NBS as an efficient catalyst for the synthesis of 1,5-benzodiazepine derivatives under mild conditions

Various biologically important 1,5-benzodiazepine derivatives were efficiently synthesized in excellent yields using catalytic amounts of NBS (10 mol %). This inexpensive, nontoxic, and readily available catalyst efficiently catalyzes the condensation of several aromatic as well as aliphatic ketones with substituted o-phenylenediamines.     

Liquid-phase microextraction and GC for the determination of primary, secondary and tertiary aromatic amines as their iodo-derivatives

Presence of iodine in aromatic amines, introduced by their reaction with iodine, and other electron withdrawing substituents such as chlorine and nitro, has been found to afford excellent liquid-phase microextraction (LPME) in toluene and separation by gas chromatography in the determination of primary, secondary and tertiary aromatic amines. The effect is due to decreased basic nature of amines when electronegative substituents are present. Single drop microextraction (SDME) of the amines in 2 μl of toluene and injection of the whole extract into GC, or LPME into 50 μl of toluene and injection of 2 μl of extract, were used. LPME has been found more robust and to give better extraction in shorter period than SDME. In SDME-GC-FID, the average correlation coefficient was 0.9939 and average limit of detection 25 μg l⁻¹ (range 12-61 μg l⁻¹) whereas the corresponding values in LPME-GC-MS were, respectively, 0.9953 and 33 ng l⁻¹ (range 18-60 ng l⁻¹). The method has been applied to determine aromatic amines in river water, dye factory effluents and food dye stuffs. The LPME was found as robust, rugged and simple extraction method.     

Lewis and Brönsted acid catalyzed Friedel-Crafts hydroxyalkylation of mucohalic acids: a facile synthesis of functionalized γ-aryl γ-butenolides

A catalytic, green and practical method for Friedel-Crafts hydroxyalkylation of mucohalic acid has been accomplished. Reaction of mucohalic acids with various electron-rich aromatic compounds in the presence of catalytic (1 mol % to 10 mol %) In(OTf)₃ or Brönsted acid, such as H₂SO₄ in acetic acid provides γ-aryl γ-butenolides in moderate to excellent yield.     

Ring opening of epoxides with alcohols using Fe(Cp)2BF4 as catalyst

Fe(Cp)₂BF₄ is an efficient catalyst for the alcoholysis of aromatic, aliphatic, and cyclic epoxides giving excellent yields of the corresponding β-alkoxy alcohols under ambient conditions. The methanolysis of styrene oxide using Fe(Cp)₂BF₄ as a catalyst (5 mol %) gave excellent yield of 2-methoxy-2-phenylethanol with complete regio-selectivity. The ring opening of cyclic epoxides gave 77–97% yields of trans-β-methoxy alcohols, in 0.5–6 h. The use of 1,2-epoxyhexane and 1,2-epoxydodecane as substrates gave both regioisomers in excellent yields. The first order rate of reaction with respect to catalyst was observed for the kinetics of ring opening of 1,2-epoxyhexane with methanol.     

Synthesis of 1,2-disubstituted acetylenes via copper-catalyzed Suzuki coupling of organoboronic acids with 1,1-dibromo-1-alkenes

An efficient synthesis of 1,2-disubstituted acetylenes has been described. Reactions of organoboronic acids with 1,1-dibromo-1-alkenes in the presence of a catalytic amount of CuI (10 mol %), 8-hydroxyquinoline (10 mol %), and using potassium phosphate as base in C₂H₅OH afforded the desired 1,2-disubstituted acetylenes in good to excellent yields. It is important to note that the formation of 1,3-diynes, which are derived from the homocoupling of 1,1-dibromo-1-alkenes, can be almost completely suppressed under these optimized conditions.     

Efficient Elemental Iodine Catalyzed One-Pot Synthesis of 2,4,5-Triarylimidazoles

Elemental iodine is used as an efficient catalyst for the synthesis of 2,4,5-triarylimidazoles in excellent yields via condensation of benzoin, ammonium acetate, and aromatic aldehydes. This is a simple, one-pot, high yielding technique using cheap, non-toxic iodine in catalytic amounts.     

Efficient Elemental Iodine Catalyzed One-Pot Synthesis of 2,4,5-Triarylimidazoles

Summary. Elemental iodine is used as an efficient catalyst for the synthesis of 2,4,5-triarylimidazoles in excellent yields via condensation of benzoin, ammonium acetate, and aromatic aldehydes. This is a simple, one-pot, high yielding technique using cheap, non-toxic iodine in catalytic amounts.     

Synthesis and properties of novel organosoluble polyimides derived from bis[3-(4-amino-2-trifluoromethylphenoxy) phenyl] ether

A new aromatic ether diamine, bis[3-(4-amino-2-trifluoromethylphenoxy) phenyl] ether, was successfully synthesized via nucleophilic substitution reaction of 3,3′-oxydiphenol and 2-chloro-5-nitrotrifluoromethylbenzene, followed by a catalytic reduction. A series of new polyimides were synthesized from the diamine with various commercially available aromatic dianhydrides via a conventional two-stage process, i.e. ring-opening polyaddition forming the poly(amic acid)s and further thermal or chemical imidization forming polyimides. The resulting polyimides exhibited good solubility in polar solvents, such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidinone and common solvents such as chloroform, tetrahydrofuran upon heating and possessed the inherent viscosities of 0.51-0.68 dL/g. The resulting strong and flexible films exhibited excellent thermal stability with the temperature at 10% weight loss is above 502 °C and the glass transition temperature in the range of 191-232 °C. The polyimides also were found to possess high optical transparency.     

Microwave-assisted alkaline digestion combined with microwave-assisted distillation for the determination of iodide and total iodine in edible seaweed by catalytic spectrophotometry

Microwave energy has been novelty applied to speed up a tetramethylammonium hydroxide (TMAH) alkaline digestion of seaweed samples and to assist distillation of iodine from seaweed alkaline digests. Iodide in the alkaline digests from seaweed and distilled iodine, reduced back to iodine in a hydroxylamine hydrochloride solution, was determined by a catalytic spectrophotometric method based on the catalytic effect of iodide on the oxidation of As(III) by Ce(IV) in H₂SO₄/HCl medium (Sandell-Kolthoff reaction). The determination of iodide was directly performed in the alkaline digests, while total iodine was assessed by analyzing the hydroxylamine hydrochloride solution after the distillation process. Microwave-assisted alkaline digestion was performed using 7.5 mL of TMAH and irradiating samples at 670 W for two 5.5 min steps. Microwave-assisted distillation was carried out using 4.0 mL of the alkaline digest and 3 mL of a 2.2 M hydrochloric acid and 0.05% (m/v) sodium nitrite solution, with a microwave power at 670 W for two 90 s steps. The distillate (iodine vapor) was bubbled in 10 mL of a 500 μg mL⁻¹ hydroxylamine hydrochloride solution (accepting solution). The linear calibration ranges were 0.30-20.0 and 0.40-20.0 μg L⁻¹ for iodide determination and total iodine determination, respectively. The limit of detection was 9.2 μg g⁻¹ for iodide and 28.5 μg g⁻¹ for total iodine. Repeatability of the overall procedures, expressed as R.S.D. for 11 determinations, was 2.6% for 196.3 μg g⁻¹ of iodide measured after microwave-assisted alkaline digestion, and 5.8% for 954.3 μg g⁻¹ of total iodine by microwave-assisted alkaline digestion followed by microwave-assisted distillation. Finally, accuracy of the methods was assessed by analyzing the NIST-09 (Sargasso) certified reference material and the methods were applied to the determination of iodide and total iodine in different Atlantic edible seaweed samples with satisfactory results.     

Iodine-alumina as an efficient and useful catalyst for the regeneration of carbonyl functionality from the corresponding 1,3-oxathiolanes and 1,3-dithiolanes in aqueous system

A simple and useful method has been demonstrated for the deprotection of 1,3-oxathiolanes and 1,3-dithiolanes to the corresponding carbonyl compounds in excellent yield by employing catalytic amount (30 mol %) of iodine supported on neutral alumina in ethanol-water or water. The major advantages of this protocol are mild reaction conditions, less reaction time, easy to handle, high yields, inexpensive reagent and environmentally benign.     

A convenient and highly efficient method for the protection of aldehydes using very low loading hydrous ruthenium(III) trichloride as catalyst

A convenient method for the chemoselective protections of both aliphatic and aromatic aldehydes has been developed. Ruthenium(III) trichloride (0.1 mol %) has found to be an highly efficient catalyst in the acetalizations of aldehydes with various simple alcohols such as methanol, ethanol, or diols such as 1,2-ethylanediol and 1,3-propanediol under mild reaction conditions.     

Iodine-catalyzed Friedel-Crafts alkylation of electron-rich arenes with aldehydes: efficient synthesis of triarylmethanes and diarylalkanes

Iodine is shown to be an efficient catalyst for the Friedel-Crafts alkylation of arenes with a wide variety of aldehydes in toluene under ‘open-flask’ and mild conditions. In the presence of 10 mol % of iodine, the reaction of arenes with aromatic aldehydes gives the corresponding triarylmethane derivatives (TRAMs), regioselectively, in good to excellent yields. On the other hand, a series of diarylalkane derivatives is synthesized smoothly by the reaction with aliphatic aldehydes.     

Highly enantioselective Michael addition of isobutyraldehyde to nitroalkenes

The asymmetric catalytic Michael reaction between isobutyraldehyde and nitroalkanes with chiral primary amine thiourea organocatalysts was described. In the presence of 10 mol % of 1-((1R,2R)-2-amino-1,2-diphenylethyl)-3-benzylthiourea, the desired products were achieved in excellent enantioselectivity (up to>99% ee) with up to 98% yield.     

Recyclable Merrifield resin-supported thiourea organocatalysts derived from l-proline for direct asymmetric aldol reaction

Four Merrifield resin-supported thiourea organocatalysts derived from l-proline were synthesized and found to be efficient catalysts for the direct asymmetric aldol reaction between ketone and aromatic aldehydes. The catalysts exhibited high catalytic activity, diastereoselectivity and excellent enantioselectivity at room temperature with a low loading (only 2 mol %). They also retained unchanged enantioselectivities even after being reused for at least four cycles.     

Benzylic-acetoxylation of alkylbenzenes with PhI(OAc)2 in the presence of catalytic amounts of TsNH2 and I2

Treatment of alkylbenzenes with (diacetoxyiodo)benzene in the presence of catalytic amounts of p-toluenesulfonamide or p-nitrobenzenesulfonamide, and molecular iodine in 1,2-dichloroethane at 60 °C gave the corresponding (α-acetoxy)alkylbenzenes in good to moderate yields. The present reaction is a simple method for the introduction of an acetoxy group to the benzylic position of alkylbenzenes.     

Novel fluorinated poly(aryl ether)s derived from 1,2-bis(4-(4-fluorobenzoyl)phenoxy)-hexafluorocyclobutane

Two novel poly(aryl ether)s were prepared from 1,2-bis(4-(4-fluorobenzoyl)-phenoxy)-hexafluorocyclobutane and aromatic bisphenols by the aromatic nucleophilic substitution reaction in a polar aprotic solvent. These polymers have good thermal stability up to 341 °C with 10% weight loss in inert atmosphere and good solubility in common organic solvents such as THF, DMAc, DMF and DMSO.     

Transition metal-mediated oxidations utilizing monomeric iodosyl- and iodylarene species

Several transition metal-mediated oxidations using hypervalent iodine species are reported. A convenient procedure for preparation of iodylarenes via RuCl₃-catalyzed oxidation of iodoarenes has been developed. This procedure allows the generation of highly reactive monomeric iodine(V) species, which are excellent oxidants toward alcohols and hydrocarbons in situ. A broad range of substrates can be oxidized to carbonyl compounds by a tandem catalytic system based on the Ru(III)-catalyzed reoxidation of ArIO to ArIO₂ using Oxone^® as oxidant. It was shown that electrophilic iodine(III) species, originating from oligomeric iodosylbenzene sulfate (PhIO)₃SO₃, are efficient oxygenating agents in catalytic oxidation of aromatic hydrocarbons in the presence of metalloporphyrin complexes.     

P(RNCH2CH2)N: efficient catalysts for the cyanosilylation of aldehydes and ketones

The 1,2-addition of trialkylsilylcyanides to aldehydes and ketones produces the corresponding protected cyanohydrins in good to excellent yields when carried out at 0 °C to room temperature in the presence of catalytic amounts of the nonionic strong base P(RNCH₂CH₂)N (R = Me, i-Pr) in THF. These catalysts are easily removed from the product by hydrolysis or column filtration through silica gel.     

Synthesis and properties of new pyridine-bridged poly(ether-imide)s based on 4-(4-trifluoromethylphenyl)-2,6-bis[4-(4-aminophenoxy)phenyl]pyridine

A novel pyridine-containing aromatic diamine monomer, 4-(4-trifluoromethylphenyl)-2,6-bis[4-(4-aminophenoxy)phenyl]pyridine (FAPP), was synthesized via the modified Chichibabin pyridine synthesis of 4-(4-nitrophenoxy)-acetophenone with 4-trifluoromethyl-benzaldehyde, followed by a catalytic reduction. A series of fluorinated pyridine-bridged aromatic poly(ether-imide)s were prepared from the resulting diamine monomer with various aromatic dianhydrides via a conventional two-step process. The resulting polyimides exhibited good solubility in aprotic amide solvents and m-cresol, such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and m-cresol, etc., which possessed the inherent viscosities of 0.76-0.91 dL/g. Strong and flexible poly(ether-imide) films were obtained, which showed excellent thermal properties with the glass transition temperatures of 268-353 °C, the temperature at 5% weight loss of 547-595 °C, and the residue at 700 °C of 65-74% in nitrogen, good mechanical properties with the tensile strengths of 87.6-104.2 MPa and elongations at breakage of 8.9-12.6%, and good optical transparency with the cut-off wavelengths of 357-380 nm, as well as low dielectric constants in the range of 2.49-3.04 at 1 MHz and low water uptake 0.43-0.69%. Furthermore, the resulted polyimides derived from FAPP were compared with non-fluorinated analogous polyimides and fluorinated analogous polyimides with trifluoromethyl groups in different positions, and the effects of substituents were also investigated and discussed.     

Nickel salt-catalyzed addition reaction of arylboronic acids to aromatic aldehydes

Arylation reaction of aromatic aldehydes with arylboronic acids proceeded smoothly in the presence of a base and catalytic amount of a nickel salt, Ni(ClO₄)₂·6H₂O, in toluene/IPA = 5:1 or IPA to afford corresponding diarylmethanols in good to excellent yields.