12829 - 12842
(2007/10/03)

Gas-phase selective N-alkylation of amines with alcohols over γ- alumina
Gas-phase conditions were successfully used for fine chemistry, in the N-alkylation of amines with alcohols as alkylating agents and γ-alumina as a catalyst. The method is also suitable for chiral compounds.
Valot, Frederic,Fache, Fabienne,Jacquot, Roland,Spagnol, Michel,Lemaire, Marc
p. 3689 - 3592
(2007/10/03)

Identification of 4-(N,N-Dipropylamino)Benzaldehyde as a Potent, Reversible Inhibitor of Mouse and Human Class I Aldehyde Dehydrogenase
As the physiologic roles for the different classes of aldehyde dehydrogenase (ALDH) enzymes are elucidated, the identification of specific, reversible inhibitors becomes of great pharmacologic interest. Previous structure-function studies identified dialkylamino substituted benzaldehyde compounds as a novel class of reversible inhibitors of class I ALDH. To examine further structural requirements for inhibition, we tested a series of 4-(N,N-dialkylamino)benzaldehyde analogs as inhibitors of propanal oxidation by mouse liver and human erythrocyte class I ALDH. 4-(N,N-dipropylamino)benzaldehyde (DPAB) was identified as the most potent, reversible inhibitor of propanal oxidation by class I ALDH in spectrophotometric enzyme assays. In kinetic studies, DPAB showed mixed-type inhibition with respect to the aldehyde substrates propanal, phenylacetaldehyde, benzaldehyde, and aldophosphamide. DPAB exhibited uncompetitive inhibition with respect to the cofactor NAD. Inhibition constants (Ki) for DPAB, estimated from Dixon plots, were 10 nM (propanal) and 77 nM (phenylacetaldehyde) for mouse ALDH and 3 nM (propanal) and 70 nM (phenylacetaldehyde) for human ALDH. These Ki values are 100-fold lower than those reported for class I specific inhibitors. At low ( 75 percent, whereas inhibition of benzaldehyde (32 percent) and phenylacetaldehyde (19 percent) oxidation was reduced markedly. These results indicate that DPAB exhibits potent, reversible inhibition of mouse and human class I ALDH. The degree of inhibition was highly dependent on the structure of the aldehyde substrate.
Russo, James,Chung, Song,Contreras, Kristi,Lian, Brian,Lorenz, Jon,Stevens, David,Trousdell, Wendy
p. 399 - 406
(2007/10/03)

N-ALKYLATION AND N-ARYLATION OF ANILINES STARTING FROM A MILD N-Mg REAGENT: ITS ACTIVATION CAUSING THE 'N-C' COUPLING TO EXTEND THE UNIFIED STRUCTURE-REACTIVITY RELATIONSHIP
New N-alkylation and N-arylation procedures starting from anilinomagnesium (ArNHMgBr) are reported.For N-alkylation with alkyl bromides, addition of hexamethylphosphoramide to an ArNHMgBr solution in tetrahydrofuran (THF) is effective.After heating at 55 deg C, N-monoalkylation product was obtained in 60-90percent yield, slight dialkylation taking place.The combined use of aryliminodimagnesium with α,ω-dibromoalkanes led to N-arylazacycloalkanes.For N-arylation with iodobenzene, replacement of THF with pyridine and additional use of copper(I) iodide are effective.After heating at 115 deg C with iodobenzene, mono- and diarylation products were obtained, the former being predominant.The combined use of ArNHMgBr and N,N,N',N'-tetramethylethylenediamine as the ligand of copper species is effective for elimination of diarylation and other undesired products, and leads to diarylamines in excellent yield.The method is of advantage over the conventional Ullmann and Chapman methods.The polar solvents and copper salt are effective additives for inducing 'inert combinations' of ArNHMgBr or ArN(MgBr)2 with alkyl and aryl halides into N-C coupling, to extend the unified view proposed for the reactivity of magnesium reagents.The difference in the roles of N-Mg and N-Cu species is discussed.
Matsuo, Koji,Shichida, Yoshiaki,Nishida, Hiroshi,Nakata, Satsuki,Okubo, Masao
p. 9 - 17
(2007/10/02)

IMPROVED SYNTHESIS OF N-ALKYLANILINES
A kinetic study and subsequent calculations showed that the reaction of aniline with aliphatic alcohols over Raney nickel follows a second-order equation.Upon changing pH from 7 to 8-10 the reaction order is retained, but the rate constant increases by a factor of ca. 10.
Ivanov, E. I.,Polishchuk, A. A.
p. 286 - 287
(2007/10/02)

Preparation of hexenedioic acid diesters
Hexene-1,6-dioates, readily hydrogenated into adipates (which in turn are conveniently hydrolyzed into adipic acid), are prepared by reacting carbon monoxide, an alcohol and at least one dichlorobutene, in the presence of a catalytically effective amount of palladium or a palladium compound and no more than two equivalents (relative to the dichlorobutene) of a tertiary amine reaction promoter; in an alternate embodiment, the tertiary amine and the dichlorobutene are first converted into a quaternary ammonium chloride intermediate.
-
(2008/06/13)

Substituted N,N-Dialkylanilines: Relative Ionization Energies and Proton Affinities through Determination of Ion-Molecule Reaction Equilibrium Constants
The relative ionization energies and proton affinities of N,N-dimethyl-, N,N-diethyl-, and N,N-di-n-propylaniline, and meta- and para-methyl-substituted analogues (as well as N,N,3,5-tetramethylaniline and 4-chloro-N,N-diethylaniline) have been determined in the gas phase through measurements of the equilibrium constants of charge-transfer and proton-transfer reactions in an ion cyclotron resonance spectrometer.Absolute values are assigned to the ionization energies and proton affinities generated in these experiments.Comparison atandards were the ionization potential (7.12 eV) and proton affinity (223.4 kcal/mol) for N,N-dimethylaniline taken from the literature.The heats of formation of the parent radical cations, M+, and the corresponding protonated molecules, MH+, vary in the same way, differing from one another by 21 +/- 2 kcal/mol over the entire set; that is, the radical cations of these compounds display a constant hydrogen affinity of 74 +/- 2 kcal/mol.This is interpreted to mean that all the compounds protonate at the nitrogen atom; previous work had suggested that meta-substituted isomers protonate on the ring.Further, it is demonstrated that variations in both the ionization energy and the proton affinity values upon changes in ring substitution can be predicted from the appropriate Hammett ? values, but not from the corresponding ?+ values; changes brought about by differing N-substituents correlate with ?* values.
Lias, Sharon G.,Jackson, Jo-Anne A.,Argentar, Harold,Liebman, Joel F.
p. 333 - 338
(2007/10/02)

ARYLATION OF PRIMARY AND SECONDARY AMINES BY MEANS OF ALKYLPYRIDINIUM SALTS
-
Sagitullin, R. S.,Lugovik, B. A.,Shkil', G. P.,Zhelyaeva, I. M.
p. 340
(2007/10/02)

Ruthenium-Catalyzed N-Alkylation and N-Benzylation of Aminoarenes with Alkohols
Aminoarenes were readily converted into secondary and tertiary amines by the reaction at 150-180 deg C with primary alcohols in the presence of a catalytic amount (1 mol percent based on the aminoarene) of a ruthenium complex.Dichlorotris(triphenylphosphine)ruthenium was the most effective catalyst precursor.Secondary amines were obtained in excellent yields when aminoarenes reacted with an equimolar amount of alcohols.With excess alcohols, tertiary amines were obtained predominantly.Kinetic measurements revealed that the rate had zero-order dependence on aminoarene concentration and first-order dependence on alcohol concentration and initial concentration of the ruthenium catalyst.From the kinetic features, the possible catalytic cycle, which includes the nucleophilic attack of the aminoarene on aldehyde intermediate, was postulated.
Watanabe, Yoshihisa,Tsuji, Yasushi,Ige, Hitoshi,Ohsugi, Yukihiro,Ohta, Tetsuo
p. 3359 - 3363
(2007/10/02)

The Transition Metal-catalyzed N-Alkylation and N-heterocyclization. A Reductive Transformation of Nitroarenes into (Dialkylamino)arenes and 2,3-Dialkyl-substituted Quinolines Using Aliphatic Aldehydes under Carbon Monoxide
The catalytic N-alkylation and N-heterocyclization of nitroarenes occur at 180 deg C under a carbon monoxide pressure of 70 atm and in the presence of aldehyde and such transitionmetal complexes as rhodium and palladium complexes, thus giving 2,3-dialkyl-substituted quinolines and (dialkylamino)arenes in good yields.The product selectivity depends greatly on the catalysts: a binary catalyst, RhCl(PPh3)3 and PdCl2, is effective for the N-heterocyclization, while is effective for the N-alkylation.
Watanabe, Yoshihisa,Suzuki, Naoki,Tsuji, Yasushi,Shim, Sang Chul,Mitsudo, Take-aki
p. 1116 - 1120
(2007/10/02)

Indolyl phthalide compounds
3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
-
(2008/06/13)

Heteroarylphthalides
3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)-phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
-
(2008/06/13)

Phthalide compounds, processes and marking systems
3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
-
(2008/06/13)

THE RUTHENIUM COMPLEX CATALYZED REDUCTIVE TRANSFORMATION OF NITROBENZENE. A NOVEL ROUTE TO 2,3-DIALKYLQUINOLINES AND N-ALKYLANILINES USING SATURATED ALCOHOLS
Nitrobenzene reacts with saturated alcohols in the presence of a catalytic amount of ruthenium complex at 180 deg C to give 2,3-dialkylquinolines and N-alkylanilines in good yields.The reaction appears to include reduction of nitrobenzene with the alcohols by hydrogen transfer reaction.
Watanabe, Yoshihisa,Tsuji, Yasushi,Suzuki, Naoki
p. 1067 - 1068
(2007/10/02)

THE RUTHENIUM CATALYZED N-ALKYLATION AND N-HETEROCYCLIZATION OF ANILINE USING ALCOHOLS AND ALDEHYDES
Aniline reacts with saturated and 2,3-unsaturated alcohols in the presence of ruthenium catalyst at 180 deg C to give N-alkylanilines and 2,3-alkylquinolines in good yields.
Watanabe, Yoshihisa,Tsuji, Yasushi,Ohsugi, Yukihiro
p. 2667 - 2670
(2007/10/02)