1633:
1672:
1699:
1198:
1379:
984:
954:
1093:
906:
1039:
1161:
1726:
169:
1148:
moderately repels the electrons in the bond attaching it to the ring. Thus, there is a weak electron-donating +I effect. There is an almost zero -M effect since the electron-withdrawing resonance capacity of the carbonyl group is effectively removed by the delocalisation of the negative charge of the
1034:
Because of the full or partial positive charge on the element directly attached to the ring for each of these groups, they all have a moderate to strong electron-withdrawing inductive effect (known as the -I effect). They also exhibit electron-withdrawing resonance effects, (known as the -M effect):
1218:
is something of an anomaly in this circumstance. Above, it is described as a weak electron withdrawing group but this is only partly true. It is correct that fluorine has a -I effect, which results in electrons being withdrawn inductively. However, another effect that plays a role is the +M effect
1173:
These groups have a strong electron-withdrawing inductive effect (-I) either by virtue of their positive charge or because of the powerfully electronegativity of the halogens. There is no resonance effect because there are no orbitals or electron pairs which can overlap with those of the ring. The
1371:
Nitrogen has a lone pair of electrons. However, the lone pair of its monomer form is unfavourable to donate through resonance. Only the dimer form is available for +M effect. However, the dimer form is less stable in a solution. Therefore, the nitroso group is less available to donate electrons.
1282:
are about the same or a little more reactive than chlorobenzene, because although the resonance donation is even worse, the inductive effect is also weakened due to their lower electronegativities. Thus the overall order of reactivity is U-shaped, with a minimum at chlorobenzene/bromobenzene
1359:
Due to the electronegativity difference between carbon and nitrogen, the nitroso group has a relatively strong -I effect, but not as strong as the nitro group. (Positively charged nitrogen atoms on alkylammonium cations and on nitro groups have a much stronger -I effect)
184:
Electron donating groups are typically divided into three levels of activating ability (The "extreme" category can be seen as "strong".) Electron withdrawing groups are assigned to similar groupings. Activating substituents favour electrophilic substitution about the
235:
The activating groups are mostly resonance donors (+M). Although many of these groups are also inductively withdrawing (–I), which is a deactivating effect, the resonance (or mesomeric) effect is almost always stronger, with the exception of Cl, Br, and I.
501:
While all deactivating groups are inductively withdrawing (–I), most of them are also withdrawing through resonance (–M) as well. Halogen substituents are an exception: they are resonance donors (+M). With the exception of the halides, they are
1089:. The negative oxygen was 'forced' to give electron density to the carbons (because it has a negative charge, it has an extra +I effect). Even when cold and with neutral (and relatively weak) electrophiles, the reaction still occurs rapidly.
1046:
Thus, these groups make the aromatic ring very electron-poor (δ+) relative to benzene and, therefore, they strongly deactivate the ring (i.e. reactions proceed much slower in rings bearing these groups compared to those reactions in benzene.)
1625:
When two substituents are already present on the ring, the third substituent's new location is relatively predictable. If the existing substituents reinforce or the molecule is highly symmetric, there may be no ambiguity. Otherwise:
1671:
1074:(known as the –I effect). However, the other effect called resonance add electron density back to the ring (known as the +M effect) and dominate over that of inductive effect. Hence the result is that they are EDGs and
543:
The inductive and resonance properties compete with each other but the resonance effect dominates for purposes of directing the sites of reactivity. For nitration, for example, fluorine directs strongly to the
2238:
1632:
1014:
Another common argument, which makes identical predictions, considers the stabilization or destabilization by substituents of the
Wheland intermediates resulting from electrophilic attack at the
943:
attack, whereas the anion releases electron density into the same positions, activating them for attack. This is precisely the result that the drawing of resonance structures would predict.
137:(EWG) will have the opposite effect on the nucleophilicity of the ring. The EWG removes electron density from a π system, making it less reactive in this type of reaction, and therefore called
144:
EDGs and EWGs also determine the positions (relative to themselves) on the aromatic ring where substitution reactions are most likely to take place. Electron donating groups are generally
1250:
This -I and +M effect is true for all halides - there is some electron withdrawing and donating character of each. To understand why the reactivity changes occur, we need to consider the
1266:
has 3p valence orbitals, hence the orbital energies will be further apart and the geometry less favourable, leading to less donation the stabilize the carbocationic intermediate, hence
1026:
positions. The
Hammond postulate then dictates that the relative transition state energies will reflect the differences in the ground state energies of the Wheland intermediates.
477:
Due to a stronger resonance effect and inductive effect than the heavier halogens, fluorine is anomalous. The partial rate factor of electrophilic aromatic substitution on
1698:
912:
Specifically, any formal negative or positive charges in minor resonance contributors (ones in accord with the natural polarization but not necessarily obeying the
1725:
2157:
Andrew, D. Abell; Brent, K. Nabbs; Alan, R. Battersby (12 February 1998). "Synthesis and
Properties of Ring-Deactivated Deuterated (Hydroxymethyl)pyrroles".
2078:
Rosenthal, Joel; Schuster, David I. (2003-06-01). "The
Anomalous Reactivity of Fluorobenzene in Electrophilic Aromatic Substitution and Related Phenomena".
1482:
The effect is illustrated for electrophilic aromatic substitutions with alkyl substituents of differing steric demand for electrophilic aromatic nitration.
1219:
which adds electron density back into the benzene ring (thus having the opposite effect of the -I effect but by a different mechanism). This is called the
1920:
1096:
The phenolate has a negatively charged oxygen. That is very unstable that the oxygen has a stronger +M effect (compared to phenol) and an extra +I effect.
899:
927:!) an electron-deficient benzyl cation or electron-excessive benzyl anion, respectively. The latter species admit tractable quantum calculation using
923:
The perturbation of a conjugating electron-withdrawing or electron-donating group causes the π electron distribution on a benzene ring to resemble (
2300:
2224:
983:
1315:
1243:
positions of fluorobenzene are considerably less reactive than benzene. Thus, electrophilic aromatic substitution on fluorobenzene is strongly
2380:
2296:
2220:
953:
1391:
145:
1894:
215:
position. This is not a case of favoring the meta- position like para- and ortho- directing functional groups, but rather disfavouring the
920:. A carbon atom with a larger coefficient will be preferentially attacked, due to more favorable orbital overlap with the electrophile.
1070:
Due to the electronegativity difference between carbon and oxygen / nitrogen, there will be a slight electron withdrawing effect through
1174:
inductive effect acts like that for the carboxylate anion but in the opposite direction (i.e. it produces small positive charges on the
157:
976:
positions, because the (partial) formal negative charges at these positions indicate a local electron excess. On the other hand, the
532:
Since the halogens are very electronegative they cause inductive withdrawal (withdrawal of electrons from the carbon atom of benzene).
1386:
As a result, the nitroso group is a deactivator. However, it has available to donate electron density to the benzene ring during the
160:. The selectivities observed with EDGs and EWGs were first described in 1892 and have been known as the Crum Brown–Gibson rule.
1085:
Phenol is an ortho/para director, but in a presence of base, the reaction is more rapid. It is due to the higher reactivity of
1223:(hence +M) and the result for fluorine is that the +M effect approximately cancels out the -I effect. The effect of this for
1749:
1310:
plays a role as well. This can also explain why phosphorus in phosphanes can't donate electron density to carbon through
149:
28:
2426:
2356:
2272:
2196:
2133:
1947:
17:
1338:
Due to the lone pair of electrons, halogen groups are available for donating electrons. Hence they are therefore
2410:
2323:
2029:
2395:
616:
1258:
of fluorine are the 2p orbitals which is the same for carbon - hence they will be very close in energy and
1769:
528:
directors, halides mildly deactivate the arene. This unusual behavior can be explained by two properties:
210:
205:
199:
2449:
1821:
642:
119:
1799:
1609:-butyl group is very bulky (there are 3 methyl groups attached to a single carbon) and will lead the
277:
1696:
When multiple substituents are comparably activating, steric hindrance dominates regioselectivity.
1117:
1197:
2021:
2014:
1613:
product as the major one. Even with toluene, the product is not 2:1 but having a slightly less
1121:
493:
positions, due to the proximity of these positions to the electronegative fluoro substituent.
1451:
positions are not generally equal. In the case of a fluorine substituent, for instance, the
1113:
1109:
992:
962:
91:
1375:
Oppositely, withdrawing electron density is more favourable: (see the picture on the right).
2087:
1964:
1847:
1187:
898:, the directing effects of different substituents can often be guessed through analysis of
2057:
1128:-butylbenzene) with the ring p orbital. Hence they are more reactive than benzene and are
485:
position, making it an activating group. Conversely, it is moderately deactivated at the
8:
1378:
317:
52:
2091:
357:
2374:
2290:
2214:
1994:
2406:
2362:
2352:
2329:
2319:
2278:
2268:
2202:
2192:
2139:
2129:
2128:. Greeves, Nick., Warren, Stuart G. (2nd ed.). Oxford: Oxford University Press.
2103:
2035:
2025:
1943:
1327:
895:
111:
87:
48:
1998:
1435:
positions reacting with the same partial rate factor, we would expect twice as much
1368:
The nitroso group has both a +M and -M effect, but the -M effect is more favorable.
1314:(i.e. +I effect) although it is less electronegative than carbon (2.19 vs 2.55, see
2166:
2095:
2065:
Handouts for
Organic Chemistry Lectures given at Imperial College London, Chemistry
1984:
1976:
1876:
1311:
1220:
1071:
209:
positions, while strongly and moderately deactivating groups direct attacks to the
95:
83:
79:
1852:"XXX.—A rule for determining whether a given benzene mono-derivative shall give a
1443:
product due to this statistical effect. However, the partial rate factors at the
928:
1319:
1259:
1251:
1154:
772:
714:
471:
44:
1630:
The most-activating substituent usually controls over the less-activating one.
1405:
1307:
1255:
1092:
988:
659:
474:
of the substituent's 3p (or higher) orbital with the 2p orbital of the carbon.
2206:
894:
Although the full electronic structure of an arene can only be computed using
2443:
2366:
2282:
2143:
2107:
1980:
1868:
1288:
1284:
1271:
1267:
1224:
917:
905:
675:
478:
470:
and beyond is relatively weak. This is mainly because of the relatively poor
127:
115:
40:
36:
2333:
1496:
1300:
1292:
1275:
1231:
position is reactivity that is comparable to (or even higher than) that of
1105:
977:
875:
824:
424:
194:
2039:
1921:"Ortho-, Para- and Meta- Directors in Electrophilic Aromatic Substitution"
1306:
Notice that iodobenzene is still less reactive than fluorobenzene because
1880:
1387:
1296:
1279:
1201:
They have formal or partial positive charges, which deactivates the ring.
1150:
1145:
1038:
739:
539:
they can donate electron density through pi bonding (resonance donation).
449:
411:
107:
32:
2170:
1989:
916:) reflect locations having a larger or smaller density of charge in the
1423:
position on benzene when a group is attached to it. When a group is an
913:
2099:
1160:
950:
has resonance structures with negative charges around the ring system:
1086:
710:
536:
361:
2012:
Hoggett, J. G.; Moodie, R. B.; Penton, J. R.; Schofield, K. (1971).
1851:
1283:(relative nitration rates compared to benzene = 1 in parentheses):
1263:
1215:
980:
resonance structures have positive charges around the ring system:
755:
679:
467:
268:
118:
to which such a group is attached is more likely to participate in
1050:
1491:
1232:
1063:
1051:
947:
859:
700:
153:
1330:(pKa = 3). (That's 10 times more acidic than hydrofluoric acid)
1235:. Because inductive effects depends strongly on proximity, the
1503:
1055:
759:
509:
391:
168:
2351:. Giuliano, Robert M., 1954- (Ninth ed.). New York, NY.
1059:
1011:
positions indicate electron deficiency at these positions.
1003:
position, since the (partial) formal positive charges at the
958:
798:
776:
365:
347:
337:
321:
297:
2011:
1620:
1719:
In particular, the position between two substituents, each
1463:
position. Aside from these effects, there is often also a
2427:"12.15. Multiple Multiple Substituent Substituent Effects"
1168:
406:–I, +M; though other interactions may be involved as well
1323:
1605:
product being the major product. On the other hand, the
1601:
The methyl group in toluene is small and will lead the
1459:, due to a stronger inductive withdrawal effect at the
180:
positions relative to a substituent X on a benzene ring
1029:
2191:. Schore, Neil Eric, 1948- (8e ed.). New York.
1164:
The negative charge was spread through both oxygens.
1108:
are electron donating groups. The carbon on that is
466:
In general, the resonance effect of elements in the
106:
effects, respectively—thus making the π system more
2013:
2346:
2077:
918:molecular orbital for a bond most likely to break
2441:
2316:Frontier orbitals and organic chemical reactions
152:, while electron withdrawing groups (except the
2239:"Substitution Reactions of Benzene Derivatives"
2189:Organic chemistry : structure and function
2156:
1938:Norman, Richard O. C.; Coxon, James M. (1993).
1802:. University of Calgary Department of Chemistry
931:: the cation withdraws electron density at the
889:
2020:. London: Cambridge University Press. p.
1793:
1791:
193:positions. Weakly deactivating groups direct
1942:(3rd ed.). CRC Press. pp. 353–354.
1455:partial rate factor is much smaller than the
1210:
1205:
1112:and less electronegative than those that are
2313:
1724:
1697:
1670:
1631:
1475:position, leading to a larger amount of the
982:
952:
904:
122:reaction. EDGs are therefore often known as
2299:) CS1 maint: multiple names: authors list (
2223:) CS1 maint: multiple names: authors list (
1937:
1846:
1788:
1467:, due to increased steric hindrance at the
1190:.) Hence these groups are deactivating and
2379:: CS1 maint: location missing publisher (
2295:: CS1 maint: location missing publisher (
2219:: CS1 maint: location missing publisher (
1962:
2123:
1988:
1965:"The alkyl group is a –I + R substituent"
1826:Illustrated Glossary of Organic Chemistry
1774:Illustrated Glossary of Organic Chemistry
1621:Directing effect on multiple substituents
564:). On the other hand, iodine directs to
552:position is inductively deactivated (86%
2159:Journal of the American Chemical Society
1377:
1196:
1159:
1091:
1037:
223:-positions more than they disfavour the
167:
1814:
1762:
1169:Alkylammonium and trifluoromethyl group
596:Substituent Name (in approximate order
248:Substituent Name (in approximate order
14:
2442:
2187:C., Vollhardt, K. Peter (2018-01-29).
1149:anion on the oxygen. Thus overall the
991:can withdraw electron density through
496:
197:to attack the benzene molecule at the
78:in structural formulas) is an atom or
2393:
2182:
2180:
2119:
2117:
2055:
2051:
2049:
1918:
1157:group) has an activating influence.
1144:Inductively, the negatively charged
961:can donate electron density through
230:
150:electrophilic aromatic substitutions
1750:Electrophilic aromatic substitution
1333:
1326:= -10) being much more acidic than
1303:reacts slower than benzene itself.
1030:Carbonyls, sulfonic acids and nitro
130:can interfere with the reaction.
29:electrophilic aromatic substitution
24:
2262:
2186:
2177:
2114:
2046:
1382:The -M effect of the nitroso group
25:
2461:
2016:Nitration and aromatic reactivity
1963:Salvatella, Luis (October 2017).
1919:James, Ashenhurst (29 Jan 2018).
1404:
1186:position and it destabilises the
520:directing groups but unlike most
2347:Carey, Francis A. (2013-01-07).
1797:
1349:
481:is often larger than one at the
2419:
2387:
2340:
2307:
2256:
2231:
2150:
2071:
1940:Principles of Organic Synthesis
1856:-di-derivative or a mixture of
1100:
2403:Some Organic Reaction Pathways
2056:Smith, Ed (12 February 2018).
2005:
1956:
1931:
1912:
1887:
1840:
1828:. UCLA Department of Chemistry
1776:. UCLA Department of Chemistry
1139:
13:
1:
2080:Journal of Chemical Education
1755:
1683:-trifluoromethyl)aniline and
1042:The -M effect of nitrobenzene
617:trifluoromethylsulfonyl group
163:
1770:"Electron withdrawing group"
1723:to the other, reacts last.
1363:
1354:
890:Traditional rationalizations
7:
2124:Jonathan., Clayden (2012).
1743:
1390:, making it still being an
1116:. They have overlap on the
10:
2466:
2265:Advanced organic chemistry
1211:Induction versus resonance
1206:Halides' competing effects
633:
605:Type of electronic effect
598:of deactivating strength)
572:positions comparably (54%
281:
257:Type of electronic effect
135:electron withdrawing group
120:electrophilic substitution
2263:E., Lewis, David (2016).
1822:"Electron donating group"
1733:to either substituent in
1679:to the amine in diethyl-(
1640:to the amine in diethyl-(
1182:positions but not on the
847:
820:
749:
735:
669:
612:
405:
387:
333:
311:
292:
82:that donates some of its
1981:10.1016/j.eq.2017.06.004
1925:Master Organic Chemistry
535:Since the halogens have
250:of activating strength)
68:electron releasing group
1850:; Gibson, John (1892).
1706:to the methyl group in
1665:directors control over
1299:(0.12). But still, all
1254:occurring in each. The
880:-F(para), -Cl, -Br, -I
278:metal-hydrogen exchange
110:. As a result of these
60:electron donating group
1738:
1715:
1692:
1653:
1383:
1316:electronegativity list
1270:is less reactive than
1202:
1165:
1097:
1043:
996:
965:
909:
392:phenyl (or aryl) group
181:
98:(or induction)—called
39:influence the overall
2394:Peter, Sykes (1979).
2314:Fleming, Ian (1976).
1895:"Substituent Effects"
1800:"Substituent Effects"
1729:New substituents add
1728:
1701:
1674:
1635:
1471:position but not the
1381:
1200:
1163:
1118:carbon–hydrogen bonds
1095:
1041:
999:Attack occurs at the
986:
956:
908:
777:alkoxycarbonyl groups
548:position because the
537:non-bonding electrons
171:
2243:Chemistry LibreTexts
1881:10.1039/ct8926100367
1644:-methyl)aniline and
1388:Wheland intermediate
1262:will be favourable.
1188:Wheland intermediate
939:positions, favoring
799:aminocarbonyl groups
711:trihalomethyl groups
172:Diagram showing the
146:ortho/para directors
31:reactions, existing
2092:2003JChEd..80..679R
1691:-fluorobenzaldehyde
1687:to the fluoride in
1122:carbon–carbon bonds
728:(X = F, Cl, Br, I)
497:Deactivating groups
139:deactivating groups
88:conjugated π system
1739:
1716:
1693:
1654:
1384:
1203:
1166:
1124:in compounds like
1098:
1044:
997:
966:
910:
900:resonance diagrams
867:–I, +M (dimer) or
506:directing groups.
358:(di)alkylphosphino
182:
112:electronic effects
55:that are formed.
2450:Functional groups
2349:Organic chemistry
2318:. London: Wiley.
2171:10.1021/ja973656+
2126:Organic chemistry
2100:10.1021/ed080p679
1969:Educación Química
1702:Substituents add
1675:Substituents add
1636:Substituents add
1599:
1598:
1328:hydrofluoric acid
1151:carboxylate group
968:Attack occurs at
896:quantum mechanics
887:
886:
740:haloformyl groups
651:(R = alkyl or H)
608:Directing effect
464:
463:
450:carboxylate group
366:sulfhydryl groups
260:Directing effect
231:Activating groups
124:activating groups
96:inductive effects
49:positional isomer
16:(Redirected from
2457:
2434:
2433:
2431:
2423:
2417:
2416:
2400:
2391:
2385:
2384:
2378:
2370:
2344:
2338:
2337:
2311:
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2304:
2294:
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2260:
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2253:
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2250:
2235:
2229:
2228:
2218:
2210:
2184:
2175:
2174:
2154:
2148:
2147:
2121:
2112:
2111:
2075:
2069:
2068:
2062:
2053:
2044:
2043:
2019:
2009:
2003:
2002:
1992:
1960:
1954:
1953:
1935:
1929:
1928:
1916:
1910:
1909:
1907:
1905:
1891:
1885:
1884:
1864:-di-derivatives"
1844:
1838:
1837:
1835:
1833:
1818:
1812:
1811:
1809:
1807:
1795:
1786:
1785:
1783:
1781:
1766:
1648:to the amide in
1485:
1484:
1419:positions and 1
1334:Directing effect
1256:valence orbitals
1252:orbital overlaps
1221:mesomeric effect
1072:inductive effect
746:(X = Cl, Br, I)
587:
586:
338:acylamido groups
239:
238:
156:) are generally
94:(mesomerism) or
84:electron density
80:functional group
21:
18:Activating group
2465:
2464:
2460:
2459:
2458:
2456:
2455:
2454:
2440:
2439:
2438:
2437:
2429:
2425:
2424:
2420:
2413:
2398:
2392:
2388:
2372:
2371:
2359:
2345:
2341:
2326:
2312:
2308:
2288:
2287:
2275:
2261:
2257:
2248:
2246:
2237:
2236:
2232:
2212:
2211:
2199:
2185:
2178:
2155:
2151:
2136:
2122:
2115:
2076:
2072:
2060:
2054:
2047:
2032:
2010:
2006:
1961:
1957:
1950:
1936:
1932:
1917:
1913:
1903:
1901:
1893:
1892:
1888:
1845:
1841:
1831:
1829:
1820:
1819:
1815:
1805:
1803:
1796:
1789:
1779:
1777:
1768:
1767:
1763:
1758:
1746:
1657:In particular,
1652:-cyanobenzamide
1623:
1409:
1366:
1357:
1352:
1336:
1320:hydroiodic acid
1260:orbital overlap
1213:
1208:
1171:
1146:carboxylate ion
1142:
1103:
1087:phenolate anion
1068:
1032:
892:
815:
806:
790:
784:
727:
718:
713:(strongest for
693:
687:
680:sulfonyl groups
667:
650:
643:ammonium groups
628:
624:
499:
472:orbital overlap
457:
439:
435:
431:
419:
403:
399:
373:
309:
305:
233:
166:
23:
22:
15:
12:
11:
5:
2463:
2453:
2452:
2436:
2435:
2418:
2411:
2405:. p. 32.
2386:
2357:
2339:
2324:
2306:
2273:
2255:
2230:
2197:
2176:
2149:
2134:
2113:
2086:(6): 679–690.
2070:
2045:
2030:
2004:
1975:(4): 232–237.
1955:
1948:
1930:
1911:
1886:
1848:Brown, A. Crum
1839:
1813:
1787:
1760:
1759:
1757:
1754:
1753:
1752:
1745:
1742:
1741:
1740:
1737:-chlorotoluene
1717:
1714:-butyl)toluene
1694:
1655:
1622:
1619:
1597:
1596:
1593:
1590:
1587:
1584:
1577:
1576:
1573:
1570:
1567:
1564:
1557:
1556:
1553:
1550:
1547:
1544:
1537:
1536:
1533:
1530:
1527:
1524:
1517:
1516:
1513:-butylbenzene
1508:
1501:
1494:
1489:
1427:director with
1408:
1406:Steric effects
1403:
1365:
1362:
1356:
1353:
1351:
1348:
1335:
1332:
1308:polarizability
1212:
1209:
1207:
1204:
1170:
1167:
1141:
1138:
1102:
1099:
1067:
1049:
1031:
1028:
891:
888:
885:
884:
883:–I, +M (weak)
881:
878:
872:
871:
865:
862:
856:
855:
846:
839:
836:
822:
818:
817:
813:
804:
801:
797:(substituted)
794:
793:
788:
782:
779:
769:
768:
762:
752:
751:
748:
742:
737:
733:
732:
729:
725:
722:
716:
707:
706:
703:
697:
696:
691:
685:
682:
676:sulfonic acids
672:
671:
668:
665:
662:
656:
655:
652:
648:
645:
641:(substituted)
638:
637:
632:
629:
626:
622:
619:
614:
610:
609:
606:
603:
600:
594:
541:
540:
533:
498:
495:
462:
461:
458:
455:
452:
446:
445:
442:
437:
433:
429:
421:
420:
417:
414:
408:
407:
404:
401:
397:
394:
389:
385:
384:
381:
371:
368:
354:
353:
350:
348:acyloxy groups
344:
343:
340:
335:
331:
330:
324:
314:
313:
310:
307:
303:
300:
296:(substituted)
294:
290:
289:
280:
274:
271:
266:
262:
261:
258:
255:
252:
246:
232:
229:
165:
162:
158:meta directors
128:steric effects
35:groups on the
9:
6:
4:
3:
2:
2462:
2451:
2448:
2447:
2445:
2428:
2422:
2414:
2408:
2404:
2397:
2390:
2382:
2376:
2368:
2364:
2360:
2358:9780073402741
2354:
2350:
2343:
2335:
2331:
2327:
2321:
2317:
2310:
2302:
2298:
2292:
2284:
2280:
2276:
2274:9780199758975
2270:
2266:
2259:
2244:
2240:
2234:
2226:
2222:
2216:
2208:
2204:
2200:
2198:9781319079451
2194:
2190:
2183:
2181:
2172:
2168:
2164:
2160:
2153:
2145:
2141:
2137:
2135:9780199270293
2131:
2127:
2120:
2118:
2109:
2105:
2101:
2097:
2093:
2089:
2085:
2081:
2074:
2066:
2059:
2052:
2050:
2041:
2037:
2033:
2027:
2023:
2018:
2017:
2008:
2000:
1996:
1991:
1986:
1982:
1978:
1974:
1970:
1966:
1959:
1951:
1949:9780748761623
1945:
1941:
1934:
1926:
1922:
1915:
1900:
1896:
1890:
1882:
1878:
1874:
1871:
1870:
1869:J. Chem. Soc.
1865:
1863:
1859:
1855:
1849:
1843:
1827:
1823:
1817:
1801:
1794:
1792:
1775:
1771:
1765:
1761:
1751:
1748:
1747:
1736:
1732:
1727:
1722:
1718:
1713:
1709:
1705:
1700:
1695:
1690:
1686:
1682:
1678:
1673:
1668:
1664:
1660:
1656:
1651:
1647:
1643:
1639:
1634:
1629:
1628:
1627:
1618:
1616:
1612:
1608:
1604:
1594:
1591:
1588:
1585:
1582:
1579:
1578:
1574:
1571:
1568:
1565:
1562:
1559:
1558:
1554:
1551:
1548:
1545:
1542:
1539:
1538:
1534:
1531:
1528:
1525:
1522:
1519:
1518:
1515:
1512:
1509:
1507:
1505:
1502:
1500:
1498:
1495:
1493:
1490:
1487:
1486:
1483:
1480:
1478:
1474:
1470:
1466:
1465:steric effect
1462:
1458:
1454:
1450:
1446:
1442:
1438:
1434:
1430:
1426:
1422:
1418:
1415:positions, 2
1414:
1407:
1402:
1400:
1398:
1394:
1389:
1380:
1376:
1373:
1369:
1361:
1350:Nitroso group
1347:
1345:
1341:
1331:
1329:
1325:
1321:
1317:
1313:
1309:
1304:
1302:
1298:
1295:(0.060) <
1294:
1290:
1286:
1281:
1277:
1273:
1272:fluorobenzene
1269:
1268:chlorobenzene
1265:
1261:
1257:
1253:
1248:
1246:
1242:
1238:
1234:
1230:
1226:
1225:fluorobenzene
1222:
1217:
1199:
1195:
1193:
1189:
1185:
1181:
1177:
1162:
1158:
1156:
1152:
1147:
1137:
1135:
1131:
1127:
1123:
1119:
1115:
1114:sp hybridized
1111:
1110:sp hybridized
1107:
1094:
1090:
1088:
1083:
1081:
1077:
1073:
1065:
1061:
1057:
1053:
1048:
1040:
1036:
1027:
1025:
1021:
1017:
1012:
1010:
1006:
1002:
994:
990:
985:
981:
979:
975:
971:
964:
960:
955:
951:
949:
946:For example,
944:
942:
938:
934:
930:
929:Hückel theory
926:
925:very slightly
921:
919:
915:
907:
903:
901:
897:
882:
879:
877:
874:
873:
870:
869:–M (monomer)
866:
863:
861:
860:nitroso group
858:
857:
854:
850:
844:
840:
837:
834:
830:
826:
823:
819:
816:
810:
802:
800:
796:
795:
792:
780:
778:
774:
771:
770:
767:
763:
761:
757:
754:
753:
747:
743:
741:
738:
734:
730:
723:
720:
712:
709:
708:
704:
702:
699:
698:
695:
683:
681:
677:
674:
673:
663:
661:
658:
657:
653:
646:
644:
640:
639:
636:
630:
620:
618:
615:
611:
607:
604:
601:
599:
595:
593:
592:deactivation
590:Magnitude of
589:
588:
585:
583:
579:
575:
571:
567:
563:
559:
555:
551:
547:
538:
534:
531:
530:
529:
527:
523:
519:
515:
511:
507:
505:
494:
492:
488:
484:
480:
479:fluorobenzene
475:
473:
469:
459:
453:
451:
448:
447:
443:
441:
426:
423:
422:
415:
413:
410:
409:
395:
393:
390:
386:
382:
380:
377:
369:
367:
363:
359:
356:
355:
351:
349:
346:
345:
341:
339:
336:
332:
329:
325:
323:
322:alkoxy groups
319:
316:
315:
301:
299:
295:
291:
288:
284:
279:
275:
272:
270:
267:
264:
263:
259:
256:
253:
251:
247:
245:
242:Magnitude of
241:
240:
237:
228:
226:
222:
218:
214:
213:
208:
207:
202:
201:
196:
195:electrophiles
192:
188:
179:
175:
170:
161:
159:
155:
151:
147:
142:
140:
136:
131:
129:
125:
121:
117:
116:aromatic ring
113:
109:
105:
101:
97:
93:
89:
85:
81:
77:
73:
69:
65:
61:
56:
54:
50:
46:
42:
41:reaction rate
38:
37:aromatic ring
34:
30:
19:
2432:. p. 7.
2421:
2402:
2389:
2348:
2342:
2315:
2309:
2267:. New York.
2264:
2258:
2247:. Retrieved
2245:. 2013-10-02
2242:
2233:
2188:
2162:
2158:
2152:
2125:
2083:
2079:
2073:
2067:. p. 3.
2064:
2015:
2007:
1990:10261/184773
1972:
1968:
1958:
1939:
1933:
1924:
1914:
1902:. Retrieved
1899:www.mhhe.com
1898:
1889:
1872:
1867:
1861:
1857:
1853:
1842:
1830:. Retrieved
1825:
1816:
1804:. Retrieved
1778:. Retrieved
1773:
1764:
1734:
1730:
1720:
1711:
1707:
1703:
1688:
1684:
1680:
1676:
1666:
1662:
1658:
1649:
1645:
1641:
1637:
1624:
1614:
1610:
1606:
1602:
1600:
1580:
1560:
1540:
1520:
1514:
1510:
1506:
1499:
1497:ethylbenzene
1481:
1476:
1472:
1468:
1464:
1460:
1456:
1452:
1448:
1444:
1440:
1436:
1432:
1428:
1425:ortho / para
1424:
1420:
1416:
1412:
1411:There are 2
1410:
1396:
1392:
1385:
1374:
1370:
1367:
1358:
1343:
1339:
1337:
1305:
1301:halobenzenes
1287:(0.18) >
1276:bromobenzene
1274:. However,
1249:
1244:
1240:
1236:
1228:
1214:
1191:
1183:
1179:
1175:
1172:
1153:(unlike the
1143:
1133:
1129:
1125:
1106:Alkyl groups
1104:
1101:Alkyl groups
1084:
1079:
1075:
1069:
1045:
1033:
1023:
1019:
1015:
1013:
1008:
1004:
1000:
998:
978:nitrobenzene
973:
969:
967:
945:
940:
936:
932:
924:
922:
911:
893:
868:
852:
848:
842:
832:
828:
825:fluoro group
811:
808:
786:
765:
745:
689:
634:
597:
591:
581:
577:
573:
569:
565:
561:
557:
553:
549:
545:
542:
525:
521:
517:
513:
508:
503:
500:
490:
486:
482:
476:
468:third period
465:
427:
425:alkyl groups
378:
375:
327:
306:, -NHR, -NR
298:amino groups
286:
282:
249:
243:
234:
227:- position.
224:
220:
216:
211:
204:
198:
190:
186:
183:
177:
173:
143:
138:
134:
132:
123:
108:nucleophilic
103:
99:
75:
71:
67:
63:
59:
57:
26:
2058:"LECTURE 2"
1875:: 367–369.
1832:16 November
1806:16 November
1798:Hunt, Ian.
1780:16 November
1439:product as
1346:directors.
1280:iodobenzene
1247:selective.
1194:directing:
1140:Carboxylate
1136:directors.
1082:directors.
989:nitro group
959:amino group
876:halo groups
835:positions)
760:acyl groups
701:cyano group
660:nitro group
412:vinyl group
269:oxido group
244:activation
174:ortho, meta
33:substituent
2412:0851869998
2325:0471018201
2249:2021-09-18
2207:1007924903
2031:0521080290
1756:References
1581:ortho/para
1488:Substrate
1318:) and why
1291:(0.064) ~
963:resonance.
914:octet rule
602:Structure
383:+M (weak)
254:Structure
164:Categories
47:effect on
43:or have a
2375:cite book
2367:822971422
2291:cite book
2283:933277973
2215:cite book
2144:761379371
2108:0021-9584
1617:product.
1479:product.
1364:Resonance
1355:Induction
1312:induction
1062:(such as
993:resonance
736:Moderate
428:(e.g. -CH
362:alkylthio
334:Moderate
126:, though
92:resonance
45:directing
2444:Category
1999:46641895
1744:See also
1563:product
1543:product
1523:product
1399:director
1264:Chlorine
1216:Fluorine
1155:carboxyl
1052:Anilines
841:–I, +M (
809:-CONHR,
773:carboxyl
576:and 45%
276:+I, +M,
265:Extreme
154:halogens
53:products
2334:2048204
2088:Bibcode
1904:2 April
1669:ones.
1492:toluene
1233:benzene
1227:at the
1064:anisole
1056:phenols
948:aniline
750:–I, –M
670:–I, –M
631:–I, –M
613:Strong
580:, 1.3%
560:, 0.6%
510:Halides
342:-NHCOR
318:hydroxy
312:–I, +M
293:Strong
86:into a
51:of the
2409:
2365:
2355:
2332:
2322:
2281:
2271:
2205:
2195:
2142:
2132:
2106:
2040:205846
2038:
2028:
1997:
1946:
1860:- and
1583:ratio
1504:cumene
1060:ethers
1058:, and
764:-CHO,
756:formyl
556:, 13%
416:-CH=CH
364:, and
352:-OCOR
219:- and
200:ortho-
2430:(PDF)
2399:(PDF)
2165:(8).
2061:(PDF)
1995:S2CID
1858:ortho
1704:ortho
1685:ortho
1677:ortho
1659:ortho
1646:ortho
1638:ortho
1615:ortho
1603:ortho
1595:0.22
1592:0.48
1589:0.76
1586:1.57
1521:ortho
1469:ortho
1461:ortho
1453:ortho
1445:ortho
1437:ortho
1429:ortho
1413:ortho
1393:ortho
1340:ortho
1241:ortho
1176:ortho
1130:ortho
1076:ortho
1016:ortho
1005:ortho
970:ortho
933:ortho
864:-N=O
849:ortho
843:ortho
829:ortho
821:Weak
812:-CONR
803:-CONH
766:-COR
744:-COX
719:group
705:-C≡N
578:ortho
566:ortho
558:ortho
550:ortho
522:ortho
514:ortho
487:ortho
388:Weak
376:-SR,
326:-OH,
283:ortho
217:ortho
212:meta-
206:para-
187:ortho
114:, an
66:) or
2407:ISBN
2381:link
2363:OCLC
2353:ISBN
2330:OCLC
2320:ISBN
2301:link
2297:link
2279:OCLC
2269:ISBN
2225:link
2221:link
2203:OCLC
2193:ISBN
2140:OCLC
2130:ISBN
2104:ISSN
2036:OCLC
2026:ISBN
1944:ISBN
1906:2015
1862:para
1854:meta
1834:2012
1808:2012
1782:2012
1735:meta
1731:para
1721:meta
1712:tert
1708:para
1689:para
1681:meta
1667:meta
1663:para
1650:para
1642:para
1611:para
1561:para
1541:meta
1511:tert
1477:para
1473:para
1457:para
1449:para
1447:and
1441:para
1433:para
1431:and
1421:para
1417:meta
1397:para
1344:para
1293:PhBr
1289:PhCl
1278:and
1245:para
1239:and
1237:meta
1229:para
1192:meta
1184:meta
1180:para
1178:and
1134:para
1126:tert
1120:(or
1080:para
1024:meta
1020:para
1009:para
1007:and
1001:meta
987:The
974:para
972:and
957:The
941:meta
937:para
935:and
853:para
833:meta
775:and
758:and
678:and
635:meta
582:meta
574:para
570:para
568:and
562:meta
554:para
546:para
526:para
518:para
512:are
504:meta
491:meta
489:and
483:para
432:, -C
379:-SH
328:-OR
320:and
287:para
225:meta
221:para
203:and
191:para
189:and
178:para
176:and
148:for
90:via
2396:"2"
2167:doi
2163:120
2096:doi
2022:200
1985:hdl
1977:doi
1877:doi
1575:73
1572:62
1569:59
1566:37
1555:11
1535:16
1532:30
1529:45
1526:58
1324:pKa
1297:PhI
1285:PhF
1022:or
902:.
838:-F
787:-CO
785:H,
781:-CO
731:–I
724:-CX
715:-CF
690:-SO
688:H,
684:-SO
664:-NO
654:–I
647:-NR
621:-SO
584:).
460:+I
454:-CO
444:-R
370:-PR
302:-NH
273:-O
133:An
102:or
72:ERG
64:EDG
58:An
27:In
2446::
2401:.
2377:}}
2373:{{
2361:.
2328:.
2293:}}
2289:{{
2277:.
2241:.
2217:}}
2213:{{
2201:.
2179:^
2161:.
2138:.
2116:^
2102:.
2094:.
2084:80
2082:.
2063:.
2048:^
2034:.
2024:.
1993:.
1983:.
1973:28
1971:.
1967:.
1923:.
1897:.
1873:61
1866:.
1824:.
1790:^
1772:.
1710:-(
1552:8
1549:6
1546:5
1401:.
1395:/
1342:/
1054:,
851:,
845:)
831:,
807:,
791:R
721:)
694:R
625:CF
524:,
516:,
440:)
396:-C
374:,
360:,
285:,
141:.
104:+I
100:+M
74:,
2415:.
2383:)
2369:.
2336:.
2303:)
2285:.
2252:.
2227:)
2209:.
2173:.
2169::
2146:.
2110:.
2098::
2090::
2042:.
2001:.
1987::
1979::
1952:.
1927:.
1908:.
1883:.
1879::
1836:.
1810:.
1784:.
1661:/
1607:t
1322:(
1132:/
1078:/
1066:)
1018:/
995:.
827:(
814:2
805:2
789:2
783:2
726:3
717:3
692:2
686:3
666:2
649:3
627:3
623:2
456:2
438:5
436:H
434:2
430:3
418:2
402:5
400:H
398:6
372:2
308:2
304:2
76:Z
70:(
62:(
20:)
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