An anisaldehyde sodium bisulfite derivative: poly[[μ4‐(hydroxy)(4‐methoxyphenyl)methanesulfonato]sodium]

The title complex, [Na(C₈H₉O₅S)]_n, is polymeric and consists of broad layers parallel to (100) made up of an inner hydrophilic core of Na⁺ cations and polar SO₃C(OH)– groups, padded on both sides by two hydrophobic layers of pendant methoxyphenyl groups. The Na⁺ cations in the inner core are six‐coordinated into highly distorted NaO₆ octahedra by four symmetry‐related (hydroxy)(4‐methoxyphenyl)methanesulfonate anions, leading to a tightly woven two‐dimensional structure. While there are some hydrogen bonds providing interplanar cohesion, interactions between adjacent layers are weak hydrophobic ones. The present compound appears to be the first reported structure containing the (hydroxy)(4‐methoxyphenyl)methanesulfonate ligand.     

Synthesis of novel 3,4‐dihydropyrimidinones on water soluble solid support catalyzed by indium triflate

Syntheses of several new 3,4‐dihydropyrimidinones (DHPMs) on sodium sulfate solid support have been reported. The microwave enhanced rapid synthesis of the title compounds yielded a good percentage of the DHPMs. The catalytic activity of indium triflate enables to prepare a wide range of DHPMs. Syntheses of 2‐hydroxyphenyl, 2‐hydroxy‐4‐methoxyphenyl pendant groups on DHPMs scaffold are advantages of the present method, which are rather prone towards cyclization and the presence of free hydroxyl groups on the phenyl ring is confirmed via D₂O exchange study. The mechanism of the reaction is expected to proceed via absorption of substrates on the solid support followed by promotion of the reaction by In(OTf)₃ coupled with microwave irradiation.     

Synthesis,Characterization, and Antimicrobial Evaluation of the Novel Triazolotriazolopyridines and Pyridotriazolotriazines

The starting compound 2‐hydrazinyl‐7‐(4‐methoxyphenyl)‐5‐oxo‐3,5‐dihydro[1,2,4]triazolo[1,5‐a ]pyridine‐6,8‐dicarbonitrile ( 5 ) was efficiently synthesized from 1,6‐diamino‐4‐(4‐methoxyphenyl)‐2‐oxo‐1,2‐dihydropyridine‐3,5‐dicarbonitrile ( 1 ). A novel series of polynuclear [1,2,4]triazolo[4′,3′:2,3][1,2,4]triazolo[1,5‐a ]pyridines 6 , 7 , 8 , 9 , 10 and pyrido[1′,2′:2,3][1,2,4]triazolo[5,1‐c ][1,2,4]triazines 11 , 12 , 13 , 14 , 15 have been synthesized. Structures of the newly synthesized products have been deduced on the basis of elemental analysis and spectral data. The synthesized compounds were screened for their antimicrobial activity.     

On the mechanism and stereochemistry of the formation of β‐lactam derivatives of 2,4‐disubstituted‐2,3‐dihydro‐benzo[1,4]diazepines

2‐Chloro‐4‐phenyl‐2a‐(4′‐methoxyphenyl)‐3,5‐dihydroazatetracyclic [1,2‐d]benzo [ 1,4]diazepin‐1 ‐one ( III _a) and 2‐chloro‐4‐methyl‐2a‐(4′‐methoxyphenyl)‐3,5‐dihydroazatetracyclic[1,2‐d]‐benzo[1,4]diazepin‐1‐one ( III _b) were synthesized. 1‐Benzoyl‐2‐phenyl‐4‐(4′‐methoxyphenyl)[1,4]‐benzodiazepine ( II _a) was formed through benzoylation of starting material 2‐phenyl‐4‐(4′‐methoxyphenyl)‐[1,4]benzodiazepine ( I _a) with the inversion of seven‐member ring boat conformation. The thus formed β‐lactams should have four pairs of stereoisomers. However, only one pair of enantiomers (2S,2R,4R) and (2R,2aS,4S) was obtained. The mechanism and stereochemistry of the formation of these compounds were studied on the basis of nmr spectroscopy and further confirmed by X‐ray diffraction.     

Investigation of Some Functionalization Reactions of 4‐Benzoyl‐5‐phenyl‐1‐(4‐methoxyphenyl)‐1H‐pyrazole‐3‐carbonyl Chloride and Their Antimicrobial Activity

The 1H‐pyrazole‐3‐carboxylic acid 1 was converted via reactions of its acid chloride 3 with various asymmetrical disubstituted urea and alcohol derivatives into the corresponding novel 4‐benzoyl‐N‐(N′,N′‐dialkylcarbamyl)‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxamide 4a , b and alkyl 4‐benzoyl‐1‐(4‐methoxyphenyl)‐5‐phenyl‐1H‐pyrazole‐3‐carboxylate 7a‐c , respectively, in good yields (57%‐78%). Friedel‐Crafts reactions of 3 with aromatic compouns for 15 min.‐2 h led to the formation of the 4‐3‐diaroyl‐1‐(4‐hydroxyphenyl)‐5‐phenyl‐1H‐pyrazoles 9a‐c , 4‐benzoyl‐1‐(4‐methoxyphenyl)‐3‐aroyl‐5‐phenyl‐1H‐pyrazoles 10a , b and than from the acylation reactions of 9a‐c were obtained the 3,4‐diaroyl‐1‐(4‐acyloxyphenyl)‐5‐phenyl‐1H‐pyrazoles 13a‐d . The structures of all new synthesized compounds were established by NMR experiments such as ¹H, and ¹³C, as well as 2D COSY and IR spectroscopic data, and elemental analyses. All the compounds were evaluated for their antimicrobial activities (agar diffusion method) against eight bacteria and two yeasts.     

Synthesis and Anticancer and Antiviral Activities of New 2‐Pyrazoline‐Substituted 4‐Thiazolidinones

2‐(4,5‐Dihydropyrazol‐1‐yl)‐thiazol‐4‐ones ( 2–5 ) have been synthesized starting from 3‐phenyl‐5‐aryl‐1‐thiocarbamoyl‐2‐pyrazolines via [2+3]‐cyclization with 2‐bromopropionic acid, maleic anhydride, N‐arylmaleimides, and aroylacrylic acids. The in vitro anticancer activity of 2a , 3a , 4a , 5b , and 5c were tested by the National Cancer Institute. Compounds 4a , 5b , and 5c demonstrated selective inhibition of leukemia cell lines growth at a single concentration (10^?5 M). The screening of antiviral activity for a broad panel of viruses revealed that N‐(4‐methoxyphenyl)‐2‐{2‐[5‐(4‐methoxyphenyl)‐3‐phenyl‐4,5‐dihydropyrazol‐1‐yl]‐4‐oxo‐4,5‐dihydrothiazol‐5‐yl}‐acetamide 4a was highly active against Tacaribe TRVL 11 573 virus strain (EC₅₀ = 0.71 μg/mL, selectivity index = 130).     

Design and Synthesis of Some New α‐Phenyl Cinnamoyl Derivatives for Selective Protection of Purine Nucleosides

Three new α‐phenylcinnamic acid derivatives [4‐methoxy‐α‐phenylcinnamic acid, α‐(4‐methoxyphenyl)‐cinnamic acid, and 4,4′‐bismethoxy‐α‐phenylcinnamic acid] were synthesized, characterized, and selectively used for protecting the exocyclic amino function of purine nucleosides (2′‐deoxyadenosine and 2′‐deoxyguanosine) via active ester generation. The acids were first activated using p‐nitrophenol, and these activated esters were used subsequently for the selective protection of amino groups. The N‐protected derivatives of 2′‐deoxyguanosine and 2′‐deoxyadenosine have been found to be sufficiently stable toward acids, thus minimizing depurination under oligodeoxyribonucleotide synthesis protocol. The ease of syntheses of N‐protected purine nucleosides, their stability under an acidic environment, and mild deprotection conditions are the key advantages of the new protecting groups.     

One‐Pot Protection‐Glycosylation Reactions for Synthesis of Lipid II Analogues

(2,6‐Dichloro‐4‐methoxyphenyl)(2,4‐dichlorophenyl)methyl trichloroacetimidate ( 3 ) and its polymer‐supported reagent 4 can be successfully applied to a one‐pot protection‐glycosylation reaction to form the disaccharide derivative 7 d for the synthesis of lipid II analogues. The temporary protecting group or linker at the C‐6 position and N‐Troc protecting group of 7 d can be cleaved simultaneously through a reductive condition. Overall yields of syntheses of lipid II ( 1 ) and neryl‐lipid II N^ε‐dansylthiourea are significantly improved by using the described methods.     

Two fac‐tricarbonylrhenium(I) azadipyrromethene (ADPM) complexes: ligand‐substitution effect on crystal structure

The crystal structures of fac‐(acetonitrile‐κN)(2‐{[3,5‐bis(4‐methoxyphenyl)‐2H‐pyrrol‐2‐ylidene‐κN¹]amino}‐3,5‐bis(4‐<!?tlsb=0.2pt>methoxyphenyl)‐1H‐pyrrol‐1‐ido‐κN¹)tricarbonylrhenium(I)–hexane–acetonitrile (2/1/2), [Re(C₃₆H₃₀N₃O₄)(CH₃CN)(CO)₃]·0.5C₆H₁₄·CH₃CN, (2), and fac‐(2‐{[3,5‐bis(4‐methoxyphenyl)‐2H‐pyrrol‐2‐ylidene‐κN¹]amino}‐3,5‐bis(4‐methoxyphenyl)‐1H‐pyrrol‐1‐ido‐κN¹)tricarbonyl(dimethyl sulfoxide‐κO)rhenium(I), [Re(C₃₆H₃₀N₃O₄)(C₂H₆OS)(CO)₃], (3), at 150 K are reported. Both complexes display a distorted octahedral geometry, with a fac‐Re(CO)₃ arrangement and one azadipyrromethene (ADPM) chelating ligand in the equatorial position. One solvent molecule completes the coordination sphere of the Re^I centre in the remaining axial position. The ADPM ligand shows high flexibility upon coordination, while retaining its π‐delocalized nature. Bond length and angle analyses indicate that the differences in the geometry around the Re^I centre in (2) and (3), and those found in three reported fac‐Re(CO)₃–ADPM complexes, are dictated mainly by steric factors and crystal packing. Both structures display intramolecular C—H...N hydrogen bonding. Intermolecular interactions of the Csp²—H...π and Csp²—H...O(carbonyl) types link the discrete monomers into extended chains.     

Conformation and tautomerism of methoxy‐substituted 4‐phenyl‐4‐thiazoline‐2‐thiones: a combined crystallographic and ab initio investigation

4‐Phenyl‐4‐thiazoline‐2‐thiol is an active pharmaceutical compound, one of whose activities is as a human indolenamine dioxygenase inhibitor. It has been shown recently that in both the solid state and the gas phase, the thiazolinethione tautomer should be preferred. As part of both research on this lead compound and a medicinal chemistry program, a series of substituted arylthiazolinethiones have been synthesized. The molecular conformations and tautomerism of 4‐(2‐methoxyphenyl)‐4‐thiazoline‐2‐thione and 4‐(4‐methoxyphenyl)‐4‐thiazoline‐2‐thione, both C₁₀H₉NOS₂, are reported and compared with the geometry deduced from ab initio calculations [PBE/6‐311G(d,p)]. Both the crystal structure analyses and the calculations establish the thione tautomer for the two substituted arylthiazolinethiones. In the crystal structure of the 2‐methoxyphenyl regioisomer, the thiazolinethione unit was disordered over two conformations. Both isomers exhibit similar hydrogen‐bond patterns [R₂²(8) motif] and form dimers. The crystal packing is further reinforced by short S…S interactions in the 2‐methoxyphenyl isomer. The conformations of the two regioisomers correspond to stable geometries calculated from an ab initio energy‐relaxed scan.     

A Convenient Synthesis of 6,8-Dimethoxy-3-[（2-（4-methoxyphenyl）ethyl）isocoumarin

6,8-Dimethoxy-3-[2-（4-methoxyphenyl）ethyl]isocoumarin was synthesized by condensation of 5,7-dimethoxyhompophthalic acid with 3-（4-methoxyphenyl）propanoyl chloride. The structure of the synthesized compound was confirmed by its mass spectrometric studies. The synthesized compound serves as a model for synthesis of DL-agrimonolide.     

3‐[5‐(4‐Chlorophenyl)‐1‐(4‐methoxyphenyl)‐1H‐pyrazol‐3‐yl]propionic acid and the corresponding methyl ester

The synthesis of 3‐[5‐(4‐chlorophenyl)‐1‐(4‐methoxyphenyl)‐1H‐pyrazol‐3‐yl]propionic acid, C₁₉H₁₇ClN₂O₃, (I), and its corresponding methyl ester, methyl 3‐[5‐(4‐chlorophenyl)‐1‐(4‐methoxyphenyl)‐1H‐pyrazol‐3‐yl]propionate, C₂₀H₁₉ClN₂O₃, (II), is regiospecific. However, correct identification of the regioisomer formed by spectroscopic techniques is not trivial and single‐crystal X‐ray analysis provided the only means of unambiguous structure determination. Compound (I) crystallizes with Z′ = 2. The propionic acid groups of the two crystallographically unique molecules form a hydrogen‐bonded dimer, as is typical of carboxylic acid groups in the solid state. Conformational differences between the methoxybenzene and pyrazole rings give rise to two unique molecules. The structure of (II) features just one molecule in the asymmetric unit and the crystal packing makes greater use than (I) of weak C—H...A interactions, despite the lack of any functional groups for classical hydrogen bonding.     

Synthesis of novel isoindolone‐based medium‐sized macromolecules and triazole containing heterocyclic compounds

A series of novel isoindolone‐based macromolecules of medium‐sized heterocyclic rings, such as 7,8‐dihydro‐6H‐benzo[4,5][1,6,3]dioxazonino[2,3‐a]isoindol‐14(9aH)‐one derivatives ( 5a‐l ), were synthesized and its frame work incorporating with a triazole moiety on phenol, ie, 2‐(4‐((1‐(2‐methoxyphenyl)‐1H‐1,2,3‐triazol‐4‐yl)methoxy)phenyl)isoindoline‐1,3‐dione ( 9a‐f ) and also a triazole moiety on carboxylic acid, ie, (1‐(2‐methoxyphenyl)‐1H‐1,2,3‐triazol‐4‐yl)methyl 4‐(1,3‐dioxoisoindolin‐2‐yl)benzoate derivatives ( 13a‐e ) with various substitutions on aryl ring system have synthesized. All the synthesized compounds were characterized and confirmed with IR, ¹H NMR_, ¹³C NMR, and ESI mass spectral analysis.     

Photocationic and radical polymerizations of epoxides and acrylates by novel sulfonium salts

Novel sulfonium salts [methyl‐, 2‐indany‐, or 1‐ethoxycarbonylethyl methyl‐2‐naphthylsulfonium hexafluorophosphate and 2‐indany‐, 1‐ethoxycarbonylethyl‐, 2‐methyl‐2‐phenylpropyl‐, 2‐phenylpropyl‐, 2‐phenylethyl‐, 2‐(4‐methoxyphenyl)‐ethyl‐, or 3‐(4‐methoxyphenyl)‐2‐propyl methylphenylsulfonium hexafluorophosphates] were synthesized by the reaction of dimethylsulfate and the corresponding sulfides followed by anion exchange with KPF₆. These sulfonium salts could polymerize epoxy monomers at lower temperatures than previously reported for benzylsulfonium salt initiators. In particular, sulfonium salts with naphthyl groups showed higher photoactivity than already reported for di(4‐tert‐butylphenyl)iodonium and triphenylsulfonium hexafluorophosphates. These sulfonium salts showed higher activity in photoradical polymerization and photocationic polymerization. The photopolymerization was accelerated by the addition of 4‐methoxy‐1‐naphthol, N‐ethylcarbazole, 2,4‐dimethylthioxanthone, phenothiazine, and 2‐ethyl‐9,10‐dimethoxyanthracene as photosensitizers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3816–3827, 2003     

The role of π–π stacking and hydrogen‐bonding interactions in the assembly of a series of isostructural group IIB coordination compounds

The supramolecular chemistry of coordination compounds has become an important research domain of modern inorganic chemistry. Herein, six isostructural group IIB coordination compounds containing a 2‐{[(2‐methoxyphenyl)imino]methyl}phenol ligand, namely dichloridobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)zinc(II), [ZnCl₂(C₂₈H₂₆N₂O₄)], 1 , diiodidobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)zinc(II), [ZnI₂(C₂₈H₂₆N₂O₄)], 2 , dibromidobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)cadmium(II), [CdBr₂(C₂₈H₂₆N₂O₄)], 3 , diiodidobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)cadmium(II), [CdI₂(C₂₈H₂₆N₂O₄)], 4 , dichloridobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)mercury(II), [HgCl₂(C₂₈H₂₆N₂O₄)], 5 , and diiodidobis(2‐{(E)‐[(2‐methoxyphenyl)azaniumylidene]methyl}phenolato‐κO)mercury(II), [HgI₂(C₂₈H₂₆N₂O₄)], 6 , were synthesized and characterized by X‐ray crystallography and spectroscopic techniques. All six compounds exhibit an infinite one‐dimensional ladder in the solid state governed by the formation of hydrogen‐bonding and π–π stacking interactions. The crystal structures of these compounds were studied using geometrical and Hirshfeld surface analyses. They have also been studied using M06‐2X/def2‐TZVP calculations and Bader's theory of `atoms in molecules'. The energies associated with the interactions, including the contribution of the different forces, have been evaluated. In general, the π–π stacking interactions are stronger than those reported for conventional π–π complexes, which is attributed to the influence of the metal coordination, which is stronger for Zn than either Cd or Hg. The results reported herein might be useful for understanding the solid‐state architecture of metal‐containing materials that contain M^IIX₂ subunits and aromatic organic ligands.     

A Lignoid Glycoside and Dimeric Phenylpropanoids from Daphne oleoides

Three new natural products, a lignoid glycoside 1 and two dimeric phenylpropanoids 2 and 3 , along with two known lignans 4 and 5 , were isolated from the BuOH‐ and CHCl₃‐soluble fractions of the whole plant of Daphne oleoides (Thymelaeaceae). The structures of the new compounds were established by spectroscopic techniques, including 2D NMR, as 4‐(β‐D ‐glucopyranosyloxy)‐9′‐hydroxy‐3,3′,4′‐trimethoxy‐7′,9‐epoxylignan ( 1 ), (1R,2S,5R,6R)‐6‐(3‐ethyl‐4‐hydroxy‐5‐methoxyphenyl)‐2‐(4‐hydroxy‐3,5‐dimethoxyphenyl)‐3,7‐dioxabicyclo[3.3.0]octane ( 2 ) and (1R,2S,5R,6S)‐2,6‐bis(3‐ethyl‐4‐hydroxy‐5‐methoxyphenyl)‐3,7‐dioxabicyclo[3.3.0]octane ( 3 ). The other lignans were identified as (+)‐pinoresinol O‐(β‐D ‐glucopyranoside) ( 4 ) and (+)‐medioresinol ( 5 ).     

1,3‐Dipolar Cycloaddition Reaction of Nitrile Oxides Revisited—Unusual Side Products Characterized by 2D NMR

Cycloaddition of (4‐trifluoromethyl)phenylnitrile oxide to N‐(4‐methoxyphenyl)acrylamide afforded bicyclic tetrahydro‐oxazolo‐(3,2‐b)[1,3]oxazine‐2‐carboxamide derivative in result of N‐acylation of the initially formed cycloadduct by the dipolarophile. 2:1 Cycloaddition of the same dipole to N‐(4‐methoxyphenyl)crotonamide yielded dihydro[1,2]‐oxazolo[2,3‐d][1,2,4]oxadiazole‐7‐carboxamide because of the second addition of the dipole to the C═N bond of the first formed 2‐isoxazoline compound. Structures of the products have been elucidated by an extensive application of 1D and 2D NMR spectroscopy.     

Norlignans and Phenylpropanoids from Metasequoia glyptostroboides Hu et Cheng

Five new compounds, i.e., the three new norlignans metasequirins G–I ( 1 – 3 ) and the two new phenylpropanoids 7‐(3‐ethoxy‐5‐methoxyphenyl)propane‐7,8,9‐triol (=1‐(3‐ethoxy‐5‐methoxyphenyl)propane‐1,2,3‐triol; 4 ) and 7‐(3‐hydroxy‐5‐methoxyphenyl)propane‐7,8,9‐triol (=1‐(3‐hydroxy‐5‐methoxy‐phenyl)propane‐1,2,3‐triol; 5 ), were isolated from the branches and stems of Metasequoia glyptostroboides Hu et Cheng . Their structures were elucidated by physical, chemical, and spectroscopic methods, including 1D‐ and 2D‐NMR and HR‐ESI‐MS. The cytotoxicites of the five compounds were tested against A549 and Colo 205 cell lines by the MTT method.     

Synthesis and Characterization of Azobenzene–Porphyrins

A new series of novel covalently connected meso‐tetrakis(3‐azophenyl‐4‐hydroxy‐5‐methoxyphenyl)porphyrins were synthesized by linking azobenzene unit at the meta‐position of the meso‐phenyl group. These are characterized by UV–vis, IR, ¹H‐NMR, CHN, and FABMS spectroscopic techniques. All the porphyrin compounds showed a typical high energy Soret band at around 435 nm and azobenzene absorption at around 350 nm in UV–vis spectra. Fluorescence intensity of meso‐tetrakis(3‐(4‐methoxyazophenyl)‐4‐hydroxy‐5‐methoxyphenyl)porphyrin ( 2c ) has been observed to be maximum compared with other azobenzene porphyrins.