Alkanoyl chlorides, reaction with

Method I Direct reaction between an amine and an acid first gives a salt strong heating converts the salt to the amide with loss of water. Method 2 Converts to alkanoyl chloride reaction with amine gives amide with loss of HCI. Often done in the presence of excess amine to consume the HC1. Method 3 Esterification with any inexpensive alcohol (ethanol chosen here), then reaction with the amine under mild heating. 

The reduction of aroyl chlorides take a different course in the presence of Ni(ll) salts. Reaction is best effected in an undivided cell with a nickel anode and a nickel foam cathode with acetonitrile containir tetrabutylammonium fluoroborate as electrolyte. Symmetrical ketones are formed [173], Substimted benzoyl chlorides yield the benzophenone in 47-72% yields. Phenacetylchloride also gives the ketone in good yield but in general, alkanoyl chlorides do not react. 

On the other hand, upon reaction with methyl glyoxalate imines, an increase in bulk of the silyl moiety [i.e., PhMe2Si, Ph2MeSi, Ph3Si and (t-Bu)Ph2Si] in fi-(triorganosilyl)alkanoyl chlorides causes a moderate increase in the anti/syn ratio of the [2 + 2] a. v-adducts113. Little effect on the cis/trans ratio is observed. 

The fluorovinyllithium reagents are thermally unstable (vu/e supra) and are reacted with electro-philes at low temperatures. These reagents undergo usual reactions with a variety of electrophiles including ketones, esters, alkanoyl chlorides, epoxides (e.g.. formation of 6 ), oxetanes, carbon dioxide, sulfur dioxide, tin and silicon halides, and trifluoromethancsulfonates. The reaction of 2,2-difluoro-1 -(tosyloxy)vinyllithium (5) with trialkylboranes followed by a second electrophile is an attractive route to functionalized 1.1-difluoroalkenes. e.g. 7. ... 

Another versatile pathway to acid iodides was described by Hoffmann (equation 13). Aliphatic and aromatic acid iodides are prepared in high yields from acid chlorides by reaction with sodium iodide in acetonitrile. A large number of alkanoyl, alkenoyl and aroyl iodides can be prepared in good yields from the corresponding acid chlorides. In the same way it was possible for the first time to obtain diiodides from aliphatic and aromatic dicarboxylic acids. The conversion of acid chlorides to iodides by sodium iodide had been known before the reaction conditions proposed by Hoffmann, however, are milder and the yields are higher. 

Electrophilic reactions. Asymmetric bromination of alkanoyl chlorides with 1,1,3,6-tetrabromo-l,2-dihydronaphthalen-2-one is catalyzed by the quinine - derived 3, it affords (5)-a-bromoaIkanoic esters on alcoholysis of the products Quatemization of quinine with... 

The Nenitzescu reaction [88] of alkanoyl chloride, cyclopentene, and an arene component directly leads to 3-alkanoyl substituted arylcyclopentanes. The scope of the reaction, as with the cyclohexene analogues (see above), has not been researched sufficiently. The alkanoyl functionality can be reduced to alkyl. The carbonyl group can also be used to construct further ring systems. 

The reaction of chlorosulfonic acid with the first three alkanoyl chlorides was extensively investigated by Krajcinovic and afforded some interesting results which were reviewed by Jackson. ... 

Chlorosulfonic acid only reacted slowly with butanoyl chloride 112 at room temperature with continuous evolution of hydrogen chloride and carbon monoxide. The reaction did not yield any butanesulfonic acid, and ether extractions gave 4-heptanone 113 (Equation 43). The results showed that with these alkanoyl chlorides, the greater the number of carbon atoms in the substrate, the fewer the number of moles of the chloride that condense. Thus, 4 moles of acetyl chloride 102 condense to form 2-methylpyran-4-one-6-acetic acid 108 (Scheme 8) while 3 moles of propanoyl chloride 109 condense to yield the pyranedione 111 (Equation 42), and 2 moles of butanoyl chloride 112 form 4-heptanone 113 (Equation 43). The condensation products from acetyl chloride are only isolated at higher temperatures, whereas those derived from the other alkanoyl chlorides decompose at higher temperatures and consequently they are only isolated at room temperature. 

Nickel tetranitrophthalocyanine can be reduced to nickel tetraaminophthalocyanine with tin(II) chloride342 or sodium sulfide.319 343 To achieve better solubility, long alkanoyl side chains can be attached by the reaction of the amino groups with carboxylic acid chlorides.342 Copper(ll) tetranitrophthalocyanine 1 is reduced to the tetraamino compound 2 with sodium suinae." "... 

Carboxy terminal amino acid or peptide thiols are prepared from various p-amino alcohols by conversion into a thioacetate (R2NHCHR1CH2SAc) via a tosylate followed by saponification.Several methods have been used to prepare N-terminal peptide thiols, the most common procedure is the coupling of (acetylsulfanyl)- or (benzoylsulfanyl)alkanoic acids or add chlorides with a-amino esters or peptide esters, followed by deprotection of the sulfanyl and carboxy groups. 8 16 Other synthetic methods include deprotection of (trit-ylsulfanyl)alkanoyl peptides, 1718 alkaline treatment of the thiolactones from protected a-sulfanyl acids, 19 and preparation of P-sulfanylamides (HSCH2CHR1NHCOR2, retro-thior-phan derivatives) from N-protected amino acids by reaction of P-amine disulfides with carboxylic acid derivatives, followed by reduction. 20,21 In many cases, the amino acid or peptide thiols are synthesized as the disulfides and reduced to the corresponding thiols by the addition of dithiothreitol prior to use. 

A comparison of the results obtained with ascorbic acid and isoascorbic acid, in the suspension polymerization of vinyl chloride at 50°C, in the presence of t-butyl peroxyoctoate (t-BPOT) at a peroxyester/reductant mole ratio of 2/1 is given in Table 20. The use of isomeric 6-O-alkanoyl-D-as-corbic acid has been found to result in a significantly higher rate of polymerization, permitting the use of lower concentrations of peroxyester to achieve faster reaction. 

---