Acetylation, with acetic anhydride

By dehydration with acetyl chloride, acetic anhydride or with phosphotus oxychloride, for example ... 

The quinaldine is separated from any unreacted aniline and from the alkyl-anilines by treatment with acetic anhydride, basified with sodium carbonate and steam distilled. Only the primary and secondary amines are acetylated the acetylated amines are now much less volatile so that separation from the steam-volatile quinaldine (a tertiary amine) is facile. 

The important chemical properties of acetyl chloride, CH COCl, were described ia the 1850s (10). Acetyl chloride was prepared by distilling a mixture of anhydrous sodium acetate [127-09-3J, C2H202Na, and phosphorous oxychloride [10025-87-3] POCl, and used it to interact with acetic acid yielding acetic anhydride. Acetyl chloride s violent reaction with water has been used to model Hquid-phase reactions. 

Other Reactions of Phospholipids. The unsaturated fatty acid groups in soybean lecithin can be halogenated. Acetic anhydride combined with the amino group of phosphatidylethanolamine forms acetylated compounds. PhosphoHpids form addition compounds with salts of heavy metals. Phosphatidylethanolamine and phosphatidjhnositol have affinities for calcium and magnesium ions that are related to interaction with their polar groups. 

Friedel-Crafts Acylation. The Friedel-Crafts acylation procedure is the most important method for preparing aromatic ketones and thein derivatives. Acetyl chloride (acetic anhydride) reacts with benzene ia the presence of aluminum chloride or acid catalysts to produce acetophenone [98-86-2], CgHgO (1-phenylethanone). Benzene can also be condensed with dicarboxyHc acid anhydrides to yield benzoyl derivatives of carboxyHc acids. These benzoyl derivatives are often used for constmcting polycycHc molecules (Haworth reaction). For example, benzene reacts with succinic anhydride ia the presence of aluminum chloride to produce P-benzoylpropionic acid [2051-95-8] which is converted iato a-tetralone [529-34-0] (30). 

Acetic anhydride (acetyl oxide) is a liquid with a strong offensive odor. It is an irritating and corrosive chemical that must be handled with care. 

Acetic anhydride, condensation with and acetylation of glycine, 46, 1 in cyclization of c-formylphenoxy-acetic acid to coumarone, 46, 28 in cyclization of hippuric acid to 2-phenyl-5-oxazolone, 47, 101 reaction with N-nitroso-N-phenyl-glycine to yield 3-phenylsydnone, 46,96... 

N-Methyl-N-f2-Nitroxy propyl) Nitramine. (Me2NENA N-(2-NitroxypropyI) methyl nitramine. (02N)N(CH3).(CH2CH(0N02).CH3, mw 179.16, N 23.46%, OB to C02 -66.80%, pale yellow oil, mp 22—23°, d 1.320g/cc at 25/4°, RI 1.478 at 25°. Prepn from 2-hydroxy-propylamine after nitration with 98% nitric acid at 10° by reaction of the amine-nitric acid mixt with acetic anhydride acetyl chloride at 35°. Reaction mixt poured on ice. Yield is 74%. No expl properties listed Reft 1) Beil - not found 2) Blomquist, OSRD 4134, 45 119 (1944)... 

Acetic anhydride, acetylation of glu conolactone with, 41, 79 acetylation of hexahydrogalhc acid with, 42, 63... 

Four different methods (vapour-phase acetylation using acetic anhydride, acetylation using ketene gas, liquid phase acetylation using acetic anhydride/xylene, or neat acetic anhydride) were used to acetylate pine wood chips to a variety of WPGs for the production of MUF-bonded particleboards (Nilsson etal., 1988). Composite boards were exposed to unsterile soil in fungal cellar tests. Boards made from ketene acetylated chips were not found to be resistant to decay at the maximum WPG level achieved (17 %) with a liquid acetic anhydride modification, no decay was recorded at a WPG level of c. 18 % after 12 months exposure, whereas with a vapour-phase treatment at the same WPG, evidence for decay was found. 

Acetic acid has been found to react with toluene to form p-methylace-tophenone (Simons et al., 49), to react with benzene to form acetophenone, and to react with phenol to form p-hydroxy acetophenone. Acetyl chloride also formed acetophenone with benzene and acetic anhydride reacted with toluene to form both p-methylacetophenone and 2,4-diace-tyltoluene. Valeric acid reacted with toluene to form p-tolyl-n-butyl ketone. Both benzoic acid and benzoyl chloride reacted with toluene to form p-tolylphenyl ketone. Acenaphthene with either benzoic acid or benzoyl chloride gave 3-benzoylacenaphthene (Fieser and Hershberg,... 

Acetylated aldose oximes with a ring structure have also been obtained during the preparation of the nitriles, both with sodium acetate-acetic anhydride and with pyridine-acetic anhydride. Thus it appears that under these conditions at least a certain amount of the oxime is present in the ring form. 

Padwa et al. (75) found that the unsymmetrical miinchnone 137, which was generated from A-acetyl-7/-benzylglycine (136) and refluxing acetic anhydride, reacts with methyl propiolate to give an 8 1 mixture of pyrroles 138 and 139. The same product ratio is obtained from the reaction of methyl propiolate and the azomethine ylide derived from 7/-benzyl-A(-(a-cyanoethyl)-A(-[(trimethylsilyl)-methyl] amine. 

Cr(CO)6 react with phthalonitrile in hot 1-chloronaphthalene to precipitate the ft form of CrnPc which is readily oxidized to CrI11(Pc)OH in air.197,198 The hydroxide coordinates other ligands to form six-coordinate complexes, Crni(Pc)(OH)X (X = ROH, H20, CN, SCN, SeCN). The hydroxy group is substituted by CN in cone. KCN solution and Cri PcXChOj - is formed. Acetic anhydride acetylates Cr(Pc)(OH)(OH2) in a stepwise fashion to Cr(Pc)(OAc)(OH2) and Cr(Pc)(OAc)(HOAc). 

The results for nitration by solutions of nitric acid in acetic anhydride were omitted from the above discussion since this reaction has several special features. Unlike the other solvents, acetic anhydride reacts with nitric acid with the result that the stoichiometric nitric acid is actually present as acetyl nitrate as shown in (30). However, the marked retardation of the reaction by trace amounts of ionized nitrates shows that the actual electrophile is a positive ion present in very low concentration (Paul, 1958 Ridd, 1966). 

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