新型噻吩基二醛及其缩氨基硫脲的合成

所合成的２，５－二（２－甲酰苯氧甲基）噻吩２及其缩氨基硫脲化合物２，５－二［（２’－甲酰缩氨硫脲基）苯氧甲基］噻吩３尚未见文献报道。对二者进行了元素分析、红外光谱、氢核磁共振谱、质谱及紫外－可见光谱表征。     

6,7-二氨基-2-(2′,4′-二甲基)苯基-1H-苯并[de]异喹啉-1,3(2H)-二酮的合成

苊经发烟硝酸硝化，稀硝酸氧化得到６，７－二硝基－１Ｈ，３Ｈ－萘并［１，８－ｃｄ］吡喃－１，３－二酮，它与２，４－二甲基苯胺缩合后用氯化亚锡还原得到６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并［ｄｅ］异喹啉－１，３（２Ｈ）－二酮。与６－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并［ｄｅ］异喹啉－１，３（２Ｈ）－二酮（Ｃ．Ｉ．溶剂黄４４，或Ｃ．Ｉ．分散黄１１）相比，其在ＤＭＦ中的最大吸收波长红移了１７．６ｎｍ，最大荧光波长蓝移了４２．７ｎｍ，荧光量子产率有所增大。     

2—噻吩乙胺的合成

２┐噻吩乙胺的合成张传新＊刘瑛孙桂荣（商丘师范高等专科学校化学系，商丘４７６０００）２－噻吩乙胺是合成预防中风的首选新药、新型抗血小板凝聚剂——噻氯匹定（Ｔｉｃｌｏｐｉ－ｄｉｎｅ）的重要中间体。据已有文献报道［１，２］，其合成工艺复杂，反应条件苛刻，...     

α－萘甲酸的简便合成

α－萘甲酸的简便合成作为显影剂、感光剂等的原料，萘甲酸有着重要的用途。迄今为止文献报道的萘甲酸的主要合成法可分为两大类：１．在Ｐｄ络合物存在下萘与ＣＯ和Ｏ２反应［１］；２．在Ｃｏ－Ｍｎ－Ｂｒ系催化剂存在下甲基萘与Ｏ２反应［２］。这些反应一般在较高的温...     

1，3－二β－萘甲酰基杯［4］芳烃的荧光光谱与光二聚反应

本文合成了含荧光发色团的杯芳烃衍生物１，３－二β－萘甲基杯［４］芳烃１，研究了它在极性溶剂及非极性溶剂中的光物理与光化学行为，并通过萘发色团荧光及光二聚反应研究了杯［４］芳烃衍生物的构象。     

新席夫碱萃取剂（HPMαFP）_2EN的合成及其在反相纸色谱中应用的研究

合成了新席夫碱萃取剂Ｎ，Ｎ’－双［（１－苯基－３－甲基－５－氧－４－吡唑啉基）α－呋喃次甲基］乙二亚胺［（ＨＰＭａＦＰ）_２ＥＮ］。通过元素分析、红外光谱、核磁共振谱、质谱和紫外光谱研究，确定了其结构及有关性质。以这种萃取剂为固定相并采用反相纸层析色谱法首次研究了试剂对稀土离子的分离性能。试剂在ｐＨＯ．２～１．２时，可实现某些多组分混合稀土离子体系的分离。     

5,6—二氨基—1,3—萘二磺酸的合成

５，６－二氨基－１，３－萘二磺酸是合成新型防光晕染料的中间体。防光晕染料的作用是接受感光材料曝光时进入乳剂层未被吸收而透过的光线，消除反射和漫反射现象，明显提高影像的清晰度和防止光晕的产生［１］。以５，６－二氨基－１，３－萘二磺酸为原料合成的新型防光晕染料是使感光材料解像力和清晰度得到提高的一类有机水溶性染料，在彩卷、电影电视胶片、半导体激光成像、红外感光材料等方面有广泛的应用［２］。合成５，６－二氨基－１，３－萘二磺酸的较好方法是以氨基Ｊ酸（６－氨基－１，３－萘二磺酸）为原料和重氮化合物偶联生…     

气相催化法合成氯化亚砜

气相催化法合成氯化亚砜唐杜陵，张曼征，黄文丰，周忠信，李建新（湖北省化学研究所．武汉４３００７４）氯化亚砜［１］在有机合成上很重要，如氯化［２］、羧酸酰氯化［３］并醇解或氨（胺）解生成酯或酰胺，胺环化生成噻唑［４］和噻吩［５］等化合物，氯磺化及硫化物...     

苯并硫杂蒽类荧光染料的合成

以４－溴－１，８－萘酐为原料，经亚胺化、乌尔曼缩合、Ｐｓｃｈｏｒｒ闭环等反应，合成了Ｎ－羟乙基－苯并硫杂蒽－３，４－二甲酰亚胺（１）和７Ｈ－苯并咪唑［２，１－ａ］苯并硫杂蒽－７－酮及异构体（Ⅱ和Ⅱ＇），测定了它们的吸收光谱和荧光发射光谱以及光化学稳定性。塑料ＡＢＳ经它们着色后，荧光效果非常明显。     

苯并硫杂蒽类荧光染料的合成

以４－溴－１，８－萘酐为原料，经亚胺化、乌尔曼缩合、Ｐｓｃｈｏｒｒ闭环等反应，合成了Ｎ－羟乙基－苯并硫杂蒽３，４－二甲酰亚胺（１）和７Ｈ－苯并咪唑［２，１－ａ］苯并硫杂蒽－７－酮及异构体（Ⅱ和Ⅱ＇），测定了它们的吸收光谱和荧光发射光谱以及光化学稳定性。塑料ＡＢＳ经它们着色后，荧光效果非常明显。     

DETERMINATION OF DIBENZO[A,L]PYRENE AND OTHER FJORD-REGION PAH ISOMERS WITH MW 302 IN ENVIRONMENTAL SAMPLES

Polycyclic aromatic hydrocarbons (PAHs) occur in the environment as complex mixtures including compounds with mutagenic and carcinogenic activity. The PAH profile routinely determined in environmental samples at present encompasses isomers with molecular weight (MW) not greater than 300. However, PAHs with MW >300 have been demonstrated for several matrices to contribute up to 50% of the total activity when tested for carcinogenicity in experimental animals. Recent studies indicate that among the dibenzopyrenes with MW 302 dibenzo[a,l]pyrene, possessing a fjord region, is by far the most carcinogenic PAH hitherto identified. To further elucidate the environmental relevance of this compound we have applied the isotope dilution GC/MS technique as analytical procedure to determine this compound and the related fjord region PAH naphtho[1,2-a]- and naphtho[1,2-e]pyrene in various matrices. Identification was based on comparison of UV and mass spectra as well as retention times of authentic reference materials. Determination of these PAHs was achieved after clean-up by several chromatographic steps including fractionation on a modified TABA-silica gel column. Quantitative data for matrices such as two cigarette smoke condensates, motor vehicle exhaust condensate (Otto-type engines), and tar-cork are reported. Based on toxic equivalent factors the relative contribution of dibenzo[a,l]pyrene (5.4–42.3%) to the total carcinogenic activity of a PAH profile will be discussed comprising 14 selected isomers (benzo[b]naphtho[2,1-d]thiophene; cyclopenta[cd]pyrene; benz[a]anthracene; chrysene/triphenylene; sum of benzo[b]-, benzo[k]-, and benzo[j]fluoranthene; benzo[a]pyrene; indeno[1,2,3-cd]pyrene; dibenz[a,h]anthracene; benzo[ghi]perylene; anthanthrene; dibenzo[a,l]pyrene determined in these matrices.     

Solvent-free,mild, facile,and rapid one-pot three-component synthesis of some novel imidazo[2,1-b]naphtho[1,2-e][1,3] thiazin-10-ones using p-TSA

Novel [2,1-b]naphtho[1,2-e][1,3]thiazin-10-ones were synthesized in 63–89% yield via a three-component reaction of an aromatic aldehyde, β -naphthol, and thiohydantoin in the presence of 10 mol% p-toluene sulfonic acid under solvent-free conditions. This is the first protocol to be reported for the synthesis of the title compounds. The significant features of the present protocol are simplicity, high yields, eco-friendliness, and convenient purification that does not require chromatography.     

Intermediates and dyes for synthetic-polymer fibres. Benzo [b]naphtho [3,2-d]thiophene-6,7-dicarboxylic acid imides and benzimidazo dibenzothio

Benzo[b]naphtho[2,3-d]thiophene-6,7-dicarboxylic anhydride (I) is obtained y Pschorr intramolecular cyclisation of 2-(2-aminophenylthio)-1,8-naphthalic anhydride. Condensation with alkylamines and arylamines gives the corresponding imides, which colour synthetic-polymer fibres in greenish-yellow hues, and reaction with o-phenylenediamines affords the isomer mixtures of derivatives of benzimidazo[1,2-b]-dibenzothiopheno-[4,3,2-d,e] isoquinolin-10-one and of benzimidazo-[2,1-a] dibenzothiopheno-[4,3,2-d,e]isoqumolin-10-one, which dye polyester fibres bright reddish-orange. Both series of dyes have excellent fastness to light and sublimation. The colour of the dyes is discussed in relation to the isomeric compounds derived from benzo[k,1]thioxanthene-3,4-dicarboxylic anhydride (III) and from benzo[d]naphtho[1,2-b]thiophene-9,10-dicarboxylic anhydride (II). The synthesis of the individual isomers resulting from reaction of I with o-phenylenediamine is reported and their absorption maxima related to polar factors operative within each isomer.     

Massenspektrometrische Fragmentierung von 4-substituierten 5-Hydroxynaphth[2,1-d]1,3-oxathiol-2-onen

Mass Spectrometric Fragmentation of 4-Substituted 5-Hydroxynaphth[2,1-d]1,3-oxathiol-2-ones The mass spectra of 5-hydroxynaphth[2,1-d]1,3-oxathiol-2-ones 1a-1x have been studied. They show characteristic fragmentations with participation of neighbouring groups. Investigations of isotopically labelled 4-alkyl and 4-acyl derivatives give evidence for the formation of cyclic ionic structures.     

Synthesis of Dihydrodiol Metabolites of Naphtho[8,1,2- GHI ]Chrysene and Dibenzo[ C,MNO ]Chrysene

Syntheses of naphtho[8,1,2- ghi ]chrysene (naphtho[1,2- e ]pyrene, N[ e ]P) 1 , dibenzo[ c,mno ]chrysene (naphtho[1,2- a ]pyrene, N[ a ]P) 2 and their dihydrodiol metabolites are described. The hydrocarbons N[ e ]P 1 and N[ a ]P 2 and their fjord region dihydrodiols 12 and 19 were synthesized using a Suzuki cross-coupling reaction followed by the appropriate manipulation of the functional groups. The K-region cis dihydrodiols of N[ e ]P-4,5-diol 20 , N[ a ]P-4,5-diol 23 , N[ a ]P-7,8-diol 24 were obtained by OsO 4 oxidation. The cis diols thus obtained were first converted to the corresponding quinones with pyridinium chlorochromate and, finally, to the desired trans dihydrodiols 22 , 27 , and 28 by NaBH 4 reduction. The mixture of trans N[ a ]P-4,5- and 7,8-dihydrodiols was separated by high-performance liquid chromatography.     

Synthesis and Dyeing Examinations of 7H, 9H-Quinazolino [3,2-b] benz [d,e] isoquinolin-7-one

The synthesis and application of a representative compound of the new group of disperse dyes derived from 7H,9H-quinazolino[3,2-b] benz[d, e] isoquinolin-7-one (II) have been investigated. The MS, IR and NMR spectra of compound (II) are analysed, and its dyeing and colour properties are compared with 7H-benzimidazo-[2,1-a] benz [d.e] isoquinolin-7-one (I).     

IDENTIFICATION OF THE C30H16 POLYCYCLIC AROMATIC HYDROCARBON BENZO[cd]NAPHTHO[1,2,3-lm]PERYLENE AS A PRODUCT OF THE SUPERCRITICAL PYROLYSIS OF A SYNTHETIC JET FUEL

Using high-pressure liquid chromatography (HPLC) with ultraviolet-visible (UV) diode-array and mass spectrometric detection, we have analyzed the products of a Fischer-Tropsch synthetic jet fuel pyrolyzed, under supercritical conditions, at 710°C and 42 atm. An eight-ring polycyclic aromatic hydrocarbon, benzo[cd]naphtho[1,2,3-lm]perylene, has been unequivocally identified among the product components by its characteristic ultraviolet-visible absorbance spectrum. First, the unknown product component's HPLC elution behavior and UV absorbance characteristics indicated that it was a planar benzologue of dibenzo[cd,lm]perylene, having a high length-to-breadth ratio. Next, the mass spectrum established the isomer family of the unknown compound as C₃₀H₁₆. The UV absorption spectrum was then progressively analyzed with different solvents to achieve the final identification of benzo[cd]naphtho[1,2,3-lm]perylene. Benzo[cd]naphtho[1,2,3-lm]perylene has never before been reported as a product in any combustion or pyrolysis study.     

Pikosekunden-Absorptionsspektroskopie an Pseudoazulenen

Picosecond Absorption Spectroscopy of Pseudoazulenes 2-Phenylcyclopenta[b] [1] benzopyran 1 and 6-phenylindeno[2,1-b][1]benzopyran 2 are excited by second harmonic or two photon absorption of the fundamental wave of a mode-locked ruby laser and the time dependence of the spectra of the second excited singlet levels are probed. The lifetime of these states are found to be (130 ± 10) ps for 2 and ⩽20 ps for 1 .     

Condensation of 4-phenyl-3,5-dicarboethoxycyclopentane-1,2-dione with primary amines

Condensation of the title compound ( 1 ) with primary aromatic amines gave the dianilides ( 2 ), which cyclized to cyclopenta[1,2-c:4,3-c′]diquinolines ( 3 ). Treatment of 1 with o-phenylenediamine or 2,3-diaminopyridine afforded cyclopenta[2,1-b:3,4- b ′]bis[1,5]benzodiazepine ( 4 ) and bis[1,5]pyrido[b]diazepine derivative ( 5 ), respectively. Whereas, with o-aminophenol a mixture of 2c and cyclopenta[2,1- b :3,4- b ′]bis[1,5]benzoxazepine ( 7 ) was obtained. Pechmann reaction of 1 with m-cresol gave the bis[1]benzopyrane ( 9 ). Mannich reaction of 1 with benzylamine afforded the 3-azabicyclo[3.2.1]octane system ( 10 ).     

Oxidative Kupplung CH-acider Verbindungen mit p-Phenylendiaminen. VII [1]. Synthese und oxidative Kupplung von 5-Hydroxy-naphth[2,1-d]1,3-oxathiol-2-onen

Oxidative Coupling of CH-acid Compounds with p-Phenylenediamines. VII. Synthesis and Oxidative Coupling of 5-Hydroxy-naphth[2,1-d] 1,3-oxathiol-2-ones 5-Hydroxy-naphth[2,1-d]1,3-oxathiol-2-ones with different substituents 1 – 21 were synthesized using the following procedures: Condensation of substituted naphthoquinones-1,4 with thiourea (A); electrophilic substitution of 5-hydroxy-naphth[2,1-d]1,3-oxathiol-2-one (B); Fries-reaction of 5-acyloxy- and 5-N-phenylcarbamoyloxy-naphth[2,1-d]1,3-oxathiol-2-ones (C). Oxidative coupling of the compounds with N,N-diethyl-quinone-1,4-diimine yielded thiazine dyes.