Butanoyl chloride, reaction with

Write out the reaction in which butanoyl chloride reacts with aqueous ammonia. 

A related synthesis is the reaction of a racemic chiral phosphonium ylide with enantiomerically enriched (—)-(/t)-2-phenylpropanovl or -butanoyl chloride in a 2 1 molar ratio, which results in partially resolved (excess) phosphonium ylide and in the enantioselective formation of (Af)-allenecarboxylic esters116. 

The construction of the pyranooxepin system shown in equation (52) proceeds by way of a dibenzox-epinone acetic acid, followed by intramolecular enol ester formation.67 The regioselective cyclization of 4-(2-naphthyloxy)butanoyl chloride proceeds as expected (equation 53) using tin(lV) chloride as the catalyst, but a mixture of products was obtained when the related carboxylic acid was treated with poly-phosphoric acid.68 The preparation of a thieno[fr]suberanone in 40% yield has been achieved by the interaction of tin(IV) chloride with 5-(2-thienyl)valeryl chloride.69 Once again, the expected increase in yield is obtained when cyclization occurs to the 2-position in thiophene. The product shown in equation (54) was isolated in 81 % yield.70 Other intramolecular reactions involving thiophenes have been reported.71... 

The carboxylic acid that is the reactant in this reaction is butanoic acid (butyric acid). By dropping the -oic acid ending of the I.U.P.A.C. name (or the -ic acid ending of the common name) and replacing it with -oyl chloride (or -yl chloride), we can write the I.U.P.A.C. and common names of the product of this reaction. They are butanoyl chloride and butyryl chloride, respectively. 

BUTANOYL CHLORIDE (141-75-3) Forms explosive mixture with air (flash point <70°F/<21°C). Slowly reacts with moist air, water, steam, and alcohols, forming hydrogen chloride and phosgene gas. Violent reaction with strong oxidizers, strong bases. Corrodes metals in the presence of moisture. May accumulate static electrical charges may cause ignition of its vapors. 

Reversible PNO-catalyzed benzoyl chloride / carboxylate systems. In contrast to the other carboxylates (see earlier subsection), a peculiar phenomenon was observed in the PNO-catalyzed IPTC reaction of PhCOCl and butanoate (PrCOO ) ion in H2O/CH2CI2 medium, which led to an equilibrium with the PNO-catalyzed reaction of butanoyl chloride (PrCOCl) and benzoate ion and vice versa [188]. It was observed that the PNO-catalyzed reaction of PrCOCl and PhCOO ion reached equilibrium much more rapidly than that of PhCOCl and PrCOO ion. For the PhCOCl/PrCOONa system, the main product was PrCOCl and the expected mixed benzoic butanoic anhydride... 

Acid chlorides are useful precursors to anhydrides, including both symmetrical and mixed (unsymmetrical) anhydrides. In one experiment, heptanoyl chloride (50) reacted with heptanoic acid (51), with benzene as a solvent and in the presence of pyridine (53), to give the symmetrical heptanoic anhydride (53) in 83% isolated yield. Unsymmetrical anhydrides are prepared by choosing which half of the anhydride comes from the acid chloride and which comes from the carboxylic acid. This choice allows one to control formation of the mixed anhydride. If heptanoyl chloride (50) and butanoic acid (7) react in the presence of triethylamine as the base, anhydride 54 is formed. Anhydride 54 can also be prepared by the reaction of butanoyl chloride with hexanoic acid, but the easiest to obtain and cheapest combination is usually used. 

When we react butanoyl chloride with ethanol in benzene solvent, it is common to add triethylamine to the reaction. What purpose does this serve and how does it help ... 

Another type of Friedel-Crafts reaction also involves a carbocation, but not the simple alkyl carbocations discussed in the previous section. When benzene reacts with butanoyl chloride (49) in the presence of AICI3, the isolated product is a ketone butyrophenone (1-phenyl-l-butanone, 50) in 51% yield. It is known that benzene does not react with 49 without the presence of aluminum chloride. Clearly, the acyl unit has reacted with benzene to form the new carbon-carbon bond, with loss of the chlorine atom of 49, but there must be a prior reaction between AICI3 and the acid chloride. This is an aromatic substitution and, based on knowledge of benzene, there must be an arenium ion intermediate. To form an arenium ion, benzene must react with a cationic species, which must arise from 49. What is the nature of this cationic intermediate ... 

Another category of reductions involves aryl ketones. The Friedel-Crafts acylation reaction reacts benzene with an acid chloride such as butanoyl chloride (49) to give an aryl ketone, 50. Complete removal of the oxygen from this ketone constitutes a method to make straight-chain arenes, which cannot be prepared via Friedel-Crafts alkylation (see Section 21.3.2). At least two classical methods are used to accomplish this reaction, which is formally a reduction. If 50 is treated with zinc metal in HCl, the product is 1-phenylbutane, 105. This acidic reduction involves a mineral acid such as HCl and an active metal, and it is called the Clemmensen reduction. 

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. 

Acylation of isobutylbenzene with acetic anhydride leads with high yield and selectivity to para-acetylisobutylbenzene (Eq. 9) which is an intermediate in the synthesis of ibuprofen, an important antiinflammatory drug [18]. With H/1 zeolite at 140 °C after 1 h the yield is 80 % with 96 % para selectivity. Acylation of tetra-lin with acid chlorides and different zeolites has also been studied [19], For this reaction again acetyl chloride is much less reactive than higher acid chlorides such as butanoyl or octanoyl chloride. The selectivity is in favor of the 2-substituted isomer (85-90%) and limited quantities of the 1 isomer (10-15%) are formed (Eq. 10). 

The most prominent cellulose ester produced on the industrial scale is cellulose acetate. The reaction is usually performed with acetic anhydride and with sulfuric acid as a catalyst. To minimize heterogeneities, acetylation is allowed to run nearly to completion, and subsequently partial ester hydrolysis is initiated by the addition of water until a desirable solubility is achieved that corresponds to a DS of about 2.5. Such higher acyl homologues as propanoyl or butanoyl exhibit more thermoplastic properties. Many specialized esters such as chiral (-)-menthyloxyacetates, furan-2-carboxylates, or crown-ether-containing acylates have been prepared on the laboratory scale and characterized by NMR spectroscopy. Various procedures have been applied, using anhydrides and acyl chlorides as acylating agents in combination with such bases as pyridine, 4-dimethylaminopyridine (DMAP), or iV,iV -carbonyldi-imidazole. The substitution pattern of cellulose acetates has also been modified by postchemical enzymatic deacetylation. Cellulose 6-tosylates have been used as activated intermediates for nucleophihc substitution to afford 6-amino-6-deoxy, 6-deoxy, or 6-deoxy-6-halo-celluloses. ... 

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