Synthese und Reaktivität von 2‐Brom‐1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol Molekülstruktur von Bis(1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol‐2‐yl)

Synthesis and Reactivity of 2‐Bromo‐1,3‐diethyl‐2,3‐dihydro‐1 H ‐1,3,2‐benzodiazaborole Molecular Structure of Bis(1,3‐diethyl‐2,3‐dihydro‐1 H ‐1,3,2‐benzodiazaborol‐2‐yl The reaction of a slurry of calcium hydride in toluene with N,N′‐diethyl‐o‐phenylenediamine ( 1 ) and boron tribromide affords 2‐bromo‐1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol ( 2 ) as a colorless oil. Compound 2 is converted into 2‐cyano‐1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborole ( 3 ) by treatment with silver cyanide in acetonitrile. Reaction of 2 with an equimolar amount of methyllithium affords 1,3‐diethyl‐2‐methyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborole ( 4 ). 1,3,2‐Benzodiazaborole is smoothly reduced by a potassium‐sodium alloy to yield bis(1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol‐2‐yl] ( 7 ), which crystallizes from n‐pentane as colorless needles. Compound 7 is also obtained from the reaction of 2 and LiSnMe₃ instead of the expected 2‐trimethylstannyl‐1,3,2‐benzodiazaborole. N,N′‐Bis(1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol‐2‐ yl)‐1,2‐diamino‐ethane ( 6 ) results from the reaction of 2 with Li(en)C≡CH as the only boron containing product. Compounds 2 – 4 , 6 and 7 are characterized by means of elemental analyses and spectroscopy (IR, ¹H‐, ¹¹B{¹H}‐, ¹³C{¹H}‐NMR, MS). The molecular structure of 7 was elucidated by X‐ray diffraction analysis.     

Synthesis and NMR characteristics of N‐acetyl‐4‐nitro,N‐acetyl‐5‐nitro,N‐acetyl‐6‐nitro and N‐acetyl‐7‐nitrotryptophan methyl esters

N‐acetyl‐4‐nitrotryptophan methyl ester (2), N‐acetyl‐5‐nitrotryptophan methyl ester (3), N‐acetyl‐6‐nitrotryptophan methyl ester (4) and N‐acetyl‐7‐nitrotryptophan methyl ester (5) were synthesized through a modified malonic ester reaction of the appropriate nitrogramine analogs followed by methylation with BF₃‐methanol. Assignments of the ¹H and ¹³C NMR chemical shifts were made using a combination of ¹H–¹H COSY, ¹H–¹³C HETCOR and ¹H–¹³C selective INEPT experiments. Copyright © 2008 Crown in the right of Canada. Published by John Wiley & Sons, Ltd     

Synthesis of some new 1‐acyl‐5‐aryl‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐4,5‐dihydro‐1H‐pyrazole

Some new compounds (E)‐3‐aryl‐1‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐prop‐2‐en‐1‐ones 5a–e were prepared by 1‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐ethanone and various aromatic aldehydes. Then one pot reaction was happened by compounds 5a–e with hydrazine hydrate in acetic acid or propionic acid, respectively, to give the title compounds 1acyl‐5‐aryl‐3‐(5‐methyl‐1‐p‐tolyl‐1H‐1,2,3‐triazol‐4‐yl)‐4,5‐dihydro‐1H‐pyrazoles 6a–i . All structures were established by MS, IR, CHN, ¹H‐NMR and ¹³C‐NMR spectral data. J. Heterocyclic Chem., (2012).     

Synthesis and antimicrobial activity of 2‐substituted‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐Oxides

Several 2‐alkylcarbamato/thiocarbamato/aryloxy/trichloromethyl‐2,3‐dihydro‐5‐propoxy‐1H‐1,3,2‐benzodiazaphosphole 2‐oxides ( 4 and 6 ) were synthesised by reacting 4‐propoxy‐o‐phenylenediamine ( 1 ) with various N‐dichlorophosphinyl carbamates ( 3 ), aryl phosphorodichloridates ( 5a‐f ) and trichloromethyl phosphonic dichloride ( 5g ) in the presence of triethylamine at 45‐65 °C. Their ir, ¹H, ¹³C, ³¹P nmr and mass spectral data are discussed. The compounds were screened for antifungal activity against Curvularia lunata and Aspergillus niger and for antibacterial activity against Bacillus subtilis and Escherichia coli. Most of these compounds exhibited moderate activity in the assays.     

New domino‐reaction for the synthesis of N4‐(5‐aryl‐1,3‐oxathiol‐2‐yliden)‐2‐phenylquinazolin‐4‐amines and 4‐[4‐aryl‐5‐(2‐phenylquinazolin‐4‐yl)‐1,3‐thiazol‐2‐yl]morpholine

The model morpholine‐1‐carbothioic acid (2‐phenyl‐3H‐quinazolin‐4‐ylidene) amide (1) reacts with phenacyl bromides to afford N⁴‐(5‐aryl‐1,3‐oxathiol‐2‐yliden)‐2‐phenylquinazolin‐4‐amines (4) or N⁴‐(4,5‐diphenyl‐1,3‐oxathiol‐2‐yliden)‐2‐phenyl‐4‐aminoquinazoline ( 5 ) by a thermodynamically controlled reversible reaction favoring the enolate intermediate, while the 4‐[4‐aryl‐5‐(2‐phenylquinazolin‐4‐yl)‐1,3‐thiazol‐2‐yl]morpholine ( 8 ) was produced by a kinetically controlled reaction favoring the C‐anion intermediate. ¹H nmr, ¹³C nmr, ir, mass spectroscopy and x‐ray identified compounds ( 4 ), ( 5 ) and ( 8 ).     

Photochemistry of 1‐Cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐ (piperazin‐1‐yl)quinoline‐3‐carboxylic Acid (=Ciprofloxacin) in Aqueous Solutions

The 1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐1‐yl)quinoline‐3‐carboxylic acid (=ciprofloxacin; 1 ) undergoes low‐efficiency (Φ=0.07) substitution of the 6‐fluoro by an OH group on irradiation in H₂O via the ππ* triplet (detected by flash photolysis, λ_max 610 nm, τ 1.5 μs). Decarboxylation is a minor process (≤5%). The addition of sodium sulfite or phosphate changes the course of the reaction under neutral conditions. Reductive defluorination is the main process in the first case, while defluorination is accompanied by degradation of the piperazine moiety in the presence of phosphate. In both cases, the initial step is electron‐transfer quenching of the triplet (k_q=2.3⋅10⁸M ⁻¹ s⁻¹ and 2.2⋅10⁷M ⁻¹ s⁻¹, respectively). Oxoquinoline derivative 1 is much more photostable under acidic conditions, and in this case the F‐atom is conserved, and the piperazine group is stepwise degraded (Φ=0.001).     

A two‐dimensional mixed‐valence CuII/CuI coordination polymer constructed from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate

Coordination polymers are a thriving class of functional solid‐state materials and there have been noticeable efforts and progress toward designing periodic functional structures with desired geometrical attributes and chemical properties for targeted applications. Self‐assembly of metal ions and organic ligands is one of the most efficient and widely utilized methods for the construction of CPs under hydro(solvo)thermal conditions. 2‐(Pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylate (HPIDC²⁻) has been proven to be an excellent multidentate ligand due to its multiple deprotonation and coordination modes. Crystals of poly[aquabis[μ₃‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ⁵N¹,O⁵:N³,O⁴:N²]copper(II)dicopper(I)], [Cu^IICu^I₂(C₁₀H₅N₃O₄)₂(H₂O)]_n, (I), were obtained from 2‐(pyridin‐3‐yl)‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PIDC) and copper(II) chloride under hydrothermal conditions. The asymmetric unit consists of one independent Cu^II ion, two Cu^I ions, two HPIDC²⁻ ligands and one coordinated water molecule. The Cu^II centre displays a square‐pyramidal geometry (CuN₂O₃), with two N,O‐chelating HPIDC²⁻ ligands occupying the basal plane in a trans geometry and one O atom from a coordinated water molecule in the axial position. The Cu^I atoms adopt three‐coordinated Y‐shaped coordinations. In each [CuN₂O] unit, deprotonated HPIDC²⁻ acts as an N,O‐chelating ligand, and a symmetry‐equivalent HPIDC²⁻ ligand acts as an N‐atom donor via the pyridine group. The HPIDC²⁻ ligands in the polymer serve as T‐shaped 3‐connectors and adopt a μ₃‐κ²N,O:κ²N′,O′:κN′′‐coordination mode, linking one Cu^II and two Cu^I cations. The Cu cations are arranged in one‐dimensional –Cu1–Cu2–Cu3– chains along the [001] direction. Further crosslinking of these chains by HPIDC²⁻ ligands along the b axis in a –Cu2–HPIDC²⁻–Cu3–HPIDC²⁻–Cu1– sequence results in a two‐dimensional polymer in the (100) plane. The resulting (2,3)‐connected net has a (12³)₂(12)₃ topology. Powder X‐ray diffraction confirmed the phase purity for (I), and susceptibilty measurements indicated a very weak ferromagnetic behaviour. A thermogravimetric analysis shows the loss of the apical aqua ligand before decomposition of the title compound.     

One‐ and two‐dimensional CdII coordination polymers constructed from 2‐(2‐methyl‐1H‐benzimidazol‐1‐yl)acetate ligands

The one‐ and two‐dimensional polymorphic cadmium polycarboxylate coordination polymers, catena‐poly[bis[μ₂‐2‐(2‐methyl‐1H‐benzimidazol‐1‐yl)acetato‐κ³N³:O,O′]cadmium(II)], [Cd(C₁₀H₉N₂O₂)₂]_n, and poly[bis[μ₂‐2‐(2‐methyl‐1H‐benzimidazol‐1‐yl)acetato‐κ³N³:O,O′]cadmium(II)], also [Cd(C₁₀H₉N₂O₂)₂]_n, were prepared under solvothermal conditions. In each structure, each Cd^II atom is coordinated by four O atoms and two N atoms from four different ligands. In the former structure, two crystallographically independent Cd^II atoms are located on twofold symmetry axes and doubly bridged in a μ₂‐N:O,O′‐mode by the ligands into correspondingly independent chains that run in the [100] and [010] directions. Chains containing crystallographically related Cd^II atoms are linked into sheets viaπ–π stacking interactions. Sheets containing one of the distinct types of Cd^II atom are stacked perpendicular to [001] and alternate with sheets containing the other type of Cd^II atom. The second complex is a two‐dimensional homometallic Cd^II (4,4) net structure in which each Cd^II atom is singly bridged to four neighbouring Cd^II atoms by four ligands also acting in a μ₂‐N:O,O′‐mode. A square‐grid network results and the three‐dimensional supramolecular framework is completed by π–π stacking interactions between the aromatic ring systems.     

A New Route for Preparation of 5‐Deoxy‐5‐(hydroxyphosphinyl)‐ D‐mannopyranose and ‐L‐gulopyranose Derivatives

Starting from methyl 2,3‐O‐isopropylidene‐α‐D ‐mannofuranoside ( 5 ), methyl 6‐O‐benzyl‐2,3‐O‐isopropylidene‐α‐D ‐lyxo‐hexofuranosid‐5‐ulose ( 12 ) was prepared in three steps. The addition reaction of dimethyl phosphonate to 12 , followed by deoxygenation of 5‐OH group, provided the 5‐deoxy‐5‐dimethoxyphosphinyl‐α‐D ‐mannofuranoside derivative 15a and the β‐L ‐gulofuranoside isomer 15b . Reduction of 15a and 15b with sodium dihydrobis(2‐methoxyethoxy)aluminate, followed by the action of HCl and then H₂O₂, afforded the D ‐mannopyranose ( 17 ) and L ‐gulopyranose analog 21 , each having a phosphinyl group in the hemiacetal ring. These were converted to the corresponding 1,2,3,4,6‐penta‐O‐acetyl‐5‐methoxyphosphinyl derivatives 19 and 23 , respectively, structures and conformations (⁴C₁ or ¹C₄, resp.) of which were established by ¹H‐NMR spectroscopy.     

Hydrogen‐bonded ribbons in ethyl (E)‐3‐[2‐amino‐4,6‐bis(dimethylamino)pyrimidin‐5‐yl]‐2‐cyanoacrylate and 2‐[(2‐amino‐4,6‐di‐1‐piperidylpyrimidin‐5‐yl)methylene]malononitrile

The pyrimidine rings in ethyl (E)‐3‐[2‐amino‐4,6‐bis(dimethylamino)pyrimidin‐5‐yl]‐2‐cyanoacrylate, C₁₄H₂₀N₆O₂, (I), and 2‐[(2‐amino‐4,6‐di‐1‐piperidylpyrimidin‐5‐yl)methylene]malononitrile, C₁₈H₂₃N₇, (II), which crystallizes with Z′ = 2 in the space group, are both nonplanar with boat conformations. The molecules of (I) are linked by a combination of N—H...N and N—H...O hydrogen bonds into chains of edge‐fused R₂²(8) and R₄⁴(20) rings, while the two independent molecules in (II) are linked by four N—H...N hydrogen bonds into chains of edge‐fused R₂²(8) and R₂²(20) rings. This study illustrates both the readiness with which highly‐substituted pyrimidine rings can be distorted from planarity and the significant differences between the supramolecular aggregation in two rather similar compounds.     

A two‐dimensional cadmium(II) coordination polymer constructed from 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate and 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate ligands

Crystals of poly[[aqua[μ₃‐4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylato‐κ⁵O¹O^1′:N³,O⁴:O⁵][μ₄‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylato‐κ⁷N³,O⁴:O⁴,O^4′:O¹,O^1′:O¹]cadmium(II)] monohydrate], {[Cd₂(C₁₅H₁₄N₂O₄)(C₁₆H₁₄N₂O₆)(H₂O)]·H₂O}_n or {[Cd₂(Hcpimda)(cpima)(H₂O)]·H₂O}_n, (I), were obtained from 1‐(4‐carboxybenzyl)‐2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃cpimda) and cadmium(II) chloride under hydrothermal conditions. The structure indicates that in‐situ decarboxylation of H₃cpimda occurred during the synthesis process. The asymmetric unit consists of two Cd²⁺ centres, one 4‐carboxy‐1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐5‐carboxylate (Hcpimda²⁻) anion, one 1‐(4‐carboxylatobenzyl)‐2‐propyl‐1H‐imidazole‐4‐carboxylate (cpima²⁻) anion, one coordinated water molecule and one lattice water molecule. One Cd²⁺ centre, i.e. Cd1, is hexacoordinated and displays a slightly distorted octahedral CdN₂O₄ geometry. The other Cd centre, i.e. Cd2, is coordinated by seven O atoms originating from one Hcpimda²⁻ ligand and three cpima²⁻ ligands. This Cd²⁺ centre can be described as having a distorted capped octahedral coordination geometry. Two carboxylate groups of the benzoate moieties of two cpima²⁻ ligands bridge between Cd2 centres to generate [Cd₂O₂] units, which are further linked by two cpima²⁻ ligands to produce one‐dimensional (1D) infinite chains based around large 26‐membered rings. Meanwhile, adjacent Cd1 centres are linked by Hcpimda²⁻ ligands to generate 1D zigzag chains. The two types of chains are linked through a μ₂‐η² bidentate bridging mode from an O atom of an imidazole carboxylate unit of cpima²⁻ to give a two‐dimensional (2D) coordination polymer. The simplified 2D net structure can be described as a 3,6‐coordinated net which has a (4³)₂(4⁶.6⁶.8³) topology. Furthermore, the FT–IR spectroscopic properties, photoluminescence properties, powder X‐ray diffraction (PXRD) pattern and thermogravimetric behaviour of the polymer have been investigated.     

Synthesis of 32‐phenyl‐substituted methyl E/Z‐pyropheophorbide‐a's from methyl E/Z‐pyropehophorbide‐a 131‐ketoximes

Methyl E/Z‐pyropheophorbide‐a 13¹‐ketoximes 2a,b and their O‐acetyl derivatives 3a,b were oxidized with osmium(VIII) oxide to give aldehydes 4a,b and 5a,b , respectively. The Wittig reactions of the aldehyde chlorines 4a,b and 5a,b with benzyltriphenylphosphonium chloride were performed to form the corresponding methyl (3¹E/Z,13¹E/Z)‐3²‐phenylpyropheophorbide‐a 13¹‐ketoximes 6aa‐bb and their O‐acetyl derivatives 7aa‐bb ; hydrolysis of these ketoximes 6aa,ba and 6ab,bb in formic acid produced methyl (E/Z)‐3²‐phenylpyropheophorbide‐a's 8a,b .     

A one‐dimensional coordination polymer formed from the reaction of 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one with MnCl2·4H2O

In the title coordination polymer, catena‐poly[[dichloridomanganese(II)]‐μ‐1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azaniumylylidene)]dibut‐1‐en‐1‐olate‐κ²O:O′], [MnCl₂(C₂₆H₃₀N₂)]_n, synthesized by the reaction of the chiral Schiff base ligand 1,1‐diphenyl‐3,3′‐[(1R,2R)‐cyclohexane‐1,2‐diylbis(azanediyl)]dibut‐2‐en‐1‐one (L) with MnCl₂·4H₂O, the asymmetric unit contains one crystallographically unique Mn^II ion, one unique spacer ligand, L, and two chloride ions. Each Mn^II ion is four‐coordinated in a distorted tetrahedral coordination environment by two O atoms from two L ligands and by two chloride ligands. The Mn^II ions are bridged by L ligands to form a one‐dimensional chain structure along the a axis. The chloride ligands are monodentate (terminal). The ligand is in the zwitterionic enol form and displays intramolecular ionic N⁺—H...O⁻ hydrogen bonding and π–π interactions between pairs of phenyl rings which strengthen the chains.     

Preparation of 2‐phenyl‐2‐hydroxymethyl‐4‐oxo‐1,2,3,4‐tetrahydroquinazoline and 2‐methyl‐4‐oxo‐3,4‐dihydroquinazoline derivatives formation

The cyclization of phenacyl anthranilate has been studied with the aim to develop the synthesis of 2‐(2′‐aminophenyl)‐4‐phenyloxazole. However, a different course of the reaction than expected was observed. 2‐Phenyl‐2‐hydroxymethyl‐4‐oxo‐1,2,3,4‐tetrahydroquinazoline ( 3a ) was formed by the reaction of phenacyl anthranilate ( 2 ) with ammonium acetate under various conditions. 3‐Hydroxy‐2‐phenyl‐4(1H)‐quinolinone ( 4 ) arose by heating compound 3a in acetic acid. The same compound was obtained by melting compound 3a , but the yield was lower. Different types of products resulted in the reaction of compound 3a with acetic anhydride. Under mild conditions acetylated products 2‐acetoxymethyl‐2‐phenyl‐4‐oxo‐1,2,3,4‐tetrahydroquinazoline ( 7a ) and 2‐acetoxymethyl‐3‐acetyl‐2‐phenyl‐4‐oxo‐1,2,3,4‐tetrahydroquinazoline ( 8 ) were prepared. If the reaction was carried out under reflux of the reaction mixture, molecular rearrangement took place to give cis and trans 2‐methyl‐4‐oxo‐3‐(1‐phenyl‐2‐acetoxy)vinyl‐3,4‐dihydroquinazolines ( 9a and 9b ). All prepared compounds have been characterised by their ¹H, ¹³C and ¹⁵N NMR spectra, IR spectra and MS.     

Efficient synthesis and spectral determination of 11‐[(o‐ m‐ and p‐substituted)‐phenyl]‐8‐chloro‐3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐1H‐dibenzo[b,e][1,4]diazepin‐1‐ones

A new synthesis to obtain eleven novel derivatives of 11‐[(o‐ m‐ and p‐substituted)‐phenyl]‐8‐chloro‐3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐1H‐dibenzo[b,e][1,4]diazepin‐1‐ones with possible pharmacological activity in the central nervous system in two efficient steps has been developed. The final products were obtained by condensation and cyclization between 3‐[4‐chloro‐1,2‐phenylenediamine]‐5,5‐dimethyl‐2‐cyclohexenone with (o‐ m‐ and p‐substituted)benzaldehyde. The structure of all products was corroborated by ir, ¹H‐nmr, ¹³C‐nmr and high resolution in ms.     

Chirale 1,3,2‐Oxazaborolidine aus chiralen 2,3‐Dihydro‐1H‐1,3,2‐diazaborolen und Diphenylketen

Chiral 1,3,2‐Oxazaborolidines from the Reaction of Chiral 2,3‐Dihydro‐1H‐1,3,2‐diazaboroles and Diphenylketene Reaction of equimolar amounts of diphenylketene with 1,3‐di‐tert‐butyl‐2‐isobutyl‐2,3‐dihydro‐1H‐1,3,2‐diazaborole ( 1 ) regioselectively afforded 1,3,2‐oxazaborolidine ( 2 ). The employment of a series of chiral diazaboroles ( 3a : X = nBu; b: iBu; c: CH₂SiMe₃; d: NHtBu) led to the formation of the diastereoisomeric oxazaborolidines ( 4a – d ) with diastereomeric excesses de, which increase with the steric demand of X from de = 55 % (X = nBu) to de ≥ 95 % (X = NHtBu). Under comparable conditions the treatment of the enantiomerically pure diazaborole ( 6 ) with the ketene yielded oxazaborolidine ( 7 ) with a de‐value of only 52 %. The new compounds, with exception of 2 and 4d , are thermolabile solids, which were characterized mainly by spectroscopy (¹H‐, ¹¹B{¹H}‐, ¹³C{¹H}‐NMR, MS). The X‐ray structure analysis of 2 revealed a slightly puckered five‐membered heterocycle with a long B–O bond.     

Synthesis of 15‐Cyano‐12‐oxopentadecano‐15‐lactone and 15‐Cyano‐ 12‐oxopentadecano‐15‐lactam

15‐Cyano‐12‐oxopentadecano‐15‐lactone was synthesized in 59% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by reaction with trimethylsilylcyanide, hydrolysis, ring‐expansion, and Nef reaction. A two‐step, one‐pot synthesis of intermediate 2‐hydroxy‐4‐(1‐nitro‐2‐oxycyclododecyl)butanenitrile from 3‐(1‐nitro‐2‐oxocyclododecyl)propanal was developed and the conditions for the Nef reaction were studied. 15‐Cyano‐12‐oxopentadecano‐15‐lactam was synthesized in 40% total yield starting from 2‐nitrocyclododecanone by Michael addition to acrylaldehyde, followed by Strecker reaction, ring‐expansion, and Nef reaction. The conditions for the Strecker and Nef reactions were studied. The structures of the target compounds, intermediates, and by‐product were characterized by IR, ¹H‐ and ¹³C‐NMR, and elemental analysis or MS.     

Synthesis of N‐(Substituted aryl/cyclohexyl)‐N'‐[5‐bromo‐5‐nitro‐2‐oxido‐1,3,2‐dioxaphosphorinane‐2‐yl]ureas

N‐(Substituted aryl/cyclohexyl)‐N'‐[5‐bromo‐5‐nitro‐2‐oxido‐1,3,2‐dioxaphosphorinane‐2‐yl]ureas RR'P(O)NHC(O)NHR' (5) were synthesized by the reactions of 2‐bromo‐2‐nitro‐1,3‐propanediol (4) with chlorides of aryl/cyclohexyl carbamidophosphoric acids (3) in the presence of triethylamine at room temperature. Their ir, ¹H, ¹³C and ³¹P nmr spectral data are discussed.     

A new one‐dimensional ZnII coordination polymer based on 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole and benzene‐1,2‐dicarboxylate

Multidentate N‐heterocyclic compounds form a variety of metal complexes with many intriguing structures and interesting properties. The title coordination polymer, catena‐poly[zinc(II)‐bis{μ‐2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole}‐κ²N³:N^3′;N^3′:N³‐zinc(II)‐bis(μ‐benzene‐1,2‐dicarboxylato)‐κ²O¹:O²;κ³O¹,O^1′:O²], [Zn₂(C₈H₄O₄)₂(C₁₁H₁₀N₄)₂]_n, has been synthesized by the reaction of Zn(NO₃)₂ with 2‐[(1H‐imidazol‐1‐yl)methyl]‐1H‐benzimidazole (imb) and benzene‐1,2‐dicarboxylic acid (H₂bdic) under hydrothermal conditions. There are two crystallographically distinct imb ligands [imb(A) and imb(B)] in the structure which adopt very similar coordination geometries. The imb(A) ligand bridges two symmetry‐related Zn1 ions, yielding a binuclear [(Zn1)₂{imb(A)}₂] unit, and the imb(B) ligand bridges two symmetry‐related Zn2 ions resulting in a binuclear [(Zn2)₂{imb(B)}₂] unit. The above‐mentioned binuclear units are further connected alternately by pairs of bridging bdic²⁻ ligands, forming an infinite one‐dimensional chain. These one‐dimensional chains are further connected through N—H...O hydrogen bonds, leading to a two‐dimensional layered structure. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.     

Synthesis,Bioactivities and Structure Activity Relationship of N‐4‐Methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl Ureas

Twenty nine novel N‐4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl‐N′‐phenyl ureas were designed and synthesized, and their structures were confirmed by proton nuclear magnetic resonance (¹H NMR), infra red spectroscopy (IR) and high‐resolution mass spectroscopy (HRMS). Compounds V‐9 , V‐11 , V‐12 , V‐15 , V‐19 , V‐21 , V‐22 and V‐24 exhibit excellent activity against Culex pipiens pallens. Compounds V‐12 and V‐22 present good insecticidal activity against Plutella xylostella L. Their median lethal concentrations (LC₅₀) are 164.15 and 89.69 mg·L^?1, respectively. Compound V‐11 also has potential wide spectrum of fungicide activity. Its median effective concentrations (EC₅₀) detected from 3.82 µg·mL^?1 against Physalospora piricola to 31.60 µg·mL^?1 against Cercospora arachidicola. Compounds V‐15 and V‐24 show outstanding induction activities as same as positive controls TDL and ningnanmycin, furthermore V‐24 has the highest induction activity of 41.85%±4.43%. To elucidate the structure activity relationship in these compounds, a 3D‐QSAR model has been built. The established model showed a reliable predicting ability with q² values of 0.643 and r² values of 0.982.