cas 5625-90-1, N,N'-Dimorpholinomethane | Articles data

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N-Heterocyclic Carbene-Stabilized Germa-acylium Ion: Reactivity and Utility in Catalytic CO2Functionalizations
The first acceptor-free heavier germanium analogue of an acylium ion, [RGe(O)(NHC)2]X (R = MesTer = 2,6-(2,4,6-Me3C6H2)2C6H3; NHC = IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene; X = (Cl or BArF = {(3,5-(CF3)2C6H5)4B}), was isolated by reacting [RGe(NHC)2]X with N2O. Conversion of the germa-acylium ion to the first solely donor-stabilized germanium ester [(NHC)RGe(O)(OSiPh3)] and corresponding heavier analogues ([RGe(S)(NHC)2]X and [RGe(Se)(NHC)2]X) demonstrated its classical acylium-like behavior. The polarized terminal GeO bond in the germa-acylium ion was utilized to activate CO2 and silane, with the former found to be an example of reversible activation of CO2, thus mimicking the behavior of transition metal oxides. Furthermore, its transition-metal-like nature is demonstrated as it was found to be an active catalyst in both CO2 hydrosilylation and reductive N-functionalization of amines using CO2 as the C1 source. Mechanistic studies were undertaken both experimentally and computationally, which revealed that the reaction proceeds via an N-heterocyclic carbene (NHC) siloxygermylene [(NHC)RGe(OSiHPh2)].
Sarkar, Debotra,Weetman, Catherine,Dutta, Sayan,Schubert, Emeric,Jandl, Christian,Koley, Debasis,Inoue, Shigeyoshi
supporting information
p. 15403 - 15411
(2020/10/20)

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
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
supporting information

(2019/04/08)

Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
p. 808 - 816
(2016/02/12)

Method for preparing kakonein derivatives
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 0037-0039

(2017/03/17)

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation
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
supporting information
p. 3247 - 3250
(2015/06/16)

Nonstabilised azomethine ylids from n-oxides: Unravelling the deprotonation of n-methylmorpholine n-oxide
Nonstabilised azomethine ylids (NAYs) are useful 1,3-dipoles, but their synthetic applications are restricted by the high temperatures often needed for their generation, and by an incomplete understanding of the effect of heteroatoms in cyclic systems. We have examined the behaviour of N-methylmorpholine N-oxide (NMO) as a NAY precursor in the Roussi reaction (low-temperature reaction of an N-oxide with strong base). The choice of base is critical to achieving cycloadduct formation. We report synthetic and computational (density functional theory) investigations of the products obtained with different bases and their mechanisms of formation.
Mirzayans, Paul Malek,Krenske, Elizabeth H.,Williams, Craig M.
p. 1309 - 1317
(2014/11/07)

Synthesis and aminomethylation of 7-hydroxy-5-methoxyisoflavones
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
p. 235 - 241
(2013/07/26)

Cooperative catalysis with aldehydes and copper: Development and application in aerobic oxidative C-H amination at room temperature
A conceptually new cooperative catalytic system via a synergistic combination of aldehyde and copper catalysis has been established based on systemic mechanistic studies. This new cooperative catalysis has been successfully applied in the direct aerobic oxidative C-H amination of azoles at room temperature, which was previously realized under harsh conditions. Mechanistic studies including isotopic labeling experiments and kinetic isotope effect (KIE) experiments support a reaction pathway that involves formation of an aminal, hydrolysis of the aminal to generate the copper-amide species, subsequent C-H amination and re-oxidation of copper(I) to copper(II) by oxygen. It not only provides an efficient method to realize the oxidative C-H amination of benzoxazoles with free amines at room temperature, but also paves the way for establishing new C-N bond formation reactions by using this efficient cooperative catalysis. Copyright
Xie, Yinjun,Qian, Bo,Xie, Pan,Huang, Hanmin
supporting information
p. 1315 - 1322
(2013/06/27)

Copper-catalyzed aerobic oxidative amination of arylboronic acid with aminal under base-free conditions
A new process involving copper-catalyzed oxidative amination reaction of various arylboronic acids with aminals under mild conditions has been developed. The key copper-amide species involved in the C-N bond-forming process was generated via C-N bond cleavage of aminal under base-free conditions. Moderate yields of desired amination products can be obtained under mild conditions when air was served as oxidant and PhCO2H was used as an additive.
Zhou, Yanping,Xie, Yinjun,Yang, Lei,Xie, Pan,Huang, Hanmin
supporting information
p. 2713 - 2716
(2013/06/05)

Synthesis of amino sulfides in the presence of rare-earth and transition metal catalysts
Efficient procedures have been developed for the synthesis of amino sulfides by aminomethylation of thiols with higher geminal diamines, thiomethylation of secondary amines with N,N-dimethylaminomethyl sulfides, and decyclization of 1,3,6-oxadithiepane or
Khairullina, R. R.,Akmanov, B. F.,Kunakova, R. V.,Ibragimov, A. G.
p. 902 - 907,6
(2020/08/31)

Molecular design and QSAR study of low acute toxicity biocides with 4,4′-dimorpholyl-methane core obtained by microwave-assisted synthesis
The solventless microwave-assisted synthesis of aldehydes (1a, 2b-h) and morpholine (3) in 1:2 (aldehyde: morpholine) ratio yielded eight 4,4′-dimorpholyl-methanes (4a-4h), which were thoroughly characterized through FT-IR, 1H, 13C and 2D NMR, confirming structures of type 4. The described compounds are dimorpholino-methane (4a), 2-(dimorpholinomethyl)-phenol (4b), 4-bromo-2-(dimorpholinomethyl)-phenol (4c), 2,4-di-tert-butyl-6-(dimorpholinomethyl)-phenol (4d), 4,4′-(pyridin-2- ylmethylene)-dimorpholine (4e), 4,4′-((4-iso-propylphenyl)methylene)- dimorpholine (4f), 4,4′-(naphthalen-1-ylmethylene)-dimorpholine (4g) and 4,4′-(pyren-1-ylmethylene)-dimorpholine (4h). Additionally, single crystal X-ray diffraction analysis for 4b, 4c, 4d and 4e derivatives was accomplished showing interesting geometrical features. The obtained 4,4′-dimorpholyl- methanes were subjected for two biological tests, (i) acute toxicity, related to Photobacterium phosphoreum (Vibrio fischeri), and (ii) biocidal activities, determined for B. subtilis, E. coli and Ps. fluorescence strains. The results show that 4a-h compounds have varying degrees of toxicity, classified as 4a, 4b, 4c, 4e and 4f as slightly to moderately toxic agents, 4g and 4h as highly toxic chemicals, and 4d as an extremely toxic compound. Besides, the biocidal activities, which is controlled mainly by the substituent directly bonded to the methinic bridge (named C5, which originally is the carbon atom of the aldehyde functionality), have shown varying degrees of inhibitory effects on the growth of selected strains, depending on the chemical structure of 4a-h. A QSAR study was developed, and quantum-chemical parameters of 4a-h were obtained with the DFT approach at the B3LYP/6-311G(d) level of theory in the gas phase. Hence ten molecular descriptors were determined, being EHOMO, ELUMO, GAP, C5 Mulliken atomic charge (ACMulliken), C5 atomic charge of NBO (ACNBO), dipolar moment (μ), molecular hydrophobicity as log P, molecular volume (Vol), electrostatic potential (ESP) and δ 13C(C5), all of them being typical determinants of biological activities in other, different or related, molecular systems. A linear combination from three to six molecular descriptors was chosen as a multivariate model to achieve correlations in order to relate them to their acute toxicity and understand the obtained trend. Three sets of descriptors accomplished the statistical goal, and through an identity analysis the conserved descriptors in these three series are log P, the ESP and the δ13C(C5), which seemed to be the tracking variables in the system. To a lesser extent, the frontier orbitals and their relations (HOMO, LUMO and GAP) are also present within the correlations. The phenol-bearing structures (4b, 4c and 4d, derived from salicylidenes) are best tuned within these variables since the substitution in the phenol fragment both governs the toxicity and the biocidal potency. Finally, we can guarantee that the best candidates in this series are 4a, 4b and 4c, because diminished toxicity and preserved biocidal potency were obtained at the same time. A more hydrophobic substitution (4d) extremely increases the Vibrio fischeri toxicity, ruling out its application. Through the full analysis presented in this piece of work it can be stated that selected prototypes could be used in industrial facilities, particularly in the petroleum industry, as a new generation of ecological chemical products.
Hernandez-Altamirano, Raul,Mena-Cervantes, Violeta Y.,Perez-Miranda, Sandra,Fernandez, Francisco J.,Flores-Sandoval, Cesar Andres,Barba, Victor,Beltran, Hiram I.,Zamudio-Rivera, Luis S.
experimental part
p. 1036 - 1048
(2010/10/03)

Preparation of (S')-3,3,-bis-morpholinomethyl- 5,5',6,6',7,7',8,8'- octahydro-1,1,-BI-2-naphthol
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Turlington, Mark,Pu, Lin,Kimmel, Kyle L.,Ellman, Jonathan A.
experimental part
p. 59 - 67
(2011/05/11)

Synthesis of 2,3-acetylenic amines by aminomethylation of acetylenes with geminal diamines
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
experimental part
p. 43 - 48
(2010/06/19)

Efficient synthesis of the first betulonic acid-acetylene hybrids and their hepatoprotective and anti-inflammatory activity
The Sonogashira reaction can be applied for the preparation of acetylenic derivatives of betulonic acid where the triterpenoid moiety can serve as either the halo- or the acetylenic component. This reaction opened access to the first derivatives of betulonic acid containing either the arylethynyl (S{cyrillic}{triple bond, long}S{cyrillic}-Ar(Het) or the ethynyl (S{cyrillic}{triple bond, long}S{cyrillic}N{cyrillic}) moieties. From the fundamental perspective, this work illustrates the possibility of selective Pd-catalyzed cross-coupling at terminal acetylenes in the presence of a terminal alkene. Hepatoprotective and anti-inflammatory properties of selected acetylenic derivatives of betulonic acid were investigated using the CCl4-induced hepatitis and carrageenan-induced edema models, respectively.
Vasilevsky, Sergey F.,Govdi, Anastasiya I.,Shults, El'vira E.,Shakirov, Makhmut M.,Sorokina, Irina V.,Tolstikova, Tatyana G.,Baev, Dmitry S.,Tolstikov, Genrikh A.,Alabugin, Igor V.
experimental part
p. 5164 - 5169
(2009/12/01)

Substituted Sulfonamide Compounds
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)

Preparation of diaminomethanes under microwave irradiation
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Khrustalev,Khamzina,Fazylov,Gazaliev
p. 331 - 331
(2008/09/18)

Tocopherols by hydride reduction of dialkylamino derivatives
Aminomethylation with Mannich reagents derived from secondary amines and paraformaldehyde under improved conditions has been used to convert non-α-tocopherol homologues into α-tocopherol, the biologically most important vitamin E compound. Mono- and bis(aminomethylated) β-, γ-and δ-tocopherol were then subsequently transformed into the corresponding tocopherols (α- and β-tocopherol) by reductive deamination. As an alternative to classical catalytic hydrogenation in the last step, efficient laboratory protocols using complex hydrides have been derived and applied to the preparation of labelled vitamin E compounds. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Netscher, Thomas,Mazzini, Francesco,Jestin, Roselyne
p. 1176 - 1183
(2008/02/08)

Direct access to functionalized cyclic enones using Mannich, Morita-Baylis-Hillman and elimination reactions
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.
p. 3025 - 3030
(2008/02/08)

Studies on the carbenium-iminium ions derived from N-methylmorpholine-N- oxide (NMMO)
Two carbenium-iminium ions, an exo-centered species 2 and a ring-centered form 3, are derived from the widely used oxidant and cellulose solvent N-methylmorpholine-N-oxide (1) by heterolytic degradation. 3 rearranges into 2 in the presence of water, in an endothermic, bimolecular reaction involving a highly organized transition state, which is the first example of a carbenium-iminium ion interconversion. The reaction mechanism was investigated by a combined approach consisting of trapping reactions, isotopic labeling, kinetic studies, and computations on the DFT level.
Rosenau, Thomas,Potthast, Antje,Kosma, Paul
p. 301 - 306
(2007/10/03)

Aminomethylation of tocopherols
A process for the production of a Mannich reagent comprises reacting formaldehyde, especially paraformaldehyde, with a secondary amine in the complete or almost complete absence of a solvent. An alternative comprises reacting a diaminomethane produced from a secondary amine, formaldehyde, especially paraformaldehyde, as well as water with one another in about equimolar amounts. The invention is also concerned with a process for the aminomethylation of δ-tocopherol or of tocopherol mixtures containing this and comprises using a Mannich reagent which has been produced in the above manner. After completion of this aminomethylation process excess Mannich reagent can be separated by distillation and can be reacted with water and formaldehyde, especially paraformaldehyde, in order to regenerate further Mannich reagent suitable for use in the aminomethylation, this regeneration representing a further aspect of the invention. Finally, the invention includes certain novel bis(aminomethyl)-γ-tocopherols.
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Example 1

(2010/01/30)

The generation of iminium ions using chlorosilanes and their reactions with electron rich aromatic heterocycles
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.
p. 2941 - 2958
(2007/10/03)

Reactions of Trimorpholinomethane with Tetraalkyldiboranes, Dialkylchloroboranes, and α-Chlorodiethyl Ether
Trimorpholinomethane reacts with tetraalkyldiboranes and dialkylchloroboranes with formation of dimorpholinomethane and chlorodimorpholinomethane respectively.Chlorodimorpholinomethane is also formed in the reaction of trimorpholinomethane with α-chlorodiethyl ether.
Bagdasaryan, G. B.,Sarkisova, E. A.,Indzhikyan, M. G.
p. 1002 - 1004
(2007/10/03)

Use of methylene chloride as a C1 unit in N,N-dialkylaminomethylation reaction
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
p. 817 - 828
(2007/10/02)

HYDROXY-, ALKOXY-, AMINOMETHYLATION OF NH-OXAZIRIDINES
3,3-Dimethyloxaziridine reacts with chloral and acetaldehyde to give crystalline N-(α-hydroxyalkyl)oxaziridines; the reaction with acetaldehyde is reversible.The N-aminomethylation of NH-oxaziridines is not realized, evidently because of the tendency of oxaziridines to iminate nucleophiles.The weakly nucleophilic chloromethylphthalimide and chloromethyl methyl ether give imidomethyl- and methoxymethyloxaziridines. 3,3-Dimethyldiaziridine reacts with excess chloromethyl methyl eter to give the N-monomethoxymethyl derivative.It is shown that α-hydroxyalkyloxaziridines and methoxymethyl-substituted oxaziridine and dizaridine do not enter into the aminomethylation of compounds with a labile hydrogen.
Varlamov, S. V.,Kadorkina, G. K.,Kostyanovskii, R. G.
p. 320 - 325
(2007/10/02)

Aminoalkylation of Enhydrazinones
Enhydrazinones, prepared from dimedone and N,N-disubstituted hydrazines, react with formaldehyde and secondary amines to C-aminoalkyl-derivatives, pyrazolinium betaines and methylenebis(enhydrazinones).With better yields the C-Mannich products result from the reaction with methyleniminium salts.The enhydrazinones give with two moles of formaldehyde and primary amines the corresponding tetrahydropyrimidines. - Keywords: Mannich Reaction, Vinylogous Hydrazides, Tetrahydropyrimidines, Pyrazolinium Betaines, Methylenebis(enhydrazinones)
Moehrle, Hans,Arz, Petra
p. 1035 - 1046
(2007/10/02)

CONSECUTIVE MENSCHUTKIN REACTION OF CYCLIC AMINES WITH DICHLOROMETHANE UNDER HIGH PRESSURE: SYNTHESIS OF METHYLENEBISAMINES
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
p. 1417 - 1420
(2007/10/02)

Nitrite Ion as a Nitrosating Reagent. Nitrosation of Morpholine and Diethylamine in the Presence of Formaldehyde
The kinetics of the nitrosation of morpholine and diethylamine in the presence of formaldehyde has been studied at pH values between 6.5-8.2 and 6.9-8.7, respectively.The results are interpreted through a mechanism that implies the reaction between both the nitrite NO2(-) and iminium R2N(+)=CH2 ions.The latter ion results from the dehydration of the conjugated acid of the carbinolamine, R2NH(+)CH2OH, the initial product of the amine-formaldehyde reaction.The results allow the calculation of the equlibrium constants of the formation of carbinolamine, R2NCH2OH, and methanediamine, R2NCH2NR2 (only for the morpholine-formaldehyde system), and their conjugate acids.
Casado, Julia,Mosquera, Manuel,Paz, L. Carlos,Prieto, M. Flor Rodriguez,Tato, Jose Vazquez
p. 1963 - 1966
(2007/10/02)

DEDISILOXANATION REACTION (ELIMINATION OF DISILOXANE) IN THE REACTIONS OF N-(SILOXYMETHYL) DERIVATIVES OF AMINES AND AMIDES WITH CHLORO-, (ACYLOXY)-, AND AMINO-SILANES
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Kozyukov, V. P.,Kozyukov, Vik. P.,Mironov, V. F.
p. 100 - 106
(2007/10/02)

REACTIONS OF N-SILYL AMINES, AMIDES, AND URETHANES WITH GASEOUS FORMALDEHYDE. SYNTHESIS OF SILYL ETHERS OF METHYLOLAMINES AND METHYLOLAMIDES
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Kozyukov, V. P.,Kozyukov, Vik. P.,Mironov, V. F.
p. 1887 - 1892
(2007/10/02)

REACTION OF 1,1-BIS(PHENYLSULFONYL)ETHENE WITH AMINES
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.
p. 74 - 77
(2007/10/02)