- Highly economical and direct amination of sp3carbon using low-cost nickel pincer catalyst
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Developing more efficient routes to achieve C-N bond coupling is of great importance to industries ranging from products in pharmaceuticals and fertilizers to biomedical technologies and next-generation electroactive materials. Over the past decade, improvements in catalyst design have moved synthesis away from expensive metals to newer inexpensive C-N cross-coupling approaches via direct amine alkylation. For the first time, we report the use of an amide-based nickel pincer catalyst (1) for direct alkylation of amines via activation of sp3 C-H bonds. The reaction was accomplished using a 0.2 mol% catalyst and no additional activating agents other than the base. Upon optimization, it was determined that the ideal reaction conditions involved solvent dimethyl sulfoxide at 110 °C for 3 h. The catalyst demonstrated excellent reactivity in the formation of various imines, intramolecularly cyclized amines, and substituted amines with a turnover number (TON) as high as 183. Depending on the base used for the reaction and the starting amines, the catalyst demonstrated high selectivity towards the product formation. The exploration into the mechanism and kinetics of the reaction pathway suggested the C-H activation as the rate-limiting step, with the reaction second-order overall, holding first-order behavior towards the catalyst and toluene substrate.
- Brandt, Andrew,Rangumagar, Ambar B.,Szwedo, Peter,Wayland, Hunter A.,Parnell, Charlette M.,Munshi, Pradip,Ghosh, Anindya
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p. 1862 - 1874
(2021/01/20)
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- One-pot synthesis of 1-butylpyrrolidine and its derivatives from aqueous ammonia and 1,4-butandiol over CuNiPd/ZSM-5 catalysts
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The synthesis of 1-butylpyrrolidine and its derivatives (1-butylpyrrolidine with a little of 1-butenylpyrrolidines) was developed via a one-pot method from ammonia and 1,4-butandiol. Here, the product of 1-butylpyrrolidine was emphatically investigated, and the yield was 76% under the optimized conditions. Such a route was realized through successive N-alkylation using aqueous ammonia as the nitrogen source over the CuNiPd/ZSM-5 catalyst, which was prepared by a simple incipient wetness method. In this route, 1,4-butandiol not only participated in the formation of the N-heterocycle, but also acted as an alkylating reagent. This work offers a straightforward, economical route for 1-butylpyrrolidine and its derivatives. This journal is
- Long, Yan,Liu, Shimin,Ma, Xiangyuan,Lu, Liujin,He, Yude,Deng, Youquan
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supporting information
p. 16708 - 16712
(2020/10/27)
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- Method for catalytically synthesizing 1-substituted pyrrolidine/piperidine derivative by using supported metal
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The invention provides a method for catalytically synthesizing a 1-substituted pyrrolidine/piperidine derivative by using a supported metal. The method comprises: carrying out a reaction with ammoniato form a pyrrolidine ring/piperidine ring by using a supported metal as a catalyst, using 1,4-butanediol/1, 5-pentanediol as a cyclization raw material and using alcohol as an N-alkylation raw material, wherein the high-selectivity synthesis of the 1-substituted pyrrolidine/piperidine derivative is achieved through the one-step reaction, the active components of the supported metal catalyst are Cu, Ni and Pd/Ru, the total loading capacity of the active components Cu and Ni is 3-15 wt% of the carrier, and the loading capacity of Pd/Ru is 0-1 wt% of the carrier. According to the invention, themethod is simple, low in cost and environmentally friendly, the conversion rate of 1,4-butanediol/1,5-pentanediol is high, the selectivity of the pyrrolidine/piperidine derivatives is high, and the method is a production route with practical application value.
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Paragraph 0015; 0025; 0028-0030
(2020/02/20)
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- Combinatorial discovery of thermoresponsive cycloammonium ionic liquids
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This work demonstrated, for the first time, the combinatorial discovery and rational identification of small-molecule cycloammonium-based thermoresponsive ionic liquids that exhibit LCST phase transition and carry attractiveTcvalues in water.
- Chu, Yen-Ho,Hwang, Chun-Chieh,Chen, Chien-Yuan,Tseng, Min-Jen
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supporting information
p. 11855 - 11858
(2020/10/13)
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- Thermophysical and Electrochemical Properties of Ethereal Functionalised Cyclic Alkylammonium-based Ionic Liquids as Potential Electrolytes for Electrochemical Applications
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A series of hydrophobic room temperature ionic liquids (ILs) based on ethereal functionalised pyrrolidinium, piperidinium and azepanium cations bearing the bis[(trifluoromethyl)sulfonyl]imide, [TFSI]?, anion were synthesized and characterized. Their physicochemical properties such as density, viscosity and electrolytic conductivity, and thermal properties including phase transition behaviour and decomposition temperature have been measured. All of the ILs showed low melting point, low viscosity and good conductivity and the latter properties have been discussed in terms of the IL fragility, an important electrolyte feature of the transport properties of glass-forming ILs. Furthermore, the studied [TFSI]?-based ILs generally exhibit good electrochemical stabilities and, by coupling electrochemical experiments and DFT calculations, the effect of ether functionalisation at the IL cation on the electrochemical stability of the IL is discussed. Preliminary investigations into the Li-redox chemistry at a Cu working electrode are also reported as a function of ether-functionality within the pyrrolidinium-based IL family. Overall, the results show that these ionic liquids are suitable for electrochemical devices such as battery systems, fuel cells or supercapacitors.
- Neale, Alex R.,Murphy, Sinead,Goodrich, Peter,Hardacre, Christopher,Jacquemin, Johan
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p. 2040 - 2057
(2017/08/10)
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- Bio-based N-alkyl-2-pyrrolidones by Pd-catalyzed reductive N-alkylation and decarboxylation of glutamic acid
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Environmental regulations boost the search for new safer and less toxic bio-based solvents to replace controversial high-boiling solvents such as N-methyl-2-pyrrolidone and N,N-dimethylformamide in the chemical industry. Recently, N-alkyl-2-pyrrolidones and 5-methyl-N-alkyl-2-pyrrolidones were proposed as attractive alternative solvents for many applications. Here, we report a bio-based two-step chemocatalytic system for the synthesis of a broad range of N-alkyl-2-pyrrolidones starting from glutamic acid and C3-C5 carbonyl compounds. In the first step N-mono-alkylated derivatives of glutamic acid were synthesized in high yields (>85%) by a mild and efficient Pd-catalyzed reductive N-alkylation. Subsequently, thermally induced lactamization to the corresponding N-alkylpyroglutamic acid followed by Pd-catalyzed decarboxylation at 250 °C under inert atmosphere resulted in N-alkyl-2-pyrrolidones. Hydrolytic degradation was partially counteracted by the neutralization of the N-alkylpyroglutamic acid substrate with a base, resulting in yields up to 82%. Finally, both reaction steps were successfully combined in a one-pot process using the same Pd/Al2O3 catalyst in different conditions of gas atmosphere and temperature.
- De Schouwer, Free,Adriaansen, Sander,Claes, Laurens,De Vos, Dirk E.
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p. 4919 - 4929
(2017/10/19)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- Solvent free N-Heterocyclization of primary amines to N-substituted azacyclopentanes using hydrotalcite as solid base catalyst
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An ecofriendly catalytic route for selective synthesis of N-substituted azacyclopentanes, nitrogen-containing heterocyclic intermediates for many bioactive compounds, was established by carrying out N-heterocyclization (di N-alkylation) of primary amines with 1,4-dichloro butane (as dialkylating agent) using catalytic amount of hydrotalcite as solid base catalyst. The hydrotalcite was found to be efficient solid base catalyst for di Nalkylation of different primary amines (aniline, benzyl amine, cyclohexyl amine and n-butyl amine) giving 82 to 96% conversion (at optimized reaction condition) of 1,4-dichloro butane and > 99% selectivity of respective N-substituted azacyclopentanes within 30 min. under solvent free condition. The reaction parameters significantly influence the conversion of 1,4-dichloro butane to N-substituted azacyclopentanes. The nature of substituent present on amino group affects the reactivity of amine substrates for di N-alkylation reaction with 1,4-dichloro butane. The 1,4-dichloro butane was found to be highly reactive alkylating agent for di Nalkylation of amines as compared to 1,4-dihydroxy butane. The reusability of the catalyst and its chemical stability in the reaction was demonstrated. Copyright
- Dixit, Manish,Mishra, Manish,Joshi,Shah
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experimental part
p. 1457 - 1464
(2012/07/27)
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- Catalyst-free one-pot reductive alkylation of primary and secondary amines and N,N-dimethylation of amino acids using sodium borohydride in 2,2,2-trifluoroethanol
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A simple and convenient procedure for the reductive alkylation of primary and secondary amines and N,N-dimethylation of amino acids is described using sodium borohydride as a reducing agent in 2,2,2- trifluoroethanol without use of a catalyst or any other additive. The solvent can be readily recovered from reaction products in excellent purity for direct reuse. Georg Thieme Verlag Stuttgart - New York.
- Tajbakhsh, Mahmood,Hosseinzadeh, Rahman,Alinezhad, Heshmatollah,Ghahari, Somayeh,Heydari, Akbar,Khaksar, Samad
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experimental part
p. 490 - 496
(2011/03/20)
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- Reductive amination of aldehydes and ketones under heterogeneous and solvent-free conditions using sodium-borohydride and silica-gel-supported sulfuric acid
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A regioselective and convenient procedure for preparation of amines by reductive amination of aldehydes and ketones using sodium borohydride in the presence of sulfuric acid supported on silica gel as an active, inexpensive, and recoverable catalyst under heterogeneous and solvent-free conditions at room temperature is described.
- Alinezhad, Heshmatollah,Tajbakhsh, Mahmood,Zare, Mahboobeh
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experimental part
p. 2907 - 2916
(2009/12/03)
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- Fluorine-containing ionic liquids from N-alkylpyrrolidine and N-methylpiperidine and fluorinated acetylacetones: Low melting points and low viscosities
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A family of new fluorine-containing ionic liquids (3-14) was synthesized in high yield by the reaction of N-alkylpyrrolidine, N-methylpiperidine and fluorinated 1,3-diketones: 1,1,1,5,5,5-hexafluoroacetylacetone, 1,1,1-trifluoro-2,4-pentanedione and 4,4,4-trifluoro-1-phenyl-1,3-butanedione. Their properties, such as the phase-transition temperature, density, and viscosity, were determined. Most of them show relatively low melting points and low viscosities. The influence of fluorinated 1,3-diketonate anions and the structural variation in cyclic amine cations on the above physicochemical properties was examined. X-ray single-crystal diffraction analysis of compound 7 confirms the proton transfer from 4,4,4-trifluoro-1-phenyl-1,3-butanedione to N-butylpyrrolidine. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Li, Xiaoju,Zeng, Zhuo,Garg, Sonali,Twamley, Brendan,Shreeve, Jean'ne M.
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experimental part
p. 3353 - 3358
(2009/02/07)
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- Compound for the aluminum film from chemical vapor depositions and the method of synthesis
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Organometallic precursor compounds useful for forming aluminum films by chemical vapor deposition are disclosed. Also disclosed are methods of preparing the organometallic precursor compounds and methods of forming aluminum films.
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- Activity of copper- and iron-containing catalysts in the reaction of diols with ammonia in the presence of hydrogen
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An investigation has been made of the vapour-phase reaction of 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol and 2,5-hexanediol with ammonia and hydrogen at a temperature of 160-230°C on oxide copper-zinc-aluminium catalyst SNM-1 and a reduced, promoted, sintered iron catalyst. The composition of the main reaction products has been established, and schemes of their formation are suggested.
- Shuikin,Glebov,Kliger,Zaikin
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- Preparation of N-substituted cyclic amines
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N-substituted cyclic amines of the general formula I STR1 where A is an alkylene group or a --(CH2)n --[--O--(CH2)m ]r group which may be monosubstituted or polysubstituted by radicals R without the radicals R in a defined compound having to be identical, R is alkyl, alkoxyalkyl, unsubstituted or alkyl-substituted or alkoxy-substituted cycloalkyl, cycloalkylalkyl, aryl or arylalkyl, n and m independently of one another are each from 2 to 8 and r is from 1 to 3, the --(CH2)n --[O--(CH2)m ]r group consisting of from 5 to 12 members, are prepared by reacting a primary amine of the general formula II with a diol of the general formula III where R and A have the abovementioned meanings, and hydrogen in the presence of a copper-containing hydrogenation/dehydrogenation catalyst at elevated temperatures and under superatmospheric pressure, by a process in which the reaction is carried out in the presence of a catalytic amount of a basic alkali metal compound or alkaline earth metal compound.
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- N-Alkylation d'amines en catalyse homogene. Synthese de mono- et de diamines cycliques
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Ruthenium compounds are appropriate catalysts in the N-alkylation of amines.The synthesis of N-alkylated cyclic amines from a cyclic amine and an alcohol or via the condensation between a diol and a primary amine are described.The reaction with cyclic amines is highly selective, especially in the presence of a phosphine, making it a high yielding preparative procedure.The catalytic condensation between cyclic amines and diols yields either an aminoalcohol (A) or a bicyclic diamine (B).The temperature, the presence of phosphine, and the ratio of amine to diol are decisive in directing the reaction toward A or B.The proposed mechanism involves the dehydrogenation of the alcohol followed by attack of the amine on the aldehyde intermediate.
- Bitsi, G.,Schleiffer, E.,Antoni, F.,Jenner, G.
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p. 343 - 352
(2007/10/02)
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- SYNTHESIS OF NITROGEN-CONTAINING HETEROCYCLES OF AN IRON CATALYST. 2. THE CONVERSIONS OF 1,4-BUTANEDIOL AND DIETHYLENEGLYCOL IN THE PRESENCE OF AMMONIA AND HYDROGEN
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The gas-phase interaction of 1,4-butanediol and diethylene glycol with ammonia and/or hydrogen on a reduced, fused, iron catalyst has been investigated.
- Kliger, G. A.,Lesik, O. A.,Marchevskaya, E. V.,Mikaya, A. I.,Zaikin, V. G.,et al.
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p. 161 - 164
(2007/10/02)
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- Transition Metal-catalysed N-Alkylation of Amines by Alcohols
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Primary and secondary alcohols effect alkylation of primary and secondary amines in the presence of rhodium, iridium, and ruthenium compounds at = 100 deg C, whereby selective monoalkylation of primary amines can be achieved, and heterocyclic rings can be constructed by both inter- and intra-molecular processes.
- Grigg, R.,Mitchell, T. R. B.,Sutthivaiyakit, S.,Tongpenyai, N.
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p. 611 - 612
(2007/10/02)
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