On the reaction of chlorodithiophosphoric acid pyridiniumbetaine with polyfunctional nucleophiles: Part II. Reaction with thiosemicarbazide derivatives

Chlorodithiophosphoric acid pyridiniumbetaine, PyPS₂Cl (I), reacts with thiosemicarbazide derivatives (RNH)(H₂NNMe)CS, R= iso-propyl, tert-butyl, in acetonitrile in the absence of any HCl-acceptor to form new compounds with a five-membered heterocycle, i.e. 5-iso-propylamino-4-methyl-2-sulfido-2-thioxo-1,3,4,2λ⁵-thiadiazaphospholan-5-onium (II) or 5-tert-butylamino-4-methyl-2-sulfido-2-thioxo-1,3,4,2λ⁵-thiadiazaphospholan-5-onium (III). The triethylammonium salt of 1,3-bis-(N-methyl-N′-tert-butyl-thioureido)-2,4-disulfido-2,4-dithioxo-1,3-diaza-2λ⁵,4λ⁵-diphosphetidine (IV) is formed when the reaction is carried out in the presence of triethylamine. The prepared compounds were characterized by ³¹P NMR, FT-IR spectroscopies, mass spectrometry and the molecular structures of II, III and IV were determined by X-ray crystallography.     

Synthese,Eigenschaften und NMR-spektroskopische Untersuchungen an 2,4-Dithioxo-2,4-dimercapto-1,3-diaza-2λ5,4λ5-diphosphetidinen

Synthesis, Properties and N.M.R. Spectroscopic Studies of 2,4-Dithioxo-2,4-dimercapto-1,3-diaza-2λ⁵,4λ⁵-diphosphetidines On the reaction of py · PS₂Cl ( 1 ) or py · PS₂F ( 2 ) (py = Pyridine) with hexamethyl disilazane in a molar ratio of 1:1 the pyridinium salt of the 1,3-bis(trimethylsilyl)-2,4-dimercapto-2,4-dithioxo-1,3-diaza-2λ⁵, 4λ⁵-diphosphetidine ( 3 ) is formed. 3 reacts with MeI to the corresponding methyl ester 9 . There exist two isomers of 9 , probable with cis and trans configuration of the MeS groups, respectively. 3 and 9 have been characterized by i.r., Raman, mass, and NMR spectroscopy. 4 reacts in acetonitrilic solution in the presence of water under hydrolytic cleavage of the trimethyl silyl groups whereas the P₂N₂ ring is preserved. The hydrolysis of 9 has been studied by ¹H-, ³¹P-, and ¹³C-NMR spectroscopy.     

Synthesis of some Mannich base derivatives and their antimicrobial activity study

A series of 2-(phenyl)-2-(morpholin-4-yl)-N-phenylacetamide I–VII were synthesized by Mannich base method. Synthesized compounds I–VII were confirmed by IR, ¹H NMR, ¹³C NMR, mass and elemental analyses. Synthesized compounds I–VII were screened for antibacterial activity against various bacterial strains and compared with standard Ciprofloxacin at concentration 100 μg/mL and for antifungal activity against various fungal strains and compared with Clotrimazole at concentration 100 μg/mL; particularly 3-(4-chlorophenyl)-3-(morp holin-4-yl)-N-phenylpropanamide lll that has high antibacterial activity against Streptococcus epidermidis was compared with standard Ciprofloxacin.     

Syntheses and characterization of tetrakis(5-tert-butylpyrazole) Fe(II) and Mn(II) complexes. Molecular structure of Fe(Pzt-Bu)4(OTF)2

Dichlorotetrakis(5-t-butylpyrazole)iron (1), dichlorotetrakis(5-t-butylpyrazole) manganese (2), and tetrakis(5-t-butylpyrazole) iron(II) bis(trifluoromethanesulfonate) (3) were prepared and characterized. The crystal structure of 3 was determined from X-ray diffraction data. Complex 3 has a distorted octahedral structure with the two triflate ligands at mutually trans positions. Complexes 1 and 2 are mild catalysts for the selective epoxidation of styrene and norbornylene. In comparison, complex 3 is an efficient catalyst for the epoxidation of norbornylene, but promotes the oxidation of styrene predominantly to benzaldehyde.     

Thermal Behavior of Pyridinium Salt of 2,4-Dimer-Capto-2,4-Dithioxo-1,3-Bis(Trimethylsilyl)-1,3-Diaza-2λ5, 4λ5-Diphosphetidine

Abstract

The reaction of P₄S₁₀with PSCL₃ in pyridine leads to Py.PS₂Cl (1). This substance yields by the reaction with hexamethyldiailazane in molar ratio 1:l a new subatance that was identified as pyridiniwn salt of 2,4-dimercapto-2,4-dithioxo-1,3-bis(trimethylsilyl)-1,3-diaza-2λ⁵,4λ⁵-diphosphetidine (PYH)₂/S₂P(NSiMe₃)₂PS₂/ (I). (2).     

Crystal Engineering of an nbo Topology Metal–Organic Framework for Chemical Fixation of CO2 under Ambient Conditions

Crystal engineering of the nbo metal–organic framework (MOF) platform MOF‐505 with a custom‐designed azamacrocycle ligand (1,4,7,10‐tetrazazcyclododecane‐N,N′,N′′,N′′′‐tetra‐p‐methylbenzoic acid) leads to a high density of well‐oriented Lewis active sites within the cuboctahedral cage in MMCF‐2, [Cu₂(Cu‐tactmb)(H₂O)₃(NO₃)₂]. This MOF demonstrates high catalytic activity for the chemical fixation of CO₂ into cyclic carbonates at room temperature under 1 atm pressure.     

Bis[μ3‐cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3–)]bis(2,2′‐bipyridine)dichloridotetracopper(II) dihydrate

The title complex, bis[μ₃‐cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3−)]‐1:2:4κ⁷N,N′,N′′,O:O′,O′′:O′′′;2:3:4κ⁷O′′′:N,N′,N′′,O:O′,O′′‐bis(2,2′‐bipyridine)‐2κ²N,N′;4κ²N,N′‐dichlorido‐1κCl,3κCl‐tetracopper(II) dihydrate, [Cu₄(C₁₂H₁₂N₃O₄)₂Cl₂(C₁₀H₈N₂)₂]·2H₂O, consists of a neutral cyclic tetracopper(II) system having an embedded centre of inversion and two solvent water molecules. The coordination of each Cu^II atom is square‐pyramidal. The separations of Cu^II atoms bridged by cis‐N‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidate(3−) and carboxyl groups are 5.2096 (4) and 5.1961 (5) Å, respectively. A three‐dimensional supramolecular structure involving hydrogen bonding and aromatic stacking is observed.     

Preparation and structures of some tetraazamacrocyclic complexes of In(III)

Treatment of the dibenzo-tetraaza macrocycle, C₂₂H₂₄N₄ (H₂tmtaa) (I), with triethylindium yields the diethylindium-macrocycle complex [Et₂In(Htmtaa)] (IV). On heating (IV) is converted quantitatively into the monoethyl complex [EtIn(tmtaa)] (V). A single crystal X-ray diffraction study on (V) shows the EtIn fragment to be bonded to the four planar nitrogen atoms of the macrocycle, with a square–pyramidal geometry around the metal. Reaction of the dilithio salt of (I), [Li₂(tmtaa)], with InCl₃ yields [ClIn(tmtaa)] (VI), and further reaction of (VI) with equimolar quantities of LiR [R=C₅H₅(Cp), Me, N(SiMe₃)₂, OSiMe₃] yields the corresponding [RIn(tmtaa)] derivatives [R=Cp (VII), Me (VIII), N(SiMe₃)₂ (IX), OSiMe₃ (X)]. An X-ray diffraction study on (VII) shows an η¹-bonded Cp group, with the metal atom also bound to the four nitrogen atoms of the tmtaa ligand.     

Immobilization of porphyrins in poly(hydroxymethylsiloxane)

Three tetracationic porphyrins differing in the position of charged nitrogen atoms on the peripheral substituents — 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP4), 5,10,15,20-tetrakis(N-methylpyridinium-2-yl)porphyrin (TMPyP2), 5,10,15,20-tetrakis(4-trimethylammoniophenyl) porphyrin (TMAPP), and hydrophobic 5,10,15,20-tetraphenylporphyrin (TPP), were immobilized by adsorption and encapsulation in poly(hydroxymethylsiloxane) (PHOMS). The so prepared porphyrin-PHOMS composites were characterized by porosimetry, scanning electron microscopy, fluorescence and diffuse reflectance UV-VIS spectroscopy. It was found that porphyrins are immobilized in the PHOMS matrix in the free base monomer form Their irradiation produced singlet oxygen O₂(¹Δ_g) with the lifetime of 10–30 μs.     

Novel chiral tetraaza ligands: synthesis and application in asymmetric transfer hydrogenation of ketones

Novel chiral tetraaza ligands, N¹,N²-bis(2-(piperidin-1-yl)benzylidene)cyclohexane-1,2-diamine 1 and N¹,N²-bis(2-(piperidin-1-yl)benzyl)cyclohexane-1,2-diamine 2, have been synthesized and fully characterized by analytical and spectroscopic methods. The structure of (R,R)-1 has been established by X-ray crystallography. Asymmetric transfer hydrogenation of aromatic ketones with the catalysts prepared in situ from [IrHCl₂(COD)]₂ and the chiral tetraaza ligands in 2-propanol gave the corresponding optically active secondary alcohols in high conversions and good ees (up to 91%) under mild reaction conditions.     

Bis(pyrimidine)-based palladium catalysts: synthesis,X-ray structure and applications in Heck–, Suzuki–, Sonogashira–Hagihara couplings and amination reactions

The synthesis of N,N-bis(pyrimid-2-yl)amine (1), N-acetyl-N,N-bis(pyrimid-2-yl)amide (2), N-norborn-2-ene-5-ylbis(pyrimid-2-yl)carbamide (4) is described. The Pd-complex N-acetyl-N,N-bis(pyrimid-2-yl)amine palladium dichloride (3) has been prepared from compound 2 and its X-ray structure has been determined. A polymer supported catalytic system (6) was prepared via ring-opening metathesis copolymerization of 4 with 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo-endo-dimethanonaphthalene (HDMN-6) and subsequent loading with PdCl₂. Both the homogeneous and heterogeneous catalysts 3 and 6 were active in Heck–, Suzuki–, Sonogashira–Hagihara-type couplings and amination reactions using aryl iodides, bromides and chlorides.     

Copper(I) complexes of heterocyclic thiourea ligands

The coordination of heterocyclic thiourea ligands (L = N-(2-pyridyl)-N′-phenylthiourea (1), N-(2-pyridyl)-N′-methylthiourea (2), N-(3-pyridyl)-N′-phenylthiourea (3), N-(3-pyridyl)-N′-methylthiourea (4), N-(4-pyridyl)-N′-phenylthiourea (5), N-(2-pyrimidyl)-N′-phenylthiourea (6), N-(2-pyrimidyl)-N′-methylthiourea (7), N-(2-thiazolyl)-N′-methylthiourea (8), N-(2-benzothiazolyl)-N′-methylthiourea (9), N,N′-bis(2-pyridyl)thiourea (10) and N,N′-bis(3-pyridyl)thiourea (11)) with CuX (X = Cl, Br, I, NO₃) has been investigated. CuX:L product stoichiometries of 1:1–1:5 were found, with 1:1 being most common. X-ray structures of four 3-coordinate mononuclear CuXL₂ complexes (CuCl(6)₂, CuCl(7)₂, CuBr(6)₂, and CuBr(9)₂) are reported. In contrast, CuBr(1)₂ is a 1D sulfur-bridged polymer. CuIL structures (L = 7, 8) are 1D chains with corner-sharing Cu₂(μ-I)₂ and Cu₂(μ-S)₂ units, and CuCl(10) is a 2D network having μ-Cl and N-/S-bridging L. Two [CuL₂]NO₃ structures are reported: a mononuclear 4-coordinate copper complex with chelating ligands (L = 10) and a 1D link-chain with N-/S-bridging L (L = 3). Two ligand oxidative cyclizations were encountered during crystallization. CuI crystallized with 6 to produce zigzag ladder polymer [(CuI)₂(12)]·½CH₃CN (12 = N-(pyrimidin-2-yl)benzo[d]thiazol-2-amine) and CuNO₃ crystallized with 10 to form [Cu₂(NO₃)(13)₂(MeCN)]NO₃ (13 = dipyridyltetraazathiapentalene).     

Cobalt(II) complexes with pentadentate Schiff bases 2,6-diacetylpyridine hydrazones: Syntheses and structures

Seven new cobalt(II) complexes based on the Schiff bases, 2,6-diacetylpyridine bis(isonicotinoylhydrazone) (H₂L¹) and 2,6-diacetylpyridine bis(nicotinoylhydrazone) (H₂L²), are synthesized and studied by X-ray diffraction analysis: [Co(H₂L¹)(NCS)₂] · 2.25H₂O (I), [Co(H₂L²)(NCS)₂] · CH₃OH (II), [Co(H₂L²)(NCS)(H₂O)]NCS (III), [Co(H₄L¹)(NCS)₂](NO₃)₂ · 2H₂O (IV), [Co(H₄L¹)(NCS)₂][Co(NCS)₄] · 0.75H₂O (V), [Co(H₄L²)(NCS)₂][Co(NCS)₄] · 1.75H₂O (VI), and [Co(H₂L²)(NCS)(CH₃OH)]₂[Co(NCS)₄] · 2CH₃OH (VII) (CIF files CCDC 941186 (I), 1457906 (Ia), 1457905 (II), 941187 (III), 1457907 (IV), 1457908 (V), 1457909 (VI), and 941188 (VII)). The organic ligands in the complexes act as pentadentate neutral H₂L or doubly protonated (H₄L)²⁺ coordinated through the same set of donor atoms N₃O₂. In all compounds I–VII, the coordination polyhedron of the Co²⁺ ion in a complex with the Schiff bases has a shape of a pentagonal bipyramid. The hydrazones are arranged in the equatorial plane of the bipyramid. Its axial vertices are occupied by the nitrogen atoms of the NCS￣ anions in compounds I, II, and IV–VI and by the nitrogen atoms of NCS￣ and oxygen of the water molecule in compound III or methanol in compound VII. The NO ₃ ^- anions or [Co(NCS)₄]^2￣ complex anions obtained by the reactions are involved along with the NCS￣ anions in the formation of compounds IV–VII.     

Synthesis, crystal structure and antibacterial activity of a group of mononuclear manganese(II) Schiff base complexes

Five mononuclear complexes of manganese(II) of a group of the general formula, [MnL(NCS)₂] where the Schiff base L = N,N′-bis[(pyridin-2-yl)ethylidene]ethane-1,2-diamine (L¹), (1); N,N′-bis[(pyridin-2-yl)benzylidene]ethane-1,2-diamine (L²), (2); N,N′-bis[(pyridin-2-yl)methylidene]propane-1,2-diamine (L³), (3); N,N′-bis[(pyridin-2-yl)ethylidene]propane-1,2-diamine (L⁴), (4) and N,N′-bis[(pyridin-2-yl)benzylidene]propane-1,2-diamine (L⁵), (5) have been prepared. The syntheses have been achieved by reacting manganese chloride with the corresponding tetradentate Schiff bases in presence of thiocyanate in the molar ratio of 1:1:2. The complexes have been characterized by IR spectroscopy, elemental analysis and other physicochemical studies, including crystal structure determination of 1, 2 and 4. Structural studies reveal that the complexes 1, 2 and 4 adopt highly distorted octahedral geometry. The antibacterial activity of all the complexes and their respective Schiff bases has been tested against Gram(+) and Gram(−) bacteria.     

Synthesis of efficient blue and red light emitting phenanthroline derivatives containing both hole and electron transporting properties

Two phenanthroline derivatives containing a hole transporting triphenylamine and an electron transporting 1,3,4-oxadiazole unit have been prepared with high yield. UV-vis absorption and fluorescence measurement indicated they are high efficient light-emitting materials. The compounds are 6-(5-(4-N,N′-diphenylaminophenyl)-1,3,4-oxadiazol-2-yl) quinoxalino[2,3-f] phenanthroline (9, λ_max = 635 nm, 40% quantum yield), and 1-ethyl-2-(4-(5-(4-N,N′-diphenylaminophenyl)-1,3,4-oxadiazol-2-yl)phenyl)imidazo[4,5-f]phenanthroline (14, λ_max = 461 nm, 78% quantum yield). Preliminary study on electroluminescence for the two fluorescent dyes prepared from vacuum evaporation resulted in blue and red light emitting organic light emitting diodes (OLED).     

From N,N-diphenyl-N-naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl-amine to propeller-shaped N,N,N-tri(naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl)-amine: syntheses and structures

Three unique propeller-shaped helicenyl amines compounds: N,N-diphenyl-N-naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl-amine (1), N-phenyl-N,N-di(naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl)amine (2), and N,N,N-tri(naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl)amine (3) were efficiently synthesized by Wittig reaction and oxidative photocyclization. The crystal structures of 1, 2 and molecular configuration optimization (DFT-B3LYP/6-31+G(d)) of 3 reveal that the steric hindrance from the moiety of trithia[5]helicene effectively forces the nitrogen atom and the three bonded carbon atoms to coplanar and the interplanar angles of the facing terminal thiophene ring and benzene ring becoming larger when the helical arm increased from 1 to 3. Electrochemical properties and UV–vis absorption behaviors of 1, 2, 3 were primarily determined by the moiety of trithia[5]helicene.     

Reactions of bis(tetrazole)phenylenes. Surprising formation of vinyl compounds from alkyl halides

The reactions of 1,2-bis(tetrazol-5-yl)benzene (1), 1,3-bis(tetrazol-5-yl)benzene (2), 1,4-bis(tetrazol-5-yl)benzene (3), 1,2-(Bu₃SnN₄C)₂C₆H₄ (4), 1,3-(Bu₃SnN₄C)₂C₆H₄ (5) and 1,4-(Bu₃SnN₄C)₂C₆H₄ (6) with 1,2-dibromoethane were carried out by two different methods in order to synthesise pendant alkyl halide derivatives of the parent bis-tetrazoles. This lead to the formation of several alkyl halide derivatives, substituted at either N1 or N2 on the tetrazole ring, as well as the surprising formation of several vinyl derivatives. The crystal structures of both 1,2-[(2-vinyl)tetrazol-5-yl)]benzene (1-N,2-N′) (1b) and 1,3-bis[(2-bromoethyl)tetrazol-5-yl]benzene (2-N,2-N′) (5d) are discussed.     

Specificity of the cyclization of 1-alkyl(aryl)sulfonylamino-9,10-anthraquinones into naphtho[1,2,3-cd]indol-6(2H)-ones

Cyclization of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)methanesulfonamides to 2,6-dihydronaphtho[1,2,3-cd]indol-6-ones in DMSO-KOH involves intermediate formation of 2,3-dihydroanthra[1,9-cd]-[1λ⁶,2]thiazin-7-one 2,2-dioxides, whereas heterocyclization of N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)-ethane- and -arenesulfonamides under analogous conditions occurs with participation of methylsulfonylmethanide.     

Synthesis and characterization of iron and cobalt dichloride bearing 2-quinoxalinyl-6-iminopyridines and their catalytic behavior toward ethylene reactivity

The 1-(6-(quinoxalin-2-yl)pyridin-2-yl)ethanone was synthesized in order to prepare a series of N-(1-(6-(quinoxalin-2-yl)pyridine-2-yl)ethylidene)benzenamines (L1-L7), which provided new alternative N^∧N^∧N tridentate ligands coordinating with iron(II) and cobalt(II) dichloride to form complexes of general formula LFeCl₂ (1-7) and LCoCl₂ (8-14). All organic compounds were fully characterized by NMR, IR spectroscopic and elemental analysis along with and magnetic susceptibilities and metal complexes were examined by IR spectroscopic and elemental analysis, while their molecular structures (L1, L4, 1, 4, 10, 13) were confirmed by single crystal X-ray diffraction analysis. Upon activation with methylaluminoxane (MAO), all iron complexes gave good catalytic activities for ethylene reactivity (oligomerization and polymerization), while their cobalt analogues showed moderate activities toward ethylene oligomerization with modified methylaluminoxane (MMAO). Various reaction parameters were investigated for better catalytic activities, the higher activities were observed at elevated ethylene pressure. The iron and cobalt complexes with para-methyl substituents of aryl group linked on imino group showed highest activity.     

Synthesis, structure, and heck cyclization of the syn- and anti-atropisomers of N-acyl-N-(4-methyl-3,6-dihydro-2H-pyran-3-yl)-2-iodo-4,6-dimethylaniline

The reaction of 2-iodo-2,4-dimethylaniline with 3,4-dibromo-4-methyltetrahydro-2H-pyran, followed by treatment with acetyl bromide or 4-nitrobenzoyl chloride, gave syn- and anti-atropisomers of N-(2-iodo-4,6-dimethylphenyl)-N-(4-methyl-3,6-dihydro-2H-pyran-3-yl)acetamide and N-(2-iodo-4,6-dimethylphenyl)-N-(4-methyl-3,6-dihydro-2H-pyran-3-yl)-4-nitrobenzamide. Heating of the acetamide derivative with palladium(II) acetate in the presence of copper(II) acetate and N,N,N′,N′-tetramethylethane-1,2-diamine resulted in heterocyclization to N-acetyl-4a,6,8-trimethyl-1,4a,9,9a-tetrahydropyrano[3,4-b]indole.