香料2-甲基-2-乙基-1,3-二硫杂环己烷的合成

以丁酮和1,3-丙二硫醇为原料,采用TiSiW12O40/TiO2作催化剂,合成了一种新型香料化合物2-甲基-2-乙基-1,3-二硫杂环己烷,并用元素分析、IR、1HNMR对其结构进行了表征。采用正交试验研究了影响目标化合物产率的主要因素,得到了优化反应条件:n(丁酮)∶n(1,3-丙二硫醇)=1.1∶1.0,m(催化剂)∶m(1,3-丙二硫醇)=0.04∶1,不需要带水剂,反应3 h,目标产物的收率为87.6%。催化剂无需处理可直接重复使用8次以上。     

(Z)-(2-溴-3,3-二氟丙-1-烯-1-基)苯衍生化反应研究

研究了新的二氟甲基砌块化合物的衍生化反应。首先以α-溴代肉桂醛和二乙胺基三氟化硫为原料合成标题化合物砌块,接着将该砌块在DMF溶剂中,以碳酸铯作碱,并将环境温度控制在80℃下反应过夜得到(3,3-二氟丙-1-炔-1-基)苯,接着与系列含氮杂环发生反应合成4个(Z)-1-(3,3-二氟-1-苯基丙-1-烯-1-基)-1H-唑化合物,产率为28.2%～62.1%。同时合成了2个含有二氟甲基的中间体和4个拓展产物,其结构经~1HNMR、~(13)CNMR、~(19)FNMR、HR-MS进行了表征。     

3-偕二硝甲基-1,2,4-三唑的合成及表征

以3-偕胺肟基-1,2,4-三唑为原料,经重氮化-氯化、硝解、成盐-酸化等反应合成了3-偕二硝甲基-1,2,4-三唑(DNMT),利用红外光谱、核磁(1H-NMR、13C-NMR)、元素分析和质谱等方法表征了化合物的结构;获得了关键中间体3-氯偕二硝甲基-1,2,4-三唑(CDNMT)的单晶并进行了晶体结构解析,该化合物晶体为单斜晶系,空间群为P2(1)/c,晶体学参数为:a=10.837(6)?,b=9.756(5)?,c=7.299(4)?,α=90°,β=92.990(8)°,γ=90°,V=770.6(7)?3,Z=4,μ=0.489 mm~(-1),F(000)=416;采用Gaussian 09程序中的CBS-4M方法计算了DNMT的生成热,基于密度和计算的生成热,利用Kamlet-Jacobs爆轰方程预估了爆轰性能:密度1.75 g×cm~(-3),爆速8 365.6 m×s~(-1),爆压29.9 GPa,生成热155.5kJ×mol~(-1),爆热为5 928.9 kJ×kg~(-1),结果表明,该化合物是一种性能较好的含能材料。     

3-醛基吲哚-7-甲酸的合成

以3-甲基-2-硝基苯甲酸为原料,用MeOH/H2SO4酯化先制得3-甲基-2-硝基苯甲酸甲酯(2),化合物2与DMFDMA缩合后经Fe/HOAc还原得到吲哚-7-甲酸甲酯(4),最后化合物4与POCl3/DMF通过Vilsmeier反应合成了标题化合物,总收率53%。产物的结构经1HNMRI、R和MS得到确证。     

2,9-二甲基-1,2,3,4,7,8,9,10-八氢-1,10-菲啰啉的晶体结构研究

通过2,9-二甲基-1,10-菲啰啉和氰基硼氢化钠的反应,成功制备了2,9-二甲基-1,2,3,4,7,8,9,10-八氢-1,10-菲啰啉(1),并用元素分析、核磁共振、高分辨质谱等方法对所合成的化合物进行了表征,并采用挥发法培养了化合物1的单晶,并利用X-射线单晶衍射技术测定和研究了化合物1的晶体结构。在化合物1中,2,9-二甲基-1,2,3,4,7,8,9,10-八氢-1,10-菲啰啉分子采取受限扭曲的椅式构象,分子之间以交错平行模式堆积,并通过弱的C-H…π作用相互连接成为一维超分子链。晶体结构数据:三斜晶系,空间群P-1,a=9.052(9),b=10.241(9),c=14.809(12),α=71.07(5),β=79.79(3),γ=77.22(4),Z=1,V=1258(2)3。     

1-（3-甲基喹喔啉-2-基）-3-苯基-2-丙烯-1-醇的合成

喹烯酮是国家的一类新型兽药。由于其在生物体内的利用率低,喹烯酮代谢物1-（3-甲基喹喔啉-2-基）-3-苯基2-丙烯-1-醇难于从生物的排泄物中分离与鉴定。文章以喹烯酮为原料,经三氯化磷以及四氢锂铝还原后,首次合成喹烯酮的代谢物1-（3-甲基喹喔啉-2-基）-3-苯慕2-丙烯-1-醇,两步收率达75％。各步化合物经高效液相色谱、质谱、氢核磁谱等分析手段,验证结构符合。     

2-甲基-4-(4-(吡啶-4-乙炔基)苯基)-3-丁炔-2-醇的合成及结构表征

由1,4-二碘代苯出发,经过两步Sonogashira偶联反应合成标题化合物2-甲基-4-(4-(吡啶-4-乙炔基)苯基)-3-丁炔-2-醇。通过1 H NMR、13 C NMR核磁共振、X射线单晶衍射等手段对化合物的结构进行了表征。结果表明,该化合物属于单斜晶系,空间群为P2(1)2(1)2(1)。晶体学参数:a=0.060754(15)nm,b=0.081700(19)nm,c=0.32073(7)nm,α=90.00°,β=90.00°,γ=90.00°,V=15.920(7)nm3,Z=8。     

3-卤-2-卤甲基-1-丙烯合成方法改进

以季戊四醇为原料经卤代、氧化、热分解三步主要反应合成了3-卤-2-卤甲基-1-丙烯.卤代反应中采用不同的卤代剂合成了三卤代新戊醇,在文献基础上加入以二氯甲烷为萃取剂的萃取过程可使三卤(氯)新戊醇产率达72%-98%;再通过氧化反应得到三卤(氯或溴)新戊酸,同样加入萃取过程可使酸的产率达到63%-80%,最后热分解脱卤化氢和二氧化碳制备3-卤-2-卤甲基-1-丙烯时(卤素为氯和溴),在文献基础上加入吡啶作催化剂可使热分解温度降至200 ℃(原分解温度为260 ℃),总产率可达45%-72%.在制备3-碘-2-碘甲基-1-丙烯时避光搅拌,可降低产物分解,产率为60%.所有的化合物经过了IR和1HNMR的确认.     

3-（2,4-二甲基-3-戊氧基）邻苯二腈的合成

以3-硝基邻苯二腈、2,4-二甲基-3-戊醇、氢化钠为原料,进行赖因德斯—林格反应缩合,合成目标化合物——3-（2,4-二甲基-3-戊氧基）邻苯二腈,主要探讨了原料摩尔比、反应温度、滴加时间对产品质量和收率的影响。确定了较优反应条件;3-硝基邻苯二腈与2,4-二甲基-3-戊醇钠的摩尔比为1∶1.25,反应温度为0℃,滴加时间为3 h,反应时间2 h,反应收率为87%。通过熔点,HNMR确证目标产物的化学结构。     

高区域选择性合成3-（芳胺）-N,N-二甲基丙酰胺衍生物

以N,N-二甲基丙烯酰胺和芳胺类化合物为原料,盐酸为促进体系,经过分子间的高区域选择性加成,成功地构建出了3-（芳胺）-N,N-二甲基丙酰胺衍生物。采用1H-NMR、13C-NMR和熔点对目标产物进行了表征。研究表明该方法具有原料便宜易得、原子经济、后处理操作简单和产品纯度高等优点,为3-（芳胺）-N,N-二甲基丙酰胺衍生物的高效、快速合成提供了一条可选的策略。     

Benzyl and Methyl Fatty Hydroxamic Acids Based on Palm Kernel Oil as Chelating Agent for Liquid-Liquid Iron(III) Extraction

Liquid-liquid iron(III) extraction was investigated using benzyl fatty hydroxamic acids (BFHAs) and methyl fatty hydroxamic acids (MFHAs) as chelating agents through the formation of iron(III) methyl fatty hydroxamate (Fe-MFHs) or iron(III) benzyl fatty hydroxamate (Fe-BFHs) in the organic phase. The results obtained under optimized conditions, showed that the chelating agents in hexane extract iron(III) at pH 1.9 were realized effectively with a high percentage of extraction (97.2% and 98.1% for MFHAs and BFHAs, respectively). The presence of a large amount of Mg(II), Ni(II), Al(III), Mn(II) and Co(II) ions did affect the iron(III) extraction. Finally stripping studies for recovering iron(III) from organic phase (Fe-MFHs or Fe-BFHs dissolved in hexane) were carried out at various concentrations of HCl, HNO(3) and H(2)SO(4). The results showed that the desired acid for recovery of iron(III) was 5 M HCl and quantitative recovery of iron(III) was achieved from Fe(III)-MFHs and Fe(III)-BFHs solutions in hexane containing 5 mg/L of Fe(III).     

Selective iron removal from spent passivation baths by ion exchange

BACKGROUND: Post‐treatment of zinc plated surfaces is required to provide corrosion protection; for this purpose chromium passivation is usually used. In the EU, the older hexavalent chromium passivation baths have been replaced by trivalent chromium conversion coatings. However, the life of Cr(III) passivation baths is reduced due to iron and zinc impurities generated in the process. Thus, the objective of this work was to investigate the regeneration of spent passivation baths from the plating industry by ion exchange using a new chelating resin (Purolite S‐957). RESULTS: Three genuine passivation baths with different iron and zinc concentrations were investigated; the effect of loading flow rate, temperature and resin regeneration conditions on the uptake of iron ions was also studied. The removal performance of iron was increased at higher temperature (55 °C) and lower flow rates. The best regeneration conditions were found to be 6 bed volumes (BV) of 30 wt% HCl. CONCLUSION: This work has shown that iron can be selectively removed from trivalent chromium passivation baths using a new chelating resin (Purolite S‐957) and no addition of chromium (III) is required. Low feed flow rate and high bath temperature (up to 55 °C) are recommended for high iron uptake. Copyright © 2008 Society of Chemical Industry     

Preconcentration and determination of chromium in water with flame atomic absorption spectrometry by thiourea-formaldehyde as chelating resin

Thiourea-formaldehyde chelating resin is synthesized simply and rapidly from thiourea and formaldehyde by condensation polymerization and characterized by IR spectra and studied for the preconcentration and determination of trace Cr(III) ion from solution samples. The optimum pH value for sorption of the metal ion was 6.5. The sorption capacity of resin for Cr(III) was determined. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 96% was obtained for the metal ion with 0.5M HNO₃ as eluting agent. The equilibrium adsorption data of Cr(III) on modified resin were analyzed by Langmuir, Freundlich and Temkin models. Based on equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined as 0.016, 0.040 and 0.074 at pH 6.5 and 20°C. The method was applied for chromium ion determination from river water sample.     

UPTAKE OF METAL IONS BY A NEW CHELATING ION-EXCHANGE RESIN. PART 5 : THE EFFECT OF SOLUTION MATRIX ON ACTINIDES

ABSTRACT

The influence of commonly occurring matrix constituents on the uptake of representative actinides in the tri-, tetra-, and hexavalent oxidation states by a new chelating ion exchange resin, called Diphonix?, has been investigated. The effect of increasing concentrations of HF at three fixed HC1 concentrations on the retention of U(VI), Np(IV), and Am(III) was measured. All three actinides showed strong retention in HF even up to a concentration of 1 M The effect of sulfuric, oxalic and phosphoric acids at three fixed HNO₃ concentrations on the retention of Th(IV), U(VI), and Am(III) was also measured. Only when the concentration of the complexing acids was above 0.1 M was the retention of the actinides decreased significantly at 0.1 M HNO₃ The effect was much less pronounced at higher HNO₃ concentrations.

Sodium, calcium, aluminum and iron were selected to study the influence of cationic matrix constituents on the uptake of actinide ions by Diphonix. In the case of tetra- and hexavalent actinides (represented by Th and U, respectively) only the very highest concentrations of Fe(III) and Al(III) caused a significant decrease in the retention of the two higher valent actinides. On the other hand, Am(III) retention was significantly lowered by Al and Fe(III) concentrations above 10^?2 M The influence of Al and Fe(III) on the uptake of Am(III) may be minimized by use of fluoride ion to complex Al and by reducing Fe(III) to Fe(II). Macroconcentrations of sodium and calcium had only minimal influence on the uptake of actinides in all three oxidation states.     

Studies of Selective Adsorption Resins. XXII. Removal and Recovery of Arsenic Ion in Geothermal Power Waste Solution with Chelating Resin Containing Mercapto Groups

Abstract

Removal and recovery of harmful arsenic ion in a geothermal power waste solution with three macroreticular chelating resins containing mercapto groups were investigated. The resin (RES), which was prepared from 2,3-epithiopropyl methacrylate-divinylbenzene copolymer beads, exhibited high affinity for arsenic(III) ion and high resistance against hot water. In the column method, arsenic(III) ion in an aqueous solution was favorably adsorbed on the RES when the sodium arsenite solution (pH 6.2) containing 3 mg/dm³ of arsenic(III) ion was passed through the RES column at a space velocity of 15 h^?1. The arsenic(III) ion adsorbed was eluted by allowing 2 mol/dm³ sodium hydroxide solution containing 5% of sodium hydrogen sulfide to pass through the column. The recycle of adsorption and elution was found to be satisfactory. The RES also exhibited high adsorption ability for arsenic ion in the geothermal power waste solution.     

Determination of mumol l level of iron (III) in natural waters and total iron in drugs by flow injection spectrophotometry

The equilibrium problems, characterized by recurring end-points, involved in the reaction of iron (III) with iodide make the batch iodometric determination of iron (III) unsuitable. Since the flow injection determination does not require attainment of steady state either for mixing of reagents or for the chemical reaction, the iodometric determination has been accurately and precisely performed using this technique in the present work. This method does not require any special reagent, including chelating agents or those which are loxic, and has a limit of detection of 0.2 mumol l(-1) (11 mug l(-1)) of iron (III). The interference of fluoride has been avoided by adding zirconyl nitrate to the test sample solution, and of copper (II) by complex formation with 2-mercaptobenzoxazole. The method has been applied to determine iron (III) in natural waters, and total iron in drugs.     

Properties of a bifunctional chelating resin containing aminomethylphosphonate and sulfonate derived from poly(ω-bromobutylstyrene-co-divinylbenzene) beads

A bifunctional chelating resin containing aminomethylphosphonate and sulfonate groups (RC4NPS) was derived from macroreticular poly(ω-bromobutylstyrene-co-divinylbenzene) beads (RC4B). First, the bromine atoms in RC4B were replaced with phthalimide groups and then sulfonate groups were introduced into the benzene rings on the polymer chains. After the phthalimide groups were hydrolyzed with an ethanol solution of hydrazine hydrate, the resulting primary amino groups at the end of the butyl groups were converted into aminomethylphosphonate groups by the Mannich condensation reaction. For comparison, a monofunctional aminomethylphosphonate resin (RC4NP) was also prepared by eliminating the sulfonation step. The nitrogen, phosphorus and sulfur contents of RC4NPS were found to be 2.07, 2.98 and 2.19 mmol/g, respectively. The nitrogen and phosphorus contents of RC4NP were 2.50 and 3.39 mmol/g, respectively. The acid capacities of RC4NPS and RC4NP were 6.97 and 6.23 meq/g, respectively. The metal ion selectivity of both resins was evaluated by measuring the pH dependence of the distribution ratios (D) of Fe(III), Lu(III), Gd(III), La(III), Pb(II), Ca(II), Mg(II), Cu(II), Zn(II) and Ni(II). This selectivity study indicates that the metal ion selectivity of RC4NPS can be expressed as a convolution of the metal ion selectivity of RC4NP with that of a sulfonate resin.     

Iron(III) ion removal from solution through adsorption on chitosan

The potential of different forms of chitosan to adsorb iron(III) ion from a Jectofer [an iron(III)–sorbitol–citric acid complex] solution was investigated. The working solution was chosen as Jectofer, to mimic the composition of excess iron(III) as may be found in biological systems. The equilibrium studies showed that chitosan powder has the highest sorption capacity for the iron(III) ion when compared to chitosan flakes and microspheres. The amount of iron(III) adsorbed onto chitosan was found to increase with the contact time to reach equilibrium within 3 h at 37°C. A higher initial concentration of a Jectofer solution resulted in a higher amount of iron(III) adsorbed. Higher pH values, in the range 2–7, also resulted in an increase in iron(III) uptake from the solution. The data of adsorption from the Jectofer solution were found to correlate well with the Freundlich isotherm equation. In vitro adsorption experiments showed that chitosan is capable of adsorbing excess iron, measured in terms of the ferritin level, in human blood. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1185–1192, 2002; DOI 10.1002/app.10416     

Synthesis and application of spherical macroporous epoxy–polyamide chelating resin for preconcentration and separation of trace Ga(III), In(III), Bi(III), V(V), Cr(III), and Ti(IV) from solution samples

An ICP‐AES method using a new spherical macroporous epoxy–polyamide chelating resin to enrich and separate trace Ga(III), In(III), Bi(III), V(V), Cr(III), and Ti(IV) ions from solution samples is established. The results show that the analyzed ions can be enriched quantitatively by 0.1 g of the resin at pH 4, with recoveries > 98%. The ions can be desorbed quantitatively with 10 mL of 2M HCl from the resin column with recoveries > 96%, and 100–1000‐fold excesses of Ca(II), Mg(II), Fe(III), Cu(II), Zn(II), Al(III), Ni(II), and Mn(II) cause little interference in the determination of these ions by ICP‐AES. The chelating resin is reused for ten times; the recoveries of these ions are still over 95%. The relative standard deviations for enrichment and determination of 100 ng ml^?1 Ga(III), In(III), and Bi(III), 10 ng ml^?1 V(V), Cr(III), and Ti(IV) are in the range 0.6–2.3%. The concentration of each ion found in the real wastewater sample and alloy sample is in good agreement with the values provided by the plant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2330–2334, 2005     

N-lauroyl-ethylenediamine chelates: Preparation and evaluation of surface tension and dispersant properties

A chelate surfactant was synthesized having a hydrophobic alkyl group and hydrophilic metal ion bonded to the former in the chelate configuration, and its properties were investigated. N-lauroyl-ethylenediamine (LEDA) was used as the hydrophobic chelating agent and salts of some transitional metals (e.g. iron, cobalt, nickel, copper and chromium) were reacted therewith. The reaction of LEDA with ferric sulfate on 1:1 equivalent reaction ratio afforded [Fe(LEDA) (H₂O)₄]3/2SO₄. In other reactions pure chelates were not obtained, but the products showed good surface activity.