- N-Methylaniline-induced Si-Si bond cleavages of perchlorooligosilanes
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This study describes Si-Si bond cleavage of perchlorooligosilane using an amine. N-Methylaniline-induced Si-Si bond cleavage reactions of cyclic perchlorosilanes Si5Cl10 (1) and Si4Cl 8 (2), and acyclic perchlor
- Park, Sung Jin,Choi, Jong Min,Cho, Hyeon Mo,Kim, Cheol Hyun,Lee, Myong Euy
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- N-Methylation and Trideuteromethylation of Amines via Magnesium-Catalyzed Reduction of Cyclic and Linear Carbamates
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A new reduction of carbamates to N-methyl amines is presented. The magnesium-catalyzed reduction reaction allows the conversion of cyclic and linear carbamates, including N-Boc protected amines, into the corresponding N-methyl amines and amino alcohols which are of significant interest due to their presence in many biologically active molecules. Furthermore, the reduction can be extended to the formation of N-trideuteromethyl labeled amines.
- Magre, Marc,Szewczyk, Marcin,Rueping, Magnus
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supporting information
p. 3209 - 3214
(2020/04/10)
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- Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution
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Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.
- Lardy, Samuel W.,Luong, Kristine C.,Schmidt, Valerie A.
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supporting information
p. 15267 - 15271
(2019/12/11)
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- N -Monomethylation of amines using paraformaldehyde and H2
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The selective N-monomethylation of amines is an important topic in fine chemical synthesis. Herein, for the first time, we described a selective N-monomethylation reaction of amines with paraformaldehyde and H2 in the presence of a CuAlOx catalyst. A variety of amines, including primary aromatic amines, benzylamine and cyclohexylamine, as well as secondary amines, have been shown to be compatible with this reaction.
- Wang, Hongli,Huang, Yongji,Dai, Xingchao,Shi, Feng
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supporting information
p. 5542 - 5545
(2017/07/06)
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- Magnesium-catalyzed mild reduction of tertiary and secondary amides to amines
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The first example of a catalytic hydroboration of amides for their deoxygenation to amines is reported. This transformation employs an earth-abundant magnesium-based catalyst. Tertiary and secondary amides are reduced to amines at room temperature in the presence of pinacolborane (HBpin) and catalytic amounts of ToMMgMe (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). Catalyst initiation and speciation is complex in this system, as revealed by the effects of concentration and order of addition of the substrate and HBpin in the catalytic experiments. ToMMgH2Bpin, formed from ToMMgMe and HBpin, is ruled out as a possible catalytically relevant species by its reaction with N,N-dimethylbenzamide, which gives Me2NBpin and PhBpin through C-N and C-C bond cleavage pathways, respectively. In that reaction, the catalytic product benzyldimethylamine is formed in only low yield. Alternatively, the reaction of ToMMgMe and N,N-dimethylbenzamide slowly gives decomposition of ToMMgMe over 24 h, and this interaction is also ruled out as a catalytically relevant step. Together, these data suggest that catalytic activation of ToMMgMe requires both HBpin and amide, and ToMMgH2Bpin is not a catalytic intermediate. With information on catalyst activation in hand, tertiary amides are selectively reduced to amines in good yield when catalytic amounts of ToMMgMe are added to a mixture of amide and excess HBpin. In addition, secondary amides are reduced in the presence of 10 mol % ToMMgMe and 4 equiv of HBpin. Functional groups such as cyano, nitro, and azo remain intact under the mild reaction conditions. In addition, kinetic experiments and competition experiments indicate that B-H addition to amide C-O is fast, even faster than addition to ester C=O, and requires participation of the catalyst, whereas the turnover-limiting step of the catalyst is deoxygenation.
- Lampland, Nicole L.,Hovey, Megan,Mukherjee, Debabrata,Sadow, Aaron D.
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p. 4219 - 4226
(2015/11/11)
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- High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation
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We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with a Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on a larger scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers at the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).
- Abdelhamid, Muhammad E.,Murdoch, Timothy,Greaves, Tamar L.,O'Mullane, Anthony P.,Snook, Graeme A.
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p. 17967 - 17972
(2015/07/07)
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- Selective monomethylation of primary amines with simple electrophiles
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Direct monomethylation of primary amines with methyl triflate was achieved with high selectivity (up to 96%). The key point of this single methyl transfer stems from the use of HFIP as the solvent that interferes with amines and avoids overmethylation.
- Lebleu, Thomas,Ma, Xiaolu,Maddaluno, Jacques,Legros, Julien
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supporting information
p. 1836 - 1838
(2014/02/14)
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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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- Synthetic routes to, transformations of, and rather surprising stabilities of (N-Methyl-N-phenylcarbamoyl)sulfenyl Chloride, ((N-Methyl-N-phenylcarbamoyl) dithio)carbonyl chloride, and related compounds
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(Figure presented) The title compound classes, (carbamoyl)sulfenyl chlorides and ((carbamoyl)dithio)carbonyl chlorides, have been implicated previously as unstable, albeit trappable, intermediates in organosulfur chemistry. The presentwork reports for each of these functional groups: (i) several routes to prepare it in the N-methylaniline family; (ii) its direct structural characterization by several spectroscopic techniques; (iii) its rather unexpected stability and its ultimate fatewhen it decomposes; (iv) a series of further chemical transformations that give highly stable derivatives, each in turn subject to thorough characterization. Relevant kinetic and mechanistic experiments were carried out, including some with p-methyl- and 2,6-dimethyl-substituted N-methylanilines. Given that the title compounds can be isolated and are relatively stable, they may find applications in the preparation of thiolyzable and/or photolabile protecting groups for the sulfhydryl function of cysteine and for the development of new protein synthesis and modification reagents
- Schrader, Alex M.,Schroll, Alayne L.,Barany, George
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experimental part
p. 7882 - 7892
(2011/12/14)
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- Efficient, direct α-methylenation of carbonyls mediated by diisopropylammonium trifluoroacetate
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A very efficient method for the direct α-methylenation of carbonyl compounds, with yields up to 99%, utilizing paraformaldehyde, diisopropylammonium trifluoroacetate, and catalytic acid or base, is presented.
- Bugarin, Alejandro,Jones, Kyle D.,Connell, Brian T.
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supporting information; experimental part
p. 1715 - 1717
(2010/07/06)
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- A General, Selective, High-Yield N-Demethylation Procedure for Tertiary Amines by Solid Reagents in a Convenient Column Chromatography-like Setup
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(Equation presented) A traditional preparative chromatographic column can be used to achieve quantitative N-demethylation of tertiary N-methylamines and alkaloids. The filling is the crucial part and is loaded with different solid reagents in three reaction zones. The parent compound is charged on the column, and the neat N-demethylated secondary amine leaves the column some minutes later.
- Rosenau, Thomas,Hofinger, Andreas,Potthast, Antje,Kosma, Paul
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p. 541 - 544
(2007/10/03)
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- Synthesis and Characterization of (Methoxy(thiocarbonyl))sulfenyl Chloride
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(Methoxy(thiocarbonyl))sulfenyl chloride (1), a previously elusive compound, has now been generated by cleavage of methoxy(thiocarbonyl) N-methyl-N-phenylamino sulfide (7) with gaseous hydrogen chloride.The sulfenyl chloride 1 had limited stability and was characterized by trapping with O,O'-dimethyl thiocarbonate or with methanethiol to yield (methoxycarbonyl)(methoxy(thiocarbonyl))disulfane (8) or (methoxy(thiocarbonyl))methyldisulfane (9), respectively.Chlorination of acetyl methoxy(thiocarbonyl) sulfide (6) could be arrested at 1 plus acetyl chloride, and further chlorination of 1 provided (methoxydichloromethyl)disulfanyl chloride (5).
- Schroll, Alayne L.,Eastep, Steven J.,Barany, George
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p. 1475 - 1479
(2007/10/02)
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- EFFECT OF STRUCTURE OF REAGENTS AND TEMPERATURE IN THE REACTIONS OF AROYL CHLORIDES WITH N-METHYLARYLAMINES IN BENZENE
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The kinetics of the reactions of aroyl chlorides with N-methylarylamines in benzene were studied with crossed variation in the structures of the reagents.The attainment of the isoparametric point with respect to the structure of the N-methylarylamine was demonstrated by crossed correlation.The energy parameters for the reactions of benzoyl chloride with N-methylarylamines are 10percent lower than those obtained for primary arylamines.The higher reactivity of the N-methylarylamines compared with the corresponding primary arylamines is due to the resonance stabilization of the transition state.
- Titskii, G. D.
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p. 1714 - 1718
(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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- Novel Symmetrical and Mixed Carbamoyl and Amino Polysulfanes by Reactions of (Alkoxydichloromethyl)polysulfanyl Substrates with N-Methylaniline
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Reactions of (alkoxydichloromethyl)polysulfanes with N-methylaniline can be rationalized by a "carbamoyl" route where the alkoxydichloromethyl group behaves via loss of alkyl chloride as a "masked" acid chloride or by a "sulfenyl" route which reflects fragmentation of the (alkoxydichloromethyl)polysulfanyl functionality into the corresponding alkoxy(thiocarbonyl) and sulfenyl components (cf.Scheme I).Application of this and related chemistry to bifunctional substrates arising from partial or complete chlorination of 2Sm, R = Me, Et, i-Pr, and m = 1-4, has led to Ph(Me)N(C=O)Sn(C=O)N(Me)Ph, n = 2-12; Ph(Me)N(C=O)SnN(Me)Ph, n = 1-6; Ph(Me)NSnN(Me)Ph, n = 1-10; RO(C=S)Sn(C=O)N(Me)Ph, n = 2, 3; and RO(C=S)SnN(Me)Ph, n = 1-5.These families allowed a test of reversed-phase high-pressure liquid chromatography for evaluating homologies in polysulfane series.Treatment of bis sulfide (27c) with sulfuryl chloride in the presence of calcium carbonate conveniently gave distillable bis(chlorocarbonyl)trisulfane (14), whereas the same procedure with SO2Cl2 alone gave directly (chlorocarbonyl)disulfanyl chloride (12) (see Scheme VII).Higher Cl(C=O)SmCl, m = 3-5, were indicated but could not be isolated in the course of studies generalizing results on 14 to the preparation of higher Cl(C=O)Sn(C=O)Cl, n = 4-6.The new bis(carbamoyl) monosulfide 61 was obtained by the relatively slow triphenylphosphine or cyanide promoted desulfurization of bis(methylphenylcarbamoyl)disulfane (4) (eq. 1 and 4); cyanide treatment of the higher polysulfanes Ph(Me)N(C=O)Sn(C=O)N(Me)Ph for n > 3 rapidly gave disulfane directly (eq 5).
- Schroll, Alayne L.,Barany, George
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p. 1866 - 1881
(2007/10/02)
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- 10. Nucleophile Aminoalkylierung mit Thiopivalamiden
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Of the twelwe thioamides 7a-e and 8a-g, only N,N-dimethylthiopivalamide (7a) could be metallated at the CH-group in α-position to the N-atom.The reagent 9 thus obtained (Table 1) reacts in high yields with primary haloalkanes, with aldehydes, and with non-enolizable ketones (Table 2).As shown in Scheme 1, the products can be hydrolyzed to pivalamides, cleaved to secondary amines, or reduced to neopentylamines (see 18/19, 15/equation (4) and (5), and 16/20, respectively).
- Lubosch, Winfried,Seebach, Dieter
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p. 102 - 116
(2007/10/02)
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- Substituted dichlorosulfenamides and their manufacture
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Substituted dichlorosulfenamides are prepared from dichloromethyl sulfenyl chlorides by reaction with a primary or secondary amine. The substituted dichlorosulfenamides are pesticidally active and particularly useful as pre-emergent herbicides.
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