{"id":370,"date":"2018-11-26T15:34:42","date_gmt":"2018-11-26T15:34:42","guid":{"rendered":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/?post_type=chapter&#038;p=370"},"modified":"2024-03-08T13:25:05","modified_gmt":"2024-03-08T13:25:05","slug":"14-2-electrophilic-aromatic-substitution-chemistry-libretexts","status":"publish","type":"chapter","link":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/chapter\/14-2-electrophilic-aromatic-substitution-chemistry-libretexts\/","title":{"raw":"14.3. Substituent Effects","rendered":"14.3. Substituent Effects"},"content":{"raw":"<div id=\"section_1\" class=\"mt-section\">\r\n<h2>Introduction<\/h2>\r\nThere are two main effects of substituents.\u00a0 The substituent will affect the <em><strong>rate of reaction<\/strong><\/em> (aka reactivity) of the ring, and it will also affect the <em><strong>position of attack<\/strong><\/em> (called \"directing effects\") on the ring by the incoming electrophile.\u00a0 Thus we need to answer the following questions:\r\n<ul>\r\n \t<li>Does the substituent activate or deactivate the aromatic ring?<\/li>\r\n \t<li>Where will the incoming group go?<\/li>\r\n<\/ul>\r\n<img class=\"aligncenter wp-image-3203\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/24190801\/SubstituentDirectingEffects.jpg\" alt=\"Graphic showing effects of (1) rate of reaction and (2) position of attack\" width=\"763\" height=\"395\" \/>\r\n<h2 class=\"editable\">Reactivity: Activation and deactivation<\/h2>\r\nBecause benzene acts as a nucleophile in electrophilic aromatic substitution, substituents that make the benzene more electron-rich can accelerate the reaction. Substituents that make the benzene moor electron-poor can retard the reaction. In the mid-twentieth century, physical organic chemists including Christopher Ingold conducted a number of kinetic studies on electrophilic aromatic substitution reactions. In table 1, you can see that some substituents confer a rate of reaction that is much higher than that of benzene (R = H). Phenol, C<sub>6<\/sub>H<sub>5<\/sub>OH, undergoes nitration a thousand times faster than benzene does.\u00a0 Nitrobenzene, C<sub>6<\/sub>H<sub>5<\/sub>NO<sub>2<\/sub>, undergoes the reaction millions of times more slowly.\r\n<table style=\"margin: auto;\" border=\"1\"><caption><em><strong>Table <\/strong> <\/em><em>: Rate of nitration in benzene derivatives<\/em><\/caption>\r\n<tbody>\r\n<tr>\r\n<td class=\"auto-style4\"><strong>R in C<sub>6<\/sub>H<sub>5<\/sub>R<\/strong><\/td>\r\n<td class=\"auto-style4\"><strong>Relative rate<\/strong><\/td>\r\n<\/tr>\r\n<tr>\r\n<td class=\"auto-style2\">OH<\/td>\r\n<td class=\"auto-style2\">1,000<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>CH<sub>3<\/sub><\/td>\r\n<td>25<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>H<\/td>\r\n<td>1<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>CH<sub>2<\/sub>Cl<\/td>\r\n<td>0.71<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>I<\/td>\r\n<td>0.18<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>F<\/td>\r\n<td>0.15<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>Cl<\/td>\r\n<td>0.033<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>Br<\/td>\r\n<td>0.030<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>CO<sub>2<\/sub>Et<\/td>\r\n<td>0.0037<\/td>\r\n<\/tr>\r\n<tr>\r\n<td>NO<sub>2<\/sub><\/td>\r\n<td>6 x 10<sup>-8<\/sup><\/td>\r\n<\/tr>\r\n<tr>\r\n<td class=\"auto-style3\">NMe<sub>3<\/sub><sup>+<\/sup><\/td>\r\n<td class=\"auto-style3\">1.2 x 10<sup>-8<\/sup><\/td>\r\n<\/tr>\r\n<\/tbody>\r\n<\/table>\r\nThese observations are consistent with the role of the aromatic as a nucleophile in this reaction. Substituents that draw electron density away from the aromatic ring slow the reaction down. These groups are called deactivating groups in this reaction. Substituents that readily donate electron density to the ring, or that effectively stabilize the cationic intermediate, promote the reaction. These groups are called activating groups in this reaction.\r\n\r\nThe roles of these groups are related to their electronic interactions with the electrons in the ring.\u00a0 Some groups (e.g., H<sub>2<\/sub>N-, HO-, RO-) have lone pairs and act as \u03c0-donors, providing additional electron density to the benzene ring via resonance.\u00a0 This is often called a +R (for resonance) effect, and this <em>activates<\/em> the ring towards EAS.\r\n\r\n<img class=\"alignnone wp-image-3246\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19163450\/AromaticEDG.png\" alt=\"An atom with a lone pair can donate electrons into an aromatic ring\" width=\"460\" height=\"101\" \/>\r\n\r\nOther groups contain an electronegative atom attached via a\u00a0\u03c0-bond (e.g., C=O) that makes the group electron-withdrawing.\u00a0 These groups act as \u03c0-acceptors, drawing electron density away from the ring via resonance.\u00a0 This may be called a \u2013R effect, and this <em>deactivates<\/em> the ring towards EAS.\r\n\r\n<img class=\"alignnone wp-image-3247\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19164239\/AromaticEWG.png\" alt=\"An electron-withdrawing group makes the nearby aromatic ring electron-deficient\" width=\"452\" height=\"129\" \/>\r\n\r\nSome groups act only through the sigma bonds via the inductive effect (I), which is based purely on electronegativity without any resonance.\u00a0 These effects are usually less than resonance effects, but they are still significant.\u00a0 Since an sp<sup>3<\/sup> carbon is less electronegative than an sp<sup>2<\/sup> carbon, a methyl or similar sp<sup>3<\/sup> alkyl (R) group can act as a \u03c3-donor, putting some extra electron density into the ring, giving a +I effect (activating).\u00a0 Groups based on more electronegative atoms (O, F, Cl) may be \u03c3-acceptors, drawing electron density away from the ring via a simple inductive effect which arises from the electronegativity of the substituent.\u00a0 This deactivates the ring, and is often referred to as a \u2013I effect.\r\n\r\n<img class=\"alignnone wp-image-3249\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19165735\/AromaticSigmaDonorAcceptor.png\" alt=\"Electropositive substituents donate electron density into the ring, whereas electronegative atoms withdraw it from the ring\" width=\"396\" height=\"120\" \/>\r\n\r\nIn some cases (e.g., OH, Cl), there may be multiple effects, and the overall influence of the substituents is determined by the balance of the R and I effects.\u00a0 One effect may be stronger in one case than the other, so it wins out in one case and loses in another.\u00a0 The substituent effects on reactivity have been studied experimentally, and the following chart summarizes the reactivity order, with strongest activators (in green) on the left and strongest deactivators (in red) on the right.\u00a0 Thus amino groups are the strongest activators listed, and nitro groups are the strongest deactivators.\r\n\r\n<img class=\"alignnone size-full wp-image-3206\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/24195541\/EAS_SubstituentActivityOrder1.jpg\" alt=\"Chart showing substituent effect on reactivity, going from activators on left to deactivators on right\" width=\"2976\" height=\"419\" \/>\r\n<h2 class=\"editable\">Directing Effects<\/h2>\r\nIn addition to exerting an effect on the speed of reaction, substituents on the benzene ring also influence the regiochemistry of the reaction. That is, they control <em>where<\/em> the new substituent appears in the product.\r\n\r\nRemember, there are three different positions on the benzene ring where a new substituent can attach, relative to the original substituent.\u00a0 Substitution could actually occur on five positions around the ring, but two pairs are related by symmetry. Isomerism in disubstituted benzenes can be described by numbering the substituents (1,2- etc) or by the relationships <em>ortho<\/em>-, <em>meta<\/em>- and <em> para<\/em>-.\u00a0 There are two positions <em>ortho<\/em>- to the initial substituent and two positions <em>meta<\/em>- to it.\r\n<p style=\"text-align: center;\"><img class=\"alignnone wp-image-3281\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1.png\" alt=\"Generic reaction of E+ with R-Ph to give an ortho, meta or para disubstituted product\" width=\"549\" height=\"154\" \/><\/p>\r\n&nbsp;\r\n\r\nIngold and colleagues investigated the question of regiochemistry in nitration.\u00a0 They reported the following observations:\r\n<table style=\"margin: auto; width: 362px;\" border=\"1\"><caption><em><strong>Table <\/strong> <\/em> <em>: Substitution patterns during nitration of benzene derivatives<\/em><\/caption>\r\n<tbody>\r\n<tr style=\"height: 12px;\">\r\n<td class=\"auto-style4\" style=\"height: 12px;\">R in C<sub>6<\/sub>H<sub>5<\/sub>R<\/td>\r\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>o<\/em>- product<\/td>\r\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>m<\/em>- product<\/td>\r\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>p<\/em>- product<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td class=\"auto-style5\" style=\"height: 12px;\">CH<sub>3<\/sub><\/td>\r\n<td class=\"auto-style5\" style=\"height: 12px;\">56<\/td>\r\n<td class=\"auto-style5\" style=\"height: 12px;\">3<\/td>\r\n<td class=\"auto-style5\" style=\"height: 12px;\">41<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">Cl<\/td>\r\n<td style=\"height: 12px;\">30<\/td>\r\n<td style=\"height: 12px;\">0<\/td>\r\n<td style=\"height: 12px;\">70<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">Br<\/td>\r\n<td style=\"height: 12px;\">38<\/td>\r\n<td style=\"height: 12px;\">0<\/td>\r\n<td style=\"height: 12px;\">62<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">OH<\/td>\r\n<td style=\"height: 12px;\">10<\/td>\r\n<td style=\"height: 12px;\">0<\/td>\r\n<td style=\"height: 12px;\">90<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">CHO<\/td>\r\n<td style=\"height: 12px;\">19<\/td>\r\n<td style=\"height: 12px;\">72<\/td>\r\n<td style=\"height: 12px;\">9<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">CO<sub>2<\/sub>Et<\/td>\r\n<td style=\"height: 12px;\">28<\/td>\r\n<td style=\"height: 12px;\">68<\/td>\r\n<td style=\"height: 12px;\">3<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td style=\"height: 12px;\">CN<\/td>\r\n<td style=\"height: 12px;\">17<\/td>\r\n<td style=\"height: 12px;\">81<\/td>\r\n<td style=\"height: 12px;\">2<\/td>\r\n<\/tr>\r\n<tr style=\"height: 12px;\">\r\n<td class=\"auto-style3\" style=\"height: 12px;\">NO<sub>2<\/sub><\/td>\r\n<td class=\"auto-style3\" style=\"height: 12px;\">6<\/td>\r\n<td class=\"auto-style3\" style=\"height: 12px;\">94<\/td>\r\n<td class=\"auto-style3\" style=\"height: 12px;\">0<\/td>\r\n<\/tr>\r\n<\/tbody>\r\n<\/table>\r\nIn looking at the table, you might see that there are two groups of substituents. One group reacts to make mixtures of <em>ortho<\/em>- and <em> para<\/em>- products. There may be different ratios of <em>ortho<\/em>- to <em>para<\/em>- and there may be small amounts of <em>meta<\/em>-, but don't get bogged down in the details. Focus on the bigger picture. Some groups are \"<em>ortho<\/em>\/<em>para <\/em>directors\".\r\n\r\nThe other group reacts to make mostly <em>meta<\/em>-substituted products. Here may be small amounts of <em>ortho<\/em>- and <em>para<\/em>- products, but these groups are best described as \"<em>meta<\/em>-directors\". These regiochemical effects are very closely related to the activating and directing effects we have already seen. If we want to understand these data, we need to think about things like \u03c0-donation, \u03c0-acceptance, inductive effects and cation stability.\r\n\r\n<\/div>\r\n<div id=\"section_2\" class=\"mt-section\"><section class=\"mt-content-container\">\r\n<div id=\"section_11\" class=\"mt-section\"><article id=\"elm-main-content\" class=\"elm-content-container\"><section class=\"mt-content-container\">\r\n<div id=\"section_16\">\r\n<div id=\"section_2\" class=\"mt-section\">\r\n<h3 class=\"editable\">Explaining directing effects in Friedel-Crafts reactions<\/h3>\r\nAs seen above, the reactivity of aromatic pi bonds in EAS reactions is very sensitive to the presence of electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the aromatic ring.\u00a0 This is due to the carbocation nature of the intermediate, which is stabilized by electron-donating groups and destabilized by electron-withdrawing groups.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220001\/image141.png\" alt=\"image134.png\" width=\"557\" height=\"174\" \/>\r\n\r\nAlkyl groups are weakly ring-activating groups, as their electron-donating ability stems only from weak inductive effects. Substituents with heteroatoms connected to the aromatic ring are significantly more ring-activating than alkyl groups, because resonance electron-donating effects are possible.\u00a0 Amines, for example, are very powerful ring-activating substituents, due to the ability of the lone pair on the nitrogen to stabilize the carbocation intermediate through resonance:\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220004\/image143.png\" alt=\"image136.png\" width=\"268\" height=\"156\" \/>\r\n\r\nOther ring-activating groups are shown below (in these figures, the R group can be a hydrogen).\u00a0 All of these groups are able, in varying degrees, to stabilize the carbocation intermediate in an electrophilic aromatic substitution reaction. Notice that plain old alkyl groups are also (weakly) ring-activating.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220007\/image145.png\" alt=\"image138.png\" width=\"577\" height=\"187\" \/>\r\n\r\nSubstituent groups that are ring-activating due to resonance effects also tend to exert a strong regiochemical influence on further substitution reactions.\u00a0\u00a0 Specifically, substitution tends to occur in the <em>ortho<\/em> and <em>para<\/em> positions relative to the existing group. This is known as the <strong><em>ortho-para<\/em> directing effect<\/strong>.\u00a0 The effect can be explained by drawing resonance contributors for the carbocation intermediate of the S<sub>E<\/sub>Ar reaction: the positive charge is in position to be delocalized by resonance only in reactions leading to <em>ortho<\/em> or <em>para<\/em> substitution.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220011\/image147.png\" alt=\"image140.png\" width=\"720\" height=\"363\" \/>\r\n\r\nThe carbocation which leads to the <em>meta<\/em>-substituted product, however, cannot be stabilized by resonance with the ring-activating group:\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220015\/image149.png\" alt=\"image142.png\" width=\"445\" height=\"172\" \/>\r\n\r\nAs an example, the Friedel-Crafts alkylation of methoxy benzene would be expected to produce a mixture of the <em>ortho<\/em> and <em>para<\/em> substituted products, but no <em>meta<\/em>-substituted product.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220018\/image151.png\" alt=\"image144.png\" width=\"660\" height=\"183\" \/>\r\n\r\nIn addition, the <em>para<\/em> product would be expected to be preferred over the <em>ortho<\/em> product, due to steric considerations.\r\n\r\nElectron-withdrawing substituents on an aromatic ring are <strong>ring-deactivating<\/strong>, making it harder for further substitution reactions to occur. These are mostly carbonyl-containing groups, as well as alkyl halides.\r\n\r\n<img class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220022\/image153.png\" alt=\"image146.png\" width=\"517\" height=\"310\" \/>\r\n\r\nWhen substitution does occur on an aromatic ring with deactivating group already attached, it tends to occur specifically at the <em>meta<\/em> position - deactivating groups are generally <strong><em>meta<\/em>-directing<\/strong>.\u00a0 The exception to this rule is the halogens, which are ring-deactivating but <em>ortho-para<\/em> directing (see next section).\r\n<h3 class=\"editable\">Halogens: A Special Case<\/h3>\r\nHalogens are very electronegative. This means that inductively they are electron-withdrawing. However, because of their ability to donate a lone pair of electrons in resonance forms, they are ortho\/para directing. Resonance effects win out in directing ortho-para, but the inductive effect is stronger in determining the reactivity: Because (on balance) they are electron withdrawing, halogens are very weak deactivators.\r\n\r\n<\/div>\r\n<\/div>\r\n<div>\r\n<div class=\"mt-section\"><article id=\"elm-main-content\" class=\"elm-content-container\"><header>\r\n<h2 id=\"title\">Directing effects of some common substituents<\/h2>\r\n<\/header><section class=\"mt-content-container\">\r\n<div id=\"section_2\" class=\"mt-section\">\r\n<table style=\"border-spacing: 1px;\" cellpadding=\"1\"><caption><em><strong>Table 1<\/strong>: Common Substituents<\/em><\/caption>\r\n<thead>\r\n<tr>\r\n<th colspan=\"4\" rowspan=\"1\" scope=\"col\"><strong>Orthe- and Para-\u00a0Directing<\/strong><\/th>\r\n<th colspan=\"2\" rowspan=\"1\" scope=\"col\"><strong>Meta Directing<\/strong><\/th>\r\n<\/tr>\r\n<\/thead>\r\n<tbody>\r\n<tr>\r\n<td><em>Strong Activating<\/em><\/td>\r\n<td><em>Moderately Activating<\/em><\/td>\r\n<td><em>Weakly Activating<\/em><\/td>\r\n<td><em>Weakly Deactivating<\/em><\/td>\r\n<td><em>Moderately Deactivating<\/em><\/td>\r\n<td><em>Strongly Deactivating<\/em><\/td>\r\n<\/tr>\r\n<tr>\r\n<td>\u00a0-NH<sub>2<\/sub> -NHR -OH\u00a0\u00a0\u00a0\u00a0 -OCH<sub>3<\/sub><\/td>\r\n<td>\u00a0-NHCOR\u00a0\u00a0\u00a0 -OCOR<\/td>\r\n<td>\u00a0-CH<sub>3<\/sub> -phenyl<\/td>\r\n<td>\u00a0-F\u00a0\u00a0\u00a0\u00a0 -Cl -Br -I<\/td>\r\n<td>\u00a0-COH\u00a0\u00a0\u00a0\u00a0 -COCH<sub>3<\/sub> -COOCH<sub>3<\/sub> -SO<sub>3<\/sub>H<\/td>\r\n<td>\u00a0-NO<sub>2<\/sub> -CF<sub>3<\/sub> -CCl<sub>3<\/sub><\/td>\r\n<\/tr>\r\n<\/tbody>\r\n<\/table>\r\n<\/div>\r\n<div id=\"section_3\" class=\"mt-section\">\r\n\r\nReferences\r\n\r\n<\/div>\r\n<div id=\"section_4\" class=\"mt-section\">\r\n<ol>\r\n \t<li>Bohm, S., and O. Exner. \"Interaction of two functional groups through the benzene ring: Theory and Experiment.\" Journal of Computational Chemistry (2008) (p. 1) <a class=\"external\" href=\"http:\/\/www.lib.berkeley.edu\" target=\"_blank\" rel=\"external nofollow noopener\">http:\/\/www.lib.berkeley.edu<\/a><\/li>\r\n \t<li>Brown, William H., Foote, Christopher S., Iverson, Brent L. Organic Chemisty. 4th ed.\u00a0Belmont, CA: Thomson Learning Inc.\/ Brooks\/Cole, 2005. (pp. 868-872)<\/li>\r\n \t<li>Schore, Neil E., Vollhardt, Peter C. <u>Organic Chemistry, Structure and Function<\/u>. 5th ed. New\u00a0York: W.H. Freeman &amp;\u00a0Company, 2007.\u00a0 (pp. 724-728)<\/li>\r\n \t<li>Laali, Kenneth K., and Volkar J. Gettwert. \u201cElectrophilic Nitration of Aromatics in Ionic Liquid Solvents.\u201d\u00a0The Journal of\u00a0Organic Chemistry\u00a066 (Dec. 2000): 35-40. American Chemical Society.<\/li>\r\n \t<li>Malhotra, Ripudaman, Subhash C. Narang, and George A. Olah.\u00a0Nitration: Methods and Mechanisms. New York: VCH Publishers, Inc., 1989.<\/li>\r\n \t<li>Sauls, Thomas W., Walter H. Rueggeberg, and Samuel L. Norwood. \u201cOn the Mechanism of Sulfonation of the Aromatic Nucleus and Sulfone Formation.\u201d\u00a0The Journal of Organic Chemistry\u00a066 (1955): 455-465. American Chemical Society.<\/li>\r\n \t<li>Vollhardt, Peter.\u00a0Organic Chemistry : Structure and Function. 5th ed. Boston: W. H. Freeman &amp; Company, 2007.<\/li>\r\n \t<li style=\"list-style-type: none;\"><\/li>\r\n<\/ol>\r\n<\/div>\r\n<div id=\"section_5\" class=\"mt-section\">\r\n<div class=\"textbox exercises\">\r\n<h3>Exercises<\/h3>\r\n<img class=\"wp-image-3259 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2.jpg\" alt=\"Three basic questions on EAS\" width=\"280\" height=\"278\" \/>\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n<img class=\"wp-image-3260 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3.jpg\" alt=\"Three basic questions on EAS\" width=\"296\" height=\"315\" \/>\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n<div id=\"section_5\" class=\"mt-section\"><\/div>\r\n&nbsp;\r\n<div id=\"section_5\" class=\"mt-section\">\r\n<h3>Solutions<\/h3>\r\n[reveal-answer q=\"862551\"]Show Answer[\/reveal-answer]\r\n\r\n<\/div>\r\n<div id=\"section_5\" class=\"mt-section\">\r\n\r\n[hidden-answer a=\"862551\"]\r\n\r\n<img class=\"wp-image-3257 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2.jpg\" alt=\"Answers to practice EAS questions (part 3)\" width=\"576\" height=\"263\" \/>\r\n\r\n<img class=\"wp-image-3258 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3.jpg\" alt=\"\" width=\"491\" height=\"269\" \/>\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n<\/div>\r\n&nbsp;\r\n\r\n&nbsp;\r\n<div id=\"section_5\" class=\"mt-section\">\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n&nbsp;\r\n\r\n[\/hidden-answer]\r\n\r\n<\/div>\r\n<div id=\"section_5\" class=\"mt-section\"><\/div>\r\n<\/div>\r\n<\/div>\r\n<\/section><section class=\"mt-content-container\">\r\n<div id=\"section_6\" class=\"mt-section\">\r\n<h3 class=\"editable\">Outside Links<\/h3>\r\n<strong>Aromatic Sulfonation<\/strong>\r\n<ul>\r\n \t<li>Wikipedia: <a class=\"external\" title=\"http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation\" href=\"http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation\" rel=\"freeklink\">http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation<\/a><\/li>\r\n \t<li>Video:\u00a0<a class=\"external\" title=\"http:\/\/www.youtube.com\/watch?v=s1qJ1MIZHic&amp;feature=related\" href=\"http:\/\/www.youtube.com\/watch?v=s1qJ1MIZHic&amp;feature=related\" rel=\"freeklink\">http:\/\/www.youtube.com\/watch?v=s1qJ1...eature=related<\/a><\/li>\r\n \t<li>Interactive 3D Reaction:\u00a0<a class=\"external\" title=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Sulfonation%20of%20benzene.html\" href=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Sulfonation%20of%20benzene.html\" rel=\"freeklink\">http:\/\/www.chemtube3d.com\/Electrophi...20benzene.html<\/a><\/li>\r\n<\/ul>\r\n<strong>Aromatic Nitration<\/strong>\r\n<ul>\r\n \t<li>Wikipedia:\u00a0<a class=\"external\" title=\"http:\/\/en.wikipedia.org\/wiki\/Nitration\" href=\"http:\/\/en.wikipedia.org\/wiki\/Nitration\" rel=\"freeklink\">http:\/\/en.wikipedia.org\/wiki\/Nitration<\/a><\/li>\r\n \t<li>Video:\u00a0<a class=\"external\" title=\"http:\/\/www.youtube.com\/watch?v=i7uclRHqfZE&amp;feature=related\" href=\"http:\/\/www.youtube.com\/watch?v=i7uclRHqfZE&amp;feature=related\" rel=\"freeklink\">http:\/\/www.youtube.com\/watch?v=i7ucl...eature=related<\/a><\/li>\r\n \t<li>Interactive 3D Reaction:\u00a0<a class=\"external\" title=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Nitration%20of%20benzene.html\" href=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Nitration%20of%20benzene.html\" rel=\"freeklink\">http:\/\/www.chemtube3d.com\/Electrophi...20benzene.html<\/a><\/li>\r\n<\/ul>\r\n<h3 class=\"editable\">Contributors<\/h3>\r\n<ul>\r\n \t<li><a href=\"http:\/\/employees.csbsju.edu\/cschaller\/srobi.htm\" rel=\"cc:attributionURL\">Chris P Schaller, Ph.D.<\/a>, <a class=\"external\" title=\"http:\/\/www.csbsju.edu\/Chemistry.htm\" href=\"http:\/\/www.csbsju.edu\/Chemistry.htm\" target=\"_blank\" rel=\"external nofollow noopener\">(College of Saint Benedict \/ Saint John's University)<\/a><\/li>\r\n \t<li><a title=\"http:\/\/chemwiki.ucdavis.edu\/Organic_Chemistry\/Organic_Chemistry_With_a_Biological_Emphasis\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)\" rel=\"internal\"><strong>Organic Chemistry With a Biological Emphasis <\/strong><\/a>by\u00a0<a class=\"external\" title=\"http:\/\/facultypages.morris.umn.edu\/~soderbt\/\" href=\"http:\/\/facultypages.morris.umn.edu\/%7Esoderbt\/\" target=\"_blank\" rel=\"external nofollow noopener\">Tim Soderberg<\/a>\u00a0(University of Minnesota, Morris)<\/li>\r\n \t<li>Lauren Rice and Samantha Spragg (UCD)<\/li>\r\n<\/ul>\r\n<\/div>\r\n<\/section><\/article><\/div>\r\n<\/div>\r\n<\/section><\/article><\/div>\r\n<\/section><\/div>","rendered":"<div id=\"section_1\" class=\"mt-section\">\n<h2>Introduction<\/h2>\n<p>There are two main effects of substituents.\u00a0 The substituent will affect the <em><strong>rate of reaction<\/strong><\/em> (aka reactivity) of the ring, and it will also affect the <em><strong>position of attack<\/strong><\/em> (called &#8220;directing effects&#8221;) on the ring by the incoming electrophile.\u00a0 Thus we need to answer the following questions:<\/p>\n<ul>\n<li>Does the substituent activate or deactivate the aromatic ring?<\/li>\n<li>Where will the incoming group go?<\/li>\n<\/ul>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-3203\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/24190801\/SubstituentDirectingEffects.jpg\" alt=\"Graphic showing effects of (1) rate of reaction and (2) position of attack\" width=\"763\" height=\"395\" \/><\/p>\n<h2 class=\"editable\">Reactivity: Activation and deactivation<\/h2>\n<p>Because benzene acts as a nucleophile in electrophilic aromatic substitution, substituents that make the benzene more electron-rich can accelerate the reaction. Substituents that make the benzene moor electron-poor can retard the reaction. In the mid-twentieth century, physical organic chemists including Christopher Ingold conducted a number of kinetic studies on electrophilic aromatic substitution reactions. In table 1, you can see that some substituents confer a rate of reaction that is much higher than that of benzene (R = H). Phenol, C<sub>6<\/sub>H<sub>5<\/sub>OH, undergoes nitration a thousand times faster than benzene does.\u00a0 Nitrobenzene, C<sub>6<\/sub>H<sub>5<\/sub>NO<sub>2<\/sub>, undergoes the reaction millions of times more slowly.<\/p>\n<table style=\"margin: auto;\">\n<caption><em><strong>Table <\/strong> <\/em><em>: Rate of nitration in benzene derivatives<\/em><\/caption>\n<tbody>\n<tr>\n<td class=\"auto-style4\"><strong>R in C<sub>6<\/sub>H<sub>5<\/sub>R<\/strong><\/td>\n<td class=\"auto-style4\"><strong>Relative rate<\/strong><\/td>\n<\/tr>\n<tr>\n<td class=\"auto-style2\">OH<\/td>\n<td class=\"auto-style2\">1,000<\/td>\n<\/tr>\n<tr>\n<td>CH<sub>3<\/sub><\/td>\n<td>25<\/td>\n<\/tr>\n<tr>\n<td>H<\/td>\n<td>1<\/td>\n<\/tr>\n<tr>\n<td>CH<sub>2<\/sub>Cl<\/td>\n<td>0.71<\/td>\n<\/tr>\n<tr>\n<td>I<\/td>\n<td>0.18<\/td>\n<\/tr>\n<tr>\n<td>F<\/td>\n<td>0.15<\/td>\n<\/tr>\n<tr>\n<td>Cl<\/td>\n<td>0.033<\/td>\n<\/tr>\n<tr>\n<td>Br<\/td>\n<td>0.030<\/td>\n<\/tr>\n<tr>\n<td>CO<sub>2<\/sub>Et<\/td>\n<td>0.0037<\/td>\n<\/tr>\n<tr>\n<td>NO<sub>2<\/sub><\/td>\n<td>6 x 10<sup>-8<\/sup><\/td>\n<\/tr>\n<tr>\n<td class=\"auto-style3\">NMe<sub>3<\/sub><sup>+<\/sup><\/td>\n<td class=\"auto-style3\">1.2 x 10<sup>-8<\/sup><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p>These observations are consistent with the role of the aromatic as a nucleophile in this reaction. Substituents that draw electron density away from the aromatic ring slow the reaction down. These groups are called deactivating groups in this reaction. Substituents that readily donate electron density to the ring, or that effectively stabilize the cationic intermediate, promote the reaction. These groups are called activating groups in this reaction.<\/p>\n<p>The roles of these groups are related to their electronic interactions with the electrons in the ring.\u00a0 Some groups (e.g., H<sub>2<\/sub>N-, HO-, RO-) have lone pairs and act as \u03c0-donors, providing additional electron density to the benzene ring via resonance.\u00a0 This is often called a +R (for resonance) effect, and this <em>activates<\/em> the ring towards EAS.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-3246\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19163450\/AromaticEDG.png\" alt=\"An atom with a lone pair can donate electrons into an aromatic ring\" width=\"460\" height=\"101\" \/><\/p>\n<p>Other groups contain an electronegative atom attached via a\u00a0\u03c0-bond (e.g., C=O) that makes the group electron-withdrawing.\u00a0 These groups act as \u03c0-acceptors, drawing electron density away from the ring via resonance.\u00a0 This may be called a \u2013R effect, and this <em>deactivates<\/em> the ring towards EAS.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-3247\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19164239\/AromaticEWG.png\" alt=\"An electron-withdrawing group makes the nearby aromatic ring electron-deficient\" width=\"452\" height=\"129\" \/><\/p>\n<p>Some groups act only through the sigma bonds via the inductive effect (I), which is based purely on electronegativity without any resonance.\u00a0 These effects are usually less than resonance effects, but they are still significant.\u00a0 Since an sp<sup>3<\/sup> carbon is less electronegative than an sp<sup>2<\/sup> carbon, a methyl or similar sp<sup>3<\/sup> alkyl (R) group can act as a \u03c3-donor, putting some extra electron density into the ring, giving a +I effect (activating).\u00a0 Groups based on more electronegative atoms (O, F, Cl) may be \u03c3-acceptors, drawing electron density away from the ring via a simple inductive effect which arises from the electronegativity of the substituent.\u00a0 This deactivates the ring, and is often referred to as a \u2013I effect.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-3249\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/19165735\/AromaticSigmaDonorAcceptor.png\" alt=\"Electropositive substituents donate electron density into the ring, whereas electronegative atoms withdraw it from the ring\" width=\"396\" height=\"120\" \/><\/p>\n<p>In some cases (e.g., OH, Cl), there may be multiple effects, and the overall influence of the substituents is determined by the balance of the R and I effects.\u00a0 One effect may be stronger in one case than the other, so it wins out in one case and loses in another.\u00a0 The substituent effects on reactivity have been studied experimentally, and the following chart summarizes the reactivity order, with strongest activators (in green) on the left and strongest deactivators (in red) on the right.\u00a0 Thus amino groups are the strongest activators listed, and nitro groups are the strongest deactivators.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone size-full wp-image-3206\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/24195541\/EAS_SubstituentActivityOrder1.jpg\" alt=\"Chart showing substituent effect on reactivity, going from activators on left to deactivators on right\" width=\"2976\" height=\"419\" \/><\/p>\n<h2 class=\"editable\">Directing Effects<\/h2>\n<p>In addition to exerting an effect on the speed of reaction, substituents on the benzene ring also influence the regiochemistry of the reaction. That is, they control <em>where<\/em> the new substituent appears in the product.<\/p>\n<p>Remember, there are three different positions on the benzene ring where a new substituent can attach, relative to the original substituent.\u00a0 Substitution could actually occur on five positions around the ring, but two pairs are related by symmetry. Isomerism in disubstituted benzenes can be described by numbering the substituents (1,2- etc) or by the relationships <em>ortho<\/em>-, <em>meta<\/em>&#8211; and <em> para<\/em>-.\u00a0 There are two positions <em>ortho<\/em>&#8211; to the initial substituent and two positions <em>meta<\/em>&#8211; to it.<\/p>\n<p style=\"text-align: center;\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-3281\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1.png\" alt=\"Generic reaction of E+ with R-Ph to give an ortho, meta or para disubstituted product\" width=\"549\" height=\"154\" srcset=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1.png 1027w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-300x84.png 300w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-768x215.png 768w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-1024x287.png 1024w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-65x18.png 65w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-225x63.png 225w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/GenericEAS-1-350x98.png 350w\" sizes=\"auto, (max-width: 549px) 100vw, 549px\" \/><\/p>\n<p>&nbsp;<\/p>\n<p>Ingold and colleagues investigated the question of regiochemistry in nitration.\u00a0 They reported the following observations:<\/p>\n<table style=\"margin: auto; width: 362px;\">\n<caption><em><strong>Table <\/strong> <\/em> <em>: Substitution patterns during nitration of benzene derivatives<\/em><\/caption>\n<tbody>\n<tr style=\"height: 12px;\">\n<td class=\"auto-style4\" style=\"height: 12px;\">R in C<sub>6<\/sub>H<sub>5<\/sub>R<\/td>\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>o<\/em>&#8211; product<\/td>\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>m<\/em>&#8211; product<\/td>\n<td class=\"auto-style4\" style=\"height: 12px;\">% <em>p<\/em>&#8211; product<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td class=\"auto-style5\" style=\"height: 12px;\">CH<sub>3<\/sub><\/td>\n<td class=\"auto-style5\" style=\"height: 12px;\">56<\/td>\n<td class=\"auto-style5\" style=\"height: 12px;\">3<\/td>\n<td class=\"auto-style5\" style=\"height: 12px;\">41<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">Cl<\/td>\n<td style=\"height: 12px;\">30<\/td>\n<td style=\"height: 12px;\">0<\/td>\n<td style=\"height: 12px;\">70<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">Br<\/td>\n<td style=\"height: 12px;\">38<\/td>\n<td style=\"height: 12px;\">0<\/td>\n<td style=\"height: 12px;\">62<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">OH<\/td>\n<td style=\"height: 12px;\">10<\/td>\n<td style=\"height: 12px;\">0<\/td>\n<td style=\"height: 12px;\">90<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">CHO<\/td>\n<td style=\"height: 12px;\">19<\/td>\n<td style=\"height: 12px;\">72<\/td>\n<td style=\"height: 12px;\">9<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">CO<sub>2<\/sub>Et<\/td>\n<td style=\"height: 12px;\">28<\/td>\n<td style=\"height: 12px;\">68<\/td>\n<td style=\"height: 12px;\">3<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td style=\"height: 12px;\">CN<\/td>\n<td style=\"height: 12px;\">17<\/td>\n<td style=\"height: 12px;\">81<\/td>\n<td style=\"height: 12px;\">2<\/td>\n<\/tr>\n<tr style=\"height: 12px;\">\n<td class=\"auto-style3\" style=\"height: 12px;\">NO<sub>2<\/sub><\/td>\n<td class=\"auto-style3\" style=\"height: 12px;\">6<\/td>\n<td class=\"auto-style3\" style=\"height: 12px;\">94<\/td>\n<td class=\"auto-style3\" style=\"height: 12px;\">0<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<p>In looking at the table, you might see that there are two groups of substituents. One group reacts to make mixtures of <em>ortho<\/em>&#8211; and <em> para<\/em>&#8211; products. There may be different ratios of <em>ortho<\/em>&#8211; to <em>para<\/em>&#8211; and there may be small amounts of <em>meta<\/em>-, but don&#8217;t get bogged down in the details. Focus on the bigger picture. Some groups are &#8220;<em>ortho<\/em>\/<em>para <\/em>directors&#8221;.<\/p>\n<p>The other group reacts to make mostly <em>meta<\/em>-substituted products. Here may be small amounts of <em>ortho<\/em>&#8211; and <em>para<\/em>&#8211; products, but these groups are best described as &#8220;<em>meta<\/em>-directors&#8221;. These regiochemical effects are very closely related to the activating and directing effects we have already seen. If we want to understand these data, we need to think about things like \u03c0-donation, \u03c0-acceptance, inductive effects and cation stability.<\/p>\n<\/div>\n<div id=\"section_2\" class=\"mt-section\">\n<section class=\"mt-content-container\">\n<div id=\"section_11\" class=\"mt-section\">\n<article id=\"elm-main-content\" class=\"elm-content-container\">\n<section class=\"mt-content-container\">\n<div id=\"section_16\">\n<div id=\"section_2\" class=\"mt-section\">\n<h3 class=\"editable\">Explaining directing effects in Friedel-Crafts reactions<\/h3>\n<p>As seen above, the reactivity of aromatic pi bonds in EAS reactions is very sensitive to the presence of electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) on the aromatic ring.\u00a0 This is due to the carbocation nature of the intermediate, which is stabilized by electron-donating groups and destabilized by electron-withdrawing groups.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220001\/image141.png\" alt=\"image134.png\" width=\"557\" height=\"174\" \/><\/p>\n<p>Alkyl groups are weakly ring-activating groups, as their electron-donating ability stems only from weak inductive effects. Substituents with heteroatoms connected to the aromatic ring are significantly more ring-activating than alkyl groups, because resonance electron-donating effects are possible.\u00a0 Amines, for example, are very powerful ring-activating substituents, due to the ability of the lone pair on the nitrogen to stabilize the carbocation intermediate through resonance:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220004\/image143.png\" alt=\"image136.png\" width=\"268\" height=\"156\" \/><\/p>\n<p>Other ring-activating groups are shown below (in these figures, the R group can be a hydrogen).\u00a0 All of these groups are able, in varying degrees, to stabilize the carbocation intermediate in an electrophilic aromatic substitution reaction. Notice that plain old alkyl groups are also (weakly) ring-activating.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220007\/image145.png\" alt=\"image138.png\" width=\"577\" height=\"187\" \/><\/p>\n<p>Substituent groups that are ring-activating due to resonance effects also tend to exert a strong regiochemical influence on further substitution reactions.\u00a0\u00a0 Specifically, substitution tends to occur in the <em>ortho<\/em> and <em>para<\/em> positions relative to the existing group. This is known as the <strong><em>ortho-para<\/em> directing effect<\/strong>.\u00a0 The effect can be explained by drawing resonance contributors for the carbocation intermediate of the S<sub>E<\/sub>Ar reaction: the positive charge is in position to be delocalized by resonance only in reactions leading to <em>ortho<\/em> or <em>para<\/em> substitution.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220011\/image147.png\" alt=\"image140.png\" width=\"720\" height=\"363\" \/><\/p>\n<p>The carbocation which leads to the <em>meta<\/em>-substituted product, however, cannot be stabilized by resonance with the ring-activating group:<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220015\/image149.png\" alt=\"image142.png\" width=\"445\" height=\"172\" \/><\/p>\n<p>As an example, the Friedel-Crafts alkylation of methoxy benzene would be expected to produce a mixture of the <em>ortho<\/em> and <em>para<\/em> substituted products, but no <em>meta<\/em>-substituted product.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220018\/image151.png\" alt=\"image144.png\" width=\"660\" height=\"183\" \/><\/p>\n<p>In addition, the <em>para<\/em> product would be expected to be preferred over the <em>ortho<\/em> product, due to steric considerations.<\/p>\n<p>Electron-withdrawing substituents on an aromatic ring are <strong>ring-deactivating<\/strong>, making it harder for further substitution reactions to occur. These are mostly carbonyl-containing groups, as well as alkyl halides.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"internal default aligncenter\" src=\"https:\/\/s3-us-west-2.amazonaws.com\/courses-images\/wp-content\/uploads\/sites\/3773\/2018\/11\/29220022\/image153.png\" alt=\"image146.png\" width=\"517\" height=\"310\" \/><\/p>\n<p>When substitution does occur on an aromatic ring with deactivating group already attached, it tends to occur specifically at the <em>meta<\/em> position &#8211; deactivating groups are generally <strong><em>meta<\/em>-directing<\/strong>.\u00a0 The exception to this rule is the halogens, which are ring-deactivating but <em>ortho-para<\/em> directing (see next section).<\/p>\n<h3 class=\"editable\">Halogens: A Special Case<\/h3>\n<p>Halogens are very electronegative. This means that inductively they are electron-withdrawing. However, because of their ability to donate a lone pair of electrons in resonance forms, they are ortho\/para directing. Resonance effects win out in directing ortho-para, but the inductive effect is stronger in determining the reactivity: Because (on balance) they are electron withdrawing, halogens are very weak deactivators.<\/p>\n<\/div>\n<\/div>\n<div>\n<div class=\"mt-section\">\n<article id=\"elm-main-content\" class=\"elm-content-container\">\n<header>\n<h2 id=\"title\">Directing effects of some common substituents<\/h2>\n<\/header>\n<section class=\"mt-content-container\">\n<div id=\"section_2\" class=\"mt-section\">\n<table style=\"border-spacing: 1px;\" cellpadding=\"1\">\n<caption><em><strong>Table 1<\/strong>: Common Substituents<\/em><\/caption>\n<thead>\n<tr>\n<th colspan=\"4\" rowspan=\"1\" scope=\"col\"><strong>Orthe- and Para-\u00a0Directing<\/strong><\/th>\n<th colspan=\"2\" rowspan=\"1\" scope=\"col\"><strong>Meta Directing<\/strong><\/th>\n<\/tr>\n<\/thead>\n<tbody>\n<tr>\n<td><em>Strong Activating<\/em><\/td>\n<td><em>Moderately Activating<\/em><\/td>\n<td><em>Weakly Activating<\/em><\/td>\n<td><em>Weakly Deactivating<\/em><\/td>\n<td><em>Moderately Deactivating<\/em><\/td>\n<td><em>Strongly Deactivating<\/em><\/td>\n<\/tr>\n<tr>\n<td>\u00a0-NH<sub>2<\/sub> -NHR -OH\u00a0\u00a0\u00a0\u00a0 -OCH<sub>3<\/sub><\/td>\n<td>\u00a0-NHCOR\u00a0\u00a0\u00a0 -OCOR<\/td>\n<td>\u00a0-CH<sub>3<\/sub> -phenyl<\/td>\n<td>\u00a0-F\u00a0\u00a0\u00a0\u00a0 -Cl -Br -I<\/td>\n<td>\u00a0-COH\u00a0\u00a0\u00a0\u00a0 -COCH<sub>3<\/sub> -COOCH<sub>3<\/sub> -SO<sub>3<\/sub>H<\/td>\n<td>\u00a0-NO<sub>2<\/sub> -CF<sub>3<\/sub> -CCl<sub>3<\/sub><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n<\/div>\n<div id=\"section_3\" class=\"mt-section\">\n<p>References<\/p>\n<\/div>\n<div id=\"section_4\" class=\"mt-section\">\n<ol>\n<li>Bohm, S., and O. Exner. &#8220;Interaction of two functional groups through the benzene ring: Theory and Experiment.&#8221; Journal of Computational Chemistry (2008) (p. 1) <a class=\"external\" href=\"http:\/\/www.lib.berkeley.edu\" target=\"_blank\" rel=\"external nofollow noopener\">http:\/\/www.lib.berkeley.edu<\/a><\/li>\n<li>Brown, William H., Foote, Christopher S., Iverson, Brent L. Organic Chemisty. 4th ed.\u00a0Belmont, CA: Thomson Learning Inc.\/ Brooks\/Cole, 2005. (pp. 868-872)<\/li>\n<li>Schore, Neil E., Vollhardt, Peter C. <u>Organic Chemistry, Structure and Function<\/u>. 5th ed. New\u00a0York: W.H. Freeman &amp;\u00a0Company, 2007.\u00a0 (pp. 724-728)<\/li>\n<li>Laali, Kenneth K., and Volkar J. Gettwert. \u201cElectrophilic Nitration of Aromatics in Ionic Liquid Solvents.\u201d\u00a0The Journal of\u00a0Organic Chemistry\u00a066 (Dec. 2000): 35-40. American Chemical Society.<\/li>\n<li>Malhotra, Ripudaman, Subhash C. Narang, and George A. Olah.\u00a0Nitration: Methods and Mechanisms. New York: VCH Publishers, Inc., 1989.<\/li>\n<li>Sauls, Thomas W., Walter H. Rueggeberg, and Samuel L. Norwood. \u201cOn the Mechanism of Sulfonation of the Aromatic Nucleus and Sulfone Formation.\u201d\u00a0The Journal of Organic Chemistry\u00a066 (1955): 455-465. American Chemical Society.<\/li>\n<li>Vollhardt, Peter.\u00a0Organic Chemistry : Structure and Function. 5th ed. Boston: W. H. Freeman &amp; Company, 2007.<\/li>\n<li style=\"list-style-type: none;\"><\/li>\n<\/ol>\n<\/div>\n<div id=\"section_5\" class=\"mt-section\">\n<div class=\"textbox exercises\">\n<h3>Exercises<\/h3>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-3259 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2.jpg\" alt=\"Three basic questions on EAS\" width=\"280\" height=\"278\" srcset=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2.jpg 590w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2-150x150.jpg 150w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2-300x297.jpg 300w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2-65x64.jpg 65w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2-225x223.jpg 225w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions2-350x347.jpg 350w\" sizes=\"auto, (max-width: 280px) 100vw, 280px\" \/><br \/>\n&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-3260 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3.jpg\" alt=\"Three basic questions on EAS\" width=\"296\" height=\"315\" srcset=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3.jpg 658w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3-282x300.jpg 282w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3-65x69.jpg 65w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3-225x239.jpg 225w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASquestions3-350x372.jpg 350w\" sizes=\"auto, (max-width: 296px) 100vw, 296px\" \/><\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<div id=\"section_5\" class=\"mt-section\"><\/div>\n<p>&nbsp;<\/p>\n<div id=\"section_5\" class=\"mt-section\">\n<h3>Solutions<\/h3>\n<div class=\"qa-wrapper\" style=\"display: block\"><span class=\"show-answer collapsed\" style=\"cursor: pointer\" data-target=\"q862551\">Show Answer<\/span><\/p>\n<\/div>\n<div id=\"section_5\" class=\"mt-section\">\n<div id=\"q862551\" class=\"hidden-answer\" style=\"display: none\">\n<p><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-3257 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2.jpg\" alt=\"Answers to practice EAS questions (part 3)\" width=\"576\" height=\"263\" srcset=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2.jpg 1325w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-300x137.jpg 300w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-768x350.jpg 768w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-1024x467.jpg 1024w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-65x30.jpg 65w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-225x103.jpg 225w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers2-350x160.jpg 350w\" sizes=\"auto, (max-width: 576px) 100vw, 576px\" \/><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"wp-image-3258 alignleft\" src=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3.jpg\" alt=\"\" width=\"491\" height=\"269\" srcset=\"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3.jpg 1317w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-300x164.jpg 300w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-768x421.jpg 768w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-1024x561.jpg 1024w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-65x36.jpg 65w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-225x123.jpg 225w, https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-content\/uploads\/sites\/3773\/2018\/11\/EASanswers3-350x192.jpg 350w\" sizes=\"auto, (max-width: 491px) 100vw, 491px\" \/><br \/>\n&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<\/div>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<div id=\"section_5\" class=\"mt-section\">\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<\/div>\n<\/div>\n<\/div>\n<div id=\"section_5\" class=\"mt-section\"><\/div>\n<\/div>\n<\/div>\n<\/section>\n<section class=\"mt-content-container\">\n<div id=\"section_6\" class=\"mt-section\">\n<h3 class=\"editable\">Outside Links<\/h3>\n<p><strong>Aromatic Sulfonation<\/strong><\/p>\n<ul>\n<li>Wikipedia: <a class=\"external\" title=\"http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation\" href=\"http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation\" rel=\"freeklink\">http:\/\/en.wikipedia.org\/wiki\/Aromatic_sulfonation<\/a><\/li>\n<li>Video:\u00a0<a class=\"external\" title=\"http:\/\/www.youtube.com\/watch?v=s1qJ1MIZHic&amp;feature=related\" href=\"http:\/\/www.youtube.com\/watch?v=s1qJ1MIZHic&amp;feature=related\" rel=\"freeklink\">http:\/\/www.youtube.com\/watch?v=s1qJ1&#8230;eature=related<\/a><\/li>\n<li>Interactive 3D Reaction:\u00a0<a class=\"external\" title=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Sulfonation%20of%20benzene.html\" href=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Sulfonation%20of%20benzene.html\" rel=\"freeklink\">http:\/\/www.chemtube3d.com\/Electrophi&#8230;20benzene.html<\/a><\/li>\n<\/ul>\n<p><strong>Aromatic Nitration<\/strong><\/p>\n<ul>\n<li>Wikipedia:\u00a0<a class=\"external\" title=\"http:\/\/en.wikipedia.org\/wiki\/Nitration\" href=\"http:\/\/en.wikipedia.org\/wiki\/Nitration\" rel=\"freeklink\">http:\/\/en.wikipedia.org\/wiki\/Nitration<\/a><\/li>\n<li>Video:\u00a0<a class=\"external\" title=\"http:\/\/www.youtube.com\/watch?v=i7uclRHqfZE&amp;feature=related\" href=\"http:\/\/www.youtube.com\/watch?v=i7uclRHqfZE&amp;feature=related\" rel=\"freeklink\">http:\/\/www.youtube.com\/watch?v=i7ucl&#8230;eature=related<\/a><\/li>\n<li>Interactive 3D Reaction:\u00a0<a class=\"external\" title=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Nitration%20of%20benzene.html\" href=\"http:\/\/www.chemtube3d.com\/Electrophilic%20aromatic%20substitution%20-%20Nitration%20of%20benzene.html\" rel=\"freeklink\">http:\/\/www.chemtube3d.com\/Electrophi&#8230;20benzene.html<\/a><\/li>\n<\/ul>\n<h3 class=\"editable\">Contributors<\/h3>\n<ul>\n<li><a href=\"http:\/\/employees.csbsju.edu\/cschaller\/srobi.htm\" rel=\"cc:attributionURL\">Chris P Schaller, Ph.D.<\/a>, <a class=\"external\" title=\"http:\/\/www.csbsju.edu\/Chemistry.htm\" href=\"http:\/\/www.csbsju.edu\/Chemistry.htm\" target=\"_blank\" rel=\"external nofollow noopener\">(College of Saint Benedict \/ Saint John&#8217;s University)<\/a><\/li>\n<li><a title=\"http:\/\/chemwiki.ucdavis.edu\/Organic_Chemistry\/Organic_Chemistry_With_a_Biological_Emphasis\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)\" rel=\"internal\"><strong>Organic Chemistry With a Biological Emphasis <\/strong><\/a>by\u00a0<a class=\"external\" title=\"http:\/\/facultypages.morris.umn.edu\/~soderbt\/\" href=\"http:\/\/facultypages.morris.umn.edu\/%7Esoderbt\/\" target=\"_blank\" rel=\"external nofollow noopener\">Tim Soderberg<\/a>\u00a0(University of Minnesota, Morris)<\/li>\n<li>Lauren Rice and Samantha Spragg (UCD)<\/li>\n<\/ul>\n<\/div>\n<\/section>\n<\/article>\n<\/div>\n<\/div>\n<\/section>\n<\/article>\n<\/div>\n<\/section>\n<\/div>\n\n\t\t\t <section class=\"citations-section\" role=\"contentinfo\">\n\t\t\t <h3>Candela Citations<\/h3>\n\t\t\t\t\t <div>\n\t\t\t\t\t\t <div id=\"citation-list-370\">\n\t\t\t\t\t\t\t <div class=\"licensing\"><div class=\"license-attribution-dropdown-subheading\">CC licensed content, Shared previously<\/div><ul class=\"citation-list\"><li>27.6: Electrophilic Aromatic Substitution. <strong>Authored by<\/strong>: Chris P. Schaller. <strong>Provided by<\/strong>: Chemistry LibreTexts. <strong>Located at<\/strong>: <a target=\"_blank\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/General_Chemistry\/Map%3A_General_Chemistry_(Petrucci_et_al.)\/27%3A_Reactions_of_Organic_Compounds\/27.06%3A_Electrophilic_Aromatic_Substitution\">https:\/\/chem.libretexts.org\/Textbook_Maps\/General_Chemistry\/Map%3A_General_Chemistry_(Petrucci_et_al.)\/27%3A_Reactions_of_Organic_Compounds\/27.06%3A_Electrophilic_Aromatic_Substitution<\/a>. <strong>Project<\/strong>: General Chemistry. <strong>License<\/strong>: <em><a target=\"_blank\" rel=\"license\" href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/4.0\/\">CC BY-NC-SA: Attribution-NonCommercial-ShareAlike<\/a><\/em><\/li><li>15.6: Synthetic parallel - electrophilic aromatic substitution in the lab. <strong>Authored by<\/strong>: Tim Soderberg. <strong>Provided by<\/strong>: Chemistry LibreTexts. <strong>Located at<\/strong>: <a target=\"_blank\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)\/15%3A_Electrophilic_reactions\/15.06%3A_Synthetic_parallel_-_electrophilic_aromatic_substitution_in_the_lab\">https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)\/15%3A_Electrophilic_reactions\/15.06%3A_Synthetic_parallel_-_electrophilic_aromatic_substitution_in_the_lab<\/a>. <strong>License<\/strong>: <em><a target=\"_blank\" rel=\"license\" href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/4.0\/\">CC BY-NC-SA: Attribution-NonCommercial-ShareAlike<\/a><\/em><\/li><li>Inductive Effects of Alkyl Groups. <strong>Authored by<\/strong>: Lauren Rice and Samantha Spragg . <strong>Provided by<\/strong>: Chemistry LibreTexts. <strong>Located at<\/strong>: <a target=\"_blank\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Supplemental_Modules_(Organic_Chemistry)\/Arenes\/Properties_of_Arenes\/Inductive_Effects_of_Alkyl_Groups\">https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Supplemental_Modules_(Organic_Chemistry)\/Arenes\/Properties_of_Arenes\/Inductive_Effects_of_Alkyl_Groups<\/a>. <strong>License<\/strong>: <em><a target=\"_blank\" rel=\"license\" href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/4.0\/\">CC BY-NC-SA: Attribution-NonCommercial-ShareAlike<\/a><\/em><\/li><li>18.4: Nitration and Sulfonation. <strong>Authored by<\/strong>: Anonymous. <strong>Located at<\/strong>: <a target=\"_blank\" href=\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Map%3A_Organic_Chemistry_(Smith)\/Chapter_18%3A_Electrophilic_Aromatic_Substitution\/18.4%3A_Nitration_and_Sulfonation\">https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Map%3A_Organic_Chemistry_(Smith)\/Chapter_18%3A_Electrophilic_Aromatic_Substitution\/18.4%3A_Nitration_and_Sulfonation<\/a>. <strong>Project<\/strong>: Chemistry LibreText. <strong>License<\/strong>: <em><a target=\"_blank\" rel=\"license\" href=\"https:\/\/creativecommons.org\/licenses\/by-nc-sa\/4.0\/\">CC BY-NC-SA: Attribution-NonCommercial-ShareAlike<\/a><\/em><\/li><\/ul><\/div>\n\t\t\t\t\t\t <\/div>\n\t\t\t\t\t <\/div>\n\t\t\t <\/section>","protected":false},"author":311,"menu_order":3,"template":"","meta":{"_candela_citation":"[{\"type\":\"cc\",\"description\":\"27.6: Electrophilic Aromatic Substitution\",\"author\":\"Chris P. Schaller\",\"organization\":\"Chemistry LibreTexts\",\"url\":\"https:\/\/chem.libretexts.org\/Textbook_Maps\/General_Chemistry\/Map%3A_General_Chemistry_(Petrucci_et_al.)\/27%3A_Reactions_of_Organic_Compounds\/27.06%3A_Electrophilic_Aromatic_Substitution\",\"project\":\"General Chemistry\",\"license\":\"cc-by-nc-sa\",\"license_terms\":\"\"},{\"type\":\"cc\",\"description\":\"15.6: Synthetic parallel - electrophilic aromatic substitution in the lab\",\"author\":\"Tim Soderberg\",\"organization\":\"Chemistry LibreTexts\",\"url\":\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Book%3A_Organic_Chemistry_with_a_Biological_Emphasis_(Soderberg)\/15%3A_Electrophilic_reactions\/15.06%3A_Synthetic_parallel_-_electrophilic_aromatic_substitution_in_the_lab\",\"project\":\"\",\"license\":\"cc-by-nc-sa\",\"license_terms\":\"\"},{\"type\":\"cc\",\"description\":\"Inductive Effects of Alkyl Groups\",\"author\":\"Lauren Rice and Samantha Spragg \",\"organization\":\"Chemistry LibreTexts\",\"url\":\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Supplemental_Modules_(Organic_Chemistry)\/Arenes\/Properties_of_Arenes\/Inductive_Effects_of_Alkyl_Groups\",\"project\":\"\",\"license\":\"cc-by-nc-sa\",\"license_terms\":\"\"},{\"type\":\"cc\",\"description\":\"18.4: Nitration and Sulfonation\",\"author\":\"Anonymous\",\"organization\":\"\",\"url\":\"https:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry\/Map%3A_Organic_Chemistry_(Smith)\/Chapter_18%3A_Electrophilic_Aromatic_Substitution\/18.4%3A_Nitration_and_Sulfonation\",\"project\":\"Chemistry LibreText\",\"license\":\"cc-by-nc-sa\",\"license_terms\":\"\"}]","CANDELA_OUTCOMES_GUID":"","pb_show_title":"on","pb_short_title":"","pb_subtitle":"","pb_authors":[],"pb_section_license":""},"chapter-type":[],"contributor":[],"license":[],"class_list":["post-370","chapter","type-chapter","status-publish","hentry"],"part":484,"_links":{"self":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapters\/370","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapters"}],"about":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/wp\/v2\/types\/chapter"}],"author":[{"embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/wp\/v2\/users\/311"}],"version-history":[{"count":43,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapters\/370\/revisions"}],"predecessor-version":[{"id":3284,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapters\/370\/revisions\/3284"}],"part":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/parts\/484"}],"metadata":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapters\/370\/metadata\/"}],"wp:attachment":[{"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/wp\/v2\/media?parent=370"}],"wp:term":[{"taxonomy":"chapter-type","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/pressbooks\/v2\/chapter-type?post=370"},{"taxonomy":"contributor","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/wp\/v2\/contributor?post=370"},{"taxonomy":"license","embeddable":true,"href":"https:\/\/courses.lumenlearning.com\/suny-potsdam-organicchemistry2\/wp-json\/wp\/v2\/license?post=370"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}