4- -benzoic resins

Benzoic and salicylic acid ointment - 230 Benzoic resin - 232 Benzol (see Benzene)... 

Benzoic Resin 22 7 5 Moderate resistance-some visual " ... 

Polyethylene, HOPE Benzenecarbonyl Chloride 9 Benzoic Resin Polystyrene, Impact (IPS) 0... 

It was first described in 1608 when it was sublimed out of gum benzoin. It also occurs in many other natural resins. Benzoic acid is manufactured by the air oxidation of toluene in the liquid phase at 150°C and 4-6 atm. in the presence of a cobalt catalyst by the partial decarboxylation of phthalic anhydride in either the liquid or vapour phase in the presence of water by the hydrolysis of benzotrichloride (from the chlorination of toluene) in the presence of zinc chloride at 100°C. 

Much of the benzoic acid produced is converted to sodium benzoate, which is used as a food preservative (as is the acid) and a corrosion inhibi tor. Other important uses of the acid are in the manufacture of alkyd resins, plasticizers, caprolactam, dyestuffs and pharmaceuticals. 

Benzoic acid had been known for several hundred years by the time of Mitscher lich s experiment Many trees exude resinous materials called balsams when cuts are made m their bark Some of these balsams are very fragrant which once made them highly prized articles of commerce especially when the trees that produced them could be found only m exotic faraway lands Gum benzoin is a balsam obtained from a tree that grows m Java and Sumatra Benzoin is a word derived from the Erench equivalent benjoin which in turn comes from the Arabic luban jawi meaning incense from Java Benzoic acid is itself odorless but can easily be isolated from gum benzoin... 

Dihydroxybenzophenones are used for the syntheses of dyes, polymers, and medicines. They are prepared by the condensation of resorcinol with benzoic acids. Catalysts used for this transformation are sulfonic resins (99), boron trifluoride (100), or zinc chloride in the presence of POCl (101). 

The most widely used process for the production of phenol is the cumene process developed and Hcensed in the United States by AHiedSignal (formerly AHied Chemical Corp.). Benzene is alkylated with propylene to produce cumene (isopropylbenzene), which is oxidized by air over a catalyst to produce cumene hydroperoxide (CHP). With acid catalysis, CHP undergoes controUed decomposition to produce phenol and acetone a-methylstyrene and acetophenone are the by-products (12) (see Cumene Phenol). Other commercial processes for making phenol include the Raschig process, using chlorobenzene as the starting material, and the toluene process, via a benzoic acid intermediate. In the United States, 35-40% of the phenol produced is used for phenoHc resins. 

In the United States all other processes have been completely phased out and virtually all benzoic acid is manufactured by the continuous hquid-phase air oxidation of toluene. In the late 1950s and the early 1960s both Dow Chemical and Snia Viscosa constmcted faciUties for Hquid-phase toluene oxidation because of large requirements for benzoic acid in the production of phenol and caprolactam. Benzoic acid, its salts, and esters are very useful and find appHcation in medicinals, food and industrial preservatives, cosmetics, resins, plasticizers, dyestuffs, and fibers. 

Benzoic acid in the free state, or in the form of simple derivatives such as salts, esters, and amides, is widely distributed in nature. Gum benzoin (from styrax ben in) may contain as much as 20% benzoic acid in the free state or in combinations easily broken up by heating. Acaroid resin (from anthorrhoca haslilis) contains from 4.5 to 7%. Smaller amounts of the free acid are found in natural products including the scent glands of the beaver, the bark of the black cherry tree, cranberries, pmnes, ripe cloves, and oil of anise seed. Pern and Tolu balsams contain benzyl benzoate the latter contains free benzoic acid as well. The urine of herbivorous animals contains a small proportion of the glycine derivative of benzoic acid, hippuric acid [495-69-2] (CgH CONHCH2COOH). So-called natural benzoic acid is not known to be available as an item of commerce. 

Although the main uses for benzoic acid are as a chemical raw material, it also has numerous direct uses. Benzoic acid is used in substantial quantities to improve the properties of various alkyd resin coating formulations, where it tends to improve gloss, adhesion, hardness, and chemical resistance. Benzoic acid terminates chain propagation in alkyd resins (qv) and promotes crystallinity in the final product. 

Benzoic acid CgHjCOjH Alkyl resins, chemical intermediate, oil drilling additive, medicines... 

Delphinine, C34H47O9N (Walz) or C33H45O9N (J. and C.). The alkaloid crystallises in rhombs, or six-sided plates, m.p. 198-200°, [a]f ° + 25° (EtOH), shows mutarotation in alcoholic solution, and forms an acid oxalate, B. H2C2O4, m.p. 168° dry), a hydrochloride, B. HCl, m.p. 208-210°, and a monobenzoyl derivative, m.p. 171-3°. On alkaline hydrolysis it yields one molecule each of acetic and benzoic acids. The basic, hydrolytic product of this action is delphonine, C24H3g07N, which is amorphous, but can be distilled at a bath temperature of 140° and a pressure of 0-001 to 0-0001 mm. The brittle, possibly semi-crystalline resin so obtained, has m.p, 76-8° and [a]f ° - - 37-5 (EtOH). 

Acid Curing. Urea-formaldehyde resins and resol-phenol-formaldehyde resins can be acid-cured by wastes from the production of maleic anhydride [1902]. The waste from the production of maleic anhydride contains up to 50% maleic anhydride, in addition to phthalic anhydride, citraconic anhydride, benzoic acid, o-tolulic acid, and phthalide. The plugging solution is prepared by mixing a urea-formaldehyde resin with a phenol-formaldehyde resin, adding the waste from production of maleic anhydride, and mixing thoroughly. 

Preparation of 6 -Diethylamino-2 -n-octylaminofluoran (74d). To a solution of 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid (0.1 mol) in 98% sulfuric acid (150 g) was added p-n-octylaminoanisole (0.1 mol) in limited amounts, while the temperature was maintained not to rise above 30 °C. The resulting mixture was stirred at room temperature for 20 h, and poured into ice water (1000 ml). The resinous precipitate was collected by decantation, and then refluxed with a mixture of toluene (250ml) and 20% aqueous sodium hydroxide (100 g) for 1 h. The toluene layer was separated, washed with hot water, concentrated, and the residue recrystallized from isopropanol (100 ml) to give 6 -diethylamino-2 -n-octylaminofluoran in 75% yield as a white powder, mp 127-128 °C. 

Fluid loss additives such as solid particles and water-thickening polymers may be added to the drilling mud to reduce fluid loss from the well bore to the formation. Insoluble and partially soluble fluid loss additives include bentonite and other clays, starch from various sources, crushed walnut hulls, lignite treated with caustic or amines, resins of various types, gilsonite, benzoic acid flakes, and carefully sized particles of calcium borate, sodium borate, and mica. Soluble fluid loss additives include carboxymethyl cellulose (CMC), low molecular weight hydroxyethyl cellulose (HEC), carboxy-methYlhydroxyethyl cellulose (CMHEC), and sodium acrylate. A large number of water-soluble vinyl copolymers and terpolymers have been described as fluid loss additives for drilling and completion fluids in the patent literature. However, relatively few appear to be used in field operations. 

Diverting agents assist in distributing acid more uniformly through the perforated formation interval (141). These are usually oil-soluble hydrocarbon resin particles. They may be dissolved by post-acid injection of xylene or similar solvents. Oil-soluble waxes, naphthalene, and solid organic acids such as benzoic acid have also been used (142). Best results are obtained using a broad range of particle sizes. 

Benzoe resin (also known as benzoin) comes from Styrax spp. (Styraceae family). In the Sty rax genus the only species that occurs in the Mediterranean is Styrax officinalis, so this was probably the source of the resin in ancient times in that area. Benzoe mainly contains free cinnamic and benzoic acids, and their corresponding esters with cinnamyl, p-coumaryl and coniferyl alcohols. The amounts of these compounds are quite variable and depend on which species the resin was obtained from [129]. 

Storax resin is extracted from Liquidambar orientalis (Hammamelidiaceae) and Altingia and its major components are cinnamyl cinnamate and 3-phenylpropanyl cinnamate, with significant amounts of benzoic and cinnamic acids, and 3-phenylpropanol and cinnamyl alcohols [130,131]. The volatile content is very low and triterpenes (oleanonic and 3-epioleanolic acids and liquid ambronovic acid) have also been observed [130,132]. 

I. Pastorova, C.G. de Koster, J.J. Boon, Analytical study of free and ester bound benzoic and cinnamic acids of gum benzoin resins by GC MS and HPLC frit FAB MS, Phytochemical... 

In another application, the group of Berteina-Raboin demonstrated the solid-supported synthesis of the indole core of melatonin analogues under microwave irradiation (Scheme 7.6) [26]. A benzoic acid derivative was coupled to Rink amide resin by... 

As a suitable model reaction, the coupling of various substituted carboxylic acids to polymer resins has been investigated by Stadler and Kappe (Scheme 7.8) [28]. The resulting polymer-bound esters served as useful building blocks in a variety of further solid-phase transformations. In a preliminary experiment, benzoic acid was attached to Merrifield resin under microwave conditions within 5 min (Scheme 7.8 a). This functionalization was additionally used to determine the effect of micro-wave irradiation on the cleavage of substrates from polymer supports (see Section 7.1.10). The benzoic acid was quantitatively coupled within 5 min via its cesium salt utilizing standard glassware under atmospheric reflux conditions at 200 °C. 

Scheme 12.9 Microwave-assisted cleavage of benzoic acid from Merrifield resin.

More detailed information on the reaction course of the three-step functionalization of an HHPA polyesteramide resin was obtained by functionalization with benzoic acid, after the polycondensation step. The reaction proceedings were monitored by multiple detector GPC (UV/RI) and titration. In the UV detector of the GPC the absorption of the aromatic acid is very dominant over the ahphatic resin itself, so that differentiation between free benzoic acid and benzoate-functionalized resin is feasible. It was observed that the titrated total acid concentration decreased much slower than the amount of free benzoic acid (Fig. 11). 

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