Condensation of 7 H -Benzo[ de ]naphthacene-7-one (9,10-Dibenzanthrone)

We have synthesized undecacyclic aromatic hydrocarbons using condensation of dibenzoanthrones. For example, dibenzo[ a,o ]dinaphtho[3,2,1- cd ;1,2,3- lm ]perylene, diphenanthra[1,2,3- cd ; 3,2,1- lm ]perylene and diphenanthra[2,3,4- cd ;4,3,2- lm ]perylene were produced from 5,6-, 8,9- and 10,11-dibenzoanthrones, respectively. In the present study, we have extended our work and aimed to synthesize new undecacyclic aromatic hydrocarbons by the use of 9,10-dibenzoanthrone (7 H -benzo[ de ]naphthacene-7-one) as a starting material. 9,10-Dibenzoanthrone was prepared by the cyclization of 1,2'-dinaphthylketone in aluminum chloride anhydride and sodium chloride, and the structure was confirmed by NMR measurements. It dissolves into ethanol and crystallizes in pale yellow needles; its melting point is 198.2-199.3°. The condensation of 9,10-dibenzoanthrone should give undecacyclic aromatic hydrocarbons such as benzo[ vwx ]naphtha[12,1,2- cde ] hexaphene.     

Synthesis of a few cyclothiadiazanones and aminosulfonyl benzamides from saccharin

Saccharin is hydrolyzed with two different acids to yield 1,2-di-acid. The di-acid, on chlorination with phosphorous pentachloride, gave 2-chlorosulfonylbenzoyl chloride. The 2-chlorosulfonylbenzoyl chloride on hydrazinolysis gave benzothiadiazinetrione, while with phenyl hydrazine it selectively yielded 2-phenylbenzothiadiazinetrione. 2-chlorosulfonoylbenzoyl chloride with different aromatic 1,2-diamines resulted in dibenzothiadiazocine derivatives. Electron-donating groups in the diamine facilitate while the electron-withdrawing groups retard the cyclization. However, aliphatic diamines, aniline and substituted anilines readily gave acyclic aminosulfonyl carboxybenzamides on condensation with 2-chlorosulfonylbenzoyl chloride. The di-acid and anhydride did not react with either hydrazine/phenyl hydrazine or amines to give the above products. However, when its ester derivative, isopropyl-2-chlorosulfonylbenzoate, condensed with hydrazine, it gave benzothiadiazinetrione. But the ester failed to react with phenyl hydrazine. All the condensation reactions were carried out at room temperature.     

Pyrolysis of phenolic resins. IV.

Thermoset resins were made from benzene, naphthalene, phenanthrene, anthracene, or pyrene by condensation with p-xylylene dichloride in presence of stannic chloride. The extent of reaction, consequently the crosslink density, was controlled by measurement of the HCl evolved. The absence of oxidation was confirmed by infrared spectroscopy. On pyrolysis at 500, 1000, and 1200°C. in vacuo (after Madorsky) it was found that the yield of char was directly related to the number fraction of carbon atoms in the aromatic nucleus used. Benzene was anomalous, and all resins gave lower char yields than standard phenol formaldehyde resins.     

5,6-二氢-4H-6-甲基噻嗯并[2,3-b]噻喃-4-酮-2-磺酰胺的合成

以丁烯酸和2-巯基噻吩为原料,经加成缩合制得3-(2-噻吩硫基)丁酸(2);以氯化亚砜氯化,三氯化铝催化环合得5,6-二氢-4H-6-甲基噻嗯并[2,3-b]噻喃-4-酮(3);再经磺化、氯化、氨解反应合成得5,6-二氢-4H-6-甲基噻嗯并[2,3-b]噻喃-4-酮-2-磺酰胺(1)。其中经均匀设计优化了环合反应条件为:n(2)∶n(氯化亚矾)∶n(三氯化铝)=1∶3∶1.5,于20℃反应2h。以2-巯基噻吩计,1合成总收率为30.49%,结构经IR、MS、1HNMR确证。     

Polycyclische aromatische Kohlenwasserstoffe in nativen pflanzlichen Ölen

Polycyclic Aromatic Hydrocarbons in Native Vegetable Oils 18 polycyclic aromatic hydrocarbons have been isolated from different native vegetable oils by liquid-liquid-extraction, column chromatography on silica gel and GPC on Biobeads S-X3. The PAHs were identified by capillary gas chromatography - mass spectrometry (MIS). High PAH-contamination has been detected in olive oils. Remarkable amounts of light PAHs were observed for Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benz(a)anthracene, and Chrysene.     

SYNTHESIS OF 1-BROMO-6H-BENZO[CD]PYREN-6-ONE

1-Bromonaphthanthrone (1-bromo-6H-benzo[cd]pyren-6-one), a useful starting material for the synthesis of undecacyclic aromatic hydrocarbons, was synthesized by means of glycerol condensation of 1-bromopyrene. The structure of the synthetic product was confirmed by NMR measurements and the ¹ H and ¹³ C chemical shifts were completely assigned. Although the synthetic method provided three possible isomers, 1-, 3-, and 5-bromonaphthanthrone, only 1-bromonaphthanthorone was obtained as a final product. An explanation for the regioselectivity was given in terms of the charge distribution obtained by molecular orbital calculations.     

氯苯嘧啶醇的合成

叙述以邻氯苯甲酰氯为起始原料,与氯苯、5-嘧啶锂等反应合成杀菌剂氯苯嘧啶醇的方法,总收率(以邻氯苯甲酰氯计)为69.6%,产品含量为95%。     

Synthesis of some new heterocyclic systems derived from 2-acetylbenzimidazole

The named compound was reacted with thiosemicarbazide and/or semicarbazide to produce the corresponding condensation products II and V respectively. Reaction of II with chloroacetic acid in ethanol containing anhydrous sodium acetate yielded III. Condensation of III with aromatic aldehydes yielded the corresponding arylidene derivatives (IV). Oxidation of the semicarbazone V with selenium dioxide gave 2-(1,2,3-selenadiazole-4-yl)benzimidazole (VIa, b) while with thionyl chloride it gave 2-(1,2,3-thiadiazole-4-yl)benzimidazole (VIIa, b). The chalcones of 2-acetyl and/or 1-methyl-2-acetylbenzimidazole were condensed with hydrazine hydrate, phenylhydrazine and/or hydroxylamine to produce 2-(5-aryl-1(H)-pyrazolin-3-yl)-, 2-(5-aryl-1-phenyl-2-pyrazolin-3-yl)- and 2-(5-aryl-2-isoxazolin-3-yl)benzimidazole (IX, X, XI) respectively.     

R-(+)硫-代四氢呋喃-2-甲酸的合成

以R-(+四)-氢呋喃-2-甲酸为原料,通过草酰氯酰化,与NaHS发生取代反应,合成R-(+)硫-代四氢呋喃-2甲-酸,粗品经柱层析,减压蒸馏纯化。产品收率53.3%,产物结构经MS,1H NMR确认。     

L-抗坏血酸-2-磷酸酯镁的合成与纯化

L-抗坏血酸与丙酮反应生成5，6-0-异丙叉-L-抗坏皿酸（IAA)，再与三氯氧磷进行磷酰化反应．往反应混合液中加入等体积的95％醇，再加入CaCl2溶液，以沉淀出L-抗坏血酸-2-磷酸酯钙晶体；把制得的钙盐溶解在搅拌的阳离子交换树脂的悬浮液中，然后通过阳离子交换柱以除去金属离子．在pH=9下转化为L-抗坏血酸-2-磷酸酯镁，收率为68．2％(以IAA计)，     

Thermal polymerization of aromatic hydrocarbons

The conversion of the aromatic hydrocarbons, anthracene and naphthalene to pitch was studied using a variety of techniques including gel permeation chromatography (GPC), field desorption mass spectrometry (FDMS), nuclear magnetic resonance (NMR), and hot-stage microscopy. The results show the importance of aromatic polymerizations in carbonization. These reactions lead to a rapid increase in molecular weight but not necessarily to a high degree of aromatic condensation. Average structures for the naphthalene- and anthracene-derived pitches are proposed, and the thermotropic nature of napthalene-derived mesophase is described.     

20(S)-9-硝基喜树碱的合成

介绍了一种以无机硝酸盐为硝化剂、喜树碱为原料、浓硫酸为溶剂合成9-硝基喜树碱(9-NC)的新方法. 在此硝化反应体系中,合成9-NC的最佳工艺条件为喜树碱0.5 g,浓硫酸40 mL, ?NO3- 0.007 mol, KNO3/Sr(NO3)2为1:1. 在冰盐浴下反应4 h,再于40℃下反应1 d得到9-NC初产物,经柱层析后,产品收率为41.1%,9-NC纯度98.8%(w),均高于文献值.     

Synthesis of cis-12, 13-epoxy-cis-9-octadecenol and 12(13)-hydroxy-cis-9-octadecenol from vernonia oil using lithium aluminum hydride

Reduction of vernonia oil methyl esters (VOME) into epoxy fatty alcohol and diols was achieved with lithium aluminum hydride (LAH), under reflux and room temperature conditions, by using hexane and tetrahydrofuran (THF) as solvents. The reactions of VOME with LAH in hexane produced cis-12,13-epoxy-cis-9-octadecenol as a major product with an isolated yield of 73.6%, whereas the reaction with LAH in THF gave isomers of 12(13)-hydroxy-cis-9-octadecenol as the major products with an isolated yield of 95.1%. LAH was similarly reacted with vernonia oil (VO) to give the same products in lower yields. ¹H nuclear magnetic resonance (NMR), ¹³C NMR, gas chromatography-mass spectrometry, and infrared were used to characterize these products. This study demonstrates the ability to control the reactivity of the epoxy functionality in VO or VOME with the choice of polar or nonpolar solvents, and extends the range of oleochemicals that can be derived from vernonia oil.     

煤基富勒烯(C_(60))的制备与提纯

<正>富勒烯是除石墨和金刚石外碳的第三种同素异构体,其代表性分子是C_（60）和C_（70）。大量研究成果表明,富勒烯的特殊球形空心分子结构赋予了它许多奇异的物理化学性质,在超导、非线性光学、催化剂等诸多领域显示出十分诱人的应用前景。目前,国内外主要以高纯石墨电极为原料制备富勒烯,由于煤的价格低廉且来源广泛,以煤炭为原料制备富勒烯的研究备受国外学者的关注。本文以冶金焦为原料用电弧法制备富勒烯,研究了实验操作条件及冶金焦性质与富勒烯收率间的关系。粗富勒烯以活性炭为固定相,甲苯为流动相的柱色谱分离提纯,考察了活性炭的孔隙结构及柱色谱的长度对C_（60）纯度和收率的影响。     

Synthesis of long-chain (E)-3-alkenoic acids by the Knoevenagel condensation of aliphatic aldehydes with malonic acid

Knoevenagel condensation of aliphatic aldehydes with malonic acid in equimolar ratio in triethylamine, which served the dual purpose of the solvent as well as the base, gave alkenoic acids in 80–88% yield as determined by acid values of the products and by gas-liquid chromatography with methyl heptadecanoate as the internal standard. The alkenoic acids were converted to methyl esters, purified by column chromatography and characterized by proton nuclear magnetic resonance, infrared and mass spectral analyses. The spectral data clearly established that the acids formed were (E)-3-alkenoic acids. The purified methyl esters were also subjected to the oxymercuration-demercuration reaction, and the mass spectra of the resulting methoxy esters confirmed the exclusive formation of 3-alkenoic acids.     

Isolation of sulphur heterocycles from petroleum- and coal-derived materials by ligand exchange chromatography

A rapid method for the isolation of sulphur heterocycles (PASH) from the aromatic fraction of complex mixtures is described, based on ligand exchange column chromatography using silica gel impregnated with palladium chloride. The application of the procedure to a coal liquid and petroleum heavy ends yielded sulphur fractions composed of PASH having two to six aromatic rings. The fractions were examined by capillary column gas chromatography with flame ionization and flame photometric detection, and by gas chromatography-mass spectrometry.     

Electroreduction of organic compounds. 28. Partial Hydrogenation of Polycyclic Aromatic Hydrocarbons by electroreduction in protic solvents

Polycyclic aromatic hydrocarbons ( PAH ) such as anthracene ( 1 ), phenanthrene ( 5 ), acenaphthylene ( 15 ), pyrene ( 17 ), chrysene ( 22 ), and fluoranthene ( 28 ) are selectively hydrogenated upon electroreduction at a lead cathode in ethanolic solution. The degree of hydrogenation and the structure of the products depend on the reaction conditions, in particular on the applied reduction potential.     

A simple method for the preparation of pure 9-d-hydroperoxide of linoleic acid and methyl linoleate based on the positional specificity of lipoxygenase in tomato fruit

Incubation of linoleic acid with crude homogenate of tomato fruit gave a high yield (69%) of linoleic acid hydroperoxides with a ratio of 9- to 13-hydroperoxide isomers of 96∶4. After chromatography of the products, as free acids or methyl esters, hydroperoxides with 9- to 13-isomeric ratios of >99∶1 were obtained. The major product was characterized as 9-d-hydroperoxy-octadeca-trans-10,cis-12-dienoic acid. The results demonstrate the positional specificity of lipoxygenase from tomato fruit.     

Reactivity of 4-acetyl-3-chloro-5,6-diphenylpyridazine towards some nucleophilic reagents,Synthesis of Some Fused Pyridazine Derivatives

4-Acetyl-3-chloro-5,6-diphenylpyridazine ( 1 ), prepared by the action of phosphorus oxychloride on 4-acetyl-5,6-diphenylpyridazin-3(2H)-one ( 2 ), reacts with hydrazine hydrate and phenylhydrazine to give the pyrazolinopyridazine derivatives ( 3a , b ) respectively. Reaction of 1 with hydroxylamine hydrochloride gave the isoxazolopyridazine derivative ( 5 ), while its reaction with sodium azide in dimethyl formamide gave the tetrazolopyridazine derivative ( 8 ). Primary amines react with 1 to give either 9 or 10 depending upon the reaction conditions. Treatment of 1 with piperidine or morpholine gave the products 11a , b , respectivly. 4-Acetyl-5,6-diphenylpyridazin-3(2H)-thione ( 13 ) was readily obtained by the action of thiourea on ethanolic solution of 1 . The reactions of 1 with phenols were also investigated.     

Synthesis of Hexabenzo[a,cd,f,j,lm,o]perylene

Hexabenzo[a,cd,f,j,lm,o]perylene (HBP), an undecacyclic condensed polycyclic aromatic hydrocarbon with two severely crowded fjord regions, was synthesized by Clar's method; the starting material 8H-benzo[fg]-naphthacene-8-one was newly prepared by the glycerol condensation of 5,12-dihydro-naphthacene-5,12-dione. ¹H and ¹³C NMR spectra of HBP were measured and the chemical shifts were completely assigned. Absorption and fluorescence spectra of HBP were also measured and the effects of nonplanarity on its spectroscopic properties was discussed.