Anhydrous Aluminium Trichloride Research Articles

The preparation of hexaphenylsilole-based conjugated microporous polymer for fluorescence sensing o-nitrophenol

A first hexaphenylsilole-based conjugated microporous polymer, termed THPS, was prepared by a Friedel-Crafts arylation reaction of 1,1,2,3,4,5-hexabenylthirole with 2,4,6-trichloro-1,3,5-triazine catalyzed by anhydrous aluminium trichloride (AlCl3) in 1,2-dichloroethane. Its Brunauer–Emmett–Teller and Langmuir surface area reached up to 1579 and 2081 m2 g−1, and total pore volume and micropore pore volume were severally 0.8325 and 0.7322 cm3 g−1. THPS could fluorescence-sense o-nitrophenol with high sensitivity and selectivity. Its fluorescence quenching constant (KSV) and limits of detection (LODs) were severally 8.32 × 103 L mol−1 and 3.61 × 10-10 mol L−1. The fluorescence quenching of THPS by o-nitrophenol was originated from the combined action of both photo-induced electron transfer mechanism and resonance energy transfer mechanism.

Preparation and characterization of glucose-based covalent organic polymer coated silica as stationary phase for high-performance liquid chromatography

Carbohydrate is a renewable, sustainable, hydrophilic, and biodegradable natural product, which is widely used in the field of adsorption. In this study, a glucose-based covalent organic polymer (COP) coated silica was fabricated by facile solvent knitting reaction between tetrabenzylglucose and silica-phenyl with anhydrous aluminum trichloride as catalyst, forming a core-shell stationary phase (donated as SiO2@COPBn-glu) for high performance liquid chromatography. The prepared SiO2@COPBn-glu was characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectrometry, solid-state 13C nuclear magnetic resonance spectrometry, X-ray photoelectron spectroscopy, and N2 adsorption-desorption experiments. Owing to the coexistence of benzene units and alkyl, hydroxyl and ether groups in the skeleton of COPBn-glu shell, the developed chromatographic packing exhibited reversed-phase/hydrophilic interaction mixed-mode with multiple retention mechanisms, such as hydrophobic, π-π, hydrogen bonding, and electron donor-acceptor interactions. The results revealed that the SiO2@COPBn-glu column demonstrated excellent selectivity and retention behavior for both hydrophilic and hydrophobic compounds with good repeatability and stability. Meanwhile, the chromatographic performance of the prepared SiO2@COPBn-glu column was compared with a C18 column to assess the role of the coating COPBn-glu shell. Therefore, the development of the SiO2@COPBn-glu stationary phase expands the potential application of COPs in separation field.

An eight‐membered cyclosiloxane conjugated microporous polymer performed a rapid and sensitive fluorescence detection of 2,4‐dinitrophenol

AbstractA nitrogen‐rich porous inorganic–organic hybrid polymer, TMPS, was successfully synthesized by Friedel–Crafts arylation with anhydrous aluminum trichloride as a catalyst, which has good sensitivity to nitro‐aromatic compounds. The material was systematically characterized by using FT‐IR, solid‐state 13C NMR, elemental analysis, powder X‐ray diffraction, solid‐state UV–Vis, and so forth. The thermogravimetric analysis experiments confirmed that TMPS has very good thermal stability. Its Brunauer Emmett Teller specific surface area measured by nitrogen adsorption desorption experiment is 115 m2 g−1. Due to its excellent conjugated structure and nitrogen‐rich features, TMPS exhibits a very high sensitivity and selectivity to 2,4‐dinnitrophenol. Based on the data obtained from the fluorescence detection experiment, the KSV and limit of detection are 1.84 × 104 L mol−1 and 1.63 × 10−11 mol L−1, respectively. Therefore, TMPS can act as a fast and sensitive fluorescent sensor to detect DNP.

2D-QSAR study of synthesized novel derivatives of 1,3,4- Oxadiazoles as anti-inflammatory activity

Oxadiazole is a five-membered heterocyclic compound containing oxygen and two nitrogen atoms at C-1, C-3 and C-4 positions respectively. These derivatives are synthesized by both conventional as well as microwave-assisted. 1,3,4-Oxadiazole have reported a wide spectrum of activities such as antibacterial, antimalarial, anti-inflammatory, antioxidant, antipyretic, and antihypertensive activities Hence, some new 1,3,4–oxadiazoles will be synthesized from 4-(morpholine-4-yl) benzohydrazide (Compound IV) refluxed with ethyl chloroformate followed by amino acid and hydrazine hydrate gives 2-({5-[4-(morpholine-4-yl) phenyl]-1,3,4-oxadiazol-2-yl}amino) acetohydrazide (Scheme-IV) which is treated with aromatic aldehyde gives 1,3,4-oxadiazoles derivatives. Compound IV refluxed with ethyl chloroformate in presence of anhydrous potassium carbonate gives an intermediate product which is treated with phosphoric tri-chloride followed by thionyl chloride gives 4-[4-(5-chloro-1,3,4-oxadiazol -2-yl)phenyl] morpholine (Scheme-V) it undergoes reflux with substituted aromatic aldehydes in presence of anhydrous aluminium trichloride in ethanol or THF (tetrahydrofuran) gives 1,3,4-oxadiazoles derivatives. These synthesized compounds were subjected to 2D-QSAR study. A series of 28 molecules belonging to 2-({5-[4-(morpholine-4-yl) phenyl]-1,3,4-oxadiazol-2-yl}amino) acetohydrazide reaction scheme-SMRB4 and 4-[4-(5-chloro-1,3,4-oxadiazol-2-yl)phenyl] morpholine reaction scheme-SMRB5 derivatives Anti-inflammatory were taken and used. The 2D-QSAR Models were generated using a training set of molecules by MLR (Multiple regressions) 2D-QSAR method.

Concurrent synthesis of vanillin and isovanillin

A method for concurrent synthesis of vanillin and isovanillin has been developed by a nonregioselective Vilsmeier–Haack reaction of O-alkyl guaiacols. O-Alkylation of guaiacol provided the corresponding O-alkyl guaiacol (1), which was then formylated with N-methylformanilide/phosphorus oxychloride to give a mixture of 4-alkoxy-3-methoxy-benzaldehyde (2) and 3-alkoxy-4-methoxybenzaldehyde (3). Finally, the obtained mixture underwent a selective dealkylation by anhydrous aluminium trichloride, while leaving methyl groups intact to simultaneously achieve the significant fine chemicals vanillin and isovanillin.

Demethylation of Quinine Using Anhydrous Aluminium Trichloride

Quinine is a natural alkaloid having a methoxy group bound to quinoline ring and an allyl group bound to quinuclidine ring. Demethylation of quinine applying strong acid such as HBr or HI at high temperature was unsuccessful. The aim of this research was to obtain demethylated quinine by means of mild and selective demethylation procedure to prevent the addition reaction of allyl group. Selective demethylation of quinine has been carried out using anhydrous aluminium trichloride as reagent. The demethylation product was achieved in 68.12% yield by mole ratio of quinine to anhydrous aluminium trichloride of 1 to 4 in dried methylene chloride under nitrogen atmosphere. The reaction was firstly carried out at 0°C for 4 h and after the reaction mixture reached room temperature, the reaction was continued up to 24 h.

Synthesis and Thermal Property of Linear Chloromethylated Polystyrene

Polystyrene (PS) was synthesized by emulsion polymerization. 1,4-bis(chloromethoxy)butane (BCMB) was synthesized using 1,4-butanediol, formaldehyde and phosphorus trichloride as raw material. The linear poly(p-chloromethyl styrene) (PS-Meyl-Cl) was prepared high effectively using BCMB and anhydrous aluminium trichloride as the chloromethylation reagent and catalyst, respectively. In this method, carcinogenic compound (chloromethyl ether etc.) was avoided. The resultant polymers were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectrometer (FTIR) and thermogravimetric analyzer. The results show that the molecular weight (Mw) of PS is big. BCMB has been prepared because of the strong absorption band observed at 1130cm-1 (due to C-O-C bond stretching vibration) and two new bands at 640 and 1315cm-1 (due to the bending vibration of C-Cl bond and stretching vibration of C-H bond in -CH2Cl, respectively). Chloromethyl groups were introduced into benzene ring of PS because of the appearance of the absorption peaks at 676 and 1419cm-1 (due to the bending vibration of C-Cl bond and stretching vibration of C-H bond in -CH2Cl, respectively) in the FTIR spectra. The thermal stability of PS-Meyl-Cl was decreased with increasing chloromethyl group. Moreover, there are two decomposing stages. The reaction condition is gentle and the operation is safe, simple and economical.

Features of the reaction of 7,7-dichlorobicyclo[4.1.0]heptane with phosphorus trichloride

Halo derivatives of bicyclic hydrocarbons have not been explored in the Kinnear–Perren–Clay reaction [1, 2]. We showed for the first time that 7,7-dichlorobicyclo [4.1.0]heptane (I) react with equimolar amounts of phosphorus trichloride and anhydrous aluminum trichloride under mild conditions. Two phosphonic dichlorides were formed (δР 46 and 51 ppm) in a 1 : 1 ratio upon controlled hydrolysis of the intermediate complex. According to the IR spectrum, they are unsaturated compounds (νС=С 1630 and 1640 сm). The Н NMR spectrum shows multiplets at 5.66–6.00, 4.55, 3.44 and 0.95–2.55 ppm, implying the presence of ring ethylene and methylene protons and РСН protons. These data together with the elemental analysis allowed the products to be assigned the structures of isomeric [2-(chloromethylene)cyclohexyl]phosphonic (II) and [chloro(cyclohex-1-enyl)methyl]phosphonic (III) dichlorides. DOI: 10.1134/S1070363208060364

The metal ion modified ionic liquids promoted free-solvent alkylations of α-methylnaphthalene with long-chain olefins

Alkylations of α-methylnaphthalene with long-chain olefins in the presence of various synthesized novel ionic liquids have been investigated. The effects of various parameters such as types of cation and anion of ionic liquids, molar fraction of anhydrous aluminum trichloride on the alkylations were studied. It is found that the alkylpyridinium bromochloroaluminate ionic liquids, especially butylpyridinium bromochloroaluminate (0.71–0.75 molar fraction of aluminum trichloride) indicated excellent catalytic performance for long-chain alkylations of α-methylnaphthalene. It is also found that the anions determine, to a large extent, both physical and chemical properties of ionic liquids, but organic cations mainly influence physical properties, and only have a slight impact on the catalytic performance. Moreover, the effects of type and dosage of transition metal in the modified ionic liquids on the catalytic performances were also investigated. For the less expensive reagents and the easier synthesis process, the Cu 2+ modified butylpyridinium bromochloroaluminate ionic liquid could be a practical catalyst for alkylations of α-methylnaphthalene with long-chain olefins.

Acylation of ferrocene: a new approach

Acylation of ferrocene by an acylating agent generated in situ from the corresponding carboxylic acid and phosphorus trichloride, in the presence of the catalyst generated electrochemically from a sacrificial aluminum anode, was investigated. The corresponding monoacylferrocenes were obtained in very high yields when the molar ratio of reactants was ferrocene/carboxylic acid/PCl 3=1:1.2:1, and by consumption 4.5 F/mol charge. The conditions for electrochemical diacylation of ferrocene were not found. However, acylation of ferrocene by the acylating agent generated in situ, but in the presence of commercial anhydrous aluminum trichloride as the catalyst, was successful in both monoacylation and diacylation processes.

Novel Synthesis of 3,4,4-Trisubstituted Thiadiazolines from 3,4-Diphenyl-1,2,5-Thiadiazole 1,1-Dioxide. Competition with the Intra-Molecular Aryl-Aryl Cyclization of 3,4-Diphenyl-1,2,5-Thiadiazole 1,1-Dioxide

3,4-Diphenyl-1,2,5-thiadiazole 1,1-dioxide (1) reacted, in the presence of anhydrous aluminum trichloride, with aromatic nucleophiles possessing electron donor substituent groups to give novel (2a-e, Figure [1] ) 3,4,4-trisubstituted 1,2,5-thiadiazoline 1,1-dioxides in good yield. In the presence of aluminum trichloride, but without the addition of nucleophiles, a slower, but practically quantitative intramolecular cyclization reaction (Scholl reaction [1] ) of 1 to phenanthro[9,10-c]-1,2,5-thiadiazole 1,1-dioxide (3), took place. Both reactions occur through the intermediation of a strong electrophile formed by 1 and aluminum trichloride. Spectral data and structure (through single-crystal X-ray diffraction, with the exception of 2c) were measured for all new compounds.

A practical route for the preparation of poly(4-hydroxystyrene), a useful photoresist material

The synthesis and characterization of poly(4-hydroxystyrene) (PHS) and poly(4-vinylphenol) (PVPh) by the polymer modification route are reported. Polystyrene prepared by free-radical and anionic polymerization was acetylated quantitatively to poly(4-acetylstyrene) (ACPS) with acetyl chloride and anhydrous aluminum trichloride in carbon disulfide. The acetylation worked equally well in a mixture of 1,2-dichloroethane (DCE) and nitrobenzene containing largely DCE. The extent of the acetylation was estimated by 1H NMR. The oxidation of ACPS was carried out with various oxidizing agents and reaction conditions. The peracetic acid oxidation in chloroform resulted in quantitative oxidation to poly(4-acetoxystyrene) (APS) as estimated by 1H NMR spectroscopy. The treatment of APS with hydrazine hydrate in dioxane resulted in the formation of PVPh. Deacetylation occurred with equal versatility in a mixture of aqueous sodium hydroxide and tetrahydrofuran. All the polymers were characterized via gel permeation chromatography, IR, UV, 1H NMR, and 13C NMR spectroscopic techniques. This is the first report on the synthesis of ACPS, APS, and PHS of reasonably narrow molecular weight distributions or otherwise by the polymer modification route. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 453–461, 2000

A practical route for the preparation of poly(4-hydroxystyrene), a useful photoresist material

The synthesis and characterization of poly(4-hydroxystyrene) (PHS) and poly(4-vinylphenol) (PVPh) by the polymer modification route are reported. Polystyrene prepared by free-radical and anionic polymerization was acetylated quantitatively to poly(4-acetylstyrene) (ACPS) with acetyl chloride and anhydrous aluminum trichloride in carbon disulfide. The acetylation worked equally well in a mixture of 1,2-dichloroethane (DCE) and nitrobenzene containing largely DCE. The extent of the acetylation was estimated by 1 H NMR. The oxidation of ACPS was carried out with various oxidizing agents and reaction conditions. The peracetic acid oxidation in chloroform resulted in quantitative oxidation to poly(4-acetoxystyrene) (APS) as estimated by 1 H NMR spectroscopy. The treatment of APS with hydrazine hydrate in dioxane resulted in the formation of PVPh. Deacetylation occurred with equal versatility in a mixture of aqueous sodium hydroxide and tetrahydrofuran. All the polymers were characterized via gel permeation chromatography, IR, UV, 1 H NMR, and 13 C NMR spectroscopic techniques. This is the first report on the synthesis of ACPS, APS, and PHS of reasonably narrow molecular weight distributions or otherwise by the polymer modification route.

Catalytic polymerization of anthracene oil with aluminium trichloride

A commercial anthracene oil was polymerized with anhydrous aluminium trichloride in the temperature range of 250–325°C. The kinetics of the process and the conversion of anthracene oil were monitored by thermogravimetric analysis, solubility parameters and carbon yield. The reactivity of the major anthracene oil components was monitored by gas chromatography. The cokes obtained at 900°C from reaction products were characterized in terms of optical texture and air reactivity. The results showed that the treatment of anthracene oil with aluminium trichloride led to pitch-like materials, temperature and aluminium trichloride concentration being the controlling parameters of anthracene oil conversion. The residue obtained by thermogravimetric analysis at 350°C was used as a measure of the degree of anthracene oil conversion. Cokes obtained by carbonization of reaction products, in which aluminium trichloride had previously been removed, showed an optical texture of a larger size and a lower air reactivity than cokes from reaction products where aluminium trichloride was present.

Effect of Solvent Diols and Ligands on the Properties of Sol-Gel Alumina-Silicas

Amorphous alumina-silicas were prepared from a tetra-alkoxysilane and anhydrous aluminum trichloride or an aluminum alkoxide by a sol-gel process using 2-methyl-2,4-pentanediol, pinacol, 1,2-propanediol, 2,3-butanediol or ethylene glycol as the solvent or complexing agent, and the effect of diols and alkoxy groups on the physical and chemical properties of the alumina-silicas was examined. When the diol or the alkoxy group was bulky, the alumina-silicas had relatively larger micropores, a larger pore volume and higher surface areas. In the conversion of methanol catalyzed by the alumina-silicas, the bulkier diols and alkoxides gave catalysts that produced dimethyl ether in higher yield and hydrocarbons in lower yield. Thus, when ethylene glycol was used as the diol, the best catalyst for the production of hydrocarbons, especially the production of olefins such as ethylene, propylene and butene, was obtained. Furthermore, in comparison with alumina-silica prepared by a traditional kneading process, it was found that the sol-gel alumina-silica could efficiently convert methanol to dimethyl ether and hydrocarbons, but the material prepared by kneading had a very low conversion of methanol to other compounds.

Síntese de β-cetoésteres cíclicos: novo procedimento para ciclizações de Dieckmann empregando ALCL3 e trietilamina

In this communication we describe a new methodology to Dieckmann cyclization of diethyl adipate (1) and diethyl pimelate (3) applying push-pull strategy using anhydrous aluminium trichloride and triethylamine in dichloromethane at room temperature. This method is very efficient, simple, safe and reproducible, giving the corresponding cyclic β-keto ester derivatives in 84% and 71% yield, respectively.

Aluminum Chloride Catalyzed Nitration of Aromatics with Sodium Nitrate/Chlorotrimethylsilane

A mixture of sodium nitrate and chlorotrimethylsilane in the presence of anhydrous aluminum trichloride is a convenient nitration system for aromatic compounds. Nitryl chloride is formed as an intermediate in the reactions.

Bromothiophene reactions. I. Friedel‐crafts acylation

AbstractFriedel‐Crafts acylation of 2,5‐dibromo‐ and 2,3,5‐tribromothiophenes with different acyl chlorides and anhydrous aluminium trichloride has been studied. The reaction afforded a mixture of acyl derivatives and tetrabromothiophene. The results obtained suggest a mechanism which involves the formation of bromine cations in the reaction medium. Several products obtained in this reaction are described.

Synthesis and study of poly(oxine‐methylene)s

AbstractThe work presented in this paper comprises synthesis and study of poly(oxine‐methylene)sSystematic name: poly(8‐hydroxyquinolinediylmethylene)s. . The synthesis is based on Friedel‐Crafts polyalkylation of 8‐quinolinol, commonly known as oxine, with dichloromethane in presence of anhydrous aluminium trichloride. Five polymer samples are prepared by varying molar proportions of the two monomers. The polymer samples are insoluble in commonly used organic solvents. They are soluble in acetic acid, formic acid, and in conc. sulfuric acid. The IR and UV spectral characteristics of the polymer samples are reported. Molecular weight of the polymer samples is estimated by conductometric titration in pyridine against standard sodium methoxide. Viscometric study is carried out both in formic acid and glacial acetic acid at 35°C. Solutions of polymer samples in formic acid show normal behaviour and those in glacial acetic acid show abnormal behaviour. Various empirical relations are applied to correlate these data in glacial acetic acid. Acetic acid containing water and simple electrolytes is used as a medium to suppress abnormal behaviour. The thermal properties of the polymer samples are also studied. All the results of analysis are adequately correlated. One oxine‐formaldehyde polymer sample was also synthesized for comparison.

Phosphorus–nitrogen compounds. Part XXXV. Friedel–Crafts reactions of chlorodimethylaminocyclotriphosphazatrienes with benzene

Chlorodimethylaminocyclotriphosphazatrienes, N3P3Cl6–n(NMe2)n(n= 1,2,2,3,3, and 3) undergo Friedel–Crafts reactions with benzene in the presence of anhydrous aluminium trichloride to give phenyldimethylamino-derivatives, N3P3PhmCl6–n–m(NMe2)n, whose structures are established by their 1H n.m.r. spectra. Replacement occurs readily at PCl·NMe2 groups and more slowly at PCl2 groups. The hydrocarbons triphenylmethane and diphenylmethane are minor by-products in these reactions but are the major products isolated from attempted Friedel–Crafts reactions of cis-non-geminal-N3P3Cl2(NMe2)4. The factors governing the positions of phenylation in the cyclotriphosphazatrienes are discussed.