Chloroform Chloride Research Articles

A Simple Way to Obtain a Decachloro Derivative of Cobalt Bis(dicarbollide)

A simple synthetic way to obtain a decachloro derivative of cobalt bis(dicarbollide) has been found. The reaction of cesium salt of cobalt bis(dicarbollide) anion with aluminum chloride in chloroform under reflux conditions results in Cs[3,3′-Co(4,7,8,9,12-Cl5-1,2-C2B9H6)2] of high purity and good yield.

One step derivatization and dispersive liquid-liquid microextraction of hydroxychloroquine sulfate for its sensitive and accurate determination using GC–MS

In the present study, a novel analytical method for the determination of hydroxychloroquine sulfate in human serum and urine samples was established. One step derivatization and dispersive liquid-liquid microextraction (DLLME) was developed for quantitative determination of hydroxychloroquine sulfate in aqueous samples. Hydroxychloroquine sulfate was first hydrolyzed and converted to its benzoate derivative by adding benzoyl chloride in chloroform which also served as extraction solvent. Significant parameters such as type/volume of extraction and dispersive solvents, concentration/volume of sodium hydroxide, type/period of mixing and concentration of derivatizing agent were carefully optimized by one variable at a time approach. Under the optimum DLLME conditions, limit of detection (LOD), quantitation (LOQ) and dynamic range were calculated as 35.2, 117.2 and 96–1980 μg/kg (ppb), respectively. Recovery studies were conducted by spiked human serum and urine samples and the results were ranged between 93 and 107% with low standard deviations. Developed method can be easily used in hydroxychloroquine sulfate based SARS-CoV-2 and malaria treatment studies.

Development and validation of the HPLC-DAD method for the quantification of 16 synthetic dyes in various foods and the use of liquid anion exchange extraction for qualitative expression determination

Synthetic dyes can cause many health problems, and their use as food additives is rigorously regulated worldwide. Two methods for the determination of synthetic dyes in food are described in this article. The visual qualitative expression method was based on the extraction of synthetic dyes using a liquid anion exchanger (0.01 M solution of trioctylmethylammonium chloride in chloroform). Using this reagent, an optimal transition of 15 anionic synthetic dyes from the aqueous to the organic phase was achieved (R > 99.8%). It was applicable for testing food that must not contain synthetic dyes (wines, juices, etc.) in a very short time (5–10 min). In the case of colouring of the organic phase, identification and quantification was carried out using the HPLC-DAD method described. The rapid and simple method allows for simultaneous determination of 16 synthetic dyes from all food types. The LOD and LOQ ranged from 0.026 to 0.086 μg mL−1 and from 0.077 to 0.262 μg mL−1 respectively, and recovery was 83.7–107.5%.Hypothesis: anionic synthetic dyes have hydrophobic properties, as a result they are retained on the non-polar stationary phase of the chromatographic column and are easily extracted from aqueous solutions by liquid anion exchangers.

Synthesis and Cytotoxic Activity of Some Novel Thieno[2,3-d:4,5-d’]Dipyrimidine Derivatives

Synthesis of some novel tricyclic compounds bearing thienodipyrimidine moiety by the reaction of ethyl 6-amino-1,3-dimethyl-2,4-dioxo-1,2,3,4-tetrahydrothieno[3,2-d]pyrimidine-7-carboxylate (1) with different types of aromatic amines to give the corresponding carboxamide derivatives 2-11, which cyclized with triethyl orthoformate in acetic anhydride to afford thieno[2,3-d:4,5-d']dipyrimidine derivatives 12-15 is described. Similarly, thieno[2,3-d:4,5-d']dipyrimidine derivative 17 was also prepared via the reaction of carboxamide derivative 2 with chloroacetyl chloride in chloroform to give thieno[3,2-d]pyrimidine-7-carboxamide derivative 16, followed by a cyclization in boiling acetic anhydride. The structure of these compounds was confirmed on the basis of their spectral and analytical data such as IR, 1H-NMR, 13C-NMR spectroscopy and mass spectral data. The synthesized compounds were screened for their cytotoxic activity.

α,α′,α″,α′″-meso-tetrahexyltetramethyl-calix[4]pyrrole: an easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

α,α′,α″,α′″-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1 or 2)Cl− in both NMR and extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. The free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.

Convergent heteroditopic cyclo[6]aramides as macrocyclic ion-pair receptors for constructing [2]pseudorotaxanes.

A strategy of using amide groups as the only functionality was developed to construct convergent heteroditopic cyclo[6]aramides that are able to strongly bind dibutylammonium chloride in chloroform (>10(5) M(-1)), leading to the formation of [2]pseudorotaxanes.

Anticomplement activity of isolated compounds from Artemisia montana

The study evaluated the anticomplement activity from isolated compounds from Artemisia montana (Nakai) Pamp. from South Korea on the classical pathway. In a previous work, A. montana (Nakai) Pamp. chloroform extracts showed inhibitory activity against complement system. The chromatographic separation of a chloroform chloride extract of A. montana (Nakai) Pamp. led to the isolation of four compounds. Their structures were characterized to be ezoartemin (1), yamayomoginin (2), ezomontanin (3) and 11,13-dihydroezomontanin (4) by spectroscopic data. This is the first report of anticomplement activity of isolated compounds from A. montana (Nakai) Pamp.

Syntheses, Electronic Structures, and EPR/UV−Vis−NIR Spectroelectrochemistry of Nickel(II), Copper(II), and Zinc(II) Complexes with a Tetradentate Ligand Based on S-Methylisothiosemicarbazide

Template condensation of 3,5-di-tert-butyl-2-hydroxybenzaldehyde S-methylisothiosemicarbazone with pentane-2,4-dione and triethyl orthoformate at elevated temperatures resulted in metal complexes of the type M(II)L, where M = Ni and Cu and H(2)L = a novel tetradentate ligand. These complexes are relevant to the active site of the copper enzymes galactose oxidase and glyoxal oxidase. Demetalation of Ni(II)L with gaseous hydrogen chloride in chloroform afforded the metal-free ligand H(2)L. Then by the reaction of H(2)L with Zn(CH(3)COO)(2)·2H(2)O in a 1:1 molar ratio in 1:2 chloroform/methanol, the complex Zn(II)L(CH(3)OH) was prepared. The three metal complexes and the prepared ligand were characterized by spectroscopic methods (IR, UV-vis, and NMR spectroscopy), X-ray crystallography, and DFT calculations. Electrochemically generated one-electron oxidized metal complexes [NiL](+), [CuL](+), and [ZnL(CH(3)OH)](+) and the metal-free ligand cation radical [H(2)L](+•) were studied by EPR/UV-vis-NIR and DFT calculations. These studies demonstrated the interaction between the metal ion and the phenoxyl radical.

Reductive Ring‐Opening of Phthalan and Isochroman: Application to the Stereoselective Synthesis of Tetrahydroisoquinolines and Tetrahydrobenzazepines

AbstractThe reaction of the dianionic intermediates 2a,b resulting from the lithiation of phthalan (1a) and isochroman (1b) with chiral N‐tert‐butylsulfinyl aldimines 9 in the presence of ZnMe2 gave, after hydrolysis, N‐tert‐butylsulfinyl amino alcohols 10 and 13, respectively, with high diastereoselectivity. Successive treatment of compounds 10 and 13 with hydrogen chloride in methanol, thionyl chloride in chloroform and sodium hydroxide led to the formation of tetrahydroisoquinolines 19 and tetrahydrobenzazepines 20. Depending on the structure of the starting chiral imine 9, benzoindolizidine 21, benzoquinolizidine 22 and benzopyrroloazepine 23 are also accessible through this methodology.

Cage-like amines in the synthesis and oxidation of camphor-10-sulfonic acid amides

Reactions of bicyclo[2.2.1]hept-5-en-exo- and -endo-2-ylmethanamines, exo-5,6-epoxybicyclo-[2.2.1]hept-exo-2-ylmethanamine, 1-(bicyclo[2.2.1]hept-2-yl)ethanamine, and 1-(1-adamantyl)ethanamine with camphor-10-sulfonyl chloride in chloroform in the presence of triethylamine gave the corresponding sulfonamides having two cage-like fragments. Stereoisomeric N-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)camphor-10-sulfonamides were oxidized with peroxyphthalic acid generated in situ from phthalic anhydride and 50% hydrogen peroxide. The exo stereoisomer was thus converted into the corresponding 5,6-epoxy derivative, while the endo isomer gave rise to 4-(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1-ylmethyl)-4-azatricyclo[4.2.1.03,7]-nonan-exo-2-ol (substituted azabrendane). The structure of the synthesized camphor-10-sulfonamides was confirmed by IR and 1H and 13C NMR spectra with the use of homo- (COSY) and heteronuclear 1H-13C correlation techniques (HMQC, HMBC). Heterocyclization of sulfonamides of the norbornene series was also simulated by quantum-chemical calculations at the PM3 and BHandHLYP/6-31G(d) levels of theory.

Stereoselective synthesis of 3-substituted tetrahydroisoquinolines from phthalan and chiral N-sulfinylimines

The reaction of the dianionic intermediate [resulting from the reductive opening of phthalan ( 1) with lithium] with chiral N- tert-butylsulfinyl aldimines 3 in the presence of ZnMe 2 gives, after hydrolysis, N- tert-butylsulfinyl amino alcohols 4 with high diastereoselectivity. Successive treatment of compounds 4 with hydrogen chloride in methanol, thionyl chloride in chloroform and sodium hydroxide yields 3-substituted tetrahydroisoquinolines 6.

Heterocyclic analogs of 5,12-naphthacenequinone 7*. Synthesis of naphtho-[2,3-f]isatin-5,10-dione derivatives

On chlorination of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione with sulfuryl chloride in chloroform, its mono-, di-, and trichloro derivatives are formed depending on the conditions. Hydrolysis of the di- and trichloro derivatives gives a new polycondensed derivative of isatin, 4,11-dimethoxynaphtho-[2,3-f]isatin-5,10-dione. Its demethylation occurs effectively on extended heating with HBr in acetic acid and leads to 4,11-dihydroxynaphtho[2,3-f]isatin-5,10-dione (4,11-di-hydroxynaphtho[2,3-f]indole-2,3,5,10-tetraone).

Development of a radiochemical neutron activation analysis procedure for determination of rhenium in biological and environmental samples at ultratrace level

Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed for accurate determination of rhenium in biological and environmental samples at the sub-ng . g-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng . g-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng . g-1 was found. Significantly elevated values of Re, up to 90 ng . g-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated 99Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process.

Synthesis, Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

AbstractThe reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H2AMTTO, 1) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO (2). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)2CuCl}2]·2CHCl3 (3). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh3)2] (4) and [(CAMTTO)Ag(PPh3)2]NO3·2CHCl3 (5). All compounds have been characterized by elemental analyses, 1H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by 31P{1H} NMR spectroscopy. Crystal data for 2 at −80 °C: monoclinic, space group P21/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R1 = 0.0379; for 3 at −80 °C: monoclinic, space group P21/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R1 = 0.0746; for 4 at −80 °C: triclinic, space group ${\rm P}{\bar 1}$, a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R1 = 0.0359 and for 5 at −80 °C: triclinic, space group ${\rm P}{\bar 1}$, a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R1 = 0.0487.

Regioregular poly(3‐alkylthiophenes): Synthesis, characterization, and application in conductive fabrics

AbstractPoly(3‐dodecylthiophene) (P3DDT) and poly(3‐decylthiophene) (P3DT) with high contents of head‐to‐tail linkages (86 and 85%, respectively) were synthesized in high yields by a facile oxidative polymerization with ferric chloride in chloroform at room temperature. We believe that the low concentration and ultraslow addition of monomers to ferric chloride contributed to the high regioregularity. Differential scanning calorimetry thermograms indicated that the formed polymers consisted of crystalline, quasiordered, and disordered phases, which is a common feature of highly regioregular polymers. We prepared conductive fabrics with specific resistance of 30 and 100 Ω/sq by impregnating polyamide fabrics in a chloroform solution of P3DDT and P3DT, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2131–2135, 2004

The photohydrochlorination of platinum(IV) chloride in chloroform

When irradiated at 240 nm, PtCl 4 in CHCl 3 is converted to H 2PtCl 6. When irradiated at wavelengths longer than 265 nm, PtCl 4 is converted to H 2PtCl 4 and H 2PtCl 6 in equal amounts. The latter reaction is suggested to proceed by dissociation of chlorine from a ligand to metal charge transfer excited state of Pt(IV) through a Pt(III) intermediate that disproportionates. The 240 nm photoreaction includes a second, solvent-initiated pathway, suggested to involve CCl 3 radicals from the photolysis of chloroform, which attack the PtCl 4 oligomer to create a Pt(V) intermediate.

The photolysis of iron(III) chloride in chloroform

In air-saturated solutions, iron(III) chloride functions as a long wavelength sensitizer of the photolysis of chloroform. In the presence of oxygen, irradiation of chloroform solutions of iron(III) chloride at wavelengths above 340 nm leads to the formation of HFeCl 4, followed by continued production of HCl and C 2Cl 6 as chlorine photodissociates from HFeCl 4, while the Fe(II) species formed is reoxidized. When iron(III) chloride is photolyzed in the absence of oxygen, conversion to HFeCl 4 and reduction to colloidal FeCl 2 occur simultaneously, ending in complete reduction. Both CCl 3OO and CCl 3OOH appear to participate in the reoxidation of iron(II) chloride.

Coordination chemistry of lipoic acid and related compounds.

N-(1-Adamantyl)lipoamide (2) has been prepared from racemic lipoic acid and reacted with hydrogen chloride in chloroform to afford [H(2)2]Cl·xCHCl3 (3). 1H and 13C NMR spectra of 3 in CDCl3 show that 2 is protonated at the carbonyl oxygen atom. There are no indications of protonation at the amide N atom or the 1,2-dithiolane S atoms. X-Ray crystal structure analysis of 3 revealed the presence of the O-protonated dimer [H(2)2]+. The central part of this proton complex consists of a CO⋯H+⋯OC hydrogen bridge with a short O⋯O distance of 2.439(4) Å. The CO bonds [1.273(5) and 1.282(5) Å] are significantly lengthened and the (O)C–N bonds [1.313(5) and 1.311(5) Å] are shortened compared to the typical bond lengths in non-protonated secondary amides. The chloride ions interconnect the [H(2)2]+ complexes into infinite chains via N–H⋯Cl−⋯H–N bridges [N⋯Cl 3.222(3) and 3.229(3) Å] and bind the solvent molecules via Cl3CH⋯Cl− hydrogen bonds [C⋯Cl 3.361(6) and 3.386(7) Å]. Theoretical DFT and MP2 investigations on the model complex [H(4)2]+, where 4 is N-methylacetamide, indicate that the central proton is highly dynamic. It can almost freely shift within a ±0.1 Å range around the center of the O⋯O separation.

Mechanism-controlled regioselective synthesis of indolyl benzo[ b]carbazoles

Benzo[ b]carbazoles can be synthesised readily and in good yields from the combination of 2,3-unsubstituted indoles and o-phthaldialdehyde in the presence of acid catalysts. Use of phosphoryl chloride in chloroform gives rapid reactions and yields 11-(3-indolyl)benzo[ b]carbazoles, whereas the use of p-toluenesulfonic acid in methanol gives slow reactions and yields the isomeric 6-(3-indolyl)benzo[ b]carbazoles.

The synthesis and reactions of dialkyl fluoroalkyl phosphates

Dimethyl and diethyl fluoroalkyl phosphates were prepared from (1) a dialkyl phosphite with a fluoroalcohol, triethylamine and carbon tetrachloride, (2) a dialkyl chlorophosphate with a fluoroalcohol and triethylamine, and (3) a dialkyl chlorophosphate with the sodium salt of a fluoroalcohol. Dimethyl and diethyl (2,2,2-trifluoroethyl) phosphates reacted with bromotrimethylsilane (TMSBr) in chloroform to give two products with loss of alkyl bromide. The major product was an alkyl (trifluoroethyl) trimethylsilyl phosphate, RO(TMSO)P(O)OCH 2CF 3 and the minor product was a bis(trimethylsilyl) trifluoroethyl phosphate, (TMSO) 2P(O)OCH 2CF 3. The mechanism presumably involves initial attack of an alkoxy oxygen atom on the silicon atom of bromotrimethylsilane. Diethyl (2,2,2-trifluoroethyl) phosphate is resistant to chlorination. It did not react with oxalyl or thionyl chloride in chloroform under prolonged reflux. Unlike triethyl phosphate, it did not react with phosphorus oxychloride in chloroform under reflux.