organic-chemistry有机化学-第五版-LGWade-JR-答案

1-1NaMgAISiCHAPTERI-INTRODUCTIONANDREVIEW1s22s22p63s11s22s22p63s2Is22s22p63s23px11s22s22p63s23px13pyIPSCIAr1s22s22p63s23px13py13pz11s22s22p63s23px23py13pz11s22s22p63s23px23py23pz11s22s22p63s23px23py23pz21-2Inthisbook,linesbetweenatomsymbolsrepresentcovalentbondsbetweenthoseatoms.Nonbondingelectronsareindicatedwithdots.HHH••+III(a)H-N-HI(b)H-O-H(c)H-O-H(d)H-C-C-C-HHHHII(e)H-C-C-N-HIIIHHHHIH:0:HIII(h)H-C-C-C-H1-3IIIHHHHHI••I(f)H-C-O-C-HI••IHHIIIIHHHHHHII(g)H-C-C-F:IIHH(i)H-B-HI(j):F-B-F:--IH:F:..Thecompoundsin(i)and(j)areunusualinthatborondoesnothaveanoctetofelectrons-normalforboronbecauseithasonlythreevalenceelectrons.(a):NN:(b)H-CN:(c)H-O-N=O(d)O==C=O(e)H-C=N-HIHH:0:II(f)H-C-O-H(g)H-C==C-CI:II••HH(h)H-N=N-HHI(i)IH-C==C-C-H(j)H-C==C==C-H(k)H-CC-C-H1-4IIIHHH(a)G}J-NQ)8(e)H-C=N-HIH(b)(f)H-CNeDC)J(DIIHH(c)88(.:)H-O-N=O0)0)•II·8O-HH-C-88(g)H-C==C-CleDII8HHTherearenounsharedelectronpairsinparts(i),(j),and(k).1(d)IH0)0)o==c=o0)0)88(h)H-N=N-H1-5Thesymbols8+and8-indicatebondpolaritybyshowingpartialcharge.(Inthearrowsymbolism,thearrowshouldpointtothepartialnegativecharge.)������(a)C-C1(b)C-O(c)C-N1-6(a)8+8-8-8+(g)N-O(h)N-SNon-zeroformalchargesareshownbesidetheatoms.HH11+..-H-C-O-H(b)H-N-H:C1:11+1HHH8-8+(i)N-BH1HH1+1(c)H-C-N-C-H111HHH..-:Cl:In(b)and(c),thechlorineispresentaschlorideion.Thereisnocovalentbondbetweenchlorineandotheratomsintheformula.H-••I+H1-(d)Na+:O-C-H(e)H-C-H(f)H-C-H1(g)Na+H-B-H(h)Na+IHH1-H-B-C-N:IHHHH,1/CH-••1/·O-C-C-H•••I'CH/1'HHH1HHH,/H(i)H-C-O-C-H/1+'H••_••H(I):F-B-F:1:F:..H-C=O-H1+HU)IHH1+H-O-N-HIHAsshownin(d),(g),(h),and(k),alkalimetalslikesodiumandpotassiumformonlyionicbonds,nevercovalentbonds.1-7Resonanceformsinwhichallatomshavefulloctetsarethemostsignificantcontributors.Inresonanceforms,ALLATOMSKEEPTHEIRPOSITIONS-ONLYELECTRONSARESHOWNINDIFFERENTPOSITIONS.:0:(a):O-C-O:....:0:..-(b):O-N-O:....+..-:0:-..1:O-C=O..-:0:-..1:O-N=O+.....2..-:0:1••-O=C-O::0:I••-O=N-O:+1-7continued..-(c):O-N=O....O=N-O:++(d)H-C=C-C-H....H-C-C=C-HIIIIIIHHHHHH(e)H-C=C-C-H....H-C-C=C-HIIIIIIHHHHHH(f)Sulfurcanhaveupto12electronsarounditbecauseithasdorbitalsaccessible.(g):0:II:O-S-O:II:0:HIH-C-HIH:0:IIH-C-C+I\H:0:IH-C-HIH....-:0:I....:O-S=O....II:0:HI:0:-••II:O-S=OI:0:HIH-C-HI+0:1/H-C-C..I\H:0:IH-C-HIH....-:0:IO==S-O:....II:0:..-:0:I....O==S==OI:0:HIH-C-HIH:0:II..H-C-CI\\H+0:IH-C-HIH/:0:II••-O=S-O:I:0:..1-8Majorresonancecontributorswouldhavethelowestenergy.Themostimportantfactorsare:maximizefulloctets;maximizebonds;putnegativechargeonelectronegativeatoms;minimizechargeseparation.••-+..-++(a)H-C-N=O....H-C-N-O:....H-C=N-O:(negativechargeonIIIIIIIelectronegativeH:0:H:0:H:0:atoms)mInorminormajor31-8continuedHHH(b)(c)(d)(e)\+C=C-N=O/11HH:0:•..\+C=C-N-O:...­/111HH:0:\++C-C=N-O:/11HH:0:majormajorminorThesetwoformshaveequivalentenergyandaremajorbecausetheyhavefulloctets,morebonds,andlesschargeseparationthantheminorcontributor.+H-C=O-H..•H-C-O-H1+1HHmajormmor(octets,morebonds)++H-C=N=N:...-H-C-NN:11HHmajor(negativechargeminoronelectronegativeatom)H-C-CN:..•H-C=C=N:11HHminormajor(negativechargeonelectronegativeatom)++(f)H-N-C-C=C-N-H•H-N=C-C=C-N-H(g)1111111111HHHHHHHHHHmmormajortthesetwoformsaremajorcontributorsbecauseallatomshavefulloctets+••+H-N-C=C-C-N-H..•H-N-C=C-C=N-H1111111111HHHHHHHHHHmmormajor..-:0::0::0::0::0::0:II••II1IIII1H-C-C-C-H-----H-C=C-C-H-----H-C-C=C-H1-11HHHmITIormajormajorthesetwohaveequivalentenergyandaremajorbecausethenegativechargeisonthemoreelectronegativeoxygenatom41-8continued(h):0:IIH-C-N-HImajorH(nochargeseparation)..-:0:I+......II----I..�H-C=N-HIminorH1-9YourLewisstructuresmayappeardifferentfromthese.Aslongastheatomsareconnectedinthesameorderandbythesametypeofbond,theyareequivalentstructures.Fornow,theexactplacementoftheatomsonthepageisnotsignificant.ALewisstructureiscompletewithunsharedelectronpairsshown.(a)(c)HHHHHHHHHIIIIIIIIIH-C-C-C-C-C-C-H(b)H-C-C-C-Cl:IIIIIIIIIHHHHCHHCH/1'HHH/1'HHHHH:0:HHH:0:IIII/IIIIH-C-C-C-C=C(d)H-C-C-C-HIII\IIHHHHHHAlwaysbealertfortheimplieddoubleortriplebond.RememberthatChastohavefourbonds,nitrogenhasthreebonds,oxygenhastwobonds,andhydrogenhasonebond.Theonlyexceptionstothesevalencerulesarestructureswithformalcharges.H:0:III(e)H-C-C-CN:HHH,1/HC:0:,IIIIH(f)H-C-C-C-O-HHH:0:HHIIIIII/IHC(g)H-C-C-C-C-C-H/1'HHH1-10(a)IIIIHHHHCompleteLewisstructuresshowallatoms,bonds,andunsharedelectronpairs.HH(b)HHH(c)HHIH,//,I1/HCC-HH-CC-H,/,/,/H-CC-HHHC,IIHI1/C-HH-C�••�C-H_I'/'N',-C-CHHIHHI\HH......CC......H/,••,.......,H0H5HHIIC-CII\\C,../C/N'HHIH1-10continued(g)H:0:HIIIIH/C:--..,/,C-C-H'ccIIIIH/C,'iC,HCHIH·0·()HH··eH,,/II(f)HH/C,/C,H-CCHIIIH-C,........C,/CHH/-HH(h)H:0:HHHH,,/••/C....,...-0H-C'C/··IIH-C,/.C,/C/'HHIHIIIIIIH-C-C-C-C-C-HIIIIHHHH1-11Thereisoftenmorethanonecorrectwaytowritecondensedstructuralformulas.Youmustoftenmakeinferencesaboutwhatacondensedformulameansaccordingtovalencerules,especiallyinstructureswithC=Oasshowninparts(a)and(d).(a)CH3COCH2CH2CH3(the0hasadoublebondtothecarbonprecedingit)(d)CH3CH2CH(CH3)CH2CHO(the0hasadoublebondtothecarbonprecedingit)(b)(CH3hCHCH2CH20HorCH3CH(CH3)CH2C