- 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 0022
(2020/02/20)
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- Alkyl coupling in tertiary amines as analog of Guerbet condensation reaction
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We report here that C-C coupling in tertiary amines for the synthesis of long chain and hindered amines might be efficiently performed over Pt and Pd catalysts. The mechanism study confirms similarity with the Guerbet reaction through dehydrogenation of the alkyl group and subsequent attack of the α-carbon atom by an alkyl group of another molecule. Finally, secondary amines and tertiary amines with longer alkyl chains are formed.
- Zhou, Yage,Wu, Dan,Hernández, Willinton Yesid,Ma, Changru,Su, Huangyang,Ordomsky, Vitaly
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p. 9845 - 9849
(2019/04/01)
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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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- Continuous N-alkylation reactions of amino alcohols using γ-Al2O3 and supercritical CO2: Unexpected formation of cyclic ureas and urethanes by reaction with CO2
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The use of γ-Al2O3 as a heterogeneous catalyst in scCO2 has been successfully applied to the amination of alcohols for the synthesis of N-alkylated heterocycles. The optimal reaction conditions (temperature and substrate flow rate) were determined using an automated self-optimising reactor, resulting in moderate to high yields of the target products. Carrying out the reaction in scCO2 was shown to be beneficial, as higher yields were obtained in the presence of CO2 than in its absence. A surprising discovery is that, in addition to cyclic amines, cyclic ureas and urethanes could be synthesised by incorporation of CO2 from the supercritical solvent into the product.
- Streng, Emilia S.,Lee, Darren S.,George, Michael W.,Poliakoff, Martyn
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p. 329 - 337
(2017/03/15)
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- Method for synthesizing trioxymethylene by cyclic reaction of formaldehyde aqueous solution catalyzed by ionic liquid
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The invention provides a method for synthesizing trioxymethylene by cyclic reaction of a formaldehyde aqueous solution catalyzed by ionic liquid. The method comprises the following steps: carrying out distillation reaction to the reactants formaldehyde aqueous solution and ionic liquid under atmospheric conditions at 97-102 DEG C so as to synthesize trioxymethylene; in percentage by weight, the addition amount of the formaldehyde aqueous solution is 30-80wt%, the addition amount of the ionic liquid is 0.1-6wt%, and water accounts for all the remaining percentage; and the ionic liquid is a liquid composed of anions and cations, wherein the anions are p-ClPhSO3-. The ionic liquid formed by 4-chlorobenzene sulfonate as anion is used as the catalyst of the method so as to synthesize trioxymethylene by cyclic reaction of formaldehyde; thus, the catalyst is high in catalytic activity and small in dosage; moreover, the reacted trioxymethylene is relatively high in concentration while the contents of the byproducts, including methanol, formic acid and the like, are low; and the reacted trioxymethylene is also good in selectivity.
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Paragraph 0138
(2017/01/17)
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- Colloid and nanosized catalysts in organic synthesis: XIV. Reductive amination and amidation of carbonitriles catalyzed by nickel nanoparticles
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Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in the presence of primary amines led to the predominant formation of unsymmetrical secondary amines. In the presence of secondary amines hydrogenation of nitrites provided enamines as main products. Hydrogenation of nitriles in the presence of formamide or acetamide afforded formyl or acetyl derivatives of primary amines.
- Popov, Yu. V.,Mokhov,Shcherbakova
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p. 798 - 805
(2016/06/13)
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- Silica-functionalized CuI: An efficient and selective catalyst for N-benzylation, allylation, and alkylation of primary and secondary amines in water
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Silica-functionalized CuI has been reported as an efficient and selective catalyst for the selective mono-N- and N,N-dibenzylation, allylation, and alkylation of primary amines with benzylic, allylic, and alkyl halides using NaOH as base in aqueous medium. By changing the reaction temperature, mono- or di-benzylation, allylation, or alkylation could be achieved in good yield and selectivity. Secondary amines have also been benzylated, allylated, and alkylated under similar conditions. SiO2-CuI has been characterized by Fourier transform-infrared, atomic absorption spectrometry, thermalgravimetric analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and found to be highly selective and recyclable under the reaction conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
- Shamim, Tahira,Kumar, Vineet,Paul, Satya
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p. 620 - 632
(2014/01/17)
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- Amination of aliphatic alcohols catalyzed by CuO-NiO/γ-Al 2O3
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The amination of aliphatic alcohols in the gas-solid phase was investigated in a fixed-bed reactor in the presence of CuO-NiO/γ-Al2O 3 as the catalyst. This catalytic system was successfully applied for both the N-methylation of aliphatic amines and N-alkylation of piperidine with primary or secondary alcohols. N-Alkylation of piperidine with low-carbon alcohols resulted in high conversions and selectivities, and the conversion of piperidine and the selectivities toward the desired products declined gradually with the increase of the carbon number of aliphatic alcohols. The influence of varied conditions on the N-cyclohexylation of piperidine was also evaluated, including liquid hourly space velocity (LHSV), temperature and the catalyst; especially the catalyst had the greatest impact. Finally, the test of the catalyst's stability was performed.
- Huang, Jia-Min,Qian, Chao,Feng, Lie,Chen, Yun-Bin,Chen, Xin-Zhi
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p. 1187 - 1190
(2013/08/23)
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- Catalytic reductive alkylation of secondary amine with aldehyde and silane by an iridium compound
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(Chemical Equation Presented) An efficient methodology for the reductive alkylation of secondary amine with aldehyde and Et3SiH using an iridium complex as a catalyst has been developed. For example, treatment of dibutylamine with butyraldehyde and Et3SiH (a 1:1:1 molar amount of amine, aldehyde, and silane) in 1,4-dioxane at 75°C under the influence of a catalytic amount of [IrCl(cod)]2 gave tributylamine in quantitative yield. In this reaction, no reduction of aldehyde took place. It was found that IrCl3, which is a starting material for preparation of iridium complexes such as [IrCl(cod)]2, acts as an efficient catalyst for the present reductive alkylation of amine. In addition, a cheaper, easy-to-handle, and environmentally friendly reducing reagent such as polymethylhydrosiloxane (PMHS) in place of Et3SiH was also useful. Thus, a variety of secondary amines could be alkylated by allowing them to react with aldehydes and PMHS in the presence of an iridium catalyst to afford the corresponding tertiary amines in good to excellent yields. From the deuterium label experiments, it was revealed that silane and water, generated during the formation of enamine by the reaction of amine and aldehyde, seem to behave as a hydrogen source. The catalytic cycle was discussed.
- Mizuta, Tomoya,Sakaguchi, Satoshi,Ishii, Yasutaka
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p. 2195 - 2199
(2007/10/03)
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- Reductive amination of carboxylic acids and [11C]magnesium halide carboxylates
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The reductive amination of carboxylic acids was shown to be promoted by 2-chloropyridine hydrochloride (3 eq). It allowed the one-pot preparation of N-alkylamines in yields up to 93% from carboxylic acid (1 eq), amine (1 eq) and sodium borohydride (5 molar eq). The reaction, carried out with [11C]magnesium halide carboxylates (11C, β+, t1/2:20 min), led to N-[11C]alkylamines in 20-25% radiochemical yields (decay corrected to the end of bombardment, 30 min preparation time from [11C]CO2). In this case, the addition of pyridinium salts led only to the corresponding [11C]carboxylic acids.
- Perrio-Huard, Cecile,Aubert, Catherine,Lasne, Marie-Claire
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p. 311 - 316
(2007/10/03)
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- PIPERIDINE-MODIFIED FISCHER-TROPSCH SYNTHESIS
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N-Alkylpiperidines with alkyl fragment length from C1 to C15 were synthesized by the reaction of CO + H2 + piperidine.The molecular mass distribution of the N-alkylpiperidines has two different distribution parameters α.Thus, α = 0.45 +/- 0.03 for C1-C5 alkyl fragments, while α = 0.65 +/- 0.02 for C6-C15.Piperidine was found to act as modifier reagent and chemical trap for the intermediates in the synthesis reaction.
- Kliger, G. A.,Lesik, O. A.,Mikaya, A. I.,Marchevskaya, E. V.,Zaikin, V. G.,et al.
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p. 435 - 438
(2007/10/02)
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- A Novel and Versatile Synthesis of 1-Alkyl-, 1-Aryl-, 1-(Alkylamino)-, or 1-Amido-Substituted and of 1,2,6-Trisubstituted Piperidines from Glutaraldehyde and Primary Amines or Monosubstituted Hydrazines
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Various primary amines and 1-mono- and 1,1-disubstituted hydrazines were converted into the corresponding N-substituted piperidines in good to excellent yields via the products of double condensations with benzotriazole and glutaraldehyde.Reduction of the 2,6-bis(benzotriazolyl) N-substituted piperidines 4 and 7 with sodium borohydride in tetrahydrofuran afforded N-substituted piperidines.The benzotriazole moieties were also replaced by alkyl groups by reaction with Grignard reagents to produce 1,2,6-trisubstituted piperidines.
- Katritzky, Alan R.,Fan, Wei-Qiang
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p. 3205 - 3209
(2007/10/02)
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- N-HYDROXYPYRIDINE-2-THIONE CARBAMATES. IV. A COMPARISON OF 5-EXO CYCLIZATIONS OF AN AMINYL RADICAL AND AN AMINIUM CATION RADICAL
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Cyclizations of the N-butyl-4-pentenaminyl radical and the N-butyl-4-pentenaminium cation radical were studied.The radicals were produced in chain reactions from the same N-hydroxypyridine-2-thione carbamate precursors.Rate constants for cyclization of the aminyl radical and ring opening of the product thus formed at 50 deg C were determined.Cyclizations of the aminium cation radical, formed by protonation of the aminyl radical, were studied under a variety of conditions.
- Newcomb, Martin,Deeb, Thomas M.,Marquardt, Donald J.
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p. 2317 - 2328
(2007/10/02)
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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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- Catalytic Hydroamination of Furfuryl and Tetrahydrofurfuryl Alcohols with Nitriles
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Reaction of furfuryl and tetrahydrofurfuryl alcohols with nitriles over copper oxide catalysts under a hydrogen pressure of 15 atm at a temperature of 230 deg C gives N-alkylfurfuryl- (yield 46-50percent) and N-alkyltetrahydrofurfurylamines (49-53percent), and N-alkylpiperidines (28-41percent).A reaction mechanism is proposed.
- Kozintsev, S. I.,Basalaeva, L. I.,Gladkikh, L. V.,Kozlov, N. S.
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- Conveniant Method for Replacement of Tertiary N-Methyl by Other Alkyl Groups: Application to Morphine Alkaloids
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The replacement of N-methyl of N-methylpiperidine (1), 4-methylmorpholine (4), 2-methyl-1,2,3,4-tetrahydroisoquinoline (7) and tropine (10) by n-propyl, n-butyl and isopropyl groups (3a-3c, 6c, 9a-9c and 12a-12c) has been achieved in high yields by quaternization of the respective tertiary amine with appropriate alkyl halide and demethylation of the resulting quaternary salt with thiophenoxide.It has been established that demethylation is strongly favoured over the removal of n-propyl and n-butyl groups, whereas deisopropylation occurs to some extent.Surprisingly, in the case of 11c, deisopropylation predominates.This method has been applied to morphine (13b), codeine (13d) and thebaine (14b) for similar replacements.The rapid quaternization of thebaine (14b) has been assigned to the absence of H-14 in this alkaloid.The fact that quaternary salts of thebaine, which are susceptible to aromatization of the nucleus by extrusion of the ethanamine chain, are smoothly demethylated to N-alkylnorthebaines (18a-18c) in good yields indicates that demethylation, a bimolecular nucleophilic displacement, competes very successfully with elimination reaction.
- Manoharan, T. Samuel,Madyastha, K. Madhava,Singh, B. B.,Bhatnagar, S. P.,Weiss, Ulrich
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- HYDROBORATION OF 1-(3-BUTENYL)PIPERIDINE AND 1-(4-PENTENYL)PIPERIDINE
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Hydroboration of 1-(3-butenyl)- (Ia) and 1-(4-pentenyl)piperidine (Ib) with triethylamine-borane followed by hydrolysis and oxidation afforded the appropriate alcohols IIIc and IIIf resp.The spirocyclic amine-borane IIa,b isolated from the hydroboration product were transformed by hydrochloric acid into the hydrochlorides of piperidinealkylboronic acids IVa,b which were oxidized in an alkaline medium with hydrogen peroxide to the primary alcohols IIIc,f.Diethyl ester V was prepared by ethanolysis of IIa.
- Kafka, Stanislav,Ferles, Miloslav
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- CATALYTIC ALKYL GROUP EXCHANGE REACTION OF PRIMARY AND SECONDARY AMINES.
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It has been shown that primary and secondary amines undergo alkyl group exchange reactions upon treatment with palladium catalyst as depicted in an operationally simple and efficient reaction which provides a convenient method for synthesis of unsymmetrical amines. The application of the reaction for the preparation of various substituted amines and heterocyclic compounds such as hexahydropyrimidine tetrahydropyrimidine, imidazolidine, and imidazoles is described. The preparation of polyamines such as H//2N(CH//2)//mNH(CH//2)//nNH//2 (10) and H//2N(CH//2)//lNH(CH//2)//mNH(CH//2)//nNH//2 (l-n, equals 2,3; 11) is readily performed by the appadium-catalyzed reactions of azetidine (6) and aziridine (7) via azetine (9) and azirine intermediates. The mechanism the palladium-catalyzed reaction has been extensively studied on the carbonylation, racemization, and deuteurium-exchange reaction of (S)-( minus )- alpha -phenylethylamine (17).
- Murahashi,Yoshimura,Tsumiyama,Kojima
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p. 5002 - 5011
(2007/10/02)
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