Crystallographic characterization of three cathinone hydrochlorides new on the NPS market: 1-(4-methylphenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-MPHP), 4-methyl-1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PiHP) and 2-(methylamino)-1-(4-methylphenyl)pentan-1-one (4-MPD)

Cathinones belong to a group of compounds of great interest in the new psychoactive substances (NPS) market. Constant changes to the chemical structure made by the producers of these compounds require a quick reaction from analytical laboratories in ascertaining their characteristics. In this article, three cathinone derivatives were characterized by X-ray crystallography. The investigated compounds were confirmed as: 1-[1-(4-methylphenyl)-1-oxohexan-2-yl]pyrrolidin-1-ium chloride ( 1 , C₁₇H₂₆NO⁺·Cl^?, the hydrochloride of 4-MPHP), 1-(4-methyl-1-oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride ( 2 ; C₁₆H₂₄NO⁺·Cl^?, the hydrochloride of α-PiHP) and methyl[1-(4-methylphenyl)-1-oxopentan-2-yl]azanium chloride ( 3 ; C₁₃H₂₀NO⁺·Cl^?, the hydrochloride of 4-MPD). All the salts crystallize in a monoclinic space group: 1 and 2 in P2₁/c, and 3 in P2₁/n. To the best of our knowledge, this study provides the first detailed and comprehensive crystallographic data on salts 1 – 3 .     

Synthesis and luminescent properties of neutral Eu(III) and Gd(III) complexes with 1-(1,5-dimethyl-1h-pyrazol-4-yl)-4,4,4-trifluoro-1,3-butanedione and 4,4,5,5,6,6,6-heptafluoro-1-(1-methyl-1H-pyrazol-4-yl)-1,3-hexanedione

Neutral [EuL₃Phen] complexes were synthesized by the reaction of EuCl₃ with heterocyclic diketones-1-(1,5-dimethyl-1H-pyrazol-4-yl)-4,4,4-trifluoro-1,3-butanedione and 4,4,5,5,6,6,6-heptafluoro-1-(1-methyl-1H-pyrazol-4-yl)-1,3-hexanedione—and 1,10-phenanthroline (Phen) in an aqueous alcohol solution in the presence of NaOH. The reaction of GdCl₃ with the same diketones under analogous conditions, but without adding 1,10-phenanthroline, yielded [GdL₃(H₂O)₂] complexes. The composition of the complexes was determined by elemental analysis, and their optical and luminescent properties were examined.     

1-(Triorganylsilyl)-2-(triethoxysilyl)ethanes

Conclusions The conditions were found for the hydrosilylation of CH₂=CHSi(OC₂H₅)₃ with triorganylsilanes in the presence of H₂PtCl₆ · 6H₂O in isopropanol, which assured a high yield (>90%) of the 1-(triorganylsilyl)-2-(tri-ethoxysilyl)ethanes. These conditions were used to synthesize 27 new 1-(triorganylsilyl)-2-(triethoxysilyl)-ethanes.The addition of (C₂H₅O)₃SiH to (CH₂=CHSi(CH₃)₃ in the presence of the same catalyst gave 1-(trimethyl-silyl)-2-(triethoxysilyl)ethane in 98.6% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1622–1625, July, 1976.     

A Simple Route to New N(3)-Substituted 5-Aryl-2-(dialkylamino)-1,3-oxazolium Salts and N(1)-Substituted 4-Aryl-2-(dialkylamino)-1H-imidazoles

In the reaction of N,N-dialkyl-dichloromethaniminium chlorides 11 with 2-aminoacetophenones 12 , a general and simple route to heretofore unknown 5-aryl-substituted 2-(dialkylamino)-1,3-oxazolium salts 13 and 5-aryl-substituted 2-(dialkylamino)oxazoles 14 was found. From the 2-(dialkylamino)-1,3-oxazoles 14 , the corresponding oxazolium salts 13 were obtained after alkylation with (MeO)₂SO₂. The new oxazolium salts 13 were converted to 1-substituted 4-aryl-2-(dialkylamino)-1H-imidazoles 9 by treatment with NH₄OAc. The possible use of these 1H-imidazoles as dye educts was explored. Analytical data, as well as AM1 calculations, reveal some remarkable differences between the structures of the neutral imidazoles 9 and their positively charged oxazolium precursors 13 .     

Laser photolysis of 1-(4-nitrophenyl)-3-methylpyrazole and 1-ethyl-3-(4-nitrophenyl)-5-chloropyrazole

The spectral kinetic characteristics of the triplet states of 1-(4-nitrophenyl)-3-methylpyrazole (1) and 1-ethyl-3-(4-nitrophenyl)-5-chloropyrazole (2) were studied by the laser nanosecond photolysis technique in different solvents. The triplet lifetimes (τ_T) of molecules 1 and 2 were found to depend strongly on the solvent nature. An increase in τ_T by approximately two orders of magnitude on going from nonpolar and polar aprotic solvents (τ_T ≤ 15 ns) to aqueous-acetonitrile solutions (τ_T = 1100 ns for a volume acetonitrile to water ratio of 1 : 3) was analyzed, taking into account the influence of the medium on the relative contribution of the n,π*- and π,π*-configurations to the lowest triplet state. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1115–1119, May, 2005.     

1-(1-Adamantyl)diaziridine

The reaction of 1-aminoadamantane with CH₂O and H₂NOSO₃H in the presence of K₂CO₃ under phase-transfer conditions leads to hitherto unknown 1-(1-adamantyl)diaziridine and (1-adamantyl)aminoacetonitrile, characterized by spectral data. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 861–862, April, 1997.     

Preparation, structural characterisation and electrochemical properties of iron(0) and tungsten(0) carbonyl complexes with 1-(diphenylphosphanyl)-1′-vinylferrocene and 1-(diphenylphosphanyl)-1′-(dimethylvinylsilyl)ferrocene as P-monodentate ligands

A new organometallic phosphanylalkene, 1-(diphenylphosphanyl)-1′-(dimethylvinylsilyl)ferrocene (2) was prepared and—together with 1-(diphenylphosphanyl)-1′-vinylferrocene (1)—studied as a ligand in iron- and tungsten-carbonyl complexes. The following complexes featuring the mentioned phosphanylalkenes as P-monodentate donors were isolated and characterised by spectral methods: [Fe(CO)₄(L-κP)] (4, L = 1; 5, L = 2) and trans-[W(CO)₄(L-κP)₂] (6, L = 1; 7, L = 2). In addition, the solid-state structures of 4 and 6 have been determined by single-crystal X-ray diffraction and the electrochemical properties of compounds 1, 2, 4 and 6 were studied by cyclic voltammetry at platinum electrode.     

Bis(diphenylphosphano)alkan- und 1-(Diphenylphosphano)-2-(2-pyridino)ethan-N-Arylsulfinylamin-Nickel(0)-Komplexe

Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph₂P(CH₂)_nPPh₂}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)₂], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh₃)₂] are described. These compounds have been characterized by i. r. and ³¹P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η²-(N, S)-side on coordinated.     

Acetylation of 2-(1-naphthyl)thiophene

Acetylation of 2-(1-naphthyl) thiophene with acetyl chloride in the presence of SnCl₄, or with acetic anhydride in the presence of H₃PO₄ gives 5-aceto-2-(1-naphthyl) thiophene. 5-Ethyl-2-[1-(3, 4-dihydronaphthyl)] thiophene, 5-ethyl-2-(1-naphthyl) thiophene and 3, 4-diacetoxymercuri-5-ethyl-2-(1-naphthyl) thiophene are now synthesized and characterized.     

喹啉氧基乙酰胺的Li(I)/Na(I)配合物及其高氯酸盐的结构和荧光性质

合成并通过X射线单晶衍射表征了配合物[Li（L）₂]ClO₄（1）和[Na（L）₂]ClO₄（2）的结构（L为2-（5-氯-喹啉-8-基氧基）1-吡咯烷酮）。单晶衍射结果表明,配合物1与2同构,金属离子与来自2个酰胺配体L的N₂O₄电子供体配位,形成扭曲的八面体配位构型。此外,还测定了配体高氯酸盐（HL） ClO₄·H₂O的结构,并详细研究了3个化合物的荧光性质。     

Trifluoromethylated 3-(Pyrazol-1-yl)propanamide (PPA) Ligands

The new PPA ligands 3-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]propanamide (CF₃MePPA; 3 ) and 3-[3,5-bis(trifluoromethyl)-1H-pyrazol-1-yl]propanamide ((CF₃)₂PPA; 4 ) were synthesized by Aza-Michael addition of the specific pyrazole derivatives to acrylamide. Both products were characterized by elemental analyses, IR and NMR spectroscopy, and mass spectrometry. X-Ray structure determination of 3 revealed the presence of a one-dimensional hydrogen-bonded structure in the solid state. The ligating ability of the new ligands towards PdCl₂ was studied, showing that 3 behaves similar to Me₂PPA and reacts cleanly with PdCl₂ to afford the sparingly soluble complex PdCl₂(CF₃MePPA-κN)₂. By contrast, the donor ability of pyrazolyl group in 4 was found to be considerably reduced, thus resulting in the formation of the unusual complex PdCl₂{(CF₃)₂PPA-κN}{(CF₃)₂PPA-κO}.     

Hydrogen Bonds in 2-(Diorganylphosphorylhydroxymethyl)-1-organylimidazoles

Structures of 2-(diorganylphosphorylhydroxymethyl)-1-organylimidazoles were studied by IR and ¹H and ^{3 1}P NMR spectroscopy, and also by ab initio calculations (HF/6-31G*). Formation of intramolecular O-H+++O = P hydrogen bonds in solutions of these compounds in CCl₄ and CHCl₃ was established.     

喹啉氧基乙酰胺的Li(I)/Na(I)配合物及其高氯酸盐的结构和荧光性质

合成并通过X射线单晶衍射表征了配合物[Li（L）₂]ClO₄（1）和[Na（L）₂]ClO₄（2）的结构（L为2-（5-氯-喹啉-8-基氧基）1-吡咯烷酮）。单晶衍射结果表明,配合物1与2同构,金属离子与来自2个酰胺配体L的N₂O₄电子供体配位,形成扭曲的八面体配位构型。此外,还测定了配体高氯酸盐（HL）ClO₄·H₂O的结构,并详细研究了3个化合物的荧光性质。     

1,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium and 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium Halides

Formerly unknown 1,1-dimethyl-1-(trialkoxysilylmethyl)- and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium halides were prepared by reaction of 1,1-dimethylhydrazine with (halomethyl)trialkoxysilanes XCH₂Si(OR)₃ (X = Cl, I; R=Me, Et) and 1-(halomethyl)silatranes XCH₂Si(OCH₂CH₂)₃N (X = Cl, Br). 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium chloride and iodide were also obtained by transetherification of corresponding 1,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium halides with tris(2-hydroxyethyl)amine.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 915–919.Original Russian Text Copyright © 2005 by Sorokin, Voronkov.     

Some Transformations of (-)-(1S,4R)-1-Vinyl-7,7-dimethyl-bicyclo[2.2.1]heptan-2-one

Reactions were studied of (-)-(1S,4R)-1-vinyl-7,7-dimethylbicyclo[2.2.1]heptan-2-one with ethyl acetate lithium derivative, potassium acetylide, ozone, with a system OsO₄-N-methylmorpholine N-oxide, and some subsequent transformations of the products obtained.     

Synthesis, structure and fluorescence of novel cadmium(II) and silver(I) complexes with in situ ligand formation of 1-(5-tetrazolyl)-4-(imidazol-1-ylmethyl)benzene

Hydrothermal reactions of cadmium(II) or silver(I) salt, NaN₃, 4-(imidazol-1-ylmethyl)benzonitrile (IBN) yield three coordination complexes, [Cd(L)₂(H₂O)₂]·3H₂O (1), [Cd₃(L)₅(OH)] (2) and [Ag₂(L)₂] (3) where HL=1-(5-tetrazolyl)-4-(imidazol-1-ylmethyl)benzene. The crystal structure analysis revealed that 1 has 1D hinged-chain structure containing 24-membered ring with a Cd···Cd intra-chain distance of 13.18 Å, while 2 is 1D ladder-like chain with Cd₃O core. However, the complex 3 is a 3D 4-connected framework with Schläfli symbol of (4²·6³·8)(4³·6²·8). The L⁻ ligand was found to show four different coordination modes in 1-3, as 2-, 3- and 4-connector, respectively. The results indicate that the coordination modes of the ligand and metal centers with different coordination geometry have great influence on the structures of the complexes. In addition, the photoluminescence of the complexes were studied in the solid state at room temperature.     

Efficient Synthesis of Novel 3-[5-(1H-Benzimidazol-2-Ylmethanesulfonyl)-4-Phenyl-4H-(1,2,4)Triazol-3-Yl]-1H-(1,8)Naphthyridin-4-One Derivatives

Abstract

of 1,4-dihydro-4-oxo-1,8-naphthyridine-3-carbohydrazide (4) with substituted phenyl isothiocyanates (5) in ethanol under reflux for 30 min gave thiosemicarbazide derivatives 6, which on cyclization in 2N NaOH under refluxing conditions for 1 h resulted in 3-(5-mercapto- 4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (7). Alternatively, 7 could also be prepared from following sequence of reactions, i.e., 4 → 8 → 7. In another sequence of reactions, condensation of 7 with chloroacetic acid in dimethylformamide (DMF) and K₂CO₃ as a mild base at 120 °C for 2 h resulted in 2-((5-(1,4-dihydro-4-oxo-1,8-naphthyridin-3-yl)-4-phenyl-4H-1,2,4-triazol-3-yl)sulfanyl)acetic acid (10). The latter, on reaction with substituted o-phenylenediamine (11) in 6N HCl for 4 h yielded 3-(5-((1H-benzo[d]imidazol-2-yl)methylthio)-4-phenyl-4H-1,2,4-triazol-3-yl)-1,8-naphthyridin-4(1H)-one (12). Alternatively, 12 could also be prepared by reacting 7 with 13 in DMF and K₂CO₃ as a mild base at 120 °C for 2 h, followed by oxidation with H₂O₂ resulting in the corresponding sulfonyl derivatives 14.     

Extraction of Iridium(IV) by 1-(2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-1H-1,2,4-triazole from Hydrochloric Solutions

Extraction of iridium(IV) by 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl)-¹H-1,2,4-triazole from hydrochloric solutions was studied. Optimal extraction parameters were determined. The mechanism of iridium(IV) extraction in this system is ion exchange (3.0 mol/L HCl and τ_cont = 5 min). Electronic, ¹H NMR, ¹³C NMR, and IR spectroscopy and elemental analysis were used to determine the composition of the extracted compound.     

Structural studies of 3-amino-4-(substituted arylazo)-5-(1H)pyrazolone compounds

Summary Transition metal complexes of cobalt(II), nickel(II), copper(II) and palladium(II) with 3-amino-4-(arylazo)-5-(1H)pyrazolones (Aryl=Ph, 4-C₆H₄CO₂H, 4-C₆H₄-OMe, 3-C₆H₄Cl, 3-C₆H₄CO₂H, 3-C₆H₄NO₂, 3-C₆H₄-Me, 3-C₆H₄OH and 2-C₆H₄CO₂H) are discussed. The stoichiometry of the complexes is: 11, 23 Co^II; 11 Ni^II; 11, 21 Cu^II and 12 Pd^II. The investigations suggest rhombic symmetry with 4- or 5-coordinate Co^II, square planar and tetrahedral configuration for Ni^II, tetrahedral Cu^II and square planar for Pd^II complexes. The complexes contain no anions.     

Preparation and study of chiral boron containing amine-cyano(pyrrolyl-1)borane complexes. Preparation of (−)-(S)-α-phenylethylamine-(−)-cyano(pyrrolyl-1)borane and (+)-(R)-α-phenylethylamine-(+)-cyano(pyrrolyl-1)borane

Several amine-cyano(pyrrolyl)borane complexes [A · BH(NC₄H₄)CN] containing a chiral boron atom were prepared from the reactions of sodium cyanohydrodipyrrolylborate-tridioxane¹ [NaBH(NC₄H₄)₂CN · 3C₄H₈O₂] with amine hydrochlorides as well as by base exchange from the appropriate 4-cyanopyridine complex [4-CNC₅H₄N · BH(NC₄H₄)CN]. Amines with an sp² N atom give stable complexes of a wide range of basicity (pK_a = 0.8?9.7), in contrast to the anines with sp³ hybridized N where only the stronger bases (pK_a ? 7.3) are capable of giving stable complexes (mainly secondary and tertiary amines). These compounds undergo hydrolysis in neutral and alkaline media, while in strong acids they give stable boronium ions by protonation at the α-C atom of the pyrrolyl group. The compounds (?)-(S)-α-phenylethylamine-(?)-cyanopyrrolylborane and (+)-(R)-α-phenylethylamine-(+)-cyanopyrrolylborane have been prepared in pure form; in solution they undergo slow epimerization. Treatment of the appropriate complexes with KH has given the chiral boron-containing borates KBH(NC₄H₄)(CN)X (X = imidazolyl-, pyrazolyl-). Dicyanohydropyrrolylborane was obtained from 4-cyanopyridine-cyanopyrrolylborane and NaCN.