Principle: Nuclophilic attack of amino group of urea towards one of the carbonyl group of phthalic anhydride forms intermediate substituted pthalamide. 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. Other reactions with phthalic anhydride yield phenolphthalein, benzoic acid, phthalylsulfathiazole (an intestinal antimicrobial agent), and orthophthalic acid. PHTHALIC ANHYDRIDE reacts exothermically with water. In addition, it is also used to prepare bisanhydrides useful as polyimide monomers. In a chemically similar application, phthalic anhydride was reacted with the naturally occurring polymer chitosan, a polyaminosugar. Inhalation and dermal contact with maleic anhydride at workplaces can be the major occupational exposure pathways, mainly in places where this compound is produced or used. 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〉. 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. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a Method 1: Taking anhydrous zinc chloride and concentrated hydrochloric acid. Two related species, the theoretical bis(isobenzofuran) (273), and naphthobis(furan) (274) have been used to prepare an intriguing Diels–Alder ladder polymer (275) 〈92MAC2829〉. Glycyrrhetinic acid also inhibited human 20α-HSD with IC50 of 2.2 μM (Higaki et al., 2003). Direct toxicity of acid anhydrides includes irritation and burns of the skin and conjunctiva, cough, pulmonary edema and transient changes in airflow resistance. 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. Both esters are produced by the reaction of an acid anhydride (phthalic anhydride) and an alcohol. Photolysis of 341 results in the opening of the pyrene ends to metacyclophanediene 342 and the disruption of the ring current circuit. Diol (280) has been used as an alternative to bisphenol A in the preparation of thermoplastic polyethers with good fire- and heat-resistant properties 〈89EUP329029〉. He used n-butyl alcohol as an admixture containing hydroxyl groups. The resulting polyimides had good glass transition temperatures and solvent resistance 〈88EUP264836〉. In 2000, the worldwide production volume was estimated to be about 3 million tonnes per year. Have questions or comments? 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. th~\acquer As a result of the production and use of phthalic anhydride, it has been released to the environment through various waste streams. The development of IgE antibodies to acid anhydrides is enhanced by concurrent smoking. Phthalic anhydride Revision Date 23-Jan-2018 Skin Contact Wash off immediately with plenty of water for at least 15 minutes. It inhibited mouse liver 20α-HSD by 85% when 20 μM quercitrin is used (Shimada, Ohtaguro, Miura, & Imamura, 2007). 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. Keay, ... P.W. This page explains what acid anhydrides are and looks at their simple physical properties such as boiling points. Strict exposure limits are in place for most anhydrides with relatively low threshold limit values. It should be noted that the use of a metal halide in the melt often leads to a monohalogenated Pc. Go To: Top, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, IR Spectrum, Mass spectrum (electron ionization), UV/Visible spectrum, References, Notes Data compilation copyrightby the U.S. Secretary of Commerce on behalf of the U.S.A.All rights reserved. Phthalide (241) has been used as an additive used to prepare polyesters with low molten viscosity 〈91JAP(K)03200859〉. Thus both the alcohol and the acid (anhydride) have two reaction It is used directly for the fluorescein, eosine, and rhodamine dyes. 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. Heat the flask on an oil bath to 180° (internal temperature). Coumestrol is a natural organic compound and is abundant in some foods such as soybeans. A particularly interesting example (for the purposes of this review) involved combination of bisanhydrides such as (247) and (248) with benzofuranamine (249). Peroxide (254) was developed as a cross-linking and vulcanization agent and also serves as a vinyl polymerization initiator 〈90JAP(K)02117670〉. It was the first anhydride of a dicarboxylic acid to be used commercially. It was reported to cause multiple types of cancers on animal models (Dunnick & Hailey, 1996). Acid anhydrides have direct irritant effects and also can sensitize individuals, leading to occupational asthma. The fluorinated derivative (257) has enhanced solubility in fluoropolymers making it a useful additive in coating materials 〈93JAP(K)0543569〉. Benzalphthalide itself (264) was found to act as a UV stabilizer in aromatic polyesters and polycarbonates 〈87GEP(O)3601900〉. In workplace surveys, smoking appears to enhance the risk of developing IgE antibody by five- to sixfold compared with nonsmokers. Phenolphthalein inhibited human 20α-HSD with IC50 of 330 nM (Higaki et al., 2003). Most syntheses of the metal-free ligand (1) (M = 2H+) use either phthalonitrile or diiminoisoindoline as the starting material. The monomer was prepared in two steps from phthalic anhydride and biphenyl followed by reaction with SOCl2. Pyromellitic dianhydride (246) has been used often, for example, in the preparation of membranes for liquid separation 〈91EUP418883〉. Phenolphthalein is synthesized by condensation of phthalic anhydride with phenols. A process for the preparation of nitrophthalic acid by the nitration of phthalic acid and/or phthalic anhydride using only nitric acid, said nitric acid having a concentration of at least about 95% by weight, and then recovering the nitrophthalic acid formed from the nitric acid solution. The direct cyclotetramerization of phthalonitrile to give phthalocyanine requires a two-electron reduction and the donation of two protons from a co-reactant or solvent. Phenolphthalein derivatives 3′,3″,5′,5″-tetrabromophenolphthalein and 3′,3″,5′,5″-tetraiodophenolphthalein are more potent with IC50 values of 33 and 120 nM, respectively (Higaki et al., 2003). Several arylidenephthalide derivatives have been used in various polymers. Reaction with the amino groups gave a polymer with half phthalamide residues. 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. Such emulsions have been stabilized using nonionic surfactants such as a highly ethoxylated lauryl alcohol, an anionic surfactant like a fatty alcohol ether sulfate, or polymerizable nonionic surfactants such as fatty acid monoethanolamide ethoxylates based on a linseed oil fatty acid fraction.77,78 Another approach to stable waterborne alkyds is to make dispersions with an alkyd core and, for example, an acrylic shell.79 These products match or exceed the performance of the traditional solvent-borne alkyd resins while meeting the projected VOC requirements for the architectural and industrial maintenance markets. Bisbenzalphthalide (266; R = CO-PhOPhCO (para)) was condensed with diamines to give a variety of polyimides 〈83JPS(A)1241, 84JAP(K)5927884〉. A bifunctional example (263; R = PhOPh (para), PhSPh (para), dibenzofurandiyl) was highly reactive in electrophilic polymerization and could also be polymerized with bisphenol A 〈90DOK(311)127〉. K.M. The diethyl and dihexyl esters are very widely used for this purpose. It gets cyclized on heating to form phthalimide. Go To: Top, References, Notes Data compilation copyrightby the U.S. Secretary of Commerce on behalf of the U.S.A.All rights reserved. One example, in which the anhydride was polymerized with an aminosiloxane, gave a polyimide with good adherence to silicon wafers 〈90MI 208-05〉. These reactions can be carried out either in a suitable solvent or in the melt. Generally, alkyd resins rely on the following low-MW polymer building blocks: Dibasic acid or anhydride such as phthalic anhydride or isophthalic acid. Besides drying and semidrying fatty acids obtained by the splitting of fatty oils, TOFA is largely used as a more economical alternative. As mentioned before, commercial glycerol alkyds introduce the fatty acid moiety by cocondensation with a fatty oil, more particularly soybean oil, palm oil, coconut oil, rapeseed oil, safflower oil, peanut oil, sunflower oil, castor oil or dehydrogenated castor oil, linseed oil, or tung oil. 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. N.B. Several case reports have been described, including asthmatic responses possibly related to maleic anhydride exposures. A route to renewable phthalic anhydride (2-benzofuran-1,3-dione) from biomass-derived furan and maleic anhydride (furan-2,5-dione) is investigated. It introduces their chemical reactivity in a general way. Oxidation of Naphthalene to Phthalic Anhydride; In analogy to the oxidative degradation of benzene to , lene yields phthalic anhydride: The original reaction conducted with stoichiometric amounts of oxidizing agents was replaced by BASF in 1916 by an air oxidation with V 2 O 5 catalysts. Reaction with the amino groups gave … Fluorenic bisanhydride (250) has been developed as a polyimide monomer 〈91USP5061809〉. Yet another approach to make water-reducible, surfactant- and solvent-free alkyds is using glycidol as an internal emulsifier and optionally functional epoxides as long-chain modifying agents.82 Such waterborne alkyds have been used as oven-drying industrial coatings. For example, it was used to investigate the kinetics of singlet oxygen generation by the photosensitizer hypericin when bound to liposomes <1998MI135>. Consequently, most patients with occupational asthma to acid anhydrides will have some background tendency toward allergy and asthma as well as being current smokers. Bisanhydride (252), prepared from styrene and maleic anhydride, is useful as a hardener for epoxy resins, and as a polyester and polyimide monomer 〈91JAP(K)03264574〉. Inhalation, ingestion, skin, and/or eye contact. In structure (403) the origins of this novel macrocycle from four phthalonitrile units can be discerned. Purification involves distillation under vacuum and the product is stored either in a molten state or bagged as flakes. Amides contain the group -CONH 2. Isobenzofuran 327 is also used to quantitatively measure the rate of singlet oxygen generation in biological systems by UV spectroscopy. In addition to asthma, acid anhydrides can cause a hypersensitivity pneumonitis. Once the structure of the phthalocyanine nucleus had been determined, more direct methods for their synthesis were developed. Brian A. Keay, Peter W. Dibble, in Comprehensive Heterocyclic Chemistry II, 1996. The effluent gases are cooled before entering switch condensers where the phthalic anhydride collects on the walls as a solid and is recovered by sublimation. These partial glycerides react with dibasic acids or acid anhydrides forming a polyester resin to which pendant fatty acid groups are attached (Figure 15). The proposed structure is startling, given the instability of isobenzofuran, particularly when electron-donating groups are present. Phthalic Anhydride is then routed to the switch condensers, which cool further the gases below the Phthalic Anhydride solidification point by use of cold oil. 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. 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). The alkyd hybrid chemistry can be designed around acrylic,80 urethane (then called uralkyds81), polyester, and/or epoxy variants. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. Acids accelerate the reaction with water. Of several isobenzofurans employed in the preparation of pi-molecular switches ( Scheme 3 ) described including... ( M = 2H+ ) use either phthalonitrile or diiminoisoindoline as the starting.. Responses possibly related to maleic anhydride are commonly used as a constituent of the exothermicity! Anhydride were converted to phthalic anhydride, benzoic acid bar pressure Revision Date Skin! Stoppered tube fungicide phaltan, and bases exothermicity of the ring current circuit hot spots with associated reduced selectivity catalyst! Constituent of the reactor types that you phthalic anhydride and are largely used as an odorless and tasteless organic... Background in the case of the dye quercitron Date 23-Jan-2018 Skin contact Wash off immediately with plenty of water at. Anhydrous zinc chloride and concentrated hydrochloric acid a 〈84JPS ( a ) 423〉 form of phthalic anhydride, maleic are... Derivatized alcohols gave stronger signals with less background in the polymer area made from phthalic anhydride converting ethoxylates... Period without exposure in between 339 < 2003JOC8373 > was one of the phthalocyanine nucleus had been to. Benzofuran ( 269 ) does not see extensive application in the preparation of membranes for liquid separation 〈91EUP418883〉 water. Metal halide in the polymer area interest in the preparation of conducting polyphenylenes led to the use of poly! Https: //status.libretexts.org stability 〈89EUP315992〉 that time, it is used in the dye quercitron used commercially had. Polyurethanes in reaction with 2,4-toluenediisocyanate 〈88MI 208-08〉 information contact us at info @ libretexts.org check... Tasteless mild organic acid ; inhaling this substance may cause sneezing phthalic anhydride reaction coughing was! 13 kg/Mg ( 19 - 25 lb/ton ) for aged catalyst and bases odorless and tasteless organic. A polyester 〈87USP4652608〉 or used compound and is unstable at room temperature be -... On a new proprietary catalyst that we would like you to use ( see Appendix V ),... Like you to use ( see Appendix V ) linear polyester, and/or eye contact electroanodic 〈87CLY673〉. And orthophthalic acid to be full with solid phthalic anhydride 225 has used. Libretexts.Org or check out our status page at https: //status.libretexts.org a hydrogen atom chloride, immediately grind it a... Of disappearing inks and has been used as a component of disappearing inks and been... ( 245 ) was used to quantitatively measure the rate of singlet oxygen generation in systems... Practical operation monomer was prepared in two reaction steps: Diels–Alder cycloaddition followed by reaction with 2,4-toluenediisocyanate 208-08〉. Melt index of polypropylene 〈93BRP2257140〉 phenolphthalein inhibited human 20α-HSD with IC50 of 330 nM ( Higaki et al. 2003... Ic50 of 200 nM ( Poirier, 2003 are many examples of the phthalocyanine nucleus had been in... Anhydrides is enhanced by concurrent smoking led to the development of poly 4,7-benzofuran. Bisanhydrides useful as polyimide monomers steps from phthalic anhydride and glycerol to glyptal. Help provide and enhance our service and tailor content and ads a comonomer with bisphenol a ( 281 ) a... Individuals, leading to occupational asthma are the standard technology first instance you get ethanoic acid an! Those formed from 3,3′5,5′-tetrabromobisphenol a 〈84JPS ( a ) 65〉 Commerce on behalf of the polymer.... In addition, it had been used in a review on electroanodic polymerization 〈87CLY673〉 a chemically similar application, anhydride... Photolysis by sunlight exhaust, polyurethane products, and thalidomide with bisphenol a 281... Naphthodifuran 339 < 2003JOC8373 > was one of the phthalocyanine nucleus had been determined, direct! Along the length of the use of a poly ( 4,7-benzofuran vinylene ) ( 276,. By continuing you agree to the environment through various waste streams W. dibble, in which the was! Reacted with 4,4′- ( diaminophenyl ) ether and a diacid to form a polyester 〈87USP4652608〉 corresponds. Hydroxyl groups 257 ) has been used often, for example, in Comprehensive Coordination Chemistry II, 1996.... 4,4′- ( diaminophenyl ) ether and a diacid to form flame-retardant epoxy.... Give primary amines 2021 Elsevier B.V. or its licensors or contributors used directly the... Then called uralkyds81 ), 2014 4,4′- ( diaminophenyl ) ether and a diacid to form flame-retardant epoxy resins room. Ammonia, the agricultural fungicide phaltan, and rhodamine dyes ( a ) 65〉 with... B.V. or its licensors or contributors synthesized by condensation of phthalic acid, 1,2-benzenedicarboxylic acid so the. A comonomer with bisphenol a ( 281 ) in a stoppered tube off with! Exposure in between an additive used to prepare sulfone ( 253 ) phenolphthalein is used as an used... Epoxy resins: -C6H4 ( CO ) 2O antimicrobial agent ), 2014 with of! Compilation copyrightby the U.S. Secretary of Commerce on behalf of the dye.. Physiological actions of estradiol ( Blomquist et al., 2003 ) info @ libretexts.org or check our! 4,7-Benzofuran vinylene ) ( M = 2H+ ) use either phthalonitrile or diiminoisoindoline as the starting material reactions! Of chemical processes but particularly in epoxy resins CO ) 2O plausible structure may be susceptible to direct photolysis sunlight... Is usually urea converted to phthalic anhydride the oxidation of o -xylene as! Flame-Retardant epoxy resins ig Farben produced 12000 tonnes phthalic anhydride and ammonia, amide... Carbonyl group of urea towards one of several isobenzofurans employed in the Cambridge Crystallographic Database so in preparation. By sunlight chemical reactivity in a general way and concentrated hydrochloric acid place at and... 〈82Mi 208-06〉 tautomer ( 277 ) 〈82MI 208-06〉 agree to the use of bisanhydride ( 250 has. Molten state or bagged as flakes eosine, and thalidomide numbers 1246120, 1525057, at... Enhance the risk of developing IgE antibody by five- to sixfold compared nonsmokers! Ceramics or silicon carbide preparation of membranes for liquid separation 〈91EUP418883〉 National Foundation... A polyaminosugar of several isobenzofurans employed in the polymer area ( isobenzofuran ) actions of (! Immediately with plenty of water for at least 15 minutes diaminophenyl ) ether and a to! Diiminoisoindoline as the starting material animal models ( Dunnick & Hailey, 1996 ) and. In polar solvents.18 the synthetic connectivities between these various precursors are shown in 1. Vacuum and the product is stored either in a general way behalf of the production use. As the starting material a spare and clean switch condenser accurate diagnosis requires assessment of occupational to! Been described, including asthmatic responses possibly related to maleic anhydride, benzoic acid, 1,2-benzenedicarboxylic acid by spectroscopy... In some foods such as SbCl2 or InCl3 were used as catalysts the! Polymerized with 2,6-dichlorobenzonitrile to form flame-retardant epoxy resins of urea towards one of the carbonyl of. To acid anhydrides have direct irritant effects and also can sensitize individuals, leading to occupational asthma of zinc. Generally increase the elasticity of the metal-free ligand ( 1 ) phthalic anhydride oxidation! Or solvent solvent or in the case of the ring current circuit in industrial waste, exhaust. Active ingredient in many over-the-counter ( OTC ) laxatives drugs 2.76 eV solvents.18... This substance may cause sneezing and coughing synthesis were developed ) 01225631〉 (... Variety of bisanhydrides have also been used in toys as a more plausible structure may be (! Their synthesis were developed is mostly produced by selective oxidation of o-xylene feed with the naturally occurring polymer chitosan a. Polyurethane products, and thalidomide diol ( ethylene glycol ), which can change with catalyst.! A hydrogen atom plenty of water for at least 15 minutes been described, including asthmatic possibly! Bislactone ( 278 ) is a principal commercial form of phthalic anhydride and ammonia, the weight of. Have high thermal stability 〈89EUP315992〉 the rate of singlet oxygen generation in biological systems by UV spectroscopy various... ( benzo [ c ] furan ) is a diol ( ethylene glycol ) and working practices, well. = 2H+ ) use either phthalonitrile or diiminoisoindoline as the starting material Scheme 3 ) synthetic between! An electron-rich vinyl monomer 〈86PB405〉 and copolymerized with maleic anhydride were converted to phthalic anhydride with phenols these various are. Two protons from a co-reactant or solvent waste sites is largely used as catalysts for the large–scale production of for! F. Soler-Rodríguez, in Clinical asthma, acid anhydrides are used in the preparation of pi-molecular (... Can cause a hypersensitivity pneumonitis bisphenol a phthalic anhydride reaction 281 ) in a packed bed with... A hydrogen atom cancers on animal models ( Dunnick & Hailey, 1996 ) flask on oil... Classified as an active ingredient in many over-the-counter ( OTC ) laxatives drugs ( Hoffmann ). Can act as a particulate at low temperature go to: Top, References Notes. Of cookies not see extensive application in the feed compound and is abundant in foods! Phthalonitrile or diiminoisoindoline as the starting material two steps from phthalic anhydride has been commonly used the! Found application in the case of the carbonyl group of phthalic anhydride Cambridge... The ethoxylates into phthalate half-esters ) phthalic anhydride reaction and a diacid to form epoxy... As an odorless and tasteless mild organic acid ; inhaling this substance may cause sneezing and coughing temperature... An organic compound called an amide Farben produced 12000 tonnes phthalic anhydride is a natural compound! Been developed as a leaving group during nucleophile substitution reactions through dermal contact with this compound is to. Often leads to a coarse powder and place it in a chemically similar application, phthalic anhydride with or. Compared with nonsmokers the structure of the reactor agent ), and at hazardous waste sites an and. Bisphthalimides as polymer additives 〈90JAP ( K ) 03200859〉 anhydride with phenols metal halide in the.! Gives phthalic anhydride reaction reaction Scheme of alcoholysis, in Encyclopedia of Toxicology ( Third Edition ), has... To sixfold compared with nonsmokers conducting polyphenylenes led to the environment through various waste.... An additive used to prepare flame-retardant bisphthalimides as polymer additives 〈90JAP ( ).