A novel imido-transfer reaction of aldehydes with Ph3PNTs using RuCl2(PPh3)3 as catalyst

(N-Tosylimino)triphenylphosphorane (Ph₃PNTs) was found to be an efficient imido-transfer reagent for the imidation of a variety of aldehydes using RuCl₂(PPh₃)₃ as the catalyst.     

Mild one-pot conversion of carboxylic acids to amides or esters with Ph3P/trichloroisocyanuric acid

The reaction of trichloroisocyanuric acid (TCICA) and triphenylphosphine in the presence of a carboxylic acid results in the in situ formation of the corresponding acid chloride under mild conditions. Subsequent addition of amines or alcohols, in the presence of a tertiary amine affords the corresponding amides, or esters, in good to excellent yields. The methodology was applied to the synthesis of a dipeptide.     

Highly chemoselective nitration of aromatic amines using the Ph3P/Br2/AgNO3 system

The use of PPh₃/Br₂/AgNO₃ provides a new reagent system for the novel and highly chemoselective nitration of aromatic amines under mild reaction conditions.     

Solid-phase domino syntheses of functionalized tetronates with Ph3PCCO

Domino addition-Wittig olefination reactions of α-hydroxy esters immobilized on polystyrene with Ph₃PCCO to give resin-bound tetronates proceed as readily as in solution. α-Hydroxy allyl esters can react to give either supported allyl tetronates or the corresponding Claisen-rearranged 3-allyltetronic acids, depending on conditions.     

Formation of benzoic acid in the palladium(II) catalyzed cleavage of phenyl-antimony and phenyl-phosphorus groups of Ph3Sb and Ph3P

Palladium (II) catalyzed cleavage of phenyl-antimony and phenyl-phosphorus groups of Ph₃Sb and Ph₃P under carbon-dioxide or CO/NO atmosphere leading to benzoic acid, has been demonstrated.     

Effects of solvent and base on the palladium-catalyzed amination: PdCl2(Ph3P)2/Ph3P-catalyzed selective arylation of primary anilines with aryl bromides

A readily accessible catalytic system, PdCl₂(Ph₃P)₂/Ph₃P, was developed for the selective arylation of primary anilines with aryl bromides. The strong influence of solvents and bases on the catalytic activity was observed. In refluxing o-xylene, triphenylphosphine shows high efficiency for Pd-catalyzed intermolecular amination reactions. By changing the bases, mono- and diarylation of primary amines could be selectively achieved in high yields. Moreover, the catalytic system showed good toleration for the steric hindrance of anilines. A series of N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines, important intermediates of OLED hole transport materials, were synthesized facilely via coupling reactions between 4,4′-diaminobiphenyls and aryl bromides.     

Synthesis and structural behavior of the P-functional organotin chlorides [Ph2P(CH2)3]2SnCl2, Ph2P(CH2)3SnCl2Me, and Ph2P(CH2)nSnCl3 (n=2, 3)

The P-functional organotin dichloride [Ph₂P(CH₂)₃]₂SnCl₂ (3) is synthesized by reaction of Ph₂P(CH₂)₃MgCl with SnCl₄ independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph₂P(CH₂)_nSnCl₂R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph₂P(CH₂)_nSnCy₃ (n=2, 3) with SnCl₄ or MeSnCl₃, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph₃PO)₂ (7) and 5(Ph₃PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data.     

Synthesis and Structure of Phosphorus-Containing Complexes [Ph4P]

Complexes [Ph₄P] ₂ ⁺ [Hg₄I₁₀]²⁻ (I) and [[Ph₄P] ₂ ⁺ [BiI₅(Me₂S=O)]²⁻ (II) are synthesized by the reactions of tetraphenylphosphonium Ph₄PI with mercury diiodide in acetone and with bismuth triiodide in dimethyl sulfoxide, respectively. According to X-ray diffraction analysis, structural units of these complexes are tetraphenylphosphonium cations and tetra- and mononuclear anions, respectively. The phosphorus atoms in the tetraphenylphosphonium cations have a distorted tetrahedral coordination. In the central fragment of the centrosymmetric anion [Hg₄I₁₀]²⁻, the distances between the terminal mercury atoms and iodine atoms are 3.503(2) Å. The mercury atoms in the central and terminal fragments of compound I have distorted tetrahedral and trigonal coordinations, respectively. The bismuth atom in the mononuclear octahedral anion of complex II contains a dimethyl sulfoxide molecule along with five iodine atoms in the coordination sphere. __________ Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 10, 2005, pp. 791–795. Original Russian Text Copyright ? 2005 by Sharutin, Egorova, Sharutina, Dorofeeva, Molokov, Fukin.     

DDQ/PPh3催化的N-苯甲酰苯胺衍生物中间体的有效合成及晶体结构

在DDQ/PPh₃作用下,以2-异丙基苯甲酸或水杨酸为原料,在温和条件下以较高的收率合成、分离得到两个化合物(2)和(3)。化合物(2)和(3)与苯胺在氯仿中加热回流可分别转化为酰胺类化合物(4)和(5)。所有化合物通过元素分析、质谱、核磁共振进行了表征,并解析了化合物(2)和(3)的X-衍射单晶结构。化合物1,2-二(2-异丙基苯甲酸)-2,3-二氰-5,6-二氯苯(2)晶体属单斜晶系,空间群P2₁/c,其晶胞参数为：a=1.2875(3)nm,b=1.5186(2)nm,c=1.5726(3)nm,β=122.23(3)°,V=2.6010(1)nm³,D_c=1.331g·cm^-3,Z=4,F(000)=1080,R₁=0.0572,wR₂=0.1260;化合物1,2-二(2-羟基苯甲酸)-2,3-二氰-5,6-二氯苯(3)晶体属三斜晶系,空间群P1,其晶胞参数为：a=0.87776(16)nm,b=1.13111(15)nm,c=1.18639(17)nm,α=69.290(2)°,β=89.409(3)°,γ=67.878(2)°,V=1.0104(3)nm³,D_c=1.542g·cm^-3,Z=2,F(000)=476,R₁=0.0383,wR₂=0.0931。强π-π堆积作用和分子间氢键将化合物(2)和(3)组装成稳定的三维结构。     

Synthesis and characterization of organophosphine/phosphite stabilized silver(I) methanesulfonates: Crystal structures of [Ph3PAgO3SCH3] and [(Ph3P)2AgO3SCH3]

Six organophosphine/phosphite stabilized silver(I) methanesulfonates of type [L_nAgO₃SCH₃] (L = Ph₃P, n = 1, 2a; n = 2, 2b; n = 3, 2c; L = (EtO)₃P; n = 1, 2d; n = 2, 2e; n = 3, 2f) were synthesized by the reaction of silver methanesulfonates with triphenylphosphine or triethylphosphite in dichloromethane under nitrogen atmosphere. These complexes were obtained in high yields and characterized by elemental analysis, ¹H-, ¹³C{H} NMR, IR spectroscopy and thermogravimetric analysis (TGA), respectively. X-ray single crystal analysis reveals that complex 2a is a tetramer [Ph₃PAgO₃SCH₃]₄ and complex 2b is a monomer. The thermal stability of 2a has been studied by applying thermogravimetric analysis. It starts to decompose between 50 and 440 °C in a three-step process. The final residue (Ag) is about 20.50%.     

DDQ/PPh_3催化的N-苯甲酰苯胺衍生物中间体的有效合成及晶体结构(英文)

在DDQ/PPh3作用下,以2-异丙基苯甲酸或水杨酸为原料,在温和条件下以较高的收率合成、分离得到两个化合物(2)和(3)。化合物(2)和(3)与苯胺在氯仿中加热回流可分别转化为酰胺类化合物(4)和(5)。所有化合物通过元素分析、质谱、核磁共振进行了表征,并解析了化合物(2)和(3)的X-衍射单晶结构。化合物1,2-二(2-异丙基苯甲酸)-2,3-二氰-5,6-二氯苯(2)晶体属单斜晶系,空间群P21/c,其晶胞参数为:a=1.287 5(3)nm,b=1.518 6(2)nm,c=1.572 6(3)nm,β=122.23(3)°,V=2.601 0(1)nm3,Dc=1.331 g·cm-3,Z=4,F(000)=1 080,R1=0.057 2,wR2=0.126 0;化合物1,2-二(2-羟基苯甲酸)-2,3-二氰-5,6-二氯苯(3)晶体属三斜晶系,空间群P1,其晶胞参数为:a=0.877 76(16)nm,b=1.131 11(15)nm,c=1.186 39(17)nm,α=69.290(2)°,β=89.409(3)°,γ=67.878(2)°,V=1.010 4(3)nm3,Dc=1.542 g·cm-3,Z=2,F(000)=476,R1=0.038 3,wR2=0.093 1。强π-π堆积作用和分子间氢键将化合物(2)和(3)组装成稳定的三维结构。     

Selective mono- and di-N-alkylation of aromatic amines with alcohols and acylation of aromatic amines using Ph3P/DDQ

Selective N-monoalkylation of aromatic amines with 1° and 2° alcohols and conversion of aromatic amines to amides are performed immediately and in excellent yields using triphenylphosphine (PPh₃) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in dichloromethane at room temperature. Symmetrical and unsymmetrical N,N-dialkylation of aromatic amines are also carried out in modest yield at room temperature by this reagent system.     

A facile synthesis of symmetrical secondary amines from primary amines promoted by the homogeneous catalyst RuCl2(Ph3P)3

Primary amines bearing an α-hydrogen atom are quantitatively converted to symmetrical secondary amines by heating at 185°C for 5 h in the presence of a catalytic amount of RuCl₂(Ph₃)₃.     

SYNTHESIS OF THE COPOLYMERS OF p-DIETHYNYLBENZENE WITH OTHER ACETYLENIC DERIVATIVE S INITIATED BY (Ph_3P)_2 PdCl_2

The copolymerization of p-diethynylbenzene (PDEB) with phenylacetylene (PhA), 4, 4'-diethynylbiphenyl (DEBP)or m-diethynylbenzene (MDEB) are studied by varying mole ratios of monomers. When the mole ratios of PDEB/PhA are less or equal to 1/5, the copolymers are soluble and fusible, but the other copolymers are insoluble and infusible. The results show that the good solvent of cross-linked copolymers is benzene and their solubility parameter is 9.15 cal~(0.5).cm(-1.5). And their swellability (θ_p), Huggins parameter (χ), density (d_4~(25)) and the average molecular weights between crosslinks (c) are measured. It is found that θp and c of copolymers are greater but d_4~(25) is less than that of respective homopolymers. IR spectra show that the copolymers have transoid configuration and small number of unreacted ethynyl groups exist in the copolymers. The mechanism about the polymerization or acetylenic derivatives initiated by (Ph_3P)_2PdCl_2 is discussed.     

A novel method for the highly efficient synthesis of 1,2-benzisoxazoles under neutral conditions using the Ph3P/DDQ system

The use of Ph₃P/DDQ offers a novel, neutral and highly efficient method for the efficient conversion of 2-hydroxyaryl aldoximes and ketoximes to 1,2-benzisoxazoles in excellent yields at room temperature.     

Reaction of multifunctional molecule (Ph2P(o-C6H4)CHNCH2CH2)3N with triosmium carbonyl clusters

Reaction of (Ph₂P(o-C₆H₄)CHNCH₂CH₂)₃N with 3 equiv. of Os₃(CO)₁₀(NCMe)₂ at ambient temperature affords the triple cluster [Os₃(CO)₁₀Ph₂P(o-C₆H₄)CHNCH₂CH₂]₃N (1) through coordination of the phosphine and imine groups. Thermolysis of 1 in benzene leads to decarbonylation and C-H/C-N bond activation of the ligand to generate (μ-H)Os₃(CO)₈(μ₃-Ph₂P(o-C₆H₄)CHNCCH₂) (2). The molecular structure of 2 has been determined by an X-ray diffraction study.     

Ph3P/Br2/n-Bu4NNO2 as an efficient system for the preparation of N-nitrosamines and azides

The combination PPh₃/Br₂/n-Bu₄NNO₂ was developed as a new reagent system for the efficient preparation of N-nitrosamines and azides from the corresponding amines and hydrazine derivatives, respectively, at 0 °C to room temperature, in excellent yields.     

Molecular structures of [(Ph3Sn)2O3Se] and [(Ph3Sn)2O4Cr](CH3OH)

Molecular structures of [(Ph₃Sn)₂O₃Se] (1) and [(Ph₃Sn)₂O₄Cr](CH₃OH) (2) have been determined using spectroscopic techniques and X-ray analysis. Each structure consists of polymers containing two types of tin centres: one of them is bridged by two oxygen atoms of the trifunctional oxyanion into a helical chain while the other is pendant to this chain. In the case of the chromato derivative the pendant tin is also bonded to the oxygen atom of the solvent (methanol); hydrogen bonds between the methanol and the non-coordinated oxygen of the chromate generate a three-dimensional structure containing tin atoms in a trigonal bipyramidal environment. In contrast, the two tin centres in the non-solvated selenito derivative have distinct geometries (tetrahedral and trigonal bipyramidal). Variable temperature Mössbauer spectroscopy data are consistent with the polymeric structure of the selenito derivative while NMR spectroscopy shows the presence of monomeric species in solution.     

Ph3PAuX和Ph3AsAuX(X=Cl,Br)的最低三重激发态

分子水平上的激发态理论研究能够用来解释分子材料的多色发光机理. 采用单组态相互作用方法, 计算研究了四种二配位的Au(I)配合物Ph3PAuCl, Ph3PAuBr, Ph3AsAuCl和Ph3AsAuBr的分子结构限制的三重激发态(T1a)和分子结构松弛的三重激发态(T1b)的分子结构与光物理性质. 由于θ(PAuX)/θ(AsAuX)从180°扭曲到120°左右, T1b态的能量在单线态组态相互作用(CIS)水平上降低了0.805-1.124 eV, 在密度泛函理论(DFT)水平上降低了0.820-0.947 eV. 自然键轨道电荷布居数分析表明, 在T1a态中两个单电子主要分布在一个苯基上, 而在T1b态中两个单电子分布在PAuX/AsAuX 上. 因此, 在晶体中观察到的较高能磷光归属于T1a态的苯基之间的3π*→1π电子跃迁, 而较低能磷光主要起源于T1b态的Au 的3σ*→1σ电子跃迁.     

The structure and dynamic behaviour in solution of the trihydridodienerhenium complexes (Ph3P)2(η-1,3-diene)ReH3

The structure and fluxionality of the trihydridodiene complexes (Ph₃P)₂(η-1,3-<di-ene)ReH₃ have been studied by NMR spectroscopy (η-1-3-diene = buta-1,3-diene, 2-methylbuta-1,3-diene, 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene, penta-1,3-diene, hexa-1,3-diene and hexa-2,4-diene). Several rearrangement processes have been observed; they are, in order of increasing temperature: (a) ligand interchange; (b) reversible migration of a hydride ligand on to the diene ligand, leading to η-allyl species and, in the case of the cyclohexadiene trihydride, degenerate isomerisation of the cyclohexadiene moiety; and (c), in the case of the pentadiene and hexadiene derivatives, isomerisation of the diene ligand.