The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

 A macrocyclic diazadioxa dibromo compound was synthesized by ring closure of 1,2-bis-(2-iodoethoxy)-4,5-dibromo-benzene and 1,4-bis-(p-tolylsulfonyl)-ethylenediamine. Its phthalonitrile derivative was obtained by cyano substitution. This diazadioxa macrocyclic dibromo derivative was directly converted into the copper(II) phthalocyanine by reaction with CuCN in tetramethyl urea. Conversion of this phthalonitrile derivative into the metal-free phthalocyanine was accomplished by refluxing with DBU. The zinc(II) phthalocyanine was prepared by reaction of the dinitrile derivative with Zn(OAc)₂ in quinoline. The lutetium bis-(phthalocyaninate) complex was obtained by treating the dinitrile derivative with anhydrous lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses and IR, ¹H NMR, mass, UV/Vis, and ESR spectra.     

The Synthesis of New Phthalocyanines Substituted with 12-Membered Diazadioxa Macrocycles

Summary.  A macrocyclic diazadioxa dibromo compound was synthesized by ring closure of 1,2-bis-(2-iodoethoxy)-4,5-dibromo-benzene and 1,4-bis-(p-tolylsulfonyl)-ethylenediamine. Its phthalonitrile derivative was obtained by cyano substitution. This diazadioxa macrocyclic dibromo derivative was directly converted into the copper(II) phthalocyanine by reaction with CuCN in tetramethyl urea. Conversion of this phthalonitrile derivative into the metal-free phthalocyanine was accomplished by refluxing with DBU. The zinc(II) phthalocyanine was prepared by reaction of the dinitrile derivative with Zn(OAc)₂ in quinoline. The lutetium bis-(phthalocyaninate) complex was obtained by treating the dinitrile derivative with anhydrous lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses and IR, ¹H NMR, mass, UV/Vis, and ESR spectra. Received May 8, 2001. Accepted (revised) June 25, 2001     

Synthesis and characterization of soluble porphyrazines bearing octakis 2-anthraquinonylmethylthio substituents

By cyclotetramerization of 1,2-bis(2-anthraquinonylmethylthio)maleonitrile in the presence of magnesium butanolate, magnesium porphyrazinate carrying eight (2-anthraquinonylmethylthio) functional groups on peripheral positions has been synthesized. The metal-free derivative was obtained by treatment with tri?uoroacetic acid; reaction of this product with copper(II) acetate, zinc(II) acetate, and cobalt(II) acetate led to the metal porphyrazinates [M?=?Cu(II), Zn(II), and Co(II)]. These new compounds have been characterized by elemental analysis, together with FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis, and mass spectral data.     

Oxidative halogenation of substituted pyrroles with Cu(II). Part III. Bromination and chlorination of 2-benzoylpyrrole

The bromination of 2-benzoylpyrrole with copper(II) bromide in the homogeneous and the heterogeneous phase is described, giving 4- and 5-monobromo derivatives whose ratio decreases as the temperature is increased. The same reaction with copper(II) chloride in acetonitrile at 60° produces 5-chloro-2-benzoylpyrrole as the major product. 4,5-Dihalopyrroles in good yields are obtained with an excess of halogenating agent.     

Equilibria in aqueous solution of cobalt(II), nickel(II) and copper(II) cations with furan-2-carboxylate. A calorimetric study

Summary The heat of reaction of the anion of furan-2-carboxylic acid with cobalt(II), nickel(II) and copper(II) cations has been determined by direct calorimetry. By means of the equilibrium constants, Gibbs function and entropy were also obtained. The measurements were carried out in aqueous medium at 25 °C and an ionic strength I=1 mol dm^–3 (NaNO₃). The data obtained seem to indicate a bidentate character of this ligand, with the participation of both carboxylate and heterocyclic oxygen in complex formation. The behaviour of furan oxygen towards 3d metals is compared with that of thiophen sulfur and pyrrole nitrogen.     

Bromination of sydnones. II Bromination of 3-(2-aminophenyl)sydnone and related compounds

Bromination of 3-(2-aminophenyl)sydnone 2 under a variety of conditions is reported. The products obtained are interrelated by a series of subsequent reactions. One major product is the bromoaryl compound 8, the first example of bromination on the aryl rather than sydnone ring when the two are in competition. Surprisingly, bromoaminosydnone 9, prepared from its nitro analogue, was not among the products obtained by direct bromination of 2.     

A Potential Method Using Ge{iPrNC[N(SiMe3)2]NiPr}2, (Et3Si)2Te and Anhydrous Hydrazine for Germanium Tellurides

A germanium(II)‐guanidine derivative of formula Ge{iPrNC[N(SiMe₃)₂]NiPr}₂ ( 1 ) was synthesized and characterized by ¹H NMR, ¹³C NMR, elemental analysis, and X‐ray diffraction method. Thermal property was also studied to identify its thermal stability and volatility. More importantly, compound 1 was synthesized to develop a new method for germanium tellurides, where anhydrous hydrazine was introduced to prompt the activity of germanium(II) guanidines (or derivatives) towards (Et₃Si)₂Te. Solution reaction of compound 1 , (Et₃Si)₂Te, and anhydrous hydrazine was investigated to pre‐identify the feasibility of this combination for ALD process. The EDS data of the black precipitate from this reaction verified the potential of this method to manufacture germanium tellurides.     

Organic Phosphorus Compounds. Part 64 synthesis of 4,6-dimethylamino-2-cyclohexyl-2H-1,3,5,2-Pv-thiadiazaphosphorin-2-thione

In the reaction of cyclohexylmonothiophosphonic anhydride, [C₆H₁₁P(S)O]₃, with dimethylcyanamide not the expected 2H-1,3,5,2-P^v-thiadiazaphosphorin-2-oxide derivative is formed, but the corresponding thione derivative, the title compound, is obtained.     

Kristallstrukturen der Terpyridin-Komplexe [Cd(terpy)Cl2], [Cu(terpy)(CN)Cl] und [Cu(terpy)][Cu(CN)3] · H2O

Crystal Structures of the Terpyridine Complexes [Cd(terpy)Cl₂], [Cu(terpy)(CN)Cl], and [Cu(terpy)][Cu(CN)₃] · H₂O By reaction of cadmium chloride with 2,2′ : 6′,2″-terpyridine (“terpy”) in water/acetone crystals of [Cd(terpy)Cl₂] ( 1) were formed. The compound crystallizes monoclinic, space group P2₁/c, a = 1111.70(10), b = 823.10(7), c = 1643.00(14) pm, β = 93.913(1)°, Z = 4. Starting from mixtures of different molar ratios of copper(II) chloride, terpyridine, and KCN in water/methanole, two complexes of different composition were obtained. At the molar ratio of 1 : 1 : 2 a copper(II) coordination compound with both halide and pseudohalide ligands, [Cu(terpy)(CN)Cl] ( 2 ), was formed which also crystallizes monoclinic, P2₁/c, a = 1065.6(3), b = 824.6(2), c = 1644.5(7) pm, β = 98.214(3)°, Z = 4. At a molar ratio of 1 : 1 : 10 a partial reduction of copper(II) occured with formation of a mixed valency compound [Cu(terpy)][Cu(CN)₃] · H₂O ( 3 ) which crystallizes in the hexagonal space group P6₅22, with a = b = 800.29(1), c = 4771.05(7) pm, Z = 6. Compounds 1 and 2 are structurally similar, the coordination of the metal atoms is square pyramidal. Networks are formed by hydrogen bridges. In 3 the copper(II) ions show a distorted square planar coordination by the three N atoms of the terpy ligand and one N atom of a bridging CN^– group, the copper(I) atoms, however, show trigonal planar coordination by three CN^– ligands to which the water molecules are bonded by hydrogen bridges. Thus helical chains are formed which stretch in the direction of the screw axes. The EPR spectrum of 3 was measured.     

A calorimetric and computational study of the thermochemistry of halogenated 1-phenylpyrrole derivatives

The standard molar enthalpies of formation, in the crystalline phase, of three halogenated 1-phenylpyrrole derivatives, namely 1-(4-fluorophenyl)pyrrole, 1-(4-chlorophenyl)pyrrole, and 1-(4-iodophenyl)pyrrole were derived from the respective enthalpies of combustion, measured by rotating-bomb combustion calorimetry. Their enthalpies of sublimation, at T = 298.15 K, were obtained from the Knudsen mass-loss effusion technique. From these two experimental parameters, the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of 1-(4-fluorophenyl)pyrrole, 1-(4-chlorophenyl)pyrrole, and 1-(4-iodophenyl)pyrrole were calculated, respectively, as (26.2 ± 2.4) kJ · mol⁻¹, (196.2 ± 2.5) kJ · mol⁻¹, and (311.5 ± 2.4) kJ · mol⁻¹.The gas-phase enthalpies of formation of both fluorine and chlorine compounds were estimated by G3(MP2)//B3LYP computations. For the iodine compound, the B3LYP/6-311G(d):ECP46MDF approach was employed. Additionally, the DFT calculations were extended to estimate the enthalpy of formation of the bromine derivative, 1-(4-bromophenyl)pyrrole, performed at the B3LYP/6-311G(d) level of theory.     

3(2H)isoquinolones. 2. Studies on the structure and formation of aminonaphthols obtained in the preparation of 3(2H)isoquinolones

The reaction of a 2-acylphenylacetic acid derivative (I) with primary amines in glacial acetic acid produces novel, colorless aminonaphthols (III) which are isomeric with the brilliant yellow 3(2H)isoquinolones (II) obtained in the same reaction. A combination of chemical and spectral techniques allowed identification of the isomers as derivatives of 4-amino-2-naphthol. A plausible mechanism of formation of aminonaphthols versus 3(2H)isoquinolones is discussed and supported by chemical synthesis of N-substituted 2-aeylphenylacetamides (VIII) and a 1,4-dihydro-1-hydroxy-3(2H)isoquinolone derivative (IX).     

Heterocycles with a benzothiadiazepine moiety. 3. Synthesis of imidazo[5,1-d]pyrrolo[1,2-b][1,2,5]benzothiadiazepine 9,9-dioxide

The synthesis of imidazo[5,1-d]pyrrolo[1,2-b][1,2,5]benzothiadiazepine 9,9-dioxide ( 5 ), a novel sulfur-containing tetracyclic benzodiazepine, is reported starting from pyrrolo[1,2-b][1,2,5]benzothiadiazepine 5,5-diox-ide ( 6 ) by cycloaddition of tosylmethyl isocyanide to the azomethine double bond. Pyrrolobenzothiadiazepine 6 was obtained by iron powder/acetic acid reduction of 1-(2-nitrobenzenefulfonyl)pyrrole-2-carboxaldehyde ( 7 ) and subsequent ring closure of intermediate aminoaldehyde or by cyclization of 1-(2-formamidobenzene-sulfonyl)pyrrole ( 8 ) with phosphorus oxychloride via a Bischler-Napieralski reaction. Formylation of 1-(2-ami-nobenzenesulfonyl)pyrrole with acetic-formic anhydride gave 8. The structure of 5 was confirmed by oxidation with activated manganese dioxide of dihydro derivative 9 , obtained through cyclization of 11-amino-methyl-10,11-dihydropyrrolo[1,2-b][1,2,5]benzothiadiazepine 5,5-dioxide ( 10 ) with triethyl orthoformate. The last compound was prepared alternatively by catalytic reduction of nitro derivative 11 , obtained by addition of nitromethane to pyrrolobenzothiadiazepine 6 , or by lithium aluminum hydride/sulfuric acid reduction of amide 13 , synthesized starting from ethyl 10,11-dihydropyrrolo[1,2-b][1,2,5]benzothiadiazepine-11-carboxyl-ate 5,5-dioxide.     

Desoxy-nitrozucker. 2. Mitteilung Herstellung geschützter 1-Desoxy-1-nitroaldosen

Synthesis of Protected 1-Deoxy-1-nitroaldoses The direct oxidation of the oxime 1 with t-butyl hydroperoxide and vanadyl acetylacetonate yielding the nitro derivative 2 (54%, Scheme 1) could not be applied to other oximes. Diastereoselective bromination of the aldonolactone oxims 7 and 10–12 according to known procedures gave the corresponding bromonitroso compounds which were oxidized to the bromonitro compounds 9, 14, 18 and 22 , respectively. Oxidation of the bromonitroso compound in the D-mannopyranose series proved difficult, but the corresponding chloronitro derivative 23 was easily obtained according to Corey & Estreicher (Scheme 2 and 3). The structure of the bromonitro compound 9 was determined by an X-ray analysis, and the configurations of the bromonitro compounds 14, 18 and 22 were deduced from their molecular rotations. Reduction of the bromonitro compounds gave the protected 1-deoxy-l-nitroaldoses 2 , 15/16 , 19/20 , and 24/25 , respectively, in good overall yields. The ribose derivatives 15 and 16 were detritylated to give the nitro compound 4 , and the mannose derivative 2 was partially deprotected to give the monoisopropylidene compound 26 . The nitro group shows a normal anomeric effect which is reflected in the IR . spectra of the pyranose derivatives 19 and 20 , and 24 and 25 .     

Thermal and structural studies of the chloro complexes of cobalt and copper with 2-amino-3-methylpyridine

The chloro complexes of 2-amino-3-methylpyridine with cobalt(II) and copper(II) have been prepared in ethanolic solution and solid compounds have been isolated. The compounds have stoichiometry ML₂Cl₂ whereM is Co²⁺ or Cu²⁺ and L is 2-amino-3-methylpyridine. Spectral and magnetic studies have been used to obtain information about the environment of the metal ion in these compounds. The compounds have tetrahedral structures. The thermal decomposition of each compound has been studied using thermogravimetry and differential thermal analysis. Thermogravimetry studies show that the cobalt complex forms an intermediate compound before the metal oxide is produced while the copper compound undergoes decomposition with loss of organic ligand and the formation of copper chloride which then decomposes to give an oxide of copper. The enthalpy of reaction for each of the processes has been calculated from the thermal analysis curves.     

Copper(II) and copper(III) complexes of pyrrole-appended oxacarbaporphyrin

The reaction of an O-confused porphyrin with a pendant pyrrole 4 and copper(II) acetate yields an organocopper(III) diamagnetic complex 4-Cu(III) substituted at the C(3) position by the pyrrole and H. The transformation of 4-Cu(III), performed in aerobic conditions, gave a rare copper(II) organometallic compound 6-Cu(II). In the course of this process, the tetrahedral-trigonal rearrangement originated at the C(3) atom but effects the whole structure. The electron paramagnetic resonance spectroscopic features correspond to a copper(II) oxidation state. A crystallographic analysis of 6-Cu(II) confirmed the formation of a direct metal-C bond [Cu(II)-C 1.939(4) A]. It was found that the Cu(II) complex of O-confused oxaporphyrin is sensitive to oxidative conditions. The degradation of 6-Cu(II) to yield copper(II) tripyrrinone complexes has been observed, which was considered as a peculiar case of dioxygen activation in a porphyrin-like environment. This process is accompanied by regioselective oxygenation at the inner C to form the 2-oxa-3-(2'-pyrrolyl)-21-hydroxycarbaporphyrinatocopper(II) complex ((pyrr)OCPO)CuII (8). The reaction of 6-Cu(II) with hydrogen peroxide, performed under heterophasic conditions, resulted in quantitative regioselective hydroxylation centered at the internal C(21) atom, also producing 8. Treatment of 8 with acid results in demetalation to form the nonaromatic 21-hydroxy O-confused porphyrin derivative ((pyrr)OCPOH)H (9).     

Synthesis,Crystal Structure,and Biological Activity of a New Cu(I) Complex of the N-Phenyl-N′-(2-nitrobenzoyl)-thiourea

The complex bis(μ-sulfur)-sulfur-[N-phenyl-N′-(2-nitrobenzoyl)-thiourea]copper (I) was obtained from the reaction between the N-phenyl-N′-(2-nitrobenzoyl)-thiourea(HL) and copper(II). The compound was characterized by IR and ¹H NMR, ¹³C NMR spectroscopy and its structure was determined by single crystal X-ray diffraction. The complex is binuclear with two copper(I) ions coordinated by a terminal sulfur, two bridging sulfurs, and a HL molecule. In addition, the compound is also a considerable plant-growth regulator.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Insights into the extraction mechanism from the coordination chemistry of copper(II) with a synergistic mixture which mimics Versatic10 and 2-ethylhexyl 4-pyridinecarboxylate ester

In the present work, a copper(II) synergist complex with methyl isonicotinate (L^I, a short chain analog of 2-ethylhexyl 4-pyridinecarboxylate ester) and isobutyric acid (HB^I, a short chain analog of Versatic10) was synthesized and studied by X-ray single-crystal diffraction. The results indicated that the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate crystallizes in the monoclinic C2/c space group and confirmed the composition [Cu(B^I)₂(L^I)]₂. The crystal structure consisted of centrosymmetric dimeric units, in which the two Cu ions are bridged in pairs by four carboxylate groups of the deprotonated isobutyric acid. In order to bridge the gap between the solid-state structure of the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate and the solution structure of the extracted copper(II) complex in the non-polar organic phase, the two copper(II) complexes were further investigated by Fourier transform infrared spectroscopy (FT-IR) and electrospray ionization mass spectrometry (ESI-MS). The results indicated that the extracted copper(II) complex in the non-polar organic phase has a similar coordination structure as the copper(II) synergist complex obtained with isobutyric acid and methyl isonicotinate.     

Nitrogen bridgehead compounds. Part 86. Synthesis and reactivity of 7,12-dihydropyrimido[1′,2′;1,2]pyrido[3,4-b]indol-4(6H)-ones. Debenzologues of rutaecarpine alkaloids

A series of 7,12-dihydropyrimido[1′2′:1,2]pyrido[3,4-b]mdole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrirmdin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H)-one 16 with bromine afforded 3-bromo derivative 25 , which was reacted with cyclic amines to give 2-ammo-7,12-dihydropyrirmdo[1′2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26–30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34 ) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35 , obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, ¹H nmr and in some cases by ¹³C ruler, CD spectra and X-ray investigations.     

cis-Bis(7-methylnaphth-1-yl)bis(triphenylphosphan)platin(II)

From the reaction of cis-dichlorobis(triphenylphosphane)platinum(II) with the lithium compound obtained as the bromination product of 2-methylnaphthalene cis-bis(7-methylnaphth-1-yl)bis(triphenylphosphane)platinum(II) (6), has been isolated. The unexpected formation of 6 has been explained.