Chloride In Acetone Research Articles

KINETICS OF QUATERNIZATION BETWEEN N, N-DIMETHYLANILINE AND BENZYL CHLORIDE IN POLAR SOLVENTS-A REVISIT TO MENSHUTKIN REACTION

This work reports an extension of Menshutkin reaction and involves the studies on kinetics of quaternization reaction between N,N-Dimethylaniline and benzyl chloride in acetone and in other various solvents at 300 K. The progress of the reaction was followed by measuring the conductance of the product formed at regular intervals of time. The effect of [benzyl chloride] and [N,N-Dimethylaniline] on reaction rate was studied under pseudo-first order condition and the rate showed first order dependence on both [benzyl chloride] and [N,N-Dimethylaniline]. The effect of dielectric constant of the medium on reaction rate was studied by employing various solvents such as methyl ethyl ketone, isopropyl alcohol, ethyl alcohol, methyl alcohol and acetonitrile and the rate is found to increase with increase in dielectric constant of the medium. The linear plot with a negative slope on plotting log k2 against 1/D where D is the dielectric constant of the medium indicates the existence of a highly charged or a polar transition state during the progress of the reaction. The quaternization reaction was also carried out at different temperatures so as to compute the various thermodynamic parameters like activation energy, enthalpy of activation, entropy of activation and Gibb’s free energy change. The higher value of activation energy is attributed for a slower reaction which is sterically controlled rather than thermodynamically controlled. The negative value of entropy of activation (ΔS*) indicates some sort of surrendering of disorder in the transition state on its formation which proves that it is highly ordered with sufficient charge separation and polar in character. The product after purification was analysed by melting point and infra-red spectral analysis and is proved to be N-Benzyl-N,N-dimethylphenylmethanaminium chloride. A plausible mechanism in accordance with the obtained experimental results is reported.

Radiolysis-Induced Crystallization of Sodium Chloride in Acetone by Electron Beam Irradiation.

In situ liquid cell transmission electron microscopy (LC-TEM) is an innovative method for studying the processes involved in the formation of crystals in liquids. However, it is difficult to capture early stages of crystallization because of the small field of view and the unfavorable changes in sample composition resulting from electron-beam radiolysis. Nevertheless, if the radiolysis required to induce the crystallization of a sample could be controlled in LC-TEM, this would be advantageous for observing the crystallization process. Here, we examined this possibility by using a mixture of sodium chlorate (NaClO3) and acetone in the LC-TEM. The electron beam induced the formation of dendritic crystals in a saturated acetone solution of NaClO3; moreover, these crystals consisted of sodium chloride (NaCl), rather than NaClO3, suggesting that chloride ions (Cl−), which were not present in the initial solution, were generated by radiolysis of chlorate ions ${\rm \lpar ClO}_3^- \rpar$. As a result, the solution then supersaturated with NaCl because its solubility in acetone is much lower than that of NaClO3. The combination of radiolysis and a solvent in which a solute is much less soluble is potentially useful for establishing crystallization conditions for materials that are difficult to crystallize directly in LC-TEM experiments.

6-Morpholino- and 6-amino-9-sulfonylpurine derivatives. Synthesis, computational analysis, and biological activity

The synthesis of novel 6-chloro/morpholino/amino/-9-sulfonylpurine derivatives was accomplished in two ways, either (i) involving the condensation reaction of 6-chloropurine with commercially available arylsulfonyl chlorides in acetone and the presence of aqueous KOH at 0 °C, followed by the substitution of C6-chlorine with morpholine, or (ii) employing a reversed synthetic approach where 6-morpholinopurine and commercially available adenine bases were reacted with the corresponding alkyl, 2-arylethene and arylsulfonyl chlorides giving the N9 sulfonylated products, the latter particularly used where prior nonselective sulfonylation was observed. In both approaches, the sulfonylation reaction occurred regioselectively at the purine N9 position lacking any concurrent N7 derivatives, except in the case of a smaller methyl substituent on SO2 and the free amino group at C6 of the purine ring. The tautomeric features of initial N9 unsubstituted purines, as well as stability trends among the prepared N-9-sulfonylpurine derivates, were investigated using DFT calculations with an important conclusion that electron-donating C6 substituents are beneficial for the synthesis as they both promote the predominance of the desired N9 tautomers and help to assure the stability of the final products. The newly synthesized 6-morpholino and 6-amino-9-sulfonylpurine derivatives showed antiproliferative activity on human carcinoma, lymphoma, and leukemia cells. Among the tested compounds, 6-morpholino 17 and 6-amino 22 derivatives, with trans-β-styrenesulfonyl group attached at the N9 position of purine, proved to be the most effective antiproliferative agents, causing accumulation of leukemia cells in subG0 cell cycle phase.

Synthesis of 6-aryl-7-arylazo-4-(N-substituted aminomethyl)-2H-thiazolo-[3, 2-a]-1, 3, 5-triazino-2-thiones as Antiviral Agents

2-amino-4-aryl thiazole was diazotised with different aromatic amines to give 2-amino-4-aryl-5-arylazo thiazoles. These compounds were refluxed with ammonium thiocyanate and chloroacetyl chloride in acetone to afford N1-chloroacetyl-N3-(4-aryl-5-arylazothiazol-2-yl)-thioureas. These thioureas were cyclized in presence of POCl3 and PCl5 to give 6-aryl-7-arylazo-4-chloromethyl-2H-thiazolo-[3, 2-a]-1, 3, 5-triazino-2-thiones. These compounds were reacted with secondary amines in methanol to give title compounds 6-aryl-7-arylazo-4-(N-substituted aminomethyl)-2H-thiazolo-[3,2-a-]1,3,5-triazino-2-thiones.Antiviral nature of these compounds was studied against Ranikhet Disease Virus (RDV), Vaccinia Virus (VV) and Sunnhemp Rosette Virus (SRV). Some of these compounds have been found to be active against RDV and Vaccinia Virus.

Synthesis of 5-aryl-2-ethylsulfanyl-[1,3,4]thiadiazolo[3,2,a][1,3,5] triazine-7-selones via a three-component condensation of 5-ethylsulfanyl-[1,3,4]thiadiazol-2-ylamine, potassium selenocyanate and an acyl chloride

A simple, one-pot synthesis of seven 5-aryl-2-ethylsulfanyl-[1,3,4]thiadiazolo[3,2,a][1,3,5] triazine-7-selones has been achieved in moderate to good yields via a three-component condensation of 5-ethylsulfanyl-[1,3,4]thiadiazol-2-ylamine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature.

Synthesis of 4-aryl-7-methoxy-9-thia-[1,3,4a]triazafluorene-2-selones via a three-component condensation of 6-methoxybenzothiazol-2-ylamine, potassium selenocyanate and an acyl chloride

A simple, one-pot synthesis of six 4-aryl-7-methoxy-9-thia-[1,3,4a]triazafluorene-2-selones has been achieved in moderate to good yields via a three-component condensation of 6-methoxybenzothiazol-2-ylamine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature.

Synthesis of 4-aryl-1,3,4a-Triazaphenanthrene-2-Selones via Three-Component Condensation of Quinolin-2-Amine, Potassium Selenocyanate and an Acyl Chloride

A three-component reaction between quinolin-2-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature provided a simple and efficient one-pot route for the synthesis of six 4-aryl-1,3,4a-triazaphenanthrene-2-selones in good yields.

Synthesis of 1-aryl-2,4,10a-Triazaphenanthrene-3-Selones Via a Three-Component Condensation of Isoquinolin-1-Amine, Potassium Selenocyanate and an Acyl Chloride

A simple, one-pot synthesis of six 1-aryl-2,4,10a-triazaphenanthrene-3-selones has been achieved with moderate to good yields via a three-component condensation of isoquinolin-1-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature.

Synthesis of fused 1,4-dihydropyridines as potential calcium channel blockers

Abstract Objective The aim of this study was to synthesize ten 1,4-dihydropyridine (DHP) derivatives in which substituted cyclohexane rings were fused to the DHP ring and to determine how different ester groups and the benzoyl substituent introduced in 4-phenyl ring affected their calcium channel blocking activity. Methods A microwave-assisted one-pot method was applied for the synthesis of compound 1–5 according to a modified Hantzsch reaction. The benzoyl moiety was introduced in the 4-phenyl ring of these dihydropyridines by refluxing with benzoyl chloride in acetone in the presence of anhydrous potassium carbonate. Synthesized products were characterized by elemental analysis, IR, 1H-NMR and 13C-NMR spectroscopy. The inhibitory actions of compounds 1–10 on calcium channel blocking activity were tested on isolated rat aorta preparations. Results The obtained pharmacological results showed that although all compounds are potent relaxing agents on isolated rat aorta smooth muscle, introduction of a benzoyloxy substitiuent on the phenyl ring (compound 6–10) decreased the relaxant effect of these compunds. Conclusion The reported 1,4-DHP derivatives have calcium channel blocking activity on rat aorta smooth muscle.

Natural Phosphate-Supported Palladium for Hydration of Aromatic Nitriles to Amides in Aqueous Medium

A new generation of natural phosphate-supported palladium was synthesized by treating natural phosphate with bis(benzonitrile)palladium(II) chloride in acetone. Its catalytic activity was evaluated in selective hydration of nitriles. The reactions proceeded in the presence of 0.4 mol% of the palladium catalyst at 160°C in water under microwave irradiation. Several nitriles, including aromatic and heteroaromatic nitriles, were converted to corresponding amides in good yields under neutral conditions. The recyclability and low cost availability of this solid support make this approach very attractive. It encourages new fields of research in the valorization of this natural resource and can change the current view of heterogeneous catalysis.

Pentamethylcyclopentadienyl-rhodium and iridium complexes containing (N^N and N^O) bound chloroquine analogue ligands: synthesis, characterization and antimalarial properties.

The synthesis and characterization of twenty new pentamethylcyclopentadienyl-rhodium and iridium complexes containing N^N and N^O-chelating chloroquine analogue ligands are described. The in vitro antimalarial activity of the new ligands as well as the complexes was evaluated against the chloroquine sensitive (CQS) NF54 and the chloroquine resistant (CQR) Dd2 strains of Plasmodium falciparum. The antimalarial activity was found to be good to moderate; although all complexes are less active than artesunate, some of the ligands and complexes showed better activity than chloroquine (CQ). In particular, rhodium complexes were found to be considerably more active than iridium complexes against the CQS NF54 strain. Salicylaldimine Schiff base ligands having electron-withdrawing groups (F, Cl, Br, I and NO2) in para position of the salicyl moiety and their rhodium complexes showed good antiplasmodial activity against both the CQS-NF54 and the CQR-Dd2 strains. The crystal structures of (η(5)-pentamethylcyclopentadienyl){N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)} chlororhodium(III) chloride and (η(5)-pentamethylcyclopentadienyl){(4-chloro-2-(((2-((7-chloroquinolin-4-yl)amino)ethyl)imino)methyl)phenolate)}chlororhodium(III) chloride are reported. The crystallization of the amino-pyridyl complex (η(5)-pentamethylcyclopentadienyl){(N(1)-(7-chloroquinolin-4-yl)-N(2)-(pyridin-2-ylmethyl)ethane-1,2-diamine)}chloroiridium(III) chloride in acetone resulted in the formation of the imino-pyridyl derivative (η(5)-pentamethylcyclopentadienyl){(N1-(7-chloroquinolin-4-yl)-N2-(pyridin-2-ylmethylene)ethane-1,2-diamine)}chloroiridium(III) chloride, the crystal structure of which is also reported.

A User-Friendly Procedure for the Preparation of Secondary Alkyl Chlorides

Secondary alkyl chlorides have been efficiently prepared from secondary alkyl sulfonates under mild and user-friendly conditions. The exchange reaction was generally performed by using benzyltributylammonium chloride in acetone (reflux, 30 min). Yields are excellent from functionalized, base-sensitive and hindered secondary alkyl sulfonates.

Synthesis of 2-methyl-2-(3-phenoxybenzoyloxy)propionitrile

2-Methyl-2-(3-phenoxybenzoyloxy)propionitrile was obtained by the reaction of the 3-phenoxybenzoic acid chloride with acetone cyanohydrine in the anhydrous diethyl ether in the presence of triethylamine as the hydrogen chloride acceptor: The synthesis was performed at room temperature (20–25°С) under stirring for 1 h using the 3-phenoxybenzoic acid chloride–acetone cyanohydrine–triethylamine in a molar ratio 1:1.2:1.2.

Synthesis,Crystal Structure and Antibacterial Activity of Nickel Complex with 5-Bromo-2- Hydroxyphenyl Ethyl Ketone Benzoyl Hydrazone

The title complex, [(C5H5N)Ni(C15H11N2O2Br)], was synthesized by the reaction of the 5-bromo-2-hydroxyphenyl ethyl ketone benzoyl hydrazone, pyridine ligand and nickel chloride in acetone. The crystal structure was determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 29.507(4) Ǻ, b = 7.7738(11) Ǻ, c = 20.205(3) Ǻ, β = 126.614(2)º, Z = 8, V = 3720.1(9) Ǻ3. Its crystal structure was determined and refined to a final R= 0.0304 for 8902 independent reflections. The center nickel atom is four-coordinated. The antibacterial activity of the ligand and its complex was also studied.The antibacterial experiments indicate that they have antibacterial activity to P.aeruginosa, S.aureus, E.coli and the complex has higher activity than the ligand.

Abstract

We report the synthesis of some mercaptotriazole derivatives in an effort to discover underlying structural requirements for antiviral activity. A preliminary antiviral study was performed and the contribution of the compounds to free radical processes was investigated. Because lipophilicity influences both biological activity and antioxidant potential we calculated lipophilicity and attempted to correlate this with antioxidant activity. Treatment of the N-(aryl)piperazineacetohydrazides (compounds 1) with 2,4-dichlorophenylisothiocyanate gave the N-(aryl)piperazinethiosemicarbazides (compounds 2) in good yield. Cyclization of these compounds after treatment with NaOH solution provided the corresponding 5-(4-aryl-1-piperazinylmethyl)-4-(2,4-dichlorophenyl)-4H-1,2,4-triazole- 3-thiols (compounds 3) in good yield. Reaction of compounds 3 with 2,4-dichloro- or 4-fluorobenzyl chloride in acetone in the presence of potassium carbonate gave the target compounds (compounds 4) in about 70% yield. The antioxidant effect of the compounds on non-enzymatic lipid peroxidation of rat hepatic microsomal membranes was studied. Most of the examined compounds were active at concentration of 0.1 mM and most were found to prevent dimethylsulphoxide oxidation moderately (20-50%) at a concentration tenfold less than that of dimethylsulphoxide. The interaction of the synthesized compounds with 1,1-diphenyl-2-picrylhydrazyl stable free radical was also studied. Correlation was found between the two expressions of calculated lipophilicity, antioxidant activity and the lipophilicity of the synthesized compounds, and a correlation was derived between antioxidant activity and delta logP, which expresses the compounds' hydrogen-bonding capacity.

Simultaneous Derivatization and Extraction of Primary Short-chain Aliphatic Amines Using an Ultrasonic-mixed Water-ionic Liquid Two-phase System for Liquid Chromatography

Here, we report on a procedure in which ultrasonic waves were used to mix a water-ionic liquid two-phase system to simultaneously derivatize amines with dansyl chloride and extract, and the resulting dansyl amines into an ionic liquid (IL) at room temperature within 15 min. The ILs used were room-temperature ionic liquids (RTILs), such as 1-alkyl-3-methylimidazolium hexafluorophosphate ([C(n)MIM][PF(6)], n = 4, 6, 8), which are insoluble in water, and can extract more than 88% of the total dansyl amines (Dns-amines) present in aqueous solution. The Dns-amines formed were separated by chromatography in 20 µL of RTIL in a mobile-phase gradient of acetonitrile-water flowing through an Agilent Zorbax SB-C18 column. The eluents were analyzed at 333 nm using a UV detector. The optimal analytical conditions were achieved by using the following: RTILs with a 4-carbon alkyl chain; a 7-mL water sample and 1 mL each of 5 mM dansyl chloride in acetone and 20 mM sodium tetraborate buffer for use with a fixed volume (1 mL) of IL; buffer pH of 10.4; duration of 15 min; and an acetonitrile-water ratio of 50:50 from zero time to 3 min, 80:20 from 4 to 10 min, and 50:50 from 11 to 16 min. In comparison to the single-phase hot-water (70°C) derivatization process reported earlier, the simultaneous process developed here showed a higher derivatization efficiency at the tested concentration. The linear range of analysis (0.14-7.14 mg/L) was determined, and the correlation coefficient (R) ranged from 0.9878 to 0.9980. Furthermore, the estimated percentage of recovery from amine-spiked river-water samples ranged from 76 to 108%. The method presented here is simple and fast, and does not involve the use of volatile organic extractants.

Cyclopalladated complexes of 4-aryl-2,1,3-benzothiadiazoles: new emitters in solution at room temperature

The cyclopalladation of the 4-aryl-2,1,3-benzothiadiazoles 1a-c with palladium acetate in acetic acid afforded the novel dimeric complexes 2a-c in good yields. These were then converted into the monomeric pyridine-, chloro-coordinated cyclometallated complexes 3a-c through reaction with lithium chloride in acetone and then pyridine in dichloromethane. All complexes were fully characterized by means of NMR, IR and elemental analysis. The X-ray structure of complex 2c revealed that it presents transoid geometry, whereas the X-ray structure of 3c shows that the pyridine ligand and the thiazole ring are mutually trans. Photophysical properties were investigated by means of UV-Vis absorption and fluorescence emission in solution. Solid-state diffuse reflectance UV-Vis spectra (DRUV) were also applied in order to better characterize the complexes photophysics in the solid state. All complexes present intense absorption at around 300 nm (λ(1)) via(1)LC transitions located in BTD ligands, and additional low energy absorption bands, higher than 450 nm (λ(2)) of (1)MLCT character. The complexes are fluorescent in solution at room temperature, where two emission bands could be observed, a high energy band (excitation @ λ(1)) ascribed to the ligand emission and an additional red shifted low intense band (excitation @ λ(2)) due to the complex emission.

Synthesis and structure of gold and copper complexes: [Ph3PhCH2P]+[AuCl4]−, [NH(C2H4OH)3]+[AuCl4]− · H2O, and [Ph3EtP] 2 + [Cu2Cl6]2−

Triphenylbenzylphosphonium tetrachloroaurate (I) and triethanolammonium tetrachloroaurate hydrate (II) were prepared by reacting tetrachloroauric acid in acetone with triphenylbenzylphosphonium and triethanolammonium, respectively. Triphenylethylphosphonium hexachlorodicuprate (III) was synthesized from triphenylethylphosphonium chloride and copper chloride in acetone. The crystal structures of complexes I to III were determined by single-crystal X-ray diffraction. The phosphorus atoms in complex I have a nearly undistorted tetrahedral coordination (CPC, 108.3°–110.6°; P-C, 1.788–1.793 A). The coordination of nitrogen atoms in the cations of complex II is a distorted tetrahedron (CNC, 111.7°–112.4°). The square coordination of aurum in I and II is only slightly distorted: the ClAuCl angles are 89.6°–90.3° (I) and 89.5°–90.6° (II) and the Au-Cl distances are 2.256–2.278 A I) and 2.280–2.285 A (II). The phosphorus atoms in complex III are tetracoordinated (CPC, 106.34°–111.73°; P-C, 1.790–1.795 A). The copper atoms in III have a distorted tetrahedral coordination (ClCuCl, 98.48°–144.85°; Cu-Cl, 2.1999–2.3263 A). The central fragment Cu2Cl2 in the anion of complex III is bent relative to the Cu2 axis (the chlorine atom deviates from the Cu2Cl plane by 0.27 A).

20-hydroxyecdysone oximes and their rearrangement into lactams

(E)-Oximes derived from 20-hydroxyecdysone diacetonides and 7,8-dihydro analog were converted into the corresponding lactams (6-oxo-5a-aza-5a-homo derivatives) via Beckmann rearrangement. 14,15-Anhydro-20-hydroxyecdysone (Z)-oxime under analogous conditions (reaction with p-toluenesulfonyl chloride in acetone in the presence of Na2CO3) gave rise to 20-hydroxyecdisone 20,22-acetonide (Z)-O-tosyloxime which did not undergo Beckmann rearrangement.

An Efficient Preparation, Spectroscopic Properties, and Crystal Structure of 1,1-Bis(4-[2-(dimethylamino)ethoxy]phenyl)-2-(3-guaiazulenyl)ethylene

Reaction of 2-(3-guaiazulenyl)-1,1-bis(4-hydroxyphenyl)ethylene with 2-chloroethyldimethylammonium chloride in acetone in the presence of K2CO3 at reflux temperature for 24 hours gives a new title compound in 89% yield. Spectroscopic properties and crystal structure of the target molecule are reported.