1—苯基—3—羟基—4—酰基—5—吡唑酮螯合萃取剂的合成

1-苯基-3-甲基-4-酰基-5-吡唑酮对于金属离子是一类优良的螯合萃取剂,其在稀土分析化学中的应用已有综述。1908年Michae1is最先合成了1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮,1959年Jensen又合成了一系列1-苯基-3-甲基-4-酰基-5-吡唑酮类化合物并     

HPMBP和二苯胍对Ho~(3+)的协同萃取机理研究

研究了 1-苯基 - 3-甲基 - 4 -苯酰基吡唑酮 - 5(HPMBP)和二苯胍 (DPG)的三氯甲烷溶液对硝酸介质中Ho3+萃取机理。实验结果表明 :在体系Ho3+(～ 10 - 4mol/L)HNO3　NaNO3( μ =0 2 ) /HPMB -DPG -CH3Cl中 ,存在明显的协同效应。利用斜率法测得萃合物的组成为 [HB]+[HoA4 ](HA代表HPMBP ,B代表DPG) ,常温时的萃取平衡常数K =2 7.2 4 ;讨论了协同萃取机理和萃合物的结构。     

1-苯基-3-甲基-4-己酰基吡唑酮〔5〕萃取、分光光度法测定重稀土矿中的钇组稀土元素

1-苯基-3-甲基-4-苯甲酞基吡唑酮(简称PMBP)是人们公认的稀土元素的最好萃取剂之一,但在铈组稀土存在下,用PMBP萃取钇组稀土,需要借助于掩蔽剂。用己酰基取代PMBP中四位上的苯甲酰基制得1-苯基-3-甲基-4-己酰基吡唑酮(简称PMCP),通过控制酸度能将铈组和钇组稀土元素分离。本文试验了用PMCP萃取分光光度法测定重稀土矿中钇组稀土元素,结果令人满意。本文所拟定的方法快速简便,可靠,因而具有应用价值。     

对甲苯磺酸催化下二乙酰苯与含有羟基的苯甲醛的Aldol缩合反应

以对甲苯磺酸(p-TsOH)作催化剂, 二乙酰苯与含有羟基的苯甲醛发生aldol缩合反应, 合成了3个1,3-双[3-(取代苯基)丙烯酰基]苯衍生物1～3, 3个1,4-双[3-(取代苯基)丙烯酰基]苯衍生物4～6和2个中间体7, 8, 中间体7, 8再与含有羟基的苯甲醛发生aldol反应合成了3个1-[3-(4-羟基苯基)丙烯酰基]-4-[3-(取代苯基)丙烯酰基]苯衍生物9～11, 反应均能在2～6 d内完成, 操作和后处理简便. 以上11个新化合物均未见报道, 其结构经1H NMR, IR, MS和HRMS加以确证.     

1-苯基-3-甲基-4-二氯乙酰基吡唑酮-5和三正辛基氧化膦协同萃取镧系离子的研究

1-苯基-3-甲基-4-三氟乙酰基吡唑酮-5(PMTFP)与磷酸三丁酯(TBP)或三正辛基氧化膦(TOPO)对三价稀土的协同萃取已有报道^[1,2]。本文研究了1-苯基-3-甲基-4-二氯乙酰基吡唑酮-5(PMDCP)和TOPO的氯仿溶液从硝酸介质中对La³⁺、Nd³⁺、Dy³⁺和Yb³⁺的协同萃取。     

新型含异噁唑环的苯腙基吡唑酮与芳偶氮基吡唑酮衍生物的合成

以乙酰乙酸乙酯为起始原料,经四步反应制备了关键中间体3-甲基-5-苯基异嗯唑甲酰肼(2);2分别与取代苯腙基乙酰乙酸乙酯和取代苯腙基乙酰丙酮反应合成了一系列新型的1.(3′-甲基-5′-苯基-异噁唑4′-甲酰基)-3-甲基4-苯腙基吡唑酮和1-(3′-甲基-5′-苯基-异噁唑-4′-甲酰基)-3,5-二甲基4-芳偶氮基...     

通过氧杂Pictet-Spengler反应从1-烷(苯)氧基-3-(3,4-亚甲基二氧)苯基-2-丙醇合成异色满衍生物

通过氧杂Pictet-Spengler反应从1-烷氧基-3-(3,4-亚甲基二氧)苯基-2-丙醇及1-苯氧基-3-(3,4-亚甲基二氧)苯基-2-丙醇合成一系列异色满衍生物,即3-烷(苯)氧基-1-苯基-6,7-亚甲基二氧异色满和3-烷(苯)氧基-1,1-二甲基-6,7-亚甲基二氧异色满,收率为50%～90%.     

含吡唑啉酮氨基脲类化合物的合成及结构

以1-苯基-3-甲基-吡唑啉酮-5 (PMP)和1,3-二苯基-吡唑啉酮-5 (DPP)为原料合成了六种4-酰基吡唑啉酮,并分别与氨基脲缩合,得到六个新的含吡唑啉酮环的缩氨基脲类化合物.用IR, ¹H NMR和¹³C NMR对各化合物进行了表征及结构确证,并用X射线单晶衍射法测定了化合物1c [1-苯基-3-甲基-4-丙酰基-吡唑啉酮-5缩氨基脲(PMPP-SC)]的晶体结构.     

茶叶中稀土元素的萃取分离-ICP-AES法测定

采用1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮(PMBP)苯溶液萃取分离-ICP-AES法同时测定茶叶中15种稀土元素,消除了基体的干扰,并对样品前处理方法、萃取分离条件进行了考查.方法回收率为: 92.3%～112%,相对标准偏差＜2.5%.在最佳工作条件下,测定了茶叶标准物质(GBW07605)中稀土元素,结果与标准值吻合.     

4-(N-对三氟甲基苯基)氨甲基-5-取代苯基硫吡唑衍生物的合成及生物活性

为了寻找高效低毒的农药,以3-甲基-1-取代苯基-5-吡唑酮、硫酚、对三氟甲基苯胺等为原料,通过4步反应,合成了5个3-甲基-1-取代苯基-4-(N-对三氟甲基苯基)氨甲基-5-取代苯硫基吡唑化合物,其结构经元素分析、1H NMR、IR确证。初步生物活性测试表明,部分化合物具有一定的杀菌活性。     

Comprehensive Comparisons between 1-Phenyl-3-methyl-5-pyrazolones, 1-(4-Methoxyphenyl)-3-methyl-5-pyrazolones and 1-(2-Naphthyl)-3-methyl-5-pyrazolones as Labeling Reagents Used in LC-DAD-ESI-MS-MS Analysis of Neutral Aldoses and Uronic Acids

Comprehensive comparisons between three 1-aryl-3-methyl-5-pyrazolone (AMP) labeling reagents were carried out for the analysis of reductive monosaccharides using reversed phase high performance liquid chromatography diode array detection coupled to electrospray ionization mass spectrometry. AMP derivatives included 1-phenyl-3-methyl-5-pyrazolone (PMP), 1-(4-methoxyphenyl)-3-methyl-5-pyrazolone (PMPMP) and 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP). The separation of AMP-monosaccharides was found to be pH-dependent under reversed phase conditions and acceptable separations were obtained at pH < 4.5. The elution orders of AMP-aldoses were rationalized by geometric factors involved in the presence of hydroxyl groups at C2 and C3 positions of the saccharide moiety. When PMP or PMPMP were used as labeling agents Glucose and galactose were completely separated, while arabinose and xylose were observed to co-elute. The use of NMP revealed that arabinose and xylose could be separated while glucose and galactose were co-eluted. MS-MS data of AMP-monosaccharides gave characteristic fragment ions resulting from cleavage between the C2–C3 bond (m/z 373 for PMP derivatives, m/z 433 for PMPMP derivatives, and m/z 473 for NMP derivatives). Bond breakage between C1–C2 (m/z 359 for PMP derivatives, m/z 419 for PMPMP derivatives, and m/z 459 for NMP derivatives) of the saccharide moiety was also found to be characteristic for AMP-saccharides. Application to the analysis of hydrolyzed rape pollen polysaccharides revealed the presence of four unexpected monosaccharides, namely ribose, erythrose, threose and glyceraldehyde.     

Catalytic Potential of Pyrazolone Based Dioxidomolybdenum(VI) Complexes for Multicomponent Biginelli Reactions,Epoxidation of Olefins and Oxidative Bromination of Phenol Derivatives

Three different types of dioxidomolybdenum(VI) complexes of 4-acetyl-3-methyl-1-phenyl-5-pyrazolone (Hmp, I )), 3-methyl-1-phenyl-4-propionyl-5-pyrazolone (Hpp, II ), 4-butyryl-3-methyl-1-phenyl-5-pyrazolone (Hbutp, III ), and 4-isobutyryl-3-methyl-1-phenyl-5-pyrazolone (isobutp, IV ) have been isolated and characterized by various spectroscopic (FT-IR, UV/Vis, ¹H and ¹³C NMR) techniques, thermal analysis and single crystal X-ray analysis. These complexes adopt a distorted six-coordinate octahedral geometry where ligands act as bidentate, coordinating through the two O atoms. These complexes have been used as catalysts to explore a single pot multicomponent (benzaldehyde or its derivatives, urea/thiourea and ethyl acetoacetate/phenyl acetoacatate) Biginelli reaction producing biologically active 3,4-dihydropyrimidin-2-(1H)-one and 3,4-dihydropyrimidin-2-(1H)-thione based biomolecules under solvent-free conditions. Presence of H₂O₂ improves the yield of dihydropyrimidin-2-(1H)-one but it acts as poison for the later molecule. Epoxidation of internal and terminal alkenes mainly resulted in the formation of the corresponding epoxide. The catalytic oxidative bromination of thymol, a reaction facilitated by vanadium dependent haloperoxidases, resulted in the formation of three product namely 2-bromothymol, 4-bromothymol and 2,4-bromothymol. Other phenol derivatives have also been brominated effectively.     

1-苯基-3-甲基-5-吡唑啉酮(PMP)柱前衍生化寡糖链的HPLC分离及其激光解吸电离质谱分析

以1-苯基-3-甲基-5-吡唑啉酮(PMP)为衍生化试剂对寡糖链进行标记, 用氨水替代氢氧化钠溶液作碱性介质, 衍生化反应后氨水可通过干燥除去, 省去了脱盐处理过程, 衍生化的寡糖可直接进行激光解吸电离质谱分析. 建立起了PMP衍生化寡糖的RP-HPLC分离分析模式, 在此HPLC分析条件下, 可以对标记的寡糖链进行样品分离及制备.     

Azines and Their Acyclic Derivatives as Transferers of One-carbon Fragment in Reactions with Pyrazolones

Enehydrazine derivatives have been obtained by the reaction of 6-phenyl-1,2,4-triazine 4-oxide with pyrazolones 2, which on further heating with pyrazolones 2 are converted into the corresponding symmetrical or unsymmetrical derivatives of dipyrazolylmethane. Enehydrazine derivatives of 1,3-dimethyl-5-nitrosouracil and 1,3-dimethylimidazolidine interact with 3-methyl-1-phenyl-5-pyrazolone (2a) with the formation of dipyrazolylmethane derivative. On interacting compound 2a or 3-methyl-1-(p-nitrophenyl)-5-pyrazolone with 3,6-diphenyl-1,2,4-triazine 4-oxide 12 the corresponding 4,4'-bispyrazolones are formed, but the interaction of compound 12 with 3-(p-nitrophenyl)-1-phenyl-5-pyrazolone leads to dipyrazolylmethane derivative. Dipyrazolylmethane derivative is obtained on heating of fervenulin 4-oxide, 2,4-dihydroxy-5-nitropyrimidine, and 1,3,5-triazines: 6-azauracil, 5-azauracil, azacytosine, and 2,4-diamino-s-triazine with pyrazolone 2a.     

Preparation of various silica-based columns for capillary electrochromatography by in-column derivatization

Chemically bonded silica gels were prepared in a capillary by pumping an ethanolic solution of a silylating reagent, such as octadecyltrimethoxysilane, 3-aminopropyltrimethoxysilane and dimethyloctadecyltrimethoxysilylpropylammonium chloride into a heated capillary packed with bare silica particles. The silylation reactions were completed in a short time and thus-prepared columns showed high column efficiency and high reproducibility. Examples are shown for the separation of 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatives of aldopentoses on a 3-aminopropylated silica column and benzoate homologues as well as PMP derivatives of the component monosaccharides of glycoproteins on an octadecylammonium column. Since the presence of frit filters hampers high efficiency separation, an attempt was made to fix the bed of modified silica gel particles to the capillary inner wall by a cross-linking technique. The results indicated that this technique is promising.     

1-苯基-3-甲基-5-吡唑啉酮衍生中药寡糖的毛细管区带电泳分离

建立了一种可用于中药寡糖分离的毛细管区带电泳(CZE)分析方法。分离条件: 未涂层熔融石英毛细管柱(48 cm×50 μm,有效长度38 cm),紫外检测波长245 nm,采用1-苯基-3-甲基-5-吡唑啉酮(PMP)为寡糖衍生试剂,50 mmol/L磷酸盐溶液(pH 2.5)为运行缓冲液,电压15 kV,重力进样10 cm×2 s。针对中药寡糖实际样品的复杂性,通过添加多种常见单糖进行方法的实用性验证,并且将方法用于板蓝根多糖的控制降解产物的分离。结果表明,板蓝根寡糖组分可按相对分子质量从小到大的顺序分离,分离效果令人满意。该分离方法操作简单、高效,可用于中药寡糖实际样品分析。另外,还对单糖、寡糖PMP衍生物的电泳迁移行为进行了初步的理论探讨。     

Analysis of the monosaccharide components in Angelica polysaccharides by high performance liquid chromatography.

An analytical method of on-line high performance liquid chromatography (HLPC) was developed to simultaneously separate and identify the monosaccharide composition of three Angelica polysaccharide fractions (APF), named APF1, APF2 and APF3. In this method, APF were hydrolyzed into component monosaccharides and subsequently labeled with 1-phenyl-3-methyl-5-pyrazolone (PMP), and then the labeled monosaccharide derivatives were separated by a reverse-phase C18 column and monitored by UV absorbance at 250 nm. The results showed that nine monosaccharide derivatives have been well separated by HPLC under optimized conditions and the composition analysis of monosaccharides from APF samples could be achieved using acid hydrolysis and a set of monosaccharide standards. With this method, the within-day and day to day precisions of the composition determinations were 3.41-4.87% and 3.12-4.93% (RSD), respectively. The method was successfully applied to the determination of the component monosaccharides of Angelica polysaccharides.     

Solvent extraction of lanthanum(III), europium(III) and lutetium(III) with fluorinated 1-phenyl-3-methyl-4-benzoyl-5-pyrazolones into chloroform

A series of chelating reagents, 1-phenyl-3-methyl-4-(2-fluorobenzoyl)-5-pyrazolone, 1-phenyl-3-methyl-4-(3-fluorobenzoyl)-5-pyrazolone and 1-phenyl-3-methyl-4-(4-fluorobenzoyl)-5-pyrazolone, has been synthesized. The extraction of Ln(III), (Ln = La, Eu and Lu) into chloroform with these reagents at 30 +/- 1 degrees has been studied. The composition of the complexes extracted has been determined by the slope method, and the extraction constants K(ex), were measured. The presence of the fluorine atom in the reagents does not make the K(ex), values much different from those obtained with the parent pyrazolone.     

Preparation and ionic hydrogenation of substituted 4-(3-oxopropyl)-5-pyrazolones

4-(3-Oxopropyl)-5-pyrazolone derivatives were obtained under mild conditions of alkaline catalysis by condensation of 1-phenyl-3-methyl-5-pyrazolone and substituted chalcones. During ionic hydrogenation of the products they undergo heterocyclization with the formation of 5,6-dihydropyrano[3,2-d]pyrazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 245–248, February, 1981.     

Addition of heterocyclic CH acids to the C=N bond of azomethines

The aminomethylation of oxindole, 1-phenyl-3-methyl-5-pyrazolone, and N-phenyl-rhodanine was studied. Derivatives of these CH acids were obtained as a result of aminomethylation. The addition products were subjected to acid and base hydrolysis; the corresponding arylidene derivatives are formed in the case of the products of aminomethylation of oxindole and 1-phenyl-3-methyl-5-pyrazolone, while thioglycolic acids are formed in the case of N-phenylrhodanine derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1088–1093, August, 1981.