具有聚集荧光增强性质的双(4-二乙氨基水杨醛)缩偶氮二甲酰肼二丁基锡的合成和晶体结构

在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)_2]n(T)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0～10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。     

Selective Spectrophotometric Determination of Palladium (II) With 2-(5-Bromo-2-Pyridylazo)-5-(Diethylamino)-Phenol

Abstract

A spectrophotometric study of the Pd(II) complex of a reagent 2-(5-Bromo-2-Pyridylazo)-5-(diethylamino)-Phenol (5-Br-PADAP) is presented. A violet complex is formed at pH 3.53, and shows maximal absorbance at 585 nm with molar absorptivity of 3.86 × 10⁴ 1. mol^?1 cm^?1. Beer's law is obeyed up to 50 μ of Pd(II). The method offers the advantages of simplicity, high precision, requires no extraction and is very selective, where 5.0 mg Pt(VI) and 0.3 mg Au(III) ions do not interfere.     

Analysis of Sub-Microgram Levels of Palladium (II) in Environmental Samples by Selective Extraction and Spectrophotometric Determination with N-p-Methoxyphenyl-2-Furylacrylohydroxamic Acid and 5-(Diethylamino)-2-(2-Pyridylazo) Phenol

Abstract

Nine new hydroxamic acids in conjunction with four pyridylazo reagents were explored for extractive separation and spectrophotometric determination of palladium in environmental samples. It was found that maximum sensitivity and selectivity was achieved by employing N-p-methoxyphenyl-2-furylacrylohydroxamic acid (MFHA) and 5-(diethylamino)-2-(2-pyridylazo) phenol (DEPAP). Palladium was first selectively extracted with MFHA in isoamyl alcohol at pH 2.7-3.5 and the extract was equilibrated with a mixture of 5 M HCl and 10^{? 3} M solution of DEPAP in ethanol. The resulting intensely green ternary complex was measured at 560 nm (σ 5.1 × 10⁴ l mole^?1 cm^?1). The extraction system is suitable for enrichment of palladium over 15 times without loss in recovery and enables determination of palladium at levels as low as 10^?4 ppm (0.1 ppb). The method tolerates the presence of a large number of diverse ions normally associated with palladium, including platinum metals, and was employed for the determination of palladium in standard catalysts, biological materials, and freshwaters.     

Ruthenium(III)-carbonyl and ruthenium(II)-nitrosyl complexes of nitrogen-containing ligands with ethoxysilane groups

Reactions of γ-aminopropyltriethoxysilane and 4-(diethylamino)salicylaldehyde in ethanol afforded a Schiff base L1H, which reacted with [Ru(CO)₂Cl₂]_n in the presence of Et₃N in THF giving a ruthenium(III) carbonyl complex RuCl(CO)₂(η¹-O-L1)(η²-O,N-L1) (1). Treatment of γ-aminopropyltriethoxysilane with 4-pyridinecarboxaldehyde gave the Schiff base L2. Interactions of L2, γ-aminopropyltriethoxysilane, and Ru(NO)Cl₃?H₂O in THF led to the formation of a ruthenium(II) nitrosyl complex RuCl₃(NO)(L2)[H₂N(CH₂)₃Si(OEt)₃] (2) with linear N≡O ligand. Complexes 1 and 2 were characterized by microanalyses and IR and MS spectroscopies and confirmed by single-crystal X-ray diffraction.     

Synthesis and antimalarial effects of 5,6-dichloro-2-[(4-||4-(diethylamino)-i-methylbutyl] amino||-6-methyl-2-pyrirnidinyl)amino] benzimidazole and related benzimidazoles and lH-imidazo[4,5-b] pyridines

A group of fifty-five 2-[(4-11[(dialkylamino)alkyI]amino11-6-methyl-2-pyrimidinyl)amino]-benzimidazoles (VII) was synthesized in 3-88% yield by the condensation of the requisite 2-[(2-benzimidazolyl)amino]-4-chloro-6-methylpyrimidine (VI) with the appropriate polyamine in ethanol-hydrochloric acid or neat with excess amine containing potassium iodide. The 2-[(2-benzimidazolyl)amino]-6-methyl-4-pyrirnidinol precursors (V), obtained in 11-51% yield by cyclization of 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine with a suitably substituted o-phenylenediamine, were chlorinated with phosphorus oxychloride to give the intermediate 2-[(2-benzimidazolyl)amino]-4-chloro-6-rnethylpyrimidines (VI) (27-99%). Oxidation of 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl] amino 11-6-methyl-2-pyrimidinyl) amino ]benzimidazole ( 29 ) with m-chloroperbenzoic acid gave the distal N⁴'-oxide ( 31 ) (19%). Fusion of 2,3-uiaminopyridine with 2-(cyanoamino)-4-hydroxy-6-methylpyrimidine provided 2-[(4-hydroxy-6-tnethyl-2-pyrimidinyl)amino]-lH-imitlazo[4,5-b]pyrimidine (VIII) (30%), which upon chlori-nation with phosphorus oxychloride (63%) followed by amination with i N, N-diethylethylene-diamine afforded 2-(4-11[2-(diethylamino)ethyl] amino 11-6-methyl-2-pyrimidinyl)-lH-imidazo [4,5-b]pyridine (X) (8%). Thirty-eight of the novel 2-[(4-amino-6-methyl-2-pyrimidinyl)amino]-benzimidazoles possessed “curative” activity against Plasmodium berghei at single subcutaneous doses ranging from 20.640 mg./kg. Orally, thirty-one compounds exhibited suppressive activity against P. berghei comparable with or superior to the reference drugs 1-(p-chlorophenyl)-3-(4-11[2-(diethylarnino)ethyl]amino 11-6-methyl-2-pyrimidinyl)guanidine (I) and quinine hydrochloride, while twelve of them were 5 to 28 times as potent as I and quinine hydrochloride. Eight compounds also displayed strong suppressive activity against P. gallinaceum in chicks. 5,6-Dichloro-2-[(4-112-(diethylamino)ethyl]amino11-6-methyl-2-pyrimidinyl] benzimidazole (18) showed marked activity against a cycloguanil-resistant line of P. berghei, and the most promising member of the series, namely 5,6-dichloro-2-[(4-11[4-(diethylamino)-l-methylbutyl]amino11-6-methyl-2-pyrimidinyl)amino]benzimidazole ( 29 ) (Q = 28), was designated for preclinical toxico-logical studies and clinical trial. Structure-activity relationships are discussed.     

Intramolecular Diastereoselective Cascade Cyclization Reaction of N,N′-Bis(Salicylidene)Cyclohexanediimine with Phosphoryltrichloride to a Bis(Chlorophosphorylated) Decahydro-2,4-DI (2-Hydroxyphenyl)Benzo[d][1,3,6]oxadiazepine

Abstract

A new type of cascade cyclization was observed in the phosphorylation reaction of (R,R)- or (S,S)-N,N′-bis(salicylidene)cyclohexanediimine with phosphoryltrichloride, which resulted in the formation of bis(chlorophosphorylated) decahydro-2,4-di(2-hydroxyphenyl)benzo[d][1,3,6]oxadiazepine with two new stereogenic phosphorus atoms and two new stereogenic carbon atoms in the oxadiazepine ring in the β-position to phosphorus. During the synthesis, the N atom attacks the phosphorodichloridate group with the formation of the P–N bond to give an asymmetric phosphorus atom and an iminium ion. This compound with six stereogenic centers crystallizes in the monoclinic centrosymmetric space group P2₁/c and the crystal structure together with solution and solid-state MAS ¹³C and ³¹P NMR studies reveals a preferential formation of stereoisomers.     

Radical Addition of Bis(Trimethylsilyl)Phosphonate to Vinyltrimethylsilane: Crystal Structure of (2-Trimethylsilylethyl)Phosphonic Acid

Abstract

The formation of phosphorus-carbon bond by free radical addition of phosphorus compounds containing P-H bond to olefins has been known since more than three decades ago. Alkyl or aryl phosphins, phosphinates, phosphonates and phosphorus or hypophosphorus acid have been used in these reactions, but a little attention have been paid to silyl phosphonates. As a part of ongoing study on the structure and reactivity of organosilicon-phosphonate compounds, we synthesized bis(trimethylsi1yl) (2-trimethylsilylethyl)phosphonate (I) by the reaction of bis(trimethylsily1) phosphonate with vinyltrimethylsilane in the presence of a peroxide. The product was characterized by its ¹H and ³¹P NMR and IR spectra. Hydrolysis of (I) led to the formation of corresponding phosphonic acid (n). The crystal structure of (11) has been determined by X-ray diffraction analysis.     

SYNTHESIS AND STEREOCHEMISTRY OF PENTACARBONYL(PHOSPHOLE)METAL(0)- AND TETRACARBONYLBIS(PHOSPHOLE)METAL(0) COMPLEXES OF 6B ELEMENTS

Abstract

Pentacarbonylphospholemetal(0) and cis-tetracarbonylbis(phosphole)metal(0) complexes were synthesized from the thermal reaction of M(CO)₃(THF) and M(CO)₄(COD) (M: Cr, Mo, W) with corresponding phosphole (1-phenyl-3,4-dimethylphosphole, 1-phenyl-3-methylphosphole, and 1-phenylphosphole). These complexes were isolated as orange crystals by column chromatography on silicagel at 253 K and crystallization from n-hexane at 223 K and characterized by means of IR and NMR (¹H, ¹³C, and ³¹P). Spectroscopic data shows that the phosphole is coordinated to the transition metal through its phosphorus atom rather than through the conjugated diene unit in the both types of complexes. The tetracarbonylbis(phosphole)metal(0) complexes were found to have cis-arrangement of two phosphole ligands. Comparing ¹³C-NMR chemical shifts of the complexes with the free ligands, one can deduce that the involvement of the phosphorus atom in the ring π-electron delocalization is drastically reduced upon coordination. This is attributed to the stronger [sgrave]-donation but weaker π-accepting ability of the phosphorus atom in the phosphole ligands compared to the carbonyl groups.     

Reactions of Halides of Tervalent Phosphorus with Imines and -Diimines

Abstract

Isobutylidenebutylamine reacts with phosphorus trichloride in the presence of organic bases to give N-butyl-N-isobutenylamidodichloro-or bis(N-butyl-N-isobutenylamido)chlorophosphites depending on the ratio of reagents. Reasons are given in Eavour of the reaction beginning with the nucleophilic attack of the nitrogen atom of the imine on the electrondeficient phosphorus atom of the chloride. Reactions of ethyldichloro- and diethylchlorophosphites with benzylidenmethylamine produce 2-chloro- and 2-ethyl-2-oxo-1,4,2-diazaphospholanes respectively. Interaction of diethylchlorophosphite with benzylidenmethylamine in the presence of triethyphosphite results in the formation of diethyl. (N-methyl-N-α-diethylphosphonobenzylamido)phosphite. As a result of interaction of bis(diethylamino)chlorophosphine with NIN-dibutyl-2,3-butandiimine in the presence of triethylamine new compounds (2-diethylamino-1,3-dibutyl-4,5-dimethyl-1,3,2-diazaphospholane and 4,8-dibutyl-3,7-bis(diethylamino)-[3.3.01-bicyclooctadiene-l15) are obtained. The structure of the latter is proved by means of ¹H, ³¹ p NMR-spectroscopy, and a complete X-ray analysis. Alkyldichlorophosphines form phosphonium salts of 1,3,2-diazaphospholene structure with a-diimines and 2-chloro-1,3-dicyclohexyl-4-chloro-1,3,2-diazaphospholene resulting from the reaction of N,N-dicyclohexylethylenediimine with PCl₃. In this product the P-C1 bond is unusually long, which is confirmed by X-ray analysis. In the course of the interaction of tervalent phosphorus halides with α,β-unsaturated imines a new reaction has been discovered with the formation of 1,2-dihydro-1,2-azaphosphorines.     

Tris(Trimethylsilyl)Phosphine in Reaction with Bis(Phenylenedioxa)Chlorophosphorane. The Way to Phosphoranylphosphines

Abstract

Tris(trimethy1silyl)phosphine (1) is the key reagent in the synthesis of one- and two-coordinated phosphorus compounds. Its characteristic features are extreme reactivity, high nucleophility of phosphorus atom and the P-Si bonds lability. The interaction of phosphine (1) with bis(catecho1)chlorophosphome (2) has been studied by dynamic ³¹P NMR method. On the reagents ratio 1:1 at first the nucleophilic substitution of chlorine occurs leading to formation of phosphome (3) with P^III-P^v bond (σ_P(III) -117.0, σ^P(V) 17.4 ppm, ¹J_pp 305.0 Hz) which converts then into more stable 2-(trimethylsiloxyphenyloxy)-4,5-bem- 1,3,2-dioxaphospholane (4).     

3,4-Dihydroxybenzoic Acid As A Reagent for the Spectrophotometric Determination of Titanium

Abstract

The reaction between titanium(IV) and 3,4-dihydroxybenzoic acid in aqueous media results in an intensely colored complex which is stable for at least 8h. It allows the spectrophotometric determination of titanium in silicate rocks. The proposed method, in pH 4.0–6.0, shows a molar absorptivity of 1.43.10⁴ L.mole^?1.cm^?1 at 380 nm. Beer's Law is obeyed up to 3.0 μg/mL of titanium(IV). The interference of iron(III) can be eliminated by reduction to iron(II) with hydroxylamine hydrochloride. The method was applied to the determination of titanium in various standard rocks and the results indicated that the accuracy and precision are satisfatory.     

Synthesis of (methylchlorosilyl)methyldichlorophosphines

(Methylchlorosilyl)methyldichlorophosphines have been synthesized by the reaction of [dimethy(diethylamino)silyl]- or [methyl-bis(diethylamino)silyl]methylmagnesium chlorides with PCl₃ in ether at –40÷–20 °C and subsequent treatment of the reaction mixture with dry HCl. The structures of the compounds thus obtained have been studied by³¹P,¹H, and¹³C NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 989–990, May, 1993.     

Über die Umsetzung von Phosphor (III)-fluoriden mit Phenylazid

On the Reaction of Phosphorus(III) Fluorides with Phenyl Azide The reaction of phenyl azide with phosphorus(III) fluorine compounds was found to proceed according to the principle of a Staudinger reaction producing, normally, fluorine-containing N-phenylphosphine imides. From diethylamino difluorophosphine and phenyldifluorophosphine the dimers, [(Et₂N)F₂PNPh]₂ and [PhF₂PNPh]₂, were obtained with phenyl azide. These compounds have previously been prepared by a different route. The compounds were characterized by elemental analysis, determination of the molecular weight, either cryoscopically or by mass spectrometry as well as through their n.m.r. spectra (¹H, ¹⁹F and ³¹P).     

Mono- und Bis(difluorphosphoranyl)ethylen,n-Hexyliden-fluorphosphoran und ein 2,4-Di-n-pentyl-1λ5,3λ5-diphosphet

Mono- and Bis(difluorophosphoranyl)ethylene, n-Hexylidene-fluorophosphorane, and a 2,4-Di-n-pentyl-1λ⁵, 3λ⁵ -diphosphete Bis(diethylamino)phosphanylethylene, 1 , is converted by SF₄ into bis(diethylamino)difluorophosphoranylethylene, 2. Analogously trans-1,2-bis(diphenylphosphanyl)ethylene, 3 , is converted into trans-1,2-bis(difluorodiphenylphoranyl)ethylene, 4. 2 reacts with n-butyllithium to give n-hexylidene-bis(diethylamino)fluorophosphorane, 5. With more n-butyllithium, the main product n-hexylidene-bis(diethylamino)-n-butylphosphorane, 7 , and the by-product 2,4-di-n-pentyl-1,1,3,3-tetrakis(diethylamino)-1λ⁵, 3λ⁵ -diphosphete, 8 , are formed. With t-butyllithium 2 yields 3,3-dimethyl-butylidene-bis(diethylamino)fluorophosphorane, 6. All new compounds 1, 2, 4–8 are characterized by their nmr and ir spectra.     

Synthesis of Phosphanes Bearing 2‐Imino‐1,3‐thiazolidine Ligands – X‐Ray Analyses and NMR Spectroscopy

Pseudo‐ephedrine derived 2‐imino‐1,3‐thiazolidine 1 reacts with tris(diethylamino)phosphane by stepwise replacement of the diethylamino group to give the mono‐, bis‐ and tris(imino)phosphanes 2 , 3 and 4 , respectively, of which 4 could be isolated in pure state. The analogous reaction with diethylamino‐diphenylphosphane affords the imino‐diphenylphosphane 5 . The iminophosphanes react with sulfur or selenium to give the corresponding phosphorus(V) compounds. In contrast, the reaction of the iminophosphanes with oxygen is very slow; anhydrous trimethylamine N‐oxide reacts in the melt with the phosphanes to give the oxides 4(O) and 5(O) . The molecular structures of 4(O) (in mixture with 4 ), 4(Se) , 5(S) and 5(Se) were determined by X‐ray analysis. In all cases the ring‐sulfur and the phosphorus atoms are in cis‐positions at the C=N bonds. The analogous solution structures were determined by ¹H, ¹³C, ¹⁵N, ³¹P and ⁷⁷Se NMR spectroscopy. In the case of the compounds 5 , 5(O) , 5(S) and 5(Se) the isotope‐induced chemical shifts ¹δ^14/15N(³¹P) were determined, using INEPT‐HEED experiments.     

Catalytic Spectrophotometric Determination of Titanium(IV) Using Methylene Blue‐Ascorbic Acid Redox Reaction

A highly selective and sensitive catalytic method for the determination of trace amounts of titanium(IV) was developed. The method is based on the catalytic effect of titanium(IV) on the methylene blue‐ascorbic acid redox reaction. The reaction was followed spectrophotometrically by measuring the change in absorbance of methylene blue at 665 nm, 5 minutes after the initiation of the reaction. In this study experimental parameters were optimized and the effect of the presence of various cations and some anions on the determination of titanium(IV) was examined. The calibration graph was linear in the range of 3‐25 ng mL^?1 of titanium(IV). The relative standard deviation for the determination of 10 and 20 ng mL^?1 of titanium(IV) were 2.64% and 1.51%, respectively (n = 8). The detection limit calculated from three times of standard deviation of blank 3S_b was 0.6 ng mL^?1. The method was successfully applied to the determination of titanium(IV) in tap water and ore samples.     

Synthesis,Reactivities, and Unique Solution Properties of 4,8-BIS(Diethylamino)-Methylene-1,2,3,5,6,7-Hexaselenacyclooctane

The heading novel heterocycle (3) which contains six selenium atoms in its eight-membered ring was prepared by reaction of 1,1-bis(diethylamino)-2-chloroethene (1) with elemental selenium. The compound 3 showed unique spectroscopic properties behaving as the bis(diethylamino)carbeniumdiselenocarboxylate (4) equivalent in reactivities.     

PHOSPHONOMETHYLATION OF AMINOALKANOLS PREPARATION OF 4-(PHOSPHONOMETHYL)-2-HYDROXY-2-OXO-1,4,2-OXAZAPHOSPHORINANES1

Abstract

Treatment of aminoalkanols 1 with phosphorous acid and formaldehyde in presence of conc. hydrochloric acid gave mixtures of [(2-hydroxy alkyl)imino] dimethylene diphosphonic acids 3 and 4-(phosphonomethyl)-2-hydroxy-2-oxo-1,4,2-oxazaphosphorinanes 2 from which 2 were isolated as crystalline solids. Similar treatment of 2-amino-2-methyl-1,3-propanediol 8 gave a complex mixture from which dimethylene diphosphonic acid of 5-amino-5-methyl-1,3-dioxane 9 was isolated. 2-Aminoethanethiol, when subjected to phosphonomethylation. gave an unexpected novel quarternary nitrogen product 11. N-Alkylaminoalkanols 4 on phosphonomethylation gave 3:1 mixtures of [N-alkyl-N-(2-hydroxyalkyl)amino] methane phosphonic acid 6 and N-alkyl-2-hydroxy-2-oxo-1,4,2-oxazaphosphorinane 5. Treatment of the crude mixtures of 5 and 6 with aqueous sodium hydroxide gave disodium salts of [N-alkyl-N-(2-hydroxyalkyl)amino] methanephosphonic acid 7. The ratio of the cyclic to the open chain structures obtained as well as the formation of any unexpected novel products is dependent on the structure of the aminoalkanol that is phosphonomethylated. The ¹H, ¹³C and ³¹P spectra are reported for all new compounds.     

A Thermochemical Study on the Formation of Oxalato-Titanium(III) Complex

The thermometric titration of titanium(III) chloride with oxalic acid was carried out at 25°C. The molar ratio of titanium (III): oxalate was found to be 1:2, which indicates the formation of Ti(C₂O₄)₂⁻ ion in acid media. The limiting value of the heat of reaction between Ti(III) ion and oxalic acid in hydrochloric acid solution was found to be −1.5 Kcal mole⁻¹ at 25°C.     

Synthesis,crystal structures and magnetic properties of two iron (II) tris(pyridyl)phosphine selenides complexes

We reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and treatment of resulted phosphines with selenium in hot toluene. These compounds were characterized by mass spectroscopy, ¹H, ¹³C and ³¹P NMR spectroscopies and the structure of MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of selenides with Fe(ClO₄)₂·6H₂O afforded two new iron(II) mononuclear metal complexes [Fe(TppSe)₂][ClO₄]₂·3DMF (1) and [Fe(MeTppSe)₂][ClO₄]₂·2DMF (2). Detailed structural analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to the high-spin state between 2 and 300 K in two iron(II) complexes.