- Selenoxide elimination triggers enamine hydrolysis to primary and secondary amines: A combined experimental and theoretical investigation
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We discuss a novel selenium-based reaction mechanism consisting in a selenoxide elimination-triggered enamine hydrolysis. This one-pot model reaction was studied for a set of substrates. Under oxidative conditions, we observed and characterized the formation of primary and secondary amines as elimination products of such compounds, paving the way for a novel strategy to selectively release bioactive molecules. The underlying mechanism was investigated using NMR, mass spectrometry and density functional theory (DFT).
- Bortoli, Marco,Gianoncelli, Alessandra,Ongaro, Alberto,Orian, Laura,Oselladore, Erika,Ribaudo, Giovanni,Zagotto, Giuseppe
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- Catalytic Transfer Hydrodebenzylation with Low Palladium Loading
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A highly-efficient catalytic system for hydrodebenzylation reaction is described. The cleavage of O-benzyl and N-benzyl protecting groups was performed using an uncommonly low palladium loading (0.02–0.3 mol%; TON up to 5000) in a relatively short reaction time. The approach was used for a variety of substrates including pharmaceutically important precursors, and gram-scale deprotection reaction was shown. Transfer conditions together with easy-to-make Pd/C catalyst are the key features of this debenzylation scheme. (Figure presented.).
- Yakukhnov, Sergey A.,Ananikov, Valentine P.
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- A New Reagent for the Selective, High-Yield N-Dealkylation of Tertiary Amines: Improved Syntheses of Naltrexone and Nalbuphine
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Secondary amine hydrochlorides are obtained in high yield by reaction of tertiary amines with α-chloroethyl chloroformate followed by warming the intermediate carbamate in methanol.
- Olofson, R. A.,Martz, Jonathan T.,Senet, Jean-Pierre,Piteau, Marc,Malfroot, Thierry
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- Synthesis, spectroscopic studies, and single crystal X-ray diffraction analysis of a lead(II) based hybrid perovskite: Morpholinium trichloroplumbate(II)
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Morpholinium trichloroplumbate(II), [cyclo-O(CH2CH2)2NH]PbCl3 (1), has been synthesized and characterized by elemental analysis, FTIR and 1H and 13C NMR spectroscopy, thermogravimetric analysis (TGA), diffuse reflectance spectra, and single-crystal X-ray diffraction analysis. An FTIR spectrum showed a shift of 100 cm-1 in the NH2 stretching due to the protonated nitrogen of the morpholinium ion. 1H NMR spectrum of the compound showed significant high-frequency shift of the resonance for the CH2 protons due to the presence of cationic charge on the adjacent nitrogen and hydrogen bonded interactions. Contrary to 1H NMR, the 13C NMR signals showed a lowering of 'δ' in the hybrid material. A diffuse reflectance spectrum (DRS) illustrated intense charge transfer in the compound. The observed band gap value for the compound is 3.23 eV based on the DRS data. TG-DT analysis showed the compound to be stable up to 241°C. Single crystal X-ray diffraction analysis of the hybrid material showed the Pb2+ ion being surrounded by six chloride anions in a distorted octahedral geometry. In addition to the six chloride anions, the oxygen atom of the morpholinium cation is also in short contact with the lead cation. Bond valence sum (BVS) calculation confirmed the formal oxidation state of lead to be +2. Continuous symmetry measure (CSM) calculations indicated the PbCl6 to be a distorted octahedron with a magnitude of 5.246 clearly far away from the trigonal prismatic geometry.
- Ramalingam, Kuppukkannu,Rizzoli, Corrado,Rajaraman, Thangarasu,Prabu, Manikandan
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- Metal-Free Synthesis of Heteroaryl Amines or Their Hydrochlorides via an External-Base-Free and Solvent-Free C-N Coupling Protocol
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Herein, a metal-free and solvent-free protocol was developed for the C-N coupling of heteroaryl halides and amines, which afforded numerous heteroaryl amines or their hydrochlorides without any external base. Further investigations elucidated that the basicity of amines and specific interactions derived from the X-ray crystallography analysis of 3j′·HCl played pivotal roles in the reactions. Moreover, this protocol was scalable to gram scales and applicable to drug molecules, which demonstrated its practical value for further applications.
- Fan, Guang-Gao,Jiang, Bo-Wen,Sang, Wei,Cheng, Hua,Zhang, Rui,Yu, Bao-Yi,Yuan, Ye,Chen, Cheng,Verpoort, Francis
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p. 14627 - 14639
(2021/11/01)
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- Photoredox-Catalyzed Addition of Carbamoyl Radicals to Olefins: A 1,4-Dihydropyridine Approach
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Functionalization with C1-building blocks are key synthetic methods in organic synthesis. The low reactivity of the most abundant C1-molecule, carbon dioxide, makes alternative carboxylation reactions with CO2-surrogates especially important. We report a photoredox-catalyzed protocol for alkene carbamoylations. Readily accessible 4-carboxamido-Hantzsch esters serve as convenient starting materials that generate carbamoyl radicals upon visible light-mediated single-electron transfer. Addition to various alkenes proceeded with high levels of regio- and chemoselectivity.
- Cardinale, Luana,Konev, Mikhail O.,Jacobi von Wangelin, Axel
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supporting information
p. 8239 - 8243
(2020/06/20)
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- Metal – organic hybrids of tin(IV) with tuneable band gap: Synthesis, spectral, single crystal X-ray structural, BVS and CSM analysis of morpholinium hexahalostannate(IV)
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Self assembled organic - inorganic hybrid materials such as morpholinium hexachlorostannate(IV) (3) and morpholinium hexabromostannate(IV) (4) have been synthesised from morpholinium chloride (1) and morpholinium bromide (2) at room temperature. The hybrids were characterized by elemental analysis, IR, NMR, TG-DTA, DRS and PL spectroscopy and single crystal X-ray diffraction. IR and NMR spectral data of (3) and (4) show very little changes compared to their parent compounds (1) and (2). However, the = NH2 + proton signal of the bromide hybrid (4), shows a relatively lower δ value due to extensive hydrogen bonding compared to its chloride analogue (3). Thermal analysis confirmed the proposed formulae of the compounds. Optical absorption measurements showed 3.80 and 2.60 eV as band gaps for (3) and (4) respectively at room temperature implying that the band gaps can be easily tuned by altering the halide ion. Single crystal X-ray structures of compounds (3) and (4) revealed extensive hydrogen bonded interactions between the morpholinium cation and the SnCl6 2? and SnBr6 2? anions in (3) and (4). In (4), two molecules of morpholinium bromide co-crystallized with the hybrid. BVS calculations performed on SnCl6 2? and SnBr6 2? anions (3) and (4) resulted in 4.10 and 4.13 respectively, which clearly established the formal oxidation state of tin in the compounds as 4+. CSM calculation on SnBr6 2? yielded a value of 0.006 signifying a near perfect octahedral geometry of the anion.
- Rajaraman, Thangarasu,Ramalingam, Kuppukkannu
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- Synthetic method of moroxydine hydrochlofide
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The invention discloses a synthetic method of moroxydine hydrochlofide. The method comprises the following steps: adding diglycol, dicyandiamide, ammonium chloride and an aqueous sulfuric acid solution with the mass concentration of 20-30% to a high pressure reaction kettle according to amass ratio of (4-6):(4-6):(2-4):(1-2), heating the obtained solution in a sealed and stirring state to 120-130DEG C, reacting under a reaction kettle pressure of 0.3-0.5MPa for 1-2h, and cooling the obtained solution to room temperature to obtain a white milk; and transferring the white milk to a reaction kettle, adding 95% ethanol according to a volume ratio of the 95% ethanol to diglycol of (7-9):1, carrying out a heating refluxing reaction for 30min to obtain a mixed solution, carrying out hot filtration on the mixed solution through a filter cylinder to a crystallization kettle, cooling the obtained filtrate in the crystallization kettle to room temperature to precipitate white crystals, centrifuging and separating the white crystals, and drying the separated white crystals in a hot wind oven at 80-85DEG C to obtain moroxydine hydrochlofide.. Moroxydine hydrochlofide is obtained through a direct reaction of dicyandiamide and morpholine hydrochloride generated through in situ reaction of diglycol and ammonium chloride under the action of sulfuric acid, so the synthetic method is simplified, side reactions are reduced, the yield is improved, and environment is protected.
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Paragraph 0053; 0054; 0055
(2016/10/10)
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- Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective
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The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography-mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.
- Di Grandi, Martin J.,Bennett, Caitlin,Cagino, Kristen,Muccini, Arnold,Suraci, Corey,Saba, Shahrokh
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supporting information
p. 2601 - 2607
(2015/11/28)
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- Nucleophilic substitution reaction at the nitrogen of arylsulfonamides with phosphide anion
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A novel nucleophilic substitution reaction at the nitrogen of arylsulfonamides by means of phosphide anions has been described. This reaction allows for the efficient transformation of arylsulfonamides into synthetically valuable phosphamides, amines, and a variety of protected amines.
- Yoshida, Suguru,Igawa, Kazunobu,Tomooka, Katsuhiko
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supporting information
p. 19358 - 19361
(2013/02/22)
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- Synthesis and reactions with N-nucleophiles of 1-(thien-2-yl)- and 1-(4-hydroxyphenyl)-3,4,4-trichloro-3-buten-1-ones
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Acylation of thiophene and phenol with 3,4,4-trichloro-3-butenoyl chloride afforded the corresponding 1-(thien-2-yl)- and 1-(4-hydroxyphenyl)-3,4,4- trichloro-3-buten-1-ones, whose reaction with amines led to the formation of 3-amino-1-(thien-2-yl, 4-hydr
- Potkin,Petkevich,Kurman
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experimental part
p. 1305 - 1312
(2011/01/04)
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- Morpholinium trifluoroacetate-catalyzed aldol condensation of acetone with both aromatic and aliphatic aldehydes
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We report a highly efficient, general and practical method for the aldol condensation of acetone with aromatic and aliphatic aldehydes, using morpholinium trifluoroacetate as a catalyst.
- Zumbansen, Kristina,Doehring, Arno,List, Benjamin
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experimental part
p. 1135 - 1136
(2010/09/05)
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- ORGANIC COMPOUNDS
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Compounds of formula I in free or salt or solvate form, where R1, R2 and R5 have the meanings as indicated in the specification, are useful for treating diseases mediated by the ALK-5 and/or ALK-4 receptor. Pharmaceutical compositions that contain the compounds and processes for preparing the compounds are also described.
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Page/Page column 5; 27; 28
(2010/08/18)
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- Highly chemoselective Pd-C catalytic hydrodechlorination leading to the highly efficient N-debenzylation of benzylamines
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(Equation Presented) In the presence of 1,1,2-trichloroethane, a novel procedure for the Pd-C catalytic N-debenzylation of benzylamines was established. The method proceeded in a synergistic catalytic system and directly gave the products as crystal amine hydrochlorides in practically quantitative yields.
- Cheng, Chuanjie,Sun, Jianwei,Xing, Lixin,Xu, Jimin,Wang, Xinyan,Hu, Yuefei
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supporting information; experimental part
p. 5671 - 5674
(2009/12/08)
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- THE USE OF 7-AZAINDOLES IN THE INHIBITION OF C-JUN N-TERMINAL KINASE
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The present invention provides a compound of formula (I); or a pharmaceutically acceptable salt thereof in the inhibition of c-Jun N-terminal kinase (JNK) activity and particularly in the treatment of neurodegenerative disorders, inflammatory diseases and
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Page/Page column 50; 122-123
(2008/12/08)
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- Synthesis of the perdeuterated cellulose solvents N-methylmorpholine N-oxide (NMMO-d11) and N,N-dimethylacetamide (DMAC-d9)
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The synthesis of the perdeuterated cellulose solvents NMMO-d11 (9) and N,N-dimethylacetamide-d9 (14) is described. NMMO-d 11 was obtained according to a five-step approach from non-labeled diglycolic acid (1) via diethylene glycole-d8 (4) and its bis-tosylate (5), which underwent cyclization with benzylamine to N-benzylmorpholine (6). The removal of the benzyl protecting group, methylation and N-oxidation completed the synthesis. DMAc-d9 (14) was obtained from deuterated acetic acid (10) and dimethylamine-carbon dioxide complex (17) with acidic alumina as the catalyst according to a solvent-free gas-solid reaction. Copyright
- Adelwoehrer, Christian,Yoneda, Yuko,Nakatsubo, Fumiaki,Rosenau, Thomas
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- Hydroxyphenstatin and the prodrugs thereof
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The benzophenone derivative of combretastatin A-1, designated “hydroxyphenstatin”, was synthesized by compiling a protected bromobenzene and a benzaldehyde to form a benzhydrol which was subsequently oxidized to the ketone. Hydroxyphenstatin was converted
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- Intermediates for the synthesis of camptothecin derivatives
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Intermediates for the synthesis of camptothecin of the formula II wherein: R1is —(CH2)2NR1R2, where R1is an amino protecting group and R2is C2-C5alkyl, hydr
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- Method for treating patient having precancerous lesions with a combination of pyrimidopyrimidine derivatives and esters and amides of substituted indenyl acetic acides
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Combinations of substituted indenyl acetic acids and pyrimido-pyrimidine derivatives are useful in the treatment of colonic polyps and inhibiting the growth of neoplastic cells.
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- Cycloadditions of nitrile oxides to amidoximes. A general synthesis of 3,5-disubstituted 1,2,4-oxadiazole-4-oxides
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The cycloaddition of nitrile oxides to amidoximes is a general method for the synthesis of 3,5-disubstituted 1,2,4-oxadiazole-4-oxides with the same or different substituents. The yields are only moderate since an equivalent amount of the nitrile oxide is consumed by reaction with the amine released in the fragmentation of the primary cycloadducts and reforms the amidoxime. With excess nitrile oxides the 1,2,4-oxadiazole-4-oxides undergo a disproportionation reaction to yield nitroso carbonyl intermediates and 1,2,4-oxadiazoles.
- Quadrelli, Paolo,Invernizzi, Anna Gamba,Falzoni, Mario,Caramella, Pierluigi
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p. 1787 - 1796
(2007/10/03)
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- New Syntheses of Methyleniminium Salts from Carbonyl Compounds and from α-Chloro Ethers; an Access to Vinylogous Viehe Salts
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Two methods for the synthesis of isolable methyleniminium salts and amidinium salts are presented.In the first case carbonyl compounds A are treated with a mixture of (dialkylamino)trimethylsilane (12) and chlorotrimethylsilane (13) or 12 and trimethylsilyl triflate (14) leading to the iminium chlorides F or iminium triflates G, respectively.With 12/13 the preparation of F is limited to non-enolizable aldehydes and dimethylformamide (10), while 12/14 enables the preparation of G, e.g. 23a-25a, 27a, also with ketones and with substituted amides.The second procedure is based on the treatment of α-chloro ethers L with 12.Both methods afford the Mannich reagent 16a in high yields.By reaction of the α-chloro ether 35 with 12 in diethyl ether the vinylogous Viehe salts 36a-c, e become available for the first time.The reaction pathways are discussed. - Key Words: Methyleniminium salts, preparation, mechanisms of formation / (Dialkylamino)trimethylsilanes / Ethers, α-chloro / Viehe salts, vinylogous
- Schroth, Werner,Jahn, Ullrich,Stroehl, Dieter
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p. 2013 - 2022
(2007/10/02)
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- Pyridine and pyrimidine ring syntheses from 4-(4-morpholino)-3-pentenone and from ethyl 3-(4-morpholino)-2-butenoate
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3-Substituted 2(1H)-pyridones are produced from reaction of 4-(4- morpholino)-3-pentenone 1 with each of the following carbon acids: cyanoacetamide, malononitrile, cyanothioacetamide, acetylacetamide, benzoyl- acetonitrile. Reaction of ethyl 3-(4-morpholino)-2-butenoate 2 with cyanoacetamide gives the corresponding hydroxypyridone. Pyrimidines are formed by reaction of 1 and of 2 with benzamidine and with S-benzylthiourea; in the last case, the eliminated morpholine displaces the benzylthio group to give the final product.
- Ratemi,Namdev,Gibson
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p. 1513 - 1516
(2007/10/02)
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- REACTION OF CYCLIC PARTIAL PHOSPHITE ESTERS WITH ENAMINES - AN ELECTROPHILIC FORM OF THE PUDOVIK REACTION
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It was established that the ease of noncatalytic addition of cyclic and acyclic partial phosphites to enamines is due to the H-donor capacity of the acids and to the degree of localization of the electron density at the C=C bond in the unsaturated partner.It was shown that cyclic phosphites add initially at the carbon-carbon multiple bond of the conjugated N-C=C-C=O system of enamino ketones with the final formation of bisphosphorylated derivatives.
- Safina, Yu. G.,Malkova, G. Sh.,Cherkasov, R. A.
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p. 562 - 574
(2007/10/02)
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- IMPROVED SYNTHESIS OF DIALKYLTHIOXAPHOSPHORANESULFENYL CHLORIDES AND BROMIDES
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Dialkylthioxaphosphoranesulfenyl chlorides and bromides can be conveniently prepared in the reaction of the corresponding thioamides with hydrogen chloride generated in situ with trimethylsilyl chloride and ethanol.Stability of the chlorides and bromides
- Lopusinski, A.,Luczak, L.,Michalski, J.
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p. 233 - 236
(2007/10/02)
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- REACTIONS OF N-POLYFLUOROPHENYLCARBONIMIDOYL DICHLORIDES WITH PRIMARY AND SECONDARY AMINES. KINETICS AND MECHANISM. SYNTHESIS OF POLYFLUORINATED CABODIIMIDES, CHLOROFORMAMIDINES, GUANIDINES AND BENZIMIDAZOLES
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The reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary aliphatic and aromatic amines have been studied.With primary aliphatic amines, the reactions led to carbodiimides or guanidines, depending on the amount of amine.The carbodiimides obtained reacted with amines to form guanidines.The reactions with primary aromatic amines produced only triarylguanidines.N-Pentafluorophenylcarbonimidoyl dichloride (I) reacted with tetrafluoro-o-phenylene diamine to give 2-pentafluoroanilino-4,5,6,7-tetrafluorobenzimidazole.Polyfluorinated benzimidazole derivatives were also produced by the thermolysis of polyfluorinated triarylguanidines.Heating of N1,N2,N3-tris(pentafluorophenyl)guanidine with K2CO3 in dimethylformamide led to 1,2,3,4,7,8,9,10-octafluoro-5-pentafluorophenyl-5H-benzimidazobenzimidazole.N-Polyfluorophenylcarbonimidoyl dichlorides reacted with various secondary amines alredy at room temperature giving N-polyfluorophenylchloroformamidines in high yields.Elevated temperature and prolonged reaction time led to formation of N-polyfluorophenylguanidines.Kinetics and mechanism of the reactions of N-polyfluorophenylcarbonimidoyl dichlorides with primary and secondary amines in acetonitrile at 25 deg C have been studied.The reactions have been found to proceed by a bimolecular nucleophilic addition-elimination mechanism via a tetrahedral intermediate.Possible reasons of formation of different products in the above transformations are discussed in terms of this mechanism.
- Kolesnikova, I. V.,Petrova, T. D.,Platonov, V.E.,Mikhailov, V. A.,Popov, A. A.,Savelova, V.A.
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p. 217 - 246
(2007/10/02)
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- SYNTHESIS AND REACTIONS OF TRANS-2-(2'-NITROPHENYLTHIO)-1-CHLOROINDANE
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The title compound was prepared by addition of 2-nitrobenzenesulphenyl chloride to indene, and proton nmr was used to prove its trans-structure.The chloro-substituent could be replaced by ethanol under very mild conditions with retention of configuration owing to anchimeric assistance by the bridging S-atom.Analogous reactions were observed with water and other alcohols (MeOH, Me2CHOH, Me3COH, PhSH).Basic nucleophiles caused dehydro-chlorination to the corresponding indenes.Reduction of the nitro-group resulted in intramolecular cyclisation to give a dihydrobenzindenothiazine 9.Thermolysis of the 2-(2'-nitrophenylthio)-1-azidoindane occurred with ring expansion to give 3-(2'-nitrophenylthio)quinoline.Oxidation of the title compound with m-chloroperoxybenzoic acid produced the corresponding sulphone which smoothly underwent reductive cyclisation to a benzindenothiazinesulphone 20.
- Einbaum, Priit,Suschitzky, Hans
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p. 231 - 240
(2007/10/02)
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- Process for manufacturing phenoxylactic acids, their derivatives and products obtained thereby
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The process is for the manufacture of phenoxylactic acids and their derivatives of the general formula: STR1 (in which R1 and R2, identical or different, can represent hydrogen atoms, methyl residues, methoxy groups or halogens; Y re
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- Process for producing fluorinated organic compounds containing a difluoromethylene group from compounds comprising at least one carbonyl function
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A novel process for producing fluorinated organic compounds containing a difluoromethylene group, essentially characterized by reacting organic compounds containing a carbonyl function with molybdenum hexafluoride at room temperature and under atmospheric
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- 2-4-DIAMINOQUINAZOLINES AS ANTITHROMBOTIC AGENTS
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2,4-diaminoquinazolines are employed as antithrombotic agents and have the following general formula: SPC1Wherein R 1 and R 2 are monovalent groups independently selected from the group consisting of EQU1 wherein R 4 and R 5 independently are selected from the group consisting of hydrogen, alkyl, and cycloalkyl, with the proviso that both R 4 and R 5 cannot be cycloalkyl, EQU2 wherein R 6, R 7, and R 8 independently are selected from the group consisting of hydrogen and alkyl, and A is a divalent organic group having from two to about six carbon atoms such that the two nitrogen atoms are separated by at least two carbon atoms, and C. heterocyclic-amino, andR 3 is a monovalent group selected from the group consisting of hydrogen, halogen, and alkyl.
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