Platinum(II) complexes containing 2-(alkenyl)pyridines

The ligands 2-(allyl)pyridine(APy), and 2-(1-methallyl)pyridine (1-MAPy) react with [Pt₂X₄(PEt₃)₂] (X = Cl or Br), in acetone solution to give complexes of the type [PtX(PEt₃)L] [PtX₃(PEt₃)], (L = APy or 1-MAPy), which contain a bidentate 2-(alkenyl)pyridine, whereas the same reaction in benzene solution gives trans-[PtBr₂(PEt₃)L], (L = APy or 1-MAPy), which contains a monodentate 2-(alkenyl)pyridine; ¹H NMR spectra indicate that both types of product undergo olefin exchange in solution. The same reaction with 2-(3-methallyl)-pyridine [2-(2-butenyl)pyridine] (3-MAPy), 2-(3,3-dimethylallyl)pyridine [2-(3-methyl-2-butenyl)pyridine] (3,3-DMAPy), and 2-(3-butenyl)pyridine (BPy), in either acetone or benzene solution, gives only trans-[PtBr₂(PEt₃)L]. The reaction of trans-[PtBr₂(PEt₃)L] (L = APy or 3-MAPy) with AgClO₄ gives [PtBr(PEt₃)L]ClO₄. Complexes of the type [PtCl₂L], which contain bidentate 2-(alkenyl)pyridines, result on reaction of L = APy, 3-MAPy, 3,3-DMAPy, BPy, MBPy with [Pt₂Cl₄(C₂H₄)₂].     

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.     

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.     

Synthesis and optical behaviors of 2-(9-phenanthrenyl)-, 2-(9-anthryl)-, and 2-(1-pyrenyl)-1-alkylimidazole homologues

Eight 2-(9-phenanthrenyl)-, 2-(9-anthryl)- and 2-(1-pyrenyl)-1-alkyl-benzimidazole compounds, three 2-(9-anthryl)-1-alkylphenanthroimidazole compounds and five 4,5-diphenyl-1-alkyl-2-(9-anthryl)imidazole compounds were synthesized by alkylation reactions of the corresponding benzimidazole, phenanthroimidazole or imidazole compounds. 2-(10-Bromo-9-anthryl)-1-alkyl-benzimidazole compounds were prepared by bromination reaction of 2-(9-anthryl)-1-alkylbenzimidazole compounds. All the synthesized compounds were characterized by elemental analysis, ¹H NMR, ¹³C NMR, MS or HRMS; their absorption coefficients (), maximum absorption λ_amax, fluorescence emission maximum λ_em, Stokes shifts and fluorescence quantum yields (Φ_F) in ethyl acetate were determined; their fluorescent lifetimes (T₁ and T₂) were measured in ethyl acetate and in solid state, respectively. The crystal structure of 2-(9-anthryl)-1-n-butyl-4,5-diphenylimidazole (12a) was determined to be triclinic, space group P-1 types, using single crystal X-ray crystallography technique. The results showed that these compounds exhibited moderate fluorescence-emission abilities and higher solubility in most organic solvents than their corresponding starting materials. The relationships between the optical behaviors and structures for these compounds were discussed.     

Synthesen und Ringerweiterungsreaktionen von 2-(4-Hydroxyalkyl)-2-nitrocycloalkanonen

Syntheses and Ring-Enlargement Reactions of 2-(4-Hydroxyalkyl)-2-nitrocycloalkanones Syntheses of the title compounds were achieved by [Pd{P(C₆H₅)₃}₄]-catalyzed reaction of 2-nitrocycloalkanones 3 with vinyloxirane followed by catalytic hydrogenation. By another route, the known methyl 4-(1-nitro-2-oxocycloalkyl)butanoates 6 were reduced to the corresponding aldehydes 7 which by NaBH₄ reduction or methylation with (CH₃)₂Ti(i-Pr)₂ were transformed to the alcohols 5 and 8 , respectively (Saheme 1). Treatment of 5 and/or 8 with KH/THF under reflux gave, via a 7-membered intermediate, the nitrolactones 12 and oxolactones 13 (Scheme 3). Compared with similar reactions running via 5- or 6-membered intermediates (see 1 and 2 ), the yields are distinctly lower. The natural occurring 12-tridecanolid ( 14 ) was synthesized.     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

Transformations of 5-(2-arylethynyl)-2-methyl-2H-tetrazoles under superelectrophilic activation

Reaction of 5-arylethynyl-2-methyl-2H-tetrazoles (acetylene tetrazoles) with arenes under the action of Brønsted superacid CF₃SO₃H or acidic zeolite HUSY CBV-720 gives rise to E-/Z-5-(2,2-diarylethenyl)-2-methyl-2H-tetrazoles, as products of hydroarylation of acetylene bond, in yields up to 98% with predominant formation of E-isomers. Cationic intermediates of these reactions have been studied theoretically by DFT calculations. Addition of CF₃SO₃H to the triple bond of acetylene tetrazoles leads to the corresponding E-/Z-vinyl triflates in high yields. Hydration of triple bond in these tetrazoles in H₂SO₄ results in the formation of 5-(2-aryl-2-oxoethyl)-2-methyl-2H-tetrazoles. Tandem hydroarylation-ionic hydrogenation of acetylene tetrazoles in the systems acid(CF₃SO₃H or AlCl₃)-arene-cyclohexane affords 5-(2,2-diarylethyl)-2-methyl-2H-tetrazoles.     

Synthesis of Ethyl 2-Hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and Ethyl 3-Arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates

Condensation of N-arylmethylene-2-naphthylamines with ethyl 2-oxocycopentanecarboxylate in the presence of HCl or CH₃COOH yields ethyl 2-hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and ethyl 3-arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates, respectively.     

Convenient and efficient stereoselective synthesis of (2Z)-2-(chloromethyl)alk-2-enoates using iron(III) or indium(III) chloride

The stereoselective synthesis of (2Z)-2-(chloromethyl)alk-2-enoates has been achieved efficiently and in high yields and in short reaction times from Baylis-Hillman adducts, 3-hydroxy-2-methylene-alkanoates, by treatment with FeCl₃ or InCl₃ at room temperature.     

Platinum(II) Mono-N1-(2"-Tetrahydrofuranyl)-5-Fluorouracilate Complexes with Ammonia

The reaction between cis-[Pt(NH₃)₂Cl₂], N¹-(2"-tetrahydrofuranyl)-5-fluorouracil (HL), and NaOH (taken in a molar ratio of 1 : 1 : 1) or between cis-[Pt(NH₃)₂Cl₂], HL, and Ag₂O (taken in the molar ratio of 1 : 1 : 0.5) was used to synthesize complexes Ia (in the case of NaOH) or Ib (in the case of Ag₂O) with composition Pt(NH₃)₂LCl. The model complex [Pt(NH₃)₃L]NO₃ (II) was synthesized by the reaction between [Pt(NH₃)₃Cl]Cl, HL, AgNO₃, and Ag₂O (1 : 1 : 1 : 0.5). The obtained compounds were characterized by chemical analysis, chromatography, thermogravimetry, conductometry, potentiometry, IR, electronic, and NMR spectroscopies. Complexes Ia and Ib were found to have both similar and different properties. The structures of the compounds and the type of L^– coordination to platinum(II) were suggested. Cytotoxic properties of Iaand Ib were studied.     

Synthesis of Novel New 2-(2-(4-((3,4-Dihydro-4-oxo-3-aryl quinazolin-2-yl)methyl)piperazin-1-yl)acetoyloxy)-2-phenyl Acetic Acid Esters

Stereoselective diazotization of (S)-2-amino-2-phenyl acetic acid (L-phenyl glycine) (4) with NaNO₂ in 6% H₂SO₄ in a mixture of acetone and water gave optically pure (S)-2-hydroxy-2-phenyl acetic acid (L-mandelic acid) (5). Esterification, gave (S)-2-hydroxy-2-phenyl acetic acid esters (6). The latter was treated with chloroacetyl chloride in the presence of triethylamine (TEA) in dichloromethane (DCM) to yield (S)-2-chloroacetyloxy phenyl acetic acid ester (2). In another sequence, the reaction of 2-(chloromethyl)-3-arylquinazolin-4(3H)-one (9) treated with N-Boc piperazine, followed by deprotection of the Boc group, to obtain 3-aryl-2-((piperazin-1-yl)methyl) quinazolin-4(3H)-one (3). Reaction of 2 with 3 in the presence of K₂CO₃ and KI gave the title compound, 2-(2-(4-((3,4-dihydro-4-oxo-3-arylquinazolin-2-yl)methyl)piperazin-1-yl) acetoyloxy)-2-phenyl acetic acid esters (1). The structures of all the new compounds obtained in the present work are supported by spectral and analytical data.     

Synthesis of (2-chlorophenyl)(phenyl)methanones and 2-(2-chlorophenyl)-1-phenylethanones by Friedel-Crafts acylation of 2-chlorobenzoic acids and 2-(2-chlorophenyl)acetic acids using microwave heating

Several 2-(2-chlorophenyl)-1-phenylethanones and (2-chlorophenyl)(phenyl)methanones were prepared by the Friedel-Crafts acylation reaction of 2-(2-chlorophenyl) acetic acids and 2-chlorocarboxylic acids, respectively, in the presence of cyanuric chloride, pyridine, and AlCl₃ or FeCl₃ using microwave heating. The yields of the ketones were significantly higher than those obtained using conventional heating. In addition, similar reactions carried out with the less inexpensive and less toxic FeCl₃ gave titled ketones in comparable yields. Interestingly, the FeCl₃ catalyzed reactions gave pure ketones (no chromatographic purification required), whereas the AlCl₃ catalyzed reaction gave impure product that required chromatographic purification.     

(E)-[4,4,4-Trifluor-1-(trifluormethyl)-1,3-bis(trimethylsiloxy)-2-butenyl]diphenylphosphin als Ligand

The Ligand (E)-[4,4,4-Trifluoro-1-(trifluoromethyl)-1,3-bis(trimethylsiloxy)-2-butenyl]di-phenylphosphine The tertiary phosphine (E)-Ph₂PC(OSiMe₃)(CF₃)CH = C(OSiMe₃)CF₃ (L), 1 and the carbonyl Fe₂(CO)₉ react to give (OC)₄FeL, 2. Bis( 1,1,1,5,5,5-hexafluoropentane-2,4-dionato)palladium(II) and 1 furnish the diphenylphosphido group bridged palladium(II) complex 3 crystallizing from chloroform triclinic in the space group P1 with a = 12.600(3), b = 13.298(3), c = 13.975(3) Å, α = 93.27(2), β = 111.67(2), γ = 106.71(2)° The elementary cell contains Z = 2 formular units and two molecules CHCl₃ with two independent molecules 3 each showing an inversion centre. The planar [PdP], four membered ring system and the planar chelate units, exhibit a torsional angle of 6.75°     

Synthesis and characterization of cobalt(II) and iron(III) complexes with the Schiff bases:N-(p-methylbenzylidene)-2-aminobenzimidazole andN-(benzylidene)-2-(2′-aminophenyl)-benzimidazole

Summary Reactions of CoX₂ (X=Cl, Br or NCS) and FeCl₃ with the Schiff bases:N-(p-methylbenzylidene)-2-aminobenzimidazole (pmbabi) andN-(benzylidene)-2-(2-aminophenyl) benzimidazole (bapbi) yield complexes of general formula CoL₂X₂ [except for Co(bapbi)(NCS)₂] and FeLCl₃. All complexes have been characterized by elemental analyses, i.r. spectroscopy conductivity and magnetic measurements at different temperatures; solid state and solution electronic spectra are reported for cobalt(II) complexes. The results show that the latter are pseudotetrahedral, the ligand acting as monodentate, except for Co(bapbi) (NCS)₂. On the other hand, the iron compounds probably contain pentacoordinated metal.     

Darstellung und Charakterisierung von Chrom(V)- und Mangan(V)- nitridophthalocyaninen(1-) und -(2-): [MNPc(1-)]+; und [MNPc(2-)] (M=Cr,Mn)

Preparation and Characterization of Chromium of Chromium(V)- and Manganese(V)- nitridophthalocyanines(1-) and -(2-): [MNPc(1-)]⁺ and [MNPc(2-)] (M=Cr, Mn) Nitridophthalocyaninatochromium(V), [CrNPc(2-)], is prepared by oxidation of [Cr(OH)₂PC(2-)] with chlorine in the presence of excess ammonia as a paramagnetic (μ_eff = 1,99 B.M.), Microcrystalline blue powder. Through chemically very stable it reacts as well as the isostructural nitridophthalocyaninatomanganese(V) with bromine or concentrated nitric acid giving ring- oxidized darkblue nitridophthalocyaninatomental(poly)bromides or -nitrates, [MNPc(1-)]X (M=Cr, Mn; X=Br_y, NO₃; y≈?2). The nitrido-metal stretching vibration (ν(N?M)) is independent of the oxidation state of the Pc-ligands at ca. 1017 cm^?1 for the chromium and at ca. 1055 cm^?1 for the manganesenitridophthalocyanines. ν(N?Mn) is resonance Raman (r.r.) enhanced, ν(N?Cr) not. The characteristic differences in the u.v. -vis., f.i.r./m.i.r. and r.r. spectra of [MNPc(2-)] and [MNPc(1-)⁺ and the influence of aggregation of phthalocyanine-radicals are discussed.     

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.     

3-(Aryl)-2-sulfanylpropenoates of mercury(II) and phenylmercury(II)

Compounds [HQ]₂[Hg(L)₂] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (¹H, ¹³C) spectroscopy. The crystal structures of the [HQ]₂[Hg(L)₂] compounds show the presence of diisopropylammonium cations and [Hg(L)₂]²⁻ anions. In each anion the Hg atom is in an HgO₂S₂ environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]⁻ anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L²⁻ determined by X-ray diffractometry in the solid remains in solution.     

Tricarbonylrhenium(I) and manganese(I) complexes of 2-(pyrazolyl)-4-toluidine

A series of tricarbonyl rhenium(I) and manganese(I) complexes of the electroactive 2-(pyrazolyl)-4-toluidine ligand, H(pzAn^Me), has been prepared and characterized including by single crystal X-ray diffraction studies. The reactions between H(pzAn^Me) and M(CO)₅Br afford fac-MBr(CO)₃[H(pzAn^Me)] (M = Mn, 1a; Re, 1b) complexes. The ionic species {fac-M(CH₃CN)(CO)₃[H(pzAn^Me)]}(PF₆) (M = Mn, 2a; Re, 2b) were prepared by metathesis of 1a or 1b with TlPF₆ in acetonitrile. Complexes 1a and 1b partly ionize to {M(CH₃CN)(CO)₃[H(pzAn^Me)]⁺}(Br⁻) in CH₃CN but retain their integrity in less donating solvents such as acetone or CH₂Cl₂. Each of the four metal complexes reacts with (NEt₄)(OH) in CH₃CN to give poorly-soluble crystalline [fac-M(CO)₃(μ-pzAn^Me)]₂ (M = Mn, 3a; Re, 3b). The solid state structures of 3a and 3b are of centrosymmetric dimeric species with bridging amido nitrogens and with pyrazolyls disposed trans- to the central planar M₂N₂ metallacycle. In stark contrast to the diphenylboryl derivatives, Ph₂B(pzAn^Me), none of the tricarbonyl group 7 metal complexes are luminescent.     

Cyclometallation of 2-(2-thienyl)pyridine and 2-(3-thienyl)pyridine with palladium(II), rhodium(III) and ruthenium(II)

Summary 2-(2-Thienyl)pyridine [H(2-tp)] and 2-(3-thienyl)pyridine [H(3-tp)] react with lithium tetrachloropalladate(II), hexachlorotetrakis(tri-n-butylphosphine) dirhodium(III), and tetrachlorohexacarbonyldiruthenium(II) to give [PdCl(C-N)]₂-(CN=2-tp and 3-tp), [RhCl₂(C-N)PBu₃]₂ (C-N = 2-tp and 3-tp), and [RuCl(2-tp)(CO)₂]₂, respectively. Some bromo analogues are also prepared. These complexes react with pyridine and tri-n-butylphosphine to give adducts in which 2-tp is chelated through pyridine-N and thiophene-3-C and 3-tp through pyridine-N and thiophene-2-C atoms. The structures of these complexes are similar to those of the corresponding complexes of cyclometallated 2-phenylpyridine.     

Unexpected formation of clusters with a nortricyclene-containing carborane ligand, 1-(η6-arene)-3-(C7H9CH2O)-isonido-1,2,4-RuC2B8H9, in the reaction of 1,1,3-(PPh3)3-1-H-1,2,4-RuC2B8H9 with 2-(hydroxymethyl)norbornadiene in arene solvents

Heating of 1,1,3-(PPh₃)₃-1-H-1,2,4-RuC₂B₈H₉ with 2-(hydroxymethyl)bicyclo[2.2.1]hepta-2,5-diene in arene solvents (benzene, toluene, or mesitylene) unexpectedly afforded the ruthenium arene complexes 1-(η⁶-arene)-3-(C₇H₉CH₂O)-isonido-1,2,4-RuC₂B₈H₉ containing the nortricyclene fragment in the carborane ligand.