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1.
Catalytic aminomethylation of pyrrole and indole with N,N,N′,N′-tetramethylmethanediamine in the presence of 5 mol % of ZrOCl2·8H2O proceeds selectively at the positions 2, 5 of pyrrole and 1, 3 of indole. Carbazole under the same conditions affords 3-formyl-9-aminomethyl derivative. The reaction in the presence of 5 mol % of K2CO3 occurs as monoaminomethylation: for pyrrole at the position 2, for indole at the position 3, and for carbazole at the nitrogen atom of the substrate. Water-soluble 1,1′-(1H-pyrrole-2,5-diyl)bis(N,N-dimethylmethanamine) exhibits a fungistatic activity with respect to phytopathogenic fungi Rhizoctonia solani.  相似文献   

2.
Reaction of N-phenyltriflamide with 1,2-dibromoethane under basic conditions in DMSO unexpectedly results in N-methyl-N-phenyltriflamide and 1,3-diphenylurea. The presumed reaction mechanism includes the formation of unstable intermediate disubstitution product TfN(Ph)CH2CH2N(Ph)Tf that suffers the the С–С bond cleavage resulting in TfN(Me)Ph and N,N′-methanediylbis(N-phenyltriflamide). The latter reacts with K2CO3 releasing two molecules of potassium triflinate and after hydrolysis of diphenylcarbodiimide PhN=C=NPh gives 1,3-diphenylurea. With propargyl bromide, N-phenyltriflamide affords N-propargyl-Nphenyltriflamide in high yield. The bromination of the latter results in a mixture of Z,E-isomers of N-(2,3-dibromoprop-2-en-1-yl)-N-phenyltriflamide which undergo dehydrobromination giving first N-(3-bromopropanedienyl)-N-phenyltriflamide and then the products of the C–N bond cleavage: N-phenyltriflamide and 3,3-dimethoxyprop-1-yne.  相似文献   

3.
The objective of this work was to explore the feasibility of using ionic liquids (ILs), namely N-ethyl-N-methylmorpholinium dicyanamide, [EMMor][DCA], (3-hydroxypropyl)-1-methylmorpholinium dicyanamide, [N-C3OHMMor][DCA], 1-(3-hydroxypropyl)-3-methylimidazolium dicyanamide, [N-C3OHMIM][DCA], 1-(3-hydroxypropyl)pyridinium dicyanamide, [N-C3OHPy][DCA], (3-cyanopropyl)pyridinium dicyanamide, [N-C3CNPy][DCA], and (3-cyanopropyl)methylpyrrolidinium dicyanamide, [N-C3CNMPyr][DCA] for the separation of ethylbenzene and styrene. The liquid–liquid equilibrium (LLE) data in ternary systems of {IL (1)?+?styrene (2)?+?ethylbenzene (3)} at T?=?298.15 K and ambient pressure is presented for the six ILs synthesized by us. The final chromatography analysis of the composition of tie-lines has shown that the studied ILs are not found in the raffinate phase and they show interesting results on the selectivity and solute distribution ratio for styrene extraction. A comparison of different ILs is presented for the studied separation problem. It was observed that the best separation selectivities were found for [N-C3CNPy][DCA] (SAv?=?2.38) and [N-C3OHMMor][DCA] (SAv?=?2.42) in comparison with other studied ILs in this work and those presented in the literature. While the data presented here are useful from a theoretical standpoint, the possibility of applications for these ILs in technological processes is questionable because of low solute distribution ratios, especially those calculated from the masses [N-C3CNPy][DCA] (βMAv?=?0.08) and [N-C3OHMMor][DCA] (βMAv?=?0.07). The experimental tie-lines were correlated with the non-random two liquid NRTL model.  相似文献   

4.
α-Silylmethylamines MeNHCH2SiMen(OMe)3?n (n=0, 2) were involved into Todd-Atherton reaction with (MeO)2P(O)H giving N-methyl-N-trimethoxysilylmethyl-and N-methyl-N-dimethyl-(methoxy)silylmethylamides of dimethylphosphoric acid. A reaction of these compounds with BF3·Et2O led to the formation of the corresponding N-methyl-N-trifluoro-and N-methyl-N-(dimethyl)fluorosilylmethylamides of dimethylphosphoric acid. (MeO)2P(O)N(Me)CH2SiF3 existed as an (O-Si)-chelate with a pentacoordinate silicon due to the occurrence of a rare and unstudied intramolecular coordinating interaction P=O → Si.  相似文献   

5.
Nitration of N,N′-bis(trimethylsilyl)carbodiimide with N2O5 or (NO2)2SiF6 afforded N-nitro-N´-(trimethylsilyl)carbodiimide, the first representative of N-nitro carbodiimides. Its further nitration led to the release of CO2, which is presumably formed in the course of N,N´-dinitrocarbodiimide decomposition. The reactions of N-nitro-N´-(trimethylsilyl)carbodiimide with nucleophiles take place both at the tri methylsilyl group (for example, with NH3) to give nitrocyanamide salts and at the carbodiimide C atom (for example, with Et2NH) to give the corresponding nitroguan idines.  相似文献   

6.
In reactions of arylsulfinyl chlorides and N-(arylsulfonyl)arylsulfinimidoyl chlorides with p-aminophenols formed N-arylthio-1,4-benzoquinone imines, evidently through a stage of N-arylsulfinyl-4-aminophenols and N-(N-arylsulfonyl)arylsulfinylimidoyl-4-aminophenols that under the reaction conditions eliminate respectively H2O and ArSO2NH2.  相似文献   

7.
Diisopropyl N-benzoyl-N-(trimethylsilyl)phosphoramidate reacts with ClCH2SiMe2Cl under mild conditions to form diisopropyl N-benzoyl-N-[(chlorodimethylsilyl)methyl]phosphoramidate (III). Diisopropyl N-methyl-N-(trimethylsilyl)phosphoramidate with ClCH2SiMe2Cl affords an N-transsilylation product which does not rearrange into diisopropyl N-[(chlorodimethylsilyl)methyl]-N-methylphosphoramidate (XV) even under severe conditions (4 h, 130°C). Compound XV was prepared by the reaction of diisopropyl phosphorochloridate with N-[(methoxydimethylsilyl)methyl]-N-methylamine followed by treatment of diisopropyl N-[(methoxydimethylsilyl)methyl]-N-methylphosphoramidate with boron trichloride. Analysis of experimental and calculated 29Si chemical shifts points to a five-coordinate silicon atom in compound III and a fourcoordinate silicon atom in compound XV. According to B3LYP calculations with due regard to solvent effects, compound III is an isomer with a C=O→Si bond. By variation of substituents at silicon, phosphorus, and carbonyl carbon atoms, chelate structures with either C=O→Si or P=O→Si dative bonds can be obtained.  相似文献   

8.
The alkylation of ambident anions of 2-(methylsulfanyl)-6-(polyfluoroalkyl)pyrimidin-4(3H)-ones with 4-bromobutyl acetate leads to concurrent formation of O- and N-(4-acetoxybutyl) derivatives. Polar aprotic solvents favor formation of the O-isomer, and weakly polar dioxane favors N-alkylation. The reaction of 2-(methylsulfanyl)-6-(trifluoromethyl)pyrimidin-4(3H)-one with an equimolar amount of 1,2-dibromoethane in polar acetonitrile gives a mixture of N,N-, O,O-, and N,O-bridged bis-pyrimidines, as well as N- and O-[2-(methylsulfanyl)ethyl] derivatives, whereas in the presence of 10 equiv of 1,2-dibromoethane the N,O-isomer is formed as the only product. The reaction in weakly polar tetrahydrofuran yields N,N- and N,O-bispyrimidines.  相似文献   

9.
Ions of Ti(III), V(III) and Cr(III) seem to be converted to the following azido complexes in acetonitrile, propanediol-1,2-carbonate and trimethylphosphate: [Ti(N3)2]+ (inTMP), Ti(N3)3 (probably distorted octahedral inAN, PDC andTMP, low solubility inTMP), [Ti(N3)4]? (probably tetragonal inAN, probably octahedral inTMP), [Ti(N3)6 3? (probably distorted octahedral inAN andPDC); [V(N3)]2+ (inAN, PDC andTMP), V(N3)3 (octahedral inAN, PDC andTMP, low solubility inTMP), [V(N3)4]? (inPDC), [V(N3)6]3? (octahedral inAN andPDC); [Cr(N3)]2+ (inTMP), [Cr(N3)2]+ (octahedral inAN andPDC), Cr(N3)3 (octahedral inAN, PDC andTMP), [Cr(N3)6]3? (octahedral inAN andPDC).  相似文献   

10.
The interaction between a water-soluble polymer polyvinylpyrrolidone (PVP) and a gemini surfactant N,N'-didodecyl-N,N,N',N'-tetramethyl-N,N'-propanediyl-diammonium dibromide (G12-3-12) was investigated by means of NMR in a D2O solution at 298 K. The critical micelle concentration (СMC), critical aggregation concentration (СAC) and adsorption reached the saturated concentration (C2) were confirmed by chemical shift and self-diffusion coefficients, respectively. The results of the relaxation time ratio (TR = T2/T1) of G12-3-12 show that the motion of the ionic head N+–CH3* proton (G6) is seriously restricted, and thus, it can be proved that the cationic head groups are situated in the hydrophilic layer of the micelle. The size of the mixed-aggregates in the G12-3-12/PVP solution is larger than pure G12-3-12 micelles according to self-diffusion coefficients, indicating that the G12-3-12 and PVP has formed mixed micelles, and ionic heads N+–CH3* become more tightly packed in the hydrophilic layer of the micelle shell. On the other hand, strong cross peaks, such as G1-P2, G1-P3, and G2-P3, appear in the 2D nuclear Overhauser enhancement spectroscopy (2D NOESY) spectra of the G12-3-12/PVP system, further indicating that the interaction sites are located between the hydrophobic tail of G12-3-12 and PVP ring.  相似文献   

11.
The reaction of N-methyl-N-trimethylsilylacetamide with silanes ClCH2SiR1R2Cl (R1, R2 = H, Me; H, Ph; Ph2) leads to the formation of (O→Si) chelate compounds with pentacoordinate silicon: N-[chloro(methyl)-silyl]methyl-, N-[chloro(phenyl)silyl]methyl-, and N-[chloro(diphenyl)silyl]methyl-N-methylacetamides. From the data of multinuclear NMR spectroscopy, the intermediates of the reaction of N-methyl-N-trimethylsilylacetamide with ClCH2SiPhHCl and ClCH2SiPh2Cl are stable in CDCl3 solution at room temperature during several days and slowly rearrange to the final (O–Si) chelate compounds.  相似文献   

12.
A four-step procedure to convert 4-(1-methyl-1-nitroethyl-1-ONN-azoxy)-3-cyanofuroxan into 3-(1-methyl-1-nitroethyl-1-ONN-azoxy)-4-aminofuroxan was developed. The pathways of transformation of the amino group of the synthesized compound into N-nitramino-, N-alkyl-N-nitramino-, N,N’-methylenediamino-, N,N’-methylene-N,N’-dinitramino-, and azo groups were studied.  相似文献   

13.
Reaction of N-ethoxycarbonyl-2-(1-cycloalken-1-yl)anilines with meta-cloroperbenzoic acid leads to the corresponding 2-[1-o-(3-chlorobenzoyl)-2-hydroxycyclopent-1-yl]anilines. 5-(2-Acetylaminophenyl)-5-oxopentanic or 6-oxohexanic acids are formed as main products in the reaction of N-acetyl-2-(1-cycloalken-1-yl)anilines with m-chloroperbenzoic acid in CH2Cl2. N-Acetyl-2-(1-cyclopenten-1-yl)-3,6-dimethylaniline is an exception in this series since its reaction stops at the stage of epoxide formation.  相似文献   

14.
Complexes of NiII with new ligands N′,N′′-bis(3-carboxy-1-oxoprop-2-enyl), 2-Amino-N-arylbenzamidine (C21H17N3O6), N′,N′′-bis(3-carboxy-1-oxopropanyl) 2-Amino-N-arylbenzamidine (C21H21N3O6) and N′,N′′-bis(3-carboxy-1- oxophenelenyl) 2-Amino-N-arylbenzamidine (C29H21N3O6) have been synthesized and characterized by elemental analyses, vibrational spectra, electronic spectra, TOF-mass spectra, magnetic susceptibility measurements, thermal studies and X-ray powder diffraction studies. Vibrational spectra indicate coordination of amide and carboxylate oxygen of the ligands along with two water molecules giving a MO6 weak field octahedral chromophore. Electronic spectra and magnetic susceptibility measurements reveal octahedral geometry for NiII complexes. The elemental analyses and mass spectral data have justified the ML complexes. Kinetic and thermodynamic parameters were computed from the thermal data using Coats and Redfern method, which confirm first order kinetics. The crystal data: C21H19N3O8 Ni is orthorhombic, space group Pmmm, a = b = 9.015360(Å), c = 10.554430(Å), V = 572.11A3; C21H23N3O8Ni is monoclinic, space group P2/m, a = 15.08206(Å), b = 5.358276(Å), c = 9.898351(Å), V = 671.58A3; C29H23N3O8Ni is tetragonal, space group P4/m, a = b = 6.328104(Å), c = 9.82213(Å), V = 393.33A3. Molecular structures of the complexes have been optimized by MM2 calculations and supported octahedral arrangements around Nickel(II) ions.  相似文献   

15.
Acetyl iodide reacted with urea and its derivatives to give the corresponding N-substituted products. The reactions of acetyl iodide with thiourea, N,N′-dimethylthiourea, imidazolidine-2-thione, and hexahydropyrimidine-2-thione resulted in the formation of S- or N-acetyl derivatives, depending on the temperature and structure of the sulfur functionality (thione or thiol). By contrast, in the reaction of acetyl iodide with N,N′-bis(3-triethoxysilylpropyl)thiourea one ethoxy group on the silicon atom was replaced by iodine with formation of N-{3-[(diethoxy)iodosilyl]propyl}-N′-[3-(triethoxysilyl)propyl]thiourea. The latter decomposed on heating to give 3-triethoxysilylpropyl isothiocyanate and silicon-containing polymer with the composition C45H97IN6O14.5S3Si6.  相似文献   

16.
Effect of the solvent nature on the kinetics of photoreduction of 3,6-di-tert-butyl-1,2-benzoquinone and its six derivatives in the presence of N,N-dimethylaniline and 4-(N,N-dimethylamino)benzaldehyde has been investigated. It has been found that for the о-quinone—amine pair, for which the free energy change of electron transfer is ΔGe > +0.11 eV, the rate constant of о-quinone photoreduction kH decreases proportionally to the increase in the acceptor number of the solvent. For the о-quinone—amine pair with ΔGe < +0.11 eV, the kH value decreases proportionally to the increase in the donor number of the solvent. It has been established that the enhancement of the electron-acceptor properties of the solvent leads to the emergence of kinetic isotope effect for the reactant pairs of 3,6-di-tert-butyl-1,2-benzoquinone and 4,5-dimethoxy-3,6-di-tert-butyl-1,2-benzoquinone with N,N-di-methylaniline (ΔGe = +0.11 and +0.22 eV, respectively).  相似文献   

17.
N-Phenylpyrazine-2-carboxamides (anilides of pyrazinoic acids with simple substituents in various positions) were previously shown to possess significant biological activities in vitro, markedly anti-mycobacterial and photosynthesis-inhibiting activity. Based on structure-activity relationships (SAR) extracted from previously published series, 25 new anilides of non-substituted pyrazinoic acid (POA), 5-CH3-POA, 6-Cl-POA, 5-tert-butyl-POA and 5-tert-butyl-6-Cl-POA were designed and synthesised. The phenyl part was substituted with simple hydrophobic substituents chosen from methyl and halogens. 5-tert-Butyl-N-(5-fluoro-2-methylphenyl)pyrazine-2-carboxamide (9), N-(3-chloro-4-methylphenyl)-5-methylpyrazine-2-carboxamide (12), 6-chloro-N-(3-chloro-4-methylphenyl)pyrazine-2-carboxamide (13) and 6-chloro-N-(5-iodo-2-methylphenyl)pyrazine-2-carboxamide (18) possessed whole cell anti-mycobacterial activity in vitro against Mycobacterium tuberculosis H37Rv with minimum inhibitory concentration (MIC) of around 10 μM. Importantly, no cytotoxicity in the HepG2 model was detected in vitro at the concentrations tested and the estimated IC50 values were in hundreds of μM, indicating promising selectivity. N-(3-Chloro-4-methylphenyl)pyrazine-2-carboxamide (11) and N-(4-chloro-2-iodophenyl)pyrazine-2-carboxamide (21) exerted significant activity against Mycobacterium kansasii with MIC 12.6 μM and 8.7 μM, respectively. No activity was detected against Mycobacterium avium. SAR were in accordance with those observed for the derivatives previously published.  相似文献   

18.
(E)-2-[2,2-Bis(tert-butyl-NNO-azoxy)-1-(methylsulfinyl)vinyl]-1-isopropoxydiazene 1-oxide reacts with boron trifluoride etherate (BF3?Et2O) producing 2-tert-butyl-N-nitro-2H-tetrazolo-5-carboxamide 4-oxide and 2-tert-butyl-2H-tetrazolo-5-carbonitrile 4-oxide but not the expected 1,2,3,4-tetrazine 1,3-dioxide derivative. This reaction direction can be explained by cationic domino cyclization, the key stage of which is coupling of the oxodiazonium ion with the geminal MeS(O) group. Structure of N-nitrocarboxamide was confirmed by X-ray diffraction analysis.  相似文献   

19.
Diels-Alder reaction of thebaine with maleimides is structurally specific and yields [7,8,3′,4′ ]-succinimido-endo-ethenotetrahydrothebaines containing N′-alkyl, cycloalkyl, aralkyl or aryl substituents. N′-[1(S)-hydroxymethyl-2-methylpropyl]-succinimido-6,14-endo-ethenotetrahydrothebaine formed in reaction of S-valinol with (7α,8α)-anhydrido-6,14-endo-ethenotetrahydrothebaine. The reduction of the adducts by LiAlH4 afforded N′-substituted 7,8-pyrrolidino-endo-ethenotetrahydrothebaines. The reduction of fused succinimides by NaBH4 resulted in the corresponding 2′α-hydroxylactam derivatives. O-Demethylation of the tetrahydrothebaine pyrrolidine derivatives effected by BBr3 afforded compounds of the tetrahydrooripavine series. The O-demethylation of tetrahydrothebaine succinimide derivatives gave rise to the corresponding 6-demethyl-endo-ethenotetrahydrooripavines. Alkylation conditions were found for N′-(4-hydroxyphenethyl)-substituted tetrahydrothebaine succinimide derivatives.  相似文献   

20.
The experimental and theoretical electron densities in complexes [6-(2,6-di-iso-propylphenyl)imino-2,4-di-tert-butylcyclohexa-2,4-diene-1-peroxo-1-olato-N,O,O′]tris(p-chlorophenyl)antimony(V), (p-Cl–C6H4)3Sb(2,6-iso-Pr–Ph–AP) · O2 (I), and [6-(2,6-dimethylphenyl)imino-2,4-di-tert-butylcyclohexa-2,4-diene-1-peroxo-1-olato-N,O,O′]tris(p-chlorophenyl)antimony(V), (p-Cl–C6H4)3Sb(2,6-Me–Ph–AP) · O2 (II), where AP is 4,6-di-tert-butyl-N-o-iminobenzoquinone dianion, are studied on the basis of high-resolution X-ray diffraction data and theoretical calculations using the density functional theory (B3LYP/DGDZVP). The nature of chemical bonds and the charge distribution on atoms are studied, and the energy of molecular oxygen addition to the Sb(V) o-aminophenolate complexes is estimated. The structures are deposited with the Cambridge Crystallographic Data Centre (CIF files CCDC nos. 1560600 (spherical refinement) and 1560601 (multipole refinement) for complex I; 1560602 (spherical) and 1560603 (multipole) for complex II).  相似文献   

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