138668-19-6

Three new water-soluble copper(II) complexes [Cu(HL)(H2O){(CH3)2NCHO}] (1), [Cu(H2L)2(im)4]·CH3OH (2) and [Cu(HL)(CH3OH)]2(μ2-py) (3) were synthe

The 1,1,3,3-tetramethyl guanidine (TMG)-based ionic liquid was used as a recyclable catalyst for Henry reactions to produce 2-nitroalcohols. Good yields were obtained even after 15 reactions.

The new nickel coordination polymer [Ni(HL1) (CH3OH)2]n (1) and co-crystal H3L1?DMF (2) were obtained by reaction of NiCl2·2H2O with 2-(2-(1,3-dioxo-1-(phenylamino)but

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A new cyclic binuclear Ni(II) complex, [Ni2(H2L) 2] · 4MeOH (1), has been synthesized using the Schiff base N′1,N′3-bis(2-hydroxybenzylidene) malonohydrazide (H4L). The X-ray crystal struct

A water-soluble iron(III) complex [Fe(H2O)3(L)] ·5H2O (1) was prepared by reaction of iron(III) chloride with 5-chloro-3-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl) -2-hydroxy-benzenesulfonic acid (H3L

Bis(1-phenylethanaminium) disulfatotetraaquazincate(II) dihydrate (C 8H12N) 2 [Zn(H2O) 4 (SO4)2]2H2O (1), bis(1H-benzo[d]imidazolium) hexaaquazinc(II) bis(sulfate) tet

The new complex [Zn(im)4](NO3)2 (1) was synthesized and crystallographically characterized. In the solid state, 1 is built up by [Zn(C3H4N2)]2+ cations and NO3?/

Reactions of 5-{(pyridin-4-ylmethyl)amino} isophthalic acid (H2L1) with copper(II), zinc(II), and cadmium(II) were studied, and the obtained metal-organic frameworks (MOFs) [{Cu(L1)(DMF)}·DMF·H2O]n (1), [Zn(L1)(H2/su

New organically templated complexes {(C4H12N 2)[MII(H2O)4(SeO4) 2]}·2H2O [MII = Co (1), Cu (2) and Zn (3)] were prepared by slow evaporation of a

Terephthalic acid derivatives bearing amide side functional groups, viz. 2-propionamidoterephthalic acid (H2L1) and 2-acetamidoterephthalic acid (H2L2), have been structurally characterized using X-ray crystallography. While H2

Commercially available, non-activated 2:1 Mg:Al hydrotalcite catalyzes the nitroaldol reaction between a variety of aromatic and aliphatic aldehydes and simple nitroalkanes such as nitromethane and nitroethane. A new mechanism is proposed for the formation of the 1,3-dinitropropanes. The threo/erythro diastereoselectivity of the nitroethane-adducts was determined by 1H NMR spectroscopy and was found to range from 50:50 to 70:30. The substituents of the aromatic aldehydes influenced the isomer ratio.

Reaction of a new hydrazone of β-diketone, 5-(2-(4,4-dimethyl-2,6-dioxocyclohexylidene)hydrazinyl)isophthalic acid (H3L), with zinc(II) nitrate hexahydrate in a mixture of DMF and water (1:1) under hydrothermal conditions affords the 1D coordin

β-Nitroalkanols are easily obtained within a few minutes, through the nitroaldol (Henry) reaction, catalyzed by a stoichiometric amount of powdered potassium hydroxide, in dry media. Satisfactory to excellent yields are obtained both with primary and seco

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Two known organotin(IV) complexes, [Sn(C6H5)3HL1] (1, H2L1 = 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzoic acid) and [Sn(C2H5)2(1κO,2κO-H3L

The new mononuclear nickel(II) complexes [Ni(HL1)(H2O)2(CH3OH)] (1, NaH2L1 = sodium (Z)-2-(2-(1,3-dioxo-1-(phenylamino)butan-2-ylidene)hydrazinyl)benzenesulfonate) and [Ni(H2Lsu

The 1D and the 2D copper(II) coordination polymers [{Cu(κN,OO′-L)}2(μ-1κN:2κN′-bpy)2]n (1) and [{Cu(μ-1κN,OO′:2κO″-L)}2(μ-1κN:2κN′-hmt)]n (2), respectively, were synthesized from copper(II) nitrate and sodium 2-(2-(1,3-dioxo-1H-inden-2(3H)-ylidene) hydrazinyl)benzenesulfonate (NaHL), in the presence of 4,4′-bipyridine (4,4′-bpy) (for 1) or hexamethylenetetramine (hmt) (for 2). 1 and 2 are water soluble and are characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. Depending on the neutral linkers, the dianionic ligand L2? displays tri- (in 1) or tetradentate (in 2) binding modes. The Cu2+ in 1 adopts a distorted N3O2 square-pyramid coordination environment, while in 2 it displays a distorted N2O3 trigonal bipyramid geometry. The catalytic activity of 1 and 2 was evaluated in the diastereoselective Henry reaction of nitroethane with a variety of aromatic and aliphatic aldehydes, in water and in organic solvents. β-Hydroxy nitroalkanes were obtained in high yields (up to 92%), and moderate-to-good syn/anti diastereoselectivities (up to 79:21), in water at room temperature.

A series of self-assembled lanthanide coordination polymers formulated as [La(L1)2]n·1n(DMF)H·3n(DMF) (1), [Ce(L1)2]n·1n(DMF)H·2n(DMF) (2), [Sm(L1)2]n·1n(HCONH2)H·2n(HCONH2) (3), [La(L2)(HL2)(H2O)(DMF)2]n (4) and [Ce(L2)(HL2)(H2O)(DMF)2]n (5) [H2L1: 2-acetamidoterephthalic acid and H2L2: 2-benzamidoterephthalic acid] has been synthesized from the reactions of H2L1 or H2L2 with different lanthanide salts under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, X-ray single-crystal diffraction, powder X-ray diffraction, thermogravimetry and photoluminescence spectroscopy. X-ray diffraction analyses reveal that frameworks 1-3 have similar types of three-dimensional structures, composed of L12- ligands and trinuclear lanthanide nodes, in which two crystallographically independent lanthanide atoms are present. Frameworks 4 and 5 are isostructural, featuring a double chain-type one-dimensional coordination polymer which expands to 3D by means of H-bond interactions. These frameworks act as heterogeneous polymeric solid catalysts for the nitroaldol (Henry) reaction of different aldehydes with nitroalkanes, in water, and can be recycled without losing appreciable activity.

Two complexes [KLa(HL1)2{(CH3)2NCHO}2(H2O)3] (1) and [Sm(H2O)9](E-H2L2)3·2H2O (2) were synthesized by the reacti

Reactions of 5-propionamidoisophthalic acid (H2L1) and 5-benzamidoisophthalic acid (H2L2) with Zn(NO3)2·6H2O under different hydrothermal conditions lead to two pairs of Zn(ii) compounds, viz. the mon

The two new metal-organic frameworks (MOFs) of zinc(ii) and copper(ii) [Zn2L2(1,4-BDC)]n·2n(DMF) (1) and [Cu(L)2]n·4n(DMF)·n(H2O) (2) (L = 4-(pyridin-4-ylcarbamoyl)benzoate; BDC = benzenedi

A novel chiral metal-organic framework, [Cu4(HL)2(H2O)4(MeO)4]n (1), has been successfully synthesized from a tripodal flexible ligand (2S,2′S,2"S)-2,2′,2"-(benzenetricarbonyltris(azanediyl

Three new compounds bearing different flexible side functional groups, viz. 2-acetamidoterephthalic acid (H2L1), 2-propionamidoterephthalic acid (H2L2) and 2-benzamidoterephthalic acid (H2L3), were synthesized and their coordination reactions with zinc(ii) were studied. X-ray crystallography showed the formation of novel metal organic frameworks with different dimensionalities, where the side functional groups of amidoterephthalic acid and/or auxiliary ligands were found to play significant roles. These frameworks [Zn2(L1)2(4,4′-bipyridine) 2(H2O)(DMF)]n (1), [Zn4(L2) 3(OH)2(DMF)2(H2O)2] n (2) and [Zn(L3)(H2O)2]n·n/ 2(1,4-dioxane) (3) act as heterogeneous polymeric solid catalysts not only for the diastereoselective nitroaldol (Henry) reaction of different aldehydes with nitroalkanes but also for transesterification reactions. These MOF-based heterogeneous catalysts can be recycled without losing their activity. This journal is the Partner Organisations 2014.

Facile, versatile, and cost-effective synthetic routes for the preparation of a range of new 3-alkyl-, 4-alkyl-, 3,4-dialkyl-, and 3-halo-4-alkyl-2, 2′-bipyrrole-5-carboxaldehydes have been developed. These 2,2′-bipyrrole-5-carboxaldehydes offer interesting potential as building blocks for making bioactive natural and unnatural products, as demonstrated by the synthesis of B-ring functionalized prodiginines (PGs) and tambjamines.

A series of double dihydromethylpiperazinediium metallic sulfates 1-7 [H2mpz]MII(SO4)2·nH 2O (mpz = 2-methylpiperazine, C5H12N 2) are prepared by slow evaporation using a racemic (R/S)-mpz (for 1, 2) or enantiopure R-mpz (for 3), S-mpz (for 4-7) and sulfates of Cu II (for 5), FeII (for 1, 4), CoII (for 7) and ZnII (for 2, 3, 6), and characterized by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. The [M II(H2O)6]2+, [(R/S)-H 2mpz]2+, [(R)-H2mpz]2+ or [(S)-H2mpz]2+ cations and 2SO42- anions are linked together via two types of hydrogen bonds, Ow-Hw...O and N-H...O, leading to supramolecular arrangements. The use of the racemic 2-mpz provides alternatives in crystallization: a centrosymmetric structure where the enantiomers are related by an appropriate crystallographic symmetry operation or one where the enantiomers occupy the same crystallographic position, generating disorder. Compounds 1-7 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The diastereoselectivity can be regulated from exclusive threo to exclusive erythro isomer preparation with typical yields of 50-99%, depending on the catalyst and the substrate used.

A one-pot template condensation of 2-(2-(dicyanomethylene)hydrazinyl) benzenesulfonic acid (H2L1, 1) or 2-(2-(dicyanomethylene) hydrazinyl)benzoic acid (H2L2, 2) with methanol (a), ethylenediamine (b), ethanol (c) or water (d) on copper(II), led to a variety of metal complexes, that is, mononuclear [Cu(H2O)2(κ O1,κN2 L1a] (3) and [Cu(H 2O)(κO1,κN3 L1b)] (4), tetranuclear [Cu4(1 κO1,κN2:2 κO1 L2a)3-(1 κO1, κN2:2 κO2 L2a)] (5), [Cu 2(H2O)(1 κO1, κN2:2 κO1 L2c)-(1 κO1,1 κN 2:2 κO1,2 κN1- L 2c)]2 (6) and [Cu2(H2O) 2(κO1,κN2- L1dd)-(1 κO1,κN2:2 κO1 L 1dd)(μ-H2O)]2× 2 H2O (7×2 H2O), as well as polymer- ic [Cu(H2O) (κO1,1 κN2:2 κN1 L 1c)]n (8) and [Cu(NH2C2H 5)(κO1,1 κN2:2 κN 1L2a)]n (9). The ligands 2-SO 3H-C6H4-(NH)N=C{(CN)[C(NH2)-(= NCH2CH2NH2)]} (H2L1b, 10), 2-CO2H-C6H4-(NH)N={C(CN)[C(OCH 3)-(=NH)]} (H2L2a, 11) and 2-SO 3H-C6H4-(NH)N=C{C(=O)-(NH2)} 2 (H2L1dd, 12) were easily liberated upon respective treatment of 4, 5 and 7 with HCl, whereas the formation of cyclic zwitterionic amidine 2-(SO3-)-C6H 4-N=NC(-C=(NH+)CH2CH2NH)(=CNHCH 2CH2NH) (13) was observed when 1 was treated with ethylenediamine. The hydrogen bond-induced E/Z isomerization of the (HL 1d)- ligand occurs upon conversion of [{Na(H 2O)2(μ-H2O)2}(HL 1d)]n (14) to [Cu(H2O)6][HL 1d]2×2 H2O (15) and [{CuNa(H 2O)-(κN1,1 κO2:2 κO 1 L1d)2}K0.5(μ-O) 2]n×H2O (16). The synthesized complexes 3-9 are catalyst precursors for both the selective oxidation of primary and secondary alcohols (to the corresponding carbonyl compounds) and the following diastereoselective nitroaldol (Henry) reaction, with typical yields of 80-99%. Copyright

Phosphonium ionic liquids exchanged with bicarbonate and methylcarbonate anions (CILs) exhibit catalytic performances comparable to those of sterically hindered (non nucleophilic) organosuperbases such as DBU. At 25-50 °C, under solventless conditions, CI

The zinc(ii) complexes with ortho-hydroxy substituted arylhydrazo-β- diketonates [Zn2(CH3OH)2(μ-L 1)2] (5), [Zn{(CH3)2SO}(H 2O)(L2)] (6), [Zn2(H

Metal complexes of boron-bridged bisoxazolines (borabox ligands) were evaluated as catalysts for the Henry reaction. Copper(II) complexes induced high enantio- and diastereoselectivity in reactions with nitroethane and nitropropane. The amount of base add

Potassium phosphate was found to catalyze condensation of nitroalkanes with various aliphatic and aromatic aldehydes to form nitroaldols in excellent yields in acetonitrile medium at room temperature.

A process of producing organic compounds, such as acetaminophen, nitroalcohols and indoles, employs a catalyst system of an oxyethylene ether and a metal containing inorganic or organic reagent. The oxyethylene ether at least partially complexes the metal of the inorganic or organic reagent. As such, the reactions may be conducted neat. The processes are environmentally friendly and operationally simple.

Our environmentally benign synthesis of nitroalcohols involves a simple solvent-free condensation of an appropriate aldehyde with a 1-nitroalkane utilizing a novel dual catalytic system consisting of a mineral base and an appropriate surfactant under homo

Bilirubin, the yellow pigment of jaundice, is a linear tetrapyrrole with a methylene group at its center, C(10), a position of crucial importance to its conformation and metabolism. The presence of the central methylene group allows the bilirubin to fold into an intramolecularly hydrogen-bonded conformation. This paper describes the first synthesis of a bilirubin analogue with an oxo group at C(10). The change from CH2 to C=O, from sp3 to sp2, is designed to stress the molecule at its hinge and relax its conformation. Such compounds have been suggested as potential oxidative metabolites of bilirubin in vivo. 10-Oxo-mesobilirubin-XIIIα (1) is a red crystalline solid, unlike its parent, mesobilirubin-XIIIα, which is a bright yellow solid. It is surprisingly polar, relative to the parent, yet it does not exhibit a significantly larger bicarbonate/chloroform partition coefficient. Like the parent, 1 appears to adopt an intramolecularly hydrogen-bonded ridge-tile-like conformation. In normal rats, 1 is metabolized to acylglucuronides, which are secreted into bile, but a portion of the administered dose is secreted into bile intact. In mutant rats (Gunn rats) lacking bilirubin glucuronyl transferase, 1 was excreted efficiently in bile in unchanged form, unlike the parent with a methylene group at C(10). Thus, introduction of the oxygen function at C(10) has little effect on hepatic uptake but a dramatic effect on canalicular secretion into bile.

The synthesis of 2-nitroalkanols from nitroalkanes and aldehydes occurs efficiently, in mild conditions without solvent, when mediated by layered Zr(KOPO3)2.The reaction has been tested in the preparation of ten different nitroalkanols and the data obtain

A general synthesis of 5-unsubstituted benzyl pyrrole-2-carboxylates was developed based on the reaction of β-nitroacetates with benzyl isocyanoacetate. The advantage of this route over other pyrrole syntheses was the regiochemical control of the substitution pattern on the pyrrole ring.

The present invention involves, in addition to many unique substituted sapphyrins, a novel method for synthesizing sapphyrins with good efficiency and high yield. An improved 9-step synthesis of substituted sapphyrins, e.g., the two C2 symmetric sapphyrins, compounds 2 and 4 of FIG. 1C, is described herein. This synthesis involves as an important step the condensation between a tripyrrane diacid and a diformyl bipyrrole. The key tripyrrane component is prepared in three high-yield steps from readily available pyrrolic precursors and the bipyrrole portion is prepared in four steps from ethyl 3-methyl-4-methylpyrrole-2-carboxylate in roughly 33% yield overall.

The synthesis and characterization of a variety of selectively metalated quinone-substituted zinc-containing octaalkyl porphyrin dimers, designed to mimic certain key electronic and structural aspects of the photosynthetic reaction centers of Rhodopseudom

Preparation of 2-nitro alkanols has been achieved by condensation of aldehydes with nitroalkanes in the presence of alumina-supported potassium fluoride.Nitroketones are produced by oxidation of nitroalkanols with montmorillonite - supported chromium trioxide.

1-Chloro-1-cyclopropyl-1-nitroethane and 2-chloro-2-nitrohept-6-ene underwent free radical chain substitution reactions in which the chlorine was replaced by the nucleophiles Me2C=NO2-, c-C3H5C(CH3)=NO2-, CH2=CH(CH2)3C(CH3)=NO2-, (EtO2C)2CMe-, Me3C(O-=CH2 or the enolate anion of 2-methyl-1,3-cyclopentanedione.Ring opening or closure reactions were not observed in these substitutions or in the reaction of 1-chloro-1-cyclopropyl-1-nitroethane with (n-Bu)3SnH to form 1-cyclopropyl-1-nitroethane.A 1-nitro substituent retards the rate of the cyclopropylcarbinyl radical ring opening by a factor of the at least 104 at 40 deg C.

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