Reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with alkyl(aryl)amines

The corresponding 3-alkylamino-2-sulfolenes are formed in the reaction of 3-chloro-3-sulfolene and 3-chloro-2-sulfolene with aliphatic amines. It was established that under the influence of the amines 3-chloro-3-sulfolene initially undergoes isomerization to 3-chloro-2-sulfolene with subsequent replacement of the chlorine atom by the amine component. 3-Chloro-3-sulfolene and 3-chloro-2-sulfolene are inert in the reaction with aromatic amines that have low basicities.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 892–894, July, 1979.     

Ce（SO4）2-mediated Oxidative Coupling of Primary Aromatic Amines in Water

The oxidative coupling of primary aromatic amines was investigated. Ce(SO4)2 can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substituents of primary aromatic amines. When 2,6-dimethylaniline or 2,6-diethylaniline was used as substrate, dimer, and tetramer were formed as major products. When 2,6-diisopropylaniline or 2,6-dihaloanilines was used as substrate, dimer, and trimer were formed. The mechanistic aspect was also investi...     

用电子吸收光谱和荧光光谱研究芳胺引发的光聚合机理

用紫外吸收光谱和荧光光谱分析了苯胺等芳胺引发光聚合的聚丙烯腈和聚甲基丙烯酸甲酯的端基,认为一级胺引发的聚合物端基为二级胺,二级胺引发的聚合物端基为三级胺,从而表明,一级芳胺和二级芳胺在光照下与烯类单体相互作用产生氮自由基引发聚合。     

Phytoremediation of industrial effluent containing azo dye by model up-flow constructed wetland

This study assessed the treatment of azo dye Acid Orange 7(AO7)containing wastewater by laboratory-scale up-flow constructed wetland(UFCW)with and without supplementary aeration.The supplementary aeration could effectively control the ratio of anaerobic and aerobic zones in the UFCW reactor.The results dearly show the supplementary aeration boosted the biodegradation of organic pollutants and mineralization of intermediate aromatic amines formed by AO7 degradation.     

A highly convenient,efficient, and selective process for preparation of esters and amides from carboxylic acids using Fe(3+)-K-10 montmorillonite clay

In the presence of Fe(3+)-K-10 montmorillonite clay as a catalyst, aliphatic carboxylic acids selectively produced the corresponding esters in the presence of aromatic carboxylic acids by treatment with alcohols. Both the aliphatic and aromatic carboxylic acids formed the amides by reacting with the aliphatic amines, but only the aliphatic carboxylic acids yielded the anilides by treatment with aromatic amines. The catalyst is recoverable and recyclable.     

An unusual Mannich type reaction of tertiary aromatic amines in aqueous micelles

An efficient, unusual Mannich type reaction of tertiary aromatic amines, formaldehyde and 1,3-dicarbonyl compounds is described in aqueous micelles catalyzed by boric acid to afford dialkylaminoarylated 1,3-dicarbonyls. In this unusual Mannich type reaction, tertiary aromatic amines react with formaldehyde to generate an N-alkyl-N-(4-methylenecyclohexa-2,5-dienylidene)alkylaminium intermediate (aza quinone methide), which undergoes nucleophilic addition with 1,3-dicarbonyl compounds. The reaction is highly regioselective, and exclusively para functionalized products are formed in high yields.     

芳香胺与电子受体相互作用的吸收光谱研究

芳香胺与电子受体相互作用形成的电荷转移复合物(CTC)的吸收峰位置与两者的结构有关。弱的电子受体使芳胺紫外吸收峰加宽,而强的电子受体如四氰基乙烯(TCNE)与芳胺作用产生的CTC显示新峰。受体的受电子能力越强,新峰红移越多。芳胺苯环上氨基对位的取代基给电子能力越强,氮原子上烷基取代基越多,其与受体形成的CTC的吸收峰红移也越多。     

Copper-catalyzed decarboxylative coupling reactions for the synthesis of propargyl amines

When aryl alkynyl carboxylic acids were allowed to react with amines and aldehydes in CH₃CN at 80 °C in the presence of 10 mol % CuI, the desired propargyl amines were formed in good yields. This coupling reaction demonstrated to work across a broad range of reagents including functionalized aryl alkynyl carboxylic acids, aliphatic and aromatic aldehydes, and cyclic and acyclic amines.     

New method for the synthesis of azolidones

A new method for the synthesis of azolidones by direct condensation of chloroacetic acid and aromatic amines was developed. sym-Dialkylureas are formed in the case of aliphatic amines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 87–89, January, 1978.     

Investigation of polyimides containing naphthalene units. II. Model compounds synthesis

A series of model compounds from 4-benzoyl-1,8-naphthalene anhydride and aromatic amines and diamines has been synthesized. The influence of the reaction conditions on the structure of the compounds obtained has been investigated to explain the high-temperature polycondensation reaction mechanism. It was found that at high-temperature polycondensation of 1,8-naphthalene-type anhydrides with aromatic amines, isoimides with cis and and trans structures are formed instead of amic acids. The only trans isoimides may isomerize to imide structure. © 1995 John Wiley & Sons, Inc.     

高效液相色谱法测定染色皮革中的致癌芳香胺

参照德国皮革偶氮染料中间体检测方法,用高效液相色谱法对皮革中禁用偶氮染料中间体－１８种芳香胺的定性、定量分析进行了研究。结果表明,在一定色谱条件下,除２,４－二氨基苯甲醚和２,４－二氨基甲苯回收率较低外,其它化合物的加收率均达到“ＤＩＮ５３３１６”方法的要求。     

Vicarious nucleophilic substitution in enamine derivatives of 1-hydroxynaphthalene-2,4-dicarbaldehyde

The reaction of aromatic amines with highly stable Schiff base enamines formed from an alkyl amine and 1-hydroxynaphthalene-2,4-dicarbaldehyde resulted in nucleophilic substitution of the alkyl amine with the aromatic amine in ethyl alcohol at room temperature within 1-2 min. This reactivity, regioselectivity and formation of stable derivatives are due to extra stabilization through extended conjugation in these systems.     

The chemistry of smoke suppression in polyurethane foams using thermogravimetry-infrared residue analysis

The analysis of TG residues using FT-IR has shown that at 270°C. pyromellitate esters can react with aromatic amines formed from polyurethane foam degradation to form a pyromellitimide structure. This stabilises the main smoke and toxic gas precursors formed during combustion.     

Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles

9-Chloro-1,10-anthraquinone 1-dichlorophosphorylimine formed in the reaction of 1-amino-9,10-anthraquinone with PCl₅ followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatic amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1-imine. In the case of aromatic amines, 1-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy- or 2-amino-7H-dibenzo[f,ij]isoquinolin-7-one derivatives, respectively. For preliminary communication, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1179–1184, June, 1998.     

Catalytic, highly enantioselective Friedel-Crafts reactions of aromatic and heteroaromatic compounds to trifluoropyruvate. A simple approach for the formation of optically active aromatic and heteroaromatic hydroxy trifluoromethyl esters.

A new catalytic enantioselective synthetic method for the formation of optically active aromatic and heteroaromatic hydroxy-trifluoromethyl ethyl esters is presented. This catalytic enantioselective Friedel-Crafts reaction of trifluoromethyl pyruvate with aromatic and heteroaromatic compounds is catalyzed by a chiral bisoxazoline copper(II) complex and proceeds in good yield and with high enantiomeric excess. For a series of substituted indoles, the corresponding 3-substituted hydroxy-trifluoromethyl ethyl esters are formed in up to 93% yield and 94% ee. Pyrrole and 2-substituted pyrroles also react with trifluoromethyl pyruvate in a highly enantioselective aromatic electrophilic reaction and up to 93% ee and good yields are obtained. Furanes and thiophenes give the corresponding 2-hydroxy-trifluoromethyl ethyl esters in high enantiomeric excess; however, the yields of the products are only moderate. Various types of aromatic compounds react in this catalytic reaction with trifluoromethyl pyruvate to give the aromatic electrophilic addition product in good yield. To obtain high enantiomeric excess (> 80% ee) it is necessary that aromatic amines are protected with sterically demanding protecting groups such as benzyl or allyl. This prevents coordination of the amine nitrogen atom to the catalyst, as aromatic amines having a N,N-dimethyl group probably coordinate to the catalyst, leading to a significant reduction of the enantioselective properties of the catalyst. On the basis of the experimental results and the absolute configuration of the formed chiral center, the mechanism for the catalytic enantioselective Friedel-Crafts reaction is discussed.     

Nuclear amination catalyzed by fungal laccases: reaction products of p-hydroquinones and primary aromatic amines

[reaction: see text] Nuclear amination of p-hydroquinones with primary aromatic amines was catalyzed by fungal laccases (EC 1.10.3.2) from Trametes spec. and Myceliophthora thermophila. This is the first report of laccase-catalyzed synthesis of aminoquinones. Incubation of two compounds with laccase in the presence of oxygen resulted in the formation of the corresponding monoaminated or diaminated quinones. No hydroquinonoids were formed. Observed differences in the reaction courses for different p-hydroquinones and aromatic amines with different laccases are discussed.     

液液萃取-分散液液微萃取-气相色谱-质谱联用测定纺织废水中痕量禁用偶氮染料

建立了液液萃取-分散液液微萃取-气相色谱-质谱联用技术测定纺织废水中痕量偶氮染料的方法。废水中的偶氮染料在碱性条件下经连二亚硫酸钠还原成芳香胺后,先用叔丁基甲醚液液萃取、盐酸反萃进行预浓缩及净化;再以乙腈-氯苯体系进行分散液液微萃取,气相色谱-质谱测定。对前处理条件进行了优化,考察了酸碱度及盐效应对芳香胺萃取效率的影响,结果表明：液液萃取过程中加入30 g NaCl,分散液液微萃取过程中加入1 mL 5 mol/L的NaOH调节体系至碱性才能达到较好的萃取效率。在优化的实验条件下,21种目标物均呈现良好的线性关系,其中13种芳香胺的线性范围为0.05~10 μg/L,7种芳香胺的线性范围为0.05~5 μg/L,2,4-二氨基苯甲醚的线性范围为20~100 μg/L,相关系数为0.996~0.999。20种芳香胺的检出限可达0.05 μg/L,2,4-二氨基苯甲醚检出限为20 μg/L。印染、机织、印花等实际废水加标试验表明,方法的回收率为75.6%~115.1%。该方法富集倍数高,检出限低,适用于纺织废水中痕量禁用偶氮染料的检测。     

Synthesis and comparative study of reactivities of δ-lactone,estor group and oxazinone ring in coumarin derivatives towards carbon or nitrogen nucleophiles

Condensation of methyl 7-methylcoumarin-4-acetate ( 2 ) with primary amines and with anthranilic acid gave 7-methyl-2-oxo-N-aryl-2H-[1]-benzopyran-4-acetamide ( 4a—d ) and (7), respectively. Compound 7 underwent cyclization to give 2-(7-methyl-2-oxo-2H-[1]-benzopyran-4-yl)-methyl-4H-3,1-benzoxazin-4-one ( 3 ). The reaction of 3 with aromatic amines gave the corresponding quinazolone derivatives 5 which tautomerises to the thermodynamically more stable isomer 6 , whereas its reaction with Grignard reagents and aromatic aldehydes gave 8a, 8b , and 9a, 9b , respectively.     

Noncovalent complex formation of tetratosylated resorcarene with aromatic,aliphatic, and cyclic alkyl ammonium ions: a mass spectrometric study of complex properties

The ability of tetratosylated resorcarene to form complexes with aromatic ammonium ions was investigated by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The formation of noncovalent complexes, [1+guest]⁺ and [1 · 1+guest]⁺, as observed with singly charged aromatic anilinium and phenylene aminoammonium guests. Comparison of the complexation efficiencies of the aromatic and aliphatic ammonium ions showed the importance of proton affinity of conjugate amines in complex formation. In collision‐induced dissociation experiments, gas‐phase stability was found to be lower for complexes formed with aromatic ions and this behavior was not found to depend on the proton affinity of conjugate amines. Fast oxidation of the para and ortho aminoammonium ions and complexation of these ions with tetratosylated resorcarene was observed. Copyright © 2005 John Wiley & Sons, Ltd.