Fluoro-substituted benzoyl chlorides

The cr-substituent effects and solvent effects (extended Grunwald-Winstein equation) for solvolyses of / -X-substituted benzoyl chlorides (X = OMe, Me, H, and Cl) in 97% wt/wt hexafluoroisopropanol/water was explained by two competing pathways. Plots of log k versus a were consistent with a cationic path and explained by an 5 n2-5n1 spectrum of mechanism. Electron-donating groups favoured the reaction and values of p increased in the order AcOH < HCO2H < TEE < HFIP. A benzoyl cation intermediate was trapped in hexafluoroisopropanol. Ab initio calculations of heterolytic bond dissociation energies of various chloro- and fluoro-substituted and other benzoyl chlorides were correlated with log k for solvolyses... 

The reaction of a solution 2-hydrazinobenzothiazoles in DMF with formic acid, benzoyl chloride, or acetyl chloride, in the presence of potassium carbonate, gave the 8-fluoro-9-substituted-[l,3]-benzothiazolo[5,l-3]3-substi-tuted-1,2,4-triazoles in good yield, as shown for 6-fluoro-7-(2 -nitrophenylamino)-2-hydrazinobenzothiazole 395 yielding compound 396 (Equation 75) <2004IJH89>. 

Amino groups in dithioacetals undergo normal substitution reactions. Conventional reactions have been reported to occur with acetic anhydride,88,90,91 benzoyl chloride,46,92 l-fluoro-2,4-dinitrobenzene,250 p-toluenesulfonyl chloride,247 and benzyloxycarbonyl chloride92 the reported92 application of sodium chloride and methyl iodide to the conversion of 2-amino-2-deoxy-D-glucose diethyl dithioacetal hydrochloride into a pentamethyl derivative is presumed to be an error. Although crude 2-acetamido-2-deoxy-D-glucose diethyl dithioacetal was in one instance converted in low yield into a poorly... 

It has not proved possible to obtain C-alkylated products from diethyl 1-(ethoxycarbonyl )meth-ylphosphonate by the action of acetyl chloride on the alkali metal salts. However, when the ethoxymagnesium salt of diethyl l-(ethoxycarbonyl)methylphosphonate is employed, diethyl 1-ethoxycarbonyl-l-acetyhnethylphosphonate is isolated in a good yield (73%, Scheme 8.20). Similarly, diethyl 1-ethoxycarbonyl-l-benzoyhnethylphosphonate has been prepared in 56% yield from diethyl l-(ethoxycarbonyl)methylphosphonate and benzoyl chloride. The diethyl 1-lithio-1-fluoro-l-(ethoxycarbonyl)methylphosphonate generated with n-BuLi in THF reacts with acid chlorides, fluorine-substituted acid chlorides, and oxalylchloride to form the corresponding acylated phosphonates. By contrast, phosphorylation of the sodium diethyl l-(ethoxycarbonyl)meth-ylphosphonate leads to the O-phosphory lation product. The synthetically useful potassium enolate of diethyl 1,2-/ .v(ethoxycarbonyl)-2-oxocthylphosphonatc is prepared by reaction of the potassium salt of diethyl l-(ethoxycarbonyl)methylphosphonate with diethyl oxalate. ... 

Pyrazolo[3,4-Z)]pyridines, the 7-chloro-6-fluoro-2,4-dimethylquinoline and its mercapto-thiadiazolyl or oxadiazolyl quinolines 21 were prepared via Diels-Alder reaction conversion of methyl 2-(3-oxo-3-phenylpropenylamino)benzoate into 3-benzoyl-l.S -quinolin-4-one 22 . A mixture of aniline derivatives and malonic ester gave a variety of 3-aryl-4-hydroxyquinolin-2(l//)-ones 23. Condensation of isatins with ketones afforded quinoline-4-carboxylic acids. 2-Aryl-l,2,3,4-tetrahydro-4-quinolinones 22 and carbazolylquinolone were also prepared. The substitution of 2-chloroquinoline gave the 2-substituted quinolines. Basic alumina has catalyzed the C-C bond formation between 2-hydroxy-1,4-naphthoquinone and 2-chloroquinoline derivative to give 21. Reaction of organic halides with 8-hydroxyquinolines gave the respective ethers. The azodye derivatives of 21 were prepared in the absence of solvent. Silica gel catalyzed the formation of 2-ketomethylquinolines from reaction of 2-methylquinolines with acyl chlorides. 

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