Anhydrous Aluminum Chloride Research Articles

Synthesis of novel poly(ether ketone diphenyl ketone ether ketone ketone)s by electrophilic Friedel–Crafts solution polycondensation

Abstract4,4′‐Bis(4‐phenoxybenzoyl)diphenyl was prepared by the Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl followed by condensation with potassium phenoxide. Novel aromatic poly(ether ketone diphenyl ketone ether ketone ketone)s were obtained by the electrophilic Friedel–Crafts solution copolycondensation of 4,4′‐bis(4‐phenoxybenzoyl)diphenyl with a mixture of isophthaloyl chloride and terephthaloyl chloride over a wide range of isophthaloyl chloride/terephthaloyl chloride molar ratios in the presence of anhydrous aluminum chloride and N‐methylpyrrolidone in 1,2‐dichloroethane. The influence of the reaction conditions on the preparation of the copolymers was examined. The copolymers were characterized with different physicochemical techniques. Because of the incorporation of diphenyl, the resulting copolymers exhibited outstanding thermal stability. The glass‐transition temperatures were above 174°C, the melting temperatures were above 342°C, and the 5% weight loss temperatures were above 544°C in nitrogen. All these copolymers were semicrystalline and insoluble in organic solvents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Cyclic tautomer of 1,5-diacetyl-4,8-dihydroxynaphthalene and its reaction with hydrazine

Demethylation of 1,5-diacetyl-4,8-dimethoxynaphthalene by the action of anhydrous aluminum chloride gave 6-acetyl-2,5-dihydroxy-2-methylnaphtho[1,8-bc]furan which reacted with hydrazine to produce 3,8-dimethyl-1,2,6,7-tetraazapyrene.

Morphological Aspects of In-Situ Compatiblized Binary Polymer Blends With Variable Viscosity Ratios of Components

The in-situ compatiblized binary polymer blend polypropylene(PP)/polystyrene(PS)/ anhydrous aluminum chloride(AlCl3) was selected as a model system of a reactive polymer blend to investigate the effect of viscosity ratio of components at a constant shear rate on the phase morphological behavior in in-situ compatibilized systems. The results showed that the well-known interfacial compatibilization effect was related to variations of viscosity ratios of components in the reactive PP/PS blends with different contents of AlCl3 catalyst. The phase morphology evolution of the in-situ compatiblized reactive blend was determined by both the interfacial compatibilization and the variation of the viscosity ratio of components under the fixed mixing conditions, which showed characteristics obviously different from and much more complex than those in binary polymer blends generally compatiblized by added compatiblizers. The results implied that the variation of the viscosity ratio of components should be checked carefully and taken into account if necessary, when the phase morphology of binary polymer blends is investigated, especially in complex in-situ compatiblized reactive polymer blends.

Aluminum chloride for accelerating hydrogen generation from sodium borohydride

Abstract The present research paper reports preliminary results about the utilization of anhydrous aluminum chloride (AlCl 3 ) for accelerating hydrogen generation through hydrolysis of aqueous solution of sodium borohydride (NaBH 4 ) at 80 °C. To the best of our knowledge, AlCl 3 has never been considered for that reaction although many transition metal salts had already been assessed. AlCl 3 reactivity was compared to those of AlCl 3 ·6H 2 O, AlF 3 , CoCl 2 , RuCl 3 and NiCl 2 . With AlCl 3 and a NaBH 4 solution having a gravimetric hydrogen storage capacity (GHSC) of 2.9 wt.%, almost 100% hydrogen was generated in few seconds, i.e., with a hydrogen generation rate (HGR) of 354 L min −1 g −1 (Al). This HGR is one of the highest rates ever reported. Higher HGRs were obtained by mixing AlCl 3 with CoCl2, RuCl 3 or NiCl 2 . For example, the system RuCl 3 :AlCl 3 (50:50 mass proportion) showed a HGR > 1000 L min −1 g −1 (Ru:Al). The hydrolysis by-products (once dried) were identified (by XRD, IR and elemental analysis) as being Al(OH) 3 , NaCl and Na 2 B(OH) 4 Cl and it was observed that even in situ formed Al(OH) 3 has catalytic abilities with HGRs of 5 L min −1 g −1 (Al). All of these preliminary results are discussed, which concludes that AlCl 3 has a potential as accelerator for single-use NaBH 4 -based storage system.

Synthesis of poly(aryl ether ketone)s containing diphenyl moieties by electrophilic Friedel–Crafts solution polycondensation

AbstractA new monomer, 4,4′‐bis(4‐phenoxybenzoyl)diphenyl (BPOBDP), was prepared by Friedel–Crafts reaction of 4‐bromobenzoyl chloride and diphenyl, followed by condensation with potassium phenoxide. Novel poly(ether ketone ketone) (PEKK)/poly(ether ketone diphenyl ketone ether ketone ketone) (PEKDKEKK) copolymers were synthesized by electrophilic Friedel–Crafts solution copolycondensation of isophthaloyl chloride (IPC) with a mixture of diphenyl ether (DPE) and BPOBDP, in the presence of anhydrous aluminum chloride and N‐methyl‐pyrrolidone (NMP) in 1,2‐dichloroethane (DCE). The copolymers obtained were characterized by various analytical techniques such as FT‐IR, DSC, TGA, and wide‐angle X‐ray diffraction (WAXD). The results showed that the resulting copolymers exhibited excellent thermal stability due to the existence of diphenyl moieties in the main chain. The glass transition temperatures are above 152°C, the melting temperatures are above 276°C, and the temperatures at a 5% weight loss are above 548°C in nitrogen. The copolymers with 50–70 mol% BPOBDP had tensile strengths of 101.5–102.7 MPa, Young's moduli of 3.23–3.41 GPa, and elongations at break of 12–17%. All these copolymers were semicrystalline and insoluble in organic solvents. Copyright © 2008 John Wiley & Sons, Ltd.

Unusual rearrangement of 1-(2-isothiocyanoaryl)-2-(2-furyl)ethane under Friedel-Crafts conditions

Treatment of 1-(2-isothiocyanoaryl)-2-(2-furyl)ethane with anhydrous aluminum chloride under Friedel-Crafts conditions yielded a pyrrolo[1,2-a]quinoline derivative via electrophilic attack of the activated isothiocyano group onto the furan ring. The analogous diarylethane under these conditions underwent intramolecular cyclization leading to an eight-membered thioamide.

High-Yield Synthesis of 1,3-Dimesityl-propane-1,3-dione: Isolation of Its Aluminum Complex as a Stable Intermediate

1,3-Dimesityl-propane-1,3-dione was synthesized in high yield, via a stable intermediate (its aluminum complex) from malonyl dichloride and mesitylene by Friedel–Crafts reaction using anhydrous aluminum chloride as catalyst. The intermediate aluminum complex was isolated and characterized by X-ray diffraction analysis, which decomposed upon reflux in concentrate hydrochloric acid to give the title compound.

Influence of initiators on isomerization of normal hexane catalyzed by ionic liquids

An ionic liquid was synthesized with anhydrous aluminum chloride and amine hydrochloride with the mole ratio of 2:1. The isomerization of n-hexane catalyzed by the ionic liquid was investigated. The results indicate that the ionic liquid can catalyze the isomerization of n-hexane, but it requires long reaction time. The influence of initiators including n-butanol, i-butene, i-butane and i-pentane on the isomerization of n-hexane was investigated. The conversion of n-hexane, the yield of liquid components and the selectivity of isoparaffins are 84.54%, 80.08% and 94.74%, respectively, when i-pentane is used as the initiator. This shows that i-pentane is a good initiator for the isomerization of n-hexane. The dosage of i-pentane shows great influence on the isomerization of n-hexane, and the suitable dosage is 30%. The initiator i-pentane can greatly accelerate the rate of the isomerization of n-hexane. The reaction time can be shortened from 6 h to 45 min to achieve the similar reaction extent.

Sequential Thermal and Catalyzed Claisen Rearrangements Toward the Synthesis of Thiocoumarin-Annulated Furopyrans

Regioselective synthesis of a hitherto unreported thiocoumarin-annulated furopyran moiety was achieved by the application of Claisen rearrangement in which a second Claisen rearrangement was achieved by anhydrous aluminum chloride. The precursor endocyclic compounds for catalyzed Claisen rearrangement were synthesized by the thermal [3,3] sigmatropic rearrangement of the corresponding ether. Keywords: Anhydrous aluminum chloride, sequential Claisen rearrangement, intramolecular hydroaryloxylation, furopyrans, 4-hydroxythiocoumarin, 1-aryloxy-4-chlorobut-2-yne

Preparative synthesis of para-tert-butylcalix[4]arene monoalkyl ethers

A new simple method of synthesis of monoalkoxy-p-tert-butylcalix[4]arenes by the selective dealkylation of 25,26-dialkoxy-p-tert-butylcalix[4]arenes with anhydrous aluminum chloride was developed.

4-(3,4-Dichloro-phen-yl)-3,4-dihydronaphthalen-1(2H)-one.

The title compound, C16H12Cl2O, was synthesized from 1-naphthol and 1,2-dichloro­benzene with anhydrous aluminium chloride as a cataylst. In the mol­ecule, the two ring systems are approximately perpendicular to one other with a dihedral angle of 82.06 (4)°. There are two CH-type hydrogen bonds.

Behaviour of 3(3-indolylmethylene)-5-aryl-2(3H)-furanones as Alkylating Agents: Intra- Versus Inter-Molecular Alkylation

5-Aryl-3-(3-indolylmethylene)-2(3 H)-furanones (6a–c) were prepared as a mixture of ( E) and ( Z) stereoisomers by condensing indole-3-carboxaldehyde with 3-aroylpropanoic acids using thionyl chloride in N,N-dimethylformamide as cyclodehydrating agent. The reaction of the furanones 6a and 6b with anhydrous aluminium chloride in benzene, toluene or anisole led to the formation of 4,4-diaryl-1-(3-indolyl)buta-1,3-diene-2-carboxylic acids (7) as mixtures of geometrical ( E, E- and E, Z-) stereoisomers via an intermolecular alkylation mode. The furanone 6c under the same reaction conditions gave 1-(4-methoxyphenyl)carbazole-3-carboxylic acid (8) via intramolecular alkylation. This represents a novel method for the synthesis of carbazole derivatives.

Preparation of mono- and diacetyl 4,4′-dimethylbiphenyl and their corresponding carboxylic acids: Reactivity, selectivity and isomer distribution studies via Lewis acid catalyzed Friedel-Crafts acetylation/oxidation

Shape selective acetylation of 4,4′-dimethylbiphenyl using anhydrous aluminum chloride as catalyst is an effective route for the production of mono- and di-acetyl-4,4′-dimethylbiphenyl. Preparations, characterization and a catalytic study of the Friedel-Crafts acetylation of 4,4′-dimethylbiphenyl, involving use of the Perrier addition procedure are carried out in a range of solvents and under a variety of experimental conditions. The obtained ketones are isolated and identified by various physico-chemical techniques. Mono acetylation of 4,4′-dimethylbiphenyl afforded a mixture of two isomeric acetyl dimethylbiphenyls. In chloroalkane or carbon disulfide solvent, the yields of isomers were in the order: 2 -> 3-; in nitromethane 3-isomer predominated. On the other hand diacetylation of the hydrocarbon gave only the 2,3′-diacetyl isomer. The mono- and di-ketones are converted to the corresponding carboxylic acids. 2-Acetyl-4,4′-dimethylbiphenyl was prepared by indirect multi-step synthetic routes. 3-D molecular modelling supports the positional assignment of the acetyl group with the results obtained from the electronic spectra.

Synthesis and characterization of benzoylated syndiotactic polystyrene

Benzoylated syndiotactic polystyrene, a functional polymer bearing benzophenone(BP) moiety, has been synthesized in a heterogeneous process by using carbon disulfide as the dispersing medium, and benzoyl chloride and anhydrous aluminum chloride as benzoylating agent and catalyst, respectively. The benzoylation reaction can be well controlled and the resultant polymer was characterized by FTIR and NMR spectroscopy. The incorporation of benzoyl groups into syndiotactic polystyrene was found to have a profound effect on the thermal properties of these new materials. The melting point and the degree of crystallinity decreased by the presence of benzoyl groups, while the glass transition temperature increased.

Synthesis of novel functional polyolefin containing carboxylic acid via Friedel–Crafts acylation reaction

The strong polar group, carboxylic acid, has triumphantly been introduced into ethylene and allylbenzene copolymers without obvious degradation or crosslinking via Friedel–Crafts (F–C) acylation reaction with glutaric anhydride (GA), succinic anhydride (SA) and phthalic anhydride (PA) in the presence of anhydrous aluminum chloride in carbon disulfide. Some important reaction parameters were examined in order to optimize the acylation process. In the optimum reaction conditions, almost all of the phenyls can be acylated with any anhydride. The microstructure of acylated copolymer was characterized by FT-IR, 1H NMR and 1H– 1H COSY. All the peaks of acylated copolymers can be accurately attributed, which indicates that all the acylation reactions occur only at the para-positions of the substituent of the aromatic rings. The thermal behavior was studied by differential scanning calorimetry (DSC), showing that the melting temperatures ( T ms) of acylated copolymers with GA firstly decrease slowly and then increase significantly with the increase of the amount of carboxyl acid groups.

Graft copolymerization of styrene or methyl methacrylate onto syndiotactic polystyrene by ATRP technique

AbstractFunctionalized syndiotactic polystyrene (sPS) copolymers, including sPS‐graft‐atactic polystyrene (aPS) copolymer or sPS‐graft‐poly(methyl methacrylate) (PMMA) copolymer, were synthesized and characterized. sPS has been synthesized by using half sandwich titanocene/methylaluminoxane catalyst in homogenous conditions. Then, α‐phenyl chloroacetylation of sPS was accomplished in a heterogeneous process by using carbon disulfide as dispersing medium and α‐phenyl chloroacetyl chloride and anhydrous aluminum chloride as acetylating agent and catalyst, respectively. The graft copolymer of sPS with aPS or PMMA were synthesized by atom transfer radical polymerization using α‐phenyl chloroacethylated sPS as initiator and CuBr and bipyridine as catalyst. The structure of obtained copolymer was investigated by 1H NMR, FTIR spectroscopy, and thermal behavior of copolymers was performed by differential scanning calorimetry analyses. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 611–619, 2007

Total Synthesis and Antiviral Activity of Enantioenriched (+)-Deoxytylophorinine

The first total synthesis of (+)-deoxytylophorinine has been accomplished in 6 linear steps and with 39.6% overall yield. An important feature of this synthesis is that Friedel-Craft acylation of (S)-1- benzyloxycarbonylpyrrolidine-2-acetyl chloride with phenylmethylether catalyzed with fresh anhydrous aluminum chloride to provide 2-(4-methoxyphenacyl)pyrrolidine and cleavage of the Cbz group have been proceeded in one pot. We have found that (+)-deoxytylophorinine shows excellent anti-TMV activity. Keywords: Phenanthroindolizidine alkaloids, (+)-deoxytylophorinine, total synthesis, antiviral activity, tobacco mosaic virus

A Facile Synthesis of 1-Phenylsulfonyl-3-substituted-2-cyanoindoles, 1-Phenylsulfonyl-2-methyl-3-cyanoindoles, and Bifunctional 1-Phenyl­sulfonylindoles

A facile 'one-pot' introduction of the cyano group into the 2/3-position of indole has been developed from the corresponding aldehydes using anhydrous aluminum chloride and sodium azide.

<b>SYNTHESIS AND ANTIBACTERIAL ACTIVITY OF INSIGNIN AND ITS 8-METHOXY- AND 6-DEMETHOXY DERIVATIVES</b>

A short and efficient synthesis of insignin (8-hydroxy-6-methoxy-3-heptyl- isocoumarin) ( 1 ), a metabolite of natural lichens, has been described. Reaction of 3,5-dimethoxyhomophthalic anhydride ( 2 ) with octanoyl chloride in the presence of 1,1,3,3-tetramethylguanidine (TMG) and triethyl amine afforded the 6,8-dimethoxy-3-heptylisocoumarin ( 3 ) in high yield. Regioselective demethylation of the latter using anhydrous aluminum chloride furnished the 8-hydroxy-6-methoxy-3-heptylisocoumarin ( 1 ) whereas, the complete demethylation of ( 3 ) yielded 6,8-dihydroxy-3-heptylisocoumarin ( 4 ). The isocoumarins ( 1 , 3 , and 4 ) were examined in vitro for antibacterial activity and were shown to exhibit moderate activity. KEY WORDS : Isocoumarin, Insignin, Antibacterial, Porpidia glaucophaea, Haematomma pachycarpum , 3,5-Dimethoxyhomophthalic anhydride Bull. Chem. Soc. Ethiop. 2006 , 20(1), 83-87.

Solvent-free, AlCl 3-promoted tandem Friedel–Crafts reaction of arenes and aldehydes

Tandem Friedel–Crafts reaction of arenes and aldehydes under the catalysis of Lewis acid was investigated. Both aromatic and aliphatic aldehydes underwent a tandem Friedel–Crafts alkylation with electron-rich arenes to afford 1,1,1-triaryl/1,1-diarylalkanes in the presence of anhydrous aluminum chloride under solvent-free conditions. The scope, limitation, and mechanism of the tandem reaction were also discussed.