- Method of Synthesizing of N-methyl-N-trimethylsilyl trifluoroacetamide, N-methyl-N-trimethylsilyl trifluoroacetamide synthesized thereby and an electrolyte for lithium secondary battery including the same
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The present invention relates to a synthesis method of N-methyl-N-trimethylsilyl trifluoroacetamide (MSTFA), MSTFA synthesized thereby and an electrolyte for a lithium secondary battery including the same. The present invention comprises the steps of: preparing N-methyltrifluoroacetamide by using ethyltrifluoroacetate and methylamine; and obtaining MSTFA by separating and removing a precipitate from a reaction mixture obtained by introducing trimethylsilyl chloride to a mixture of N-methyltrifluoroacetamide and triethylamine. According to the present invention, since BSA (N,O-bis(trimethylsilyl)acetamide) is not used, it is relatively easy to remove a starting material and a side reaction material which are not reacted by fractional distillation. Therefore, it is possible to obtain a high-purity MSTFA of 99.0% or more and if the high-purity MSTFA of 99.0% or more is used as an additive of an electrolyte for a lithium secondary battery, it is possible to improve lifespan characteristics of a lithium secondary battery.COPYRIGHT KIPO 2015
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Paragraph 0017-0018; 0040-0042
(2016/12/16)
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- Convenient one-pot synthesis of N-substituted 3-trifluoroacetyl pyrroles
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A new one-pot strategy for the synthesis of a series of new N-substituted 3-trifluoroacetyl pyrroles is presented. These compounds were obtained by the reaction of 3-trifluoroacetyl-4,5-dihydrofuran with primary amines, which generated 1,1,1-trifluoro-3-(2-hydroxyethyl)-4-alkylaminobut-3-en-2-one intermediates. In most cases these intermediates were not stable enough to be isolated. Thus, in the same reaction vessel they were directly submitted to oxidation with PCC (Corey's reagent) to furnish 1,1,1-trifluoro-3-(2-ethanal)-4- alkylaminobut-3-en-2-ones, which under reflux underwent intramolecular cyclization to give the desired N-substituted 3-trifluoroacetyl pyrroles, in moderate yields. All of these pyrroles were tested against pan-susceptible Mycobacterium tuberculosis H37Rv and clinical isolates INH- and RMP-resistant strain and some of these compounds showed significant in vitro antimicrobial activity. Georg Thieme Verlag Stuttgart.
- Zanatta, Nilo,Wouters, Ana D.,Fantinel, Leonardo,Da Silva, Fabio M.,Barichello, Rosemário,Da Silva, Pedro E. A.,Ramos, Daniela F.,Bonacorso, Helio G.,Martins, Marcos A. P.
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experimental part
p. 755 - 758
(2009/07/18)
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- Novel compounds and methods for synthesis and therapy
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Novel compounds are described. The compounds generally comprise an acidic group, a basic group, a substituted amino or N-acyl and a group having an optionally hydroxylated alkane moiety. Pharmaceutical compositions comprising the inhibitors of the invention are also described. Methods of inhibiting neuraminidase in samples suspected of containing neuraminidase are also described. Antigenic materials, polymers, antibodies, conjugates of the compounds of the invention with labels, and assay methods for detecting neuraminidase activity are also described.
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- MCH antagonists and their use in the treatment of obesity
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The present invention discloses compounds which, are novel antagonists for melanin-concentrating hormone (MCH), as well as methods for preparing such compounds. In another embodiment, the invention discloses pharmaceutical compositions comprising such MCH antagonists as well as methods of using them to treat obesity, metabolic disorders, eating disorders such as hyperphagia, and diabetes.
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- N-Substituted trifluoroacetimidoyl halides: Synthesis and properties
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N-Substituted trifluoroacetimidoyl halides in ionic-type transformations readily undergo nucleophilic substitution and dehydrofluorination rather than 1,3-dehydrohalogenation to give nitrile ylides.
- Romanov,Vasil'ev,Zatonsky
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p. 1639 - 1644
(2007/10/03)
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- Compounds and methods for synthesis and therapy
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Novel compounds are described. The compounds generally comprise an acidic group, a basic group, a substituted amino or N-acyl and a group having an optionally hydroxylated alkane moiety. Pharmaceutical compositions comprising the inhibitors of the invention are also described. Methods of inhibiting neuraminidase in samples suspected of containing neuraminidase are also described. Antigenic materials, polymers, antibodies, conjugates of the compounds of the invention with labels, and assay methods for detecting neuraminidase activity are also described.
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- Clean nitrations: Novel syntheses of nitramines and nitrate esters by nitrodesilylation reactions using dinitrogen pentoxide (N2O5)
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In this novel nitration method dinitrogen pentoxide (N2O5) in an inert solvent is used as the nitrating agent, thereby removing the need for strong acids as the reaction medium. The N2O5 cleaves heteroatom-silicon bonds, in silylamines and silyl ethers respectively, to yield the desired energetic groupings (nitramines or nitrate esters respectively) without liberation of acids which would occur with conventional substrates (amines or alcohols). These nitrodesilylation reactions proceed cleanly and in good yield, and the scope of the reaction is illustrated by 29 examples, some of which produce high energy compounds, notably plasticisers and an energetic polymer precursor. These reactions are therefore potentially clean nitrations for the manufacture of energetic compounds which will minimise the impact of this activity on the environment in the future.
- Millar, Ross W.,Philbin, Simon P.
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p. 4371 - 4386
(2007/10/03)
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- Synthesis and reactivity of trifluorodithioacetates derived from trifluorothioacetamides
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A general synthesis of trifluorodithioacetates is described by thiolysis of trifluorothioamidium salts, derived from trifluorothioacetamides. The reactivity of these CF3 bearing C2 building blocks has been investigated towards nucleophiles and in cycloaddition reactions. Trifluorodithioacetates react with dienes to give thiopyrans and with diazo compounds to give trifluoromethyl vinyl sulphides via thiirane intermediates. With amines, trifluorodithioacetates give rise to trifluorothioacetamides while thiols add by thiophilic attack leading to new trifluoroethane dithioacetal disulphide. Two equivalents of phosphite furnish one equivalent of thiophosphate and one of phosphorylated trifluoroethane.
- Laduron, Frederic,Nyns, Claire,Janousek, Zdenek,Viehe, Heinz G.
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p. 697 - 707
(2007/10/03)
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- Unsaturated nitrogen compounds containing fluorine. Part 19. Cycloaddition reactions of 2,5-dichloro-1,1,1,6,6,6-hexafluoro-3,4-diazahexa-2,4-diene with cycloalkenes and cyclodienes
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Thermal reaction (20-70 deg C) of the dichloroazine CF3CCl=NN=CClCF3, 2, with cyclopentene (in CH2Cl2 solvent), cycloheptene, indene, acenaphthylene, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, norbornadiene and dicyclopentadiene afforded, as the major product in each case, the corresponding rearranged cycloadduct 3 containing a grouping.The direction of cycloaddition to the unsymmetrical carbocycles indene and cyclopentadiene was consistent with the reactions being LUMO (azine)-HOMO (dipolarophile) controlled.On attempted chromatographic purification on silica gel, the rearranged adducts 3 were hydrolysed to the corresponding amides 4 (-->).The cyclopentene reaction, unexpectedly, also gave the cyclopentadiene cycloadduct 3b, while from the norbornadiene reaction a hydrolysed 2:1 adduct 9 (4percent) was isolated by chromatography.Other products obtained by chromatographic separation from the 3,4-dihydro-2H-pyran reaction were the substituted azine (5) (29percent), equimolar amounts of the ketone (6) (18percent) and the chlorohydrazone (7) (18percent), possibly arising via the cycloadduct 15 of 5 and the pyran, and the hydrazone (8) (4percent), formed via 15 or by hydrolysis of the amide 4g.Treatment of amide 4d, derived from indene with ethanolic methylamine, gave the expected amino compound 21a (94percent) and CF3CONHMe (22) (91percent).In contrast, treatment of the exo-amide 4h, derived from norbornadiene with ethanolic methylamine, afforded the N-formyl compound 23 (87percent), while corresponding treatment of a mixture of the exo- and endo-amides (4h and 4i) gave the exo- and endo-amino compounds (21b and 21c) (88percent), together with compound 22 (ca. 10percent) and the azapropenylindazole 24 (ca. 5percent); compound 24 hydrolysed to 23 on storage.It is proposed that the amines 21b and 21c arose mainly via the sequence: --> (24)--> (23)-->. - Keywords: Unsaturated nitrogen compounds; Cycloaddition reactions; Dichlorohexafluorodiazahexadiene; NMR spectroscopy; IR spectroscopy; Mass spectrometry
- Abdul-Ghani, Mohammad M.,Tipping, Anthony E.
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p. 189 - 202
(2007/10/02)
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- CONTRIBUTIONS TO THE CHEMISTRY OF ORGANIC SILICON-NITROGEN-COMPOUNDS, I. SYNTHESIS OF N,N-BIS-(TRIMETHYLSILYL)AMINES
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The preparation of N,N-bis-(trimethylsilyl)amines 1 has been investigated.Three convenient methods are reported: A, Transfer of (catalytically) activated Tms-groups to amines starting from N-silylated carbonamides, B, silylation of amines with trimethylsilylchloride 5/NEt3 in the presence of TiCl4, C, silylation of primary amines 4 or mono-(trimethylsilyl)amines 16 with CF3SO3 Tms/NEt3 or TmsI/NEt3.Methods A and B are limited to the silylation of (ar)alkylamines which have no branched α-position. Key words: N,N-bis-(trimethylsilyl)amines; N,N-bis-silylamines; N-silylcarbonamides.
- Schorr, Manfred,Schmitt, Wilfried
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- Silicon-Oxygen and Acyl-Oxygen Bond Cleavage in Reactions of Sterically Hindered Organosilicon Carboxylates
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Because of steric hindrance to attack at the functional silicon centre in VsiSiMe2OCOR with R = CF3 (1a) or Me (1b), nucleophiles in MeOH can preferentially attack at the carbonyl group to give VsiSiMe2OH, rather than at Si as would be usual for less hindered silicon carboxylates.With CsF or KSCN in MeOH the products are exclusively VsiSiMe2F and VsiSiMe2NCS, respectively, whereas KOCN gives exclusively VsiMe2OH, and NaN3 gives very predominantly VsiSiMe2OH along with a little VsiSiMe2N3.The overall effectiveness of the salts is KOCN > CsF, NaN3 > KSCN; the sequence of the ease of attack of the nucleophiles at Si is F- > SCN- (>N3-?), and that for attack at carbon is OCN- > N3- > F- > SCN-.The sequence of ability of various nucleophiles to catalyse cleavage of the SiO-COR bond of (1a) in MeOH is RNH2 (R=H2N, Me, Et, HOCH2CH2, or H2NCH2CH2), OCN-, HO2-, > MeO- > N3- > Me2NH > Me3N > 4-Me2NC5H4N >> C5H5N > PhNH2, and the sequence for reactions of the less reactive (1b) is HO2- > H2NNH2 > MeO- > H2NCH2CH2NH2 > MeNH2 > HOCH2CH2NH2 > EtNH2.Except for the unexpected effectiveness of OCN-, the sequences are reasonably consistent with those established, for example, for reactions of aryl acetates in water (and also with Ritchie's nucleophilic parameters N+); it is suggested that, as in the latter reactions, the cleavage of the acyl-oxygen bond is rate-determining.Reactions of (1a) with salts MX, namely NaN3, CsF, KSCN, and KOCN in MeCN, give exclusively the corresponding species VsiSiMe2X.In the representative reactions examined the reactivities of (1a) and (1b) were very similar to those of the corresponding compounds (Me3Si)3CSiMe2OCOR.
- Ayoko, G. Adefikayo,Eaborn, Colin
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p. 1357 - 1362
(2007/10/02)
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- Conformations and Vibrational Dynamics of Six Monoalkyltrifluoroacetamides. Low-Resolution Microwave and Gas-Phase NMR Spectroscopic Studies
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Low resolution microwave spectra of six N-alkyltrifluoroacetamides (F3C(O)NHR; r = CH3, C2H5, i-C3H7, n-C3H7, i-C4H9, t-C4H9) display band series consistent with a single species having the R group oriented syn to the carbonyl moiety. 5JH-F coupling constats observed in gas- and liquid-phase NMR spectra of N-methyltrifluoroacetamide confirm this assignment.For each molecule the observed rotational constats, anomalously broad microwave bandwidths, and absence of resolvable fine structure are consistent with predicted effects of rapid intramolecular vibrational redistribution (IVR).Sufficient state density for IVR in these molecules occurs at low internal energies.
- True, Nancy S.,Ross, Brian D.
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p. 3216 - 3220
(2007/10/02)
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- The photochemical addition of N-haloamides to olefins: the influence of various factors on the competition between 1,2-addition and hydrogen abstraction
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In the photodecomposition of N-haloamides (ZCONRX) in the presence of olefins, the 1,2-addition chain competes with the hydrogen abstraction chain(s) leading to the parent amide (the quantum yields for these processes are greater than unity).The following factors were shown to have an influence on this competition as measured by the yield of 1,2-addition and the yield of parent amide in methylene chloride solutions: (i) the N-halogen (higher yields of addition with X=Cl than with X=Br); (ii) the electronegativity of Z (increase of the yield of addition as the electronegativity of Z increases); (iii) the temperature (higher yields of addition at lower temperatures, and at -70 degC, better yields of addition (>90percent, R=H) for X=Br than for X=Cl); and (iv) the size of R (dramatic decrease of the yield of 1,2-addition in going from R=H to R=CH3).Surprisingly, the presence of a scavenger for HX had no influence on the yield of 1,2-addition.Both the size and electronegativity of Z had an effect on the stereochemistry of 1,2-addition to cyclohexene.High yields of addition to a variety of olefins were obtained with N-chloroamides such as ClCH2CONHCl, C2H5OCONHCl, CF3CONHCl.Their addition to enol ethers at -70 degC led to the synthesis of α-amido acetals or ketals (aldehydes or ketones) and to an α-amido glycoside in good yields.
- Lessard, Jean,Mondon, Martine,Touchard, Daniel
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p. 431 - 450
(2007/10/02)
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- Primary and Secondary Binding Sites for Lanthanide Shift Reagents with Amides. Differential Behavior of cis vs trans Amide Isomers with LSR
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Lanthanide induced shifts (LIS) were measured for four dimethylamides, RCON(CH3)2, and four monomethyl amides, RCONHCH3, R=H, CH3, CF3 and CCl3, using Eu(fod)3 in CCl4 and benzene (C6D6) solution.Structural correlations for HCON(CH3)2 and CH3CON(CH3)2 in both solvents yield a preferred binding site for the Eu(fod)3 on one of the lone-pair orbitals of the oxygen atom, with a probable site of secondary importance on the other lone-pair orbital.The cis vs trans isomers of HCONHCH3 and CH3CONHCH3 exhibit remarkably different chemical shift behavior upon addition of Eu(fod)3.
- LaPlanche Graham, Laurine
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