REACTIONS OF A PHOSPHORANIMINE ANION WITH SOME ORGANIC ELECTROPHILES

Abstract

The reactions of a variety of electrophiles with the N-silyl-P-trifluoroethoxyphosphoranimine anion Me₃Sin°P(Me)(OCH₂CF₃)CH^? ₂ (1a), prepared by the deprotonation of the dimethyl precursor Me₃SiN[dbnd]P(OCH₂CF₃)Me₂ (1) with n-BuLi in Et₂O at-78°C, were studied. Thus, treatment of 1a with alkyl halides, ethyl chloroformate, or bromine afforded the new N-silylphosphoranimine derivatives Me₃SiN[dbnd]P(Me)(OCH₂CF₃)CH₂R [2: R = Me, 3: R = CH₂Ph, 4: R = CH[sbnd]CH₂, 5: R = C(O)OEt, and 6: R = Br]. In another series, when 1a was allowed to react with various carbonyl compounds, 1,2-addition of the anion to the carbonyl group was observed. Quenching with Me₃SiCl gave the O-silylated products Me₃SiN[dbnd]P(Me)(OCH₂CF₃)CH₂°C(OSiMe₃)R¹R² [7: R ¹ = R ² = Me; 8: R ¹ = Me, R ² = Ph; 9: R¹ = Me, R ² = CH[sbnd]CH₂; and 10: R ¹ = H, R ² = Ph]. Compounds 2–10 were obtained as distillable, thermally stable liquids and were characterized by NMR spectroscopy (¹H, ¹³C, and ³¹P) and elemental analysis.     

NEW CARBON-PHOSPHORUS BOND CONTAINING COMPOUND IN THE REACTION OF 2-ACETYLTHIOPHENE WITH PHOSPHORUS PENTACHLORIDE

Abstract

The treatment of 2-acetylthiophene with phosphorus pentachloride led, besides other products reported in previous studies, to 2-(2-thienyl)-2-chloroethenephosphonic acid in 16% yield. This compound was transformed, in the course of purification attempts, into 2-(2-thienyl)-2-oxoethanephosphonic acid. Full spectroscopic data for both compounds are provided.     

ON SOME INCORRECTNESS IN THE INTERPRETATION OF RESULTS OF THE REACTION OF SULPHINYLAMINES WITH ALDEHYDES

Abstract

In contradiction to reports by others, it was shown that sulphinylamines do not give products of cycloaddition on reaction with aldehydes in aprotic solvents. However, in the presence of a protonogenic agent, crystalline products were precipitated for which an ammonium α-aminosulphonate salt structure was confirmed. These salts are formed as a result of consecutive hydrolysis of sulphinylamines, condensation of aldehydes with the resulting amines, and bisulphite anion addition to Schiff bases.     

ESR SPECTRA OF THE SQUARE PLANAR COPPER(II) COMPLEXES WITH VARIOUS N4-MACROCYCLIC LIGANDS

Abstract

The ESR parameters were determined for copper(II) complexes with various 14-, 15- and 16-membered N₄-macrocyclic ligands. Of these ESR parameters g^‖ has the most simple relation to the covalency of the coordination bonds in the present compounds, i.e., the smaller the g^‖ value the larger the covalency. The order of covalencies derived from the g^‖ values nicely matches with that supposed from the size of macrocyclic rings and the charge of the ligands. The approach to the estimation of covalency of the coordination bonds by use of copper hyperfine coupling constant was examined, but it was found that this approach gives rather unreliable results for the present compounds.     

3,5-diCl-DMPAP光度法同时测定铜和锌

研究了在乳化剂OP存在下,以2 (3,5 二氯 2 吡啶偶氮) 5 二甲氨基酚(3,5 diCl DMPAP)为显色剂使铜和锌同时显色,再以硫脲 硫代硫酸钠掩蔽铜,利用两次所测吸光度之差以差减法同时测定铜、锌。试验结果表明,pH6.0～10.0时,铜和锌与试剂均形成1∶2的紫红色配合物。铜配合物的最大吸收波长位于558nm处,锌配合物的最大吸收波长位于565nm处。两者在562nm波长处的吸光度具有良好加和性,其表观摩尔吸光系数分别为εCu=9.6×104L·mol-1·cm-1,εZn=1.2×105L·mol-1·cm-1。方法灵敏度高、操作简单,用于地质化探样品和人发中微量铜、锌的同时测定,结果满意。     

乳化剂OP—3,5—diCl—DMPAP吸光光度法测定微量锰

报道在非离子表面活性剂OP存在下,2-(3,5-二氯-2-吡啶偶氮)-5-二甲氨基苯酚(3.5-diCI-DMPAP)与 Mn(Ⅲ)的显色反应.在pH 8.5～10.5的 NH_3-NH_4Cl缓冲溶液中.Mn(Ⅲ)与试剂形成稳定的红色络合物,络合比为1:4,表观摩尔吸光系数.ε_(575)=1.11×10~5.锰浓度在0～0.52mg·L~(-1)内遵守比耳定律.在邻二氯菲存在下,可直接测定合金钢和镁合金中微量锰.     

固相配位化学反应研究——ⅩⅩⅩⅩⅠ.[Co(NH_3)_5(H_2O)]Br_3,[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应动力学研究

本文主要用气相色谱逸出气体分析方法,借助于红外、紫外可见漫反射谱等手段研究了[Co(NH_3)_5(H_2O)]Br_3、[Cr(NH_3)_5(H_2O)](NO_3)_3与无机盐KY(Y=Cl,Br,Ⅰ)的固相反应,计算了失水与失氨的动力学参数,发现第一步反应失水生成一取代中间产物,其活化能与外加阴离子无关,为S_N1过程。第二步失氨反应活化能与中心离子M以及取代基Y有关,当M=Co(Ⅲ)时,反应体系的失氨活化能大小有下列顺序:Cl>Br>Ⅰ(E值分别为187、155、98kJ·mol~(-1)),M=Cr(Ⅲ)时则正好相反:Ⅰ>Br>Cl(E值分别为213、146、79 kJ·mol~(-1))。     

Ru(Ⅲ)-CPA-DBC-KIO4褪色反应催化光度法测定微量钌

报道了以钌(Ⅲ)催化KIO4氧化CPA-DBC为基础的测定微量钌的催化光度分析,建立了一种在水相中直接测定微量钌的方法.钌(Ⅲ)含量在4.0～30.0μg·L-1范围内符合比耳定律,检出限为4.0μg·L-1.方法用于贵金属精矿中钌的测定,结果满意.     

二溴对甲基偶氮溴羧与钡显色反应的研究与应用

研究了新显色剂二溴对甲基偶氮溴羧与钡显色反应的条件。在磷酸介质中,试剂与钡形成2:1的络合物,最大吸收波长为610nm,摩尔吸光系数为2.13×10~4L·mol~(-1)·cm~(-1),钡量在0～20μg/25ml范围内符合比耳定律。两倍的锶和五倍的钛不干扰,钙的允许量较大,方法用于直接测定钛酸钡烧结物中微量钡,结果满意。     

新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯的合成及其与汞的显色反应研究

合成了新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯(DCNPNPT),测定了试剂的亚氨基离解常数pKa＝9．2。在TritonX-100存在下,pH9．8～11．0范围内,试剂与Hg2+形成14黄色型配合物,用双波长法测得其表观摩尔吸光系数为2．27×105L·mol-1·cm-1。汞含量在0～10μg／25ml范围内符合比耳定律,用此法测定了天然水和实验室废水中微量汞含量,结果满意。     

新显色剂1,5-二(2-羟基-5-溴苯)-3-氰基甲月替光度法测定锌的研究和应用

合成了新试剂1,5-二(2-羟基-5-溴苯)-3-氰基甲月替(HBPCF),并研究了它与锌的显色反应。在pH9．5的氨-NH     

新试剂1-(2,3,5-三氮唑偶氮)-2-萘酚与锌的显色反应研究及应用

研究了１－（２,３,５－三氮唑偶氮）－２－萘酚（ＴＺＡＮ）锌显色反应,结果表明,在ＰＨ６．０－８．５的乙醇水溶液中ＴＺＡＮ与锌形成稳定的红色络合物,其最大吸收波长为５２５ｎｍ,表观摩尔吸光系数为３．５６＊１０＾４Ｌ．同,络合物的组成为Ｚｎ：ＴＺＡＮ＝ｌ：２,锌浓度在０－１．２μｇ．ｍｌ＾－１范围内遵守比耳定律,方法用于人发中微量锌的直接测定,结果满意。     

MECHANISM OF THE REACTION OF DIPHENYL N-BROMOSULFILIMINE WITH SULFIDES,PHOSPHINES AND TERTIARY AMINES

Abstract

The mechanism of the reactions of diphenyl N-bromosulfilimine (I) with such nucleophiles as sulfides, phosphines and tertiary amines was investigated. In the presence of water, (I) reacts with sulfides or phosphines to afford the corresponding sulfoxides or the phosphine oxides in moderate yields; however, the reaction with tertiary amine gave only the N-t-aminosulfilimine derivative. The effect of ring size in the reaction with cyclic sulfides suggests that the reaction proceeds via initial bromine transfer from the nitrogen atom to the sulfur atom of the cyclic sulfides followed by S_N2 type substitution of bromide on the sulfur atom of the cyclic sulfide with the sulfilimino group. The phosphine oxide obtained in the reaction of (I) with optically active methyl n-propyl phenyl phosphine was racemized but retained a small portion of the optical activity. In the case of tertiary amines, even 1,4-diazabicyclo-(2,2,2)-octane (DABCO), in which the back side of the nitrogen atom is blocked, reacted smoothly to afford the corresponding ammonium salts, suggesting the reaction to be of S_N2 type on the nitrogen atom of the sulfilimine.     

3—甲氧基—甲亚胺H光度法测定植物中硼的研究及应用

研究了3-甲氧基-甲亚胺H与硼的显色反应。在乙酸-乙酸铵缓冲溶液中。硼与3-甲氧基-甲亚胺H形成1:2的黄色配合物,最大吸收在420nm波长处,摩尔吸尤系数为7.19×10~3,Sandell灵敏度为0.0015/μg·cm~(-2)。当硼含量在0～35μg/25ml范围内符合比耳定律,应用于植物中硼的测定获得满意的结果。     

4—（2—羟基—4—硝基苯偶氮）—1—苯基—3—甲基吡唑啉酮光度法测定烟草中钙的研究

在弱碱性介质中,4－（2－羟基－4－硝基苯偶氮）－1－ 苯基－3－甲基吡唑啉酮与钙生成红色络合物,λmax=510nm,ε=2.89*10^4L.mol^-1.cm^-1,钙含量在0－20ug/25ml内符合比耳定律,方法用于烟草样品中钙的测定,结果满意。     

显色剂1-羟基-2-(5-NO2-2-吡啶偶氮)-8-氨基-3,6-萘二磺酸与镍显色反应的研究

探讨了显色剂 1 羟基 2 (5 NO2 2 吡啶偶氮 ) 8 氨基 3,6 萘二磺酸 (简称 5 NO2 PAH )与镍离子显色的适宜条件及其共存离子的影响 ,建立了 5 NO2 PAH测定镍的新显色体系。结果表明 ,在 pH 8.5～ 10 .0范围内 ,镍与试剂形成稳定的 1∶2配合物 ,其最大吸收峰位于 6 5 3nm ,表观摩尔吸光系数εNi=1.0 7× 10 5L·mol- 1·cm- 1,镍的浓度在 0～ 5 μg/ 10ml范围内遵守比耳定律。方法用于合金中镍的测定 ,结果满意。     

SYNTHESIS,PROPERTIES AND AN ELECTROACTIVE FILM OF RUTHENIUM(II) COMPLEXES WITH THE PYRIDINE DERIVATIVE LIGAND: trans-[RuCl2(pmp)4].(pmp=3-(PYRROL-1-YLMETHYL)PYRIDINE)

Abstract

In this work we report the synthesis, characterization and electrochemistry of the complex trans-[RuCl₂(pmp)₄], where pmp=3-(pyrrol-l-ylmethyl)pyridine. The complex was characterize by electronic spectroscopy (Λ_max = 404 nm and ε = 27000), vibrational FT-IR spectroscopy, ¹H and ¹³C NMR, showing results typically in agreement with trans geometry. Cyclic voltammetry reveals a redox process centered on the Ru(II) center (E^1/2 = 0.53V vs. NHE), which is electrochemically and chemically reversible. Spectroelectrochemistry shows the progressive disappearance of bands at 404 and 475 nm and the appearance of a new band at 302 nm during the oxidation process. Cyclic voltammetric experiments were performed to characterize the redox properties of the ruthenium complex; its electropolymerization produced a strongly adhesive conducting polymeric film on platinum and palladium electrodes.     

新显色剂2-(5-羧基-1,3,4-三氮唑偶氮)-5-二乙氨基酚与钴的显色反应的研究

研究了新显色剂2-(5-羧基-1,3,4-三氮唑偶氮)-5-二乙氨基酚与钴的显色反应,试剂与钴在pH 6.0～8.0范围内形成稳定的紫红色络合物,其组成比为1:3,λ_(max)=540nm,络合物表观摩尔吸光系数为5.7×10~4,Co~(2+)在0～0.8mg·L~(-1)范围内符合比耳定律,络合物在强酸溶液中能稳定存在,可消除大量离子的干扰,有良好的选择性,方法可以不经分离直接测定维生素B_(12)和合成工业废水中的微量钴,结果满意。     

离子色谱法测定大豆木质部汁液中的Cl-、SO42-、NO3-、PO43-、柠檬酸和苹果酸

建立了离子色谱法测定大豆木质部汁液中Cl~-、SO_4~(2-)、NO_3~-、PO_4~(3-)、柠檬酸和苹果酸的方法。Cl~-、SO_4~(2-)、NO_3~-、PO_4~(3-)、柠檬酸和苹果酸的检出限分别为0.01、0.04、0.05、0.05、0.30和0.10 mg/L,相对标准偏差分别为8.34％、4.68％、9.54％、6.86％、5.52％和7.50％,线性范围分别为0.5～50.0、1.0～100.0、0.5～50.0、1.0～100.0、5.0～100.0和1.0～100.0 mg/L,回收率分别为103％～106.7％、92％～98.7％、93％～95.5％、91.7％～92％、93.2％～106％和94％～108.3％。方法简便、快速,测定结果准确,无干扰。