trans‐3‐Ethyl‐cis‐2,6,6‐trimethyl‐4‐oxocyclohexanecarboxylic acid: an intermediate in the synthesis of a highly potent estrogen

The title compound, C₁₂H₂₀O₃, (IV), the ethyl ester of which is an intermediate in the synthesis of a compound reported to be highly estrogenic, has been prepared. After the initial steps reported for the synthesis of this ester intermediate were followed, it was converted into the crystalline acid, (IV), for X‐ray analysis. It was verified that (IV) was racemic when prepared. X‐ray analysis showed that anti‐hydrogenation of the double bond had occurred in the synthesis, making the orientation of the carboxyl group cis to the 2‐methyl group and trans to the 3‐ethyl group. NMR spectroscopy showed that the stereochemistry of (IV) was identical with that of its ester precursor. While the earlier report did not note the stereochemistry of this ester, it pointed out that the estrogenic product derived from it possessed the opposite carboxyl‐2‐methyl orientation, i.e.trans, although no X‐ray analysis was performed. In the light of these results and the importance of correlating biological activity with compound structure, the unequivocal characterization of the highly estrogenic compound is warranted.     

Synthesis and Investigation of 2,6‐Bis(picrylamino)‐3,5‐dinitro‐pyridine (PYX) and Its Salts

2,6‐Bis(picrylamino)pyridine ( 1 ; pre‐PYX) and 2,6‐bis(picrylamino)‐3,5‐dinitropyridine ( 2 ; PYX) were synthesized using an improved literature method. Compounds 1 and 2 were reinvestigated in detail and the X‐ray structures ( 1 : ρ=1.698 g cm^?3 at 173 K; 2 : ρ=1.757 g cm^?3 at 298 K) are given. The reactions of 2 with different bases, such as alkali metal hydroxides (sodium, potassium, rubidium, cesium), and N‐bases (ammonia, hydrazine, hydroxylamine, guanidinium carbonate, aminoguanidine bicarbonate) are reported, as well as metathesis reactions producing energetic salts. Several energetic compounds were synthesized and characterized for the first time using vibrational (IR, Raman) and multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and DSC. The crystal structures of four energetic salts were determined using low temperature single‐crystal X‐ray diffraction. Heats of formation for the metal‐free species were calculated using the Gaussian 09 software. Detonation parameters were estimated using the EXPLO5 program. The sensitivities towards impact, friction, and electrostatic discharge were also determined.     

Synthesis and Characterization of 3,3′‐Bis(Dinitromethyl)‐5,5′‐Azo‐1H‐1,2,4‐Triazole

The synthesis of 3,3′‐bis(dinitromethyl)‐5,5′‐azo‐1H‐1,2,4‐triazole ( 5 ) using the readily available starting material 2‐(5‐amino‐1H‐1,2,4‐triazol‐3‐yl)acetic acid ( 1 ) is described. All compounds were characterized by means of NMR, IR, and Raman spectroscopy. The energetic compound 5 was additionally characterized by single‐crystal X‐ray diffraction and DSC measurements. The sensitivities towards impact, friction and electrical discharge were determined. In addition, detonation parameters (e.g. heat of explosion, detonation velocity) of the target compound were computed using the EXPLO5 code based on the calculated (CBS‐4M) heat of formation and X‐ray density.     

A clothes‐peg‐shaped binuclear trans‐bis(2‐aminotroponato)palladium(II) complex bearing pentamethylene spacers

rac‐Bis{μ‐trans‐2,2′‐[pentane‐1,5‐diylbis(azanediyl)]ditroponato}dipalladium(II), [Pd₂(C₁₉H₂₀N₂O₂)₂], has been synthesized and fully characterized using single‐crystal X‐ray diffraction, ¹H NMR, FT–IR and mass spectroscopy. The trans coordination, vaulted structure and anti conformation have been unequivocally established from the X‐ray diffraction studies. This is the first example of a bis(aminotroponato)palladium complex. In the crystalline state, the molecule has twofold symmetry and each molecular unit undergoes intermolecular offset π‐stacking of the tropone rings to afford heterochiral interpenetrating dimers that are aligned in a lamellar manner with a herringbone packing motif.     

A 1,1‐Carboboration Route to Bora‐Nazarov Systems

Hydroboration of the conjugated enynes 1 a and 1 b with Piers’ borane [HB(C₆F₅)₂] gave the respective dienylboranes trans‐ 2 c and trans‐ 2 d . Their photolysis resulted in the formation of the dihydroborole products 3 c and 3 d . Both were converted to their pyridine adducts 5 c and 5 d , respectively. Compounds 3 c and 5 c,d were characterized by X‐ray diffraction. The reaction of the bis(enynyl)boranes 6 a and 6 b with B(C₆F₅)₃ resulted in the formation of the dihydroboroles 7 a and 7 b , respectively. This reaction is thought to proceed by 1,1‐carboboration of one of the enynyl substituents at boron to generate the dienylborane intermediates 8 a / 8 b , followed by thermally induced bora‐Nazarov ring‐closure and subsequent stabilizing 1,2‐pentafluorophenyl group migration from boron to carbon. Compound 7 a was characterized by X‐ray diffraction and solid‐state ¹¹B NMR spectroscopy.     

3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮衍生物的合成，晶体结构与固态光致变色及光致自由基性质研究

本文合成了一系列3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮新化合物,并通过¹H NMR, IR, MS 和元素分析数据进行了结构表征,其中化合物1,5,6的结构通过单晶X-Ray衍射进行了确证。分别用固体紫外光谱和电子自旋共振光谱研究了化合物的光致变色性能和光致自由基性质,结果表明：该类化合物在200W高压水银灯光源照射下产生光致变色现象,同时具有光致自由基性质。本文还根据分子结构和及分子内的作用力讨论了性质与结构之间的关系。     

Silver Salt and Derivatives of 5‐Azido‐1H‐1, 2, 4‐triazole‐3‐­carbonitrile

This study features the preparation of three new energetic C‐azido‐1, 2, 4‐triazoles, with the anion of one being a new binary C–N compound. 5‐Azido‐1H‐1, 2, 4‐triazole‐3‐carbonitrile ( 1 ) was prepared from 5‐amino‐1H‐1, 2, 4‐triazole‐3‐carbonitrile and further derivatized to 5‐azido‐1H‐1, 2, 4‐triazole‐3‐carbohydroximoyl chloride ( 5 ) with 3‐azido‐1H‐1, 2, 4‐triazole‐5‐carboxamidoxime ( 3 ) as an intermediate. The ability of 1 and 3 for salt formation was shown with the respective silver salts 2 and 4 . All compounds were well characterized by various means, including IR and multinuclear NMR spectroscopy, mass spectrometry, and DSC. The molecular structures of 1 , 3 , and 5 in the solid state were determined by single‐crystal X‐ray diffraction. The sensitivities towards various outer stimuli (impact, friction, electrostatic discharge) were determined according to BAM standards. The silver salts were additionally tested for their potential as primary explosives.     

Synthesis and Characterization of 3,4,5‐Triamino‐1,2,4‐triazolium and 1‐Methyl‐3,4,5‐triamino‐1,2,4‐triazolium Iodides

3,4,5‐Triamino‐1,2,4‐triazolium iodide ( 1 ) was obtained in good yield and purity and characterized using vibrational (IR, Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N), EA, MS, DSC, and X‐ray crystallography. The compound was synthesized by two different methods rendering two different polymorphs (α and β) as proved by X‐ray measurements, vibrational spectroscopy and DSC. 1‐Methyl‐3,4,5‐triamino‐1,2,4‐triazolium iodide ( 2 ) was synthesized by reaction of guanazine with methyliodide and fully characterized by the same techniques mentioned above. Both compounds showed to be suitable starting materials for the synthesis of guanazinium salts of energetic interest.     

Synthesis and Characterization of the Germanium Sulfonate Ge(CH3SO3)2 – a 3D Coordination Network Solid

The reaction of germanium(II)‐bis(2‐methoxyphenyl)methoxide with methanesulfonic acid provides the germanium(II) sulfonate Ge(CH₃SO₃)₂ ( 1 ), which was characterized by X‐ray diffraction, elemental analysis, NMR spectroscopy, and IR spectroscopy. The decomposition process of 1 was investigated by thermal gravimetric analysis (TGA) and temperature‐dependent X‐ray powder diffraction (PXRD) and both are consistent with the formation of GeO₂ as major final product. Single crystal X‐ray diffraction at 110 K revealed the chiral tetragonal space group P4₁2₁2 and formation of a three‐dimensional (3D) coordination network solid. The 3D network is composed of interconnected twenty four‐membered rings comprising bridging methanesulfonate groups, which link the germanium atoms.     

Nitration Products of 5‐Amino‐1H‐tetrazole and Methyl‐5‐amino‐1H‐tetrazoles – Structures and Properties of Promising Energetic Materials

The nitration of 5‐amino‐1H‐tetrazole ( 1 ), 5‐amino‐1‐methyl‐1H‐tetrazole ( 3 ), and 5‐amino‐2‐methyl‐2H‐tetrazole ( 4 ) with HNO₃ (100%) was undertaken, and the corresponding products 5‐(nitrimino)‐1H‐tetrazole ( 2 ), 1‐methyl‐5‐(nitrimino)‐1H‐tetrazole ( 5 ), and 2‐methyl‐5‐(nitramino)‐2H‐tetrazole ( 6 ) were characterized comprehensively using vibrational (IR and Raman) spectroscopy, multinuclear (¹H, ¹³C, ¹⁴N, and ¹⁵N) NMR spectroscopy, mass spectrometry, and elemental analysis. The molecular structures in the crystalline state were determined by single‐crystal X‐ray diffraction. The thermodynamic properties and thermal behavior were investigated by using differential scanning calorimetry (DSC), and the heats of formation were determined by bomb calorimetric measurements. Compounds 2, 5 , and 6 were all found to be endothermic compounds. The thermal decompositions were investigated by gas‐phase IR spectroscopy as well as DSC experiments. The heats of explosion, the detonation pressures, and velocities were calculated with the software EXPLO5, whereby the calculated values are similar to those of common explosives such as TNT and RDX. In addition, the sensitivities were tested by BAM methods (drophammer and friction) and correlated to the calculated electrostatic potentials. The explosion performance of 5 was investigated by Koenen steel sleeve test, whereby a higher explosion power compared to RDX was reached. Finally, the long‐term stabilities at higher temperatures were tested by thermal safety calorimetry (FlexyTSC). X‐Ray crystallography of monoclinic 2 and 6 , and orthorhombic 5 was performed.     

Trans‐bis(saccharinato)cadmium(II) Complexes with 2‐Aminomethylpyridine and 2‐Aminoethylpyridine — Synthesis,Crystal Structures,Spectral and Thermal Characterization of trans‐[Cd(sac)2(ampy)2] and trans‐[Cd(sac)2(aepy)2]

Two trans‐bis(saccharinato) (sac) complexes of cadmium(II ) with 2‐aminomethylpyridine (ampy) and 2‐aminoethylpyridine (aepy) were synthesized and characterized by means of elemental analysis, FT‐IR spectroscopy and thermal analysis. In addition, their solid‐state structures were determined by single crystal X‐ray diffraction studies. The [Cd(sac)₂(ampy)₂] ( 1 ) and [Cd(sac)₂(aepy)] ( 2 ) complexes consist of neutral monomeric units and crystallize in the orthorhombic (Pbca) and monoclinic (P2₁/c) crystal systems, respectively. The cadmium(II ) ions in 1 and 2 sit on inversion centres andexhibit distorted octahedral coordination by two sac anions and two aminopyridine ligands. The sac ligands in both complexes are N‐coordinated and located in trans positions, while the ampy and aepy ligands act as a bidentate ligand forming two symmetrically chelate rings around cadmium(II ). IR spectra and thermal decompositions of the complexes are also discussed.     

Synthesis,Characterization and Crystal Structure of 4‐Amino‐1,2,4‐Δ2‐triazoline‐5‐thione and its Silver(I) Complex

The reaction of 4‐amino‐1,2,4‐Δ²‐triazoline‐5‐thione (ATT, 1 ) with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, ¹H NMR, IR, and Raman spectroscopy as well as single‐crystal X‐ray diffraction. The molecular structure of 1 was also determined by single crystal X‐ray analysis. Crystal data for 1 at ?80 C: space group C2/c with a = 2107.4(2), b = 1425.1(1), c = 688.4(1) pm, β = 104.55(1)°, Z = 16, R₁ = 0.0514, crystal data for 2 at ?80 °C: space group P2₁/c with a = 675.7(1), b = 1321.1(1), c = 1311.2(1) pm, β = 90.03(1)°, Z = 4, R₁ = 0.0437.     

Synthesis and Antimicrobial Activity of N‐[(2Z)‐3‐(4,6‐Substitutedpyrimidin‐2‐yl)‐4‐phenyl‐1,3‐thiazol‐2(3H)‐ylidene]‐3, 5‐dinitrobenzamide Analogues

In this study, we have synthesized 1‐(4,6‐disubstitutedpyrimidin‐2‐yl)‐3‐(3,5‐dinitrobenzoyl)‐thiourea derivatives ( 1a , 1b , 1c , 1d , 1e , 1f , 1g , 1h ) and N‐[(2Z)‐3‐(4,6‐disubstitutedpyrimidin‐2‐yl)‐4‐phenyl‐1,3‐thiazol‐2(3H)‐ylidene]‐3, 5‐dinitrobenzamide ( 2a‐2h ) analogues and characterized by IR spectroscopy, NMR spectroscopy, elemental analysis, and single crystal X‐ray diffraction data. The compounds ( 2a‐2h ) were screened for antimicrobial activity against Gram positive, Gram negative, and fungal species. The results of antimicrobial study indicated that compounds showed most potential and appreciable antibacterial and antifungal activities.     

Novel Octahedral Bis[2‐(1‐aziridinyl)ethanol‐κ2N,O] Complexes of Cobalt(II)

The synthesis and molecular structure of trans‐{bis[(acetato‐κO)‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) ( 4 ) and cis‐{bis[chlorido‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) ( 5 ) is reported. Both neutral chelate complexes are prepared from the corresponding Co^II salt [CoX₂; X = OAc ( 1 ), Cl ( 2 )] and 2‐(1‐aziridinyl)ethanol (azolH, 3 ) in dry dichloromethane. A third, ionic complex, cis‐{bis[aqua‐(2‐(1‐aziridinyl)ethanol‐κ²N,O)]}cobalt(II) diacetate ( 6 ) is formed from 4 in the presence of water and could be crystallized from aqueous dichloromethane. In all cases, 2‐(1‐aziridinyl)ethanol is coordinating as bidentate chelate ligand by the nitrogen and oxygen atom of the aziridinyl and hydroxy moiety. After purification, the compounds have been fully characterized using IR spectroscopy and FAB⁺‐MS. The single‐crystal X‐ray structure analysis revealed a distorted octahedral geometry for all complexes with either trans ( 4 ) or cis ( 5 , 6 ) configuration.     

Engineering a Cu‐MOF Nano‐Catalyst by using Post‐Synthetic Modification for the Preparation of 5‐Substituted 1H‐Tetrazoles

A new nano scale Cu‐MOF has been obtained via post‐synthetic metalation by immersing a Zn‐MOF as a template in DMF solutions of copper(II) salts. The Cu‐MOF serves as recyclable nano‐catalyst for the preparation of 5‐substituted 1H‐tetrazoles via [3 + 2] cycloaddition reaction of various nitriles and sodium azide in a green medium (PEG). The post‐synthetic metalated MOF were characterized by FT‐IR spectroscopy, powder X‐ray diffraction (PXRD), atomic absorption spectroscopy (AAS), and energy dispersive X‐ray spectroscopy (EDX) techniques. The morphology and size of the nano‐catalyst were determined by field emission scanning electron microscopy (FE‐SEM).     

Synthesis,Crystal Structure,and DNA‐Binding Properties of a New Cd(II) Complex Involving 2‐(2‐1H‐Imidazolyl)‐1H‐Imdazolium Ligand

A new Cd(II) complex of Cd(H₃biim)₂(NCS)₂Cl₂ [H₃biim=2‐(2‐1H‐imidazolyl)‐1H‐imidazolium] was synthesized and characterized by elemental analyses, FT‐IR and X‐ray single crystal diffraction. In the X‐ray crystallography structure, the cadmium(II) ion is coordinated by two nitrogen atoms of two 2‐(2‐1H‐imidazolyl)‐ 1H‐imdazolium, two nitrogen atoms of two thiocyanate ions and two Cl^?. The interaction of the complex with calf thymus DNA was investigated through electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurement, cyclic voltammetry and gel electrophoresis. These results show that the Cd(II) complex can electrostatically bind to the phosphate group of DNA backbone. Interestingly, we found that the complex can cleave the pBR322 DNA at pH=7.2 and 37°C.     

fac‐Tricarbonyl[bis(2‐pyridylmethyl) ether‐N,O,N′]molybdenum(0)

Reaction of bis(2‐pyridylmethyl) ether with [Mo(CO)₃­(Me­CN)₃] in MeCN gives the title compound, [Mo(C₁₂H₁₂‐N₂O)(CO)₃], (I), as a yellow crystalline product. Compound (I) has been characterized by ¹H NMR and IR spectroscopy, and single‐crystal X‐ray crystallography. In contrast with other examples of low‐valent early transition metal complexes of ethers, the ether linkage of (I) appears relatively inert. Nevertheless, the weak donor property of the ether ligand is evidenced by a trans effect manifested as a short Mo—CO bond length for the carbonyl ligand trans to the ether ligand.     

Synthesis and Characterization of 11‐Amino‐3‐methoxy‐8‐substituted‐12‐aryl‐8,9‐dihydro‐7H‐chromeno[2,3‐b]quinolin‐10(12H)‐one Derivatives

A series of 2‐amino‐7‐methoxy‐4‐aryl‐4H‐chromene‐3‐carbonitrile compounds 2 were obtained by condensation of 3‐methoxyphenol with β‐dicyanostyrenes 1 in absolute ethanol containing piperidine. The intermediate enamines 3 were prepared by compounds 2 with 5‐substituted‐1,3‐cyclohexanedione using p‐toluenesuflonic acid (TsOH) as catalyst. The title compounds 11‐amino‐3‐methoxy‐8‐substituted‐12‐aryl‐8,9‐dihydro‐7H‐chromeno[2,3‐b]quinolin‐10(12H)‐one 4 were synthesized by cyclization of the intermediate enamines 3 in THF with K₂CO₃ /Cu₂Cl₂ as catalyst. The structures of all compounds were characterized by elemental analysis, IR, MS, and ¹H NMR spectra. The crystal structure of compound 4i was determined by single‐crystal X‐ray diffraction analysis.     

Synthesis,characterization and application of 3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate as nanostructured catalyst for the tandem reaction of β‐naphthol with aromatic aldehydes and amide derivatives

3‐methyl‐1‐sulfonic acid imidazolium tetrachloroferrate {[Msim]FeCl₄} was prepared and fully characterized by fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), thermal gravimetric analysis (TGA), differential thermal gravimetric (DTG), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray analysis (EDX) and vibrating sample magnetometer (VSM) and used, as an efficient catalyst, for the tandem reaction of β‐naphthol with aromatic aldehydes and benzamide at 110 °C under solvent‐free conditions to give 1‐amidoalkyl‐2‐naphthols in high yields and very short reaction times.     

Regio‐ and Stereocontrolled Synthesis of (2R*,3R*,4R*)‐3,4‐Dichloro‐1,2,3,4,5,8‐hexahydronaphthalen‐2‐yl Acetate via Tandem SN2′ Reactions

The hydroperoxy endoperoxide 3 , obtained by photooxygenation of isotetralin (= 1,4,5,8‐tetrahydronaphthalene; 1 ), was reduced with thiourea, and the resulting intermediate 4 was converted, after acetylation with acetyl chloride, to the interesting, double‐chlorinated acetate 5 in an unprecedented tandem reaction (Scheme 1). The structures and relative configurations of 3 and 5 were determined by NMR spectroscopy and by single‐crystal X‐ray‐diffraction analyses (Figs. 1 and 2, resp.). A mechanistic rationalization for the conversion of 4 to 5 is proposed (Scheme 2).