Iron(Ⅲ) phthalocyanine chloride-catalyzed oxidation–aromatization of α,β-unsaturated ketones with hydrazine hydrate: Synthesis of 3,5-disubstituted 1H-pyrazoles

We have developed an iron（III） phthalocyanine chloride‐catalyzed oxidation–aromatization ofα,β‐unsaturated ketones with hydrazine hydrate. Various 3,5‐disubstituted 1H‐pyrazoles were obtained in good to excellent yields. This method offers several advantages, including room‐tem‐perature conditions, short reaction time, high yields, simple work‐up procedure, and use of air as an oxidant. The catalyst can be recovered and reused five times without loss of activity.

Iron Chloride Hexahydrate-catalyzed Friedel-Crafts Akylation of Cyclic Ketene Dithioacetals with Alcohols

A cost-effective and environmentally compliance FeCl3·6H2O catalyzed Friedel-Crafts alkylation of cyclic ketene dithioacetals with alcohols was developed. The reaction was efficient in the presence of catalyst loading as low as 5%（molar fraction） in CH2Cl2 solvent at room temperature or under reflux conditions. A wide range of alkylated ketene dithioacetals were synthesized in excellent yields.

A Novel Green Preparation of a, a'-Bis (substituted benzylidene)-cycloalkanones Promoted by FeCl_3 6H-2O in Ionic Liquid

a, a'-Bis(substituted benzylidene)cycloalkanones were efficiently prepared from cycloalkanones and benzaldehydes in [bmim][BF4] by using iron(III) chloride hexahydrate as a catalyst. It is shown that [bmim][BF4] and iron(III) chloride hexahydrate can be quantitatively recovered and be reused effectively for many times. Compared with the known methods, this novel process has the advantage of being an envkonmentally benign process together with good yields and mild reaction conditions.

Iron（Ill） Chloride Catalyzed Oxidative Coupling Reaction of 1,2-Diarylethylene Derivatives

A nontoxic FeCI3 catalyzed intramolecular oxidative coupling reaction was developed for mild synthesis of a series of phenanthrenes with different substituents. The method involves cross dehydrogenative coupling of a vari- ety of 1,2-diarylethylene derivatives with di-tert-butylperoxide （DTBP） as a sole oxidant at room temperature in CHzC1jTFA （9 ; 1 V/V） to yield phenanthrenes in good to excellent yields.

Application of Hydrazine Hydrate in the Synthesis of Octa(aminophenyl)silsesquioxane (OAPS) Poss

Octa(aminophenyl)silsesquioxane (OAPS) was prepared from octaphenyl silsesquioxane (OPS) in two steps, first nitration to obtain Octa(nitrophenyl)silsesquioxane (ONPS) then reduction by using the stable, inexpensive, and readily available hydrazine hydrate as the reducing agent in the presence of Iron(III)Chloride catalyst with a yield of around 87%. Hydrazine is a two-electron reducing agent whereas nitro group is a four-electron reduction process. The activated carbon serves as an adsorbent and electrical conductor enabling the reaction to occur by acting as a mediator between a two-electron reagent and a four-electron process. Adsorption provides a reducing potential and a supply of electrons from many hydrazines making possible the initial four-electron process even though each individual hydrazine is a two-electron donor. The product was characterized by FTIR and 1H NMR. The time period for preparation of ONPS from octaphenyl silsesquioxane was considerably shortened to avoid double nitration of the aromatic rings.

Chloride-intercalated continuous chemical vapor deposited graphene film with discrete adlayers

Heteroatom doping can open the bandgap and increase the carrier density, thus extending the applications of graphene. Iron chloride （FeC13） intercalation has proven to be an efficient method for the heavy doping of graphene. In this study, we prepared continuous chemical vapor deposited graphene （CVD-G） consisting of hexagonal adlayer domains to study the FeC13 intercalation. The structure of the FeC13-treated CVD-G was easily characterized via atomic force microscopy because of the change in the interlayer distance. FeC13 crystals several nanometers thick were integrated with the graphene surface, and FeC13 layer flakes were intercalated between the CVD-G adlayers. The G-band position and two-dimensional band shape in the Raman spectra confirmed the intercalation of the FeC13 between the graphene layers. The FeCI~ intercalation increased the electrical conductivity of the CVD-G with a well-maintained transmittance, which could be beneficial for a sensitive photodetector.

Hg^0 removal from flue gas over different zeolites modified by Fe Cl_3

The elemental mercury removal abilities of three different zeolites（Na A, Na X, HZSM-5）impregnated with iron（Ⅲ） chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy, and temperature programmed desorption（TPD） analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury（Hg0）into oxidized mercury（Hg2＋）. The crystallization of Na Cl due to the ion exchange effect during the impregnation of Na A and Na X reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of Fe Cl3–HZSM-5 was mainly in the form of mercuric chloride（Hg Cl2）, while on Fe Cl3–Na X and Fe Cl3–Na A it was mainly mercuric oxide（HgO）.

Catalytic Conversion of 2-Naphthol to 2-Hydroxy-1,4-naphthoquinone Under Mild Conditions

2-Hydroxy-1,4-naphthaquinone (HNQ) was selectively synthesized from catalytic oxidation of 2-naphthol by molecular oxygen over tetra(4-methoxyl-phenyl)porphyrinate iron(III) chloride (TMOPPFeCl) catalyst in an alkali methanol solution under mild conditions. The influences of solvents, temperature, time, as well as amounts of cata-lysts and alkali were studied. The quantitative data show that 32.9% of 2-naphthol (0.093 mol/dm3) was catalyti-cally converted to HNQ with the selectivity of 100% at 323 K for 9 h over TMOPPFeCl catalyst (2.54×10-4 mol/dm3) in alkali media (30 mL of methanol containing 2.5 mol/dm3 of NaOH) by flowing molecular oxygen (flowing rate of 45 mL/min).

Synthesis of pillar[7]arene

The first synthesis of pillar[7]arene is reported with two methods.Method A：the FeCl_3-catalyzed condensation reaction of 1,4- dimethoxybenzene（1） with paraformaldehyde in CHCl_3 gave dimethoxypillar[7]arene（3）.Method B：the p-toluenesulfonic acid catalyzed condensation reaction of 2,5-bis（benzyloxymethyl）-1,4-dimethoxybenzene（2） in CH_2Cl_2 gave compound 3.Demethylation of 3 with BBr_3 gave pillar[7]arene（4）.The pillar[7]arene might be a perspective macrocyclic host in host-guest chemistry.

FeCl3-6H2O-Catalyzed Synthesis of β-Ketothioesters from Chain α-Oxo Ketene Dithioactals

A FeCl3-6H2O-catalyzed synthesis of β-ketothioesters from the hydrolysis reaction of chain α-oxoketene dithioacetals was carried out. Subsequently, we explored the FeCl3-6H2O-catalyzed Friedel-Crafts alkylation of the synthesized fl-ketothioesters with alcohols in CH3CN at 25 ℃, affording the desired α-alkylated fl-ketothioesters in excellent yields. Wide scope of the substrates, use of inexpensive reagents, high yields under mild reaction conditions are notable features of these reactions.

A facile synthesis of per (poly )fluoroalkyl substituted α-amino acid derivatives

Initiated by CrCl3/Fe redox couple, per(poly)fluoroalkyl iodides added to methyl a-acetylamino acrylate, giving B-per(poly)fluoroalkyl a-amino acid derivatives in good yields.