Methanolic FeCl

Triehlorosilane was supplied by Tokyo Kasei Kogyo Co., and dichloromethylsilane and H-PDMS, HSi(CH3)20-[Si(CH3)20] -(CH3)2Si-H (number average molecular weight, M , = 580 and 6) and Pt2[(CH2=CH(CH3)2Si)20]3 (0.1 mol/L in xylene) were purchased from Aldrich. Triehlorosilane and dichloromethylsilane were distilled under reduced pressure. Toluene, -hexane and tetrahydrofuran were supplied by Kanto Kagaku Co. Methanol, FeCls, CaCl2, -xylene and H2PtCl6 6H20 were purchased from Wako Pure Chemical Industries. Distillation of toluene, p-xylene and tetrahydrofuran was performed with sodium and benzophenone. 

A more practical solution to this problem was reported by Larson, in which the amide substrate 20 was treated with oxalyl chloride to afford a 2-chlorooxazolidine-4,5-dione 23. Reaction of this substrate with FeCL affords a reactive A-acyl iminium ion intermediate 24, which undergoes an intramolecular electrophilic aromatic substitution reaction to provide 25. Deprotection of 25 with acidic methanol affords the desired dihydroisoquinoline products 22. This strategy avoids the problematic nitrilium ion intermediate, and provides generally good yields of 3-aryl dihydroisoquinolines. 

Sulfur transfer can also occur from sulfurated borohydride exchange resin <2001TL6741> the reaction proceeds in methanol at ambient temperature rapidly (<5min) and in high yield (91%). From l,4-di(acetylthio)butane, 1,2-dithiane can be obtained by a one-pot synthesis in excellent yield (98%) using BuzSn(OMe)2, FeCls, and a catalytic amount of CsF as a promoter in THF solution <1990TL3595>. 

The blue-colored V 2+ -FeCl 4 complex decomposed in water or in methanol, and the solution became colorless, whereas a CT band appeared at 450nm in a mixture of ethanol and methanol (1 4), the absorption of which was not affected by near-UV irradiation. In contrast, a pale purple-colored aqueous solution of V2+ with K4 [Fe(CN) 6 ] 4 having a low redox potential turned an intense violet upon near-UV irradiation, and there was no absorption peak around 398nm, which is characteristic of a radical cation, as shown in Figure 9.8. 

The direct transformation of silyl ethers into esters can also be performed by reaction with an acid chloride in CH2CI2 (0 °C to room temperature) in the presence of FeCls (1.5 equiv.) [18]. The formation of allyl ethers from allylic alcohols and methanol is catalyzed by RUCI3 [19]. The reaction is likely to occur via a jr-allyl Ru intermediate. Allylic rearrangements and racemization of optically active allylic alcohols take place. 

Synthetic analogues of nonheme iron proteins include Fe tetramers, which form in good yield from FeCls and Na2S in methanol followed by treatment with NaHS and NaOCHs. Addition of a large cation precipitates (R4N)2(Fe4S4(SR)4) with R = Me, Et, and Bz" ... 

If all of the rate is attributed to FeCl2, the data at various concentrations can be fitted reasonably well with a value of K = 5 X 10 . The study of the conductance of FeCL in methanol by de Maine and McAlone (9) indicates that the compound behaves as a weak electrolyte. Although the data are not suitable for rigorous analysis, a value of the dissociation... 

Figure 6. Ultraviolet spectra of iron(III) chloride in methanol with added metallic chlorides in OJ-mm cells FeCl, 0.0262M...

Iron dichloride is a hygroscopic white solid readily soluble in water and ethanol. It may be prepared by reaction of metallic iron with HCl at red heat, under mild conditions in THF or methanol, or with a mixture of the acid and chlorine at 700 °C. The trichloride decomposes at 300 °C in vacuo or may be reduced for example with Hj or H2S to yield FeCl2. Thermal decomposition of FeCls aids purification of FeCl2 by vacuum sublimation. Anhydrous FeCl2 may aliso be prepared by dehydration of [FeCl2(H2 0)4] and the reaction of metallic iron with CCI4. ... 

Aryl 3,4-dihydroisoquinolinesJ Isoquinolines are generally prepared by the Bis-chler-Napieralski reaction, but this classical route is not useful in the case of 3-aryl-isoquinolines. In a modified procedure, the precursor, (phenylethyl)amide (I), is treated with oxalyl chloride to form a, which on treatment with FeCl.i forms an N-acy-liminium ion b. This ion cyclizes to 2, which is converted into 3,4-dihydroisoquinoline 3 by treatment with sulfuric acid in methanol. Overall yields of 3 are in the range 55-90%. 

A titration vial was charged with 0.5 nil ethanol, 2 pmoles of catechol type siderophore in 0.2 ml ethanol, 2 ymoles of FeCl, in 0.1 ml methanol and 0.5 ml of water. The pH was brought to about 7 with standard 0.1 N NaOH and 0.2 ml containing 2 ymoles of competing catechol type siderophore was then added. If necessary, the pH was readjusted to 7. 

Anhydrous iron(III) chloride (3-4 equiv, FeCls) is placed into a Schlenk flask under an inert atmosphere (glove box). Anhydrous chloroform is added into the flask, which is then connected to a Schlenk line under an inert atmosphere (Ar or N2). A solution of 9,9-dialkylfluorene in anhydrous chloroform is slowly added to the stirred solution of FeCls in chloroform. The mixture is stirred for 70 h at room temperature. The reaction mixture is then quenched by adding it to methanol. The precipitated solid material is separated by filtration and washed with methanol. The crude product is dissolved in chloroform and reprecipitated with methanol. The refined polymer is washed with methanol and dried at room temperature under vacuum overnight. 

A solution eontaining 10 w/w% of polyearbonate in ehloroform is prepared, and pyrrole (5 to 30 w/w%) is then added. A saturated solution of FeCls in methanol is prepared separately and added to the previous solution under vigorous stirring the quantity of ferric chloride is always in a 2.2 to 1 ratio with pyrrole. The mixture is stirred for one day, and then the polymer is collected by filtration and thoroughly washed with methanol and water before being dried at 50 °C in oven. 

Polypropylene particles (5 g) of about 35 pm in diameter are dispersed in 160mL of a waterrmethanol mixture (volume ratio 5 2) and then FeQs is added. Pyrrole is separately dissolved in 20 mL methanol and injected dropwise under vigorous stirring. The pyrrole concentration range may vary from 1 to 10% w/w. The mole ratio of FeCls to pyrrole is 2.3. The reactional mixture is then stirred for a few hours. The reaction product is filtered off and washed successively with distilled water and methanol. The composite particles are dried in a vacuum oven at 50 °C for 6 h. 

Anhydrous FeCls (0.590 g, 3.64 mmol) is added to a solution of monomer lla " (255 mg, 0.91 mmol) in 25 mL of dry CHCI3, under N2 atmosphere. The resulting mixture is stirred at room temperature for 24 h. The solvent is removed under vacuum and the solid is washed with methanol. The crude product is filtered and further purified by Soxhlet extraction for 24 h against acetone. The... 

In a 3.0-mL conical vial containing a boiling stone, and equipped with an air condenser, place 1 drop of the liquid unknown (—10 mg if a solid) followed by 0.5 mL of 1.0 M ethanolic hydroxylamine hydrochloride solution. Add 10% methanolic KOH to this solution (dropwise) until the resulting solution has pH —10 (pH paper). Heat this mixture to reflux temperature using a sand bath for 5 min, cool to room temperature, and acidify to pH = 3 by dropwise addition of 5% aqueous HCl solution. Now add 2 drops of 5% aqueous FeCls solution. The formation of a red-to-purple color is a positive test. 

The rate constants for the formation of FeCl + from Fe and Cl have been measured as a function of solvent composition in water-methanol mixtures. As with most complexation reactions of iron(m), the apparent rate constant Arobs is dependent on pH, indicating the existence of two parallel pathways (Scheme 1). Both... 

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