Table Of ContentI SO8-N(cid:15)E-(cid:15)hL(cid:14)(cid:14)2-9
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LUOTN SM ANUAL
JaWni llSiiamme k
CalifornPioal ytechSntiactU en iversity
OR CC HEMISTRY
SIXTHE DITION
L.G . WaJdre.,
".�JL.-':'
Prentice
Hall
07458
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AssistEadnitt oCra:r oSlney der
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ManufactBuuryinegrI :l eKnaeh n
CoveIrm agCer ediJto:s eGpahl luc(c2i0o0 4)
200P6e arsEodnu catIinocn.,
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PrenticPee arsEodnu catIinocn.,
Hall
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Allr ighrtess ervNeod p.a rotf t hibso okm ayb er eproduicnea dn yf ormo rb ya nym eansw,i thout
permisisniw orni tfirnogtm h peu blisher.
PearsPorne ntHiaclel i™sa t rademoafrP ke arsEodnu catIinocn.,
Thea uthaonrd p ublisohfte hrib so okh avues etdh ebiers etf foirntp sr epartihnibgso okT.h eseef forts
inclutdhee d evelopmreenste,a racnhd,t estionftg h et heoriaensdp rogratmosd etermitnhee ir
effectivTehneae ustsh.ao nrdp ublismhaekren ow arraonfta yn yk inedx,p resosrie mdp liweidtr,he gatrod
thesper ograomrts h ed ocumentactoinotna iinnte hdi bso okT.h ea uthaonrdp ublisshheanrlo ltb el iable
ina nye venfto irn cideonrtc aoln sequednatmiaaglie nsc onnectwiiotnoh r,a risoiuntogf t,h feu rnishing,
performaonruc seeo, f t hepsre ograms.
Thisw orki sp rotectbeydU niteSdt atecso pyriglhatw sa ndi sp rovidseodl efloyr t eachicnogu rsaensd
assesssitnugd enlte arniDnigs.s eminatoiros na loef a nyp arotf t hiwso rk( includoinnt gh eW orldW ide
Web)w ildle strotyh ei ntegroiftt yh ew orka ndi sn otp ermittTehde.w orka ndm aterifarlosm i ts hould
neverb e made availabelxec epbty instructuosrisn tgh ea ccompanyitnegx ti nt heicrl asseAsl.l
recipieonftt sh iwso rka ree xpectteoda bidbey t hesree strictainodtn osh onort hei ntendpeedd agogical
purposaensd t hen eedosf o theirn strucwthoorr se loyn t hesmea terials.
Printiendt heU niteSdt atoefsA merica
10 9 8 7 6 5
ISBN 0-13-147882-6
PearsEodnu catLitodnL. o,n don
PearsEodnu catAiuosnt raPltiyLa.t dS.y,d ney
PearsEodnu catSiionng apPotreeL.,t d.
PearsEodnu catNioorntA hs iLat dH.o,n Kgo ng
PearsEodnu catCiaonna dIan,c T.o,r onto
PearsEodnu cacdie6M ne xicSo.,Ad .e
PearsEodnu cation-JTaopkayno, c .y.
PearsEodnu catMiaolna ysPitaeL,.t d.
TABLE CONTENTS
OF
Prefa...c..e... ................................................................................................................................v
Symbolasn dA bbreviat.i.o.n.s. .................................v.i.i. .............................................................
Chapt1er IntroducatnidRo env ie..w... ................................................................................. 1
Chapt2e r StructaunrdeP ropertoifOe rsg anMiocl ecul...e..s... ..........................................2 5
Chapt3e r Structure and SteroefAo lckhaenm.e.i..s.s.. t...r...y... ..........................................4 5
Chapt4e r TheS tudoyf C hemicRaela cti.o...n...s.. ............................................................. 59
Chapt5e r Stereochem..i...s...t..r...y... ................................................................................. 79
Chapt6e r AlkyHla lideNsu:c leophSiulbisct ituatnidEo lni minat...i...o..n... ..................... 99
Chapt7e r Structure and oSfAy lnktehne.es...si...s .. .........................................................1 35
Chapt8e r ReactioofnAs l ken.e..s... ................................................................................. 159
Chapt9e r Alkyne...s.. ...................................................................................................... 191
Chapt1e0r StructaunrdeS yntheosfiA sl coho...l...s.. .........................................................2 11
Chapt1e1r ReactioofnA sl coho...l..s... .............................................................................. 229
Chapt1e2r InfraSrpede ctrosacnodpM ya ssS pectrom..e..t...r..y... ..................................... 259
Chapt1e3r NucleMaarg netRiecs onanScpee ctros.c...o..p...y... ......................................... 271
Chapt1e4r EtherEsp,o xidaensd,S ulfi.d...e...s.. ................................................................ 299
Chapt1er5 Conjugated SyOsrtbeimtSsay,lm metrayn,dU ltraviSopleectt ros.c...o...p..y... 317
Chapt1e6r AromatCiocm poun.d..s... ................................................................................3 41
Chapt1e7r Reactions of CAormopmoautni.dc..s. .. ............................................................ 365
Chapt1e8r Ketonaensd A ldehyd..e...s.. ............................................................................4 01
Chapt1e9r Amine.s... ......................................................................................................4.. 39
Chapt2e0r Carboxylic ...A...c...i..d...s.. .............................................................................4 69
Chapt2e1r CarboxyAlciicdD erivat..i..v...e...s.. ................................................................4 99
Chapt2e2r CondensatainodnA sl phSau bstituotfiC oanrsb onCyolm pound..s... ............... 537
Chapt2e3r CarbohydraantdeN su cleAicci d..s.. ................................................................ 585
Chapt2e4r AminoA cidsP,e ptidaensdP, r ote.i..n...s... ...................................................... 617
Chapt2e5r Lipi.d..s... ........................................................................................................ 645
Chapt2e6r SynthePtoilcy me.r...s... ...................................................................................6 59
Appendix Summaroyf I UPACN omencla.t..u...r...e.. .......................................................6 75
I:
Append2i:x Summaroyf A cidiatnyd B asic.i..t....y.. ........................................................... 689
iii
PREFACE
HintfsoP ra ssing OCrhgeamniisct ry
Do youw antt op asyso urc oursieno rgancihce mistrHye?r ei sm y besatd vicbea,s eodn o ver
thiryteya rosfo bservisntgu denltesa rnionrgg ancihce mistry:
Hin#t1 : Its eemsst raigrhwatfrodb,u th uman,si ncludsitnugd esn,tt rtyo t ake
thee aswy ay ouDtuo nt thitpelhr eodyib slceomvtseh.re riesn os hort-cUuntl.e syso uh avea measurIeQda bov2e 00
andc omfortacbrluyi isnet het op1 ofy ourc lasdso,t hpero blemUss.u alyloyu tre ach(eprr ofesosr or
%
teachiansgs istwainltrl)e commencde rtaoinne st;r yt od oa llth osree commendeIdfy. o ud oh aloff
themy,o uw illb eh alf-prepaattr eestdti me(.D o youw anty ours urgecoonm intgo y oura ppendectomy
havinpgr actiocneldhy al/thper ocedurAen?d)w heny oud ot hep roblemkse,e pt hiSso lutiMoannsu al
CLOSED.A void looaktim nyg a nswer beyfoouwr rei tyoe uran swery-our traynidns gt rugglwiintgh
thep robleimst hem ostv aluabplaero tf t hep robleDmi.s coveirsay m ajopra rotf l earniRnegm.e mber
thatth ep rimagroya olf d ointgh ese proibsln eomjtsu sgte ttitnhger ighatn swebru,tu nderstantdhien g
materiwaell l enotuogg ehtr ighatn swetrost heq uestiyoonush aven't yseete.n
Hin#t2 : Keeupp . Gettibnegh inidny ouwr orki na c oursteh amto vesa sq uickalsyt his iosn e
theK isosf D eathF.o rm osts tudenotrsg,a ncihce misitsrt yh em ostr igorous intcehlallelcettnuhgaeely
havef acesdo f ari nt heisrt ud.i eSsomea ret akebny s urpraitst eh ed iligeintrc eeq uirDeosn.' tth ink
thayto uc ans tudayl olf t hem ateritahlec ouploefd aybs eforteh ee xam- welly,o uc anb,u ty ouw on't
passS.t udoyr gancihce mistlriyka e f oreilgann guagter:yt od os ome evdearyys ot hatth ef reshly
trainneedu rosntsa syh arp.
Hin#t3 :G eth wheyno u Usey ourt eacheorf'fsi hcoeu rwsh eny ouh aved ifficulty.
elp neeidt .
Manys chools have tuto(riiwnnh gi ccoher ngtaenrcishc e misitsra y p opuloafrf erinHge)r.e 'as s ecret:
absoluttehleby e swta yt oc ementth imsa teriianyl o urb raiinst og ett ogethweirta hf ewo fy oufre llow
studenatnsdm akeu p problefmosr e acho thetrh,e nc orreacntd d iscutshse m.W heny ouw ritteh e
probleymosu,w ilgla ignr eaitn sigihnttw oh att hiissa lalb out.
Purpoosfte h iSso lutiMoannsu al
Sow hati st hep oinotf t hiSso lutiMoannsu alF?i rsItc ,a n'dto y ours tudyifnogr yoSue.c ond,
sincIea m notl eanionvge yro urs houldaesyr o uw rityeo uar nswerIsc ,a n'gti vyeo ud irefcete dbaocnk
whaty ouw ritaen dt hink-tphrei nt mediislu imm itiendi tuss efulneWshsa.t I cand of ory oui s:
provicdoer rect antshwepe urbsl;i shPerrosf,e sWsaodre ,P rofesKsaonrt orow(smkyir eviewearn)d,
I)
Ih aveg onet og realte ngtthosa ssutrhea wth atIh avew rittiescn o rrefcotrw, e aluln dersthaonwdi tc an
shakae s tudencto'nsf idetnocd ei scovtehrat th ea nswebroo kf lubbuepd; 2 )pr oviad ceo nsiderable
degreoef r igobre;y ontdh ef undamental reqoufic roermreenctt nIe hsasv,et rietdof lesohu tt hese
answerbse,i ncgo mplebtuets uccin3ct)p;r oviidnes igihntth oo wt os olvae p robleamn di ntwoh eret he
sticiknyt ellepcotiunaatlrs e .I nsigihstt h et oughetsoat c complibsuhto, v etrh ey earIsh ,a vec omet o
understwahnedr set udenhtasv et roubsloeI ,h avet rietdoa nticipyaoutreq uestiaonndst oa dde nough
detasiolt hatth e concaeswp etl,al s t hea nsweirsc, l ear.
Iti sd ifficfuolrst t udenttous n derstoarna dc knowletdhgaett h eir teaacrhehe urmsa n( somaer e
moreh umant hano thersS)i.n cIe a m human( despwihtaet m y studenmtisg hrte porIt c)a,n a ndd o
makem istakeIsft. h eraer em istakienst hibso okt,h eayr em y solree sponsibainldiI ta ym, s orryI.f
youf inodn eP,L EASEl emte knows ot haittc anb ec orrecitnef du tuprrei ntinNgispi. ti nt heb ud.
What'Nse wi nt hiesd ition?
Bettaenrs wersP!a rotf m y goailn t hiesd itihoansb eent oa ddm oree xplanatmoartye rial to
clarihfoyw t oa rriavtet hea nswerT.h ep ossibiolfim toyr et hano nea nswetro a problehma sb een
noted.Th e IUPANCo menclatauprpee ndhiaxs b eene xpandetdo i nclubdiec yclihcest,e roatom
replacemeanntdts h,eC ahn-Indg-oPlrelsoygs teomfs tereochedmeisciagln ation.
Bettgerra phicTsh!e p rinmte diumi sv eryl imitiendi tasb ilittocy o nvetyh ree-dimensional
structiu�froarlm atiao pnr,obletmh ahta sp laguoerdg ancihce misftosro vera centurIy h.a vea dded
.
someg raphicCrSe atedth es oftwaCrhee,m 3D®t,o t rtyo s howa tomisn s pacweh erteh aitn formation
1I1
isa keyp arotf t hes olutioInn.d rawinNgM R spectrreap,r esentaltiinodenr aalw inhgasv er eplaced
rudimentaatrtye mpattds r awinpega kfsr omp revioeudsi tions.
Bettjeork esT?o om ucht oh opef or.
v
SomeW eb Stuff
Prenticem-aHianltla ai wnseb sitdee dicattoet dh eW adet extt:r wyw w.prenhall.com/wade.
Twoe ssentwieba sli tperso vidsipnegc tarrael istoendt heb ottoomfp .2 70.
Acknowledgments
No projeocftt h issc opiese vedro nea loneT.h esaer et eame fforatnsdt, h eraer es everpaelo ple
who havea ssisatnedd faciliinot naetf eads hioorna nothwehro desermvye t hanks.
ProfessLo.Gr . Wade,J r.y,o urt extbook aiusta h roerm,a rkabpleer sonH.e hasg onet o
extraordilneanrgytt hosm ake ttheex tboaoskc leaorr,g aniziendf,o rmatainvdie n sighatsfp uols sible.
Heh ass oliciatnedfd o llowmeyd s uggestioonhn isst exatn,d h isc ommentosn m y solutihoanvseb een
perceptainvdev aluablWee. agreeeda rloyn thaotu rp rimargyo ali st oh elpt hes tudenltesa ran
fascinaatnidnc gh allengsiunbgj eacntd,a lolf o ure fforhtasv eb eend irectteodw artdh agto alI.h ave
apprecioautrec do llaboration.
My newc olleagDure.E, r iKca ntorowshkaisr, e vieedwt hee ntimraen uscrfioprat c curaacnyd
styleH.i sd iligenactet,e nttiood ne taainld c hemicwails domh avem adet hias b ettmearn ualE.r ic
stanodnst hes houldoefrp sr evioruesv iewwerhos s coureeadr lieedri tifoonrse rrorJse:s siGcial man,
Dr.K ristMeeni senheiamnedrD ,r .D anM atterMnr.. R ichaKridn gh aso fferneudm eroussu ggestions
onh owt oc larimfuyr kye xplanatiIoa nms g.r atetfout lh ema ll.
Thep eoplaet P rentice-hHaavleml a det hipsr ojepcots siblGeo.o db ooksw ouldn ote xist
without dtehdeiicra tpiroonf,e ssionaanldie sxmp,e rienAcmeo.n gt hem anyp eoplweh o contributed
are:L eeE nglandwehro, c onnectmeed w itthh ipsr ojeNcitc;o lFeo 1chetti, AdvancedE diCthoerm;i stry
andK ristKeani saenr dC arolSen ydePrr,o jeMcatn agers.
Thee ntimraen uscrwiapstp roducuesdi nCgh emDrawth®e,r e markabsolfet wafroerd rawing
chemicsatlr uctduerveesl opbeydC ambridgeCSoorfptC. a,m bridge, We,t heu serosfs ophisticated
MA.
softwalriek Ceh emDrawa,r et heb eneficioafrt iheeis n telligaenndcc ree atiovfit thye p eoplient he
computienrd ustWrey .a ref ortuntahtaett h eayr es os mart.
Finallya,p precimayt fer ienwdhso s upportmeed t hroughtohuitps r ojemcots,t n otabmlyy
I
good froifea nldm ost forty yeLaarnsg,.T heJs utduyd enatrset oon umeroutsol isbtu,ti ti sf ort hem
thaatl tlh ihsa ppens.
JanW illiaSmi mek
DepartmoefnC th emistarnydB iochemistry
CalP olSyt atUen iversity
SanL uiOsb ispCoA, 93407
Emailj:s [email protected]
DEDICATION
Tom y inspiratcihoenmails try teachers:
JoeP laskwahos m,a det heb atter;
KutrK afmuan,w ho baketdh ec ake;
CarDlj era,ws hso iputo nt hei cing;
andt om y parents:
Ervina ndI milBd.Sa i emk,
J.
whoh adt heo rigicnoanlc ept.
vi
SYMBOLSA NDA BBREIVAT IONS
Bleoiawsl iossfyt m abnaodbl bsr uesveitdahSt iuoiistlno Mi naoslnnc ,usosa inwsitttehhunos tsie end
thteex btWyba o.d(o eDnkooe tx apoletflch ttem osa seke etny oson euo. Y w owulil letarnh em
throyuosguthrouoo fdur ytgc ahneimci stry.)
BONDS
as ibnognlde
ad oubbolned
at rbiopnlde
ab ointndh d riemee cnosmoiiuoonttfnghp s ea,t p oewtrahr reed a der
-
ab ointndh d rmieeieno, gsn osbienhtgihp neaad pw efarryt o hrmee ader
111111111111
as trbeot,inc tndhhp eerd oo cffeo srmiosnbre gr a king
ARROWS
ianr easchtdoiiworsnfe ,rcr otemia tocpontr aondtusc ts
-
sigenqiufii(ltenti sboobc e ro inwufimurt sehes do nance)
sigrneisfo(inntebaooscent o c newf iuetsqheu di librium)
.. ..
shdoiwrsoe efcl temicvootenrm: o enn t
thaer rowwiohtnbeheaa s rdhb mo owmvsnee otof ne el ectron;
the awritrtwbohoaw s rhhbemosaow dvs e oamfp e aonieftcrl t erons
shpoowlsoa afbr oionmtrdoy l teahceru rlosewi,hg entaihmdfeon y reiegn eagnot tdfih vee
dilpeo
SUBSTTUIEGNORTUP S
Me am etghryoClu3H p ,
Et aent hyCl2HC 3Hg roup,
Pr ap rgorppoay,tu l h craergebr (ootnupw poo sa srirmbaelnnegt es)
Bu ab ugtryaolf u ocpua,rrg br(oofnupo pou sarsrr iabnlgee ments)
R thgee naebrbarfleao vanril agktry(iolaouo nrpnsy u bstintouutnse dcnertru tgirnoyu)p
Ph ap hegnryolu po,afb ethnrezia enassnng uae bm esr teipttreuedes:ne tn,
or
< » 0-
Ar thgeerl nna eafmoear r oagmnra otuipc
coinnotunnee pdxa tg e
vii
SymabnAodbl bsr ecvoinattiinounesd,
SUSBTITGUOREUNPcTSo ,n tinued
oI I
Ac aanc gertoyCulHp -3:C-
Cy a cygcrloouhpe:x yl
0-
o
Ts toospry- lt,ol lfugoernnoyCeulH�sp 3 u: S-
"==1-
oII
o
II
Bco at -brubtgoornx(oyyauclmapa i caninpodde pcthiedme(i Cs)Ht-33r0Cy C)--:
orac arbo(bbeennzzoyxglyro(o xauymapcic aanirnpdobde o pcnthyieldm)ei st0r y):
Cbz
Z,
< C2H-)-0-g-
REGAENATNSSD O LVENTS
DCCd icxycycallrobhoediimNi=Cd=eN
o- -Q
DMSdOi methylsoI Iu lfoxide
S
....... '
H3CC H3
ehterde itehtyChlHCe 3Hr,22C 0HC3H
Cl
0
MCBPAm eta-chlaocr;odp erg-o x0yO -hHe nzo;c
<
>
metvhikynelyt lo no e
g
MVK
H3C�
.......
NSB -bronmiomOsiudcec iO
�N
N
I
Br
coinnotune pdna egxet
viii
SymabnAodbl bsr ecvtoiinantuieodn s,
REEANGATNSS DLO VESNc,Toi nntued
PCC pyricdhilnoiruoCmcr3 ·h0H rCoNIm ate,
� ')
•
C3HH H C3HH
I I I I I
Sai2BdHi siamyHl-Cb-oCr-anBe- C-C-H
I I I I
C3HC 3H C3HC 3H
THF tetrahydrofuran
o
SEPCTCRPOOYS
IR infsrpaserccetodrp oy
NMR nucmlaeegtranioercns asnptcereco scopy
MS masspse cyt rometr
UV ultrscaprvtesooicpoyl et
ppm papremtris l aul niueiosidtnNn ,M R
Hz hecryetpcszesl ,cre o ,nu tdnao fi fer quency
MHz megamhielorlcftiye zopcs,nesl sre cond
TMS tetranme(e,C3)4tS H,hti yhrleeesf nciecolrema piNonMu Rn d
sd,t,q , s indgolutebrltltieq,e,pu t ar,rte enfttgeo, r rithopefe aanNnukM msaRb b esrog ripvteiso n
nm noamnetmeerts(e,ur suussaa easlud lno ywif at v elength)
10-9
mJz mass-rtaoitm-niac soshp,tsae r rcogmee try
iNnMR c,eh mischviaaflmlt eu aeis,pnu p rme d
8 wavelength
A ferqcuye n
v
OTHER
ax(iciahnlfa oiormrcfs y clohexane)
a,
ax euqat(ocirihnfaa olior rcfm y sc lohexane)
e,e q
higohcpecimsuelotcdel u oarrb ital
HOMO
louwnespoticm ecodul oercbuiltaarl
LUMO
nroe action
NR
(poosanian tr ioormniasnt gi)c
m,p arthmae,t paa,r a
0, whweritnteo nvae nr a"rhrewoahwwter:"ni b; t etafle oenrt" etc ehiran:n" g e
paprtoisacilht apirtavlginre eae ,gc ahtairvgee
eenrfgreyol tmer gconimrecaat d(ilaitgihotn)
spercoitafattithD clie ioo snnfoe d (8i5n9um m)
ix
