- Selective one-pot synthesis of asymmetric secondary amines via N-alkylation of nitriles with alcohols
-
The synthesis of asymmetric secondary amines (ASA) is commonly achieved by N-alkylation of primary amines with alcohols. Here, we investigated the ASA synthesis via the direct amination of alcohols with nitriles, which avoids the synthesis, separation and purification of the primary amines in a first step. Specifically, the ASA synthesis via N-alkylation of butyronitrile (BN) with primary (n-propanol, iso-butanol and n-octanol) and secondary (2‐propanol, 2‐butanol and 2‐octanol) alcohols was studied on SiO2-supported Co, Ni and Ru catalysts. Competitive BN hydrogenation‐condensation reactions formed dibutylamine (the symmetric secondary amine) and tertiary amines as main secondary products. On Co/SiO2, the ASA selectivities for BN/primary alcohol reactions were between 49 and 58% at complete BN conversion, forming dibutylamine and tertiary amines as byproducts. For BN/secondary alcohol reactions, Co/SiO2 formed selectively (ASA + dibutylamine) mixtures containing 78–85% of ASA, thereby showing that the alcohol amination with nitriles is an attractive alternative route for the synthesis of valuable asymmetric secondary amines.
- Segobia,Trasarti,Apesteguía
-
p. 178 - 185
(2019/11/13)
-
- Alkyl coupling in tertiary amines as analog of Guerbet condensation reaction
-
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
-
p. 9845 - 9849
(2019/04/01)
-
- N-ethyl-n-butylamine production method
-
The invention relates to a production method of N-ethyl-n-butylamine. According to the production method, n-butanol and monoethylamine are taken as raw materials; a supported non-noble metal catalyst is used under hydrogen conditions; and amination synthe
- -
-
Paragraph 0047; 0050; 0053
(2017/01/05)
-
- The synthesis of N-ethyl-n-butylamine by amines disproportionation
-
A synthesis of N-ethyl-n-butylamine with simple separation method in a fixed-bed reactor using CuO-NiO-PtO/γ-Al2O3 as the catalyst was proposed and investigated. The present catalytic system gave high activity and good selectivity, and the reaction conditions such as temperature and liquid hourly space velocity were optimized. Since no water was generated, the protocol proved to be easy to separate, and N-ethyl-n-butylamine was collected at 110 °C by distillation. The yield and the purity were 60.7 and 99.5 %, respectively.
- Xu, Lu-Feng,Huang, Jia-Min,Qian, Chao,Chen, Xin-Zhi,Feng, Lie,Chen, Yun-Bin,He, Chao-Hong
-
p. 2697 - 2704
(2013/07/26)
-
- Catalytic hydrogenation of amides to amines under mild conditions
-
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
-
supporting information
p. 2231 - 2234
(2013/03/28)
-
- Hydrogenation of nitriles to primary amines on metal-supported catalysts: Highly selective conversion of butyronitrile to n-butylamine
-
The selective liquid-phase hydrogenation of butyronitrile to n-butylamine was studied in a batch reactor on Co(9.8%)/SiO2, Ni(10.5%)/SiO 2, Cu(9.2%)/SiO2, Pt(0.27%)/SiO2, Pd(0.33%)/SiO2, and Ru(1.8%)/SiO2 catalysts. At 373 K and 13 bar (H2), the initial butyronitrile conversion rate (rBN0, mmol/h g) followed the order Ni > Co > Pt > Ru > Cu > Pd. Cu/SiO 2 and Pd/SiO2 did not form n-butylamine and rapidly deactivated during the progress of the reaction. Pt/SiO2 produced mainly dibutylamine and only minor amounts of n-butylamine and tributylamine. In contrast, Ru/SiO2 formed preponderantly n-butylamine but also produced significant amounts of dibutylamine and butylidene-butylamine, an intermediate in the formation pathway of the secondary amine. The highest yield to n-butylamine was obtained on Ni/SiO2 (84%). Co/SiO2 was initially highly selective to n-butylamine but with the progress of the reaction the butylamine concentration in the reaction mixture diminished because it partially reacted with the solvent (ethanol) to form N-ethylbutylamine. In an attempt to reduce the formation of byproducts, Ni/SiO2 and Co/SiO2 catalysts were tested at lower temperatures and higher H 2 pressures. Butyronitrile was selectively converted to n-butylamine on Co/SiO2 at 343 K and 25 bar, yielding 97% of n-butylamine, similarly to the highest yields reported on Raney Co catalysts.
- Segobia,Trasarti,Apesteguía
-
-
- A novel method for N-alkylation of aliphatic amines with ethers over ?3-Al2O3
-
A novel and simple method for the N-alkylation of amines with different ethers as alkylating reagents has been developed, using cheap ?3-Al2O3 as the catalyst at atmospheric pressure in the temperature range of 260-320?°C. For example, the reaction of equ
- Chen, Hangeng,Zhang, Tao,Qian, Chao,Chen, Xinzhi
-
p. 537 - 540
(2015/03/05)
-
- Discovery and mechanistic study of AlIII-catalyzed transamidation of tertiary amides
-
Cleavage of the C-N bond of carboxamides generally requires harsh conditions. This study reveals that tris(amido)AlIII catalysts, such as Al2(NMe2)6, promote facile equilibrium-controlled transamidation of tertiary carboxamides with secondary amines. The mechanism of these reactions was investigated by kinetic, spectroscopic, and density functional theory (DFT) computational methods. The catalyst resting state consists of an equilibrium mixture of a tris(amido)AlIII dimer and a monomeric tris(amido)Al III-carboxamide adduct, and the turnover-limiting step involves intramolecular nucleophilic attack of an amido ligand on the coordinated carboxamide or subsequent rearrangement (intramolecular ligand substitution) of the tetrahedral intermediate. Fundamental mechanistic differences between these tertiary transamidation reactions and previously characterized transamidations involving secondary amides and primary amines suggest that tertiary amide/secondary amine systems are particularly promising for future development of metal-catalyzed amide metathesis reactions that proceed via transamidation.
- Hoerter, Justin M.,Otte, Karin M.,Gellman, Samuel H.,Cui, Qiang,Stahl, Shannon S.
-
p. 647 - 654
(2008/10/09)
-
- 2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION
-
The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.
- -
-
-
- Perfluoro-tagged benzyloxycarbonyl protecting group and its application in fluorous biphasic systems
-
The synthesis of a new perfluoro-tagged benzyloxycarbonyl protecting group is reported, as well as its application in the parallel protection of amines. Isolation of the protected amines was performed by simple liquid-liquid extraction between perfluorinated and organic solvents. Deprotection was achieved by standard hydrogenolysis. The novel protecting group was also applied to cyclization protocols leading to quinazoline-2,4-diones. These products were isolated by simple extraction procedures.
- Schwinn, Dominik,Bannwarth, Willi
-
p. 255 - 264
(2007/10/03)
-
- Preparation of amines
-
A process for preparing an amine by catalytic reaction of an olefin with ammonia or a primary or secondary amine by contacting a mixture of the reactants in a reactor at 200° to 400° C. and an elevated pressure up to 700 bar in the presence of a catalyst consisting essentially of an X-ray amorphous (non-crystalline) mesoporous catalyst, some of which may have a microporous non-crystalline content. The catalyst has the composition where Q is at least one of the trivalent elements aluminum, boron, chromium, iron or gallium, and M is at least one of the tetravalent elements silicon, titanium or germanium. The molar ratio of a:b is from 0.5:1 to 1000:1 and the molar ratio of c:b is from 0 to 2:1. As prepared and used in the process, this non-crystalline catalyst has a specific BET surface area of from 200 to 1000 m2 /g.
- -
-
-
- Preparation process of aminoacetamide derivative
-
Disclosed herein are novel processes for preparing aminoacetamide derivatives, wherein: (1) a secondary amine is reacted with a 2-haloacetamide in the presence or absence of at least one solvent selected from water, lower alcohols, aromatic solvents and acetic acid esters; (2) an N-benzylideneamine derivative is reacted with dimethyl sulfate or diethyl sulfate to form a secondary amine, and this secondary amine is then reacted with a 2-haloacetamide; and (3) a primary amine is reacted with benzaldehyde to form an N-benzylideneamine derivative, this product is then reacted with dimethyl sulfate or diethyl sulfate to form a secondary amine, and this secondary amine is further reacted with a 2-haloacetamide. The 2-aminoacetamide derivatives are useful as intermediates for the preparation of novel antibiotics.
- -
-
-
- ELECTROCHEMICAL REDUCTIVE AMINATION. II. AMINATION OF ALIPHATIC ALDEHYDES WITH PRIMARY AMINES
-
The formation of a secondary amine by the electrolysis of an aqueous solution containing an aldehyde and a primary amine was studied.The formation of the secondary amines passes through the intermediate stage of an aldimine.The highest yield of secondary amine is attained at a molar ratio of primary amine to aldehyde of 1.2:1.As electrode material lead, cadmium, zinc, and copper may be used.As supporting electrolyte a phosphate buffer with a pH close to the pKa of the primary amine is recommended.By the method developed 32 amines with various structures were synthesized.
- Smirnov, Yu. D.,Pavlichenko, V. F.,Tomilov, A. P.
-
p. 374 - 380
(2007/10/02)
-
- PHOSPHONIUM DIAZA-DIYLIDS AND AZA-YLDIID AS NEW AND EFFICIENT REAGENTS FOR PRIMARY AND SECONDARY AMINES SYNTHESIS
-
Metallated aminophosphonium ylids, diaza-diylids and aza-yldiid, are investigated as reagents for primary and secondary amines synthesis.
- Cristau, Henri-Jean,Garcia, Chantal,Kadoura, Jumah,Torreilles, Eliane
-
p. 151 - 154
(2007/10/02)
-
- Organoboranes for synthesis. Reaction of organoboranes with representative organic azides. A general stereospecific synthesis of secondary amines and N-substituted aziridines
-
Reaction of trialkylboranes with organic azides in refluxing xylene, followed by hydrolysis, leads to good yields of secondary amines. This reaction is highly dependent on the steric effects around both boron and the azide moiety. The reaction becomes much slower when the steric bulk of one of the reagents is increased and fails when both are hindered. The dialkylchloroboranes are more reactive than trialkylboranes and provide better yields of the desired secondary amines with a11 azides tested. The alkyldichloroboranes react with organic azides at temperatures between room temperature and 60°C and produce excellent yields of secondary amines. Furthermore, the stereochemistry of the original carbon-boron bond is retained. The mechanism of these reactions is discussed and the reaction applied to the synthesis of N-alkyl- and N-arylaziridines.
- Brown, Herbert C.,Midland, M.Mark,Levy, Alan B.,Brown,Wetherill,Suzuki, Akira,Sono, Sunao,Itoh, Mitsuomi
-
p. 4079 - 4088
(2007/10/02)
-
- Monoalkylation of Primary Aliphatic Amines via N-Alkyl-N-(alkylthiomethyl)ammonium Chlorides. Evidence for the Formation of Stable N-Methylenealkylamines
-
Monomeric N-methylenealkylamines (3), formed from N-alkyl-N-(alkylthiomethyl)ammonium chlorides (5) are stable at -60 deg C and may be trapped with organometallic reagents to provide the N,N-dialkylamines (8).
- Barluenga, Jose,Bayon, Ana M.,Asensio, Gregorio
-
p. 427 - 428
(2007/10/02)
-
- O-Arenesulfonyl-N-alkylhydroxylamines as Aminating Reagents
-
O-(p-Toluenesulfonyl)-N-methyl-, -N-ethyl-, and -N-isopropil-hydroxylamines and O-mesitylenesulfonyl-N-methylhydroxylamine were prepared.The N-methyl and N-ethyl derivatives were found to react with tertiary amines and triphenylphosphine to give the corresponding N-(alkylamino)ammonium salts and P-(alkylamino)phosphonium salts, but the N-isopropyl derivative was less reactive, probably due to steric effects.These reagents also reacted with tri-n-butylborane to give the corresponding alkyl-n-butylamines.Keywords-- electrophilic aminating reagent; tert-butoxycarbonylation; di-tert-butyl dicarbonate; N-(methylamino)ammonium salts; P-(methylamino)triphenylphosphonium salt; N-(methylamino)pyridinium salt; secondary amines
- Tamura, Yasumitsu,Ikeda, Hiroyuki,Morita, Iwao,Tsubouchi, Hidetsugu,Ikeda, Masazumi
-
p. 1221 - 1224
(2007/10/02)
-