1‐Dodecene Hydroformylation Catalyzed by Water Soluble Rhodium Phosphine Complex in Two‐Phase System

1‐Dodecene hydroformylation catalyzed by water soluble rhodium complex [RhCl(CO) (TPPTS)₂] was studied in the presence of TTPTS [P(m‐C₂H₄SO₃Na)₃] and CTAB (cetyltrimethyl ammonium). The influence of reaction parameters was discussed in detail based on micelle effect in biphasic system. The modification for the microcircumstance of micelle interface was conducted by the introduction of a catalyst promoter TPPDS [PhP(m‐C₂H₄SO₃Na)₂] into the reaction solution. A synergistic effect between TPPDS and TPPTS on the regioselectivity of 1‐dodecene hydroformylation was observed. The selectivity of linear aldehyde in the products was so high as 95.7% at the molar ratio of [TPPDS]/[TPPTS] = 0.5.     

十六烷基三羟乙基溴化铵促进1-辛烯氢甲酰化水/有机两相反应研究

研究了水/有机两相体系中表面活性剂十六烷基三羟乙基溴化铵(CTHAB)对Rh/TPPTS (TPPTS: 三[间-磺酸钠基苯基]膦)催化的1-辛烯氢甲酰化反应的促进作用, 初步证实了CTHAB分子中的羟基可与催化活性物种的铑之间发生配位. 与传统表面活性剂十六烷基三甲基溴化铵(CTAB)相比, 表面活性剂CTHAB的添加不仅加速了水/有机两相1-辛烯氢甲酰化反应, 而且提高了成醛的正/异比, 促进作用明显. 在 [Rh]=0.8 mmol/L, [TPPTS]/[Rh]=40, [CTHAB]=4.0 mmol/L, 90 ℃, 0.5 MPa, 1.5 h时, 生成醛的TOF为497 h^-1, 正/异比(L/B)可达25.6. 催化剂经7次循环后, 反应活性和成醛正/异比无明显下降. 该催化体系对不同长链烯烃氢甲酰化反应同样具有促进作用.     

New rhodium(I) water‐soluble complexes with 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phospha‐adamantane iodides and their catalytic activity

The water‐soluble phosphine ligands, 1,3,5‐triaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane (tpa) and 1‐alkyl‐1‐azonia‐3,5‐diaza‐7‐phosphatricyclo[3.3.1.1^3,7]decane iodides (Rtpa⁺I⁻), with alkyl=methyl(mtpa⁺I⁻), ethyl (etpa⁺I⁻) and n‐propyl, (ptpa⁺I⁻), and mtpa⁺Cl⁻ react with [Rh₂Cl₂(CO)₄] giving the rhodium(I) complexes [RhCl(CO)(tpa)₂], [RhI(CO)(Rtpa⁺I⁻)₂], [RhCl‐­(CO)(mtpa⁺Cl⁻)₃] and [RhI(CO)(Rtpa⁺I⁻)₃]. The properties and reactivities of the complexes have been investigated using ¹H and ³¹PNMR and IR spectroscopies. The five‐coordinate complexes in solutions show dynamic properties. The complexes are catalysts of the water‐gas shift reaction, the hydrogenation of CC and CO bonds, the hydroformylation of alkenes and the isomerization of unsaturated compounds. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthesis,characterization and hydroformylation activity of 7‐azaindolate‐bridged dinuclear rhodium(I)phosphines with pendant polar‐groups

New dinuclear Rh(I)–Phosphines of the types [Rh(µ‐azi)(CO)(L)]₂ ( 1,3 – 7 ) and [Rh(µ‐azi)(L)]₂ ( 8 ) with pendant polar groups, and a chealated mononuclear compound [Rh(azi‐H)(CO)(L)] ( 2 ) (where azi = 7‐azaindolate, L = polar phosphine) were isolated from the reaction of [Rh(µ‐Cl)(CO)₂]₂ with 7‐azaindolate followed by some polar mono‐ and bis‐phosphines ( L ₁ – L ₈ ). A relationship between Δδ³¹P‐NMR and ν(CO) values was considered to define the impact of polar‐groups on σ‐donor properties of the phosphines. These compounds were evaluated as catalyst precursors in the hydroformylation of 1‐hexene and 1‐dodecene both in mono‐ and biphasic aqueous organic systems. While the biphasic hydroformylations (water + toluene) gave exclusively the aldehydes, the monophasic one (aqueous ethanol) showed propensity to form both aldehydes and alcohols. The influence of bimetallic cooperative effects, and σ‐donor and hydrophilic properties of the phosphines with pendant polar‐groups in enhancing the yields and selectivity of hydroformylation products was emphasized. In addition, when strong σ‐donor phosphine was used, the π‐acceptor nature of pyridine ring of 7‐azaindolate spacer was found to be a considerable factor in facilitating the facile cleavage of CO group during hydroformylation and in supplementing the cooperative effects. Copyright © 2009 John Wiley & Sons, Ltd.     

Radical polymerization of 2,5‐norbornadienes containing ester groups by AIBN and oxygen gas

New 2,5‐norbornadiene‐type monomers bearing 1‐adamantyl and cyclohexyl ester groups on their 2‐position polymerized with azobisisobutyronitrile to form the polymers consisting of two types of polymer unit structures. The major part had a saturated nortricyclene framework, which was formed by 2,6‐addition along with intramolecular cyclization on the norbornadiene moiety. The minor part consisted of 2‐norbornene‐type units constructed via 2,3‐addition. A series of norbornadiene‐based monomers spontaneously polymerized in the presence of oxygen. Because a radical inhibitor, namely hydroquinone, could suppress this spontaneous reaction, it was indicated that the oxygen‐induced polymerization proceeds via free‐radical polymerization mechanism. Changing a quantity of provided oxygen gas (O₂) to a norbornadiene monomer significantly affected on polymerization results, in specific, molecular weight of the formed polymer, which indicated that oxygen serves as one of the key reagents for the formation of free‐radical initiating species. It was proven that the combination of norbornadiene ethyl ester with O₂ was applicable as a new free‐radical initiator for polymerization of methyl methacrylate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2528–2536     

Mechanisms of norbornadiene dimerization to Binor‐S using cationic CoI,RhI, and IrI catalysts

We investigated the transition metal‐catalyzed reaction mechanisms of NBD dimerization to Binor‐S using cationic Co^I, Rh^I, and Ir^I catalysts, using mPW1PW91, mPW1K, and B3LYP density functional methods. Our results indicate that the monomeric metal center has the ability to bind with four double bonds of two NBD molecules with a syn spatial geometry to form a penta‐coordinated complex. We designed three possible pathways, but found two of them blocked. The favored pathway involves three steps from the reactant precursor to the product precursor: the first step is the formation of a single bond to connect two NBD units, the second is the alkene insertion leading to the formation of the three‐membered ring structure, and the final step is the formation of the final product precursor. Orbital analysis showed metal…C? C σ agostic interaction in the product precursor, which is in agreement with the previous experimental findings. In addition, we found that the solvent and counter‐ions had significant effects on the dimerization reactions. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010     

Thermoregulated ionic liquids and their application for the hydroformylation of 1‐dodecene catalyzed by Rh/TPPTS complex

Based on the synthesis of a new kind of room temperature ionic liquids, quaternary ammonium alkanesulfonate salts tailed with polyether chain to their alkyl group, a thermoregulated ionic liquid biphase system composed of IL_PEG750, n‐heptane and toluene was developed. The system was applied in the hydroformylation of 1‐dodecene catalyzed by Rh/TPPTS complex. Under the optimum conditions, the conversion of 1‐dodecene and yield of aldehyde are 99% and 97%, respectively. In addition, the catalyst could be easily separated from products by phase separation and efficiently recovered. Copyright © 2008 John Wiley & Sons, Ltd.     

超临界二氧化碳和水复合溶剂中铑膦配合物催化丙烯氢甲酰化反应

 以乙酰丙酮羰基铑为催化剂母体,以水溶性三苯基膦三间磺酸钠(TPPTS)为配体,在超临界CO2和水复合溶剂中成功地实现了超临界条件下的均相丙烯氢甲酰化反应. 最佳反应条件为: 温度55 ℃,铑的浓度15 μg/ml, P/Rh摩尔比18. 在压力为12.0～14.0 MPa下反应6 h后,产物正丁醛/异丁醛摩尔比可达4.3～4.5,丁醛的时空收率达190.1～205.3 g/(g·h). 反应过程中体系处于超临界状态,反应结束后分为水、油两相,铑催化剂溶于水相,产物处于油相,油相中铑的含量仅为1.0 ng/ml,基本上消除了铑的流失,实现了催化剂与产物的有效分离,便于催化剂的回收和循环使用. 与相同反应条件下的水-有机两相氢甲酰化反应相比,超临界CO2和水复合溶剂中的丙烯氢甲酰化反应具有更高的反应速率和产物正异比.     

Synthesis and properties of fluorinated polyimides based on 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐2,5‐di‐tert‐butylbenzene and various aromatic dianhydrides

A novel fluorinated diamine monomer, 1,4‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐2,5‐di‐tert‐butylbenzene ( 2 ), was prepared through the nucleophilic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and 2,5‐di‐tert‐butylhydroquinone in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. Fluorinated polyimides ( 5a – 5f ) were synthesized from diamine 2 and various aromatic dianhydrides ( 3a – 3f ) via thermal or chemical imidization. These polymers had inherent viscosities of 0.77–1.01 dL/g. The 5 series polyimides were soluble in N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, and N,N‐dimethylformamide and were even soluble in dioxane, tetrahydrofuran, and dichloromethane. 5 (C) showed cutoff wavelengths between 363 and 404 nm and yellowness index (b*) values of 6.5–40.2. The polyimide films had tensile strengths of 93–114 MPa, elongations to break of 9–12%, and initial moduli of 1.7–2.1 GPa. The glass‐transition temperatures were 255–288 °C. The temperatures of 10% weight loss were all above 460 °C in air or nitrogen atmospheres. In comparison with a nonfluorinated polyimide series based on 1,4‐bis(4‐aminophenoxy)‐2,5‐di‐tert‐butylbenzene, the 5 series showed better solubility and lower color intensity, dielectric constants, and moisture absorption. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2272–2284, 2004     

Binuclear ruthenium complexes of fluorous phosphine ligands: Synthesis, properties, and biphasic catalytic activity. Crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2

The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O₂CMe)(CO)₂L^F]₂, where L^F is the perfluoroalkyl substituted tertiary phosphine, P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃, or P(CH₂CH₂(CF₂)₅CF₃)₃, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O₂CMe)(CO)₂P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃]₂ (1) or [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ (2). The X-ray crystal structure of [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing.     

Aqueous/organic biphasic hydroformylation of 1‐octene catalyzed by Co2(CO)8/Ph2P(CH2CH2O)nMe

The aqueous/organic biphasic hydroformylation of 1‐octene catalyzed by Co₂(CO)₈/Ph₂P(CH₂CH₂O)_nMe, an in situ formed thermoregulated phase‐transfer cobalt catalyst, has been developed. The catalyst activity in this biphasic system was as high as that in the homogeneous system. The yield of oxo‐products was 93% when the reaction was carried out at 180 °C and under 4.0 MPa syngas pressure for 20 h. The catalyst could be easily recovered in the aqueous phase by decanting after the reaction system was cooled, and reused in consecutive reaction without any treatment. The loss of Co in the organic phase was less than 1% on average of five successive runs. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of Deuterium Labeled (±)‐2,5‐Dimethoxyamphetamine (DMA), (±)‐4‐Bromo‐2,5‐Dimethoxyamphetamine (DOB), and (±)‐4‐Methoxyamphetamine (PMA) as Internal Standards for Quantitative Analyses by GC‐MS

DMA, DOB and PMA are increasingly abused central nervous system stimulants with neurotoxic properties. In recent years, many controlled substance analogs (designer drugs) with a large variety of structures have reached the illegal market, making their identification difficult. Therefore, this work studies the synthesis of DOB‐d₆, DMA‐d₆ and PMA‐d₃ as internal standards for use in gas chromatography‐mass spectrometry (GC‐MS) to identify controlled substances.     

Polymerization of substituted phenylacetylenes with a novel,water‐soluble Rh–vinyl complex in water

A novel, water‐soluble Rh complex, (nbd)Rh[PPh₂(m‐NaOSO₂C₆H₄)] [C(Ph)?CPh₂] ( 1 ) was synthesized by the reaction of [(nbd)RhCl]₂, Ph₂P(m‐NaOSO₂C₆H₄) and Ph₂C?C(Ph)Li, whose structure was determined by NMR and IR spectroscopies. The Rh catalyst 1 induced the polymerization of phenylacetylene (PA) in water to give two kinds of polymers; one was soluble in organic solvents such as tetrahydrofuran (THF) and CHCl₃, and the other was insoluble in common organic solvents. The polymerization of sodium p‐ethynylbenzoate (p‐NaOCO‐PA) homogeneously proceeded with 1 in water at 60 °C to give the polymer in high yield. Poly(p‐NaOCO‐PA) was treated with 1 N HCl and then reacted with (CH₃)₃SiCHN₂ to obtain poly(p‐MeOCO‐PA). The methyl‐esterified polymer was insoluble in THF and CHCl₃, which suggests that the formed poly(p‐MeOCO‐PA) has cis–cisoidal structure. The polymer obtained from the polymerization of [p‐CH₃(OCH₂CH₂)₂O₂CC₆H₄]C?CH with 1 in water was soluble in methanol, ethanol, and THF, and partly soluble in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2100–2105, 2004     

Synthesis and evaluation of some polymeric surfactants for treating crude oil—Part II. Destabilization of naturally occurring water‐in‐oil emulsions by polyalkylphenol formaldehyde amine resins

In the present work, three polymeric surfactants were prepared and used as demulsifiers; polyalkyl phenol formaldehyde monoethanol amine ethoxylate, eo, 136(D1), polyalkyl phenol formaldehyde diethanol amine ethoxylate, eo, 37(D2) and polyalkyl phenol formaldehyde triethanol amine ethoxylate, eo, 21.5(D3). Their demulsification potency in breaking water‐in‐crude oil emulsions was investigated. In this respect, two naturally occurring Egyptian water‐in‐oil (w/o) emulsions, one of them was waxy and the other was asphaltenic, were used in order to study the demulsification power of these compounds. The data revealed that, the resolution of water from waxy crude emulsion was easier than asphaltenic crude emulsion. The demulsification efficiency increases with increasing demulsifier concentration, contact time and temperature. The interfacial tension (IFT) at the crude oil–water interface was measured, it was found that the concentration of demulsifiers required to cause a minimum IFT are always less than these indicating a maximum demulsification efficiency. All the results were discussed in relation to emulsifier chemical structure and crude oil composition. Copyright © 2002 John Wiley & Sons, Ltd.     

A novel two‐dimensional cobalt(II) complex composed of one‐dimensional twisted pair‐like chains: poly[[tetraaquabis(μ3‐pyridine‐2,5‐dicarboxylato‐κ4N,O2:O5:O5′)dicobalt(II)] dihydrate]

A novel neutral polymer, {[Co₂(C₇H₃NO₄)₂(H₂O)₄]·2H₂O}_n, was hydrothermally synthesized using pyridine‐2,5‐dicarboxylate (2,5‐PDC²⁻) as the organic linker. It features a two‐dimensional layer structure constructed from one‐dimensional {[Co(2,5‐PDC)₂]²⁻}_n chains interlinked by [Co(H₂O)₄]⁺ units. The two Co^II cations occupy special positions, sitting on inversion centres. Each 2,5‐PDC²⁻ anion chelates to one Co^II cation via the pyridine N atom and an O atom of the adjacent carboxylate group, and links to two other Co^II cations in a bridging mode via the O atoms of the other carboxylate group. In this way, the 2,5‐PDC²⁻ ligand connects three neighbouring Co^II centres to form a two‐dimensional network. The two‐dimensional undulating layers are linked by extensive hydrogen bonds to form a three‐dimensional supramolecular structure, with the uncoordinated solvent molecules occupying the interlamellar region.     

Water‐soluble metalated and non‐metalated A2B‐ and A3‐corrole/amino acid conjugates: syntheses,characterization and properties

In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A₂B‐ and A₃‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A₃‐corrole towards O₂ evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A₃‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A₃‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd.     

Transfer Hydrogenation of Ketones Catalyzed by Surface‐Active Ruthenium and Rhodium Complexes in Water

An improved, high‐yield, one‐pot synthetic procedure for water‐soluble ligands functionalized with trialkyl ammonium side groups H₂N(CH₂)₂NHSO₂‐p‐C₆H₄CH₂[NMe₂(C_nH_2n+1)]⁺ ( [HL ⁿ ]⁺ ; n=8, 16) was developed. The corresponding new surface‐active complexes [(p‐cymene)RuCl( L ⁿ )] and [Cp*RhCl( L ⁿ )] (Cp*=η⁵‐C₅Me₅) were prepared and characterized. For n=16 micelles are formed in water at concentrations as low as 0.6 mM , as demonstrated by surface‐tension measurements. The complexes were used for catalytic transfer hydrogenation of ketones with formate in water. Highly active catalyst systems were obtained in the case of complexes bearing C₁₆ tails due to their ability to be adsorbed at the water/substrate interface. The scope of these catalyst systems in aqueous solutions was extended from partially water soluble aryl alkyl ketones (acetophenone, butyrophenone) to hydrophobic dialkyl ketones (2‐dodecanone).