- In situ generated amine as a Lewis base catalyst in the reaction of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study
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The problem how ammonium nitrate affects the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) in nitric acid to prepare 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) has puzzled chemists for decades. In this paper, experimental work and theoretical calculation are described to investigate the long-standing challenge. The experiment results showed that ammonium nitrate or alkylammonium chlorides were in favor of the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX) but hindered the conversion of MNX to HMX. A plausible catalytic mechanism was proposed. In which ammonia or amines, in situ generated from the unfavorable balance with their salts, act as Lewis base catalysts. At the same time, the DFT computation results reveal that rigid bicyclic transition states established with 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane, ammonia (or amines) and three water molecules lead to very low activation energies. Then, a novel process for the preparation of MNX with excellent yield up to 78.5% was developed, which is free of the use of NaNO2 or N2O4 as nitroso resources.
- Zhang, Yu,Chi, Guoli,He, Ying,Xu, Zishuai,Zhang, Luyao,Luo, Jun,Zhou, Baojing
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supporting information
(2019/04/08)
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- A General Acid-Mediated Hydroaminomethylation of Unactivated Alkenes and Alkynes
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In comparison to the extensively studied metal-catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State-of-the-art protocols for hydroaminomethylation of alkenes rely largely on transition-metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid-mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench-stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported.
- Kaiser, Daniel,Tona, Veronica,Gon?alves, Carlos R.,Shaaban, Saad,Oppedisano, Alberto,Maulide, Nuno
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supporting information
p. 14639 - 14643
(2019/09/17)
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- Method for preparing kakonein derivatives
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The invention discloses a puerarin derivative preparation method. Puerarin derivative has the structural formula as shown in the specification, and the puerarin derivative is obtained by that puerarin reacts with CH2(R)2, wherein R is a tertiary amine gene. The puerarin derivative preparation method is characterized in that reaction is carried out under hydrochloric acid catalysis. Compared with the prior art, the puerarin derivative preparation method is characterized in that the yield of a puerarin derivative product can be obviously improved after the class of reaction adopts hydrochloric acid catalysis.
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Paragraph 0045-0047
(2017/03/17)
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- Syntheses and Structures of [CH2(NCnH2n)2]Mo(CO)4 (n = 4,5) Complexes with Bis(cycloamine) Ligands Easily Prepared from CH2Cl2
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Dipyrrolidylmethane, CH2(pyr)2, and dipiperidylmethane, CH2(pip)2, are synthesized via the condensation of their respective secondary amine precursors and dichloromethane at room temperature in the absence of light. Their use as chelating ligands is shown by the isolation and complete characterization of [CH2(pyr)2]Mo(CO)4 and [CH2(pip)2]Mo(CO)4 complexes. X-ray analysis reveals the methylene bis(cycloamines) to possess a sharp bite angle between 61° and 63° and a strong steric impact on the surrounding carbonyl ligands as a result of their ring conformations. (Chemical Equation Presented).
- Kyran, Samuel J.,Sanchez, Sergio G.,Arp, Christopher J.,Darensbourg, Donald J.
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p. 3598 - 3602
(2015/08/06)
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- (E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation
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A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO. This journal is
- Shi, Renyi,Zhang, Hua,Lu, Lijun,Gan, Pei,Sha, Yuchen,Zhang, Heng,Liu, Qiang,Beller, Matthias,Lei, Aiwen
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supporting information
p. 3247 - 3250
(2015/06/16)
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- Cu(I) metal organic framework catalyzed C-C and C-N coupling reactions
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DABCO (1,4-diazabicyclo[2.2.2]octane) based Cu(I) metal organic framework (here after represented as Cu(I)-MOF) catalyzed Sonogashira cross-coupling reaction of iodobenzene and phenylacetylene was conducted smoothly to afford diphenylacetylene in excellent yield under N2atmosphere. For comparative study, piperidine based Cu(I) clusters were also investigated. Among these catalysts, Cu(I)-MOF exhibited higher activity with good selectivity for the C-C cross-coupled product. Cu(I) catalysts investigated in this study exhibited similar activity in the C-C homo-coupling reaction of phenylacetylene in O2atmosphere. Application of these catalysts was extended in the C-N coupling reactions between phenylboronic acid and aromatic/aliphatic/heterocyclic amines. Cu(I)-MOF can be readily recovered from the reaction mixture and reused for several cycles without loss in the catalytic activity.
- Rani, Poonam,Srivastava, Rajendra
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p. 5256 - 5260
(2015/01/16)
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- Photochemical synthesis, structure and spectroscopic properties of [W(CO)4(C5H10N)2CH2]
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Dipiperidylmethane (CH2dipip) coordinates to photochemically created W(CO)4 species to give a tungsten(0) complex [W(CO) 4(CH2dipip)]. The structure of the new bidentate amine complex of tungsten(0) was established by spectroscopic methods (NMR, IR, UVVis) in solution and by single-crystal X-ray diffraction studies. A preliminary experiment indicates that the tungsten complex emits light at λmax. 556 nm, when it is excited by λmax. 523 nm in the solid state at room temperature.
- Koci?cka, Paulina,Kochel, Andrzej,Szymańska-Buzar, Teresa
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p. 105 - 107
(2014/06/09)
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- Synthesis and aminomethylation of 7-hydroxy-5-methoxyisoflavones
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A synthetic method for 7-hydroxy-5-methoxyisoflavones starting from 5,7-dihydroxyisoflavones was developed. Dimethylcarbamoylchloride was proposed for protection of the 7-hydroxy group. Aminomethylation of the synthesized 7-hydroxy-5-methoxyisoflavones by formaldehyde aminals was studied.
- Mrug,Bondarenko,Khilya,Frasinyuk
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p. 235 - 241
(2013/07/26)
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- Synthesis of 2,3-acetylenic amines by aminomethylation of acetylenes with geminal diamines
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A general and effective procedure has been developed for the synthesis of symmetrical and unsym- metrical 2,3-acetylenic amines by aminomethylation of terminal mono- and diacetylenes with geminal diamines in the presence of transition metal salts and complexes.
- Shaibakova,Titova,Makhmudiyarov,Ibragimov,Dzhemilev
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experimental part
p. 43 - 48
(2010/06/19)
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- Substituted Sulfonamide Compounds
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Substituted sulfonamide compounds corresponding to the formula I wherein m, n, p, Q, R1, R2, R3, R4, X, Y and Z have the respective meanings defined herein, pharmaceutical compositions containing such compounds, a process for their preparation, and the use of such compounds for the treatment and/or inhibition of pain and other conditions mediated by bradykinin receptor 1 (B1R) and/or bradykinin receptor 2 (B2R).
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Page/Page column 36-37
(2009/07/25)
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- Gem-diamines as highly active organocatalysts for carbon-carbon bond formation
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Diamines with neighbour nitrogen atoms have been used as base catalysts in the Knoevenagel condensation reaction between benzaldehyde and ethyl cyanoacetoacetate. The catalytic results show that a good basic catalyst requires a combination of two factors: high proton affinity and the ability to return the proton to the oxoanion intermediate. Computational chemistry calculations show this by characterizing the reactants, products, and transition states and by calculating the activation energies of the different reaction steps. A diamine, di(3-methylpiperidine)methane (B), has been found with a higher catalytic activity than DMAN despite its lower proton affinity, demonstrating that not only the proton affinity, but also the steric ability to abstract the protons, are important in explaining the catalytic results.
- Climent, Maria J.,Corma, Avelino,Dominguez, Irene,Iborra, Sara,Sabater, Maria J.,Sastre, German
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p. 136 - 146
(2007/10/03)
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- Direct access to functionalized cyclic enones using Mannich, Morita-Baylis-Hillman and elimination reactions
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A series of highly functionalized cyclic enones were obtained from Mannich, Morita-Baylis-Hillman and elimination reaction with cyclic enones. Georg Thieme Verlag Stuttgart.
- Porzelle, Achim,Williams, Craig M.
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p. 3025 - 3030
(2008/02/08)
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- Synthesis of dialkyl(4-hydroxy-2-butynyl)amines
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2-Propynyl alcohol smoothly reacts with secondary amines and formaldehyde, following the Mannich reaction pattern and yielding the corresponding dialkyl(4-hydroxy-2-butynyl)amines.
- Chukhadzhyan,Gevorkyan,Chukhadzhyan,Shakhatuni
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p. 1263 - 1264
(2007/10/03)
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- Amines and Ammonium Compounds: CCXXXI. Synthesis of Tertiary Allenic 1,5-Diamines
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Dialkylammonium salts containing both 4-penten-2-ynyl and 2-propynyl groups react with aqueous secondary amines to give 1,5-bis(dialkylamino)penta-2,3-dienes. Optimal reaction conditions are found and a mechanism of elimination of the 2-propynyl group from the initial salts is proposed.
- Kocharyan,Osyan,Grigoryan,Grigoryan,Lulukyan,Babayan
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p. 446 - 450
(2007/10/03)
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- The generation of iminium ions using chlorosilanes and their reactions with electron rich aromatic heterocycles
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Dichlorodimethylsilane and trichloromethylsilane have been used to generate iminium ions from aminals and aminol ethers derived from secondary alkylamines, including glycine derivatives, in aprotic media which were shown to undergo reactions with electron rich aromatic heterocycles, including furan, to give mono-aminoalkylation products in good yields. Whereas chlorotrimethylsilane has been shown to generate iminium ions from aminol ethers, no evidence was adduced for the involvement of iminium ions using aminals. 2,5-Disubstitution of N-methylpyrrole was the major result in reactions of N-methylpyrrole with aminals in the presence of chlorotrimethylsilane where no build up of hydrogen chloride occurs and where chlorotrimethylsilane can function catalytically. Experimental results, including the use of bis(trimethylsilyl)acetamide as a proton scavenger, and some relative rate data, are presented that allow possible mechanisms to be evaluated.
- Heaney, Harry,Papageorgiou, George,Wilkins, Robert F.
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p. 2941 - 2958
(2007/10/03)
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- Use of methylene chloride as a C1 unit in N,N-dialkylaminomethylation reaction
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Mannich products have been isolated in good yields with methylene chloride as a C1 unit, instead of formaldehyde. It is evidenced that, contrary to previous understanding, a high pressure procedure is not necessary required and that the methylene bisamines function as intermediates.
- Souquet,Martens,Fleury
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p. 817 - 828
(2007/10/02)
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- CONSECUTIVE MENSCHUTKIN REACTION OF CYCLIC AMINES WITH DICHLOROMETHANE UNDER HIGH PRESSURE: SYNTHESIS OF METHYLENEBISAMINES
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The reaction of heterocyclic amines such as pyrrolidine, piperidines, and morpholines with dichloromethane in methanol in the kilo bar region affording the corresponding methylenebisamines is described.
- Matsumoto, Kiyoshi,Hashimoto, Shiro,Ikemi, Yukio,Otani, Shinichi
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p. 1417 - 1420
(2007/10/02)
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- AMINE RADICAL CATIONS : AN ELECTRON SPIN RESONANCE STUDY OF CATIONS GENERATED BY RADIOLYSIS
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Amine radical cations have been generated by exposing dilute solutions of amines to 60Co γ-rays at 77 K.They are well characterised by their e.s.r. spectra, the method and interpretation being established by showing that the e.s.r. data for Me3N(.+) cations are indentical with literature values.Results for the triethylammonium cation show that the β-protons do not occupy the most favourable sites for maximum hyperconjugation, in contrast with other radical cations.This is explained in terms of steric factors, and an equilibrium between two preferred conformations. 1,1-Diamines, R2NCH2NR2, give cations having localised structures, R2N(.+)CH2NR2, rather than the delocalised structure adopted by acetal cations.Possible evidence for weak N-N bonding and delocalisation is adduced for NN'-dimethylpiperazine cations, but we confirm that the cation of triethylenediamine has a truly delocalised ?(*) structure.There is no tendency for R3N(+.) cations to react with neutral amines to give ( dimer cations, in marked constrast with results for corresponding trialkylphosphine systems.
- Eastland, George W.,Rao, D. N. Ramakrishna,Symons, Martyn C. R.
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p. 1551 - 1558
(2007/10/02)
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- REACTION OF 1,1-BIS(PHENYLSULFONYL)ETHENE WITH AMINES
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The reactions of 1,1-bis(phenylsulfonyl)ethene with aliphatic, aromatic, and heterocyclic amines in anhydrous aprotic solvents take place in two directions, depending on the basicity of the amine.They lead to the formation of secondary 1,1-bis(phenylsulfonyl)-ethyl-N-aryl(heteryl)amines as addition products, or to 1,1,3,3-tetrakis(phenylsulfonyl)propane, or to their mixtures.By analysis of the reaction mixtures and identification of the intermediate products a scheme was proposed for the reactions of 1,1-bis(phenylsulfonyl)ethene with amines.
- Bazavova, I. M.,Neplyuev, V. M.,Lozinskii, M. O.
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- Nitrosamine Photolysis as a Synthetic Method: The Addition of Aminium Radicals to Unsaturated Carbon-Carbon Bonds
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Acid complexed nitrosamines decompose from their lowest singlet excited state to gine aminium radicals and nitric oxide radical transients.Aminium radicals initiate addition of various unsaturated groups to give 1-amino-2-nitroso compounds under an inert atmosphere, or 1-amino-2-nitrates under oxygen.In this report, photoaddition of nitroamines to olefins, acetylenes and fused aromatic hydrocarbons, and the subsequent transformations of the intermediates are described.Aminium radical initiated intramolecular cyclization to prepare tetracyclic aza compounds is also described.While photoaddition of nitrosamines to 4-propenylanisole or 3-butenol wes efficient, that to 3-butenyl benzoates under oxidative conditions was only fair, obviously due to the presence of a benzene ring.The oxidative photoaddition to 3-butenyl halide was followed by spontaneous cyclization to an azaspiro compound.The photoaddition to phenyl-substituted acetylenes gave β-nitroso enamines which hydrolyzed to diketomonoximes under neitral conditions but decomposed extensively under acidic conditions.Certain fused aromatic hydrocarbons acted as singlet sensitizers as well as substrates to induce similar addition giving amino nitroso adducts.These adducts took different courses of conversion dependent on reaction conditions, and on steric and electronic factors.
- Chow, Yuan L.,Colon, Carlos J.,Chang, Dawid W. L.,Pillay, K. Somasekharen,Lochart Robert D.,Tezuka, Takahiro
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p. 622 - 634
(2007/10/02)
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