Structural and conformational study of 3-phenethyl-3-azabicyclo[3.2.1] octan-8-β-ol

The infrared and ¹H and ¹³C NMR spectra of 3-aza-bicyclo[3.2.1]octane-8-β-ol have been examined in several media. To assist in interpretation of the spectroscopic data, the crystal structure has been determined by X-ray diffraction.The bicyclic system adopts a chair—envelope conformation with OH and phenethyl groups, respectively, in axial and equatorial positions with respect to the piperidine ring. The crystal structure is stabilized by means of OH…N intermolecular hydrogen bonding. In CCl₄ solution the initial chair—envelope conformation changes to a boat—envelope conformation which is stabilized by an intramolecular hydrogen bond.The unambiguous assignment of all protons of the bicyclic system, not previously described, has also been carried out.     

Photochemical formation and decomposition of 8-[β-arylethenyl]-2,2,6-trimethyl-7,9,10-trioxa-tricyclo[6.2.2.0]dodec-11-ene to novel 6-hydroxy-1,7,7-trimethyl-2-oxa-bicyclo[4.4.0]dec-4-en-3-one in the presence of oxygen

Irradiation of (E,E)-arylidene-β-ionones in the presence of oxygen leads to the formation of 8-[β-arylethenyl]-2,2,6-trimethyl-7,9,10-trioxa-tricyclo[6.2.2.0^1,6]dodec-11-enes (3). However, prolonged irradiation in the presence of oxygen leads to their conversion to 6-hydroxy-1,7,7-trimethyl-2-oxa-bicyclo[4.4.0]dec-4-en-3-one (4), apparently proceeding through addition of oxygen to the side chain π-bond in 3.     

Synthesis and Crystal Structure of catena-Poly[[[2,4-dibromo-6-[（3-dimethylaminopropylimino）-methyl]phenolato]copper（II）]-μ-azido]

A novel end-to-end azido-bridged polynuclear Schiff-base copper（II） complex, [Cu（C12H15Br2N2O）（N3）]n, was prepared and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbcn with a = 24.588（5）, b = 10.377（2）, c = 13.022（3） A, V= 3322.6（12） A^3, Z = 8, Dc = 1.874 g/cm^3, Mr = 468.65, λ（MoKa） = 0.71073 A,μ = 6.130 mm^-1, F（000） = 1832, R = 0.0637 and wR = 0.1176. The Cu atom in the complex is five-coordinated in a square pyramidal geometry by three donor atoms of the Schiff-base ligand, and two N atoms from two bridging azide ligands. The [2,4-dibromo-6-[（3-dimethylaminopropylimino）methyl]phenolato]copper（II） units are linked by the bridging azide ligands, giving zigzag polymeric chains with backbones of the [--Cu-N-N-N--Cu]n type running along the b axis.     

Synthesis, X-ray crystallographic, and dynamic H NMR studies of crown-tetrathia[3.3.3.3]metacyclophanes—conformational control by cooperative intramolecular C-H?π interaction both in solid state and in solution

Crown-tetrathia[3.3.3.3]metacyclophanes 3a-c were synthesized via intermolcular coupling reaction in 22-30% yields. X-ray crystal analysis of 3b revealed that it adopted a perpendicular conformation (3b-B or 3b-C) in which two aromatic rings were inclined to be perpendicular to the opposite aromatic rings, driving two internal methyl groups into the π-cloud of the corresponding benzene rings. Furthermore, this perpendicular structural feature led to benzylic protons of thia-bridges being in close proximity to the adjacent aromatic rings. As a result, the induced upfield shifts for the two internal methyl protons and four benzylic protons were clearly observed in dynamic ¹H NMR spectra at low temperature, indicating that the intramolecular C-H?π interaction became increasingly important at low temperature. The energy barrier for inter-conversion between 3b-B and 3b-C was estimated to be 12.1 kcal mol⁻¹ by using a coalescence method. The total stabilization enthalpy of the C-H?π interactions was quantitatively calculated to be 7.9±0.8 kcal mol⁻¹ by the dynamic NMR spectroscopy. In contrast, 3a showed two non-interconvertible conformers at room temperature, which tended to interconvert at elevated temperature, however, many conformers co-existed at low temperature.     

Synthesis and Study of Tetraamminenickel 9-Molybdomanganate [Ni(NH3)4] · H4[MnMo9O32] · 6H2O

Tetraamminenickel 9-molybdomanganate [Ni(NH₃)₄] · H₄[MnMo₉O₃₂] · 6H₂O (zbdI) has been synthesized and studied by thermogravimetry, IR spectroscopy, and X-ray powder diffraction analysis. The crystals of compound I are monoclinic: a = 11.5961 Å, b = 11.1609 Å, c = 8.7200 Å, β = 109.23°, V = 1065.59 ų, ρ_calcd = 3.067 g/cm³, Z = 1.     

Synthesis and Reductive Transformations of 11-Deoxyprostanoids with a 4,5,6,6a-Tetrahydro-3aH-cyclopenta[d]isoxazole Fragment in the ω-Chain

A new prostanoid precursor with a 4,5,6,6a-tetrahydro-3aH-cyclopenta[d]isoxazole fragment in the -chain was synthesized using the nitrile oxide technique. Its reduction afforded new 11-deoxyprostanoids with modified - and -chains.     

Synthesis of linked symmetrical [3] and [5]rotaxanes having an oligomeric phenylene ethynylene (OPE) core skeleton as a π-conjugated guest via double intramolecular self-inclusion

Linked symmetrical [3] and [5]rotaxanes consisting of an oligomeric phenylene ethynylene (OPE) framework as a π-conjugated guest moiety and lipophilic permethylated α-cyclodextrins (PM α-CDs), as macrocyclic hosts have been prepared by double intramolecular self-inclusion of an OPE guest unit carrying two PM α-CDs followed by capping with bulky stopper groups using click azide-alkyne Huisgen cycloaddition or Sonogashira coupling. The structures of these linked rotaxanes were determined by MALDI-TOF mass spectrum and two-dimensional NMR spectroscopy.     

Synthesis,crystal structure,vibrational and 31P-NMR spectroscopy of the thiophosphate NaMg[PO3S]·9H2O

NaMg[PO₃S]·9H₂O was obtained as single-phase crystalline powder starting from NaOH, PSCl₃ and MgCl₂·6H₂O. At room temperature NaMg[PO₃S]·9H₂O crystallises in space group Cmc2₁ (no. 36) (a=638.58(4) pm, b=1632.31(10) pm, c=1217.16(7) pm, Z = 4; R_int = 0.032, R_σ = 0.034, R1 = 0.036, wR2 = 0.071). The data collection at 100 K reveals an ordering of the PO₃S tetrahedra by undergoing a symmetry reduction to P2₁ (no. 4) and an according formation of twins (C112₁, unconv. setting of P2₁, a=631.41(3) pm, b=1630.00(7) pm, c=1219.24(5) pm, γ=90.00(2)^°, Z = 4; R_int = 0.115, R_σ = 0.064, R1 = 0.045, wR2 = 0.070). NaMg[PO₃S]·9H₂O comprises isolated PO₃S tetrahedra, distorted MgO₆ octahedra and trigonal NaO₆ prisms. ³¹P NMR spectroscopy showed a chemical shift of 33.7 ppm. The vibrational spectra of NaMg[PO₃S]·9H₂O were recorded and the relevant bands were assigned.     

Synthesis and Crystal Structure of 2-Methoxy-benzoic Acid 2-Oxo-3-（2,4,6-trimethyl-phenyl）-1-oxa-spiro[4.4]non-3-en-4-yl Ester

The new title compound 2-methoxy-benzoic acid 2-oxo-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-4-yl ester(3,C25H26O5) has been synthesized by the condensation reaction of 4-hydroxy-3-(2,4,6-trimethyl-phenyl)-1-oxa-spiro[4.4]non-3-en-2-one(2) with 2-methoxylben-zoyl chloride,and characterized by 1H NMR and MS spectra.Its crystal structure was determined by single-crystal X-ray diffraction.The crystal is of monoclinic,space group P21/c with a = 10.6945(7),b = 12.8176(7),c = 16.4223(10) ,β = 103.5665(17)o,V = 2188.3(2) 3,Z = 4,Dc = 1.234 g/cm3,F(000) = 864.000,μ = 0.085 mm-1,the final R = 0.0520 and wR = 0.1132 for 2732 observed reflections with I 2σ(I).In the crystal structure,the C(1)-C(2)(1.478 ) bond is significantly shorter than the normal single C-C bond(1.53 ),suggesting that the carbonyl group on C(1) has formed a conjugated system with a double bond on C(2) and C(12).     

Synthesis and photoluminescence of the chiral compounds [ZnLCl2] · EtOH and ZnLCl2, where L is the (+)-3-Carene derivative containing pyrazoline and quinoline fragments: crystal structure of [ZnLCl2] · EtOH

The following chiral compounds were synthesized: [ZnLCl₂] · EtOH (I) and ZnLCl₂ (II), where L is the pyrazolin-5-ol derivative obtained from terpene (+)-3-carene. According to the X-ray diffraction data, the crystal structure of compound I is built of acentric molecules of the mononuclear ZnLCl₂ complex and EtOH molecules. In molecules of the complex, the Zn²⁺ ion is coordinated by two N atoms of the bidentate chelating ligand L and two Cl atoms at the vertices of the distorted tetrahedron. The intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) between the adjacent ZnLCl₂ molecules result in the formation of chains parallel to the y axis. The reactant L and solvate I possess weak photoluminescence in the visible spectral range. Complex II exhibits more intense photoluminescence at λ_max = 416 and 517 nm.     

Synthesis of 2,3,5,6-tetrahydro-1-alkyl/aryl-1H-benzo[f]chromen-3-ol derivatives from β-tetralones and α,β-unsaturated aldehydes

Organocatalytic domino Michael-hemiacetalization of β-tetralones with α,β-unsaturated aldehydes is presented. Treatment of β-tetralones with α,β-unsaturated aldehydes in the presence of diphenylprolinol silyl ether gave 2,3,5,6-tetrahydro-1-alkyl/aryl-1H-benzo[f]chromen-3-ol derivatives with high to excellent chemical yields (50-99%) and high levels of enantioselectivities (up to 96% ee).     

Synthesis,spectroscopic characterization,and in vitro antimicrobial activity of fused pyrazolo[4′,3′:4,5]thieno[3,2-d]pyrimidine

4-Amino-3-methyl-1-phenyl-1H-thieno[2,3-c]pyrazole-5-carboxamide ( 1 ), which had been previously synthesized according to literature, was used for synthesizing pyrazolothieno-pyrimidine ( 2 ) in the presence of triethyl orthoformate and acetic acid. Chlorination of the latter compound upon reflux with phosphorus oxychloride afforded the chloropyrazolothienopyrimidine ( 3 ), which underwent heterocyclization reaction with sodium azide to produce the tetrazolo-pyrazolothienopyrimidine ( 6 ). The chloropyrimidine ( 3 ) reacted with hydrazine hydrate to give the hydrazinopyrimidine derivative ( 4 ), which in turn underwent intramolecular condensation reactions with various 1,3-dicarbonyl compounds, namely ethyl acetoacetate, ethyl benzoylacetate, ethyl cyanoacetate, acetylacetone, diethyl malonate, and ethyl (ethoxymethylene) cyanoacetate, yielding new pyrazolyl pyrazolothienopyrimidine ring systems. Also triazolopyrazolothieno-pyrimidines and benzylidene Schiff's base compounds were obtained as a result of the reactions with carbon disulfide in pyridine and benzaldehyde, respectively. The chemical structures of the newly synthesized compounds were elucidated using elemental and spectroscopic analyses (FT-IR, ¹ H-NMR, ¹³ C-NMR, and mass spectroscopy). Some of the synthesized compounds possess high antibacterial and antifungal activities.     

Synthesis of 1,3,5-triazabicyclo[3.1.0]hexanes containing the fragments of α-amino acids and their esters at the N(3) atom

With 3,3-pentamethylene-1,2H-diaziridine as an example, it was shown that 3,3-dialkyl-1,2H-diaziridines can undergo cyclocondensation with -amino acids and their esters to give the corresponding N(3)-substituted 1,3,5-triazabicyclo[3.1.0]hexanes, including pure enantiomers.     

Synthesis and properties of azoles and their derivatives. 45. Regio-and stereoselectivity of the [2+3]-cycloaddition ofE-β-nitrostyrene toZ-C-phenyl-N-arylnitrones

It is shown using spectroscopic methods that the [2+3]-cycloaddition of Z-C-phenyl-N-arylnitrones to E--nitrostyrene is regiospecific and leads to a mixture of the corresponding (3SR,4SR,5SR)- and (3SR,4SR,5SR)-2-aryl-4-nitro-3,5-diphenylisoxazolidines. The regioselectivity of the reaction is explained in terms of hard and soft acid and base theory.For communication 44, see [1]Institute of Organic Chemistry and Technology, T. Kosciuszko Krakow Polytechnic, 31–155 Krakow. Poland: e-mail: pebarans(ausk.pk.edu.pl. Translated from Khimiya Geterotsiklicheskikh Soedinenii No. 6. pp. 840–846, June, 2000.     

Synthesis and Crystal Structure of {4-[2-（9- Hexyl-9H-carbazol-3-yl）vinyl]phenyl} Dimethylamine

The title compound {4-[2-(9-hexyl-9H-carbazol-3-yl)vinyl]phenyl} dimethylamine has been synthesized by the well known Wittig reaction, and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 47.87(2), b = 10.222(4), c = 9.612(4) , β = 92.401(9)o, V = 4699(3) 3, Z = 8, C28H32N2, Mr = 396.56, Dc = 1.121 g/cm3, F(000) = 1712 and μ(MoKa) = 0.065 mm-1. The final R and wR are 0.0793 and 0.1983, respectively for 3524 observed reflections with I > 2σ(I). In the title compound, the bond lengths are normal, and the crystal is stabilized by Van der Waals’ forces.     

Synthesis and structure of 4,9-diaryl-3a,4,9,9a-tetrahydrospiro-[furo[3,4-f]chromene-8,1’-cyclopentane]-1,3,7(9bH)-triones

Reactions of (E)-10-aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-en-6-ones with maleic anhydride result in the formation of 4,9-diaryl-3a,4,9,9a-tetrahydrospiro[furo[3,4-f]chromene-8,1′-cyclopentane]-1,3,7(9bH)-triones whose structure was established by XRD analysis.     

Synthesis and physicochemical study of diazabicycloundecene hexamolybdochromate [C9H16N2]H3[CrMo6O18(OH)6] · 2H2O

Quinazoline hexamolybdochromate [C₉H₁₆N₂]H₃[CrMo₆O₁₈(OH)₆] · 2H₂O has been synthesized and studied by mass spectroscopy, X-ray powder diffraction, thermogravimetry, and IR and NMR spectroscopy. The compound crystallizes in triclinic system with the unit cell parameters a = 15.06 Å, b = 13.08 Å, c = 8.17 Å, α = 59.85°, β = 123.15°, γ = 107.01°, V = 1165.62 ų, ρ_pycn = 3.58 g/cm³, and Z = 2.     

Synthesis and characterisation of a calix[4]pyrrole functional polystyrene via ‘click chemistry’ and its use in the extraction of halide anion salts

A polystyrene with pendant calix[4]pyrroles was prepared via ‘click reaction’ strategy. First, a poly(styrene-co-chloromethylstyrene) with approximately 12% of chloro groups was prepared by conventional free radical polymerisation. The chloro groups were then converted to azido groups using NaN₃ in N,N-dimethylformamide. An alkyne-functionalised calix[4]pyrrole was then coupled to the azido-functionalised polystyrene by click chemistry with high efficiency. The resulting polystyrene with pendant calix[4]pyrroles was used to extract fluoride and chloride anions (as their tetrabutylammonium salts) from their aqueous solutions to organic media.     

Comparative study of crystal structures of [M(NH3)5NO2]XY and [M(NH3)5ONO]XY. Crystal structure of [Co(NH3)5NO2](NO3)2·0.25H2O

The crystal structure of [Co(NH₃)₅NO₂](NO₃)₂·0.25H₂O has been determined. Co₁N₈O_8.25H_15.5, a=7.582(3), c=10.331(3) Å, V=593.9(5) ų, d_calc=1.782 g/cm³ for Z=2, space group I 4mm (C _4v ⁹ , No. 107). The structure is of the island type. Complex (distorted octahedral) cations are bonded to the NO ₃ ^? anions by electrostatic forces. Crystallization water is located in the vicinity of the labile NO₂ group.