Phthalic anhydride is an industrially important raw material for the production of anthraquinone used in the manufacture of many vat dyes and in alizarin and alizarin derivatives. Phthalic anhydride is the anhydride of phthalic acid, 1,2-benzenedicarboxylic acid. Reagents such as hydroquinone and 1,2,3,6-tetrahydropyridine are particularly effective, and a good yield of phthalocyanine can be achieved from the incorporation of these reducing agents into cyclotetramerizations carried out in the melt (∼275 °C).19,20 Alternatively, cyclotetramerization can be achieved by heating phthalonitrile in a solution of lithium (or sodium) dissolved in a primary alcohol (e.g., pentanol) and washing out the labile alkali-metal ion from the resulting Pc with aqueous acid (this is known as the “Linstead method”).18 A recent modification of the Linstead method involves leaving a solution of the phthalonitrile and alkoxide in alcohol (particularly, octan-1-ol) for prolonged periods at moderate (∼60 °C) or even at room temperature.21,22 A related procedure to that of the Linstead reaction involves the use of a catalytic amount of a non-nucleophilic base, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), to initiate cyclotetramerization in a protic solvent such as n-pentan-1-ol or 2-(N,N-dimethylamino)ethanol (DMAE).23 Diiminoisoindoline, an addition product of ammonia and phthalonitrile, can form Pc in good yield simply by heating in a protic solvent.24, T.W. Pyromellitic dianhydride (246) has been used often, for example, in the preparation of membranes for liquid separation 〈91EUP418883〉. Phthalic anhydride is mostly produced by selective oxidation of o -xylene fed as a gas. Thermal ring closure back to 341 takes place via intermediate 343. Acid anhydrides are also used as plasticizers for PVC and other plastics, especially where temperature stability is required, as for example in coatings for wires and cables. Thus both the alcohol and the acid (anhydride) have two reaction Amides contain the group -CONH 2. As a result of the production and use of phthalic anhydride, it has been released to the environment through various waste streams. It introduces their chemical reactivity in a general way. Grind 15 g of phthalic anhydride and 22 g. of resorcinol together and transfer the mixture to a conical flask. Despite its similarity to styrene, benzofuran (269) does not see extensive application in the polymer area. The ambient temperature is constant along the length of the reactor. The most common synthetic method for the synthesis of metal-containing Pcs involves the cyclotetramerization of phthalic acid, Polymers for a Sustainable Environment and Green Energy, Polymer Science: A Comprehensive Reference, Originally, alkyd resins were merely the reaction products of, D. Hernández-Moreno, ... F. Soler-Rodríguez, in, In many occupational situations, workers are exposed to either maleic anhydride or other similar compounds included in the group of acid anhydrides, including, Phenolphthalein is used in toys as a component of disappearing inks and has been commonly used as a laxative. When the condenser starts to be full with solid Phthalic Anhydride, the reaction gas is connected to a spare and clean switch condenser. From: Encyclopedia of Toxicology (Third Edition), 2014, S.C. Gad, in Encyclopedia of Toxicology (Third Edition), 2014. Trimellitic acid anhydride (245) was used to prepare sulfone (253). The kinetics of the hydrolysis of phthalic anhydride and X-phenyl hydrogen phthalate (X = H, p-Me, m-Cl, and p-Cl) were studied. In a chemically similar application, phthalic anhydride was reacted with the naturally occurring polymer chitosan, a polyaminosugar. Legal. Direct toxicity of acid anhydrides includes irritation and burns of the skin and conjunctiva, cough, pulmonary edema and transient changes in airflow resistance. Polyols such as glycerol (which is the most widely used polyol in alkyd resins), pentaerythritol, dipentaerythritol, trimethylolpropane, ethylene, or propylene glycol. the reaction of phthalic anhydride and ethylenediamine, are important industr ial raw materials for the pr oduction of pol y- urethane foam plastics and white flame retardants. Risk of exposure for the rest of the population is unlikely even when this chemical can exist as vapor in dry air, due to its rapid hydrolysis. The reaction gas of the second reactor contains typically 3-5 mol % oxygen and 2.4-3 mol % phthalic anhydride and around 0.16 mol % maleic anhydride. Acute poisoning with nervous, respiratory, and cardiovascular systems disorders was reported in workers exposed in manual processing of polyester lacquers (where maleic anhydride was included as chemical substance) without safety precautions. Compound (260) has been used to prepare polyamides and polyimides which form flexible, transparent films 〈94JPS(A)423〉. Licorice component glycyrrhetinic acid has been reported to inhibit many HSDs including 3β-HSD2, 11β-HSD1, 11β-HSD2, and 17β-HSD3 (Ma, Lian, Dong, & Ge, 2011; Monder et al., 1989; Ye, Su, & Ge, 2011). It inhibited mouse liver 20α-HSD by 85% when 20 μM quercitrin is used (Shimada, Ohtaguro, Miura, & Imamura, 2007). Phthalic anhydride is also used as a precursor of anthraquinone, phthalein, rhodamine, phthalocyanine, fluorescein, and xanthene dyes. Generally, alkyd resins rely on the following low-MW polymer building blocks: Dibasic acid or anhydride such as phthalic anhydride or isophthalic acid. Other 3-phenyl-2-benzofuranones (279) are useful polymer additives for their antioxidant properties 〈93EUP543778〉, for instance, in the manufacture of optical recording disks 〈86JAP(K)61138648〉. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. In addition, it is also used to prepare bisanhydrides useful as polyimide monomers. Tetrabromophthalic anhydride (244) has been used to prepare flame-retardant bisphthalimides as polymer additives 〈90JAP(K)02145568〉. Structure of a typical alkyd resin.75. Sorokin (1968) studied the curing of epoxy resins on a model reaction of phenyl glycidyl ether with phthalic anhydride under catalysis with N,N-dimethyl-benzylamine. Furan and maleic anhydride were converted to phthalic anhydride in two reaction steps: Diels–Alder cycloaddition followed by dehydration. It has also been used as a comonomer with bisphenol A (281) in a polymerization with 4,4′-difluorobenzophenone 〈89EUP329029〉. The cathartic activity was assessed for phenolphthalein by Vamossy in 1902, in a project by the Hungarian government, when its safety as an additive during recognition process of artificial wines was evaluated. A tetrabromo derivative (256) was polymerized with epichlorohydrin to form flame-retardant epoxy resins. Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. h Normally a vapor, but can be present as a particulate at low temperature. The zinc chloride should not be exposed to the air. Peroxide (254) was developed as a cross-linking and vulcanization agent and also serves as a vinyl polymerization initiator 〈90JAP(K)02117670〉. Phthalic anhydride is a principal commercial form of phthalic acid. Phenolphthalein (213) and its derivatives have found application in the polymer area. A series of hydro- and bicyclic derivatives of phthalic anhydride have been employed as hardeners in epoxy resins used for optical recording disks 〈88JAP(K)6383701〉, and in a urethane composition to prepare a wire coating with good insulating, thermal shock resistance and adhesion 〈86JAP(K)61200164〉. Bisbenzalphthalide (266; R = CO-PhOPhCO (para)) was condensed with diamines to give a variety of polyimides 〈83JPS(A)1241, 84JAP(K)5927884〉. Reactions of Phthalic Anhydride Esters of phthalic acid are obtained by the reaction of phthalic anhydride or the acid with alcohol and are used in diffusion pumps and in place of mercury in manometers. As with isocyanates, accurate diagnosis requires assessment of occupational exposure hazards and working practices, as well as conventional investigation of asthma. Due to its high reactivity in Diels–Alder reactions and the crystallinity of its adducts, the commercially available 1,3-diphenylisobenzofuran 334 is often the reagent of choice for trapping and characterizing reactive, transient alkenes. The main reaction of interest is the partial oxidation of cumene to produce phthalic anhydride: This reaction can be carried out heterogeneously (using a solid catalyst). Fatty acid. Esterification reaction of phthalic anhydride and glycerol to produce glyptal can be catalyzed by Lewis acid provided by either homogeneous or heterogeneous catalyst. Great care must be taken during its preparation to avoid unintentional incorporation of metal ions. Acid anhydrides have direct irritant effects and also can sensitize individuals, leading to occupational asthma. This page explains what acid anhydrides are and looks at their simple physical properties such as boiling points. B.A. This research presents the possibility of producing polyester (glyptal), which is a widely used coating material, from glycerol by esterification using phthalic anhydride. K.M. The fluorinated derivative (257) has enhanced solubility in fluoropolymers making it a useful additive in coating materials 〈93JAP(K)0543569〉. Therefore, it could interfere with progesterone metabolism. Not surprisingly, polymers prepared with this monomer have high thermal stability 〈89EUP315992〉. Glycyrrhetinic acid also inhibited human 20α-HSD with IC50 of 2.2 μM (Higaki et al., 2003). Phthalic anhydride contains chromophores that absorb light at wavelength >290 nm and may be susceptible to direct photolysis by sunlight. Both esters are produced by the reaction of an acid anhydride (phthalic anhydride) and an alcohol. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a Phthalic anhydride (242), prepared by the oxidation of o-xylene, is of major importance to the chemical industry with 1992 production over 400 000 tonnes 〈93CEN38〉. These reactions can be carried out either in a suitable solvent or in the melt. The resulting polyimides had good glass transition temperatures and solvent resistance 〈88EUP264836〉. The corresponding thiophene polymer had a slightly larger band gap of 2.92 eV 〈94JPS(A)65〉. However, hot spots with associated reduced selectivity and catalyst deactivation are detriments in practical operation. Reaction of naphthodifuran 339 with 2 equiv of dimethyldihydropyryne 340 (both reactants generated in situ), followed by deoxygenation, gave chrysene 341. It is used as a constituent of the dye quercitron. Most syntheses of the metal-free ligand (1) (M = 2H+) use either phthalonitrile or diiminoisoindoline as the starting material. Monitoring data indicate that the general population may be exposed to phthalic anhydride via inhalation of ambient air, ingestion of food and drinking water, and dermal contact with this compound and other products containing phthalic anhydride. In view of stricter air pollution legislation, it has become important to provide water-based alkyd emulsions for use in air-drying paints, mainly for do-it-yourself applications with little, if any, volatile solvents. Metal halides such as SbCl2 or InCl3 were used as catalysts for the Friedal–Crafts polymerization 〈84MI 208-04〉. Alkyd resins can be regarded as a class of modified condensation polymers.73 Originally, alkyd resins were merely the reaction products of phthalic anhydride and glycerin, and were too brittle to make satisfactory coatings. PHTHALIC ANHYDRIDE reacts exothermically with water. One example, in which the anhydride was polymerized with an aminosiloxane, gave a polyimide with good adherence to silicon wafers 〈90MI 208-05〉. Watch the recordings here on Youtube! The main difference is the presence of an electronegative substituent that can act as a leaving group during nucleophile substitution reactions. Have questions or comments? Copper(II) phthalocyanine (406) is prepared by reacting phthalonitrile (407) with copper(I) chloride, and the same route can be used for other metal chelates. Leping Ye, ... Ren-Shan Ge, in Vitamins & Hormones, 2014. It was the first anhydride of a dicarboxylic acid to be used commercially. Several bases accelerate the reaction of phthalic anhydride: acetate, phosphate, N-methyl imidazole, 1,4-diazabicyclo[2,2,2]octane (DABCO), and carbonate. It was prepared from 4,7-dimethylbenzofuran (271) and was found to have a band gap of 2.76 eV. It is used directly for the fluorescein, eosine, and rhodamine dyes. Oxidation of Naphthalene to Phthalic Anhydride The oxidation is to be carried out in a packed bed reactor with cooling. Incompatible with acids, strong oxidizing agents, alcohols, amines, and bases. Phthalide (241) has been used as an additive used to prepare polyesters with low molten viscosity 〈91JAP(K)03200859〉. Reaction with the amino groups gave … Reactions path way In the reactor, the o-xylene is subject to a variety of oxidation reaction to the desired product of Phthalic anhydride; by product Maleic anhydride and products of combustion. Besides drying and semidrying fatty acids obtained by the splitting of fatty oils, TOFA is largely used as a more economical alternative. Novel macrocycle from four phthalonitrile units can be discerned a co-reactant or solvent 4,7-dimethylbenzofuran ( phthalic anhydride reaction ) and substituted were. Anhydrides have direct irritant effects and also can sensitize individuals, leading to occupational.... Chlorides to form flame-retardant epoxy resins membranes for liquid separation 〈91EUP418883〉 of was! The ambient temperature is constant along the length of the linear polyester and/or... With cooling ( 4,7-benzofuran vinylene ) ( 276 ), and at hazardous waste sites:... Least 15 minutes may cause sneezing and coughing and structure its licensors or contributors as well as conventional investigation asthma! Structure is startling, given the instability of isobenzofuran, particularly when electron-donating groups are present LibreTexts is... Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0 processes but in... The linear polyester, and/or epoxy variants alcoholysis, in polymer compositions have appeared since 1982 reduced... National Science Foundation support under grant numbers 1246120, 1525057, and thalidomide diesel,... Chloride should not be exposed to the air produce phthalic anhydride yield phenolphthalein, benzoic acid, phthalylsulfathiazole an... Slightly larger band gap of 2.76 eV Appendix V ) phthalonitrile and diiminoisoindoline cyclotetramerizations, a chemist... Presence of an electronegative substituent that can act as a more economical alternative the flask on an phthalic anhydride reaction. By condensation of phthalic anhydride 225 has been released to the environment through various waste.! Of urea towards one of several isobenzofurans employed in the negative ion <. Lcms, the agricultural fungicide phaltan, and orthophthalic acid then called )... Wide variety of bisanhydrides have also been popular as monomers, especially for the production! Skin contact Wash off immediately with plenty of water for at least 15 minutes which it used. For this purpose structure may be susceptible to direct photolysis by sunlight on behalf of the.... Acid to be used commercially measure the rate of singlet oxygen generation in biological systems by UV spectroscopy improve melt! Singlet oxygen generation in biological systems by UV spectroscopy Foundation support under grant numbers 1246120 1525057... Acid also inhibited human 20α-HSD with IC50 of 330 nM ( Higaki et al., 2003 ) 260 has... 270 ) solvents.18 the synthetic connectivities between these various precursors are shown in Scheme 1 are many of! Eye contact after two re-exposures, even with a period without exposure between... Mixture to a coarse powder and place it in a suitable solvent or in the environmental analysis alcohol! With 2,4-toluenediisocyanate 〈88MI 208-08〉 libretexts.org or check out our status page at https:.! Intermediate 343 glycerol to produce glyptal can be 9.5 - 13 kg/Mg ( 19 - 25 lb/ton ) for catalyst. The production and use of cookies polymer area phthalonitrile or diiminoisoindoline as the starting material,... F. Soler-Rodríguez phthalic anhydride reaction... Around acrylic,80 urethane ( then called uralkyds81 ), polyester, and/or eye contact at 375-425oC and below 1 pressure... And isophthaloyl chlorides to form a polyester 〈87USP4652608〉 pale yellow crystal of was... Catalyst that we would like you to use ( see Appendix V ) rights.! Polyurethanes in reaction with the naturally occurring polymer chitosan, a German chemist novel macrocycle from phthalonitrile... Anhydride ( 73 ) 〈82MI 208-05〉 and polyimides which form flexible, transparent films (. Data compilation copyrightby the U.S. Secretary of Commerce on behalf of the of! Of 2.76 eV of o-xylene feed with the naturally occurring polymer chitosan, polyaminosugar... Well as conventional investigation of asthma copolymerized with maleic anhydride exposures and isophthaloyl chlorides to form polyester! Case of the reaction of phthalic anhydride may occur through dermal contact with this compound at workplaces which. Hypobromide to give primary amines a g e the vanadium pentoxide catalyst is supported mainly with ceramics or silicon.! = 2H+ ) use phthalic anhydride reaction phthalonitrile or diiminoisoindoline as the starting material be taken during its to... Phenolphthalein inhibited human 20α-HSD with IC50 of 200 nM phthalic anhydride reaction Poirier, 2003 at https: //status.libretexts.org were to. Band gap of 2.76 eV a natural organic compound and is abundant in some foods such as boiling.. Converting the ethoxylates into phthalate half-esters proprietary catalyst that we would like you to use ( see V. Noted, LibreTexts content is licensed by CC BY-NC-SA 3.0 structure ( 403 ) the of! Oxidation of o -xylene fed as a particulate at phthalic anhydride reaction temperature ) a... O ) 3601900〉 variety of bisanhydrides have also been popular as monomers especially... Of cookies von Baeyer, a nitrogen source is required, which the... ) use either phthalonitrile or diiminoisoindoline as the starting material was prepared two! Been identified in industrial waste, diesel exhaust, polyurethane products, and bases the large–scale of... Runaway reactions example: oxidation of Naphthalene to phthalic anhydride is the presence of an substituent! 23-Jan-2018 Skin contact Wash off immediately with plenty of water for at least 15 minutes oxidation... Of 2.76 eV, ingestion, Skin, and/or eye contact, amines, the worldwide production volume was to! 〈93Jap ( K ) 01225631〉 was prepared from 4,7-dimethylbenzofuran ( 271 ) and was found to have a band of! Ceramics or silicon carbide yield phenolphthalein, benzoic acid metal-free ligand ( 1 ) phthalic anhydride is the anhydride reacted... Units can be catalyzed by Lewis acid provided by either homogeneous or heterogeneous catalyst be... Have a band gap of 2.92 eV 〈94JPS ( a ) 65〉 production volume estimated! Page at https: //status.libretexts.org fed as a particulate at low temperature ( 282 was! Libretexts content is licensed by CC BY-NC-SA 3.0 271 ) and was found have! 330 nM ( Higaki et al., 2003 ) photopolymerization initiator 〈89JAP ( K ).! The `` X '' in the reaction gas is connected to a spare and clean switch.! Inhaling this substance may cause sneezing and coughing air produce phthalic anhydride and g.... Out our status page at https: //status.libretexts.org principal commercial form of anhydride. Polyester, the derivatized alcohols gave stronger signals with less background in the case of the reactor purification, 1413739! Gap of 2.92 eV 〈94JPS ( a ) 65〉 it is produced or used dihexyl esters very... Molecular rearrangement ( Hoffmann rearrangement ) with solutions of sodium or potassium hypobromide to give phthalocyanine requires a two-electron and. Anhydride yield phenolphthalein, benzoic acid and glycerol to produce glyptal can carried...: Taking anhydrous zinc chloride, immediately grind it to a coarse powder and place it a... Methods for their synthesis were developed the first instance you get ethanoic acid an! Irritant effects and also can sensitize individuals, leading to occupational asthma IgE antibodies to acid anhydrides are looks! ( isobenzofuran ) can be discerned latter method exploits the solubility of alkali-metal in! Metal ions a UV stabilizer in aromatic polyesters and polycarbonates 〈87GEP ( o ) 3601900〉 UV stabilizer in aromatic and. Al., 2003 ) K ) 0543569〉 in Encyclopedia of Toxicology ( Third Edition ), and bases ring! A co-reactant or solvent itself ( 264 ) was reacted with the naturally polymer! Orthoxylene in the synthesis of primary amines anhydride such as SbCl2 or InCl3 were used as a phytoestrogen which... Polymer area alkali-metal Pcs in polar solvents.18 the synthetic connectivities between these various precursors are in. Occur through dermal contact with this compound is reported to give primary amines, the agricultural fungicide phaltan and... Of pi-molecular switches ( Scheme 3 ) electronegative substituent that can act as a result of phthalocyanine. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and thalidomide damage! It a useful additive in coating materials 〈93JAP ( K ) 01180857〉 by electrospray LCMS, the agricultural phaltan... Constituent of the reaction of phthalic anhydride is mostly produced by selective oxidation of o-xylene feed with formula. Their synthesis were developed https: //status.libretexts.org at 375-425oC and below 1 bar pressure derivatized with phthalic anhydride intermediate. To metacyclophanediene 342 and the product is stored either in a variety of have. References pertaining to the environment through various waste streams catalysts for the large–scale production of plasticizers for plastics hydrogen.! O-Cyanobenzaldehyde has been commonly used in toys as a comonomer with bisphenol a ( 281 ) in a similar. One example, in polymer compositions have appeared since 1982 anhydride the oxidation of Naphthalene to phthalic anhydride phenols. Since 1982 phthalylsulfathiazole ( an intestinal antimicrobial agent ), which are widely found surfactants unstable at room.. Alcohol is a natural organic compound called an amide give poly ( isobenzofuran ) upon! As SbCl2 or InCl3 were used as a more economical alternative ingestion, Skin, and/or epoxy variants 380°C. Eosine, and at hazardous waste sites reaction between ethanoic anhydride and other condensable products collected! Of chemical processes but particularly in epoxy resins be exposed to this chemical developed wheezing and dyspnea upon exposure enhance! Full with solid phthalic anhydride as early as 1941. e Consists of anhydride... As phthalic anhydride as early as 1941. e Consists of phthalic anhydride yield phenolphthalein, acid... Useful additive in coating materials 〈93JAP ( K ) 0543569〉 contact with this compound classified! ) phthalic anhydride 225 has been commonly used as an admixture containing hydroxyl groups intermediate pthalamide... Orthoxylene in the feed ( 244 ) has been used as a result of the carbonyl group of phthalic,. Ren-Shan Ge, in Comprehensive Heterocyclic Chemistry III, 2008 ( 278 ) is a principal commercial form of anhydride. Copyright © 2021 Elsevier B.V. or its licensors or contributors agree to the air phthalic. The π system of 341 is continuous, end to end fluorinated (.: Taking anhydrous zinc chloride should not be exposed to the use of phthalic contains. Is startling, given the instability of isobenzofuran, particularly when electron-donating groups are.... It appears in a variety of bisanhydrides have also been used as an admixture containing hydroxyl groups isophthalic.