. 926: } ° more tha 8 econ: se prt) (©) The first resonance form of CO; tas no equivalent form in O3, Oxygen, a second row element, does not have d orbitals, so it must adhere strictly to the octet rule, » { §=8-3 © 1.30 ) (@ CANNOT EXIST NF; violates the octet rule: nitrogen can have no more than eight electrons (or four atoms) around it Phosphorus, a third-row element, can have more than eight electrons because phosphorus can use d_ orbitals in bonding, so PF is a stable, isolable compound, 1-31 Your Lewis structures may look different from these, As long as the atoms are connected in the same order and by the same type of bond. they are equivalent structures. For now. the exact placement of the atoms on the page is not significant HOH OH @ @ @1.42 When drawing resonance fooms with charges on ring atoms, it helps to keep track of the charge by ‘writing the C or N or O with the caarge. (In Chapter 1, artows will be shown when drawing resonance forms, equivalent to the green arrows inthe text. This important skill should beeome automatic by Chapter 2 when the arrows will net be shown.) ‘more electronegative atom iujr—pezatve cago ie fa) S a : rt a HOH OH HOH OH HOH OH ‘major—negative charge on the ‘more electronegative atom © @ fF a cn For reasons tobe Ch <> CH <> (CH, | discussed in alater ‘major — — chapter, the ra structure withall ® = double bonds in the Ch <> Hy ring isthe mayor ° \. * contributor, major cH @ Ho ® S —_ 7) —_ CO eon fom at of oS 8 oe fm*major—negative change on the more electronegative atom ‘major—all atofs have octets —-© 2 ‘major—all atoms have octets B . Ory O- sajor—nepative charg onthe ‘more elestonesative tem ® —C=C—CH, ) Allresonance I forms are of HOH ‘equal energy. ) No resonance forms—the charge must be on an atom next ro a double or triple bond, or next toa non Donded pair of electrons, in order for resonance to delocalize the charze. co) [Note that the double bond on the right does not contribute its electrons to the resonance forms, :major—all atoms have octetsOO) Ovuy HO NCH it sp}, = 109° H LHL behind the plane He ofc pape S sp*,no bond angle because 0, C=C has sp? carbons, =120° angles; onygenis bonded to only one atom has sp C and N, 180° angle { HO Ne New \ H Ls ® LH . [> o c Bee Sy * 4 fy angles around sp! atom ~ 109° angles around sp* atoms ~ 12 both sp3, all = 109° amples around ep atoms ~ 109° amples around ep? carbon ~ 120° behind the plane sfthe paper) Gi) QE 7 0 Il ol #, su we " H Xe e H both sp all ~ 109° in fom of the plane ofthe2-4L The critical principle: she strength of an acid is determined by the stability of its conjugate base. (a) conjugate bases y 10) (b) Xis a stronger acid than W because the more electronegative N in X can than carbon, so the anion of X is more stable than the anion of W. ipport the negative charge better (©) Yisa stronger acid than X because the negat electronegative oxygen substituent, the OTF. charge in Y is stabilized by the inductive effeet from the (@) Zisa stronger acid than ¥ because of two effects: O is more electronegative than N and can support the negative charge of the anion better, plusthe anion of Z has two EQUIVALENT resonance forms, which is particularly stable. nucleophile electrophile Lewis base Lewis acid2-50 continued O a gisek «uae on Boon, + gi—u Hey copie electrophile Lewis acid CH, Lewis base © electrophile ‘rophile pucleophile Tewisacid Lewis base (@) CHy—Na, CHCH,~ ucleophile —__electrophile Lewislase Levis ail H rot 1 o™ © CH—C—cH, + H-G— nucleophile w iirdanad elecirophile Levis acid SON a ® CHF: alc, —e Hc—E@ + iicleophile lectrophile Lewis base Lewis acid ‘ me This may also be written in two steps: association of the Cl with Al, and a second step where the C—Cl bond breaks. © @ Ch—CTO electrophile 7 nucleophile Lewis acid Lewisbase — F o) F-B—F »— rec L nucleophile I electrophile Lewis base Lewis acid 8 @N ° ® (@) BF,—CH,—CH, + CH,=CH, —> BF,— CH, —CH, =CH,—CH, electrophile nucleophile Lewis acid Lewis base2-51 Ineach product, the new bond is shown in bold. 1 Lewis yy base— nucleophile o) cHy— cH, Lewis base— Ht nucleophile © cue H+ Lewis base— nucleophile @ CH—CHH + Notice in parts (d) and (e) that the a identical reactants can generate two electrophile separate products. iy © H-c—C=H + Lewis | Lewis u acid — base— electrophile nucleophile 3.2 Use hyphens to separate letters from mumbers. Stmetures might not display their longest chains left to it—you have to search for them. In the name, write substituents in alphabetical order, even though that might be different from the numerical order of position numbers, (2) Sethypentne (Always ind the longest chain: imay nor be writen ina ssight ine) 2-bromo-3-methyipentane (Always find the longest chain.) © 5.ethyl-2-methyl-4-propylheptane ("When there are two longest chains of equal length, use the chain ‘with the greater number of substtuents.") (@) A-isopropyl-2-methyldecane ("Number from the end closest to the first substituent." —also for (c)) 3-4 Separate numbers from mumbers with commas. Separate numbers from letters with hyphens. (a) 2-methylbutane (b) 2.2-dimethylpropane (@) 3-cthyl-2-methylhexane (6) 24-dimethythexane ——(e) F-ethyl-2,2.4:5-tetramethylhexane ({). 4-fert-mutyl-3-methylheptane3-44. In each case, put the largest groups on adjacent carbons in anti positions to make the most stable conformations (a) 3-methylpentane “CHACH, —Nevma projections were ivotucet i ext seein 3-7 They ate used extensively 2 show te tteesdinensinal 3 iweangeient of ats in “~ rane 2 is the front carbon with H, H, and CH Hs C-3 is the back carbon with H. CH. and CH,CHy ‘Catboo-3 is behind carbon? 56 (b) 3.3-dimethythexane GACH, (Cis the back carbon with H, H. and CHJCH oHcH, 3-46 The more stable conformer places the larger group equatorial. © CH(CH,)> © CHLCH, ‘CH(CH3)> H a) CH; : @ i A) H ww TAN, She je HCH CH,CH; => TE HCH: uh ae Hn” gs Et~ ethyl more stable— roe stable— larger group equatorial ‘oth groups equatorial ax © Ga, CCH eg eg 7 LET H CH, CH CH; i CH CH; fn H H axCH; H ‘more stable— ‘mere stable— ‘both groups equatorial larger group equatorial 346 continued gx ax = a CH.CH, CH, CH.CH, oH pa wk w fu cah~ ey CH. = CHSCHs —4 CH.CH; fs H Hi; more stable— more stable— larger group equatorial both groups equatorial3.48 Solutions are given in the boxes, The front and back carbons from the Newman projection are denoted by a dark dot. 56 @ — CHCH; H cl 8 CH CHCH) 21 21 7 © — CCHS); SCH Br H H a ‘CH, H THCH, | +bromo-3-ciloro- #76 2.2,3-trimetbylhexane 3-48 continued @ F 4, H CBr, F F F H 1 A,1-tibromo-3.3.3- twitluoropropane 24 @ — CHCHY; } Br Hi Br H sigh HCH} 1-bromo-L-chloro-1- 597609 $3.4-dibromo-2- GH:CH; — } 1-bromo-1-chloro-1 { fluoro-2-methylbutane methylhexane444 bw initiation =a) GY Be 2 ® H ——~ +~=Hcl + -C LJ propagation ® a " . 4 Say gts ey LI ‘Termination steps are any two radicals combining. 445 (a) a I _— CHy-CH ‘CHCH; “cH roa xx nae Xx 4" cH, cH cH cu, cH i "{ CH3-CHy-C-0 <> : } @ H nH H H H H ZY H H 5 3 Ce} H “HH ony ony o Oy 4H a HWS u ues H H H CH; CH, CH446 (@) Mechanism inition eepr e Bre A, Kes 8 soe roy ey on, second “The 3° allylic His abstracted selectively caster econ ee than any other type in the molecule), fomning whe ala res p an intermediate represented by to nc equivalent resonance forms. Partial radical character on two different carbons of he allylic — Ha Hy The, radical leads to two different products. H Br + Bre Br’ (b) There are two reasons why the H shown is the one that is abstracted by bromine radical: the His 3° and itis allylic, that is, neighboring a double bond. Both of these factors stabilize the radical that is ereated by removing the H atom