109-76-2Relevant articles and documents
OXIDATION OF POLYAMINES BY PYRROLOQUINOLINE QUINONE (PQQ)
Houen, G.,Larsen, C.,Larsson, L.-I.
, p. 4235 - 4242 (1989)
Pyrroloquinoline quinone (PQQ) was found to oxidize the polyamines spermine and spermidine in stoichiometric amounts with diaminopropane as the main product identified by reversed phase high performance liquid chromatography and mass spectroscopy of the reaction products.Putrescine was oxidized much slower than the polyamines and cetyl-trimethyl-ammonium bromide did not promote oxidation.A model for the PQQ oxidation of polyamines is suggested to account for these observations.
Continuous amination of propanediols in supercritical ammonia
Fischer, Achim,Mallat, Tamas,Baiker, Alfons
, p. 351 - 354 (1999)
Enhancements in selectivity by a factor of 4 to 18 were observed in the near critical regions of ammonia during the Co- and Ni-catalyzed synthesis of 1,3-diamino-propanes. These results are attributed to the higher concentration of ammonia at the surface of the catalyst, which favors the amination and suppresses degredation reactions.
Cobalt-catalyzed amination of 1,3-propanediol: Effects of catalyst promotion and use of supercritical ammonia as solvent and reactant
Fischer,Maciejewski,Buergi,Mallat,Baiker
, p. 373 - 383 (1999)
The catalytic synthesis of 1,3-diaminopropane from 1,3-propanediol and ammonia was studied in a continuous fixed-bed reactor in the pressure range 50 to 150 bar. The unsupported Co-based catalysts applied were characterized by N2 physisorption, XRD, XPS, TPR, and ammonia adsorption using pulse thermal analysis and DRIFT spectroscopy. The latter investigations revealed that the best catalyst, 95 wt% Co-5 wt% Fe, contained only very weak acidic sites, unable to chemisorb ammonia. The absence of strong acidic and basic sites was crucial to suppress the various acid/base-catalyzed side reactions (retro-aldol reaction, hydrogenolysis, alkylation, disproportionation, dimerization, oligomerization). Other important requirements for improved diaminopropane formation were the use of excess ammonia (molar ratio NH3/diol > 20) and the presence of the metastable β-Co phase. A small amount of Fe additive could efficiently hinder the transformation of this phase into the thermodynamically stable α-Co phase and thus prevent catalyst deactivation up to 10 days on stream. Application of supercritical ammonia almost doubled the selectivity to amino alcohol and diamine. The selectivity enhancement in the near-critical region is attributed to elimination of the interphase mass transport limitations and to the resulting higher surface ammonia concentration.
Oxidation of acetylpolyamines by maize polyamine oxidase
Federico, Rodolfo,Ercolini, Luca,Laurenzi, Maria,Angelini, Riccardo
, p. 339 - 341 (1996)
The oxidation of acetylpolyamines by celt wall polyamine oxidase from maize shoots was investigated. The purified enzyme catalysed the oxidation of N1-acetylspermine, N1-acetylspermidine, and N8-acetylspermidine at the same optimal pH (6.5), but with lower relative velocities and higher K(m) than those found for spermine and spermidine oxidation. The enzyme cleaved N1-acetylspermine and N8-acetylspermidine, at the same positions as in spermine and spermidine oxidation, with the production of H2O2, 1,3- diaminopropane and the corresponding aminoaldehydes. Polyamine oxidase was quickly inactivated by catalysis, and the aminoaldehyde derived from N1- acetylspermine behaved as a competitive inhibitor of the enzyme (K(m) = 20 μM). These findings suggest that cell wait polyamine oxidase from maize shoots does not effect the interconversion pathway of acetylpolyamines found in vertebrates.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
Enantioselective synthesis of cyclic and linear diamines by imine cycloadditions
Chang, Tsung-Che,Pradipta, Ambara R.,Tanaka, Katsunori
, p. 1160 - 1168 (2020/07/08)
Imine is one of the most versatile functional groups in chemistry and biochemistry fields. Although many biochemical reactions involve imine formation, the inherently unstable property of N-alkyl-α,β-unsaturated imines still hindered their utilization in organic synthesis. In this article, we described that the N-alkyl-α,β-unsaturated imines, which prepared from alkylamines and acrolein, could smoothly react through [4 + 4] cycloaddition to give eight-membered diazacyclooctane derivatives in excellent yields. Under a similar condition, in the presence of formaldehyde, the [4 + 2] and [4 + 2 + 2] cycloadditions could lead to the formation of six-membered hexahydropyrimidine or eight-membered triazacyclooctanes, depending on the substituent of aldehydes. Moreover, an easy functional group manipulation of the cyclic products obtained from these cycloadditions can provide variously substituted chiral linear diamines. We can utilize these novel reactivities to reveal the unknown and essential properties of many biological processes that involve N-alkyl-unsaturated imines.
Imprinted Apportionment of Functional Groups in Multivariate Metal-Organic Frameworks
Feng, Liang,Wang, Kun-Yu,Lv, Xiu-Liang,Powell, Joshua A.,Yan, Tian-Hao,Willman, Jeremy,Zhou, Hong-Cai
supporting information, p. 14524 - 14529 (2019/10/02)
Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials. As a proof of concept, the imprinted apportionment of functional groups within ZIF-8 was achieved by exchanging imine-based linker templates with original linkers initially. The removal of linker fragments by hydrolysis can be achieved via postsynthetic labilization, leading to the formation of architectures with controlled heterogeneity. The distributions of functional groups in the resulting imprinted MOFs can be tuned by judicious control of the interlocked chain length, which was further analyzed by computational methods. This work provides synthetic tools for precise control of pore environment and functionality sequences inside multicomponent materials.
The invention relates to a propylene glycol and liquid ammonia as raw materials for preparing propylene diamine method and apparatus thereof
-
Paragraph 0080-0081; 0090, (2017/08/31)
The invention relates to a method for preparing propane diamine by taking propylene glycol and liquid ammonia as raw materials. Propylene glycol and liquid ammonia are mixed in a certain ratio and are pumped into a reactor by virtue of a pump, and reaction is carried out in presence of a catalyst and hydrogen. The method for preparing the propane diamine by taking the propylene glycol and liquid ammonia as the raw materials has the advantages that a novel catalyst is adopted, catalytic performance is excellent, and long-time operation can be easily carried out; propylene glycol is subjected to hydroamination for producing a propane diamine product at lower reaction pressure, and reaction conditions are adjusted and changed, so that composition of the product can be flexibly adjusted and changed, selectivity of a target product is improved, a reaction process is simple, one-time investment of a production unit and production cost are reduced, a reaction product and a catalyst can be simply separated, and large-scale continuous industrial production can be easily realized.
Applications of dynamic combinatorial chemistry for the determination of effective molarity
Ciaccia, Maria,Tosi, Irene,Baldini, Laura,Cacciapaglia, Roberta,Mandolini, Luigi,Di Stefano, Stefano,Hunter, Christopher A.
, p. 144 - 151 (2015/02/19)
A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring. This journal is
· Uniform catalyst by using alcohol aminosilicone di-, tri-and a method of manufacturing a polyphenylenepolyamine
-
Paragraph 0099; 0113, (2016/10/09)
The invention relates to a method for producing primary amines, which contain at least one functional group of the formula (-CH2-NH2) and at least one further primary amino group, by the alcohol amination of reactants, which contain at least one functional group of the formula (-CH2-OH) and at least one further functional group (-X), wherein (-X) is selected from hydroxyl groups and primary amino groups, using ammonia with removal of water, wherein the reaction is carried out in a homogeneously catalyzed manner in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.
