- A Formal CH Insertion Reaction of Aryl Nitrene into an Alkyl CH Bond. Implications for Photoaffinity Labelling.
-
Triplet m-nitrophenyl nitrene reacts with frozen polycrystalline toluene at the benzylic position to give appreciable yields of a formal CH insertion adduct.This reaction does not occur on photolysis of m-nitrophenyl azide in toluene solution.
- Torres, Mary Jennifer,Zayas, Jose,Platz, Matthew S.
-
-
Read Online
- HSiCl3-Mediated Reduction of Nitro-Derivatives to Amines: Is Tertiary Amine-Stabilized SiCl2 the Actual Reducing Species?
-
The mechanism of a recently reported, highly chemoselective metal-free protocol of wide general applicability for the reduction of aromatic and aliphatic nitro-derivatives to amines has been investigated. The reaction is supposed to occur through the gene
- Orlandi, Manuel,Benaglia, Maurizio,Tosi, Filippo,Annunziata, Rita,Cozzi, Franco
-
-
Read Online
- Magnetic acyclovir-copper nanoparticle: DFT study and application as an efficient, magnetically separable and recyclable catalyst for N-arylation of amines under green condition
-
A copper(I)‐acyclovir complex supported on magnetic was designed and successfully synthesized. Catalytic activity and stability of two structures of copper(I)‐acyclovir complex supported on magnetic were investigated by the theoretical method. The more active and stable copper(I)‐acyclovir complex supported on magnetic was applied as a catalyst for C–N cross‐coupling reaction with high yield in a deep eutectic solvent (DES) as a green solvent. Also, these nanoparticles could be easily recovered and reused for new rounds of reaction without any considerable loss in catalytic activity.
- Heydari, Akbar,Pazoki, Farzane
-
-
- Heterostructured Hybrid rGO@α-MnO2/rGO@δ-MnO2 Nanoflower: An Efficient Catalyst for Aerobic Solvent-Free N-Alkylation Reactions and Energy Storage Material
-
A new reduced graphene oxide (rGO) based bi-phasic crystal of MnO2, namely α-MnO2 nanorods and δ-MnO2 nanoflakes containing heterostructured hybrid nanoflower rGO@α-MnO2/rGO@δ-MnO2 has been fabricated through a facile hydrothermal method followed by annealing treatment. The successful synthesis of the hybrid material was studied by XRD, Raman, BET, FESEM with EDX, FTIR and TEM analyses. An efficient N-alkylation reaction of substituted aromatic amines with aromatic alcohols was carried out under solvent-free aerobic conditions in the presence of catalytic amount of rGO@α-MnO2/rGO@δ-MnO2. The catalyst shows excellent activity in terms of high yields (up to 98 %), short reaction time (10 h) along with a simple work-up process. The spent material can be regenerated several times without causing any serious decrease in catalytic activity. Moreover, cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and cyclic stability techniques were executed to evaluate the performances of rGO@α-MnO2, rGO@δ-MnO2, and rGO@α-MnO2/rGO@δ-MnO2 as energy storage materials. Among all those materials, rGO@α-MnO2/rGO@δ-MnO2 exhibited a proficient specific capacitance, CS (267 F/g at 1 A/g) along with excellent cycling ability (~83 % retention up to 10000 cycles). The superb electrochemical performance of rGO@α-MnO2/rGO@δ-MnO2 might be ascribed to the combination of bi-phasic α-MnO2 and δ-MnO2 with rGO sheets, resulting in a flower-like structure.
- Chaudhuri, Haribandhu,Karak, Niranjan
-
p. 1617 - 1629
(2020/02/18)
-
- Ru(II) complexes containing (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole: Synthesis, solid-state structure, computational study and catalysis in N-alkylation reactions
-
Reactions of (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole (L) with ruthenium(II) prefabricated precursors [RuHCl(CO)(EPh3)3] and [RuH2(CO)(EPh3)3] (E = P or As) afforded new Ru(II) complexes [RuCl(CO)(EPh3)2(L)] and [RuH(CO)(EPh3)2(L)] (E = P or As) (1–4). All the Ru(II) complexes (1–4) were characterized by IR, NMR spectroscopies, ESI-mass spectrometry and elemental analyses. The solid-state structures of Ru(II) complexes (2 and 3) were established by single crystal X-ray analyses and revealed distorted octahedral geometries around the ruthenium(II) ion and mono anionic bidentate N^N coordination mode for hydrazine ligand. The Ru(II) complexes 2 and 3 were also analyzed using Hirshfeld surface analysis and DFT calculations. Moreover, all the complexes (1–4) were utilized in the N-alkylation reactions of amines using alcohol. Complex 3 was found to be highly active towards N-alkylation of different aromatic amines with alcohol.
- Murugan, Kaliyappan,Ojwach, Stephen O.,Saravanan, Kandasamy,Vijayan, Paranthaman,Vijayapritha, Subbarayan,Viswanathamurthi, Periasamy
-
-
- A microwave-assisted SmI2-catalyzed direct N-alkylation of anilines with alcohols
-
A new protocol for the alkylation of aromatic amines has been described using alcohols in the presence of SmI2 as a catalyst with the generation of water as the sole byproduct. The reaction proceeds under MW conditions and selectively generates monoalkylated amines. This protocol features a broad substrate scope and good functional-group tolerance with moderate to high yields.
- Gour, Jitendra,Gatadi, Srikanth,Malasala, Satyaveni,Yaddanpudi, Madhavi Venkata,Nanduri, Srinivas
-
p. 7488 - 7494
(2019/06/14)
-
- Well-Defined Amidate-Functionalized N-Heterocyclic Carbene -Supported Rare-Earth Metal Complexes as Catalysts for Efficient Hydroboration of Unactivated Imines and Nitriles
-
Four amidate-functionalized N-heterocyclic carbene (NHC) rare-earth metal amido complexes [(κ2-N,O-κ1-L)2REN(SiMe3)2] (L = 1-(C6H5CONCH2CH2)-3-(CH3)3C6H2(N(CH)2NC)) [RE = Er (1), Y (2), Dy (3), Gd (4)] were synthesized by one-pot reactions of 2 equiv of (1-(C6H5CONHCH2CH2)-3-(CH3)3C6H2-(N(CH)2NCH))Br (H2LBr) with 5 equiv of KN(SiMe3)3 followed by treatment with 1 equiv of RECl3 in tetrahydrofuran at -40 °C. These complexes were fully characterized, and their catalytic activities toward hydroboration of unactivated imines and nitriles were investigated, and it was found that these complexes displayed excellent activities as well as remarkable functional group compatibility for imine and nitrile substrates such as halo-, alkyl-, hydroxyl-, N,N-dimethylamino-, and nitro- substituents. Among those, the chemoselectivity for this reaction among the common unsaturated functional groups was achieved in the order CO CN > C=N > CO2Et > CC in the current catalytic system, which may facilitate their further application in synthetic chemistry.
- Huang, Zeming,Wang, Shaowu,Zhu, Xiancui,Yuan, Qingbing,Wei, Yun,Zhou, Shuangliu,Mu, Xiaolong
-
supporting information
p. 15069 - 15078
(2018/12/14)
-
- Unmodified Fe3O4 nanostructure promoted with external magnetic field: safe, magnetically recoverable, and efficient nanocatalyst for N- and C-alkylation reactions in green conditions
-
Transition metal compounds have emerged as suitable catalysts for organic reactions. Magnetic compounds as soft Lewis acids can be used as catalysts for organic reactions. In this report, the Fe3O4 nanostructures were obtained from Fe2+ and Fe3+-salts, under an external magnetic field (EMF) without any protective agent. The X-ray photoelectron spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy tools were used to characterize these magnetic compounds. The two-dimensional (2-D, it showed nanometric size in the two dimensions, nanorod structure) Fe3O4 compound showed high catalytic activity and stability in N- and C-alkylation reactions. A diverse range of N- and C-alkylation products were obtained in moderate to high yield under green and mild conditions in air. Also the N- and C-alkylation products can be obtained with different selectivity and yield by exposure reactions with EMF. Results of alkylation reactions showed that the presence of Fe(II) and Fe(III) species on the surface of magnetic catalysts (phase structure of magnetic compounds) are essential as very cheap active sites. Also, morphology of magnetic catalysts had influence on their catalytic performances. After the reaction, the catalyst/product(s) separation could be easily achieved with an external magnet and more than 95% of catalyst could be recovered. The catalyst was reused at least four times without any loss of its high catalytic activity for N- and C-alkylation reactions.
- Rafiee, Ezzat,Joshaghani, Mohammad,Abadi, Parvaneh Ghaderi-Shekhi
-
p. 2503 - 2522
(2018/01/04)
-
- A quick Chan-Lam C-N and C-S cross coupling at room temperature in the presence of square pyramidal [Cu(DMAP)4I]I as a catalyst
-
A rapid and efficient protocol for C-N and C-S cross coupling has been developed using a new square pyramidal copper complex, [Cu(DMAP)4I]I. The complex was successfully synthesized via a disproportionation reaction of CuI and DMAP in DMSO. The catalytic activity of the complex was found to be excellent for Chan-Lam coupling reaction between aryl boronic acid and amine, amide, azide or thiol. The reaction could be carried out in the presence of only 2 mol% of the copper catalyst in methanol at room temperature within a short time.
- Roy, Subhasish,Sarma, Manas Jyoti,Kashyap, Bishwapran,Phukan, Prodeep
-
supporting information
p. 1170 - 1173
(2016/01/15)
-
- Synthesis and antimalarial activity of N-benzylated (N-arylcarbamoyl)alkylphosphonic acid derivatives
-
A series of novel and readily accessible N-benzylated (N-arylcarbamoyl)alkylphosphonate esters and related compounds have been prepared as potential antimalarial agents. Bioassays reveal that some of these compounds exhibit promising activity against Plasmodium falciparum, and exhibit no significant growth inhibition of HeLa cells.
- Adeyemi, Christiana M.,Faridoon,Isaacs, Michelle,Mnkandhla, Dumisani,Hoppe, Heinrich C.,Krause, Rui W.M.,Kaye, Perry T.
-
p. 6131 - 6138
(2016/12/06)
-
- Method of producing higher amine (by machine translation)
-
PROBLEM TO BE SOLVED: To provide a method of producing a secondary or tertiary higher amine. SOLUTION: The method of producing a higher amine comprises allowing a primary or secondary amine to react with an alcohol in the presence of at least one species of hydrogen halide selected from hydrogen chloride, hydrogen bromide and hydrogen iodide, or in the presence of a compound capable of producing a hydrogen halide (such as 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-chloride). If the raw material amine is a primary amine, a secondary higher amine and a tertiary higher amine can be produced. If the raw material amine is a secondary amine, a tertiary higher amine can be produced. COPYRIGHT: (C)2012,JPO&INPIT
- -
-
Paragraph 0048; 0070
(2016/10/08)
-
- Direct reductive amination using triethylsilane and catalytic bismuth(III) chloride
-
Direct reductive amination (DRA) using triethylsilane (TESH) and catalytic bismuth(III) chloride (BiCl3) is described for the first time. The use of TESH and BiCl3 provides easy handling, low cost, non-toxicity, and a mild Lewis acid activity, thereby meeting the demand for green and sustainable chemistry. The developed DRA is highly chemoselective and applicable to less-basic amines. The experimental results of this study revealed that the developed DRA could be catalyzed by BiCl3, which was gradually reduced to Bi(0) or bismuth with a low valency by TESH, but TESCl, Bi(0), and Bi(0) with TESCl catalyzed the DRA to some extent.
- Matsumura, Takehiko,Nakada, Masahisa
-
p. 1829 - 1834
(2014/03/21)
-
- SiO2-Cu2O: An efficient and recyclable heterogeneous catalyst for N-benzylation of primary and secondary amines
-
A mild, effective, and selective procedure is reported for the mono N-benzylation and N,N-dibenzylation of primary amines as well as mono N-benzylation of secondary amines using silica-supported copper(I) oxide in water. The silica-supported Cu2O was generated in situ by the reaction of Fehling solution and glucose at 100 C onto activated silica. The catalyst was filtered, washed with water, and oven-dried, and was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and atomic absorption spectroscopy. The prepared Cu2O-SiO2 was found to be thermally stable up to 325 C. The copper was uniformly distributed onto the surface of the silica, and the mean particle diameter was 7 nm. The catalyst served as a selective heterogenous catalyst for the N-benzylation of primary and secondary amines. The catalyst is recyclable and was used effectively upto fifth run without a significant loss of catalytic activity. Various reaction solvents including water, acetonitrile, and toluene were screened for N-benzylation of amines, and the success of the aqueous system highlights the low environmental impact of the procedure.
- Gupta, Manjulla,Paul, Satya,Gupta, Rajive
-
p. 444 - 450
(2014/04/03)
-
- Selectivity control during the solid supported protic acids catalysed synthesis of 1,2-disubstituted benzimidazoles and mechanistic insight to rationalize selectivity
-
Selectivity control during the formation of 1,2-disubstituted benzimidazoles has been achieved for the reaction of o-phenylenediamine with aldehydes in the presence of solid supported protic acids as catalysts and choosing an appropriate reaction medium. Perchloric acid adsorbed on silica-gel (HClO4-SiO2) was found to be the most effective catalyst system for the synthesis of 1,2-disubstituted benzimidazoles in EtOH at rt. Apart from the catalyst and solvent, the electronic and steric factors of the aldehyde and the electronic factor of the o-phenylenediamine are also significant contributory factors in dictating the selectivity. An understanding of the mechanistic course of the formation of the 1,2-disubstituted benzimidazoles has been outlined that would rationalise the origin of selectivity control under the set experimental parameters. The Royal Society of Chemistry.
- Kumar, Dinesh,Kommi, Damodara N.,Chebolu, Rajesh,Garg, Sanjeev K.,Kumar, Raj,Chakraborti, Asit K.
-
-
- The triflic acid-mediated cyclisation of N-benzylcinnamanilides
-
N-Benzylcinnamanilides cyclise with triflic acid to form 1-benzyl-4-aryl-2,4-dihydro-1H-quinolin-2-ones and 2,5-diaryl-benzazepin-3-ones. The product ratio is determined by the preferred orientation of the amide and by the electronics of the substituents. With ortho-substituted anilides, N-debenzylation also occurs to give 4-aryl-2,4-dihydro-1H-quinoline-2-ones.
- King, Frank D.,Caddick, Stephen
-
p. 8592 - 8601
(2013/09/12)
-
- N-Alkylation of amines with alcohols over nanosized zeolite beta
-
Direct N-alkylation of amines with alcohols was successfully performed by using nanosized zeolite beta, which showed the highest catalytic activity among other conventional zeolites. This method has several advantages, such as eco-friendliness, moderate to high yields, and simple work-up procedure. The catalyst was successfully recovered and reused without significant loss of activity and only water is produced as co-product. In addition, imines were also efficiently prepared from the tandem reactions of amines with 2-, 3- and 4-nitrobenzyl alcohols using nanosized zeolite beta.
- Reddy, Marri Mahender,Kumar, Macharla Arun,Swamy, Peraka,Naresh, Mameda,Srujana, Kodumuri,Satyanarayana, Lanka,Venugopal, Akula,Narender, Nama
-
supporting information
p. 3474 - 3483
(2013/12/04)
-
- Highly selective mono-N-benzylation and amidation of amines with alcohols or carboxylic acids using the Ph2PCl/I2/imidazole reagent system
-
Chlorodiphenylphosphine, imidazole, and molecular iodine in refluxing dichloromethane are used for the efficient preparation of amides under mild reaction conditions. This reagent system also shows excellent selectivity for mono-N-alkylation of amines with alcohols. In this system, the resulting phosphorus byproduct (diphenylphosphinic acid) is easily removed by extraction using an aqueous basic solution in the workup processes, which avoids the tedious and time-consuming chromatographic methods.
- Nowrouzi, Najmeh,Jonaghani, Mohammad Zareh
-
experimental part
p. 498 - 509
(2012/07/30)
-
- Selective N-alkylation of amines with alcohols by using non-metal-based acid-base cooperative catalysis
-
Learning to cooperate: A straightforward method for the selective N-mono- and dialkylation of amines with alcohols by means of non-metal-based catalysis promoted by TAPC is reported (see scheme). Selectivity of the N-mono- and dialkylation, substrate scope and functional-group tolerance are highlighted with respect to each amine (1° and 2°; aromatic and aliphatic) and alcohol (1°, 2° and 3°; benzylic and aliphatic) component. Copyright
- Du, Ya,Oishi, Shunsuke,Saito, Susumu
-
supporting information; experimental part
p. 12262 - 12267
(2011/11/29)
-
- Ligands for copper-catalyzed C-N bond forming reactions with 1 Mol% CuBr as catalyst
-
Several new ligands were designed to promote copper-catalyzed Ullman C-N coupling reactions. In this group, 8-hydroxyquinolin-N-oxide was found to serve as a superior ligand for CuBr-catalyzed coupling reactions of aryl iodides, bromides, and chlorides with aliphatic amines and N-heterocycles under a low catalyst loading (1% [Cu] mol). Reactions with the inexpensive catalytic system display a high functional group tolerance as well as excellent chemoselectivity.
- Yang, Kai,Qiu, Yatao,Li, Zheng,Wang, Zhaoyang,Jiang, Sheng
-
experimental part
p. 3151 - 3159
(2011/06/23)
-
- An Ullmann coupling of aryl iodides and amines using an air-stable diazaphospholane ligand
-
(Chemical Equation Presented) A copper-based catalytic system, using an air-stable diazaphospholane as the ligand, was developed for an efficient Ullmann reaction between aryl iodides and alkyl or heterocyclic amines.
- Yang, Minghua,Liu, Fei
-
p. 8969 - 8971
(2008/03/27)
-
- Mild and efficient copper-catalyzed N-arylation of alkylamines and N-H heterocycles using an oxime-phosphine oxide ligand
-
A mild and efficient copper-catalyzed system for N-arylation of alkylamines and N-H heterocycles with aryl iodides using a novel, readily prepared and highly stable oxime-functionalized phosphine oxide ligand was developed. The coupling reactions could even be performed in solvent-free conditions with moderate to good yields.
- Xu, Lei,Zhu, Di,Wu, Fan,Wang, Rongliang,Wan, Boshun
-
p. 6553 - 6560
(2007/10/03)
-
- Amino acid promoted CuI-catalyzed C-N bond formation between aryl halides and amines or N-containing heterocycles
-
CuI-catalyzed coupling reaction of electron-deficient aryl iodides with aliphatic primary amines occurs at 40 °C under the promotion of N-methylglycine. Using L-proline as the promoter, coupling reaction of aryl iodides or aryl bromides with aliphatic primary amines, aliphatic cyclic secondary amines, or electron-rich primary arylamines proceeds at 60-90 °C; an intramolecular coupling reaction between aryl chloride and primary amine moieties gives indoline at 70 °C; coupling reaction of aryl iodides with indole, pyrrole, carbazole, imidazole, or pyrazole can be carried out at 75-90 °C; and coupling reaction of electron-deficient aryl bromides with imidazole or pyrazole occurs at 60-90 °C to provide the corresponding N-aryl products in good to excellent yields. In addition, N,N-dimethylglycine promotes the coupling reaction of electron-rich aryl bromides with imidazole or pyrazole to afford the corresponding N-aryl imidazoles or pyrazoles at 110 °C. The possible action of amino acids in these coupling reactions is discussed.
- Zhang, Hui,Cai, Qian,Ma, Dawei
-
p. 5164 - 5173
(2007/10/03)
-
- Reduction of polyfunctional aromatic nitro compounds using lithium aluminium hydride
-
Aromatic nitro compounds containing yet another functional group are reduced using lithium aluminium hydride in ether. The reduction of nitrobenzanilides results in preferential reduction of amide functionality while the isomeric N-(nitrophenyl) benzamides results in preferential cleavage of the amide bond. Besides, the reduction of 2,2′-dinitrodiphenyl amine 5a, reduction of (bis-2-nitroanilino) methane 5b, 2,2′ -dinitrodiphenylether 5c, 2-nitrophenyl-2′-nitrophenoxymethane 5d, 1,3-dinitrobenzene 6a, 2-nitrobenzaldoxime 6b, 2-N(2′-nitrophenylmethyl) amino benzoic acid 6c, 2-nitrophenoxymethyl phenyl ketone 6d are carried out. Nitro group is found reluctant towards reduction in some cases whereas in some others it is reduced into different extents. This points to the limitation of the suggested azo test for aromatic nitro compounds.
- Joseph,Jacob, Dominic E.
-
p. 432 - 436
(2007/10/03)
-
- Synthesis of N-Benzylated Anilines from the Reaction of Anilines and Benzyl Chloroformate
-
Reactions of benzyl chloroformate with a series of substituted anilines produced N-carbobenzyloxy "CBZ" products along with the unexpected N-benzylated "Bn" compounds. Reaction of aniline, 1a, gave the CBZ, or 2a, and Bn, or 3a, products in 29% and 14% yi
- Pati, Hari,Weisbruch, Paul,Lemon, Adrienne,Lee, Moses
-
p. 933 - 940
(2007/10/03)
-
- Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
-
The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.
- -
-
-
- One-pot reductive amination of acetals with aromatic amines using decaborane (B10H14) in methanol
-
Aldehyde acetals and ketone ketals were reductively aminated in one pot with aromatic amines to give the corresponding amines in methanol or aqueous methanol in good to high yields. This direct method might be important because acetals and ketals are used as a popular protecting group for aldehyde and ketones. The advantage of our method is effective even in an aqueous solution and in the application to selective reaction.
- Park, Eun Soo,Lee, Ji Hee,Kim, Soo Jung,Yoon, Cheol Min
-
p. 3387 - 3396
(2007/10/03)
-
- Mild method for ullmann coupling reaction of amines and aryl halides
-
(Matrix presented) Ullmann-type aryl amination of aryl iodides and aryl bromides in DMSO at 40-90°C gave the corresponding N-arylamines or N,N-diarylamines in good to excellent yields by using either N-methylglycine or L-proline as the ligand.
- Ma, Dawei,Cai, Qian,Zhang, Hui
-
p. 2453 - 2455
(2007/10/03)
-
- Copper-catalyzed coupling of alkylamines and aryl iodides: an efficient system even in an air atmosphere.
-
[reaction: see text] A mild method for the copper-catalyzed amination of aryl iodides is reported. This operationally simple C-N bond-forming protocol uses CuI as the catalyst and ethylene glycol as ligand in 2-propanol. A variety of functionalized aryl iodides as well as several amines were efficiently coupled using this method. This catalytic amination procedure is relatively insensitive to moisture and can be performed under an air atmosphere with comparable yield. Preliminary results on the amination of aryl bromides are also described.
- Kwong, Fuk Yee,Klapars, Artis,Buchwald, Stephen L
-
p. 581 - 584
(2007/10/03)
-
- Inversion of the reactivity of benzyl bromides in reactions with anilines in dioxane and its mixtures with dimethyl sulfoxide. Experimental proof for isoparametric relationships
-
Analysis of the structure-reactivity cross correlations shows the existence of isoparametric relationships in the reaction of Y-substituted benzyl bromides with X-substituted anilines in dioxane and 2, 3, and 5 M solutions of dimethyl sulfoxide in dioxane
- Shpan'ko
-
p. 1010 - 1013
(2007/10/03)
-
- 1-SUBSTITUTED-2-(N-PHENYL-N-(PHENYL-METHYL)METHANAMINE)-4,5-DIHYDRO-IMIDAZOLES AND RELATED COMPOUNDS AND THEIR USE IN TREATING CALCIUM OVERLOAD IN BRAIN CELLS
-
The present patent application discloses compounds of the formula STR1 wherein R 1 is C 1-10 saturated or unsaturated alkyl; or STR2 wherein R'" is H or STR3 R 2 is phenyl which is unsubstituted or substituted one or more times with halogen, CF 3, C. sub.1-6-alkoxy, NO 2, CO 2--C 1-6-alkyl, methyl; benzyl which may be substituted one or more times with halogen, CF 3, C 1-6-alkoxy, NO 2, CO 2--C 1-6-alkyl, methyl; pyridyl; or cyclohexyl;R 3 phenyl which is unsubstituted or substituted one or more times with halogen, CF 3, C 1-6-alkoxy, NO 2, CO 2--C 1-6-alkyl, methyl; naphthyl which may be substituted one or more times with halogen, CF 3, C 1-6-alkoxy, NO 2, CO 2--C 1-6-alkyl, methyl; pyridyl; C 1-6 unsaturated alkyl; furanyl;R 4 is H, C 1-6-alkyl, or benzyl; or STR4 together form STR5 R' and R" are each hydrogen or together form an extra benzo ring; and wherein the dotted line represents an optional extra bond between the two carbon atoms designated α and β, or a pharmaceutically-acceptable addition salt thereof.The compounds are useful as pharmaceuticals, for example in the treatment of Ca overload in brain cells. "
- -
-
-
- Imidazole derivatives as calcium channel blockers
-
The present patent application discloses compounds of the formula ψψ ψwhereinψ R1 is C1-10-alkyl which may be branched; C1-10-unsaturated alkyl; or CHR'''''' ψψ ψwherein R'''''' is H or ψψ ψRy is phenyl which may be substituted one or more times with halogen, CF3, C1-6-alkoxy, NO2, CO2-C1-6-alkyl, methyl; benzyl which may be substituted one or more times with halogen, CF3, C1-6-alkoxy, NO2, CO2-C1-6-alkyl, methyl; pyridyl; or cyclohexyl;ψ R3 phenyl which may be substituted one or more times with halogen, CF3, C1-6-alkoxy, NO2, CO2-C1-6-alkyl, methyl; naphthyl which may be substituted one or more times with halogen, CF3, C1-6-alkoxy, NO2, CO2-C1-6-alkyl, methyl; pyridyl; C1-6 unsaturated alkyl; furanyl;ψ R4 is H, C1-6-alkyl, or benzyl;ψ or ψψ ψtogether form ψψ ψR5 is H, or C1-6-alkyl;ψ R'' and R'''' are each hydrogen or together form an extra benzo ring;ψ and wherein the dotted line represents an optional extra bond between the two carbon atoms designated à and á, or a pharmaceutically-acceptable addition salt thereof. ψThe compounds are useful as pharmaceuticals, for example in the treatment of Ca overload in brain cells.ψ
- -
-
-
- Annulation Reactions with Iron(III) Chloride: Oxidation of Imines
-
Aromatic imines react with phenylacetylene or styrene in an acetonitrile solution of iron(III) chloride to give quinolines 3 or their tetrahydro derivatives 11 together with variable amounts of products 4 arising from the reduction of the imines.The initial step appears to be a one-electron oxidation to generate iron(II) and an imine radical cation.When the reactions are carried out in the presence of stoichiometric amounts of tetrachloro-p-benzoquinone (chloranil), only quinolines 3 are obtained.
- Leardini, Rino,Nanni, Daniele,Tundo, Antonio,Zanardi, Giuseppe,Ruggieri, Fabrizio
-
p. 1842 - 1848
(2007/10/02)
-
- Substituent Effects on Transition-state Structures for Dissociative and Associative SN2 Reactions
-
α-Deuterium secondary kinetic isotope effects (KIEs) have been investigated for the reactions of anilines with benzyl, methyl and ethyl benzenesulfonates involving deuteriated aniline nucleophiles and substrates.The secondary KIEs observed are normal, kH/kD > 1.0, only for the deuteriated benzyl system and are of an inverse type, kH/kD N2 mechanism), in contrast to the reverse trend, i.e., the strain incurred by bond formation of the nucleophile is greater than the relief of steric congestion by bond breaking of the leaving group in the reactions of alkyl compounds (associative SN2 mechanism).The effects of substituents in the nucleophile (X) and leaving group (Z) on the secondary KIEs are in complete agreement with the transition-state variation predicted by the sign and magnitude of the cross-interaction constant, ρxz.
- Lee, Ikchoon,Koh, Han Joong,Lee, Bon-Su,Sohn, Dong Sook,Lee, Byung Choon
-
p. 1741 - 1746
(2007/10/02)
-
- Kinetic Isotope Effects involving Deuteriated Aniline Nucleophiles
-
Primary and secondary α-deuterium kinetic isotope effects are observed with deuteriated aniline nucleophiles in the SN2 reactions of 1-phenylethyl and benzyl benzenesulphonates, providing evidence in support of the four centre transition state mechanism for the former reaction.
- Lee, Ikchoon,Koh, Han Joong,Lee, Bon-Su,Lee, Hai Whang
-
p. 335 - 336
(2007/10/02)
-
- Photochemistry of Fluorinated Aryl Azides in Toluene Solution and in Frozen Polycrystals
-
Several fluorinated triplet aryl nitrenes have been generated in low-temperature polycrystals by photolysis of the corresponding azides.Upon extended photolysis at -196 deg C the nitrenes abstract hydrogen from frozen toluene to give anilino-benzyl radical pairs, which subsequently combine to give CH insertion products.The radical pairs and the triplet nitrenes have been detected by EPR.In toluene solution, the major reaction products are tar, the corresponding fluorinated anilines, and azo compounds.
- Leyva, Elisa,Munoz, Daniel,Platz, Matthew S.
-
p. 5938 - 5945
(2007/10/02)
-
- The NMR Spectra of the Porphyrins 17. Metalloporphyrins as Diamagnetic Shift Reagents, Structural and Specificity Studies
-
The nature of the metalloporphyrin-ligand complexes produced by zinc, magnesium and cobalt porphyrins with basic ligands has been investigated using the diamagnetic ring current shifts of the porphyrin on the ligand protons.The metal to nitrogen bond lengths in some metallo-meso-tetraphenylporphyrin (pyridine) complexes have been determined and compared with the data of the crystalline complexes.The geometry of the Zn meso-tetraphenylporphyrin complexes with 2-picoline, quinoline and isoquinoline has been investigated.Steric interactions between the ligand and the porphyrin in 2-picoline and quinoline produce a dramatic increase in the Zn-N bond length when compared to the unstrained analogues pyridine and isoquinoline.This large increase is associated with comparatively minor angle distortions in the complex.The specificity of the Zn meso-tetraphenylporphyrin complexation shifts has been determined for a range of benzyl and butyl compounds.The complexation shift is linearly related to the basicity of the ligand for a wide range of basicities.
- Abraham, Raymond J.,Bedford, Geoffrey R.,Wright, Brian
-
-
- MUTUAL EFFECTS OF STRUCTURE IN THE REACTIONS OF BENZYL BROMIDES WITH PRIMARY ARYLAMINES IN A MIXTURE OF NITROBENZENE AND DIMETHYLSULFOXIDE
-
The kinetics of the reaction of benzyl bromides with primary arylamines in a 1 M solution of dimethyl sulfoxide in benzene were studied.The joint effect of the substituents on the reactivity of the benzyl bromide-primary arylamine system was evaluated qua
- Litvinenko, L. M.,Shpan'ko, I. V.,Korostylev, A. P.
-
p. 854 - 859
(2007/10/02)
-