The synthesis of 4,4′-arylmethylene-bis(3-(trifluoromethyl)-1-phenyl-1H-pyrazol-5-ol) in aqueous media without catalyst

The synthesis of 4,4′-arylmethylene-bis(3-(trifluoromethyl)-1-phenyl-1H-pyrazol-5-ol) was performed effectively in aqueous media without catalyst by the reaction of aryl aldehydes and 1-phenyl-3-trifluoromethylpyrazol-5-one. All of the compounds obtained were characterized by elemental analysis, FTIR and ¹H NMR. The structure of compound 3g was further confirmed by the X-ray single crystal diffraction. The method has the advantages of mild condition, without any catalyst, high yields and environmentally benign procedure.     

Peculiarities of the reaction of (SPY-5-34)-dichloro-(κ2(C,O)-2-formylbenzylidene)(1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene)ruthenium with potassium hydridotris(pyrazolyl)borate

The reaction of (SPY-5-34)-dichloro-(κ²(C,O)-2-formylbenzylidene)(H₂IMes)ruthenium (H₂IMes=1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) with potassium hydridotris(pyrazolyl)borate (KTp) in dichloromethane yielded an unusual ruthenium complex chloro(κ³(N,N,N)-chlorotris(pyrazolyl)borate)(κ²(C,C)-1-(2,4,6-trimethylphenyl)-3-(4,6-dimethylphenyl-2-methylidene)-4,5-dihydroimidazol-2-ylidene)ruthenium (2). In 2, a chlorotris(pyrazolyl)borate ligand, which had been created during this reaction, binds in κ³(N,N,N)-mode to the central ruthenium atom. Additionally, a double C–H activation of a methyl group of the H₂IMes resulted in the formation of a chelating N-heterocyclic biscarbene ligand and liberation of the former 2-formylbenzylidene as 2-methylbenzaldehyde. Formally, a double hydrogen transfer from a methyl group of the H₂IMes to the initial carbene carbon occurred. 2 was characterized by NMR spectroscopy, elemental analysis and single crystal X-ray structure determination. The reaction of KTp with (SPY-5-34)-dichloro(κ²(C,O)-2-ethoxycarbonylbenzylidene)(H₂IMes)ruthenium, on the other hand, gave the expected product chloro(κ³(N,N,N)-hydridotris(pyrazolyl)borate)(H₂IMes)(2-ethoxycarbonylbenzylidene)ruthenium (6). Compound 6 was characterized by NMR spectroscopy, elemental analysis and single crystal X-ray structure determination. Investigations of the relative activities of these complexes in model ring opening metathesis polymerizations showed a pronounced thermal latency. Polymerizations proceeded at temperatures above 100 °C in case of 6 and 130 °C in case of 2.     

Spectroscopic characterization,X-ray structure and DFT studies on 4-[3-(2,5-dimethylphenyl)-3-methylcyclobutyl]-N-methylthiazol-2-amine

The titled molecule 4-[3-(2,5-dimethylphenyl)-3-methylcyclobutyl]-N-methylthiazol-2-amine (C₁₇H₂₂N₂S) is synthesized and characterized by ¹H NMR, ¹³C NMR, IR, and X-ray single crystal determination. The compound crystallizes in the monoclinic space group P2_1/c with a = 6.3972(4) Å, b = 9.4988(6) Å, c = 26.016(2) Å and β = 93.496(7)°. In addition to the molecular geometry from the X-ray determination, vibrational frequencies and gauge, including the atomic orbital (GIAO), ¹H and ¹³C NMR chemical shift values of the titled compound in the ground state are calculated using the density functional (B3LYP) method with 6-31G(d), 6-31++G(d,p) and 6-311+G(2d,p) basis sets. The calculated results show that the optimized geometries can well reproduce the crystal structure. Moreover, the theoretical vibrational frequencies and chemical shift values show good agreement with the experimental values. The predicted nonlinear optical properties of the titled compound are greater than those of urea. DFT calculations of the molecular electrostatic potentials and frontier molecular orbitals of the titled compound are carried out at the B3LYP/6-31G(d) level of theory.     

Single crystal X-ray structure of 2,6-di-tert-butyl-4-(3-(4-chlorophenyl)-4-methyl-4,5-dihydroisoxazol-5-yl)phenol 1,4-dioxane hemisolvate

The title compound (2,6-di-tert-butyl-4-(3-(4-chlorophenyl)-4-methyl-4,5-dihydroisoxazol-5-yl)phenol is synthesized and studied by the single crystal X-ray diffraction method. The structure of the product was confirmed by IR, ¹H and ¹³C NMR spectroscopy. The crystal structure of 1,4-dioxane hemisolvate of the product is solved in the monoclinic space group P2₁/c with a = 17.713(6) Å, b = 9.529(3) Å, c = 13.972(4) Å, β = 94.09(4)°, V = 2352.3(13) ų, Z = 4, T = 120(2) K.     

Synthesis, biological activity and crystal structure of ethyl 6-amino-8-(4-methoxy phenyl)-9-nitro-2,3,4,8-tetrahydropyrido[2,1b][1,3]thiazine-7-carboxylate

The compound ethyl 6-amino-8-(4-methoxy phenyl)-9-nitro-2,3,4,8-tetrahydropyrido[2,1b][1,3]thiazine-7-carboxylate (C₁₄H₂₂N₄O₄S₂) has been synthesized by multicomponent reactions, and characterized by ¹H NMR, IR, and X-ray diffraction. The crystal structure analysis shows that the thiazinane ring displays a half-chair conformation. The benzene ring is almost vertical to the tetrahydro-pyridine ring. Intramolecular H-bonding of N–H···O type exists and completes an S (6) ring. In the crystal, the molecules are connected into a 3D network by a N–H···O and C–H···O intermolecular hydrogen bond. The bioassay indicates that the compound shows moderate insecticidal activity against Aphis craccivora.     

Preparation,crystal and molecular structure of,and NMR parameters for,the exopolyhedral heterocyclic platinaundecaborane [μ-2,7-(SCSNEt2)-7-(PMe2Ph)-NIDO-7-PtB10H11]

The compound [μ-2,7-(SCSNEt₂)-7-(PMe₂Ph)-nido-7-PtB₁₀H₁₁] has been obtained in a yield of 52% from the reaction of [7,7-(PMe₂Ph)-nido-7-PtB₁₀H₁₂] and [AuBr₂(S₂CNEt₂)], and identified by single crystal X-ray diffraction analysis and multi-element single and double resonance NMR spectroscopy. The yellow-orange compound crystallizes in the monoclinic space group P2₁/n with a 1179.2(2), b = 1244.9(5), c = 1641.4(2) pm, β = 95.45(1)°, Z = 4, and the structure (R 0.0209, R_w = 0.0211 for 3719 observed reflections) is that of a nido-7-platinaundecaborane with an exopolyhedral N,N-diethyldithiocarbamate ligand bridging the Pt(7) and B(2) positions to give a $\text{-Pt-B-C-S-}$ five-membered ring. The tetrahapto platinum-to-borane bonding has a considerable twist distortion relative to other nido-7-platinaundecaboranes which do not possess this cyclic feature. The NMR parameters exhibit no anomalies and are consistent with the crystal molecular structure. A plot of δ(¹¹B) vs δ(¹H) for directly bound exo-terminal hydrogen atoms shows good correlation with the slope 16 : 1.     

Preparation,molecular definition,spectroscopic characterization and density functional theory calculations on N’-(4-(3-methyl-3-phenylcyclobutyl)-3-phenylthiazol-2(3H)-ylidene)benzenesulfonohydrazide

Abstract

A new sulfonyl derivative (C₂₆H₂₅N₃O₂S₂), N’-(4-(3-methyl-3-phenylcyclobutyl)?3-phenylthiazol-2(3H)-ylidene)benzenesulfonohydrazide, was prepared from a mixture of benzenesulfonylhydrazide and phenylisothiocyanate in ethanol. The 3?D crystal structure, unit-cell dimensions, space group and crystal system of compound were investigated by single-crystal X-ray diffraction (SCXRD). FT-IR spectrum in solid state was observed in the region 4000–400?cm^?1 and the ¹H and ¹³C NMR spectra were recorded in CDCl₃ solution. In order to support the experimental results, the molecular geometry, vibrational frequencies, ¹H and ¹³C chemical shifts in the ground state have been calculated by using the density functional method (DFT/B3LYP) together with 6-311?G+(d, p) basis set. A good linear correlation between experimental and theoretically predicted structural and spectral parameters was observed (R²～0.9).     

Synthesis and crystal structure of 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate

The compound 2-{5-[2-(2,6-dichlorophenylamino)benzyl]-4-p-tolyl-4H-1,2,4-triazol-3-ylthio}acetate has been prepared and characterized by IR, ¹H NMR, ¹³C NMR and mass spectra. The crystal and molecular structure were further confirmed using single crystal X-ray diffraction. The crystal structure has been found to be stabilized by intermolecular C–H···O interaction generating bifurcated hydrogen bonds whereas the C–H···N interactions generate chain of molecules. The intramolecular N–H···N hydrogen bond forms a ring with S(7) graph-set motif.     

Synthesis,crystal structure and photoluminescence of 3-(4-(anthracen-10-yl)phenyl)-benzo[5,6]coumarin

A new coumarin derivative, 3-(4-(anthracen-10-yl)phenyl)-benzo[5,6]coumarin, was synthesized and characterized by FT-IR, ¹H NMR, element analysis and single crystal X-ray crystallography. The dihedral angle of benzo[5,6]coumarin ring and phenyl group is 36.15°, and the dihedral angle of phenyl group and anthracene skeleton is 89.37°. The UV–vis absorption and photoluminescence of the compound were discussed. The result shown that the compound exhibits high fluorescence quantum yield (Φ_F), large Stokes shift and green emission (508 nm). The molecular structure of the compound was optimized using density functional theory (DFT) at B3LYP/6-31G(d) level, and the HOMO and LUMO levels of the compound were deduced.     

Synthesis and characterization of tribenzyltin(IV) and dibenzyltin(IV) complexes of 2-{[(2Z)-3-hydroxy-1-methyl- 2-butenylidene]amino}acetic acid: Crystal structure of tribenzyl{2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene] amino}acetato}tin(IV)

Reactions of equimolar quantities of potassium 2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene]amino}acetate, with R _n SnX_4?n (R: benzyl– and n=2 or 3) in methanol yielded products of compositions LHSn(PhCH₂)₃ and LSn(PhCH₂)₂, respectively. The complexes were characterized by microanalysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn) and ^119mSn Mössbauer spectroscopy. A full characterization of the structure of the complex, tribenzyl{2-{[(2Z)-3-hydroxy-1-methyl-2-butenylidene]amino}acetato}tin(IV), was carried out by single crystal X-ray crystallography. The compound exists as centrosymmetric dimers in which two ligand molecules bridge the two tin centres. Each of the tin atoms in the dimeric unit is five coordinate in an approximately trigonal bipyramidal configuration, with carbon atoms in the equatorial positions and oxygen atoms arranged axially.     

Molecular and crystal structure of 2-(2-methyl-2-propenyl)-1,3-cyclopentanedione (C9H12O2)

An x-ray crystal structure study of 2-(2-methyl-2-propenyl)-1,3-cyclopentane-dione (C₉H₁₂O₂) has been carried out. It has been shown that in the solid this compound occurs exclusively in the enol form. The molecules are bound together by strong hydrogen bonds and form infinite chains along the b-axis. According to the spectroscopic data (¹H and¹³C NMR), the same compound in solution has a mesomeric structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1794–1797, August, 1991.     

5-(3,4-dichlorophenyl)-3-{[4-(2-pyridyl)piperazine-1-yl]methyl}-1,3,4-oxadiazole-2(3H)-one: Synthesis, characterization, X-ray and DFT structures

5-(3,4-Dichlorophenyl)-3-{[4-(2-pyridyl)piperazine-1-yl)]methyl}-1,3,4-oxadiazole-2(3H)-one C₁₈H₁₇Cl₂N₅O₂ (3) is synthesized and characterized by IR, ¹H NMR, ¹³C NMR, elemental analyses, single-crystal X-ray diffraction, and the molecular structure is also optimized at the B3LYP/6-31G(d,p) level using density functional theory (DFT). All data obtained from the spectral studies support the structural properties of 3. The molecules are linked principally by C-H??O hydrogen bonds involving carbonyl atoms and carboxylate O atoms, forming R ₂ ² (16) and R ₄ ² (20) rings that link to give a one-dimensional network of molecules. An extensive two-dimensional network of C-H??O hydrogen bonds and ?С??? interactions are responsible for crystal stabilization.     

Synthesis,crystal structure,and density functional theory study of a new compound 4-(2-chlorobenzyl)-1-(5-fluoro-2-hydroxy-3-(thiomorpholinomethyl)phenyl [1,2,4]triazolo[4,3-a]quinazolin-5(4H)-one

In this paper, a novel SHP244 derivative 4-(2-chlorobenzyl)-1- (5-fluoro-2-hydroxy-3- [thiomorph-olinomethyl] phenyl)- [1,2,4]triazolo [4,3-a] quinazolin-5(4H)-one was synthesized through five steps. The single crystals were grown in a suitable solvent system (dichloromethane and methanol). Its structure was confirmed by ¹H NMR, ¹³C NMR spectroscopy, ESI-MS, m/z: 534.12[M-H] (MS), FT-IR, and X-ray single crystal diffraction. The crystal structure of the title compound was optimized by density functional theory (DFT) calculation. The crystal structure after X-ray single crystal diffraction was compared with the structure optimized by DFT calculation, and the result shows that the two structures are consistent. In order to explore certain physical and chemical properties, the frontier molecular orbital and molecular electrostatic potential of the title compound were analyzed. In addition, the docking of the title compound to the target protein was studied to understand the docking effect of the compound with the target protein.     

(Iodomethyl)fluorosilanes: Synthesis and Reactions

The methods of synthesis of bifunctional (iodomethyl)fluorosilanes of general formula ICH₂SiMe_nF_3–n (n = 0, 2) have been elaborated; the structure was proved by ¹H, ¹³C, ²⁹Si NMR spectroscopy. The reaction of (iodomethyl)dimethylfluorosilane with O-trimethylsilyl derivative of N,N'-dimethylhydrazide of trifluoroacetic acid gives rise to the formation of 2,2,4,4-tetramethyl-6-(trifluoromethyl)-3,4-dihydro-2Н-1,4,5,2-oxadiasilin-4-ium iodide with tetracoordinate silicone atom.     

A Series of monohapto pyrazolates of iridium(I) and iridium(III)

The reaction of trans-IrCl(CO)L₂ with pz^?1 gives trans-Ir(pz-N)(CO)L₂, where pzH is 3,5-dimethyl-, 3,5-dimethyl-4-nitro- or 3,5-bis(trifluoromethyl)-pyrazole, and L = PPh₃. The nitrogen atom not involved in coordination can be protonated with HBF₄ to give the corresponding [Ir(CO)L₂(pzH-N]⁺ cation. The iridium(I) pyrazolates undergo oxidative addition, yielding Ir(H)₂(pz-N)(CO)L₂ species, while gaseous HCl cleaves the IrN bond, affording IrH(Cl)₂(CO)L₂. The iridium(I) derivatives can be obtained in several solid-state forms, each characterized by a slightly different CO stretching frequency. The presence of a monodentate pyrazolato ligand in trans-Ir(3,5-(CF₃)₂pz-N)(CO)L₂, in the form with ν(CO) at 1975 cm^?1, is supported also by an X-ray crystal structure determination. The compound crystallizes in the monoclinic system, space group P2₁/n, with cell dimensions a = 21.106(6), b = 19.700(5), c = 9.437(2) Å, and β = 94.34(2)° and Z = 4.     

Synthesis and Characterization of New Schiff Bases 2-(2-(2-(Aryl)Methyleneamino)Phenylthio) Ethylthio)-N-((aryl)Methylene)Benzeneamine

A series of Schiff bases containing four to six coordination sites N₂S₂ X₂(X = O,N) 2-(2-(2-(aryl)methyleneamino)phenylthio)ethylthio)-N-((aryl)methylene)benzeneamine (2c–f) were prepared from the reaction of 1,2-di(2-aminophenylthio)ethane (1) with aromatic aldehydes. All compounds were characterized by means IR, mass, ¹H and ¹³C NMR spectroscopy, and elemental analysis, and in the case of 2b with a single crystal X-ray diffraction. The X-ray crystal structure of 2b showed that the resonance occurs between aromatic rings, through the C=N bonds of the molecule.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Indenols, indenones and (arylcyclohexadienyl)Mn(CO)3 π-complexes from the thermally promoted reactions of alkynes with ortho-Mn(CO)4 aryl ketone, amide, ester and aldehyde derivatives

Thermally promoted reactions of a range of alkynes with the orthomanganated acetophenone (η²-2-acetylphenyl)Mn(CO)₄ generally give 1H-inden-1-ols in good yield; effects of substituents and solvent on these reactions are reported, along with the crystal structure of 1-methyl-2,3-diphenyl-1H-inden-1-ol. The corresponding orthomanganated benzophenone similarly gives the indenol with diphenylacetylene but by exception, orthomanganated 3-acetylthiophene with phenylacetylene reacts via triple alkyne insertion and cyclisation, shown by crystal structure determination of the π-complex product [(1,2,3,4,5-η)-2-(3-acetylthien-2-yl)-1,3,5-triphenylcyclohexadienyl]tricarbonylmanganese. Corresponding orthomanganated derivatives of N,N-dimethylbenzamide, methyl 3,4,5-trimethoxybenzoate and 4-dimethylaminobenzaldehyde all give indenones with diphenylacetylene, but with (excess) acetylene only the aldehyde gives an indenone, the amide and ester giving instead [(1,2,3,4,5-η)-6-arylcyclohexadienyl]Mn(CO)₃ complexes. ¹H NMR analysis of these complexes shows H at C6 to be on the same face of the cyclohexadienyl ring as Mn(CO)₃ (endo-6-H; exo 6-aryl) as expected from three successive syn additions of alkyne at metallated carbon followed by intramolecular syn addition of alkene in the final cyclisation stage.     

Molecular and crystal structure of (E)-4-chloro-N-(3,4-dimethoxybenzylidene)aniline

The reaction of 3,4-dimethoxybenzaldehyde with 4-chloroaniline (1:1 molar ration) leads to the formation of a new Schiff base (E)-4-chloro-N-(3,4-dimethoxybenzylidene)aniline (1) that is successfully obtained and characterized by elemental analyses, FT-IR and ¹H NMR spectroscopy, and single crystal X-ray diffraction. The strong absorption band at 1620 cm⁻¹ in the FT-IR spectrum and a singlet signal at 8.32 ppm in the ¹H NMR spectrum of 1 clearly proves the presence of the C=N (azomethine) group. Single crystal X-ray analyses reveal that the title compound adopts an E configuration with respect to the C=N bond.     

Study of protonation and Zn(II), Cd(II), Cu(II) and Mn(II) complexation with a glutamic acid N-pyrimidine derivative: Crystal structure of a neutral Cd(II) complex of the bianionic ligand

The compound N-(4-amino-1-methyl-5-nitroso-6-oxo-1,6-dihydropyrimidin-2-yl)-(s)-glutamic acid (H₃L) was synthesised and structurally characterised by analytical methods and ¹H, ¹³C and ¹⁵N NMR spectroscopy. This compound (H₃L) shows the same topology as other model receptors previously used to develop chemical functionalization at the surface of an active carbon when they adsorb on it. Protonation of H₃L and its coordination ability towards Cd²⁺, Zn²⁺, Cu²⁺ and Mn²⁺ ions in water solution was also studied by potentiometric methods, UV–Vis and ¹H, ¹³C NMR spectroscopies. The obtained results allow us to fit the operative conditions for the use of the activated carbon–H₃L adsorbent for the retaining of the above-mentioned metal ions in aqueous solutions. The molecular structure of {[Cd(HL)H₂O] · 3H₂O}_n was solved by single-crystal X-ray diffraction methods.     

Structure and spectral property of 8-(2-(5-(4-methylphenyl)-2-thienyl)vinyl)-10,10-dimethyl-10H-pyrido[1,2-a]indolium perchlorate

The title compound 8-(2-(5-(4-methylphenyl)-2-thienyl)vinyl)l-10,10-dimethyl-10H-pyrido[1,2-a]indolium perchlorate (3) has been synthesized by cycloaddition and condensation reactions, and characterized by elemental analysis, IR, ¹H NMR, and single-crystal X-ray diffraction. The crystal structure analysis exhibits that the molecule of 3 possesses good coplanarity, and the three rings (10H-pyrido[1,2-a]indolium, thienyl and phenyl) and vinyl moiety can make up a large conjugated system. Its UV-Vis and fluorescence spectra were measured, and found that it displays larger maximum absorptions and emission wavelengths in comparison with 8-(4-methylphenyl)vinyl analogue.