Benzoic acid anhydride synthesis

An acyl transfer agent which can be used for the synthesis of acid anhydrides is obtained from the reaction of an acid chloride with 4-benzylpyridine (equation 24). In this way benzoic acid anhydride and cinnamic acid anhydride were obtained in 72% and 57% yields, respectively. As the intermediate, 1-acyl-4-benzylidene-l,4-dihydropyridines, can be isolated, Ais procedure should be well suited for the preparation of mixed anhydrides. Mixed aromatic and aliphatic anhydrides can be prepared with 2-ben-zoylthio-l-methylpyridinium chloride and salts of carboxylic acids. These reactions are carried out in aqueous solution. Iliey make use of the high reactivity of esters of thiocarboxylic esters towards nucleophiles. The mixed anhydrides of benzoic acid with 3-phenylpropanoic acid, phenoxyacetic acid, isobu-tyric acid, p-toluic acid and cinnamic acid were formed in 82, 79,61,91 and 66% yields, respectively. 

Phthalic anhydride condenses with the aniline derivative in the presence of zinc or aluminum chlorides to yield the intermediate benzoyl-benzoic acid, which subsequently reacts with l,3-bis-V,V-dimethylaniline in acetic anhydride to yield the phthalide. The above compound gives a violet-gray image when applied to a clay developer. Clearly this synthesis is also very flexible and variations in shades of color formers have been obtained by varying the aniline components and also by using phthalic anhydrides substituted, for example, by nitro groups or chlorine atoms. Such products have excellent properties as color formers and have been used commercially. Furthermore, this synthetic route is of great importance for the preparation of heterocyclic substituted phthalides, as will be seen later. 

Pigment Yellow 138,56300, has the chemical structure 138 with X = C1 [4], The synthesis of halogenated compounds (138), for instance P.Y.138, can also be achieved by stepwise heating of tetrachloro phthalic anhydride and 8-amino-chinaldine in molten benzoic acid from 125 to 140 and then to 160°C [5],... 

Formerly, benzoic acid was produced by the decarboxylation of phthalic anhydride. Oxidation of acetophenon, benzyl bromide, and toluene with sulfur and water has been described in the literature, but are not commercially feasible routes of synthesis. Carboxylation of benzene with carbon dioxide is not practical due to the instability of benzoic acid at the required reaction conditions [8]. 

Methyl anthraquinone has been obtained by the oxidation of /3-methyl anthracene by several investigators 1 and material of the same origin, obtained by the benzene-extraction of crude commercial anthraquinone,2 has been fully described. As regards the synthesis from phthalic anhydride and toluene, both the preparation and properties of />-toluyl-o-benzoic acid 3 and the complete synthesis 4 have been the subject of several papers. This acid has also been prepared from o-carbomethoxy benzoyl chloride and toluene.5 The phthalic anhydride synthesis of anthraquinone derivatives in general has received considerable attention. An account of this work, together with extensive references, is given by Barnett.6... 

Velsicol Chemical LLC, formerly Velsicol Chemical Corporation, designs, manufactures, markets and distributes high performance specialty chemicals and industrial intermediates, primarily based on benzoic acid and the organic compound cyclopentadiene. Its products include chlorendic anhydride and hexachlorocyclopentadiene (HEX). Chlorendic anhydride is corrosion resistant, fire resistant and has high UV stability, and is used in the synthesis of flame retardant polymers such as polyurethanes, unsaturated polyester and epoxy resins. HEX, a reactive intermediate used in the manufacture of agricultural pesticides in the production of flame retardants for the wire and cable industry and in the preparation of chlorendic anhydride. The company s products are produced primarily at a plant in Memphis, Tennessee Velsicol also maintains the Memphis Environmental Center (MEC), which focuses on managing legacy environmental liabilities. The firm is owned by Arsenal Capital Partners, a private equity firm. 

Catalysis of the synthesis of benzoic anhydride and the hydrolysis of benzoyl chloride, diphenyl phosphorochloridate (DPPC), and benzoic isobutyric anhydride in dichloromethane-water suspensions by water-insoluble silanes and siloxanes, 3- and 4-trimethylsilylpyridine 1-oxide (3b and 3c, respectively), 1,3-bis(l-oxypyridin-3-yl)-l,1,3,3-tetramethyldisiloxane (4), and poly[methyl(l-oxypyridin-3-yl)-siloxane] (5) was compared with catalysis in the same systems by water-soluble pyridine 1-oxide (3a) and poly(4-vinylpyridine 1-oxide) (6). All catalysts were effective for anhydride synthesis and promoted the disproportionation of benzoic isobutyric anhydride. Hydrolysis of benzoyl chloride gave benzoic anhydride in high yield ( 80%) for all catalysts except 3a, which gave mixtures of anhydride (52%) and benzoic acid (39%). The order of catalytic activity for DPPC hydrolysis was 5 > 4 > 3b > 3a > 3c > 6. The results suggest that hydrophobic binding between catalyst and lipophilic substrate plays an important role in these processes. 

Naphthalene to Anthranilic Acid.—Such a cheap source was found in naphthalene which was converted into anthranilic acid, orthoamino benzoic acid, and this by treatment with chlor acetic acid yields phenyl glycine ortho-carboxylic acid. The complete synthesis is as follows Naphthalene is oxidized to or// o-phthalic acid which then yields phthalic anhydride. This with ammonia, as ammonium carbonate, yields phthalimide or phthalamidic acid. 

Glaessner, Austria, 1931), ammoniacal bleached shellac (Wruble, 1933), stearic acid, carnauba wax, petrolatum, elm bark, and agar (Miller, 1935, and Worton, 1938), and abietic, oleic, and benzoic acids with methyl abietate (Eldred, 1937). Since 1940, research on enteric coatings has focused on the synthesis of resinous polymers, which are insoluble in acids, such as cellulose acetate phthalate (Hiatt, 1940) and a glycerol-stearic acid-phthalic anhydride ester (Volweiler and Moore, 1940). 

Mixed anhydride synthesis. For use of the reagent in peptide synthesis, see Butyl chloroformate. The principle involved is illustrated by a procedure for the preparation of diethyl benzoylmalonate (3). Benzoic acid is condensed with cathyl chloride in toluene in the presence of triethylamine to produce the mixed anhydride (I), and an ethereal solution of ethoxymagnesium malonic ester (2), prepared from mulunic ester, magnesium, ethanol, and a trace of carbon tetrachloride as catalyst, is added... 

Mixed anhydride synthesis. A method widfely used for the synthesis of peptides provides a general method of acylation, illustrated by the benzoylation of diethyl malonate. Benzoic acid is converted into the triethylamine salt in toluene, and the solution is treated at 0 with ethyl chloroformate to form the mixed benzoic-carbonic anhydride, with precipitation of triethylamine hydrochloride. The second component, ethoxymagnesium malonic ester, is prepared from diethyl malonate in ethanol-ether... 

Polyester fibres, specifically PETP, possess high thermal stability and sufficient resistance to light effect and atmospheric action. However, effect of high temperatures, to which PETP is subjected in the process of synthesis and processing into products, may cause thermal destruction of polymer and in the absence of oxygen. Decrease of molecular mass, increase of end groups quantity, extraction of volatile products, the main of which are terephthalic acid, acetaldehyde and carbon oxide are observed at PETP thermal destruction. Besides these substances, anhydride groups, benzoic acid, p-acetyl-benzoic acid, ketones, acetals are identified in the compound mixture of the products of thermal decay [34]. 

The formation of anthraquinone from phthalic anhydride and benzene by the Friedel and Crafts synthesis is conducted in the presence of aluminum chloride.58 Ortho-benzoyl benzoic acid is first formed and then... 

Kricheldorf has reported the synthesis of lyotropic poly(amide-imide)s and poly(benzoxazole-amide)s. These were prepared by the polycondensation of N,N-bis(trimethylsilyl)-p-phenylenediamine or N,AT -bis(trimethylsilyl)-3,3 -dim-ethylbenzidine with the diacyl chloride of trimellitimide of p-aminobenzoic acid, or the imide formed from p-amino benzoic acid and terephthalic acid. Lyotropic behaviour was observed in cone, sulphuric acid solution [38]. A series of thermotropic poly(imide-amide)s was prepared based on trimellitimides formed from trimellitic anhydride and an a, -bis(4-aminophenoxy) alkane with carbon chain lengths 9-12. Melting points were in the range 250-300 °C. They formed smectic A phases and tended to degrade around the isotropisation temperatures (around 350 °C). Pendant methyl groups or occupied meta- groups tended to prevent mesophase formation [39]. Novel LC poly(imide-amides) have also been synthesised from new diamine spacers derived from linear diaminoalkanes and 4-nitrophthalic anhydride. A smectic and nematic phase were observed when 4,4 -biphenyl dicarboxylic acid was used as co-monomer [40]. 

The Dakin-West synthesis of a>acylamino ketones16 is closely related to the decarboxylation of a-amino carboxylic acids. Interaction of a carboxylic acid anhydride, e.g., acetic or benzoic anhydride, and an amino acid in the presence of pyridine or some similar base affords the derived a>acylamino ketone by decarboxylation. 

Similarly to the preparation of polynaphthoylenebenzimidazoles from sulfide-containing bis(naphthalic anhydrides) [92, 107-110], tlw synthesis has been carried out by a high-temperature catalytic polycondensation method in m-cresol using benzoic acid as catalyst. 

The properties of polynaphthoylenebenzimidazoles can be affected by the introduction of 1,1-dichloroethylene and 1,1-dibromoethylene groupings into the macromolecules using the application of the corresponding bis(naphthalic anhydrides) [148-151, 196]. Synthesis of polynaphthoylenebenzimidazoles containing 1,1-dichloroethylene and 1,1-dibromoethylene bridging groups [114,148-151,196] was carried out in m-cresol using benzoic acid as a catalyst ... 

Hydroxy-l,2-benziodoxole-3(l//)-one (104) is commercially available or can be easily prepared by direct oxidation of 2-iodobenzoic acid or by basic hydrolysis of 2-(dichloroiodo)benzoic acid [232,233,274]. A more recent preparative procedure for 104 involves the oxidation of 2-iodobenzoic acid with acetyl nitrate in acetic anhydride at room temperature followed by aqueous work-up [275]. In the 1980s benziodoxole 104 and other hydroxybenziodoxoles attracted considerable research interest due to their excellent catalytic activity in the cleavage of toxic phosphates and reactive esters. This activity is explained by a pronounced O-nucleophilicity of the benziodoxole anion 105 due to the a-effect [234,272,276]. Spectroscopic and kinetic mechanistic studies indicate that the highly unstable iodoxole derivatives, such as the phosphate 107, are reactive intermediates in catalytic cleavage of phosphates, as shown for the catalytic hydrolysis of a typical substrate 106 (Scheme 2.39) [277-279]. This mechanism was proved by the synthesis and reactivity studies of the phosphate intermediate 107. 

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