Diphenyl iron chloride

FeBgCigHso, [l,l-commo-bis(2,3-dicarba-l-ferra-c/oio-heptaborane)](12),2,2, 3,3 -tetraethyI-l,l-dihydro-, 22 215 FeBrMg02PC29H4s, Magnesium, bromo(Ti -cyclopentadienyI)[l, 2-ethanediyl-bis(diphenylphosphine)]bis-(tet ahy-d ofu an)i on-, (Fe-Mg), 24 172 FeBrP2C3iH29, Iron, bromo(Ti -cyclopenta-dienyl)[l,2-ethanediylbis(diphenyl-phosphine)]-, 24 170 FeQO, Iron chloride oxide intercalate with 4-aminopyridine (4 1),22 86... 

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

Reagent 1 Spmy solution 1 Dissolve 1 g iron(III) chloride and 1 g diphenyl-amine in 100 ml cone, sulfuric acid. 

The dianion of 6,6 -bis(2,2 -diphenyl-2-sulfanylethyl)-2,2 -bipyridine (201) gives a chloro-iron(III) complex in which the metal is pentacoordinated (distorted square pyramid with the tetradentate ligand equatorial, chloride axial) and in the 5=3/2 state. 

Crich and Rumthao reported a new synthesis of carbazomycin B using a benzeneselenol-catalyzed, stannane-mediated addition of an aryl radical to the functionalized iodocarbamate 835, followed by cyclization and dehydrogenative aromatization (622). The iodocarbamate 835 required for the key radical reaction was obtained from the nitrophenol 784 (609) (see Scheme 5.85). lodination of 784, followed by acetylation, afforded 3,4-dimethyl-6-iodo-2-methoxy-5-nitrophenyl acetate 834. Reduction of 834 with iron and ferric chloride in acetic acid, followed by reaction with methyl chloroformate, led to the iodocarbamate 835. Reaction of 835 and diphenyl diselenide in refluxing benzene with tributyltin hydride and azobisisobutyronitrile (AIBN) gave the adduct 836 in 40% yield, along with 8% of the recovered substrate and 12% of the deiodinated carbamate 837. Treatment of 836 with phenylselenenyl bromide in dichloromethane afforded the phenylselenenyltetrahydrocarbazole 838. Oxidative... 

Friedel-Crafts sulfonylation of benzene and its derivatives can also be carried out using iron(III) chloride-based ionic liquids, as was shown by Samant and coworkers [23]. For example, the synthesis of diphenyl sulfone, an important intermediate for the anti-leprosy drug Dapsone, was achieved in 78% yield catalyzed by 1-butyl-3-methylimidazolium chloride combined with FeCl3 (Scheme 6.7). 

Fe reduction. Sections of roots can then be viewed under the microscope and the stain located. Bell et al. (1988) have evaluated the use of ferricyanide and the use of nitro-BT, [2,2 -di-/>-nitro-phenyl-5,5 -diphenyl]-3,3 -(3,3 -dimethoxy-4,4 -biphenylene)-di-tetrazolium chloride. With ferricyanide, iron-stressed tomato plants were mainly stained on the younger roots hairs located on the laterals or primary root tip. Nitro-BT is thought to compete with Fe(III) at the same transmembrane ferric reduction site (Sijmons and Bienfate, 1983). A purple diformazan precipitate is produced on reduction. Although the roots were stained in a similar way to those incubated with ferricyanide, Bell et al. (1988) point out that further research is required to determine if nitro-BT reduction completes with ferric reduction at the same site in the tomato. The iron-stress redox activity has been shown to be localised on the plasma membrane in tomato roots (Buckout et al., 1989), and electron microscopic examination (see next section) of the roots stained with Prussian blue indicated that the PB had accumulated between the plasma membrane and the cell walls of the root hairs and epidermal cells (Wergin et al., 1988). 

Handbook of Chemistry and Physics" (1983), 63. Edition, CRC Press, Boca Raton Kurz J, Ballschmiter K (1995), Fresenius J. Anal. Chem. 351 98-109. Isomer-specific determination of 79 polychlorinated diphenyl ethers (PCDE) in cod liver oils, chlorophenols and in a fly ash" Nestrick TJ, Lamparski LL, Crummett WB (1987), Chemosphere 16 777-790. Thermolytic surface reaction of benzene and iron(III) chloride to form chlorinated dibenzo-p-dioxins and dibenzofurans"... 

The most frequently applied ligands are 2,2 -binaphthol (BINOL la) and 2,2 -bis(diphenyl-phosphino)binaphthyl (BINAP lb). Both antipodes of these compounds are commercially available in enantiopure form, though not at little cost [3]. It is rewarding, therefore, to become acquainted with the syntheses of these compounds, which have been described in detail [4J and have been simplified substantially on the basis of recent publications [5J. The iron(lIl)-catalyzed dimerization of 2-naphthol (2) to give racemic BINOL (rac)-la succeeds smoothly and on a large scale (Scheme 1). Its resolution can be achieved easily with N-benzylcinchoidinium chloride (3) and yields both (/ )- and (5 )-la in high enantiomeric excesses. After conversion into the ditri-flate 4, enantiopure la can be coupled with diphe-nylphosphine (or, in lower yield, with cheaper chlorodiphenylphosphine) in a nickel-catalyzed... 

The mixture is stirred continuously and maintained for 3 hours at 15° C., when sodium phenyl arsenate is formed. This is neutralised with hydrochloric acid and filtered through a press in order to separate resinous substances which are formed. The phenyl arsenic acid in the filtrate is reduced to phenyl arsenious oxide by passing a current of sulphur dioxide through. A heavy oil deposits at the bottom of the vessel and this is removed by decantation and redissolved in 40° B. sodium hydroxide solution. After diluting with 8 cu. m. of water, the solution is cooled to 15° C. and run slowly into another solution of diazobenzene chloride prepared as before. The sodium salt of diphenyl arsenic acid which is formed is slightly acidified with hydrochloric acid, the diphenyl arsenic acid filtered off and redissolved in 20° B6. hydrochloric acid (i part of the arsenic acid requires 3 parts of hydrochloric acid) and the solution obtained is then run into an iron vessel, lined internally with tiles. Sulphur dioxide is then passed through for 8 hours while the temperature is maintained at about 80° C. Diphenyl chloroarsine then separates as an oil which forms a layer at the bottom of the vessel. It is separated off and dried in vacuo. 

Unlike diphenyl chloroarsine, phenarsazine chloride attacks iron, steel, bronze and copper. 

Ferrox Test. In a dry test tube grind together, with a stirring rod, a crystal of iron(III) ammonium sulfate (or iron(III) chloride) and a crystal of potassium thiocyanate. Iron(III) hexathiocyanatoferrate(III) will adhere to the stirring rod. In a clean tube place 3 drops of a liquid unknown or a saturated toluene solution of a solid unknown and stir with the rod. The salt will dissolve if the unknown contains oxygen to give a red-purple color, but it will not dissolve in hydrocarbons or halocarbons. Diphenyl ether does not give a positive test. 

In a synthesis of trans,Irons-1,4-diphenyl-1,3-butadiene the required phos-phonium chloride is prepared by heating a mixture of triphenylphosphine and cinnamyl chloride with stirring under reflux for 12 hrs. The salt, which separates as... 

Radicals Azobisisobutyronitrile. a,T-Bis(diphenylene)-d-phenylallyL r-Butyl perbenzoate. 7-Butyrolactone. Dibenzoyl peroxide. Di-r-butyl nitroxidc. Di-r-butyl peroxide. Diphenyl-picrylhydrazyl. Galvinoxyl. Hydrogen peroxide-iron salts. Lead dioxide. N-Phenyl-N -benzoyldiimide. Potassium nitrosodisulfonate. Thiolacetic acid. Trichloromethanesulfonyl chloride. 

Uranium. A sample containing ca. 2 millimols of uranium is fumed down with sulfuric acid in a 150-ml. beaker to remove nitrate. Then 20 ml. of 18 M sulfuric acid and 20 ml. of 85% phosphoric acid are added, and the solution is diluted with water to 75 to 80 ml. and cooled. This solution is passed over amalgamated zinc in a reductor at a rate of 30 ml./min. The reductor is washed successively with one 20-ml. portion of 3 Af sulfuric acid, three 40-ml. portions of 7.5% sulfuric acid, and one 40-ml. portion of water, the washings being added to the reduced solution. The resulting light bluish-green uranium (IV) solution is treated with 30 ml. of iron(III) chloride solution (100 g. of the 6-hydrate per liter) and allowed to stand for 5 to 10 min. or until it becomes distinctly yellow. Fifteen milliliters of 85% phosphoric acid and 8 drops of diphenyl-aminesulfonic acid indicator are added, and the solution is titrated immediately with 0.1 N potassium dichromate to a sharp purple end point. 

Diphenyl thioether and (meso-tetraphenylporphyrinato)iron(lll) chloride supported on silica, by treatment with 1 mole of iodosobenzene at ambient temperature, gave with stirring during 3 hours under nitrogen, diphenylsulphoxide in 74% yield with 7% of the corresponding sulphone, formation of which was suppresed by adsorption of the main product on the silica (ref. 123). 

Condensation Reactions. Condensation of substituted benzaldehydes with 2-arninophenol in the presence of a catalyst (aluminum, iron, zinc or phosphoms chlorides) yidds a Schiff base, with the elimination of water, in 52—88% yields (29). In general, substituted diphenyl amines or diphenyl ethers are obtained from arninophenols and suitable reactants by elimination of ammonia or hydrogen chloride. 

The dihalides, RgShHaLg, may be obtained by heating mercury diphenyl with antimony trichloride at a high temperature in an autoclave, or as by-products in the preparation of triarylstibmes by the Fittig reaction. Halogens also add on directly to triarylstibines, gi nng the dihalides, and in the case of chlorine, the following chlorides may replace the free element in the preparation copper, iron, thallium, phosphorus or arsenic chloride. 

Micellar and microemulsion effects on reactivity in aquation and base hydrolysis reactions of iron(II)-diimine complexes have been much studied/ The latest contribution deals with the effects of added potassium chloride or bromide to micelles of the respective cetyltrimethylammonium halides. Effects on base hydrolysis of [Fe(phen)3] and its 4,7-diphenyl and 3,4,7,8-tetramethyl derivatives can be interpreted in terms of competitive binding to the micelles in a pseudophase-ion exchange model. In connection with these secondary effects of added halides it should be mentioned that further studies of kinetics of aquation of [Fe(bipy)3] and of [Fe(phen)3] in strong aqueous solutions of chlorides have been interpreted in terms of water and of chloride attack, with the postulation of transient diimine-chloride-iron(II) intermediates. ... 

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