And acyl halides

Rearrangement is especially prevalent with primary alkyl halides of the type RCH2CH2X and R2CHCH2X Aluminum chloride induces ionization with rearrangement to give a more stable carbocation Benzylic halides and acyl halides do not rearrange... 

Furan can also be acylated by the Vilsmeier-Haack method. Acylation of furans can also be carried out with acid anhydrides and acyl halides in the presence of Friedel-Crafts catalysts (BF3-Et20, SnCU or H3PO4). Reactive anhydrides such as trifluoroacetic anhydride, however, require no catalyst. Acetylation with acetyl p-toluenesulfonate gives high yields. 

Ketenes undergo rapid addition by nucleophilic attack at the sp-carbon atom. The reaction of tertiary amines and acyl halides, in the absence of nucleophiles, is a general preparation for ketenes. ... 

Ruonnated carboxylic anhydrides and acyl halides as common acylating reagents to convert amines to amides and to acy late suitable heterocyclic nitiogen atoms have already been described in the first edition [10] Like in the acylation at oxygen, much synthetic activity was concentrated m the past few years on the denvatization of biomolecules by fluoroacylation reactions, that is, tnfluoroacetylation of amino sugars,... 

The salts of the thiol react with alkyl and acyl halides to form alkyl or acyl derivatives (Table II). For a discussion of the constitution of these compounds see Section IV, D. 

TBAF has been used as a source of fluoride ions in a number of substitution reactions studied by Cox et al. [23]. Allcyl and acyl halides react with TBAF to give the corresponding allcyl or acyl fluoride in good yield. In the reaction between (R)-2-tosyloctane and TBAF, the product was (S)-2-fluorooctane, confirming an Sn2 mechanism for the reaction (Scheme 5.1-5) [18, 23]. 

When nitronium salts are used, NOj is of course present to begin with. Esters and acyl halides of nitric acid ionize to form NOj. Nitrocyclohexadienones are converted to NO2 and the corresponding phenol." ... 

Rearrangement of hydroxamic acids and acyl halides (Lossen)... 

Reaction of alkyl and acyl halides with peroxide ion... 

The cross-coupling reactions of benzylic halides and acyl halides produced the expected ketones in good to high yields(39,47). The present method can supplement the corresponding Grignard reaction, which does not work well since benzylmagnesium halides undergo dimerization readily. 

The reaction may be reasonably explained by the smooth oxidative addition of benzylic and acyl halides to nickel to afford benzylnickel halides and acylnickel halides. The metathesis of these complexes could give the acylbenzylnickel complex, which upon reductive elimination would yield the benzyl ketone. 

As with carboxylic acids obtained by palladium hydroxycarbonylation, their derivatives esters, amides, anhydrides and acyl halides are synthesized from alkenes, CO and HX (X = OR, NR2 etc.). The Pd-catalyzed methoxycarbonylation is one of the most studied reactions among this type of catalyzed carbonylations and has been reviewed and included in reports of homogeneous catalysis.625, 26 The methoxycarbonylation has been applied to many different substrates to obtain intermediates in organic syntheses as well as specific products. For instance, the reaction has been applied for methoxycarbonylation of alkynes666 Highly efficient homogeneous Pd cationic catalysts have been reported and the methoxycarbonylation of alkynes has been used to develop economically attractive and environmentally benign process for the production of methyl... 

Fig. 2.4. Generation and O-alkylation of nucleophilic acyl complexes from metallates and acyl halides [101].

Friedeb Crafts reaction Anisole undergoes Friedel-Crafts reaction, i.e., the all rl and acyl groups are introduced at ortho and para positions by reaction with alkyl halide and acyl halide in the presence of anhydrous alurntnlurn chloride (a Lewis acid) as catalyst. 

Detailed studies have also been reported of the ability of the [IrX2(CO)2] anions to add a variety of molecules such as halogens, alkyl and acyl halides, mercuric halides, and On the other hand, the attempted oxidative... 

As hydrogen fluoride functions with equal ease in alkylation with olefins, alkyl halides, or alcohols, and in acylation with acids, acid anhydrides as well as acyl halides, a wide choice of reagents is possible and a separate operation of the reconversion of them is often saved. With aluminum chloride the alkyl halides and acyl halides are the preferred reagents and frequently must be made from more plentiful, cheaper, and readily available substances. 

Alkyl and acyl halides react directly with quinoline to give A-alkyl-or A-acylquinolinium salts (Scheme 3.4). Whereas the A-alkyl salts are stable and can often be isolated as crystalline solids, the A -acyl analogues are unstable and undergo rapid hydrolysis in moist air or in aqueous solution. 

Alkynylzinc chlorides are useful imermedtates in Pd°-catalysed couplings with vinyl, heteroaryl [56) and acyl halides [89] tsee Chaps. V and X). The conversion of lithium alkyn-vlides into alkynylzinc halides with anhydrous zinc chloride in THF proceeds smoothly and quantitatively under mild conditions. 

Carboxylic acids and their derivatives like esters, amides, anhydrides, and acyl halides are formally synthesized from olefins, carbon monoxide, and compounds represented by Nu-H such as H2O, ROH, RNH2, RCOOH (Equations (4) and (5)). Alkynes also react under similar conditions to afford the corresponding unsaturated carboxylic acid derivatives. These reactions have been named hydrocarboxylation, hydroalkoxycarbonylation, and hydroaminocarbonylation. 

Organic carbonyl compounds—aldehydes, ketones, amides, and acyl halides—in which the carbonyl group is not part of a cyclic structure have interesting conformational properties that may differ widely according to the molecular system bearing these substituents. 

Halogenation of Carboxylic Acids and Acyl Halides Halogenation or Halo-de-hydrogenation... 

Decarbonylation of Aldehydes and Acyl Halides Carbonyl-extrusion... 

Introduction of the cyano group through anhydrous [Ph3P=N=PPh3]+CN-proceeds smoothly and quantitatively on alkyl and acyl halides (phase-transfer catalysis reactions required higher temperatures and gave by-products)536. 

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