Dimethylformamide Chloride Research Articles

Synthesis and properties of asymmetricly substituted Mn(III)-nitro-phenylporphirins

Mn(III)-5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and Mn(III)-5,10,15-tri-(4-nitrophenyl)-20-phenylporphyrin were synthesized using the reactions of complex formation of corresponding porphyrins and metal exchange of their Cd complexes with MnCl2 in dimethylformamide. Partial reduction of Mn(III) to Mn(II) is observed upon dissolution of manganese(III) complexes in dimethylformamide. When NaOH solid is added to a solution of dimethylformamide and in ethanolamine unstable Mn(II) porphyrins are formed. The photochemical stability and oxidative degradation of Mn(III)-porphyrins have been studied. The metal exchange reaction of asymmetricaly substituted Cd(II)-porphyrins with manganese chloride in dimethylformamide has been studied. The kinetic parameters of the reaction were calculated. The influence of substituends and the nature of the salt on the kinetic parameters of the metal exchange reaction was revealed. The synthesized compounds were identified by methods UV-Vis, IR, 1H NMR spectroscopy and mass spectrometry.

Synthesis and characterization of novel polyurethanes, polypyridazine, and polyamide based on s‐1,2,4,5‐tetrazine

AbstractThe synthesis and analysis of new polymeric materials based on 1,2,4,5‐tetrazine are discussed in this study. Tetrazine was mixed with thermoplastic polyurethane in dimethylformamide (DMF) as solvent and dibutyl tin dilaurate as catalyst at 50°C for 24 h to create brush polyurethane‐urea, which was then reacted with an unsaturated center in dimethyl sulfoxide as solvent at 60°C for 48 h made of either polyenol or thermoplastic polyurethane through π–π interaction. Because 1,2,4,5‐tetrazine (red color) is known to act as an electron‐deficient dine in inverse electron demand Diels–Alder reactions and can be easily converted to pyridazine (peach color) via [4 + 2] cycloaddition with suitable followed by expulsion of molecular nitrogen (cycloreversion), we observed a highly colored red shift to peach and this monitor for this reaction. Additionally, polyamide was prepared via reaction of 3,6‐diamino‐1,2,4,5‐tetrazine with terephthaloyl chloride in DMF as a suitable solvent and triethylamine as basic catalyst at 0°C for 3 h and then 36 h at room temperature. The new polymers that were produced were elucidated by spectral data.

Complex formation of halogen substituted tetraphenylporphyrins and Cd(II)-tetraphenylporphyrins with MnCl2 in DMF

Reactions of complex formation of 5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin, 5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin and metal exchange of their cadmium complexes with manganese chloride(II) in dimethylformamide were investigated. ortho -Substituted manganese complexes were synthesized by prolonged refluxing of the corresponding porphyrins with an excess of MnCl2 in dimethylformamide. Using the metal exchange reaction of Cd(II)-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin and Cd(II)-5,10,15,20-tetra-(2,6-difluorophenyl) porphyrin, the corresponding Mn(III)-tetraphenylporphyrins were obtained. On the contrary, the coordination reactions of porphyrins substituted at the pyrrole and phenyl rings with manganese chloride in dimethylformamide proceed under mild conditions with the formation of complexes Mn(II)-2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin [the compound oxidizes in air to a mixture of Mn(II) and Mn(III)-porphyrins] and Mn(II)-2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetra-(2,6-difluorophenyl)porphyrin. The synthesized compounds were identified using UV-Vis, 1H NMR spectroscopy and mass-spectrometry. Metal exchange reaction of ortho -substituted Cd(II)-porphyrins and complex formation of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra-(2,6-dichlorophenyl)porphyrin with manganese chloride in dimethylformamide were studied by the spectrophotometric method. The kinetic parameters of the reactions were calculated. A strong effect of β- and ortho -substitution on the reactions of complex formation and metal exchange of the studied compounds was found.

Meso-nitro substitution as a means of Mn-octaethylporphyrin redox state controlling

Mn(II,III)- and Cd(II)-complexes of 5-mononitro-2,3,7,8,12,13,17,18-octaethylporphyrin, 5,15-dinitro-octaethylporphyrin, 5,10,15-trinitro-2,3,7,8,12,13,17,18-octaethylporphyrin and 5,10,15,20-tetranitro-2,3,7,8,12,13,17,18-octaethylporphyrin have been synthesized and identified. A comparative study of the coordination reactions of the corresponding porphyrin ligands with manganese (II) chloride and metal exchange of their cadmium complexes with manganese (II) chloride in dimethylformamide was carried out to find the optimal conditions for the synthesis of Mn(II, III)-porphyrins. The obtained compounds were identified by UV-vis, 1H NMR spectroscopy and mass spectrometry. The structural parameters of the synthesized compounds were calculated by the DFT method and their NBO analysis was carried out. The electrochemical properties of the synthesized manganese complexes were studied by the cyclic voltammetry method. It is shown that nitro substitution determines Mn-porphyrin redox state.

Transacylation in Ferrocenoyl-Purines. NMR and Computational Study of the Isomerization Mechanism

In the reaction of purines with ferrocenoyl chloride in dimethylformamide (DMF), a regioselective acylation occurred. The two products have been isolated and, according to detailed NMR analysis, identified as N7- and N9-ferrocenoylated isomers. In a more polar solvent, for example, in dimethylsulfoxide (DMSO), the two isomers interconvert to each other. The N7/N9 isomerization was followed by 1H NMR spectroscopy, until dynamic equilibrium was reached. Both kinetics and thermodynamics of the transacylation process are governed by a C6-substituent on the purine ring (R = NH2, Me, NHBz, OBz). The observed rate constant for the N7/N9-isomerization in the adenine system (R = NH2) is kobs = 0.3668 h-1, whereas the corresponding process in the C6-benzyloxypurine is 56 times slower. By use of density functional theory calculations and molecular dynamics simulations, several reaction pathways were considered and explored. Only the reaction mechanism involving DMSO as a nucleophilic reactant is in harmony with the experimental kinetic data. The calculated barrier (ΔG⧧ = 107.9 kJ/mol; at the M06L/6-311+G(d,p)/SDD level of theory) for this SN2-like reaction in the adenine system agrees well with the experimental value of 102.7 kJ/mol. No isomerization was detected in other organic solvents, for example, acetonitrile, N,N-dimethylformamide, or acetone, which indicated the exceptional nucleophilicity of DMSO. Our results raise a warning when treating or dissolving acylated purines in DMSO as they are prone to isomerization. We observed that the N7/N9-group transfer was specific not only for the organometallic moiety only, but for other acyl groups in purines as well. The relevance of this isomerization may be expected for a series of nucleobases and heterocyclic systems in general.

Synthesis and Spectral Characteristics of Sn(IV) Tetraphenylporphyrinates

Coordination reactions of 5,10,15,20-tetraphenylporphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin and metal-exchange reactions of their cadmium complexes with tin(II) chloride in dimethylformamide are described. Optimum conditions for the synthesis of Sn(IV) tetraphenylporphyrinates have been elaborated. The obtained substances have been identified by electron absorption spectroscopy, 1H NMR spectroscopy, and mass-spectroscopy.

STUDY OF CADMIUM OCTA(4-METHOXYPHENYL)PORPHYRINATE IN REACTION OF METAL EXCHANGE WITH TIN CHLORIDE IN DMF

Metal-exchange reaction for complexes with macrocyclic ligands refers to a special type of complex coordination interactions. The reaction of metal exchange has founded wide application for the synthesis of complexes of natural and synthetic porphyrins. In the general form, the metal-exchange reaction may be written as follows:MР + M/Xn(Solv)m-n® M/Р + MXn(Solv)m-nwhere МP and M/P are metalloporphyrins, M/Xn(Solv)m-n are metal salts of solvate complexes. Cd-octa(4-methoxyphenyl)porphyrin was obtained by the reaction of octa(4-methoxyphenyl)-porphyrin-ligand with cadmium chloride in the presence of potassium acetate in dime-thylformamide. The obtained compound was identified by the methods of UV-VIS spectroscopy, 1H NMR and mass-spectrometry. The reaction order on the salt and the complex of cadmium in the case of the reactions of the Cd-octa(4-methoxyphenyl)porphyrin metal-exchange with tin chloride in dimethylformamide is equal to 1. Thus, the metal-exchange reaction is bimolecular and its total rate obeys to the second-order kinetic equation. It is suggested that the metal-exchange reaction of Cd-оcta(4-methoxyphenyl)porphyrin with tin chloride in dimethyl-formamide proceeds through a bimolecular associative mechanism.

Synthesis and antimicrobial evaluation with DFT study for new thiazole derivatives

Two compounds,[2-amino-4-(4-nitro phenyl) 1,3-thiazole],(4) and [2-amino-4-(4-bromo phenyl) 1,3-thiazole],(5), were synthesized by refluxing thiourea (1) with each of para-ntiro and para-bomophanacyl bromides(2) and (3) respectively, in absolute methanol. Then, by reaction of [5] with 3,5-dinitrobenzoyl chloride in dimethylformamide (DMF) yielded (6) .On the other hand, reaction of (4) with chloroacetyl chloride in dry benzene afforded (7), which is upon treatment with thiourea in absolute methanol, afforded (8) . The characterization of the titled compounds were done utilizing FTIR spectroscopy, 1HNMR, CHNS elemental analysis and by measurements of their physical properties. The synthesized compounds had been screened for their, in vitro preliminary antimicrobial activity against four Gram positive bacteria (Staph. aureus, Micrococcus luteus, Bacillus subtilis and Bacillus pumilus), and four Gram negative bacteria (Pseud.aeroginosa, E.coli, Proteus mirabilis and Klebsiella pneumoniae)and three fungi species: (Saccharomyces cerevisiae, Candida Tropicalis and Candida albicans) using a minimum inhibitory concentration (MIC) of 100 µg\ml of derivative in dimethylsulfoxide, by well diffusion method.
 Compound (6) showed moderate antibacterial activity against some tested Gram positive bacteria (Bacillus pumilus and Bacillus Subtilis) and a moderate antifungal activity towards Candida albicans. Computational study was performed to calculate some of the thermodynamic parameters of synthesized derivatives by using density functional theory (DFT).

Cobalt(III) tetrabenzoporphyrin: Synthesis, spectral and coordination properties

Comparison of tetrabenzoporphyrin complexation reactions and transmetalation of cadmium(II) tetrabenzoporphyrinate with cobalt(II) acetate and chloride in dimethylformamide (DMF) has been carried out Cobalt(III) tetrabenzoporphyrinate has been prepared and identified. Acido ligands displacement in Co(III) tetrabenzoporphyrinate by pyridine, imidazole, and quinuclidine molecules has been studied.

Metal exchange reaction between Mg(II) and Cd(II) octa(4-bromophenyl)tetraazaporphyrinates with manganese(II) chloride in dimethylformamide

Reaction of metal exchange of Mg(II) and Cd(II) octa(4-bromophenyl)tetraazaporphyrinates with MnCl2 in dimethylformamide has been studied by means of spectrophotometry. Kinetic parameters of the reaction have been determined; the reaction stoichiometry mechanism has been suggested.

Preparation and spectral properties of β-bromo-substituted Mn(III) tetraphenylporphyrinates

Interaction of 5,10,15,20-tetraphenylporphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with manganese(II) chloride in dimethylformamide has been studied by means of spectrophotometry. The corresponding chloride acido complexes of manganese(III) has been so prepared and identified. The complexes could be reduced into manganese(II) tetraphenylporphyrinates in the presence of potassium hydroxide in dimethylformamide.

Study of the metal-exchange reaction between Cd(II) octa(4-bromophenyl)tetraazaporphyrinate and cobalt chloride in organic solvents

The metal-exchange reaction between Cd(II) octa(4-bromophenyl)tetraazaporphyrinate and cobalt chloride in dimethylformamide and dimethyl sulfoxide was studied by spectrophotometry. Kinetic parameters of the metal-exchange reaction were determined. A possible stoichiometric mechanism of the reaction was proposed. Cobalt(III) octa(4-bromophenyl)tetraazaporphyrinate was synthesized and characterized.

Transmetalation of (octaphenyltetraazaporphyrinato)magnesium(II) with manganese(II) chloride in dimethylformamide

The reaction of (octaphenyltetraazaporphyrinato)magnesium(II) with manganese(II) chloride in dimethylformamide gave (chloro)(octaphenyltetraazaporphyrinato)manganese(III). Reactions of the latter with nitrogen-containing bases were studied. The kinetic parameters of the transmetalation of (octaphenyltetraazaporphyrinato) magnesium(II) with MnCl2 in dimethylformamide at 323, 333, and 343 K were determined, and a probable reaction mechanism was proposed.

Crystal structure of chloro-(5,10,15,20-tetraphenylporphyrinato)-manganese, C44H28ClMnN4

Abstract C44H28ClMnN4, monoclinic, P21/c (no. 14), a = 12.3044(6) Å, b = 21.688(1) Å, c = 17.0016(8) Å, β = 123.536(3)°, V = 3781.9 Å3, Z = 4, Rgt(F) = 0.0645, wRref(F2) = 0.0939, T = 293 K

N-(4-Methoxybenzyl)phthalimide: a triclinic polymorph

The title compound [systematic name: 2-(4-meth­oxy­benz­yl)­isoindoline-1,3-dione], C16H13NO3, represents a triclinic polymorph of the previously reported monoclinic form [Warzecha et al. (2006 ▶). Acta Cryst. E62, o5450–o5452]. The reaction of potassium phthalimide and 4-meth­oxy­benzyl chloride in dimethyl­formamide gave platelet-shaped crystals; these were harvested and then needle-shaped crystals were deposited. The platelet- and needle-shaped crystals correspond to the triclinic and monoclinic forms, respectively. The N—C—Car—Car torsion angles between the ring systems are −82.66 (14) and 95.28 (13)°, resulting in a roof-shaped conformation. In the crystal, mol­ecules are accumulated by offset face–face π–π inter­actions between phthalimide units [centroid–centroid distances = 3.640 (2) and 3.651 (2) Å], with inter­planar distances of 3.321 (1) and 3.435 (1) Å. Weak inter­molecular Car­yl—H⋯O=C and Calk­yl—H⋯O=C contacts form C(8) and C(11) infinite chain motifs, respectively.

Synthesis and Kinetic Study of Thermal Cycloimidization of Novel Poly(Amide Amic Acid) to Poly(Amide Imide) by Thermogravimetric Analysis

A new series of fluorinated poly(amide imide)s (PAIs) were prepared by polycondensation of diamine amic acid (DAA) with isophthaloyl, terephthaloyl, or trimellitic anhydride chloride in dimethylformamide, and their subsequent thermal cycloimidization. DAAs were obtained by reacting 4, 4′ (hexafluoroisopropylidene) diphthalic anhydride (6FDA) with diamines in dimethylformamide at 0–5°C. The kinetics of thermal cycloimidization of poly(amide amic acid) (PAA) to PAIs was investigated by thermogravimetric analysis under isothermal conditions at four different temperatures, i.e. 175, 200, 225, and 260°C, for 75 min. A generalized equation to calculate the theoretical amount of weight loss upon complete imidization, i.e. Tw % = 18Nw/R Mw, was developed. In the above equation numeral 18 corresponds to the molecular weight of water, N is the number of water molecules, which are eliminated per repeat unit of PAA upon cycloimidization, w is the weight of PAA taken for TGA, and R Mw is the molecular weight of the repeat unit of PAA. The polymers were characterized by FT-IR spectra. Complete cycloimidization process is discussed in terms of monomer structure (diamines and acid chlorides), effect of imidization temperature and time, types of linkages (meta or para) present, and influence of electron withdrawing groups, such as sulfone, in the monomer structure. It was observed that cycloimidization occurred at a faster rate at the beginning, up to about 30 min, and then proceeded at a slower rate till the end of curing. The thermal and thermooxidative stabilities of PAIs were also investigated in nitrogen and oxygen atmosphere.

1-Benzyl-3-[(trimethylsilyl)methyl]benzimidazolium chloride monohydrate

The title compound, C18H23N2Si+·Cl−·H2O, was synthesized from 1-[(trimethyl­sil­yl)meth­yl]benzimidazole and benzyl chloride in dimethyl­formamide. The benzimidazole ring system is approximately planar, with a maximum deviation of 0.022 (2) Å, and makes an angle of 74.80 (12)° with the phenyl ring. The crystal packing is stabilized by O—H⋯Cl, C—H⋯Cl, C—H⋯O and C—H⋯π inter­actions between symmetry-related mol­ecules together with π–π stacking inter­actions between the imidazolium and benzene rings [centroid–centroid distance = 3.5690 (15) Å] and between the benzene rings [centroid–centroid distance = 3.7223 (14) Å].

Dichloridobis[5-nitro-1-trimethylsilylmethyl-1H-benzimidazole-κN3]cobalt(II)N,N-dimethylformamide solvate

The title compound, [CoCl2(C11H15N3O2Si)2]·C3H7NO, was synthesized from 5-nitro-1-trimethyl­silylmethyl-1H-benzimid­azole and cobalt(II) chloride in dimethyl­formamide. The CoII atom is coordinated in a distorted tetra­hedral environment by two Cl atoms and two N atoms. In the crystal structure, there are a number of C—H⋯Cl and C—H⋯O hydrogen-bonding inter­actions between symmetry-related mol­ecules.

1,3-Difurfurylbenzimidazolium chloride monohydrate

The title compound, C17H15N2O2 +·Cl−·H2O, was synthesized from benzimidazole and furfryl chloride in dimethyl­formamide. The cationic benzimidazolium ring is connected to two furan rings via methyl­ene bridges. The furan rings make dihedral angle of 79.09 (18)° with respect to each other, and make dihedral angles of 73.92 (12) and 72.58 (13)° with respect to the benzimidazole ring. O—H⋯Cl, C—H⋯O and C—H⋯Cl hydrogen bonds and C—H⋯π inter­actions contribute to the stabilization of the crystal structure. Furthermore, there is a π–π inter­action between adjacent five- and six-membered rings of the benzimidazole groups [centroid–centroid distance = 3.5305 (8) Å].

Microwave Irradiation 및 촉매로서 실리카 지지 술팜산을 사용한 아닐 리드의 합성(Beckmann 자리옮김 반응)

A unique product of 1;2 Shift, Beckmann reaction has it’s good many synthesis application. Beckmann reaction is a general tool in organic chemistry. The reaction requires high reaction temperature; strong acidic conditions and dehydrating media. Amides are important biological and commercial compounds. Because amide constitutes the backbone of protein molecules, their chemistry is of extreme importance. The penicillin and cephalosporin antibiotics are among the best-known products of the pharmaceutical industry. Keep all such things in mind we go for preparation of anilides, which also contribute excellent role to synthesis, various organic compounds. The Beckmann rearrangement requires strong acidic conditions such as conc. Sulphuric acid or Phosphoric acid these have a large amount of side products and serious corrosion problems. So, In recent days the milder conditions were tried and investigated on clean, simple, ecofriendly benign and excellent process became the chemists interesting undertaking. Several improved or developed process are reported using modified reagents and solid acid catalyst like clay, zeolites and silica sulfuric acid. However, the reactions are sluggish when they are performed in the liquid phase. Relatively few solid phase methods have been developed. Also the Beckman reaction using a Stoichiometic amount of cynuric chloride and Dimethyl formamide salt, Reactions was observed with solvents other than Dimethyl formamide and the reaction rate decreased noticeably with a reduced amount of cyanuric chloride in Dimethyl formamide. Also some methods are available for one-pot Beckmann reaction of Acetophenone (ketone). Hence, overcome all such disadvantages we report clean, effective, and simple method for one-pot synthesis of anilides in presence of catalytic amount of silica supported Sulphamic acid using microwave irradiation under solvent free condition.