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Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates
Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).
Banerjee, Amit,Hattori, Tomohiro,Yamamoto, Hisashi
(2021/06/16)

Rapid and Mild Lactamization Using Highly Electrophilic Triphosgene in a Microflow Reactor
Lactams are cyclic amides that are indispensable as drugs and as drug candidates. Conventional lactamization includes acid-mediated and coupling-agent-mediated approaches that suffer from narrow substrate scope, much waste, and/or high cost. Inexpensive, less-wasteful approaches mediated by highly electrophilic reagents are attractive, but there is an imminent risk of side reactions. Herein, a methods using highly electrophilic triphosgene in a microflow reactor that accomplishes rapid (0.5–10 s), mild, inexpensive, and less-wasteful lactamization are described. Methods A and B, which use N-methylmorpholine and N-methylimidazole, respectively, were developed. Various lactams and a cyclic peptide containing acid- and/or heat-labile functional groups were synthesized in good to high yields without the need for tedious purification. Undesired reactions were successfully suppressed, and the risk of handling triphosgene was minimized by the use of microflow technology.
Fuse, Shinichiro,Komuro, Keiji,Otake, Yuma,Masui, Hisashi,Nakamura, Hiroyuki
supporting information
p. 7525 - 7532
(2021/03/17)

Preparation of alkylated compounds using the trialkylphosphate
[Problem] trialkylphosphate strong base used reaction agent, a carboxylic acid, a ketone, an aldehyde, amine, amide, thiol, ester or Grignard reagent to a variety of substrates, and/or high efficiency to generate a highly stereoselective alkylation reaction, the alkylated compounds capable of producing new means. [Solution] was used as the alkylating agent in the alkylation of compound trialkylphosphate, strongly basic reaction production use. [Drawing] no
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Paragraph 0184-0185; 0210

(2021/11/02)

Triazinetriamine-derived porous organic polymer-supported copper nanoparticles (Cu-NPs@TzTa-POP): an efficient catalyst for the synthesis of: N -methylated products via CO2fixation and primary carbamates from alcohols and urea
In recent times, carbon dioxide fixation has received much attention for its potential application as an abundant C1 source and a range of important fine chemicals can be manufactured via this fixation. Here, a copper nanoparticle-decorated porous organic polymer-based (Cu-NPs@TzTa-POP) material was prepared by a simple in situ process. The catalyst was characterized by various techniques such as UV-vis spectra, FTIR spectra, HR-TEM, PXRD, N2 adsorption-desorption, TG-DTA, XPS, and AAS analysis. The synthesized heterogeneous catalyst showed excellent activity in an atmospheric carbon dioxide fixation reaction to produce N-methylated products from aromatic/heterocyclic amines in the presence of polymethyl-hydrosiloxane (PMHS) as the reducing agent at 80 °C within 12 h of the reaction. Through this catalytic N-methylation reaction, we obtained 98% yield of the product with turnover frequency ranging from 18 to 42 h-1. The catalyst is also very stable for the formation of primary carbamates from alcohols using the eco-friendly carbonylating agent, urea. Diverse alcohols (such as benzylic alcohols, phenols, heterocyclic alcohols, as well as aliphatic alcohols) showed much acceptance to this catalytic reaction and produced moderate to excellent yields of the respective carbamate products under ambient reaction conditions. Moreover, Cu-NPs@TzTa-POP is effortlessly recyclable and reusable without the extensive loss of active copper metal centres for many catalytic rounds (up to six catalytic rounds were examined).
Haque, Najirul,Biswas, Surajit,Basu, Priyanka,Haque Biswas, Imdadul,Khatun, Resmin,Khan, Aslam,Islam, Sk Manirul
supporting information
p. 15446 - 15458
(2020/10/22)

Lignin-fueled photoelectrochemical platform for light-driven redox biotransformation
The valorization of lignin has significant potential in producing commodity chemicals and fuels from renewable resources. However, the catalytic degradation of lignin is kinetically challenging and often requires noble metal catalysts to be used under harsh and toxic conditions. Here, we report the bias-free, solar reformation of lignin coupled with redox biotransformation in a tandem structure of a BiVO4 photoanode and perovskite photovoltaic. The tandem structure compensates for the potential gap between lignin oxidation and biocatalytic reduction through artificial Z-schematic absorption. We found that the BiVO4-catalyzed photoelectrochemical oxidation of lignin facilitated the fragmentation of higher molecular weight lignin into smaller carboxylated aliphatic and aromatic acids. Lignin oxidation induced photocurrent generation at the photoanode, which enabled efficient electroenzymatic reactions at the cathode. This study successfully demonstrates the oxidative valorization of lignin as well as biocatalytic reductions (e.g., CO2-to-formate and α-ketoglutarate-to-l-glutamate) in an unbiased biocatalytic PEC platform, which provides a new strategic approach for photo-biocatalysis using naturally abundant renewable resources.
Boonmongkolras, Passarut,Choi, Eun-Gyu,Han, Seunghyun,Kim, Jinhyun,Kim, Kayoung,Kim, Yong Hwan,Lee, Sahng Ha,Lee, Yang Woo,Park, Chan Beum,Shin, Byungha,Trang, Nguyen Vu Thien,Wang, Ding
supporting information
p. 5151 - 5160
(2020/08/25)

N-Alkylation of N-trimethylsilyl derivatives of lactams, amides, and imides with alkyl sulfonates
The reaction of N-trimethylsilyl derivatives of amides and imides with alkyl sulfonates on heating affords the corresponding N-alkyl derivatives and trimethylsilyl sulfonates.
Baukov, Yu. I.,Kramarova, E. P.,Negrebetsky, Vad. V.,Shagina, A. D.,Shipov, A. G.,Tarasenko, D. V.
p. 398 - 400
(2020/04/15)

One-pot synthesis of: N -methylpyrrolidine (NMPD) using Cu- and Ni-modified ZSM-5 as an efficient catalyst
In this study, a green, efficient and low-cost process for the synthesis of N-methylpyrrolidine (NMPD) from 1,4-butanediol (BDO) and methylamine (MA) via a one-pot method was developed. Under the optimized reaction conditions, more than 90% yield of NMPD was achieved over a Cu and Ni modified ZSM-5 catalyst. The catalyst could be reused for several runs retaining a satisfactory catalytic performance, and the scale-up operation showed the potential of industrial application. Characterizations of BET, XPS, XRD, TEM, SEM, H2-TPR and NH3-TPD were conducted for the developed composite catalyst, which suggested that Cu2O and NiO were the main species on the support. Meanwhile, it was found that the H2 atmosphere, the high dispersion of metal oxides and the synergic effect between Cu and Ni species on ZSM-5 contributed to the excellent catalytic performance. Furthermore, a possible mechanism based on a borrowing-hydrogen process was also proposed.
Long, Yan,Wang, Peixue,Fei, Yuqing,Zhou, Dawei,Liu, Shimin,Deng, Youquan
p. 141 - 148
(2019/01/11)

Facile Preparation of N -Alkyl-2-pyrrolidones in a Continuous-Flow Microreactor
N-Alkyl-2-pyrrolidones have been widely used in the petrochemical industry, the agricultural chemical industry, electronic materials, etc. The distinct advantages of using N-alkyl-2-pyrrolidones as solvents or reaction media make them particularly important. A continuous-flow microreactor was exploited for the preparation of N-methyl-2-pyrrolidone (NMP) and N-ethyl-2-pyrrolidone (NEP) in a highly controlled and safe manner; thus, its use improved the efficiency of the process. Various conditions (temperature, residence time, molar ratio of amine to γ-butyrolactone (GBL), GBL concentration, water content, and presence of H3BO3 catalyst) were investigated to improve the synthesis of NMP/NEP. A microreactor was employed for the conversion of GBL to NMP and NEP, and the yields reached 94.7% for NMP and 93.9% for NEP under the optimized conditions. Furthermore, a kinetic model based on the reaction mechanism was proposed to guide the design and optimization of the synthesis of NMP/NEP.
Zhou, Feng,Zhang, Boyu,Liu, Hongchen,Wen, Zhenghui,Wang, Kejun,Chen, Guangwen
p. 504 - 511
(2018/04/27)

AN IMPROVED PROCESS FOR THE SELECTIVE PRODUCTION OF N-METHYL-2-PYRROLIDONE (NMP)
This invention relates to an improved process for the selective production of N-methyl pyrrolidone (NMP) from gamma-butyrolactone and monomethyl amine preferably in aqueous form in the presence of a catalyst under comparatively milder conditions than the processes well known in the prior art of literature. The process is economically viable as it provides higher yield and selectivity for NMP which reduces the cost of separation of NMP from GBL. The catalyst shows good recyclability without significant loss in catalytic activity and no frequent regeneration is required.
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(2017/02/28)

A N - methyl pyrrolidone continuous preparation method (by machine translation)
The invention relates to a N - methyl pyrrolidone continuous preparation method, the method includes the steps of: (1) the pre-reaction and dehydration unit: γ - butyrolactone with methylamine aqueous solution mixed at room temperature after the pre-reaction, off part of the water does not participate in the reaction, thereby obtaining a reaction intermediate product; (2) high-temperature reaction unit: in the middle of the reaction product is added to the aqueous solution of methylamine, by heating, the boost to enter in a high-pressure reactor, a condensation reaction, condensation reaction to obtain the NMP; (3) product separation unit: reaction to obtain the high temperature and high pressure condensation reaction solution, after cooling, after dropping into the separation device, to get rid of moisture and residual methylamine, then, refining, NMP products obtained. The invention pre-removing methylamine aqueous solution with most of the water, preventing the large amount of water involved in the follow-up reaction, reduces the energy consumption of the NMP preparation process, reduces the volume of the use of the reactor, the reactor amplifying technique solves the difficult. (by machine translation)
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(2017/06/19)

Phosphovanadomolybdic acid catalyzed desulfurization-oxygenation of secondary and tertiary thioamides into amides using molecular oxygen as the terminal oxidant
In the presence of phosphovanadomolybdic acids, e.g., H6PV3Mo9O40, desulfurization-oxygenation of various kinds of structurally diverse secondary and tertiary thioamides proceeded efficiently using molecular oxygen as the terminal oxidant, affording the corresponding amides in moderate to excellent yields. In addition, 18O-labeled amides could readily be synthesized using H218O as the oxygen source.
Xu, Ning,Jin, Xiongjie,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 4865 - 4869
(2016/07/06)

Aerobic Oxidation of Cyclic Amines to Lactams Catalyzed by Ceria-Supported Nanogold
Abstract: The oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) and Aerosil 200 in the presence of an atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5?h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5?h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3?h. During the oxidation of pyrrolidine, two transient species, 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C. Graphical Abstract: [Figure not available: see fulltext.]
Dairo, Taiwo O.,Nelson, Nicholas C.,Slowing, Igor I.,Angelici, Robert J.,Woo, L. Keith
p. 2278 - 2291
(2016/11/09)

Supported Gold Nanoparticles for Efficient α-Oxygenation of Secondary and Tertiary Amines into Amides
Although the α-oxygenation of amines is a highly attractive method for the synthesis of amides, efficient catalysts suited to a wide range of secondary and tertiary alkyl amines using O2as the terminal oxidant have no precedent. This report describes a novel, green α-oxygenation of a wide range of linear and cyclic secondary and tertiary amines mediated by gold nanoparticles supported on alumina (Au/Al2O3). The observed catalysis was truly heterogeneous, and the catalyst could be reused. The present α-oxygenation utilizes O2as the terminal oxidant and water as the oxygen atom source of amides. The method generates water as the only theoretical by-product, which highlights the environmentally benign nature of the present reaction. Additionally, the present α-oxygenation provides a convenient method for the synthesis of18O-labeled amides using H218O as the oxygen source.
Jin, Xiongjie,Kataoka, Kengo,Yatabe, Takafumi,Yamaguchi, Kazuya,Mizuno, Noritaka
supporting information
p. 7212 - 7217
(2016/07/06)

PROCESS FOR PREPARING OF N-METHYL PYRROLIDONE
A method for preparing N-methyl prolidone is provided to save energy and easily isolating N-methyl pyrolidone. The method for preparing N-methyl prolidone comprises: a step of supplying monomethylamine(MMA) solution and gamma-butyrolactone(GBL) into a reactor; a step of separating N-methyl pyrolidone(NMP) and water; a step of mixing the water and monomethylamine to prepare monomethylamine solution; and a step of introducing the solution into a reactor. The monomethyl amine solution contains 25-65 weight% of monomethylamine and 35-75 weight% of water.
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(2016/12/22)

PROCESS FOR MICROWAVE ASSISTED SYNTHESIS OF N-METHYL PYRROLIDONE
The present invention relates to a process for microwave assisted synthesis of N-methyl pyrrolidone (NMP). Particularly the process relates to the synthesis of N-methyl succinimide or corresponding analogues by using microwave irradiation which on hydrogenation in the presence of a hydrogenating catalyst gives N-methyl pyrrolidone. Compared to the conventional heating microwave process requires less energy inputs and reduces the reaction time drastically from 5-6 h to 2-5 min.
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Paragraph 0053

(2015/03/16)

Novel integrated carbon particle based three dimensional anodes for the electrochemical degradation of reactive dyes
Three-dimensional carbon bed electrochemical reactors have been recently applied for the degradation of several organic pollutants. However, the carbon particles in such reactors slowly undergo attrition. We fabricated a novel flow-through three-dimensional anode using granular activated carbon (GAC) particles and polyvinylidene fluoride (PVDF) binder that potentially avoids such attrition. Optimization of the composition of GAC and PVDF with respect to mechanical integrity and electrical conductivity is reported. The anodes were tested in the electro oxidation of the reactive dyes: Reactive Orange-16 (RO-16), Reactive Red-2 (RR-2), and Reactive Blue-4 (RB-4). A tentative mechanism of dye degradation was proposed based on the observed role of the supporting electrolyte and the cyclic voltammetric, UV-vis, FT-IR and GC-MS data. The decolorization efficiencies were 75 ± 3, 81 ± 5 and 88 ± 4% for RB-4, RO-16 and RR-2, respectively. The integrated 3-D anodes are advantageous because of the absence of carbon attrition, which is otherwise found when a bed of GAC is used in the electrochemical reactors.
Misra, Rohit,Neti, Nageswara Nao,Dionysiou, Dionysios D.,Tandekar, Mahendra,Kanade, Gajanan S.
p. 10799 - 10808
(2015/02/05)

Oxidant-free conversion of cyclic amines to lactams and H2 using water as the oxygen atom source
Direct conversion of cyclic amines to lactams utilizing water as the only reagent is catalyzed by pincer complex 2. In contrast to previously known methods of amine-to-amide conversion, this reaction occurs in the absence of oxidants and is accompanied by liberation of H2, with water serving as a source of oxygen atom. Formation of a cyclic hemiaminal intermediate plays a key role in enabling such reactivity. This represents an unprecedented, conceptually new type of amide formation reaction directly from amines and water under oxidant-free conditions.
Khusnutdinova, Julia R.,Ben-David, Yehoshoa,Milstein, David
supporting information
p. 2998 - 3001
(2014/03/21)

Method for Producing Bio-Based Homoserine Lactone and Bio-Based Organic Acid from O-Acyl Homoserine Produced by Microorganisms
The present invention relates to a method of producing bio-based homoserine lactone and bio-based organic acid through hydrolysis of O-acyl homoserine produced by a microorganism in the presence of an acid catalyst. According to the present invention, O-acyl homoserine produced by a microorganism is used as a raw material for producing 1,4-butanediol, gamma-butyrolactone, tetrahydrofuran and the like, which are industrially highly useful. The O-acyl homoserine produced by a microorganism can substitute conventional petrochemical products, can solve environmental concerns, including the emission of pollutants and the exhaustion of natural resources, and can be continuously renewable so as not to exhaust natural resources.
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Paragraph 0228; 0229; 0230

(2014/10/16)

Hexaalkylguanidinium salts as ionic liquids - Applications in titanium and aluminium alcoholate assisted synthesis
The solubility of titanium and aluminium alcoholates and of titanium tetrakis(trimethylsilanolate) in several hexaalkylguanidinium-based room temperature ionic liquids was screened. The solvent/solute combinations which displayed the highest alcoholate solubility and stability were applied as Lewis-acidic catalytic media for several dehydrating cyclocondensations: lactamisation of ω-aminocarboxylic acids, direct amidation of carboxylic acids, synthesis of oxazolines from carboxylic acids and 2-aminoethanol, lactonisation of 6-hydroxyhexanoic acid, and Paal-Knorr synthesis of pyrroles.
Arkhipova, Maria,Eichel, Svetlana,Maas, Gerhard
p. 56506 - 56517
(2015/02/05)

Asymmetric synthesis and evaluation of α-quaternary chiral lactam derivatives as novel anticancer agents
Asymmetric synthesis of α-quaternary chiral lactam derivatives as novel anticancer agents and evaluation of their cytotoxic potentials and spectrums are reported. Among the developed lactam derivatives, the most active new compounds (S)-4m and (S)-4n synthesized via asymmetric phase-transfer catalytic alkylation in very high optical yields (98 % ee) show promising in vitro anticancer activities with low micromolar IC50 values against colon, uterus, lung, and breast human cancer cells.
Lee, Hwanhyuk,Hwang, Su Jung,Jung, Jisung,Hong, Suckchang,Lee, Myungmo,Park, Hyeung-Geun,Lee, Hyo-Jong,Park, Yohan
p. 1264 - 1270
(2015/10/05)

Copper-catalyzed N-methylation of amides and O-methylation of carboxylic acids by using peroxides as the methylating reagents
The copper-catalyzed N-methylation of amides and O-methylation of carboxylic acids by using peroxides as the methylating reagent are described. Various amides and carboxylic acids were methylated affording N-substituted amides and esters. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.
Xia, Qinqin,Liu, Xiaolong,Zhang, Yuejiao,Chen, Chao,Chen, Wanzhi
supporting information
p. 3326 - 3329
(2013/07/26)

Red-emitting rhodamines with hydroxylated, sulfonated, and phosphorylated dye residues and their use in fluorescence nanoscopy
Fluorescent dyes emitting red light are frequently used in conventional and super-resolution microscopy of biological samples, although the variety of the useful dyes is limited. We describe the synthesis of rhodamine-based fluorescent dyes with absorption and emission maxima in the range of 621-637 and 644-660 nm, respectively and demonstrate their high performance in confocal and stimulated emission depletion (STED) microscopy. New dyes were prepared by means of reliable chemical transformations applied to a rhodamine scaffold with three variable positions. They feature polarity, water solubility, variable net charges, improved stabilities of N-hydroxysuccinimidyl (NHS) esters, as well as large fluorescence quantum yields in dye solutions and antibody conjugates. The photophysical and imaging properties of dyes containing three different polar groups, namely primary phosphate, sulfonic acid (in two different positions), and hydroxyl were compared. A dye with two primary phosphate groups was explored as a valuable alternative to dyes with "classical" sulfonic acid groups. Due to the increased net charge of the phosphorylated dye (q=-4 at pH 8), it demonstrated a far better electrophoretic mobility compared with analogues with two sulfonic acid groups (q=-2). As an example, one fluorescent dye was designed to be especially convenient for practical use. It is characterized by sufficiently high chemical stability of the NHS ester, its simple isolation, handling, and solubility in aqueous buffers, as well as in organic solvents. All these features, accompanied by a zero net charge in conjugates, were accomplished by the introduction of hydrophilic groups of two types: two hydroxyl groups and one sulfonic acid residue. A study in scarlet: Rhodamines that absorb at 621-637 nm and emit at 644-660 nm were prepared and used in fluorescence microscopy and nanoscopy. They are photostable and feature variable polarities and net charges, high stabilities of N-hydroxysuccinimidyl (NHS) esters, large fluorescence quantum yields in aqueous solutions, and antibody conjugates. Copyright
Kolmakov, Kirill,Wurm, Christian A.,Hennig, René,Rapp, Erdmann,Jakobs, Stefan,Belov, Vladimir N.,Hell, Stefan W.
p. 12986 - 12998
(2013/01/15)

Dibutylphosphate (DBP) mediated synthesis of cyclic N,N′- disubstituted urea derivatives from amino esters: A comparative study
The N,N′-disubstituted urea derivatives such as amino acid hydantoins and dihydrouracil derivatives were prepared starting from natural and unnatural amino acid esters using dibutylphosphate (DBP). During the attempted synthesis of N-heterocycles with larger than six-membered rings containing the N,N′-disubstituted urea functionalities, three unexpected products namely squamolone, N-methyl pyrrolidine-2-one, and diketopiperazine were isolated.
Agrawal, Sumit K.,Sathe, Manisha,Kaushik, M. P.,Halve, A. K.
supporting information
p. 5996 - 5999,4
(2020/08/20)

Synthesis, spectral and catalytic activity of some Manganese(II) bis-benzimidazole diamide complexes
Four Mn(II) complexes bound to a neutral bis-benzimidazole diamide ligand N,N′-bis(2-methyl benzimidazolyl 2,2′-oxy-diethanamide) (GBOA) have been synthesized and characterized. Anionic ligand associated with the complexes varies as Cl- CH3COO-, SCN- and ClO4-. X-ray structure of one of the complexes [Mn(GBOA)2(H2O)2]Cl2·4H 2O was solved and shows that the Mn(II) ion is hexacoordinate. Two equatorial positions are occupied by benzimidazole imine nitrogen atoms while the other two sites are occupied by amide carbonyl oxygens. The imine nitrogen and carbonyl oxygens are bound to Mn(II) by different arms of the two ligands while axial sites are occupied by two water molecules. Two Cl- anions are outside the coordination sphere and form an extensive 3D H-bonded network. Axially distorted octahedral geometry is confirmed for all the four complexes by low temperature EPR spectroscopy. Distortion parameter D was found to be similar for [Mn(GBOA)2(H2O)2]Cl 2·4H2O and [Mn(GBOA)2(H 2O)2]·(CH3COO)2·H 2O. Cyclic voltammograms have been obtained for all the four complexes and E1/2 values are dependant on the anionic ligand being in the coordination sphere or outside. [Mn(GBOA)2(H 2O)2]Cl2·4H2O and [Mn(GBOA)2(H2O)2]·(CH 3COO)2·H2O carry out the selective oxidation of N-benzyldimethylamine, and 1-methyl-pyrollidine to their respective carbonyl products with catalytic efficiency of 35-50%.
Mohapatra, Subash Chandra,Hundal,Mathur, Pavan
experimental part
p. 1634 - 1641
(2011/10/03)

Microwave irradiation versus conventional heating in the synthesis of N-Methyl-2-pyrrolidone catalyzed by highly active copper powder
A convenient one-pot synthesis of N-methyl-2-pyrrolidone is achieved either by conventional heating or microwave irradiation. The intermediate N-methyl-4-hydroxybutyramide formedfromthe exothermic reaction of γ-butyrolactone with aqueous methylamine undergoes an intramolecular condensation reaction catalyzed by highly active copper powder to formthe pyrrolidone in good yield.
Jumbam,Phuthuma,Ndebvu,Ngarivhume
experimental part
p. 42 - 43
(2012/03/27)

Method for producing pyrrolidones from succinates from fermentation broths
The present invention relates to a process for preparing a compound II or a composition comprising the compound II to a composition comprising succinimide and to a composition prepared by the process according to the invention.
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(2011/10/03)

Exploration of photochemical reactions of N-trimethylsilylmethyl- substituted uracil, pyridone, and pyrrolidone derivatives
Photochemical reactions of N-trimethylsilylmethyl-substituted uracil, pyridone and pyrrolidone derivatives were carried out to determine if silicone containing substituents have an impact on excited state reaction profiles. The results show that ultraviolet irradiation of N-trimethylsilylmethyl substituted uracils in the presence of substituted alkenes leads to efficient formation of both dimeric and cross [2+2]-cycloaddition products. Qualitatively similar observations were made in a study of the photochemistry of N- trimethylsilylmethyl-2-pyridone. The combined results demonstrate that [2+2]-photocycloaddition is a more efficient excited state reaction pathway for the uracil and pyridone substrates as compared to other processes, such as ylide-forming trimethylsilyl group C-to-O migration. Finally, photoreactions of N-trimethylsilylmethyl-2-pyrrolidone in solutions containing dipolarophiles, such as methyl acrylate, lead to the formation of the desilylation product, N-methyl-2-pyrrolidone by way of a simple, non-ylide generating, protodesilylation process. In addition, observations were made which show that orbital symmetry allowed photocycloreversion reactions of dimeric uracil derivatives, involving cyclobutane ring splitting, to take place. These processes, which lead to the formation of monomeric uracils, appear to be stimulated by the presence of electron donor groups on the cyclobutane ring, a likely result of a new SET promoted cyclobutane ring cleavage pathway. In the cases of N-trimethylsilylmethyl-substituted cyclobutane derivatives that possess phthalimide groups, highly efficient excited state cleavage of the cyclobutane moiety occurs to produce uracil derivatives and corresponding vinyl phthalimide. The Royal Society of Chemistry and Owner Societies 2011.
Cho, Dae Won,Lee, Chan Woo,Park, Jong Gu,Oh, Sun Wha,Sung, Nam Kyoung,Park, Hea Jung,Kim, Kyung Mok,Mariano, Patrick S.,Yoon, Ung Chan
experimental part
p. 1169 - 1180
(2012/06/01)

Design, synthesis, and cyclization of 4-aminobutyric acid derivatives: Potential candidates as self-immolative spacers
Self-immolative spacers have gained significant interest in recent years due to their utility in numerous prodrug, sensor and drug delivery systems. However, there are a very limited number of spacers that are capable of undergoing spontaneous and rapid reactions under mild conditions. To address this need, 4-aminobutyric acid derivatives were explored as a potential class of self-immolative spacers. Using a modular approach, eleven N- and α-substituted derivatives of 4-aminobutyric acid were synthesized, and their intramolecular cyclizations to γ-lactams were studied. Kinetics experiments were carried out at physiological pH and temperature, and the observed half-lives for the spacers ranged from 2 to 39 s, depending on the molecular structure. In addition, the pH dependence of the cyclization rate was also explored and it was found that cyclization still occurred rapidly at mildly acidic pH. Therefore, this class of compounds exhibits promise for incorporation into a variety of self-immolative systems where rapid cyclization reactions are desired.
Dewit, Matthew A.,Gillies, Elizabeth R.
p. 1846 - 1854
(2011/05/03)

Amidite for synthesizing modified nucleic acid and method for synthesizing modified nucleic acid
The disclosure provides an excellent amidite for synthesizing a modified nucleic acid, which enables a protective group therein to be removed under a moderate condition, thereby stably producing a hydroxyl group-containing modified nucleic acid. The disclosure also provides a method for synthesizing a modified nucleic acid using the amidite. Specifically, an amidite for synthesizing the modified nucleic acid is expressed by General Formula (I): where X represents a base, Y represents a substituent, Z represents a protective group for protecting a hydroxyl group in the substituent, and Q represents one of a hydrogen atom, a hydroxyl group and a hydroxyl group protected by a protective group, wherein the protective group can be removed in an aprotic solvent, and when the protective group is removed, the hydroxyl group emerges in the substituent.
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(2011/04/18)

Synthesis of biobased N-methylpyrrolidone by one-pot cyclization and methylation of γ-aminobutyric acid
N-Methylpyrrolidone (NMP) is an industrial solvent that is currently based on fossil resources. In order to prepare it in a biobased way, the possibility to synthesize NMP from γ-aminobutyric acid (GABA) was investigated, since GABA can be obtained from glutamic acid, an amino acid that is present in many plant proteins. Cyclization of GABA to 2-pyrrolidone and subsequent methylation of 2-pyrrolidone to NMP was achieved in a one-pot procedure, using methanol as the methylating agent and a halogen salt (i.e. ammonium bromide) as a catalyst. A selectivity above 90% was achieved, as well as a high conversion. Methylation of 2-pyrrolidone could also be done with dimethyl carbonate, but then the selectivity for NMP was less (67%).
Lammens, Tijs M.,Franssen, Maurice C. R.,Scott, Elinor L.,Sanders, Johan P. M.
body text
p. 1430 - 1436
(2010/09/05)

PROCESS FOR PREPARING OF N-METHYL PYRROLIDONE
The present invention relates to a process for preparation of N-methyl pyrrolidone, and more particularly to a process for preparing high purity, high yield N-methyl pyrrolidone, comprising a first step of dehydrogenating 1,4-butandiol under a hydrogen atmosphere in the presence of a metal oxide solid catalyst to prepare γ-butyrolactone, and a second step of subjecting the γ-butyrolactone obtained in the first step without purification to a dehydration with monomethylamine under a metal oxide solid catalyst. The process for preparation of N-methyl pyrrolidone according to the present invention is a continuous two-step process using a metal oxide catalyst, wherein the second step continuously progresses without purification of the reaction product of the first step, γ-butyrolactone. According to the present invention, little of a reaction intermediate γ-butyrolactone, which is difficult to separate because of a small difference in boiling point (about 2 "C) from the final product, N-methyl pyrrolidone, remains after reaction, and thus separation and purification are easy. Further, its simple process enables mass production and lowers purification equipment cost.
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Page/Page column 16-18

(2009/07/25)

Oxidative conversion of α,α-disubstituted acetamides to corresponding one-carbon-shorter ketones using hypervalent iodine (λ5) reagents in combination with tetraethylammonium bromide
(Chemical Equation Presented) α,α-Disubstituted acetamides undergo oxidative dehomologation to give one-carbon-shorter ketones when reacted with a hypervalent iodine (λ5) reagent in combination with tetraethylammonium bromide (TEAB) in various solvents. In further studies, one such combination of a hypervalent iodine (λ5) reagent, o-iodoxybenzoic acid, and TEAB has been established as a new, mild, efficient, and general method for the transformation.
Bellale, Eknath V.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
supporting information; experimental part
p. 9473 - 9475
(2009/04/06)

Mechanistic investigation of the cobalt-catalyzed selective conversion of diallylanilines to quinolines involving C-N and C-H activations
2,3-Substituted quinolines were readily prepared from diallylanilines in good yields under mild conditions by using Co2(CO)8 as catalyst.1,2 Regioselectivity has been explored by examining a series of electron-donating and electron-withdrawing functional groups at ortho, meta, and para positions of the diallylanilines. The results show that both steric and electronic effects influence the isolated yields. Electron-withdrawing groups inhibit the reaction. Solvent effects, temperature effects, and catalyst loadings have also been investigated. Isotopic labeling experiments were devised to permit delineation of the mechanism of reaction.
Li, Ng,Jones, William D.
p. 10707 - 10713
(2008/03/12)

METHOD FOR CLEANING DEPOSITS FROM EQUIPMENT THAT HAVE ACCUMULATED DURING A METHOD FOR RECOVERING NMP, BY THE INTRODUCTION OF HOT WATER AND AGITATION
The invention relates to a method for cleaning deposits from equipment that have accumulated during a method for recovering purified N-methyl pyrrolidone (NMP), by the evaporation of NMP from a contaminated NMP stream, the latter accumulating during a method for the extractive separation of acetylene from a reaction mixture of the partial oxidation of hydrocarbons after the acetylene has been stripped. Said method is characterised in that hot water is introduced into the equipment and is agitated.
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Page/Page column 4-5

(2008/06/13)

Facile desulfurization of thioamides and thioureas with tetrabutylammonium periodate under mild conditions
Thioamides and thioureas were reacted with tetrabutylammonium periodate at room temperature to afford the corresponding amides and ureas, respectively, under aprotic conditions. Springer-Verlag 2005.
Pourali, Ali Reza
p. 733 - 737
(2007/10/03)

PROCESS FOR THE PRODUCTION OF LACTAMS
A homogeneous process for the hydrogenation of dicarboxylic acid and/or derivative thereof with an amine in the presence of a catalyst comprising: (a) ruthenium or osmium; and (b) an organic phosphine; and wherein the hydrogenation is carried out in the presence of water.
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Page/Page column 11

(2008/06/13)

PROCESS FOR THE PREPARATION OF N-AKYL-PYRROLIDONES
A process for the production of N-alkylpyrrolidone from γ-butyrolactone and monoalkylamine in the liquid phase comprising the steps of: feeding monoalkylamine and γ-butyrolactone, in the absence of water or in the presence of less than about 1 wt % of water, to a reaction zone to form a reaction mixture; heating the reaction mixture; withdrawing a product stream from the reaction zone and passing the stream to a distillation zone comprising at least one distillation column operated at sub-atmospheric pressure; adding water to the distillation zone; isolating at least one overhead stream from the distillation zone comprising monoalkylamine, water and optionally N-alkyl-pyrrolidone and condensing the overhead stream against cooling water.
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Page/Page column 9

(2008/06/13)

PROCESS FOR PRODUCING N-METHYL SUCCINIMIDE
The invention includes methods of processing an initial di-carbonyl compound by conversion to a cyclic compound. The cyclic compound is reacted with an alkyating agent to form a derivative having an alkylated ring nitrogen. The invention encompasses a method of producing an N-alkyl product. Amonia content of a solution is adjusted to produce a ratio of ammonia to di-carboxylate compound of from about 1:1 to about 1.5:1. An alkylating agent is added and the initial compound is alkylated and cyclized. The invention includes methods of making N-methyl pyrrolidinone (NMP). Aqueous ammonia and succinate is introduced into a vessel and ammonia is adjusted to provide a ratio of ammonia to succinate of less than 2:1. A methylating agent is reacted with succinate at a temperature of from greater than 100 °C to about 400 °C to produce N-methyl succinimide which is purified and hydrogenated to form NMP.
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Page 16; 17

(2008/06/13)

Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts
The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH3OH) promoted by the conventional solid acids (H-mordenite, β-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and γ-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH 3OH in the reaction of 2-aminoethanol with methanol (amine/CH 3OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 °C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P2O5/SiO2 and Cs/SiO2, respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO2. The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.
Oku, Tomoharu,Arita, Yoshitaka,Tsuneki, Hideaki,Ikariya, Takao
p. 7368 - 7377
(2007/10/03)

Method for preparing lactam
The present invention is related to a method for preparing lactam represented by the following formula: wherein R is C2-10alkylene which may be optionally substituted with C1-6alkyl or phenyl; R′ is a hydrogen atom, C1-6alkyl, C1-6hydroxyalkyl or phenyl. The method for preparing lactam comprises an amination reaction using crystalline aluminosilicate zeolites as catalysts under the condition of gas phase in the presence of (a) lactone, (b) amine and/or ammonia and (c) water.
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Example 1,2

(2008/06/13)

Preparation of N-methyl-2-pyrrolidone (NMP)
N-Methyl-2-pyrrolidone (NMP) is prepared by preparing a mixture comprising monomethylamine, dimethylamine and trimethylamine and ammonia in a first process step by reacting ammonia with methanol at elevated temperature in the presence of a catalyst, separating 10 off the ammonia, reacting the mixture comprising the methylamines with gamma-butyrolactone (γ-BL), in a molar ratio of monomethylamine to γ-BL of at least 1 in a second process step at elevated temperature and superatmospheric pressure, separating NMP and unreacted methylamines from the reaction product and returning unreacted methylamines to the first process step for reaction with methanol and ammonia.
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Page column 6

(2008/06/13)

Process for the preparation of lactams
The present invention is related to a method for preparing lactam represented by the following formula: wherein R is C2-10 alkylene which may be optionally substituted with C1-6 alkyl or phenyl; R is a hydrogen atom, C1-6 alkyl, C1-6 hydroxyalkyl or phenyl. The method for preparing lactam comprises an amination reaction using crystalline aluminosilicate zeolites as catalysts under the condition of gas phase in the presence of (a) lactone, (b) amine and/or ammonia and (c) water.
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Example 1,2,9-11

(2008/06/13)

Enhanced product selectivity in continuous N-methylation of amino alcohols over solid acid-base catalysts with supercritical methanol
The unique properties of supercritical fluids can be exploited for fine-tuning product selectivity. Under the conditions listed for the N-methylation of amino alcohols (see scheme) over solid acid-base bifunctional catalysts, the total yield and product selectivity could be improved. Enhanced product selectivity might be attributed to the milder reaction conditions possible with supercritical methanol, as well as the increased concentration of methanol on the catalyst.
Oku, Tomoharu,Ikariya, Takao
p. 3476 - 3479
(2007/10/03)

An yttrium-based system to evaluate Lewis base coordination to an lectropositive metal in a metallocene environment
The unsolvated bimetallic yttrium complex (C5Me5)2Y(μ-Cl)Y(C5Me5 )2Cl (1) provides a convenient platform upon which to compare the coordination chemistry of oxygen-donor ligands and monomers with Lewis acidic metal ions. Reaction of 1 with 2 equiv of oxygen-containing substrates formed the monomeric complexes (C5Me5)2YCl(L) (L = THF (2), benzophenone (3), methyl methacrylate (4), ε-caprolactone (5), hexamethylphosphoramide (6), ε-caprolactam (7), 1-methyl-2-pyrrolidinone (8), N,N′-dimethylpropyleneurea (9)). Each of these readily crystallize, which allows comparison of the Y-O interaction in the solid state. The X-ray data show that the numerical values of the measured Y-O lengths decrease in the order THF > benzophenone > methyl methacrylate > ε-caprolactone > hexamethyl-phosphoramide > ε-caprolactam > 1-methyl-2-pyrrolidinone > N,N′-dimethylpropyleneurea, although these bond lengths span only a short range and some are the same within experimental error. In the case of e-caprolactam, a bis adduct, (C5Me5)2YCl(ε-caprolactam)2 (10), can be isolated from the reaction of 1 and excess ε-caprolactam. 1H NMR spectroscopy indicates that (C5Me5)2YCl(L)L′ ligand displacement reactions in solution with 2-9 follow a trend consistent with the bond lengths except for (C5Me5)2YCl(ε-caprolactam) (7), in which L participates in hydrogen bonding to the chloride.
Evans, William J.,Fujimoto, Cy H.,Johnston, Matthew A.,Ziller, Joseph W.
p. 1825 - 1831
(2008/10/08)

Vinyl-λ3-iodanes act as efficient sulfur atom acceptors: Vinylic SN2-based strategy for conversion of tertiary thioamides to amides
Exposure of tertiary thioamides to (E)-1-hexenyl(phenyl)-λ3-iodane results in vinylic SN2 reaction to give the inverted (Z)-S-vinylthioimidonium salts, which under alkaline hydrolysis (Na2CO3 or K2CO
Ochiai, Masahito,Yamamoto, Shinji
p. 2802 - 2803
(2007/10/03)

Selective regeneration of carbonyl compounds from aldoximes and ketoximes, catalyzed by FeCl3 and SeO2
An oxidative deblocking procedure of aldoximes using FeCl3 and ketoximes using SeO2 in aprotic solvent is reported. Reaction yields are competitive as compared to previous methods. Reactions are easy to work and conditions are mild. Some important features of FeCl3 are mentioned.
Hangarge,Mane,Chavan,Shingare
p. 1302 - 1304
(2007/10/03)

Solvent for biopolymer synthesis, solvent microdroplets and methods of use
The present invention provides a method of biopolymer, esp. oligonucleotide, synthesis. The method consists of coupling a first nucleotide to a second nucleotide in a high surface tension solvent. The invention also provides microdroplets of a soln. comprising a solvent having a b.p. of 150 degree. C. or above, a surface tension of 30 dynes/cm or above, and a viscosity of 0.015 g/(cm)(sec), e.g., propylene carbonate. Such microdroplets are useful for the synthesis of chem. species, particularly biopolymers such as oligonucleotides and peptides, as well as arrays of chem. species. An automated system for oligonucleotide synthesis is described, which comprises delivery of microdroplets by inkjet technol. and computer control of the process. The high surface tension solvent used is selected for compatibility with the inkjet technol.
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(2008/06/13)

Fluorination agent and preparation and use of same
The invention disclose a hydrogen fluoride containing composition comprising hydrogen fluoride and a compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more and pka of 12 or more at 25° C., and use of the composition for a fluorination agent. The compound which can be preferably used is represented by the formula (1): wherein R1 to R4 are a substituted or unsubstituted alkyl or aryl group and can be the same or different, and R1 or R2 or R3 and R4 can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom, or R1 and R3 can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom. The fluorination agent of the invention exerts effect with a similar reaction mechanism to hydrogen fluoride, can be applied to the halogen exchange reaction of a halogen containing organic compound, and can produce a fluorine containing compound with safety and ease without specific equipment or technique.
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(2008/06/13)

Novel 3-(2-adamantyl)pyrrolidines with potent activity against influenza A virus - Identification of aminoadamantane derivatives bearing two pharmacophoric amine groups
The 3-(2-adamantyl)pyrrolidines 8a-g, 14 were synthesized and evaluated for activity against influenza A virus. The parent N-H compound 14 was several times more active than amantadine against H2N2 and H3N2 influenza A virus. The combined use of NMR spectroscopy and computational chemistry showed that the conformation around the pyrrolidine-adamantyl carbon-carbon bond is trans and the pyrrolidine heterocycle has an envelope conformation with C-2 out of the plane of the other ring atoms. N-Dialkylaminoethyl substitution of compound 14 resulted in the potent diamine analogues 8e,f,g. Interestingly, their lactam amine precursors were also active. Compounds 8e,f,g are the first adamantane derivatives, bearing two amine groups, reported to be active against influenza A virus.
Stamatiou, George,Kolocouris, Antonios,Kolocouris, Nicolas,Fytas, George,Foscolos, George B,Neyts, Johan,De Clercq, Erik
p. 2137 - 2142
(2007/10/03)

Preparation of N-methy1-2-pyrrolidone (NMP)
N-Methyl-2-pyrrolidone (NMP) is prepared by preparing a mixture comprising monomethylamine, dimethylamine and trimethylamine and ammonia in a first process step by reacting ammonia with methanol at elevated temperature in the presence of a catalyst, separating off the ammonia, reacting the mixture comprising the methylamines with gamma-butyrolactone (γ-BL), in a molar ratio of monomethylamine to γ-BL of at least 1 in a second process step at elevated temperature and superatmospheric pressure, separating NMP and unreacted methylamines from the reaction product and returning unreacted methylamines to the first process step for reaction with methanol and ammonia.
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(2008/06/13)