Synthesis and NMR Characterization of Two Novel Anthracene-Derived BIS-Aminophosphonates. Basic Hydrolysis of Some Aminophosphonate Derivatives

Abstract

The synthesis of two novel bis-aminophosphonates bearing anthracene rings – bis[N- methyl(diethoxyphosphonyl)-1-(9-anthryl)]benzidine (3) and 4,4′-bis[N-methyl(diethoxy-phosphonyl)-1-(9-anthryl)]diaminodiphenylmethane (4) – via the Kabachnik–Fields reaction is reported. The compounds have been characterized by elemental analysis, TLC, IR, NMR (¹H, ¹³C, ³¹P) and fluorescent spectra. The reaction leads to a mixture of the two possible forms (meso and racemic), with predominant formation of one of the diastereomers. The recrystallized compounds 3 and 4 consist of only one diastereomer. A racemization at the chiral centers and a cleavage of the C-P bond are observed in the alkaline hydrolysis of the new compound 4 and three previously described aminophosphonate derivatives 5–7.

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.     

SYNTHESIS AND NMR SPECTROSCOPIC STUDY OF NEW 5-METHYLFURYL-CONTAINING SCHIFF BASES AND RELATED BIS(AMINOPHOSPHONATES)

The synthesis of three novel 5-methylfuryl-containing Schiff bases: N,N′-bis(5-methylfurfurylidene)-4,4′-diaminodiphenylmethane, N,N′-bis(5-methylfurfurylidene)-1,4-phenylenediamine, and N,N′-bis(5methylfurfurylidene)benzidine and the corresponding bis(aminophosphonates) derived from them, 4,4′-bis{N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]} diaminodiphenylmethane, 1,4-bis { N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]} diaminobenzene, and bis{N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]}- benzidine, is reported. The compounds have been characterized by elemental analysis, TLC, IR, and NMR ( ¹ H, ¹³ C, and ³¹ P) spectra. For comparison, new ¹³ C and ³¹ P NMR data of three furyl-containing analogues of the above bis(aminophosphonates) are also regarded. The NMR studies of the two series of bis(aminophosphonates) reveal the presence of one diastereomer (meso or racemic form).     

Syntheses,characterizations, crystal structures,and biological activities of two new mixed ligand Ni(II) and Cu(II) Schiff base complexes

Two mixed-ligand complexes, [Cu(L)(2imi)] (1) and [Ni(L)(2imi)]·MeOH (2) [L = 2-(((5-chloro-2-oxyphenyl)imino)methyl)phenolato) and 2imi = 2-methyl imidazole], have been prepared by the reaction of appropriate metal salts with H₂L and 2-methyl imidazole. Their structures were characterized by microanalysis, FT-IR, UV–vis, molar conductivity, and ¹H NMR for [Ni(L)(2imi)]·MeOH. The structures were determined using single crystal X-ray diffraction. Each four-coordinate metal center, Cu(II) in 1 and Ni(II) in 2, is surrounded by donors of Schiff base (L^2?) and N of 2-methyl imidazole in square planar geometries. α-Amylase activities of these compounds have also been investigated. The experimental data showed that α-amylase was inhibited by Ni(II) complex while the Cu(II) complex causes a 1.3-fold decrease in K_m value. Antimicrobial results show that these compounds, especially the Cu(II) complex, have potential for antibacterial activity against Gram negative and Gram positive bacteria and antifungal activity against Aspergillus fumigatus.     

Isolation and antiproliferative activity of chemical constituents from Asystasia buettneri Lindau

N-hexane and methanol extracts of Asystasia buettneri Lindau aerial parts exhibited antiproliferative activity on leukaemia blood carcinoma, K-562. Hexadecane (1), 1,3-propan-2-ol (9Z,12′Z,15″Z)-bis(doeicos-9,12,15-trienoate) (2), hydrocarbon, 2,3,3,10,23-pentamethyl tetraeicos-10,13,16-trien-1-ol (3), hexadecanoic acid (4) and taraxerol (5) were isolated from n-hexane extract; stigmasterol (6) and (Z)-9-octadecenoic acid (7) were isolated from ethyl acetate extract; while unsaturated hydrocarbons, octadecene (8), 8-methyl tetradec-6-ene (9) and 19-methyl eicos-1-ene (10), fatty acids, (Z)-5-hexadecenoic acid (11), 11,22-dimethyl ethyltrieicos-11-enoate (12) and taraxasterol (13) were isolated from methanol extract of the plant. Compounds 4, 5, 7, 11, 12 and 13 exhibited antiproliferative activity against K-562, while compounds 5, 6, 7 and 9 revealed antiproliferative activity by inhibiting hepatic liver (WRL68) cell lines.     

Biological evaluation of copper(II) complexes on N(4)−substituted thiosemicarbazide derivatives and diimine co-ligands using DNA interaction,antibacterial and in vitro cytotoxicity

Abstract

A number of alternatives were made to overcome numerous life-threatening infectious diseases by metal-based anticancer compounds. At present, thiosemicarbazones and their metal complexes have received significant consideration as a result of their metal DNA-interaction, structural diversity and availability of bonding modes. In this study, the coordination characteristics of nine diimine copper(II) complexes with sulfur containing ligands, [Cu(L)₂] (1–3), [Cu(L)(bpy)]Cl (4–6) and [Cu(L)(phen)]Cl (7–9) (L?=?H(L1)–H(L3), phen = 1,10-phenanthroline, bpy = 2,2′-bipyridyl, H(L1) = (Z)-2-((4-methoxynaphthalen-1-yl)methylene)-N-methylhydrazinecarbothioamide, H(L2) = (Z)-N-ethyl-2-((4-methoxynaphthalen-1-yl)methylene)hydrazinecarbothioamide and H(L3) = (Z)-2-((4-methoxynaphthalen-1-yl)methylene)-N-phenylhydrazinecarbothioamide] have been synthesized from 4-methoxy-1-naphthaldehyde along with N(4)-substituted thiosemicarbazide derivatives. The synthesized ligands and their Cu(II) complexes were characterized through different spectroscopic techniques and square-planar coordination was proposed. Biological evaluation such as DNA-cleavage, antibacterial and in vitro cytotoxicity of thiosemicarbazone ligands and their resultant Cu(II) complexes were analyzed. Interestingly, Cu(II) complex containing heteroaromatic moiety 9 had potential cytotoxic activity with strong DNA-interaction. In the future, these may be helpful to design more effective novel chemotherapeutic drugs.     

Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MS or HRMS; their absorption coefficients (), maximum absorption λ_amax, fluorescence emission maximum λ_em, Stokes shifts and fluorescence quantum yields (Φ_F) in ethyl acetate were determined; their fluorescent lifetimes (T₁ and T₂) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.     

New organotin(IV) complexes with N(4)-methylthiosemicarbazone derivatives prepared from 2,3-dihydroxybenzaldehyde and 2-hydroxy-5-methylbenzaldehyde: synthesis,characterization, and cytotoxic activity

Abstract

The N(4)-methylthiosemicarbazone derivatives H₂DDMT (1) and H₂DMMT (2) have been prepared from the reaction of 4-methylthiosemicarbazide with 2,3-dihydroxybenzaldehyde and 2-hydroxy-5-methylbenzaldehyde, respectively. Six new organotin(IV) complexes, [MeSnCl(DDMT)] (3), [BuSnCl(DDMT)] (4), [PhSnCl(DDMT)] (5), [MeSnCl(DMMT)] (6), [BuSnCl(DMMT)] (7), and [PhSnCl(DMMT)] (8) have been synthesized by direct reaction of corresponding organotin(IV) chloride(s) with these ligands. The ligands and their compounds have been characterized by elemental analysis, molar conductivity, UV–Vis, FT-IR, and NMR (¹H, ¹³C, and ¹¹⁹Sn) spectroscopy. The molecular structures of 1 and 2 were determined by X-ray crystallography. Spectroscopic data suggested that the ligands were coordinated to tin(IV) as dinegative tridentate via phenoxide-O, azomethine-N, and thiolate-S atoms. The crystal structures revealed that the ligands exist in thione form in the solid state. In vitro cytotoxicity assays were carried out for all the compounds against MCF-7 cancer cell line. The results have shown that different organotin(IV) groups showed characteristic differences in their biological activity.     

Syntheses,crystal structures,and catalytic properties of dioxomolybdenum(VI) complexes with hydrazone ligands

Two new dioxomolybdenum(VI) complexes, [MoO₂L¹(CH₃OH)] (1) and [MoO₂L²(H₂O)] (2), where L¹ and L² are dianionic form of N′-(2-hydroxy-3-methoxybenzylidene)-4methoxybenzohydrazide and N′-(2-hydroxy-3methoxybenzylidene)-2-hydroxybenzohydrazide, respectively, have been synthesized and structurally characterized by spectroscopic methods and single-crystal X-ray determination. The complexes are mononuclear molybdenum(VI) compounds. Mo in each complex is octahedral. The difference in the substituent groups in the benzohydrazides leads to coordination of different solvent molecules. Crystals of the complexes are stabilized by hydrogen bonds. The complexes are effective catalysts for sulfoxidation.     

Thermal and spectroscopic investigation on N,N-dimethylbenzylamine based cyclopalladated compounds containing isonicotinamide

Synthesis, spectroscopic characterization and thermal analysis of the [Pd(dmba)(Cl)(iso)] (1), [Pd(dmba)(NCO)(iso)] (2), [Pd(dmba)(N₃)(iso)] (3) and [Pd(dmba)(Br)(iso)] (4) (dmba = N,N′-dimethylbenzylamine; iso = isonicotinamide) compounds are described in this work. The complexes were investigated by infrared spectroscopy (IR), differential thermal analysis (DTA) and thermogravimetry (TG) and the residues of the thermal decomposition were identified as Pd^o by X-ray powder diffraction. The thermal stability order of the complexes varied as [Pd(dmba)(Cl)(iso)] (1) > [Pd(dmba)(Br)(iso)] (4) > [Pd(dmba)(NCO)(iso)] (2) > [Pd(dmba)(N₃)(iso)] (3).     

Synthesis,crystal structures,and biological activity of oxovanadium(V) complexes with similar tridentate hydrazone ligands

Two new oxovanadium(V) complexes, [VOL¹(OEt)(EtOH)] (1) and [VOL²(OMe)(MeOH)] (2), were prepared by reaction of [VO(acac)₂] (where acac?=?acetylacetonate) with N′-(3-bromo-2-hydroxybenzylidene)-4-methylbenzohydrazide (H₂L¹) in ethanol and N′-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H₂L²) in methanol, respectively. Crystal and molecular structures of the complexes were determined by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. The V ions have octahedral coordination. Thermal stability and the inhibition of urease of the complexes were studied.     

Synthesis of new macrocyclic aminomethylphosphines based on 4,4"-diaminodiphenylmethane and its derivatives

The reaction of bis(hydroxymethyl)phenylphosphine with 4,4"-diaminodiphenylmethane in DMF afforded 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)aminomethyl]}di(P-phenyl)phosphine sulfide (4).     

Synthesis and characterization of two binuclear nickel(II) complexes of thiophenol-based “end-off” compartmental ligands and their application as catalysts for selective oxidation of sulfides

Reaction of the binucleating S-protected ligand precursors 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy anil (I) and 2-(N,N-dimethylthiocarbamato)-5-methylisophthalaldehyde di-2′-hydroxy 5′-methyl anil (II) with nickel(II) acetate tetrahydrate in the presence of pyrazole afforded the binuclear nickel(II) complexes [L^INi₂(pz)] (1) and [L^IINi₂(pz)] (2), respectively. The complexes have been characterized by routine physicochemical studies as well as by X-ray single crystal structure analysis. In both complexes, Ni(II) ions are doubly bridged by the thiophenolic sulfur of the pentadentate Schiff base ligand and a pyrazolate group. Efficient protocols for the oxidation of sulfides to sulfoxides with high selectivities, catalyzed by binuclear μ-thiophenolato-μ-pyrazolatonickel(II) in the presence of urea hydrogen peroxide (UHP) were explored. We obtained predominantly the monooxygenated product. The resulting products are obtained in good to excellent yields within a reasonable time.     

Synthesis,structure, cytotoxic activities,and DNA-binding of 1-D copper(II) and zinc(II) coordination polymers

Two 1-D coordination polymers have been synthesized and identified as [Zn(ox)(en)] _n (H₂O)_{2 n} (1) and [Cu₂(dmeo)(N₃)₂] _n (2), where en represents diaminoethane, ox and dmeo stand for dianions of oxalic acid and N,N′-bis[2-(dimethylamino)ethyl]oxamide, respectively. Polymer 1 was characterized by elemental analysis, molar conductance measurement, IR and electronic spectra, and single-crystal X-ray diffraction. Polymer 1 consists of 1-D chains bridged by oxalate. The Zn^II can be described as a distorted octahedral environment and the Zn^II···Zn^II separation through the μ-oxalato-bridge is 5.5420(9)?Å. Hydrogen bonds assemble the coordination polymers to a 3-D supermolecular structure. The crystal structure of 2 has been reported previously. However, the bioactivities were not studied. The DNA-binding properties and cytotoxic activities of the two coordination polymers are investigated. The results suggest that the two polymers interact with HS-DNA in groove binding with binding affinity following the order of 1?>?2, which is consistent with their anticancer activities.     

Synthesis,crystal structures and properties of two Cd(II) complexes based on Zaltoprofen

Abstract

Two metal-organic coordination complexes, [Cd(Zaltoprofen)(phen)]_n (1) and [Cd(Zaltoprofen)(btz)]_n (2) (where Zaltoprofen = 5-(1-carboxyethyl)-2-(phenylthio)phenylacetic acid, phen = 1,10-phenanthroline, btz = thiabendazole), have been synthesized by reaction of Cd(NO₃)₂ with Zaltoprofen, 1,10-phenanthroline or thiabendazole under hydrothermal conditions and characterized by single crystal X-ray diffraction, IR spectra, elemental analyses, powder X-ray diffraction (XRD), electronic spectra (UV-vis) and fluorescent properties. Compound 1 crystallizes in the monoclinic P21/c space group and 2 in the monoclinic system with space group P21/n. [Cd(Zaltoprofen)(phen)]_n (1) features a 1-D zigzag chain. The zigzag chains are linked to form a 2-D layer through π–π stacking interactions. [Cd(Zaltoprofen)(btz)]_n (2) displays a 2D net with alternately arranged left- and right-handed helical chains.     

New Poly(4-Chloro)Maleimides. I. Synthesis and Characterization of Poly[Ether-Ester-(4-Chloro)Maleimides]

Abstract

New poly[N-(ester)-3-(ether)-4-(chloro)]maleimides were synthesized by the reaction of N-(4-chlorocarbonylphenyl)-3,4-dichloromaleimide (3) with various bisphenols such as hydroquinone (8a), 2,2-bis-(4-hydroxyphenyl)propane (8b), 4,4′ -(hexafluoroisopropylidene)diphenol (8c), and 2,5-bis(4-hydroxybenzylidene)cyclopentanone (8d). The structures of the resulted polymers were confirmed by IR and elemental analyses. A series of model compounds (4–7) was synthesized to facilitate confirmation of the structure of the polymers. The polymer containing hydroquinone units (9a) exhibited LC behavior in the melt, as observed by PLM measurements.     

Synthesis,characterization, antibacterial,and cytotoxic activities of organotin(IV) complexes derived from N(4)-cyclohexylthiosemicarbazone: X-ray crystal structure of [Ph2SnCl(L)]

Reaction of organotin(IV) chloride(s) with 2-benzoylpyridine-N(4)-cyclohexylthiosemicarbazone, [HL] (1) yielded [MeSnCl₂(L)] (2), [BuSnCl₂(L)] (3), [Me₂SnCl(L)] (4), and [Ph₂SnCl(L)] (5). The ligand (1) and its organotin(IV) complexes have been characterized by CHN analyses, molar conductivity, UV-Vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectral studies. The molecular structure of 5 was also determined by X-ray diffraction. There are two independent molecules in the asymmetric unit and the central tin(IV) atom is six-coordinate in distorted octahedral geometry. The ligand (1) and complexes were screened for their in vitro antibacterial activities. The cytotoxic activities of 1–5 were tested against A2780 and A2780/Cp8 cancer cell lines. The compounds have better antibacterial activities than the free ligand; 2–5 are more potent cytotoxic agents than 1, while the diphenyltin(IV) 5 is more active with IC₅₀ values of 0.05 and 0.54?µmol?L^?1 against A2780 and A2780/Cp8 cell lines, respectively.     

EFFICIENT RESOLUTION OF (±)-1-(9-ANTHRYL)ETHYLAMINE

ABSTRACT

Conditions for efficient resolution of (±)-1-(9-anthryl)ethylamine ((±)-1) by fractional crystallization of its salts with (S)-(+)-mandelic acid (2) are reported. When crystallization was performed by fast addition of chloroform solution of an equivalent of (±)-1 to the hot chloroform solution of (+)-2, crystals of mandelate of (+)-1-(9-anthryl)ethylamine ((R,S)-3) are collected in 56% yield. (R)-(+)-1 (98.6% e.e.) is isolated by extraction from bicarbonate solution of mandelate salt. Ulterior collection of four crops afforded (R,S)-3 with 71.5% cumulative yield and >98% e.e. of (+)-1 in a any single crop. With only 0.5 equivalents of (+)-2 crystallization afforded (R,S)-3 in 47.4% yield and (+)-1 with 98.1% e.e.     

A Facile Synthesis of Novel 9-Methyl[1, 2, 3]Selenadiazoles[4, 5-b]Quinoline and 9-Methyl[1, 2, 3]Thiadiazole[4, 5-b]Quinoline as a New Class of Antimicrobial Agents

2-chloro-4-methyl quinoline 2 on condensation with semicarbazide hydrochloride gave its semicarbazone. This on reaction with SeO ₂ and SOCl₂ yielded a new class of novel selenadiazoles 4 and thiadiazoles 5, respectively. The structure of all the compounds were elucidated on the basis of elemental analysis, IR, ¹ H NMR, and the mass spectral data. Some derivatives of 9-methyl[1, 2, 3]selenadiazole[4, 5-b] quinoline and 9-methyl[1, 2, 3]thiadiazole [4, 5-b]quinoline have been screened for antimicrobial activities.     

Acetylene chemistry,part 32: Alkinylation and cyclic rearrangement of theophylline with unsaturated alcohols by Mitsunobu reaction

Summary The reaction of theophylline (1) with 2-methyl-3-butyn-2-ol and 1-butyn-3-ol under Mitsunobu conditions gave the respective 9-substituted derivatives 9-[2-(2-methyl-3-butynyl)]-theophylline (2) and 9-[2-(3-butynyl)]-theophylline (3). On reaction with 2-methyl-3-buten-2-ol, theophylline yielded in addition to the 9-[2-(2-methyl-3-butenyl)]-theophylline (4), two more cyclic products, identified as 1,5,5a,8-tetrahydro-1,3,8,8-tetramethyl-2H-pyrrolo[1,2-e]purine-2,4(3H)-dione (5) and 8a,9-dihydro-1,3,6,6-tetramethyl-1H-pyrrolo[2,1-f]purine-2,4(3H,6H)-dione (7).

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Acetylenchemie, 32. Mitt.: Alkinylierung und cyclische Umlagerung von Theophyllin mit ungesättigten Alkoholen mittels Mitsunobu-Reaktion

Zusammenfassung Die Reaktion von Theophyllin (1) mit 2-Methyl-3-butin-2-ol und 1-Butin-2-ol unter Mitsunobu-Bedingungen führte zu den 9-substituierten Derivaten 9-[2-(2-Methyl-3-butinyl)]-theophyllin (2) bzw. 9-[2-(3-Butinyl)]-theophyllin (3). Bei der Reaktion mit 2-Methyl-3-buten-2-ol ergab Theophyllin außer 9-[2-(2-Methyl-3-butenyl)]-theophyllin (4) noch zwei weitere cyclisierte Produkte, die als 1,3,8,8-Tetramethyl-1,5,5a,8-tetrahydro-pyrrolo[1,2-e]purin-2,4(3H)-dion (5) und 1,3,6,6-Tetramethyl-8a,9-dihydro-1H,6H-pyrrolo[2,1-f]purin-2,4-dion (7) identifiziert wurden.

     

Syntheses and crystal structures of neutral oxorhenium(V) complexes of N2O2-donor tripodal ligands

The neutral distorted octahedral complexes [ReOCl(L)] {H₂L = N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H₂had); N,N-bis(2-hydroxybenzyl)-aminomethylpyridine (H₂hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H₂hae)} were prepared by the reaction of trans-[ReOCl₃(PPh₃)₂] with a twofold molar excess of H₂L in ethanol. X-ray structure determinations of [ReOCl(had)] (1) and [ReOCl(hap)] (2) were performed, and the structures compared. In both complexes the choride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.