Q5. In the box below, you are given the pK, values for a series of compounds, the least acidic is cyclohexanol (pK, = 16.0). The pK, value for phenol is 10.0, and two series of substituted phenols are given: 2-fluorophenol, 3-fluorophenol, and 4-fluorophenol have pK, values of 8.7, 9.3, and 9.9, respectively; 2-nitrophenol, 3-nitrophenol, and 4-nitrophenol have pK, values of 7.2, 84, and 7.2, respectively. Note: both -F and -NO, are strong electron withdrawing groups, 56566 cyclohexanol phenol 2-X-phenol_ © 3-X-phenol_—4-X-phenol 16.0 10.0 pKa 87 93 99 X=F values 72 84 72 X=NO, (a) Briefly explain (using words AND illustrations) why phenol is (literally and actually!) a million times more acidic than cyclohexanol (5 points). + CYCLONE Xe! FOGATE ie a) 7 oe COmswGeaTe BASe OF PHEeL 1S ResOMKE co ee STABURED LOHERCAS THAT OF CHCLOREXA ROL NS STABIUZATION YS NST, SO PHEDOL OF CHARGE iat nan are ° Prewo o& ° G- dp xb CONTUCATE te Base STANGER > STABIIZED BY REBNAWCE => ACID(b) Briefly explain (using words and illustrations as you feel necessary) the trend observed in the acidity of 2-, 3-, and 4-fluorophenol (5 points). of o® o' o® oaa, Ga je Nu =. te 7 Eack Staucreee 18 STASIUZED BY RESONANCE, Amo THERe 1s pm imovenve Erect Cruat Aso STAGUIZES THE AraIOD)/THAT ESOLTS FROM THE CLECTROMSEGATIVE FE ATOUS. “THE Ciose2e THE F To The ©, THe B1GGEeR THE momocTwE EFCECT, So R-F 1S meee AUME THAD B-F, LoMcH IS MORE AGC THAN LE (0) Briefly explain and illustrate why the trend observed in the acidity of 2-, 3, and 4-nitrophenol is different to that observed for the analogous series of phenolic compounds containing fluorine G points). | LOATH THE No, GRooP In THE 2- ALO 4- PosiTONS, EXTRA ReSomemice STABUIZATION IS POSSIGLE, AOD THs DEES VST HAPFES WD THE B- HSITION) © ,¢> i O-8 ve ofte coSP So t, Resonemce 1S A MUCH LARGER Elect ir CH THAR Inspections, PRO SO 2-0, ond 2 Gama UND, ARE Moe ATIOIT THArS m0. “THIS, ReSomemICE ADT POSSIBLE IN F SERICSEXTRA CREDIT. The pK, values for 4-cyanophenol (1) and 4-nitrophenol (If) are approximately the same, i.e,, the phenolic protons (bold) in each of these compounds are equally acidic. In contrast, however, the dimethyl-substituted compounds differ significantly in their acidity; the dimethyl-cyano compound (III) is much more acidic than the dimethyl-nitro compound (IV). Explain (using both words and drawings as you feel appropriate) this observation in the box below. (15 points) Hint: think resonance... OH OH OH OH vs vs Mer Me Me" Me cN NO, CN NOp ! 1 a v ALL OTHER RESODARCE ComTRBUTORS BE APPROMIMATELY EQUAL, CoNsioee THE Russe: ° WHEN) R=H, BOTH CONTRIBUTORS ARE OK, BT Wien) R= He, Steaic wirteeactions BeTIICeN) THE Me. GRosts AWD THE OMGED ATOMS iw TL DISFAVOR “Tris RESorANCE ConTRauTER . THe CN GROVE DoES WOT surceR Geom THIS PeoBiem AS IT 1S UNEAR (moO. 1S Rance) PrmO So TT 1S MRE aAcioie than BL