DIRECTIVITY AND RING ACTIVATION / DEACTIVATION

1. DIRECTIVITY AND RING ACTIVATION / DEACTIVATION

2. ACTIVATED RING Nitration of Anisole HNO3 + H2SO4 anisole ortho para Reacts faster than benzene = “ACTIVATED” The -OCH3 group when it preexists on the ring gives only ortho and para products, and no meta. Substituents that cause this result are called o,p directors and they usually activate the ring.

3. DEACTIVATED RING Nitration of Methyl Benzoate HNO3 H2SO4 meta methyl benzoate Reacts slower than benzene = “DEACTIVATED” The -COOMe group when it preexists on the ring gives only meta, and no ortho or para products. Substituents that cause this result are called m directors and they usually deactivate the ring.

4. SUBSTITUENT CATEGORIES Most ring substituents fall into one of these two categories: o,p - directors m- directors activate the ring deactivate the ring We will look at one of each kind in order to understand the difference…..

5. NITRATION OF ANISOLE

6. Nitration of Anisole ortho meta para activated ring actual products para ortho +

7. : ortho EXTRA! meta : para EXTRA!

8. RECALL: HAMMOND POSTULATE Ea Energy Profiles NITRATION OF ANISOLE benzenium intermediate meta benzenium intermediates have more resonance ortho para ortho-para director

9. BENZENIUM IONS GIVE ELIMINATION INSTEAD OF ADDITION ADDITION REACTION doesn’t happen resonance would be lost X ELIMINATION REACTION restores aromatic ring resonance ( 36 Kcal / mole )

10. NITRATION OF METHYL BENZOATE

11. Nitration of Methyl Benzoate ortho meta para deactivated ring actual product meta

12. d- d+ BAD! ortho meta d- d+ para BAD!

13. Energy Profiles NITRATION OF METHYL BENZOATE some benzenium resonance structures have a bad situation ortho para meta meta director

14. DIRECTIVITY OF SINGLE GROUPS

15. ortho, para - Directing Groups Groups that donate electron density to the ring. PROFILE: : E+ increased reactivity +I Substituent +R Substituent .. These groups also “activate” the ring, or make it more reactive. CH3-O- .. CH3- .. R- CH3-N- .. -NH2 .. The +R groups activate the ring more strongly than +I groups. -O-H ..

16. meta - Directing Groups Groups that withdraw electron density from the ring. PROFILE: d+ d- E+ decreased reactivity -I Substituent -R Substituent These groups also “deactivate” the ring, or make it less reactive. + + - -SO3H

17. THE EXCEPTION Halides - o,p Directors / Deactivating Halides represent a special case: .. : : They are o,p directing groups that are deactivating E+ They are o,p directors (+R effect ) They are deactivating ( -I effect ) Most other other substituents fall into one of these four categories: +R / -I / o,p / deactivating 1) +R / o,p / activating -F -Cl -Br -I 2) +I / o,p / activating 3) -R / m / deactivating 4) -I / m / deactivating

18. PREDICT ! o,p m o,p m

19. DIRECTIVITY OF MULTIPLE GROUPS

20. GROUPS ACTING IN CONCERT steric crowding o,p director m-director very little formed HNO3 H2SO4 When groups direct to the same positions it is easy to predict the product. major product

21. GROUPS COMPETING o,p-directing groups win over m-directing groups too crowded X HNO3 + H2SO4

22. RESONANCE VERSUS INDUCTIVE EFFECT +R HNO3 H2SO4 major product +I resonance effects are more important than inductive effects

23. SOME GENERAL RULES 1) Activating (o,p) groups (+R, +I) win over deactivating (m) groups (-R,-I). 2) Resonance groups (+R) win over inductive (+I) groups. 3) 1,2,3-Trisubstituted products rarely form due to excessive steric crowding. 4) With bulky directing groups, there will usually be more p-substitution than o-substitution. 5) The incoming group replaces a hydrogen, it will not usually displace a substituent already in place.

24. HOW CAN YOU MAKE ... only, no para

25. BROMINE - WATER REAGENT PHENOLS AND ANILINES

26. BROMINE IN WATER This reagent works only with highly-activated rings such as phenols, anisoles and anilines. .. .. .. .. .. .. - : : : : : .. .. .. .. + .. .. : + .. + bromonium ion etc

27. PHENOLS AND ANILINES REACT Br2 H2O All available positions are bromiated. Br2 H2O

28. AROMATICITY THE HUCKEL RULE

29. AROMATICITY QUESTION: Are all fully-conjugated, cyclic systems aromatic? 36 kcal/mole RE ? ? ? KNOWN AROMATIC ? ? Do these other rings have the same kind of stability as benzene?

30. AROMATICITY .. HUCKEL 4n+2 RULE Prediction: Compounds that have 4n+2 pi electrons in a cyclic array will be aromatic. 4n+2 series = 2, 6, 10, 14, 18, 22, 26, 30 …….. etc. The rule was derived by observation of POLYCYCLIC AROMATIC COMPOUNDS 6 10 14 benzene naphthalene anthracene 14 18

31. Aromatic Compounds Have Special Properties Aromatic compounds: 1) Must be cyclic and fully conjugated 2) Must have 4n+2 p electrons in the system 3) Must have the entire system planar 4) Will have no unpaired electrons in the p system molecular orbitals planar system Characteristic Properties: 1) Special chemical stability 2) Give substitution reactions instead of addition 3) Show a ring currrent in the NMR (Chapter 13, Section 13.8)

32. A proton placed in the middle of the ring would be shielded! Ring Current in Benzene Circulating p electrons Deshielded H H Secondary magnetic field generated by circulating p electrons deshields aromatic protons Bo

33. RING CURRENTS CAN BE SEEN IN THE NMR AROMATIC - SHOWS A RING CURRENT -1.0 ppm 2.0 ppm 18 p inner hydrogens -1.8 ppm outer hydrogens 8.9 ppm -1.4 ppm

34. HUCKEL MNEMONIC CYCLIC p MOLECULAR ORBITAL ARRAYS 1) Draw a circle 2) Inscribe the ring in the circle point down 3) Each point where the polygon (ring) touches the circle represents an energy level. 4) Place the correct number of electrons in the orbitals, starting with the lowest energy orbital first. E N E R G Y

35. BENZENE Aromatic compounds will have all of the occupied p M.O. levels completely filled with no unpaired electrons. 6p electrons AROMATIC E N E R G Y closed* shell (*completed level)

36. CYCLOBUTADIENE ANTI-AROMATIC Does not have a completed shell and has unpaired electrons. 4p electrons Does not have 4n+2 p electrons. open* shell E N E R G Y . . (*incomplete level) DIRADICAL

37. CYCLOOCTATETRAENE ANTI-AROMATIC 8p electrons Does not have a completed shell and has unpaired electrons. Does not have 4n+2 p electrons. open* shell E N E R G Y not planar (*incomplete level)

38. SOME CYCLIC POLYENES ANNULENES 10 p = 4(2) + 2 16 p BUT CANNOT BE PLANAR (see the hydrogens) [10]-annulene [16]-annulene 12 p 18 p = 4(4) + 2 AROMATIC [12]-annulene [18]-annulene [20]-annulene 14 p = 4(3) + 2 20 p AROMATIC [14]-annulene

39. HETEROCYCLIC COMPOUNDS The unshared pairs are in the cyclic pi system (one pair in each case). .. .. .. .. .. .. pair not in p system pyridine pyrrole furan thiophene All have 6p electrons in a cyclic array. These compounds have reactions similar to benzene, rather than to alkenes. They will give substitution reactions under conditions similar to those for benzene.

40. CYCLOPENTADIENYL ANION AND CATION The methylene hydrogens are acidic. This compound does not dissolve in water. NaOEt EtOH X 6p 4p .. AROMATIC ANTI-AROMATIC - + - Cl The cation does not form at all. The anion forms readily.

41. CYCLOHEPTATRIENYL ANION AND CATION This compound ionizes easily in water. The methylene hydrogens are not acidic. X NaOEt EtOH 8p 6p .. + - ANTI-AROMATIC AROMATIC - Cl Doesn’t form easily. Dissolves in water.