Organic halides acyl chloride reactions

Organozinc compounds can be prepared by direct metallation of organic halides with zinc metal. The procedure makes the coupling reaction more convenient. A mixture of alkyl halide, acyl chloride, and zinc metal upon stirring in the presence of palladium catalyst at room temperature gives the desired ketone.f - " While direct metallation can be carried out efficiently when the zinc-copper couple is used in some cases, the presence of copper ion sometimes prevents the coupling reaction with acyl chloride.f ... 

An intermediate acylnickel halide is first formed by oxidative addition of acyl halides to zero-valent nickel. This intermediate can attack unsaturated ligands with subsequent proton attack from water. It can give rise to benzyl- or benzoin-type coupling products, partially decarbonylate to give ketones, or react with organic halides to give ketones as well. Protonation of certain complexes can give aldehydes. Nickel chloride also acts as catalyst for Friedel-Crafts-type reactions. 

Acyl-transfer reactions are some of the most important conversions in organic chemistry and biochemistry. Recent work has shown that adjacent cationic groups can also activate amides in acyl-transfer reactions. Friedel-Crafts acylations are known to proceed well with carboxylic acids, acid chlorides (and other halides), and acid anhydrides, but there are virtually no examples of acylations with simple amides.19 During studies related to unsaturated amides, we observed a cyclization reaction that is essentially an intramolecular acyl-transfer reaction involving an amide (eq 15). The indanone product is formed by a cyclization involving the dicationic species (40). To examine this further, the related amides 41 and 42 were studied in superacid promoted conversions (eqs 16-17). It was found that amide 42 leads to the indanone product while 41... 

To synthesize a series of organic azides, the authors pumped a solution of the acyl chloride (1.0M in MeCN) through the azide monolith 177, at room temperature (0.5 ml min-1), to afford a residence time of 13 min. In the case of the substrate 3-bromobenzoyl chloride, removal of the reaction solvent in vacuo afforded the respective azide, 3-bromobenzoyl azide, in quantitative yield and excellent purity. Having demonstrated the successful conversion of acyl chlorides to acyl halides, the next step of the investigation was to decompose the acyl azide under flow, in situ, to afford the respective isocyanate. 

Organozinc addition reactions to unsaturated systems lead to an intermediate zinc compound which is in most cases further hydrolyzed to give the corresponding protonated organic compound. This intermediate can also be trapped by reaction with electrophiles (see Electrophile) (E+) such as aldehydes, acyl chlorides, organic halides, silyl halides, and so on. Depending on the nature of the electrophile (see... 

Derivatives of Sn , Ti Cr , V , Cu, Sm are well-known as reductants [108, 109]. In particular, Kagan s reagent Sml2 reduces acyl chlorides to diketones, aldehydes, and ketones to pinacols in aptotic media and to alcohols in protic media [110], It has also been applied to many other organic reactions [110], Cr salts have been extensively used to reduce alkyl- and aryl halides [109]. These reduced metal complexes have been known as reductants of transition metal ions since Taube s pioneering work [108, 109]. 

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. 

Successful reactions of complexes 15 and 33, some occurring in very high yield, with various organic halides (Equations 14-19) will be presented in approximately chronological order. Acyl and aroyl chlorides react to form hydrazido and diazenido complexes, respectively. The latter complexes were treated with one mole of hydrogen chloride to form the hydrazido complexes.The hydrazido complexes can be deprotonated reversibly to give the corresponding diazenido complexes (Equation 14) ... 

---