液膜法处理含铜废水的试验研究

以某湿法铜业公司外排含铜废水为研究对象,系统考察了煤油-LIX984-CTMAB(十六烷基三甲基溴化铵)液膜体系对含铜废水中铜的分离。考察内容主要包括料液酸度、内相酸度、搅拌时间、LIX984用量、乳化液用量、乳化剂(CTMAB)用量、膜相和内相体积比。在最优条件下,铜离子的萃取率达到95%左右。     

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧B

研究了 1 苯基 3 甲基 4 苯甲酰基 -吡唑酮 5 (HPMBP)和中性有机磷 (膦 )类萃取剂Cyanex 4 71X(TIBPS ,B)在硝酸介质中对稀土元素La 的萃取 ,用斜率法和恒摩尔法探讨了萃取机理 ,确定了萃合物的组成为La(NO3 ) 2 ·PMBP·B ,计算了萃取平衡常数。比较了HPMBP与Cyanex 4 71X、Cyanex 92 1、Cyanex 92 3、Cyanex 92 5、DEH/EHP、P35 0及TBP的单独及混合体系萃取La 的性能 ,结果表明 :所有混合体系对La 均有协同效应 ,其中HPMBP与Cyanex 92 3、Cyanex 92 1、Cyanex 92 5的混合体系是萃取La 的有效体系。     

聚乙二醇-硫酸铵-二甲酚橙体系萃取分离钯

研究了萃取剂二甲酚橙与Pd(Ⅱ)离子的螯合物在聚合物-硫酸铵-水体系中两相间的分配行为。在pH1．0～6．0条件下，Pd(Ⅱ)几乎被二甲酚橙完全萃取到PEG相中，而Fe(Ⅱ)、Co(Ⅱ)、Zn(Ⅱ)萃取率随pH变化显著，Mn(Ⅱ)、Cd(Ⅱ)基本不被萃取。在HClO4介质pH1．0～2．0条件下，实现了Pd(Ⅱ)与Fe(Ⅱ)、Co(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)、Cd(Ⅱ)的定量萃取分离。     

2-乙基己基膦酸单(2-乙基己基)酯对两价金属离子的萃取平衡

酸性磷(膦)酸酯是一类广泛应用于金属元素萃取分离的重要萃取剂。这类萃取剂对金属离子的萃取性能和机理以及它们与中性磷(膦)酸酯混合体系萃取金属离子的平衡等均有文献报道。然而2-乙基己基膦酸单(2-乙基己基)酯(1,HA)对某些金属离子如Sn(Ⅱ),Pb(Ⅱ)和Cd(Ⅱ)的萃取及其与中性磷(膦)酸酯混合体系萃取金属离子的研究,尚未见文献报道。本文报道用1在煤油溶剂中萃取Sn(Ⅱ),Pb(Ⅱ),Zn(Ⅱ)和Cd(Ⅱ)等的平衡,应用斜率法研究了萃取平衡;合成了1-Zn(Ⅱ)和1-Pb(Ⅱ)固体萃合物;在元素分析和有关离子分析的基础上结合最小二乘法线性回归探讨了萃取机理及有关萃合物组成;考察了在加入三辛基氧化膦(TOPO)时,1对金属离子萃取性能的影响。     

硫酸铵-碘化钾-乙醇体系萃取分离铋

1　引言利用高聚物水溶液在无机盐存在下可以分成两相的非有机溶剂萃取分离方法已引起人们的重视[1 ,2 ] 。本文研究发现 ,在硫酸铵存在下 ,乙醇与水分相过程中 ,Ｂｉ(Ⅲ )与Ｉ- 形成的ＢｉＩ3-6 络阴离子能被乙醇相定量萃取 ,控制一定的酸度 ,可以实现Ｂｉ(Ⅲ )与Ｆｅ(Ⅲ )、Ｃｏ(Ⅱ )、Ｍｎ(Ⅱ )、Ｃｕ(Ⅱ )、Ｎｉ(Ⅱ )、Ｍｏ(Ⅵ )之间的分离。该萃取体系与传统的有机溶剂萃取分离方法相比 ,具有平衡时间短 ,相分离速度快 ,无三相乳化 ,不使用有毒害有机溶剂 ,操作简单 ,快速均相萃取 异相分离等优点 ,既能萃取离子缔合物 ,又能萃取络阴…     

固-液萃取法研究1-苯基-3-甲基-4-苯甲酰基吡唑酮-[5]对钍、钪的萃取及钪的分析应用

本文以固体石蜡为溶剂,1-苯基-3-甲基-4-苯甲酰基吡唑酮-[5](HPMBP)为萃取剂,研究了钍、钪的萃取及反萃取条件。斜率比法示明石蜡中配合物组成分别为Th(PMBP)_4,Sc(PMBP)_3,人工合成钢铁样品的分析结果Sc~(3+)的回收率分别为99.6％和100％。     

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧(Ⅲ)

研究了1-苯基-3-甲基- 4-苯甲酰基-吡唑酮-5(HPMBP)和中性有机磷(膦)类萃取剂Cyanex 471X(TIBPS,B)在硝酸介质中对稀土元素La（Ⅲ）的萃取,用斜率法和恒摩尔法探讨了萃取机理,确定了萃合物的组成为La(NO3)2·PMBP·B,计算了萃取平衡常数.比较了HPMBP与Cyanex 471X、Cyanex 921、Cyanex 923、Cyanex 925、DEH/EHP、P350及TBP的单独及混合体系萃取La（Ⅲ）的性能,结果表明所有混合体系对La（Ⅲ）均有协同效应,其中HPMBP与Cyanex 923、Cyanex 921、Cyanex 925的混合体系是萃取La（Ⅲ）的有效体系.     

乙醇-盐-水-5-Br-PADAP体系萃取分离测定钯

研究了在硫酸铵存在下 ,5 Br PADAP乙醇体系中Pd(Ⅱ )、Rh(Ⅲ )、Pt(Ⅳ )的萃取行为及乙醇溶液的分相条件 ,讨论了影响萃取率的各种因素 ,试验表明 ,室温下 ,一定 pH范围内 ,该体系中的Pd(Ⅱ )几乎可完全被乙醇相萃取 ,而Rh(Ⅲ )、Pt(Ⅳ )不被萃取或萃取率很低 ,从而可实现Pd(Ⅱ )、Rh(Ⅲ )、Pt(Ⅳ )混合离子的定量分离 ,同时建立了Pd(Ⅱ )的测定方法。乙醇相中Pd(Ⅱ ) 5 Br PADAP配合物表观摩尔吸光系数为 1.18× 10 5L·mol- 1·cm- 1,钯量在 0～ 9.6 0 μg/10ml范围内符合比耳定律 ,检出限为 0 .0 90 μg/10ml。用该法分离混合样和测定两种活性碳钯催化剂中钯 ,结果满意     

聚乙二醇-硫酸铵-铝试剂体系中镧、镨、镝的分离研究

研究了在聚乙二醇2000(PEG)-硫酸铵-铝试剂双水相体系中, 铝试剂作萃取剂, 对镧、镨、镝的萃取行为. 实验结果表明, 在pH1～7酸度条件下, La(Ⅲ)完全被PEG相萃取, 而Pr(Ⅲ)几乎不萃取, Dy(Ⅲ)部分被萃取. 在pH5的缓冲溶液中实现了La(Ⅲ)与Pr(Ⅲ)的分离. 通过加入表面活性剂, 测定溶液光谱等方法, 探讨了金属离子在聚乙二醇相中存在形态.     

1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5萃取镓的研究

首次报道了1-苯基-3-甲基-4-苯甲酰吡唑啉酮-5(HPMBP)萃取镓的热力学和动力学, 指出在体系中形成Ga(PMBP)3(H2O)2萃合物, 配体PMBP既有一次溶剂化作用, 又有二次溶剂化作用, 并得到红外光谱和核磁共振谱的证实。镓的萃取过程为水相化学反应控制, 决速步骤为一次溶剂化过程: Ga^3^++HPMBP→Ga(PMBP)^2^++H^+。添加剂三辛基氧化膦(TOPO)不影响HPMBP萃取镓的分配比, 但降低了HPMBP萃取镓的正向速率, 表明动力学抑萃作用与热力学抑萃作用无对应关系。     

The reaction of (4R,5R)- and (4S,5S)-4,5-epoxy-2(E)-hexenoates and secondary amines.

A reaction of methyl (4R,5R)-4,5-epoxy-2(E)-hexenoate 1 with N-benzylmethylamine gave a diastereomerically pure methyl (4R,5R)-4,5-epoxy-(3S)-N-benzylmethylamino hexanoate 6 and methyl (4S,5R)-4-N-benzyl-methylamino-5-hydroxy-2(E)-hexenoate 7. The former was chemoenzymatically converted to (-)-osmundalactone 11, which is an aglycone of osmundalin. On the other hand, the directly conjugated addition of dimethylamine to methyl (4S,5S)-4,5-epoxy-2(E)-hexenoate 1 followed by treatment with MeOH at 40 degrees C exclusively provided methyl (4R,5S)-4-dimethylamino-5-hydroxy-2(E)-hexenoate 16, which was converted into L-(-)-forosamine 18.     

Synthesis and certain conversions of 3-(3,3-dichloroallyl)-4-hydroxycoumarin

A method has been developed for the synthesis of 3-(3,3-dichloroallyl)-4-hydroxycoumarin and 2-thioxo-3-(3,3-dichloroallyl)-4-hydroxy-2H-chromene, and certain conversions of these compounds have been studied. They undergo acid hydrolysis readily, forming (respectively) 3-(4-hydroxy-3-coumarin)- and 3-(2-thioxo-4-hydroxy-2H-chromene-3)propionic acids; these compounds are converted to the corresponding lactones by the action of acetic anhydride.Erevan State University, Erevan 375049. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 48–51, January, 1997.     

Studies on the syntheses of heteroeyelie compounds. Part DV. Cyclization products of i-substituted 2-benzyl-1,2,5,6-tetrahydropyridines [syntheses of analgesics. Part XXXV]

Treatment of 1,2,5,6-tetrahydro-2-(4-hydroxy- and/or 4-methoxybenzyl)-3,4-dimethyl-I-(3-methyl-2-butenyl)pyridines (IV and V) and 2-(4-methoxybenzyl)-3,4-dimethyl-1-(3-methyl-2-butenyl)-4-piperidinol (X) with acid afforded 9-(4-hydroxy- and/or 4-methoxybenzyl)-4,4,5,6-tetramethyl-1-azabicyelo[3,3,1]non-6-ene (XIII and XIV). In contrast, the corresponding 1-allyl-substituted derivatives VI, VII, and XI were converted into the expected 3-allyl-1,2,3,4,5,6-hexahydro-8-hydroxy- and/or 8-methoxy-6,11-dimethyl-2,6-methano-3-benzazocine (II and III).     

Cyanoacetylene and Its Derivatives: XXXII. Addition of Ammonia and Methylamine to 4-Hydroxy-4,4-diphenyl-2-butynenitrile

Nucleophilic addition of ammonia (25% aqueous solution) and methylamine to 4-hydroxy-4,4-diphenyl-2-butynenitrile occurs under mild conditions to afford 4-amino(or methylamino)-2,5-dihydro-5,5-diphenyl-2-iminofurans. 4-Hydroxy-4,4-diphenyl-2-butynenitrile in anhydrous liquid ammonia gives rise to 3-amino-4-hydroxy-4,4-diphenyl-2- butenenitrile which is quantitatively converted into the corresponding iminodihydrofuran or iminodihydrofuran hydrochloride in the presence of 10 wt % of KOH or gaseous hydrogen chloride. 4-Amino- and 4-methylamino-2-iminofurans react with 4-hydroxy-4-methyl-2-pentynenitrile to give 3-(4-amino- and 4-methylamino-5,5-diphenyl-2,5-dihydrofuran-2-ylideneamino)-4-hydroxy-4-methyl-2-pentenenitriles.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 64–69.Original Russian Text Copyright © 2005 by Mal’kina, Sokolyanskaya, Kudyakova, Sinegovskaya, Albanov, Shemyakina, Trofimov.     

Enantioselective organocatalytic formal [3 + 3]-cycloaddition of alpha,beta-unsaturated aldehydes and application to the asymmetric synthesis of (-)-isopulegol hydrate and (-)-cubebaol

[reaction: see text] The first highly enantioselective organocatalyzed carbo [3 + 3] cascade cycloaddition of alpha,beta-unsaturated aldehydes is reported. Using this methodology, crotonaldehyde is converted to 6-hydroxy-4-methylcyclohex-1-enecarbaldehyde, which is used in the synthesis of (-)-isopulegol hydrate, (-)-cubebaol, and p-tolualdehyde as well as (-)-6-hydroxy-4-methyl-1-cyclohexene-1-methanol acetate, an intermediate in the total synthesis of lycopodium alkaloid magellanine. Other alpha,beta-unsaturated aldehydes give rise to chiral cyclohexadienes via formal [4 + 2] reactions.     

Chiral Cyclopentane-Based Mimics of D-myo-Inositol 1,4,5-Trisphosphate from D-Glucose

Two routes from D-glucose to chiral, ring-contracted analogs of the second messenger D-myo-inositol 1,4,5-trisphosphate are described. Methyl alpha-D-glucopyranoside was converted by an improved procedure into methyl 4,6-O-(p-methoxybenzylidene)-alpha-D-glucopyranoside (6) and thence into methyl 2-O-benzyl-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hexodialdopyranoside (1,5) (14) in four steps. In the first ring-contraction method 14 was converted into methyl 2-O-benzyl-6,7-dideoxy-3,4-bis-O-(p-methoxybenzyl)-alpha-D-gluco-hept-6-enopyranoside (1,5) (15), which on sequential treatment with Cp(2)Zr(n-Bu)(2) followed by BF(3).Et(2)O afforded a mixture of (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]-5-vinylcyclopentane (16) and its 4S,5R diastereoisomer 17. Removal of the p-methoxybenzyl groups of 16 and subsequent phosphorylation and deprotection afforded the first target compound, (1R,2R,3S,4R,5S)-3-hydroxy-1,2,4-tris(phosphonooxy)-5-vinylcyclopentane (3). In the second route, intermediate 14 was subjected to SmI(2)-mediated ring contraction to give (1R,2S,3S,4R,5S)-3-(benzyloxy)-4-hydroxy-5-(hydroxymethyl)-1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (20). Benzylation of 20 provided (1R,2S,3S,4R,5S)-3-(benzyloxy)-6-[(benzyloxy)methyl]-4-hydroxy-1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (22) and (1R,2S,3S,4R,5S)-3,4-bis(benzyloxy)-5-(hydroxymethyl)-1,2-bis[(p-methoxybenzyl)oxy]cyclopentane (21), which were elaborated to the target trisphosphates (1R,2R,3S,4R,5S)-3-hydroxy-5-(hydroxymethyl)-1,2,4-tris(phosphonooxy)cyclopentane (4) and (1R,2S,3R,4R,5S)-1,2-dihydroxy-3,4-bis(phosphonooxy)-5-[(phosphonooxy)methyl]cyclopentane (5), respectively. Both 3 and 4 mobilized intracellular Ca(2+), but 4 was only a few fold less potent than D-myo-inositol 1,4,5-trisphosphate, demonstrating that effective mimics can be designed that do not bear a six-membered ring.     

3-methylthio-1,2-dithiolylium salts—II: Reaction with 4-hydroxy-3h-pyran-2,6-dione. 1,3-bis-(1,2-dithiol-3-ylidene)-2-propanones

A simple route to the hitherto unknown 1,3-bis-(1,2-dithiol-3-ylidene)-2-propanones is reported: 3-Methylthio-1,2-dithiolylium salts condense with 4-hydroxy-3H-pyran-2,6-dione to 3,5-bis-(1,dithol-3-ylidene)pyran-2,4,6-triones, which are converted by acidic hydrolysis into the propanones.     

Metabolism of aloesin and related compounds by human intestinal bacteria: a bacterial cleavage of the C-glucosyl bond and the subsequent reduction of the acetonyl side chain

By anaerobic incubation with a bacterial mixture from human feces, aloesin (aloeresin B; 1) was converted to 2-acetonyl-7-hydroxy-5-methylchromone (aloesone; 3) and dl-7-hydroxy-2-(2'-hydroxypropyl)-5-methylchromone (aloesol; 4a + 4b) through a cleavage of the C-glucosyl bond, followed by reduction of the acetonyl side chain. An analogous compound, aloeresin A (2), was converted to p-coumaric acid and aloesin (1), the latter being subsequently transformed to aloesone (3) and dl-aloesol (4a + 4b). On the other hand, 7-O-methylated derivatives (7, 5a and 5b) of aloesin and of 8-C-glucosylaloesol were not cleaved to the corresponding aglycones, suggesting the importance of a free hydroxy group adjacent to the C-glucosyl group in the molecule for the bacterial cleavage of aloesin derivatives. This is the first report on the cleavage of the C-glycosyl bond of chromone C-glucosides by intestinal bacteria.     

Synthesis of pyrido[1,2-c][1,3]benzoxazines based on 1-benzyl-3-hydroxy-3-methyl-6-(2-benzyloxyphenyl)-4-piperidones

The stereomeric 1-benzyl-3-hydroxy-3-methyl-6e-(2-bemyloxyphenyl)-4-piperidones on debenzylation and subsequent reaction with formaldehyde are converted into cis- and trans-1,3,4-10b-tetrahydro-3-hydroxy-3-methyl-2-oxopyrido-[1,2-c][1,3]benzoxazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–127, January, 1991.     

Preliminary studies on the synthesis of rancinamycins from nitrosugars: first total synthesis of (3S,4S,5S,6R)-5-benzyloxy-6-hydroxy-3,4-(isopropylidendioxy)-cyclohex-1-enecarbaldehyde

The first total synthesis of (3S,4S,5S,6R)-5-benzyloxy-6-hydroxy-3,4-(isopropylidendioxy)-cyclohex-1-enecarbaldehyde from d-glucose is described. The key steps of this synthesis are the stereoselective Michael addition of 2-lithio-1,3-dithiane to 3-O-benzyl-5,6-dideoxy-1,2-O-isopropylidene-6-nitro--d-xilo-hex-5-enofuranose followed by the enantioselective two-step transformation of 3-O-benzyl-5,6-dideoxy-5-C-(1,3-dithian-2-yl)-6-nitro-β-l-idofuranose into (1S,2S,3S,4S,5S,6R)-5-benzyloxy-6-hydroxy-3,4-(isopropylidendioxy)-2-nitro-cyclohexanecarbaldehyde propylene dithioacetal, which was finally converted into the target compound.