Ferric chloride-Dimethylformamide

OXIDATIVE COUPLING Cuprous chloride. Ferric chloride-Dimethylformamide. Manganese dioxide. Palladium(ll) chloride. Potassium ferricyanide. Silver carbonate-Celite. Thallium(Ill) trifluoroacetate. 

Faraneol, 361 Famesol, 295 Famesyl acetate, 50 Favorskii rearrangement, 457 Ferric chloride, 69,110,111,236,250 Ferric chloride-Dimethylformamide, 236-237... 

By the reaction in tetrahydrofuran at 45°C over 12 hours of 3-ethynylphthalide and a pentacarbonyl chromium carbene complex of the cyclohexenone ketal depicted, followed by treatment of the product with ferric chloride-dimethylformamide (2 moles) a 74% yield of an anthracycline-type structure was obtained (ref.51). 

The most suitable oxidizing agent is potassium ferricyanide, but ferric chloride, hydrogen peroxide ia the presence of ferrous salts, ammonium persulfate, lead dioxide, lead tetraacetate or chromate, or silver and cupric salts may be useful. Water mixed, eg, with methanol, dimethylformamide, or glycol ethers, is employed as reaction medium. 

Bamford et have also determined l<2 for the reduction of ferric chloride in dimethylformamide by different R-, viz. and regard their results as evidence for an electron-transfer mechanism... 

Bromo-ll//-pyrido[2,l-b]quinazolin-ll-one and its 8-methyl and 8-isopropyl derivatives (127, R = Br, R1 = H, Me, iPr) were treated with carbon monoxide and nickel carbonyl in wet dimethylformamide in the presence of calcium hydroxyde to yield 2-carboxylic acid derivatives (127, R = COOH, R1 = H, Me, iPr). 2-Bromo-8-isopropyl-ll//-pyrido[2,l-b]-quinazolin-ll-one (127, R = Br, R1 = iPr) was reacted with copper(I) cyanide in iV-methyl-2-pyrrolidone at 180°C for 10 h, then with ferric chloride hexahydrate in diluted hydrochloric acid at 90°C for 30 min to give the 2-cyano derivative (127, R = CN, R1 = iPr) (85CP1189509). 

The diketone (15.20 g, 100 mmol) is dissolved in 27 mL of dry tetrahydrofuran in a 50-mL, round-bottomed flask and added dropwise through a 16-gauge cannula (nitrogen pressure) during 35 min to the lithium diisopropylamide solution. This mixture is stirred for 30 min at -78°C and is added in turn to 280.4 mL (300 mmol) of a 1.07 M solution of anhydrous ferric chloride (Note 10) in dry dimethylformamide diluted with 39 mL of dry dimethylformamide and contained in a 1-L, three-necked, round-bottomed flask equipped with an efficient mechanical stirrer and cooled to -78°C (Note 11). This addition is accomplished as rapidly as possible through an 8-gauge cannula... 

Very recently, it has been shown that A-halosuccinimides in dimethylformamide convert phenanthridone and its 3,8-dihalo derivatives into the corresponding 2-halophenanthridones under forcing conditions 2,4-dihalophenanthridones are formed in low yields. Although phenanthridone is chlorinated successfully with excess chlorine in acetic acid containing traces of ferric chloride, bromination does not occur with the milder reagent, aqueous hydro-bromic acid in dimethyl sulfoxide.101... 

Esters of carboxylic acids undergo oxidative coupling in the a positions with respect to ester groups when treated in the enolate form with ferric chloride. Thus ethyl acetate stirred with lithium diisopropylamide in tet-rahydrofuran at -78 °C for 10 min and subsequently with anhydrous ferric chloride in dimethylformamide yields 69% of diethyl succinate [911]. 

It is possible to demonstrate the chain-transfer properties of hydrogen peroxide and utilize this reagent to control the product molecular weight distribution by polymerizing N-vinylpyrrolidone in ethanol using AIBN as initiator and hydrogen peroxide as a chain-transfer agent [61]. In dimethylformamide, ferric chloride acts as a polymerization retarder [62]. 

Sodium dithionite in water or aqueous dimethylformamide is an economic, efficient system for the dehalogenation of a-halo-ketones. Other reagents that have been described recently for dehalogenation include iron-graphite (prepared by reduction of ferric chloride with potassium-graphite), sodium 0,0-diethyl phosphorotelluroate, and sodium borohydride in the presence of a catalytic amount of bis(2-thienyl) ditelluride. ... 

NO2 NO2 0 NO2 -C.N.(CH2)2.N.(CH2)2.N.C.0.CH2.C.CH20-N02 CH2 mw (425.32)n, N 23.06%, OB to CO2 -58.31%, amorph solid, mp 70—80°. Sol m acet. The imtial polymer is prepd by dropwise addition of a sob of the diisocyanate in dimethylforma-mide to a dimethylformamide sob of an equiv wt of diol plus 1x10" mole ferric acetylacetonate catalyst over a period of 15 mbs. Polymerization is completed b 136 hrs at 50°. After dilution with dimethylformamide, the polymer is pptd b w and vacuum dried. Post polymerization nitration is accomphshed by soln of the polymer b 100% nitric acid at 0° b the ratio of 1 g polymer to 15ml acid. Nitration is completed on sob of the polymer. The excess acid is vacuum distd at RT, the polymer is dissolved b acet and pptd in methylene chloride... 

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