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1.
Thiocarbamoylation of aliphatic amines with tetramethylthiuram disulfide (TMTD) was studied. The reactions were established to proceed according to a two-stage mechanism. In the first stage,S-(thiocarbamoyl)thiohydroxylamines and dimethyl dithiocarbamates are formed. The latter exist in equilibrium with dimethyldithiocarbamic acid, which can undergo decomposition to give dimethylamine and carbon disulfide. In the second stage, several competitive transformations of these intermediates into the final products occur,viz., (1) the reactions of CS2 with primary amines on heating (70–110 °C) yield mixed and symmetrical thioureas and the reactions of CS2 with secondary amines give symmetrical dithiocarbamates, and (2) insertion of CS2 intoS-(thiocarbamoyl)thiohydroxylamines affords thiuram disulfides. Thiuram disulfides formed from primary amines decompose to give isothiocyanates, which are converted into thioureas by condensation with amines, whereas thiuram disulfides which are obtained in the reactions with secondary amines and which cannot form thioureas react with amines analogously to TMTD. For Part 4, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 334–342, February, 2000.  相似文献   

2.
Formylation of N-phthaloylglycine with the POCl3-DMF system afforded N,N,N′, N′-tetramethyl-2-(N-phthaloyl)vinamidinium perchlorate (2). X-ray diffraction study showed that molecule 2 is planar and contains two equivalent nitrogen atoms in the three-carbon vinamidinium fragment. Salt 2 undergoes transamination with primary aromatic amines to give the corresponding bis-azomethines. The reactions with hydrazines produce substituted 4-aminopyrazoles. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 832–835, May, 2006.  相似文献   

3.
Reactions of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with aliphatic amines and sodium hydroxide resulted in removal of one N-oxide oxygen atom and formation of 4-alkylamino- or 4-hydroxy-substituted 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1-oxides, respectively. The title compound reacted with ammonia and methylamine in the presence of MnO2 with conservation of both N-oxide moieties, and the products were 4-amino- and 4-methylamino-5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxides. The reactions with aromatic amines were accompanied by removal of both N-oxide oxygen atoms with formation of N-aryl-5-nitrospiro[benzimidazole-2,1′-cyclohexane]-4-amines. In the reactions of 5-nitrospiro-[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with sodium azide and aromatic amine hydrochlorides nucleophilic replacement of the 5-nitro group by azido or arylamino occurred, in the first case both N-oxide fragments being conserved. The reactions with aromatic amine hydrochlorides afforded N-aryl-5-nitrospiro[benzimidazole-2,1′-cyclohexan]-4-amine 1-oxides. Treatment of 5-nitrospiro[benzimidazole-2,1′-cyclohexane] 1,3-dioxide with sodium cyanide led to the formation of 5-oxo-3,5-dihydrospiro[benzimidazole-2,1′-cyclohexane]-4-carbonitrile 1-oxide.  相似文献   

4.
Reaction of secondary amines (morpholine and piperidine) with sulfur and iodine affordedN,N′-thiobisamines in good yields. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1891–1892, October, 1997.  相似文献   

5.
Kinetics of the reaction of urethane formation from oligopolyols with primary and secondary hydroxy groups and the influence exerted on their interaction by products formed in the reaction of N,N,N′,N′-tetrakis-(-2-hydroxypropyl)-ethylenediamine with an isocyanate were studied. Samples of high-strength polyurethane composites based on mixtures of oligoetherpolyols and the oligomeric diamine were obtained. These samples approximately twice surpass in strength materials based on oligoepoxides. The working capacity of the samples under severe climatic conditions was demonstrated.  相似文献   

6.
The equilibrium constants, K 2, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ+, with several amines {triethylamine (TEA), N,N,N,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF) and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K 2 value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K 2 value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The change in the K 2 value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of PQ+ (the deprotonated product of PHQ+). The effect of THF on the K 2 value is consistent with that of the peak wavelength of the absorption spectrum of PQ+. The change in the K 2 value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The effect of EtOH on the K 2 value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities were adjusted to that of EtOH. The K 2 value increased with increasing vol-% of EtOH because of the stabilization of PQ+ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of PQ+ demonstrated a blue shift as the vol-% of EtOH increased.  相似文献   

7.
5-(4-Chlorophenyl)- and 5-phenylfuran-2(3H)-ones reacted with guanidine carbonate at the methylene group in the unsaturated lactone molecule, leading to the formation of 4-(2-aryl-5-oxo-2,5-dihydrofuran-2-yl)-5-aryltetrahydrofuran-2-ones, while 5-(4-methylphenyl)furan-2(3H)-one under analogous conditions gave rise to N,N′-bis[4-(4-methylphenyl)-4-oxobutanoyl]guanidine. The reactions of 5-arylfuran-2(3H)- ones with thioacetamide afforded 4-aryl-N-{1-[5-aryl-2-oxo-2,3-dihydrofuran-3-ylidene]ethyl}-4-oxobutanamides. The corresponding N-(4-aryl-4-oxobutanoyl)thioureas were obtained by heating 5-arylfuran-2(3H)-ones with thiourea.  相似文献   

8.
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-hydroxyphenyl)-4,4-dichloro-2-buten-1-ones The heterocyclization of the initial ketones into pyrazole structure was not observed, and the reaction with hydrazine hydrate provided bispyrazole products, N,N′-bis(5-thien-2-yl)- and N,N′-bis[5-(4-hydroxyphenyl)-1H-pyrazol-3-ylmethylene]hydrazines.  相似文献   

9.
The reactions of primary amines withN,N-bis(trimethylsilyloxy) enamines can give products of both mono-and bis-α-oximinoalkylation of primary amines. The steric restrictions in both reactants substantially retard bis-α-oximinoalkylation. A general method for the synthesis of α-amino-substituted oximes from primary amines and bis-silyl derivatives of aliphatic nitro compounds was developed. For Part 1, see Ref. 1. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1265–1272, July, 2000.  相似文献   

10.
N-(2-Vinyloxyethyl)-N′-cyclohexylidene-1,2-ethylenediamine and N,N′,N″-tris-[2-(2-vinyloxyethyl)-aminoethyl]hexahydro-1,3,5-triazine were synthesized by reactions of N-(2-vinyloxyethyl)-1,2-ethylenediamine with cyclohexanone and formaldehyde with yields of 91 and 90%, respectively. The IR and 1H and 13C NMR spectral data and the results of studying their anticorrosion properties are given.  相似文献   

11.
Thiomethylation of heteroaromatic amines with formaldehyde-hydrogen sulfide gave linear and cyclic heteroatom compounds: N,N′-[methylenebis(sulfanediylmethylene)]bishetarenamines and 5-hetaryl-1,3,5-dithiazinanes. N,N′-[Methylenebis(sulfanediylmethylene)]bishetarenamines were found to undergo transformation into 5-hetaryl-1,3,5-dithiazinanes by the action of CH2O-H2S. Transamination of 5-methyl-1Hpyrazol-3-amine, 6-nitro-1,3-benzothiazol-2-amine, and 5-bromopyridin-2-amine with 5-methyl-1,3,5-dithiazinane selectively afforded the corresponding 5-hetaryl-1,3,5-dithiazinanes.  相似文献   

12.
The extraction of uranyl nitrate with the novel extractant N,N′-dimethyl-N,N′-dioctylmalonamide (DMDOMA) from aqueous sodium nitrate (and nitric acid) was investigated. The extraction mechanism was established and the stoichiometry of the main extracted species confirms to UO2(NO3)2 · DMDOMA. The IR spectral study was also made of the extracted species. Methyl substituent improves the extraction ability of malonamide for U(VI) compared with that of N,N,N′,N′-tertrabutylmalonamide (TBMA).  相似文献   

13.
A Mannich reaction of 4-amino-3-R-furoxans with paraformaldehyde in 10% aqueous H2SO4 led to the high yields of N,N′-bis(3-R-furoxan-4-yl)methylenediamines, whose structure (using R = Me as an example) was confirmed by X-ray diffraction study. The N,N′-bis-(3-R-furoxan-4-yl)methylenediamines obtained were nitrated to N,N′-dinitro-N,N′-bis-(3-R-furoxan-4-yl)methylenediamines upon the action of 100% HNO3 in acetic or trifluoroacetic anhydride.  相似文献   

14.
Effects of several heterocyclic compounds containing nitrogen, trisubstituted amines and diamines and molecules based on N,N,N′,N′,N′′,N′′-substituted-[1,3,5]triazine-2,4,6-triamine in preventing thermooxidative degradation of styrene–butadiene rubber (SBR) have been studied using non-isothermal DSC measurements. The aim of this study was to determine and compare the stabilizing effect of individual compounds and to select the structures with the best antioxidative properties. In order to compare the stabilizing effect of the compounds, induction periods and protection factors have been calculated. The treatment of the experimental data was carried out using a method based on a non-Arrhenian temperature function. The results show that better antioxidative properties can be assigned to heterocyclic compounds. On the other hand, molecules containing triazine structures exhibited only negligible stabilizing effect on SBR at lower temperatures and even destabilizing effect at higher temperatures.  相似文献   

15.
3,5,7,11-Tetraazatricyclo[7.3.1.02,7]tridec-2-ene derivatives were prepared in one-pot manner from N-methylmorpholinium 6-amino-3,5-dicyano-4-spiro(1′-cycloalkane)-1,4-dihydropyridine-2-thiolates, primary amines, and formaldehyde in 70–88% yields. The structure of 5,11-dibenzyl-13-spiro(1′-cyclopentane)-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene-1,9-dicarbonitrile was determined by X-ray diffraction analysis.  相似文献   

16.
Copper(I) complexes of thioureas having the general formulae [CuLnBr] and [CuLn]Br [where, n = 1 − 4 and L = thiourea (Tu), N-methylthiourea (Metu), N-ethylthiourea (Ettu), N,N-dipropylthiourea (Dprtu), N,N-dibutylthiourea (Dbtu) or N,N-diphenylthiourea (Dphtu)] were prepared and characterized by elemental analysis, IR, and NMR (1H and 13C) spectroscopy. The crystal structure of one of them, [Cu(Metu)4]Br (1), was determined by X-ray crystallography. The X-ray structure of 1 describes a tetrahedral geometry around copper(I) with all Metu ligands binding through sulfur atoms. An upfield shift in the 13C NMR and downfield shift in the 1H NMR spectra are consistent with the thione coordination to copper(I). Antimicrobial activities of the complexes were evaluated by the minimum inhibitory concentration method. The results showed that only [Cu(Ettu)3Br] was effective in inhibiting the growth of all the tested organisms (gram-positive, gram-negative bacteria, and Candida sp.), while the other complexes were not effective against all the organisms.  相似文献   

17.
The iminium salt, N,N-dimethyl-N-[2-(2-phenyl-4H-l-benzopyran-4-ylidene)ethylidene] imin-ium perchlorate ( 3 ), reacts with secondary amines by exchanging the dimethylimino group for the added amine. Primary amines also reacted with 3 in the same manner. The bis iminium salts, N,N,N',N'-tetramethyl-N,N'-[2-(2-phenyl-4H-l-benzopyran-4-ylidene)-1,3-propanediylidene]-bis(immium perclilorate) ( 4 ) and the corresponding thiapyran derivative ( 5 ), react with ammonia to give 5-dimethylamino-2-phenyl-5H-1-benzopyrano[3,4-c]pyridine ( 10 ) and the thia analog 11 . The reactions of 4 and 5 with primary amines give 3-alkyl-5-dimethylamino-2-phenyl-5H-l-beiizopyrano[3,4-c]pyridinium perclilorate salts or the corresponding thiapyrano compounds. Compounds 4 and 5 react with secondary amines by exchanging the dimethylimino groups with the secondary amine and addition of the amine at the 2-position of the pyran or thiapyran ring.  相似文献   

18.
Summary. 3,5,7,11-Tetraazatricyclo[7.3.1.02,7]tridec-2-ene derivatives were prepared in one-pot manner from N-methylmorpholinium 6-amino-3,5-dicyano-4-spiro(1′-cycloalkane)-1,4-dihydropyridine-2-thiolates, primary amines, and formaldehyde in 70–88% yields. The structure of 5,11-dibenzyl-13-spiro(1′-cyclopentane)-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene-1,9-dicarbonitrile was determined by X-ray diffraction analysis.  相似文献   

19.
Reactions ofN,N-bis(chloromethyl)amides withN,N′-diacyl derivatives of ethylenediamine (oro-phenylenediamine) result in formation of the corresponding 1,3,5-triacylated perhydro-1,3,5-triazepines (or their benzoanalogs) or 1,3-diacylated imidazolidines (or their benzoanalogs). Reactions ofN,N-bis(chloromethyl)amides withN,N′-ditosylated trimethylenediamine occur in a similar way. The direction of the reactions depends on the type of the acyl substituents and the strength of the bases. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2270–2273, November, 1998.  相似文献   

20.
    
Several mixed ligand complexes of nickel(II) and cobalt(II) acetylacetonates with N-substituted thioureas such as ortho, meta and para chlorophenyl, parabromophenyl and orthotolyl thioureas and N,N′-substituted thioureas such as N-benzoyl N′-ethyl thiourea, N-benzoyl N′-phenyl thiourea, N-benzoyl N′-o-chlorophenyl thiourea, N-benzoyl N′-o-tolyl thiourea, N-benzoyl N′-o-methoxyphenyl thiourea, N-benzoyl N′-cyclohexyl thiourea, N-benzoyl N′-2,5 dimethoxyphenyl thiourea, N-benzoyl N′-2,5 diethoxyphenyl thiourea, N-benzoyl N′-β-hydroxyethyl thiourea, N-benzoyl N′-furfuryl thiourea, N-benzoyl N′-orthohydroxyphenyl thiourea and N-phenyl N′-orthomethoxyphenyl thiourea, have been synthesized and characterized on the basis of elemental analysis, conductivity, molecular weight determination and magnetic moments. The nature of the bonding and the structure of the complexes have been proposed from the infrared and electronic spectral studies.  相似文献   

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