- Reaction of aliphatic amines with 49% formic acid. 1-hexylamine, di-1-hexylamine, N,N-dimethyl-1-hexylamine, 1-dodecylamine, N,N-dimethyl-1-dodecylamine and N,N-dimethyl-1-butylamine
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Two primary amines, 1-hexylamine 2, 1-dodecylamine 19, one secondary amine, di-1-hexylamine 18, and three tertiary amines, N,N-dimethyl-1-hexylamine 6, N,N-dimethyl-1-butylamine 3, and N,N-dimethyl-1-dodecylamine 22 were each heated at 150°C, 250°C or 350°C with 49% aqueous formic acid for varying periods of time. The aliphatic primary amines underwent easy N-formylation and subsequent reduction to give N-methyl- and N,N-dimethylalkylamines. Especially at higher temperatures, other reactions intervened including elimination of NH3 to the corresponding alkenes followed by partial double bond isomerization. Tertiary amines were more reactive at higher temperatures undergoing hydrolysis and reductive cleavages to secondary and primary amines, which subsequently followed the reaction sequences seen for primary amines. This series of saturated amines showed none of the cleavage into smaller fragments that was observed in the reductive alkylation of pyridine and 4-methylpyridine to a series of N-alkylpiperdines. This result reinforces the bis-aza-retro-Aldol-fragmentation mechanism postulated for the formation of the N-alkylpiperidines. Johann Ambrosius Barth 1997.
- Katritzky, Alan R.,Parris, Roslyn L.,Ignatchenko, Elena S.,Allin, Steven M.,Siskin, Michael
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- Amines made easily: A highly selective hydroaminomethylation of olefins
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A highly chemo- and regioselective hydroaminomethylation of simple as well as functionalized α-olefins using a cationic rhodium precatalyst together with Xantphos as ligand is reported. Studies of the influence of ligands and reaction conditions led to an unprecedented selective hydroaminomethylation procedure. The novel procedure constitutes an economically attractive and environmentally favorable synthesis of secondary and tertiary aliphatic amines.
- Ahmed, Moballigh,Seayad, Abdul Majeed,Jackstell, Ralf,Beller, Matthias
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- Dramatic Effect of the Specific Solvation on the Reactivity of Quaternary Ammonium Fluorides and Poly(hydrogen fluorides), (HF)n*F-, in Media of Low Polarity
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A quantitative study of how the intrinsic reactivity (nucleophilicity and basicity) of the fluoride anion of hexyl4N+F- is affected in solvents of low polarity by the specific solvation of a limited number of water molecules has been performed.The nucleophilicity enhancement is extrapolated to be about 3 orders of magnitude by reducing the specific hydration n of the anion from 8.5 to 0.Such enhancement is much higher (ca100 times) than that obtained, under the same conditions, by dehydrating the other halides.The nucleophilicity scale of anhydrous anions found,F- >> Cl- > Br- > I-, reflects those well-known in dipolar aprotic solvents and in the gas phase.Comparison in the same hydration range shows that the basicity of the fluoride anion is much more affected by specific solvation than is its nucleophilicity.Extension of this study to quaternary ammonium poly(hydrogen fluorides) Q+(HF)n*F-, where n = 1, 2, provides the following reactivity scale: F- >> HF2- > H2F3-.The increasing stabilization of F- anion, by interaction with hydrogen fluoride in the sequence F- - -, accounts for the much lower reactivity observed in the case of poly(hydrogen fluorides) with respect to that of the hypothetical anhydrous fluoride (F- : HF2- : H2F3- = 8.5*105 : 1.2*102 : 1).This also explains the different sensitivity of these anions to the specific hydration which decreases in the same order: F- >> HF2- > H2F3-.
- Landini, Dario,Maia, Angelamaria,Rampoldi, Alessandro
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- Stability of Quaternary Onium Salts under Phase-Transfer Conditions in the Presence of Aqueous Alkaline Solutions
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The parameters that affect the stability of a series of quaternary ammonium and phosphonium salts R4M+Y- under phase-transfer catalysis (PTC) conditions in a chlorobenzene-aqueous NaOH two-phase system have been defined.Quaternary ammonium salts are much more stable than phosphonium derivatives.When the quaternary cation R4M+ is the same, the stability is in the order I > Br- >> Cl-.It dramatically increases either by diminishing the concentration of the base in the aqueous phase (from 50percent to 15percent aqueous NaOH) or by adding to the heterogenous system a molarexcess of the corresponding inorganic salt NaY.In all cases the degradation reactions are found to proceed in the organic phase via extraction of OH- as R4M+OH-, interfacial phenomena being unimportant.As a consequence quaternary onium salts are stable in the presence of aqueous alkaline solutions provided that the extractability and/or the reactivity of OH(-) in the organic phase are minimized.
- Landini, Dario,Maia, Angelamaria,Rampoldi, Alessandro
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- Amination of 1-hexanol on bimetallic AuPd/TiO2 catalysts
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AuPd/TiO2 catalysts, synthesized using controlled surface reactions, are active for the gas-phase amination of 1-hexanol using ammonia. The bimetallic active sites for these catalysts have been characterized using CO chemisorption and XAS techniques, and the absence of monometallic Pd species in the AuPd catalysts was confirmed using UV-vis and STEM-EDS analysis. The bimetallic catalysts exhibit synergy between Au and Pd, as the rate of hexanol conversion increases from 8.7 μmol ks-1 (μmol total Pd)-1 over Pd/TiO2 to up to 42 μmol ks-1 (μmol total Pd)-1 over AuPd/TiO2 with a Pd/Au atomic ratio of 0.06. The rate of hexanol conversion is also enhanced with respect to Au content, with a 5-fold increase in the total Au-normalized rate from Au/TiO2 to AuPd0.67/TiO2. As Pd is added to Au/TiO2 in increasing quantities, the production rate of primary species (i.e., hexylamine and hexanenitrile) is preferentially increased. The rate of dihexylamine production increases to a lesser extent, while trihexylamine formation remains relatively constant across Pd loadings. Moreover, trihexylamine, which cannot be formed via the condensation of dihexylamine and hexanol, is shown to be produced via the secondary aldimine, N-hexylidene hexylamine. The AuPd bimetallic catalysts also exhibit reduced hydrogenolysis activity compared to monometallic Pd/TiO2.
- Ball, Madelyn R.,Wesley, Thejas S.,Rivera-Dones, Keishla R.,Huber, George W.,Dumesic, James A.
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- Extraction of Highly Hydrophilic Anions in Low Polarity Media under Phase-transfer Catalysis Conditions: Dramatic Enhancement of the OH- Reactivity by Reduction of its Specific Hydration
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In the chlorobenzene-aqueous NaOH two-phase system, an increase in NaOH concentration from 5 to 20 M reduces the OH- hydration sphere of the tetrahexylammonium hydroxide (1a) dissolved in chlorobenzene from 11 to 3.5 molecules of water, thus producing a dramatic increase (up to 104 times) in OH- reactivity.
- Landini, Dario,Maia, Angelamaria
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- Oxidant-free conversion of cyclic amines to lactams and H2 using water as the oxygen atom source
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Direct conversion of cyclic amines to lactams utilizing water as the only reagent is catalyzed by pincer complex 2. In contrast to previously known methods of amine-to-amide conversion, this reaction occurs in the absence of oxidants and is accompanied by liberation of H2, with water serving as a source of oxygen atom. Formation of a cyclic hemiaminal intermediate plays a key role in enabling such reactivity. This represents an unprecedented, conceptually new type of amide formation reaction directly from amines and water under oxidant-free conditions.
- Khusnutdinova, Julia R.,Ben-David, Yehoshoa,Milstein, David
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- Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions
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Flow reaction methods have been developed to selectively synthesize tertiary, secondary, and primary amines depending on heterogeneous platinum-group metal species under catalytic hydrogenation conditions using nitriles as starting materials. A 10 % Pd/C-packed catalyst cartridge affords symmetrically substituted tertiary amines in good to excellent yields. A 10 % Rh/C-packed catalyst cartridge enables the divergent synthesis of secondary and primary amines, with either cyclohexane or acetic acid as a solvent, respectively. Reaction parameters, such as the metal catalyst, solvent, and reaction temperature, and continuous-flow conditions, such as flow direction and second support of the catalyst in a catalyst cartridge, are quite important for controlling the reaction between the hydrogenation of nitriles and nucleophilic attack of in situ-generated amines to imine intermediates. A wide variety of aliphatic and aromatic nitriles could be highly selectively transformed into the corresponding tertiary, secondary, and primary amines by simply changing the metal species of the catalyst or flow parameters. Furthermore, the selective continuous-flow methodologies are applied over at least 72 h to afford three different types of amines in 80–99 % yield without decrease in catalytic activities.
- Furugen, Chikara,Ito, Naoya,Jiang, Jing,Park, Kwihwan,Sajiki, Hironao,Shimizu, Eisho,Yamada, Tsuyoshi
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- Amination of aliphatic alcohols with urea catalyzed by ruthenium complexes: effect of supporting ligands
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In the present study, ruthenium-catalyzed amination of alcohols by urea as a convenient ammonia carrier in the presence of free diphosphine ligands has been described. A number of ruthenium-phosphine complexes have been studied among which, [(Cp)RuCl(dppe)] was found as an efficient catalyst for alcohol amination reaction. The crystal structures of two new half-sandwich ruthenium complexes, [(Cp)RuCl(dppe)] and [(C6H6)RuCl2(PHEt2)], were determined by X-ray crystallographic analysis. Also the effect of using different supporting phosphines, ratio of raw materials and reaction temperature on conversion and selectivity was investigated. Under optimum reaction conditions high conversion (98percent) and chemo-selectivity toward secondary amines were obtained.
- Dindar, Sara,Nemati Kharat, Ali
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- Molecular Catalysts for Selective Hydrogenolysis of Amides
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A compound by the name 1,1,1-tris(di(3,5-dimethoxyphenyl)phosphino-methyl)ethane. The compound can be represented by the structure of formula (I): The compound is useful as a ligand for ruthenium to form an organometallic complex. The complex is an active catalyst for the hydrogenolysis of amides to form amines and optionally alcohols.
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Paragraph 0079-0080
(2019/11/22)
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- Selective Synthesis of Secondary and Tertiary Amines by Reductive N-Alkylation of Nitriles and N-Alkylation of Amines and Ammonium Formate Catalyzed by Ruthenium Complex
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A new ruthenium catalytic system for the syntheses of secondary and tertiary amines via reductive N-alkylation of nitriles and N-alkylation of primary amines is proposed. Isomeric complexes 8 catalyze transfer hydrogenation and N-alkylation of nitriles in ethanol to give secondary amines. Unsymmetrical secondary amines can be produced by N-alkylation of primary amines with alcohols via the borrowing hydrogen methodology. Aliphatic amines were obtained with excellent yields, while only moderate conversions were observed for anilines. Based on kinetic and mechanistic studies, it is suggested that the rate determining step is the hydrogenation of intermediate imine to amine. Finally, ammonium formate was applied as the amination reagent for alcohols in the presence of ruthenium catalyst 8. Secondary amines were obtained from primary alcohols within 24 hours at 100 °C, and tertiary amines can be produced after prolonged heating. Secondary alcohols can only be converted to secondary amines with moderate yield. Based on mechanistic studies, the process is suggested to proceed through an ammonium alkoxy carbonate intermediate, where carbonate acts as an efficient leaving group.
- Alshakova, Iryna D.,Nikonov, Georgii I.
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p. 5370 - 5378
(2019/06/14)
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- Chemoselective hydrogenation of nitriles to secondary or tertiary amines catalyzed by aqueous-phase catalysts supported on hexagonal mesoporous silica
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The first supported aqueous-phase catalyst for the hydrogenation of nitriles is revealed. The catalyst prepared from Pd(PhCN)2Cl2, water-soluble ligand 2,2′-biquinoline-4,4′-dicarboxylic acid dipotassium salt and mesoporous silica is a highly efficient catalyst for the selective formation of secondary or tertiary amines from aromatic or aliphatic nitriles. The catalytic system is stable and can be recycled and reused three times without loss of activity and selectivity. This environmentally friendly process is, in addition, an attractive alternative to many homogeneous and heterogeneous catalysts because of its easy preparation and the moderate operational conditions under which it is highly active.
- Nait Ajjou, Abdelaziz,Robichaud, André
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- Conversion of Primary Amines to Symmetrical Secondary and Tertiary Amines using a Co-Rh Heterobimetallic Nanocatalyst
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Symmetrical tertiary amines have been efficiently realized from amine and secondary amines via deaminated homocoupling with heterogeneous bimetallic Co2Rh2/C as catalyst (molar ratio Co:Rh=2:2). Unsymmetric secondary anilines were produced from the reaction of anilines with symmetric tertiary amines. The Co2Rh2/C catalyst exhibited very high catalytic activity towards a wide range of amines and could be conveniently recycled ten times without considerable leaching. (Figure presented.).
- Chung, Hyunho,Han, Seulgi,Chung, Young Keun,Park, Ji Hoon
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supporting information
p. 1267 - 1272
(2018/02/12)
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- Synthesis of Symmetric and Unsymmetric Secondary Amines from the Ligand-Promoted Ruthenium-Catalyzed Deaminative Coupling Reaction of Primary Amines
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The catalytic system generated in situ from the tetranuclear Ru-H complex with a catechol ligand (1/L1) was found to be effective for the direct deaminative coupling of two primary amines to form secondary amines. The catalyst 1/L1 was highly chemoselective for promoting the coupling of two different primary amines to afford unsymmetric secondary amines. The analogous coupling of aniline with primary amines formed aryl-substituted secondary amines. The treatment of aniline-d7 with 4-methoxybenzylamine led to the coupling product with significant deuterium incorporation on CH2 (18% D). The most pronounced carbon isotope effect was observed on the α-carbon of the product isolated from the coupling reaction of 4-methoxybenzylamine (C(1) = 1.015(2)). A Hammett plot was constructed from measuring the rates of the coupling reaction of 4-methoxyaniline with a series of para-substituted benzylamines 4-X-C6H4CH2NH2 (X = OMe, Me, H, F, CF3) (ρ = -0.79 ± 0.1). A plausible mechanistic scheme has been proposed for the coupling reaction on the basis of these results. The catalytic coupling method provides an operationally simple and chemoselective synthesis of secondary amine products without using any reactive reagents or forming wasteful byproducts.
- Arachchige, Pandula T. Kirinde,Lee, Hanbin,Yi, Chae S.
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p. 4932 - 4947
(2018/05/08)
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- Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines
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In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.
- Monguchi, Yasunari,Mizuno, Masahiro,Ichikawa, Tomohiro,Fujita, Yuki,Murakami, Eri,Hattori, Tomohiro,Maegawa, Tomohiro,Sawama, Yoshinari,Sajiki, Hironao
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p. 10939 - 10944
(2017/10/27)
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- Ruthenium-phenol catalysts and method of preparing menthone from isopulegol
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The present invention is directed towards a catalyst which is obtainable by contacting in situ a ruthenium precursor and a phenol derivative. Furthermore, the present invention is directed towards the use of said catalyst in transfer hydrogenation reactions. In particular, the present invention is directed to a method for preparing menthone starting from isopulegol.
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Page/Page column 26
(2017/11/09)
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- A ruthenium racemisation catalyst for the synthesis of primary amines from secondary amines
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A Ru-based half sandwich complex used in amine and alcohol racemization reactions was found to be active in the splitting of secondary amines to primary amines using NH3. Conversions up to 80% along with very high selectivities were achieved. However, after about 80% conversion the catalyst lost activity. Similar to Shvo's catalyst, the complex might deactivate under the influence of ammonia. It was revealed that not NH3 but mainly the primary amine is responsible for the deactivation.
- Pingen, Dennis,Altinta?, ?i?dem,Rudolf Schaller, Max,Vogt, Dieter
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p. 11765 - 11771
(2016/07/28)
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- Using aqueous ammonia in hydroaminomethylation reactions: Ruthenium-catalyzed synthesis of tertiary amines
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The direct synthesis of tertiary amines from ammonia and olefins is presented. Using a combination of Ru3(CO)12 and 2-phosphino-substituted imidazole ligand as catalyst system allows for hydroaminomethylation reactions of bulk aliphatic and functionalized olefins. Tertiary amines are obtained in an atom-efficient domino process in moderate to good isolated yields (45-76%) with excellent regioselectivities (n/iso up to 99:1).
- Wu, Lipeng,Fleischer, Ivana,Zhang, Min,Liu, Qiang,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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p. 3260 - 3263
(2015/03/03)
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- PROCESS FOR PREPARING FORMIC ACID BY REACTING CARBON DIOXIDE WITH HYDROGEN
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A process for preparing formic acid by reacting carbon dioxide with hydrogen in a hydrogenation reactor in the presence of a catalyst comprising an element of group 8, 9 or 10 of the Periodic Table, a tertiary amine and a polar solvent to form formic acid-amine adducts which are subsequently dissociated thermally into formic acid and tertiary amine.
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Paragraph 0371
(2013/03/26)
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- PROCESS FOR PREPARING FORMIC ACID
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A process for preparing formic acid by hydrogenation of carbon dioxide in the presence of a tertiary amine (I) and a catalyst at a pressure of from 0.2 to 30 MPa abs and a temperature of from 20 to 200° C., wherein the catalyst is a heterogeneous catalyst comprising gold.
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Page/Page column 11
(2013/02/28)
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- Selective alkylation of amines with alcohols by Cp*- iridium(III) half-sandwich complexes
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[Cp*Ir(Pro)Cl] (Pro = prolinato) was identified among a series of Cp*-iridium half-sandwich complexes as a highly reactive and selective catalyst for the alkylation of amines with alcohols. It is active under mild conditions in either toluene or water without the need for base or other additives, tolerates a wide range of alcohols and amines, and gives secondary amines in good to excellent isolated yields.
- Wetzel, Alexander,Woeckel, Simone,Schelwies, Mathias,Brinks, Marion K.,Rominger, Frank,Hofmann, Peter,Limbach, Michael
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supporting information
p. 266 - 269
(2013/03/14)
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- Coupling of two multistep catalytic cycles for the one-pot synthesis of propargylamines from alcohols and primary amines on a nanoparticulated gold catalyst
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A one-pot reaction was performed with a nanoparticulated gold catalyst. A secondary amine is formed through N-monoalkylation of a primary amine with an alcohol by a borrowing hydrogen methodology in a three-step reaction. The secondary amine formed enters into a second A3-coupling cycle to give propargylamines. The multistep reaction requires a gold species formed and stabilized on a ceria surface. Copyright
- Corma, Avelino,Navas, Javier,Sabater, Maria J.
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p. 14150 - 14156
(2013/01/15)
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- Highly efficient heterogeneous gold-catalyzed direct synthesis of tertiary and secondary amines from alcohols and urea
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Urea, the white gold: The efficient synthesis of tertiary and secondary amines is achieved by heterogeneous gold-catalyzed direct amination of stoichiometric alcohols with urea in good to excellent yields. Via a hydrogen autotransfer pathway, the reactions of primary alcohols with urea give tertiary amines exclusively, while secondary alcohols selectively afford secondary amines.
- He, Lin,Qian, Yue,Ding, Ran-Sheng,Liu, Yong-Mei,He, He-Yong,Fan, Kang-Nian,Cao, Yong
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experimental part
p. 621 - 624
(2012/05/20)
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- Preparation of secondary and tertiary amines from nitroarenes and alcohols
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Various secondary amines were obtained selectively from the reaction of nitroarenes with primary alcohols in the presence of ruthenium(ii) complexes having phosphine-amine ligands as the catalyst. Secondary amines could be further alkylated with a primary alcohol using the same catalyst, but different conditions.
- Lee, Chun-Chin,Liu, Shiuh-Tzung
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scheme or table
p. 6981 - 6983
(2011/08/06)
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- Shvo's catalyst and [IrCp7z.ast;Cl2(amidine)] effectively catalyze the formation of tertiary amines from the reaction of primary alcohols and ammonium salts
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The reaction of (pentamethylcyclopentadienyl)iridium dichloride dimer, [IrCp*Cl2]2, with bis(2,4,6-trimethylphenyl) formamidine allows the preparation of two new [IrCp*Cl 2(amidine)] and [IrCp*Cl(amidinate)] complexes, which have been fully characterized. Both complexes have been tested in the β-alkylation of 1-phenylethanol with primary alcohols, and in the formation of tertiary amines from the reaction of ammonium salts with primary alcohols, and the results have been compared with those shown by Shvo's catalyst. Our studies demonstrate that both [IrCp*Cl2(amidine)] and Shvo's catalyst are very efficient in both catalytic processes. The high activity of the Ir-amidine complex may be attributed to the presence of the NH group in the amidine ligand. Copyright
- Segarra, Candela,Mas-Marza, Elena,Mata, Jose A.,Peris, Eduardo
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experimental part
p. 2078 - 2084
(2011/10/11)
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- PROCESS FOR PREPARING AMINES FROM ALCOHOLS AND AMMONIA
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The present invention provides novel ruthenium based catalysts, and a process for preparing amines, by reacting a primary alcohol and ammonia in the presence of such catalysts, to generate the amine and water. According to the process of the invention, primary alcohols react directly with ammonia to produce primary amines and water in high yields and high turnover numbers. This reaction is catalyzed by novel ruthenium complexes, which are preferably composed of quinolinyl or acridinyl based pincer ligands.
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Page/Page column 22; 31; 32
(2010/04/03)
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- Multialkylation of aqueous ammonia with alcohols catalyzed by water-soluble Cp*Ir-ammine complexes
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Novel water-soluble Cp*Ir-ammine complexes have been synthesized, and a new and highly atom-economical system for the synthesis of organic amines using aqueous ammonia as a nitrogen source has been developed. With a water-soluble and air-stable Cp*Ir-ammine catalyst, [Cp*Ir(NH 3)3][I]2, a variety of tertiary and secondary amines were synthesized by the multialkylation of aqueous ammonia with theoretical equivalents of primary and secondary alcohols. The catalyst could be recycled by a facile procedure maintaining high activity. A one-flask synthesis of quinolizidine starting with 1,5,9-nonanetriol was also demonstrated. This new catalytic system would provide a practical and environmentally benign methodology for the synthesis of various organic amines.
- Kawahara, Ryoko,Fujita, Ken-Ichi,Yamaguchi, Ryohei
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supporting information; experimental part
p. 15108 - 15111
(2010/12/24)
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- A new atom-economical and selective synthesis of secondary and tertiary alkylamines by means of Cp*Iridium complex catalyzed multiple N-alkylation of ammonium salts with alcohols without solvent
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A new atom-economical and selective synthetic method for secondary and tertiary alkylamines has been achieved by means of (pentamethylcyclopentadienyl) iridium (Cp*Ir) complex catalyzed multiple N-alkylations of ammonium salts with primary and secondary alcohols without solvent. Georg Thieme Verlag Stuttgart.
- Yamaguchi, Ryohei,Mingwen, Zhu,Kawagoe, Shoko,Asai, Chiho,Fujita, Ken-Ichi
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experimental part
p. 1220 - 1223
(2009/12/04)
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- Selective synthesis of primary amines directly from alcohols and ammonia
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(Chemical Equation Presented) Air stable and waterproof: Selective and efficient synthesis of primary amines directly from alcohols and ammonia is achieved under mild conditions (see scheme). The reaction is homogenously catalyzed by a novel air-stable ruthenium pincer complex and can proceed in toluene or even in the absence of solvent or "on water".
- Gunanathan, Chidambaram,Milstein, David
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supporting information; experimental part
p. 8661 - 8664
(2009/05/15)
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- Selective synthesis of secondary and tertiary amines by Cp*iridium-catalyzed multialkylation of ammonium salts with alcohols
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(Chemical Equation Presented) The efficient selective synthesis of secondary and tertiary amines has been achieved by means of Cp*Ir- catalyzed multialkylation of ammonium salts with alcohols without solvent: the reactions of ammonium acetate with alcohols gave tertiary amines exclusively, while those of ammonium tetrafluoroborate afforded secondary amines selectively. Using this method, secondary 5- and 6-membered cyclic amines were synthesized from ammonium tetrafluoroborate and diols in one pot.
- Yamaguchi, Ryohei,Kawagoe, Shoko,Asai, Chiho,Fujita, Ken-Ichi
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p. 181 - 184
(2008/09/18)
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- Reaction of primary amines with Pt/C catalyst in water under microwave irradiation: A convenient synthesis of secondary amines from primary amines
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Upon microwave irradiation in water, Pt/C converts primary amines into secondary amines in good yield via retro-reductive and reductive amination.
- Miyazawa, Akira,Saitou, Kaori,Tanaka, Kan,G?dda, Thomas M.,Tashiro, Masashi,Prakash, G. K. Surya,Olah, George A.
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p. 1437 - 1439
(2007/10/03)
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- SELECTIVITY IN NITRILE HYDROGENATION CATALYZED BY GROUP VII METALS.
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This work is devoted to an analysis of the factors which affect the selectivity of this process in the direction of obtaining primary amines and which are connected primarily with the strength of adsorption of intermediate reaction products on transition metals. Experimental data on the hydrogenation of capronitrile over various catalysts are given. They show that both the activity of metals of group VIII and also the proportion of hydrogenation products observed for them vary within a wide range. Thus, over cobalt, a more than 90% yield of primary amine is attained, while on Pd it is not formed at all. This difference may be caused by a different ability of the metals to adsorb the intermediate reaction products. Although the results of the calculations performed and the conclusions drawn from them relate primarily to the catalytic hydrogenation of aliphatic nitriles, it may be assumed that the same catalyst properties determined their selectivity in the other process of aldehyde hydroamination, which is related to hydrogenation in mechanism also.
- Dobrotvorskii,Yakushkin,Smaeva
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p. 1026 - 1030
(2007/10/02)
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- SELECTIVE CONVERSION OF PRIMARY AMINES INRO N,N-DIMETHYLALKYL- OR N,N-DIALKYLMETHYL-AMINES WITH METHANOL AND RuCl2(Ph3P)3
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N,N-dimethylalkyl- or N,N-dialkylmethyl-amines are selectively obtained from the reaction between aliphatic amines and methanol at 180 deg C for 7 h in the presence of RuCl2(Ph3P)3 catalyst.
- Arcelli, Antonio,Khai, Bui-The,Porzi, Gianni
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- Oxidation of thiols employing cobalt molybdate/triethylamine catalyst
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A thiol is oxidized to a corresponding disulfide employing a supported cobalt molybdate catalyst in combination with a liquid tertiary amine. 2-propanethiol is converted to diisopropyl disulfide with conversions of the order of 94% and selectivities of the order of 98%.
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- Cyclization of α,ω Aliphatic Diamines and Conversion of Primary Amines to Symmetrical Tertiary Amines by a Homogeneous Ruthenium Catalyst
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α,ω Aliphatic diamines were cyclized to heterocyclic amines by being heated at 180 deg C for 5 h with RuCl2(Ph3P)3 in diphenyl ether.Primary amines having an α-hydrogen atom are converted to symmetrical tertiary amines by being heated at 185 or 235 deg C for 8 h with RuCl3*3H2O and Ph3P in THF solution.
- Bui-The-Khai,Concilio, Carlo,Porzi, Gianni
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p. 1759 - 1760
(2007/10/02)
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