INURPRETAfION OE'MASS SREC:YRA ,. 0 U
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INURPRETAfION OE'MASS SREC:YRA ,. 0 U
'T H
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1-1, ~ conIr iblJtiOM; 1M u rbtJn . M1 nw~ It _ _ • '" 1M A .. •00 /. " . ~"rr_o n lor Isotopic COn!' _ ' ,., ;/A If!«> ibl ~ ;Ii N :
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m • "• • " ".1;, aU-a_ "S mo" , pcetJ"''''lr ) CTili",,] to 10;' bocl. He loa' made ~..p«iall)' imlX'l tJn[ "" ntribulion, 10 Ibe med ...' '' .t",,, tbe'" " "-",h. nlSrr,, ~re apphc:ml~ to the unim,>k· ~lL l~ r di....x:iolll O'" or i o,, ~ r d by an y i"n;zaj ,on method , ; "" l uJi n~ t h~ ~'; li n~ v....., y .~ new m,: lhod, for ot>I. ' ning nla"" 'lJ"'Clra of 1. ' ll" Jnclee the Ul1 k ~ "",,,, b::fore u.." f d Ol 'or u, Pm,,,,,,, In til. 1"'0 ed ill(>l>' 1>... had qu" la.;" .... from the rM1JIUS 11)01'" ' pcc\m m.lf" l "1. 0 T,. -T Ll n ~ As .u g gc , ( e ~ Do. Roy W . K i,, ~ a r>d Kain Sa K...~,l. W,lhJll1 Sha k""l"""'" MI, ,, 'J. io n, in Chapl' l ~ " 'ilh hi. "'0'''' in O"iul"'m" "(;"1 yu ho me ,
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Contents
Pr.t."" to ltle F_
1h Edilion
. du>owl ~ .
I j~
Gl olI...Yend Abb.eyi . Uonl
1
f
Intr04\lctlo n
Ii 'v
1
1.~
"'P P""OU1oC
\.1i ""
' .S 1-9
St. M a,d Inl. 'prel ' ''Cln P'OO@d Uf' ~ e 'A " "' _ 15
1.1 I .~
I' 14
""lyOi' ' Z : 01. ' $ trun.,. Infoo.... oon
:l I Elem.nlal Co m position 2.1
2,2
2.4
2.5
13
11
Sta b- . l.o!cI>e. Clus,fi" ICl n "'coo,aing tCl Na'", ,1 " O
120
C" l c " la ~ ..... ol ~ I E I
FunOIl"" . US The rmo
2!>ll
Th'D1e . "" "'W'de '
~ _IO
265 Am,,,,,,, 210 An",l.. .74 Nit,; I. a nd Nitro Compoo"".
9"
.'I' ivh aticH.lim_ " ioo . of M o lecu l. r Ta ble A. 1 Table A..2
CIllo"""',
Ie ,," ~del
361
35!i
" 8.4 8.S
RUeI,on I_ Ii"" .o' Rad iCa l ", Chio r!1"5O'e. Re llCl''''' C '~ t i c.\ i "". 185
86
8'llmt-Bo 'l
aI Cyclic S"uo;t~r .. liyd rOOl'" R"'''...gements 111 1 Othe r R.....' . _ _ m. 213 GeM ' .. ' PeI...... ..",.. ~ 1
113
\ 7~
9 / M. .s Spectr a 01 C om m on Compound Cle nes g, ~2
9.3 9.4
9.5 9.6 9.7 ~8 ';1'1
Hy:; "\Q~l ""Olll1g Ihe od d tl K ffQn(but "' ,. th~ lx>nd!o the lalle, a to m,.
ama . II
Atom ic m,,, unJl, dolto n
AF
IIppear allOO energy; formerly oppearo,>«: poo l. m ial. M un"i «:>lopic clome" t (h yMo~.n il , 1>0 oonl Je pea k
Peak rep,,;;eot jng Ihe mo st .bund811t jon jn lhe . pec!r llm
n
M agnelic r..ld str ength: magneti c analy<er
e ll
Colli'io nal activa tio n. colli, iol1 . 1excit. tio n
CAD
Colli, io na lly aCliva,,,,1di",,,i,, li" n; .1.0 , cU g~ n cT a l j o n of wn' lrum ~ ..~ ",dc n", d pha ' r " u nplc. K~J C l i oll
in .. hid . cycl u..IJM 10 fo rm a "",",' ho.. ":r a , alod rad ical " 00
~h. ,1lC
..1...
R n ion in ,,·hich cyd Jzation 10 r"m, J ,, ~ ..' bond be1 n lwo I'~r\ . "r ." io" re" dll in ll>." k" . of lhe ~,l u al
g rQllp CCDnc.;linl.l ' he."., l>arlS ,
eIllical " "'J~)' tOf . he ,,,,,..I i,,,, M +- --> 0 ' ,~ I" , ..-li.auOfl en. Jn . 1': ,
c~ ll c d f~. ( M -
_ O' )
I"ft ill1e.-nal . ... r~y rC4 ui, cU '" thJ t hJ lf of M " ~ .n . ..,ill ,10"'''11' '''''' 10 ~'i cld f)' h,.;,,~ leaYJII~ , "" ion SOUle
ardn.. nT.
rrvs
F"uri."T- lJ~ " l!o,m
OCi MS
,\
" l h, id M S/MS
' l1Io t LL tilizinj( two l~'"" , ,,j" n"'" ' p"ctronw"''" , , ,,cll '" J "" ble-focu "", "Td <j";"h,,po l. instrument.
l e ll
Ion . yd<m"n InOD"n,,,.
II'
I "" i' J tlon e"".~y, rormerly i"ni zal ion ['OIen ' ;. l
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~rr.n ill-
",,'e,-,hell oloel"'''' l'~ r" Ur "" ,ra\;
Fi "l ~
..n i,,,,j,,atio n, citJ!ln ,n "'l"'n ie>
epara led by the next ana lyzer, m ~"
Non ho ml; n~ ct""(rn
n
t
a
1 I '• ..."...110.
No", Ir)' another ,imple 'pectrum, Unknown 1.2. Your stnletUfe wiD be correel jf the molecule and it, picce, have rna,,", co"nl'onding '" th"," of Ihe ,pectrum. (\1" ke a ,eri"us attempt to ,oh-e each llllknown before looking al lhe ,,,luLion. rhi, is a vilal pan of the book-, in,lruciion.) Unknown 1.2 100-
t.
Unknown U contain< ~aTf> lhal run Ix: ;mportanl ("lnL" is Lhe peak inlen,;ty rdali"e [() the most intense peak as 100). The mass speell'ome!., has a dynamic range mud, greater lhan the lloree ordeT< "I magnilude ,h",m; lhal i" ion ahundances
' .1 _ ,.... 0< ......
_
a
or « O, I~~ can l-.. mca'un.'I! "'rrodlleil>l.y, Fo. th.: m.... ' pectr al data "f (l>c unknov..m in ,hi, a re pr oclu ~jb i' i l.l' "r ± l~~ ffl Qliw or 1-0.2 ~ b ",l u l.e, whik,
""Ono ... , ,1
miL
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, "" ' "00 o •" " dis played in the m a" ' rcd uocJ. into l he i.... IUmCnl. Suc h a 'peo· (rum is rJ>.. n _ I )nLoo wu 1.4, Can )'nll .denlil)- any of l he co mpo n, nt, '
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O ne "I the compo nent, in il, p ure , la lC Can you iden tify it'
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' be 'p"c lrum ofl nknown 1.5
Un' " ". ,.• ml
ro u. ion >; !~ c.1n no'" be t,,,mcd by • wi,lc ""-Tictj' of met hod•. ~nd CJD be m "",,anal y",d ~n J dc'''''ted "' ilb ~ ...-id< ,'ar~t y of i"'!lllmolltat;on. Of nc, >:." . ily t ni' boot ~i,'C< a limned d",cu . , ;un \ hc""" m mplete det ail' a", .v~ila bl . in tho ~,.,.I1 lu oon ••n lh~ ....mple int~ mea..... bk pr OO lloik d "IT'" in in ;"c~ nde=nl IiIiIm cn i. a nd ' T. .. I t h rou gh the io n c haml\c r tQ an a" ode ("elecllo n \l4 P"')rm ' OC ""pooile ,"doe. The ,IITam 0 p;lMJd t-btarn tt - ~M G I (- ~
~I
imoi:tllitHl. By incr~~loi nl' 1M p, ~"' ur~ in , be iDnizauOJl cLim b.. 10 - lOll I'"~ (0.15 lm . l. ""'" ""n enOft, y ",l d i o ~ Sl a bl ~ prOOIl0 molecular ",. lj!hl. btcau.. tMy a~ oft.n pr=nl in 1bo CI ' pecI,a or rompou nds " hl<cuLo.r 'fI«."'"
.""'pes.
"""CC'
W
I,,,,,,,
i"".,
I .J lilian _
lysis of Ions
I he ion bea m fw m l he .... UTCC lY"-"T. all" ,,';" g a ..ti .a' ttt rali" ,mil) I" be focu soJ on the . naly.." ""it . Iit. 11Ie mag nctio: f>eld lOt:l . ~ . tho: ro.", analy'..,r. "Tbe "'il nIne in Tho m",ns nf Ihe wns which rn n pa" th (o ,, ~h the n ;t . Iil depend. QA I h ~ , ad ,,,, (r . ......l ' Mtoc i" n "",Ih in tlte n..gne tic lield. (be field stre llf.(h ( U, ~atl .. ~ and the in" · acceJenling 1" >lenliJl.I I l-'; "li t,) a . de fined b~ the fa nd " mcm ,,1 ""'n "" .... (Beynon
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.....' a u . S.ingk- I"" , ,, n' ~ _ fi\1lgnotL'·'<eto , m. .. 'I"'C', om cld. wilh 0l'l""ile p"l ~ril ie . un the p.i" of oppo, i" & rod " Palh osciJIaliJ" cau.. proportional to the 'on abundance. and thi, curren! "an hc itltro;l...-td thWUf.h a fC•• ~1" l1her ",,,,,,rm in! do' -,en. , uch ~. rho high_pcrlon naocc- li,,"i ~ chcomal0gca pr. ( 1.t:("1:S~ hd>O aho be. n 'k_ 't!,h;ut..-p"'l lho raid u.J "P"'·1Jam. NO\ w ,,0k i. 10 ' how hew mol •• ule, ~ a r, be , tructUI;,J!y characleri , cu from Ihc ,n.,,,,,, of their i"" iU
.'.1u- c ke ~ ", n" (ll(!) ion. NIe ;n F
Ihe
"'...edur.
.01 - 1" c"f11y 'lu" lion' · th, mo>,1 e/fl'; 'cnl "I'1"l"" h u.u.illy 11 to> rUIl bc:twoen maj or "'leg",i" e,g.. - Is ' '''' person male', Mo l<cu"'r .. ruct ~re cJw; id"li" n i, , imllar : - !>lind al"ys~ ClIo b,,,l ble
an
Otlor, _ ph "" "'lfHttiNo. II '. import.lnl III i"corp " alt aD :>ll>k , In"l ural informalion l.e"" m;'a!, ' pc"I,al, 'ampl" hi>!ory) in!" 11K> i nt~ rp r el a . Ii,,,, ..here,e, ~ ppropti ~te When " ...~m pk i• • ubmitled b~ anot "" r rese"cn ..orker e" tht 1lU/»"" per an "'., ,,,,, ,t i' ",,,,d llOuld he ",bTIJ..1.cJ from ' l>c ""n' pk i.Olo pie abun "a n,~ are a",;",al.l:l)' l'fedietabk: (Ch " rlet 2~
))0""
M~lrif'IJ ..I' Mrt eJ .... . MOlt in " .1\IlSS $pectr urn I J>rear, c<m" :,, ienllJ , . 1 inl egra l rn"'" num hi>n (fo r rMc exact rna .. dill'e..""""'" , ee ""eli" ,, f> J). H_ eye.,., mult;pl) char,w io n' call arrear at f. ~< [i o " al rna" ,, ; 1m t '4.,mpk, in Vn. "","" l.3 Ih, n: i, a pe. k at Itt! ' 1 ~5 01 o,r~ i ~l.l: n ";[ )'. rcp,ncntOn! tr.. do ubly d "n gc,1 i""" of rna" 31 (1jOC Cha pler 61.
..-N,,,,,,,,.
1,8 G_ r..1
Wil h IHttIlz in~ " i, io n, Sir J J. Tloom" ,n , 19 13) wr Ole: 'T""no an fn;l.n)' problem, in chtm" lry whieh coa lt6; r~ CC h. tli [9R5; G ""-ell 1 1I ~ 6; Oro., 1971l; H a nlm i n ~ and F" m,. 1911; Hill 11l72; Ho"", eI aL 19&1; Kara ,,' " nd Clom""l 1 ~ ~ ~, Ki'e< 1% ~ I eh"""n ~ nd Dursey I n h; le'WD 191 H; \I " c" ,, 11 1tull J our",,1or ,\.1 W .\'f « " """,rry ~'l/"' 1,1> 10 1.9. "Kain ignOTing I'" ' 11'011 ",a" adjacent to ~,, ~ "n ~.... Wi ll u nt ~ }'Oll ar e n;;o lly ""uck- bolore Ibcnins h ' Chapter 11 for hd p .\f=
St>nl """'r".I' ~
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The etIca or ;'>OfollC< on a rna.. 'J'C'-~ r ...m i. iIl....... ~I ..1 il> U"l"o....n 2,1, \....hich ".... .tai... m" I"""h .. io... ~ , Jl> ~ nd 3&. Th elf ct..\r,,.;r.ri9l1 c i.otopie ratio or l: 1 ;/wold Dl3ke lhe rltmenl u " ly rocolfTI;,,," lu fr,,'" lho.: .l ~I" "r I ~ ble 1.1. :>rOle that the interpnobl,i,m . of "'.." 36 a> ~ l' aSlnml io n (Iou of tWO II] fro m m-/I ~ R .. o uld he to' aUy m isl .."d jn~ . It i> hlghl)' im potl" nt Ih"t Y" ~ " ,,,,,,m,, Iauuliar ,.,nh 1'" data or T ~ b1c 2. 1. " Ole l h ~ l ~ ho.: i .,mop. tif (1J ~·._'1 ", ~." ,. r" lh • ...".., Q/>uMlln' fOT all 11>0.- .. d en"' ''l';, q uite forrunJ rely, Note also th"r the Il"t" · p,c abuooances or the "an be cla"i flCd inlo Ihrce lI'-"1\cra l cBtt~o rie;, ..... ~ IboloC clemen!> .. ith nnl)' " ne nal ura l ",m o t'" ," nprJl'eci.'oJt abundance: . ,\ -t I ." lh" .... c1emenu (hat haw two isOlOp", th e so"o nd of which i. ,,~" maR 1In ll hea vier Ih" n tl'l< m,,,t ah undanl i,,,lnpc, an d "A + 2," t h~.., tl~ mtJlt ; lh. ' ha w ~n i,,, tope thaI i' two ma" unit ' heavier thall the ......"t " hu n d ~ n l ' SOtope. Th e ~ A -l T d em ent, arc Ihe ea,ic,! In Tce"J':IIize; '" ynu < fi r" _We ",ill uSC a ' imilar clas,ificat ion fnr ma. n pectr al reak " ~ ~ '" ~~k il one who.. m ain element" l formula i, eom l'" ,ed of ,,~I y Ihe m,,,,t ~ h u n · (\Mn t IK'l Opeo; ih iA + I) I',,,..k i, Ihe JlCa k one mo" unit hi ~ hc I he pre..nce of Ih..., elem~nt, in an ion i. of' '''' ea.dJ Te ",, ~ nj ..,d trom Iht ~ i S O! C>i'I ~ cl",,~ I'm dllI", ;,1C ... "", I"" f il" ~ 2 I } """""'" u ~,
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The Ch~T~"'""'. ti c pattern. =l """' ai,, Ihe mo'" """"dll ~' il.Ol01'" of thc ckmcnl' Si. S. or Hr III A ront~in. m" , e ' ....n one ion form ",la. thi••",ti" dolerm i"" , 1he proportio n "I i" n. free " f th= e1.mL"'''l- Ta ~l. 2.1 (i" lid. fro nt cover) "'''W'< th l if I""' ~ A oonl~JnS "no "Si Atom. fl." oj ZlJi[Aj ;> :\.4 :.~, t..·\OO u"" in nat u", 3.4 ' oS, at om _ mil"' "" rr ..ti--
On Ih. c' rn "' '''''', 1 ' '''Ufllq~ th " to-olaDC< "" the rn a,.. "" the
",,"k m..., he d"" '" Ihc mo n" "" " " .,;.. " I\" "':;men" . The " " ill"m""l " fl lIc ,,,tal elemental co mpotuion I" r of tit" ..' o ral plS'ibl. rom l'O"itiOQ , j is th. " oomh~ """ 'II n u"'t.;.... of 'hc...: clement, oo n, l>t conlai" ed C , and C" r"' f'ol' of hy
"r
• I • _
''''I"''''. , ~ \10""'" ''''''''' '' C,H,N,O. ",,"c,., ;",1>1) unli ~.ly ion for mula. m"l i", C. IlK f~\'"rro ~ .. jgnn'~b1. The L" lumll headed A I I . S, W t ,w, ~ ~ ~ of "c, ' ·'c " s "'111 bo accompanied by .l...l.~.;, ~ 8,8 = 0.4 i"n< of "C,>" C ' · S. pn:d; "t i n~ ~ . o rrc, po nd ing conln l:>u,," n lo ",h J43. (, i) ..... ign lhe (AI 01" '......... I>y d,lf".nc. , T!>c p" .lulot.d C ,S f.. , mula ,'CCollnt, f,,< % + ~ 128 of 1"'= 140 <no" units 01 po " ~ ..., H 12 IS 1'" " hi,,", choi"" 1m Ihc T >.ho,,'.
io""
n
L " ng thi> p$s f,om M ' u, ind icat ed. No,," "f
U,"",,' wnU mi'
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''.. '..."' ' 00
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............ . .10
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n
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ee
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00
Un""'". 2."
Unkn own 1.13
M, 11 ~
se
,.,m
113 110
'.1 100
no
111
0. '
11 ~
e.'
llA
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0'
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'00
00.
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lhe, . contain nitr ogen, it. idenlllicatioll is discus sed in Ch ~pl" J. Untnowll 2. 10 m nlai",. me" , " ",,,,,,,,l 01 hi~h"t .. b,ol ule ,"ccmaC}' than tli< 'Imed ±O.2.
2.7 Com po sit ions 010111 p.. aks where possible
1'". ~h< 1'"'-='
" f lhu mole"" '" di,pln}'M in ie, ma., ' P"Clru m, knowledge of til by using i Wh'P ~ ·a bun d ~nct dall II ... the chid difficulty i. lll . t tll1I" mu,t r.r,t , uhtrac! the ccmll ,l>uno n 01 t!tc . , Dr ;""I'>JI(: of Ihe l" ..... r-m,'" ' p<Xie,: so on e find, a 4';';' tn" t ~~ I "",nu i"'"',,,,, from Cll ,o ' Or' al "'i~ 9S, Thi. fiiu re n"'Sl then Ilt s"hl riIL1c.J [,om , he mt3.~red Jnlenmy .al"" to c,hm~lC the " m ,'~n l due [0 lhe "c conlribulion flom ...;1 94. H" wcyc", il ia much Ilnlpler (an d !lc,e more acooratt) to c.ak U"'IC lhe "'\ + I~ eleme nt s fro m !hc ["',.'1 Q7JI r'~I: % ] n,h". , ineur-h " "h' p' C iut., feTel' c",. Ahernativ"ly, u"," [(A .. 211 + Il l:[" + 1,,)] co rrt ' )X1 ndlng to lhc pc.k~ oJf high"S! ma , ... ,i OOl: lhe (A I] ""ak ",m o1 make Oil i.otopic . " nlri· butioll to th o.."
Errbl''''''oJ, ,,,... .-.J... .... J,,,..,,,, ~ 'l o n" l1 y a , i ~ n i fic a nt proportH>n of
I he !"'~~ A " llenSlly w~1 be due t" ,I>.; j"'L"pi' .ontr ihlllian of aD " ,\ + I " .....""nl in 1M 1"I) ""o\;, Of an -A + 2" oJom eDt ill the ( A - 2. pea\; . r Ot c, ,,,,,plo:. 11M: 'f'I«lrum crf hmylhns.
2,. D.cIuc ln9 e le me nta l compo5ltlon . Abo~ e W(
detiwll
p, , '''' ..." ," acy or ck",e"'al com-
pm illO" ""Icul.llou, oh,i uLLll y shouill improve " ilh
I nc re a,i n~
pe.o k imcm ity
J......~ qj'" .\ puIt. . 1he Je.in::ri ble 11/,,, irol o pOc r i tl e,n, IT ~hlo, :.3 an u... . lly much leu . l>und'l nl lha D cilher ~r' Dr (M -I)', t",ca · S!o... lly. ho,...,',r, (M - JI' i • .,,,,,,, .. bU...... Dl ' h,'I\ M -'. N<Xl, ".lLwale 1"" po" ibk . k m c N ~ 1 comp",il;"'m ror thi, IA) peak; i f~" assi~n~ " nl ou, P"~". Bee"U", m/, 91 conn,,' co n!;l\n n\ O~ th an ,,",ven ' " roo n " lo ms. no c lcm em .1 co mpt" ltio n [Of Ini, (A) peaL can a«oun l for the I ~UI1J """" 0/ "'" ~2; ;1 la lls 11' " '' be u>cd 0' A
pea.
4. 0,,, ,,
( A) J't.lk. SimiLotl;t. tile fl ,,~me"\ ion ~"m ",,, il ion' " ill ll, ual!y , ho", '01\l(: mu tual conli",,,c;,,,; UIlC the "" l" infer tlc "'~" I""' il.i o". 01 a.. tl(r,l~m""l ionu rc ~'k"'u lar iOl~ alt oo ugb I""",, 1""'- ,;;onn,, ' J<mo",UJ le tlte con,"r,"" W
'i""
3.1 Require me nt. ..... Ih. m olecul • • IOn
"".k!
The follo1 • will be u""d ,m ly 10 m~ , 10 ovon·electrOll iOn! f hi, ,"~m c o pt can be ,·i, u. Ii....... in il ~ >impk' l lor m "' ito , tmcmre, (Equali" ...
'- I to lJ) that ind aclc
tlo ~ 0> ~ K hol .,..,·, 4~ L , uaU)' ,..",al ",,"onic;d tu, (">o F,• . H,C , . lId C,H ... " -' hiell oi lhe'«: ion' "' ,I] appear al ~.,-"" rna" lIumt..,,·;'
"'o.
oe-: ions h.;l~C a ' ped a l "'''''hani'tic .;,nif""... nce. a. .:.. an: ,irded), T hi' i, Iho ...." Ile p m the "'Sla" Ja ' d In le, plOlatio" Prou d lln:- IInlOde ~",,: k e",· c, ). The ~iml"" la n ,,,,- . .. ... peak, afle, o n~ ha. cor,ec ted it. a hun d4...." rOt COlll rib ,,' " '''' "f i,,,,,, , o ll.a minil k"",,omnl on 1>010....... ll""""'11, ;.... r.a~ " 'ilh;
(" i d ",, ~'; n ~ intensily; Iii) ,ocn:u ing m" " in the ' I"«t' "lh; (iii) illC,e a! lnH m ~" in II" puk i!(>lI 1' '1"' , liL',da, ly the mO, t or the = ndm, ,,1 numt.., of hydrogen ~toH ... IOJ ~n OF ' pea.)
'0"' . . ",
Iml>ort. 1l1 OE- ' ",en k"" pr obll bl. in thc I""'·,.,·m. ......d of lhe ' pectrum; lh ;n " """" .' ccn ' )/,l ~;"'-..t ("'m a•• unidt mified r UT< "" mpo und, "', . 57 mj~ht he n-
c.r
compoulJd, M"" 1u.. ul 4 Lo 14 al.d 21 .... 2~ , h~, ,i~< lml"" I"nl po:ak , a '" h\ghl ~ u n l .~ , l y, N" m"mlx'u" da..' IIIan m her \f ' '" IM - II " (Section 2,6, If 1M ment,,1 c.m>",,,,ili,m or Lh. fmgme,,' lost ~; m lx: OCrlu=.l, thl< gi.... an ~ ~ ro..-erf" llesl, For e",,,, plc. thc p' o",: n" e ofa major 1M 151' ion is common, l>ur " (M - NH t· ion j , prob..N)' an . "" malou. ion; 11M: loss of35 i>; l o ~ I ' >n l)' ,1" ch10 rj". i, present. Ca 8 lh. ion 01 h l ~h~'1 m"" Ix: lh" ltI. c ,0H " . ,4 "n J B . Hint. In L' a ka"'''n ) .\, " 5
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If lei S eno'IU' "' ""l"'~ 10 ion;' " lnc 'Mol..:.,I. (t h;" i., if i' hal a 10...... "'" i"' I;"" cl>er¥y~ 1Jl(>I< m" lc.. ular iou, olio,"" , inlernal ell" gy t -~''' ,j ;,m, -, can be r". ","(l. an d [ M ' J ,,'ill ' .,Id 10 be h ,~"",_ '•• •hown in T.llk ... J. I"" eJSc or iOrima.,. ~ m i n •• (Fi g u, o l l61 a , mallc[.lh, ... ~h . igllJr",ant . inc " :.. ...· in [""'1>."""' tho: c<m espond"'M .It:ohol•.
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ld < " l ~ nd ,b. ,,,,1.or , lhal "",,1 '01!ragmenH OII abunda " ces. A I" climJnary, ..,,,,,,...'h~1 a,i. PI""C' ''''" in. oJ-al '" forming rna.. ' p"e'".....'ill be cumined iD ( 'hIlp""" 7. ttm .. ~I. In 4) ClI" be ""'''' " " ble 1111, = CH
•
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/4,6 ,
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; uW'. T.I . ( 1)72). In EE + ion de~ompo.iho", !Q[mi~ thc ....mc 1;[ - (l1"Odocl. ' he tendency of" \loulr al to k a vc n'ilh" " l tilt d lMJ!'l' is &""~ter I", m ollll: uk . of 10....« pr o lon affi nit y (pAl. In Eq uation 4,6. the fOl1Wll JOD of C"H, ' wilh o C H, (PA - 1.4 t V) ",,,uk! be ~a l ly r.. ...,rtd 0....,. I"" I,,,,,,,,,[;()l'l orC , H, • "'Jlh S=CH , (P A ,. 8.9 .'.-"1 !."m ( :, H,S ' -( ' H, _ Tho .."en main tyl"" of (:31100 f [~ ,mc n l;l1i """ ,1...""",J in lhi, chapt"1 lIr rho," not in brackct . ;n Ta hk 4 ,1, f>'inj1 tho clca,'a,'c of",,", noM art d ,~Uf:lotd ,n Sections 4,5 ro 4,7. of 11"0 bon,l. in 4 R ~nd ( .9. 3nd of mitt bt>nds ;" ( \ 1: f E ' C inc""'''''' lhe b. c:m then :t=l lhe fo' mation of tbe ke y mi. 113 II{' 4 3 and 57 r',""od try- ",,"on,,, ~-dea..... &.. IO re. n Inn miofl "f the , [ahle a cylium ....." as in Eq l18M" 4.14 (Stt Filu~s J II) .>nd ~ . l l ).
~ CA · " C,I\--e=O
(4.141
,=
_, "' ;M.~ "'" ;mtJalc"d by 3JJ ,,1.-1inie ... represent s SS':-; or all LOll' ""I I.-.:ted. Th cr< ~rc (..." 3-melhyl, and r..... . ·bydIc rcma inilll: Ih' '''' , -mc thyl"m "",, : y; 1 on}'] ~j O UP IEqu.hoo 4.2 S~ d ,,'ored Heyburn ;" n ,"oL11d be o.hc " ....' f"'mN l!m' uV! 10M 01 the largot oll yl ~wup , " nd Iho Fav ored ,a rboniuon j"n Ih ould be the mor e st"hle one. ltllkn"w lls 4.9 and 4.10 'I e the l(>eCtla .
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n
Eqlla' ;"'" 4,22 a nd 4.25. ""'f'C'-'t,,
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J[r..... p.. , he rno..H p... l ,ro ,..., a . poc1......1 _ : 1) 5 11-t mO'd>ani, m, in tl"cidal;DK1'" "roeWre of IbIS molec ult, (I I ",,. l'l>e molecula r i"" ,nfnrmal;nn f,...... T a... l. A.4 is ab." 'al.......I"-I
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"..it h con,~"";' a n l cleavago « a no' '''", bond to thaI ZrC.1 ... !~ . t thi, corr c""l" or>ds 10 a '"t ", .Dicl ,· .~ l!l~ ~ Un!",,,,,,n, clrOJ, .nd I n~...., p,.."Ia.;t ;n' ;lft rh u> 'a1ua t>k for deducing mu clnr•. 1I)'d w~e tl·. tom realU ntnnem, 'nai al od >I a r.di~J I Iii., lOC mai n .,ub;",,\ hi, = \i,,'l , " rc a n 1mPcn~l.d~ ~ tran'itiml , lal e. nowever. in lhil prore" the initial clt avagt d~ 1 net le' ull In
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j in~ lhe se.:on;! ' 1q> i' the "'ilOll"nCC " d ,;l;' ali" n nf the ra;! 3, I'I ~,..J 3. 2Cl~ ca'bon~ ' ell, phosph"n;lt
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ma
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V"lJk' ,,"" 4,l j , Wh ~l is Ihe mas. 01 the .h" ract"ri. he O E · · ion {ut io n" which willbe Iorrned by lnis , i., ."",m bcn.:ri., ;nt H ",arr a"&emml (rom u dl of toc roll"",--;n.. :1.1 " :
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which i, which? Unk n. ..n 4.1'
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Note thaI Ih..e j", m. r< ",-0 [C,H ,( "OO H ' J Allh" uth l h ~ cha, g< « ten tion O F" " ",d ud ha> gained an H ~, nm ,n lilt rta "an~eme nt, 1M ch a,~c miK,,,t;,,n Ill> " I"rciduct has {o ,, , a It)' d rog e~ ;' h u ' the 101m" ,",u.ll) has t he mo't" alom , in ils pt.ok iJ O ~" .
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hLlL Iho l. lL<J ut l -CH.CH , 0 ' H , .. Il(I belt'" ,.... 0 l"" t I" the imermedi" ,c ( ' H ,K llo I, O ' H, _ l,, 'l~~ "f a bond to the hc t,-",aWftL (Wal• • 1...., i ' m uch mar< fa'ftr~ hIc f.... pr im a ry " k" h ,-~ , lhall [", >a.'O< cl> ~'Se ·nll$,a tJO ll rcacl;"n fa,'()1'1 tlrd step in 51 0.,,1 ;n> olvL" • r~ J ic . I- ,it e rY='~ (U J )
V"l.lki.... t !O I' rodi do """ wvoive , h•• hargo '''0 ("", a" un... lu'ated ....1C'''. lom~ _h ". ,c;Krion 4,44. Tl>e r mtl ll n~ peaks s,h ould be- used ",·jlll n "llO" lOr aW ~n Jn8 f.. nc:tj,m ~l group
•
locat ions,
h ow e ' ~ r' ll ot ~
~ ic h lv ", b u l ane
tlla l (Figure 4.111)
c',,,,j,·tJ ioni",fl ill" .
I~i:
55 is til. 00.", peak in htb 1,3- and U -
Ilccau,," CI produce, ma inll' e"""-ctcctroll ions, for such , ['Col' a it ;, "'1'«';" Uy iml'Ortam Co reco gnize tha i r e " [n n~:m cn l i. "" mmon _ pla,e in EE+ di, ,,,,,ia liom (Ha rr iwn 199J; Kings.ton "t al. 19 83: eron,ble and Ha" i, oD 1988). Alt hough 110 . , ite or CI """",," tio,, in a molecule . hould be th dt or hig hc"ndanoo. ~."" , hould be a\>k; to, "-'C ",Ifonc, (I(, SO " H g\Ire :l.n~ lhi, j , why ~..ou , h" " IJ mark importan t (M C.II , . , )- iom of o~y gen. led compound . (Slep 4, Sta ndard J lllerp rciali nn Pmcedure)_Hc ,,"c>cr, I" r _ mation 01' the 0 c, ' pmdue la<ust is l"' neT~lIy r. voroJ . ~01C ,,1... lha l III thl.! JU mm ~ J~·." well a, ;n l h ~ ~ St of 111 . h",k Ihe J..i"", tinn 01 a hom o.l ~ I c ....md cl~ J\' J ~c " I\l'' ' " milS lh. "'e,md fi,hbool; II . .... .uld be ~ l1d.r · " "..d '..... , tM second electro n of , he bond r.ccomc, Ih. tlnl"' in:d el..n on " f the radical prod u. '.
",In
5 Postulation of Molecular Structures
T he, e ar e ..,,·.. ,,1 ......jut krnd. of ~. lle f; 1 1 ' [m otll....1 ;" IOI'n;lli,m ayailabl . \~ th. rna" spc.:tn.m f hes< are p" rli cul~, I) hel pful if ) " U "";'~ no jnform au " n h om "ther ""ore"" c o ~ " "m iT1 g tilt llnkc(>wn m,*"ulln l ~ f' ",ccpt M' an: e"en-electron io",. Th~ rale, of the initial decomposition reacliom of any mok~ular JOn i""olving dea,'ages of the dillerem ""rbon-carn",, "o",i, are campara ble to e,""h oth"" a, arc the ,ccondary decompositions of the primary product ions, This account, for the TegulaT incn,a," in abundances witb de",ea,;(OJ ",," or the alkyl ions. The possibility of rearwnge,l product, or grea ler stability becomes higher with the ,e~onJary "'"Clion" '0 that the structures of the ,man"r io,,", ,uch a, C.1H,+ aond" compare Figure, 3.2 :lA and 4.1. Aher you reread Sectiou 4,5. try Lnkno"'", 55 lo 5.7. which are C j611,. i,omers, Don'! forge! th,,1. ,,_bond cleavages give EE- C,H, ._,' io"" nor OF' C.H,"" ion,. In tbese unknowns ignore such important OF' ion" which arc di"'u"ed in Section 9,2,
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f."
;, t " "'/" , 'ofany structuralleamre, give ri... to " siJl-ll,fi. can l homologous snies of iOM ""rl; n~ al t~e low·ma" end or the '1"'~l ru m, sw:b o. lh. ronlin uou. ""ridIL)'1 ~ro\lp tT abl. 5,1~ Both of ' h"", "", ie.. al, o "f'T'dI' in lh. ' "",,trun, of l -dodooenc (FiMU{' J. ~~ ~ Ho w•• er, for an llukno", n ,how;n~ impo t llln! I",..'·m".. i""' .11 e, -. n rna" numberere IS acI "" lI ~ ~ seric, of wei> c ........""'.... io",., and do no t be 1oIc,' b)' l"""h (in Fi~w,.".. l . lO a lld 3.11 lht til ': 30, 44, 72, ano! ~~ I""'x. I~ en' irdj 01... to ' -'(: ' '''TOptC ""ntri bul;,""} " wt h a ..ries of eveu-rna ... ions Can ;01", tln.e , ~ ~ , llknllfied h) "'''I,n ~ ~, Ihe 1,_ _m a.. ffld of the , peot, um). ""' hl l""" i!>k ~ in"" "r m" k]"1< .~ ,h · , or and .. ·T- ~ul the," oan u'u alJj' Ix: """'9,,;zed by th" 'c' y unusual ma " diffc... , t = l he)' . " u,c.
NftCo>(.....; nx ion >UiN. o..,," i' l' qUlrkl}' """'>JIlt aille to Kk'll ify """ t>o uy'l pea k< in lin inf,anod . po.'lrum or C H, iu a prol" n N',{R . p"':lm m. Simila rly, you ...·,11 led much mOtc "al h" me' with rna" ' p«'tra if J Oll can ~,li ( l~ recoglliu ,he J'OS , ible ,i llnll'i ,'llnce 01 rna" _alue. , t;.... lhc C. II ••~ ,· ",ria 1'2 ~, 4J. ~ 7, ,~(" ,11 yo ur rck... nee ",ak Note tha' in ,he I()()o; rUn'lll< m ucr" .., inf"nn~l i"n ' Will a larger 10 0 i, more diffIC ult. becau' " ,,( tno largO( " umber otl l>eole1 ic.c ~bil i tie ,_ thcsc TemainiT1 g will be much mote me.nin!:f"L r ,"";hlc ~ ";If", ... nu lor 10m are gin n '" P'lrl of tOe ion ..ri.. ofTahl..· A.... .W..." S,'
, .,
,
'T
,-rTl.. -\ojo,-,-,-~;.,
'110
1110
""
' >l
'" 19821 shows what elelllemal compositions a"d ,Uutlun:" arc p""ihlo for a pcak, and what the "elari". prohabilit}' is for oach of these postulation,_ The Important Peak Index of Ihe Key;,,,")' of Ma.'," Spe"lral J)ara (Md.un.rty "nd Stauffer 1991 i pro\'ides a listing of compounds which give a particular m,/' ,',,-Iue 'lS the mo,l imporlant- 'econd mo,t important, etc" peak inlheir spectra,
5.5 Postulating possible structures Oflen [he 1i"1 '" ,Lep' or I~" Slandarc,lw concentrate 11,,1 un the ,truclural features indicated tho most clearly. Review (or 'veir" down) the general type of fragmcntali"m ,,,po",od (imide had oo"er) for the indioared substnlOlur"S 01' compound classes. These product ion' will appear in ion ",ric, wh"", ma"e' depond on the size and kind of sllbstituenrs: such ion '"ries ditTering by CJJ, groups were discussed in Section 5.2, hut an ion ,OTic, oan "lso contain high mass ions from sl'ec!/k cl"avag"s typical of functional gm~p'. Now chock tho unknmm ma" 'pcdrum for il' m"'l important Deaks belonging to "aeh of rhes" '"ries, and use their po,ition in the series to lin'it tho number ofmuotnn~ possihihties for eaoh correspouding Sll bstrllctur" or compound cia". For e,am_ pie, in L'nkn(}w" 3.1:1 there aro strong indication, th"t thi, i' a chloroalka"e' th" alkyl moiety accouuts for rhe peaks at mi. 29, 43, 57, 71. and ~9, and tho ohloroalkyl moioty acooum, for th. peak, at mi~ 63/65, 77i79, 91i93 and 119,/ 121. Mechani'tically, ,igma-bond ckavagc at alkanc bT"nehe' ,hould be the mo,t I'\cil" dissociation pathway: the important [>Cab in thc'" ",n" at mi. 57, ~~. and [I 9il:' 1 thus ,hould repre,ent the ,,,h,titueuts C.1I 9, CII,CI (loss of 49), and C,II" Placing these on a tefliar~ CH Can aomunt fnT the m/z 14g m"koular ion, making thi,,, possible ,tructure of the unknown. In rigure 5.3, the "obtcd mi= 47 peak indioalCd that this might be a formate ester (S"ction 5,2), 'vI"chanistic.ally. the alkyl functionality w()~ld produo" an alkyl ion ;erie,; both C.H'.+lO+ and C.H'._jO,- product.' at m.'·. 31. 45, 59, 7J. 87. 101 would be ",pcoted, ", ob,er"ed, Aary by more (hon an 0""'" of ""'J:nit uJc bo(ween
U...._ ~,
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rn,lrumc-n. tInal rna.. r.poctrum elln he .,..rtJy oIJ~1 b)' l ~la l rna,,·, pcclml techn;ques, _ " llho l' ih" ...,mrle " de-'ICIlplion ,,' l"'-"" i, t>.:) M d t he scop< of Ihi, b<w ,~ . ~(I~ . hould h... .... a bIo,;e " m ; "" , il ~' \Oll il thell c.lpa bilitic, .
I,ow...,,,,,,!:.>' dUfF"" ~ja:,u... Lo"" 'll;I l l>< """"-n 0' the bomb.'rd in~ CI"" ITOn> (o.g., lO \5 i V) ",~J also "'''..r tho . ""'''1'~ l ~ ionil" uo n. cn.. ~ CJlCh.1 " "",. 0 , p/lo I01Oll;''''li, m (Section 7.4), Fo r ", w , la' o Ii", ~" u n · ,I;,nc. "r (he mlecular ion incre" ",". it n" . e"hel~ IS noo,.. d lfficul' I" .1lcoo t y..ld st,ch [P molrc nlar ~ /!'.ct:l;,m to .2~ "'O~L
c.-.........
n-. ,..", ("I lhe ' ''''I:em lIilS R is introd uced tnte the iou SOU!QI1 ( _ 0.5 Lun-. _70 Pal al a u """",n' r..l;,,n in I;o,~e e.-I:, rK; ,Ji""M ariC (HUDI [ 915~ Thc R' ion, 1O'l' Iny fo, med can . eact f'ln hcl ",'lth ,-,tilt . R hlOle· cu les to form reaCli... ,,,n >pctJooo. the mo,1 com11l00 a re: rroh' naun (I!q ualit,n. 6.3 . Dd 6. 4 ~ ..hir h i. ra m nxl f", .."'pic mollX'ul"" 01proton iermic Of, + reacl;"n. an d minor I'm (he N H ~ ' 'cae-1;"o. Such uoimol.l:".1.", Iragm e"lan"ns be)' tilt mcoha ni,,,,, outlined;n Chart." 4 and R; til. major m.iT I J1 l' rod",-'t ion;" formed by CH"CO OH 10", consi,te"t with Field', Rule, PA(CH ,COOH) _ ~ . 2 cV, I'A«" "H ,. ) _ _ K7 e V. The m i2 IS4 product ;n Ih" "IH .,/C I ' 1'O.:l rum corre, po LK1, to CH ,COOH loss from (M +- NH , l" , Thul C l lpcctra Cil D pro"ide " ' Ul: tuTal a, well a' mok cular weight inl",m;« ;oo. Sim;!ar Cl ' ......1. 11. c awli,:ati" n of m,,~ ' P, 'oo u" na l pol~' me r s. and pelra leu' n ~ d lLt$. I nl ~ 1> , i"e ~m re;e arcll I'r"'8te>.< ha> ",." Ill..... in hight, u..,;rul mc," ... l.. Tloc m."" widdy ".. ')' ;Itoml (e . ~ .. X ~ : ions I uc!\ R' C. - ~i .c .i mil", rL" ul..\ in the ioll '>n frag""ll1at ill, rO" i,,,:Hion of m" lec"ic, 'IS large a, 50 kDa ..i,h ''''''"'' " ",,,,unn8 c, m " "r ± 0.1'\: 11J~":"- ,*,--t, ost" h. r.~ulli~ u prod ucei "H"t~r and , ,,,,,II, ,, droplet" no bl I'" macromolecul. ;. ~' l"'II",1 H",,~u"l":d" with ch rg"" (h nn e' ",- l'IllIII Thu. a prolCln n b«Ir J protOn ro)r ~ , .,. ) 5- 17 amino acid>, yield i"!,, peak> ... ",.I.. !lI.l---20 ~ ' ~.,, 10 1 ~ U)" pN lerni tFent "I
......, _. "'''''.'.'.' al. I'I
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,
01.1 • • • • • I " \ ~'\ :
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.'gu,. '-I, {' ltJ()ro lh.> " , h
(:. 3 """":I Ih.
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--
1.,....,,,< ;0'" of m/: ; 10 ..."'.... l.ar io n 11"''''''' '» 'h"u kl be tilt ,arne a, til""" rfl>Jueing DOnnal m_ ' reel/a, MS/M S h, 1"'0 m8jo,>r app/1 em iom (McLafferty 198); Ru""h ct al. 1 ')ll 8 ~ o..c applic-.,i"n ,"'" the first '1'r ~<Jd ;njl: • .,erg)', ",,,l tne I',,>duct iollS ",pa rated ,n MS ·lt to provide n" arly 0011>1'1110 KG""""C info rnl" tion I M ~ I ..alJc.- , y el ,J. 1970; Wipl" . 1 ,,/. 1913; Iliem~M "nd Marlin 1987; T"nlCT I'l H9). lbc I~ ml<m ,h'u~l ... lo 1 1~"U pro....n J'I'o, ticularly "Jln a1:>k ft th ~ "'ith F T/K R ptmi'ill g [o r Ia"i"r pept i up to ~ 2.5 ~ D a Riemann aTI ,1 M ~ n; n 19Sn bul of multiply cba ,ged ESI 'VlI\ ~' Jar~c a, /Xi kDu (loa er ",. 19911. t he """.nJtlDl'O'llions yield " ,htr a1'>
,
I"
(6,' )
~ ""
"
GH,-i fiC ,Hr CH,Cfi;r
t ,. ,
'",
~~ ",t
- C~
'-"
- C~H , o
u
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......"...
Of!"n Ih. ,,,:k" l;"'n or a 11 ru",1i,,,,, L1 ~ I' O U p to a large m" I""'uk ""'b as an a lb l" i,1 ~h~n~e' tbe 'P"d m m•.,.el y h~ ;n,r.~,ing the rna"" " f ine .~f", ;"'n lr~~m.m, ",'ni" n mn l" ill Ihi' fun"1,ona l gtc ~ n aJ'l'f''I'''''''' d t ri\c. l1~ CoI n >(>fOt" 11m... lmpT","e the r~ lllDS ma'l5-spcl1all' " ' Ih the de't lopme" t of IOntul ion mel bod, fo r .lOo, ·olatile oom p.>unoh (Secli"" ... .2~ Inlr OO ....1 i" " or a 1.."",jo". 1 ~p ...1ucl1 ...-tIl stro ,, ~ly dum lbe rra!UDenlat ,O" dor e. ample, ami_ Cl h" ylcrJe ketall ..dl , ubo,O "r NH,iN D. ". the IQ1,izin~ ""'f"nl ~"'" Ilium ... «I. 1972: l la lTl" , ,, l'l ~ l. Pr. 1:t9- I], I
Beckey 1977; Bud de 19 N ; B " rH ,,~ .n\ e a nd ('u,tag",,11 . ?R}; lIu...t. eI aI ' 'lKK; Crl L"'.LaIly foll1ld. w oo n den~ - f'l'''''' reacoou 'J'''' initiaU) r",fMd M+- iOIl> I1Inse from cokl III ''tr, 10 Ih. "' ~ ru n~". ml:..1 I'trlni n ~ AD ' I""••",,,, bond' "rt r"rmed. oIf. n oerilical ene'lYfor ,\ll + form1' ''''' i. h;~b.r. "'00;>,: Ih;. '"'1ui,.. B C d .av age. H o ~'er, . he . I.. requ i ,"mc ~t< r,..,. AD " 1"'0' 41'" '' at . much mu t . " riel than t"~ ror '\!J - [u,m, li" ,,; i" lhe I .' mm " l, ~ oft~ n II ICealizoJ char8'=' an d r:l,Q.ili QIl , Howeyor, Ih. pr ot>abilit)' th£t M -, io", or im.mal e uef~ Y > t.', will p roo uce AU - in a LCiml , " u",", uOf"'nu, un tm:
--_._-
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,...,.. U . l1lcrmod":lIIucool ,: IU:r lt ,....,.... . """ 1ft the m. .. "f"d n .... C~'T.
"If"........1:' 01.... 10" ... I"" 100< f(JU/ CC ~~j , .. iI.Il etlCflY'MalI a\>o.Yn: l it< cQDillll !tlUft>O( """' ..., 01"
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it)' 10 l>o: b;5JloCt IlI.o" F.. _ f;' ~"h .. 1 ............ ttw "'k "~lC , hiff", aJd.o«p Itt.. to .. finl < 0111 e~ . It .... q be u ,,,'" ". leV jl if"" ;.. I Q ~ !, R u.uo~ ."d Duo h . Im l ~_ Lbal lblt _"u",,Jc or 1M 1",_.. "'if! .1 I", l .., 10" ~- ' fur M -· ... A1\ ' ...·'11rlOC'.ld 1 beI"'""" 10" "n
\ 1.,., illCIlk•.h I(), llpp<m.imllling P(EI of a molecular i"n ;n>ol,·" me""" eme nl " . ' L>loc"u1;n r nod",:ing M - from \1, t" ",h i"h must '" added lhe "" trnal e"" ' IlY of M bet..« ioni:. ._._ .
~ -
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l
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'* N, nor, v.r''''1
' _~1 ",ol,), """'~l>U"du'jj
'""'"",ic.',-i "fali0".1 """ illY Icvol . of r-" .od N, ' -, .. od "",Jc",,'. , urb,"'b 1~':l. ., i ,h permi""ionl
at.
"r ~ , (0 .." ,
1 ~1l. 'I11e phOlocled ron ,peclrum lTu me l tt at. 197U, Uho,h 1 9H ~ , MOIri'on 19% , Song \ 'J'-) which 'cp,,"c,,', 'uc h lr>t n,id ,,,, p",,,,, hilj,b fnr P""t, .. ioni, ., ion , pro, 'ido, a usef,,] appraxim. tioll of P(El frolD eloctr o.tl ionizarion IMoi'cl, er ai, 1912J. Pcnnin.ll ionization, lr. ,,,ferr ;nll . ncllO' no m tI' e 19 H·rY 2"S He a,o m" i' 1ll0ro fa ""ra l~ o I", lh~ " u,o, ",,,Iccul. , ",nj,•.I, '. Fuji... ",. ,I u/ 19M). "', a ,impl' ,umpl, I Fig",o 1.4 ), t he p hol"" lc ~t loll sp¢ ct , ~m of " , 11 , lIo"11 with a ,."lIeal e" ergy scnle (a, in F igur, '- ~J oOl'rela"d with ,h~ e ""r~} d,IT~I'. en"", he'w""n tho gTO'Jn ~ elo"tr onic " " ,. of no~ tra l .... , and Iho thl... 10lOi elt N, ~, ,I,clronic m.xhlicd £rom t~.' of •.''!t'"'' "I ,,, . ""'" \"" d hl of OMldin. th, p-NH, , ,,b'1;I>1onl
'" i" ni/.aL;on. -r h. man}' v j hra li n n~ll"'a~, ar< also consi".nt with tho high bo ndin ~ char",,!«. Wilh th. lll<JIl'-inlcn.c """,,00 pc ~k r~ ", L1lin g [mm il> more f~ ' '' r ahl " ,'"r lie,,1 l'am i 1~11l. L" ", "r\1", H' )Inin a ll)' a nliho nJ ing 2.u. electron , ho,", a ,l i ~ h t l y iocr.a,.d (0.297 ~V) yibrational , pacing, consistent wilh bond mm~th· ewnl wil h ionization ~l hi~ her e llcr~i c,_ Th e 2~. ;md I. ckc(r"nio "rbilalo ' "'1uite .1 ~ an, l 4 10 "V, "" jICdi,'d y. f" r d ~ cl"," removaL A larger number of m ~kcul a r bond, im;",a,", Ill" dcmily ction, CClmpetitive wiIh A + forma,ion (M " --+ H' , M - ' • C ~ ~ and (41partili ouing or Iho e, ,,,,,, onol iIY in :-1 +' botween the.\ - ion ;",d lt>."\llar ;00 yicldin ~ "R ' . M""o pr.f;'" ....,.h\ld. ~ r e a ".i la ~ 10 Ol" d;' lhe diswcia tioll 01 ioJlS for"",d olmO
,.
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_ ,.. t(E l _
0; ...........
.U
=......,:
1"-
'I
~
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,
..
"-~-
"
. -..... ,
•
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, _. n
n., ~
"nd rClU!nlp}; ' ",T~ l i." " , IhI: p up ul~ lj un "r . 11 otloet ~"~reY ing ion. I h.. IS do.-. .... ibod b ~ \11.: Ih "'. h m,1o,jo", In lhe ' C I1 , at~ w mple, one: del ..... 1 ("",Jom h ~, be"" I". "..ronn'
17.6\ •
"Hr!AB·j + IEIAB_I + AH!I·Crlj -
AH,IAOCD) -
IE(ABCD)
(77)
N"lc Ihat F'I uali"" 7.8 u'os !:>"",l_di""..-iatio" c""orgic, "f "eut,al ,pccic, frahlc A.J), w which Ihe organic chemist's inluilion and knowledge of mechaniSlic
p,inciple, should be dir<elly appJicabk. For two competing rcacliun, of the ,arne molccular ion (and thu, the ""lILe .I:(M) \'alue,\ I;q uali"" 78 predict' thai ,V:" i, determined ill' AI/-; 01the Te,poeli.-e mdie" I, (Steven,on', Ruld a"d "'J) "f the ,~,poeti"c b"nd,. Further. a structural chang~ llsllaUy affects I HAD· ) much more thun D(AB COlor IE(ABCDI. which is wh}' product ion stobility i, u'Llally thc mo,t influential factor det£rmi"ing product ion ahundano.; ISceli"n 8.2) Potentinl-.nergy diagram, (FigUT.' 7.8 7.101 call provide a mor~ graphic Wlly l() pre'ent the lhernlochemicul rro""" ..c1i" " lMJn ""'''!~', wilh D(AB ----CD" ) lor the Il-( : t>mtd grealer , ltan lhe II>c, m llC hermc. 1 ,·" It", " nd
"R. nd",,,·' rr"",."xr--./I. l lT« u lead ing 10 closely li m ~a J 'peena f," iorooc" 4. ~1 ".., .lw boo ,·i>" .al,m ";Ib " ""I'~ ",,1_= W'K"" -: Wi_Th..,
Ix "Ii ,,"
elfe, l, "an r.: ... '" ' plc• . c" lIlllini" Il ..........·ul ~ """I ",jn,ma an d u I" ...1i" n , tal .. ("'oil J $ ;on·ne .lral oolTlf'k~e.~ alld IUcl ;"n$,""1 .re cit"'" fF ' I"• •1I","u) ~'f Of ' · IHI. AIK:V' - .. 1.,Mll\".' -_ 0 .\'· + 1I-"('., '1"0 I"'" "'" clk ", " ,.."di" 41.",, " , , ,,,,b a ,'8... "'" ,uul hd imonslOnal. ";m:e Ihey .vnl~w. I~ O 1e~'h l d the oollds k m, I:>f(\Len ~ ~en.,," or "IL~hln.,," of the aclivatcd cvm pk" arc illu'tralcd by a fcw murkl c"kulai;"n, Ihal h", bt;en carried oul fur largor mokeulcs 1E4U"lioTl< 7.~ to 7.11). 'I he be,1 agreem,nt btlween ltle experlmenlal data and ttle cakulateJ k(LI fum:liuu, (Fi~u,.e 751 wa, obtained by "ssu",in~ thallhe ""li.ated ~~HTlpk, und,r~,-"" an iTlc",a", 01 onoud will btantially d",ociated, lbus lowering thc balTier to rotalion aboUI litis Imlld. and iner,a,i,,!\ the nUllll"'r uf rrce rolor, ill the acli"aled comple., (E, _1.3,
E, _I.B e','l
17.91
p-H,NC,H6' IE, - 0.7
E. _ I.~.','I
17.10) 17.11)
-C"~,",---@ .
«.!)--- CH,O
GH'--@
~
C,H/
t.
C,H7
(7.12)
(,luile n d;lIc"nl 0 (h~ 1 "high~l-.Mrg)' r"clion mUlt have 3 1,,(1;ei.," I) 1~1 ~"jVillN ,omrle. in " , dc' 10 t:oc """,po:tirive, SUUu\lh i""i,..l;un .. l [he ni lm b""' lUp. no, ""11m, ;" ~ ",, ",~I.(, , ~I ;"eTC""" in Ihe ion . hlLnd. nce .,,,,ng from til< m.U...hie 0.
"" -er. IIlN , 1'n4; h ur. U 1 ~ ~6; G hOih 19 ~): Holme' 1986; Lov,cn 1978; I ; "~ ..'. l H" I"'..... 19f,4; M~ rk 1 ') ~ \ M"rri,,'n I n />; Robi"'on and Holbrul,k 1'172;
T u rn ~ ,
19 7{\.
8 Detailed Mechanisms of Jon Fragmentation
"''''t
lnlcTfl d i",. ni"" WI' ''''' 8.11 s""~1d m;)}; e oil!, m~th~11 nlmgf l-l" "" ,-c" ~ ".". "l.. ne
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81';"
radIcal a nd charge , ilC'1..1,," , ... . ,1. 19841, 0.11" CH,C H" CH,CH, q -O- HIt' H3 llvnl ~-heunOllC " 1 f.'11L~ li o n R.2: lhe v e.ev b.1ITi., i, ~IJC In " In ", ,,., lI~ l; ,· a tio .. e.... ~ y 01 U . ~ oV): lhi' ion i' M t nl ,t;Jut>k b y (lie"et ionin lJo n of ~ . 1~l>Ic .;m p{>o:,';~lI , d", "'''''1....1..... ionic proo uct. Quahfyinl: thi i, the 10 " " r the 1d--n II' ~nd ,),11, " al" . , of iom Ihan on t h,,!~ ..., nell'" \, ""li n . ,. " he >=fI rnr " I....' I" M h"" ahllr l 1 Table A.J, For the iOni.:At",n ~J1luli" " " f a hck " ". " "" in l" "1' alkyl radi,.._
'."1;"
cal can fT ~ ble 8,II ;'lC[!'d'" IC"H.,C H , - .... C H.,O ,
~ ,I
...
~, 6
"Tt:""" I('H,( H, · ... HOCH, '. 11.1 , · 7,6 . \11 the IE , ~\u~ r_ ' ,f. ~flC~ ~ ", ~"np '6 r6d IC6i"
• "
"II,. '"
ioC,H,
,..l--C,H.'
o.
., ;1.7
.' ,
'" '" •• HVCH.
CH,
"
'-' l" ' I O.311 6l
. Vj a, .....011 ~ , d"" CH, O' j;
I ,w~k:l
61'
A lk y l
, od ~, ."
..,
....1011' )
r.H,v
C H,V "
IEf" ' !
M '-,(A 'I
,.
u
.."
.e.e
,>
t ••
-... ",
S-_ _ ,•......,. ...
r
M ~ ~£}
' ,J ' I, ' I 0.1 (HI
.
". " "" "
..,.
• I "".,.., , , _, . ,_
.. ... ... ..
, .
"",1;0""'.
and 11< Iri pl~t ~ - l ,1 e V I"" "a ble ,h' D C H , O H I ~ ""'1ill"'" heteroal om ~d,Ni"" ~1k'\:I ' lh. !le"nal mNe th "" til< w'...... pondwf jon' dJI} Ph -) - ,l.Ii,l l'hO ' ) ",',1 ~ . V, hul M ! / Ph . I - M t;4rhO · , = ! .) c\i , reo ncctj n ~ betto, ' tat-ili, ,,\i(l11 hl monM. lenl ox}'" ,n of lhe .. npooin>J i lily_ tt,.. u," ubslituted a l~ }' l i:lOG!" "onded , ,, the ... mc. Ol ~ '1 .. i¥ ~I.n l. cJ roon "100* ), tho pmd ucl_i" n ~ ~ u oda ~ r rodu ced by lheir l<J;"", ...·ill f ~ n~ ~ 1 I h~ "'~ of th, alkyl group, NOl~ l h ~. ( f.l" ~ lin 8.1) C, H, n .)( :H, · yickl, 2:-, C . H.CO~ " •. 100\ ', CH,CO ' . C\'tn ' ....."i!h " ",on.,I;"" " r lh e latter roqui lo, {1 4 c V m"te ClK' j)M¥ide 'M exc'pt ion T he~ , how ~ hj~ t>c, pref'....ooe f.' r H - 1. - I h ~n m,>,< 1 "" ",,po und, do, wito [1M - H))" > r M +-I; for elampJc. f"" M",Cl ICS · , [ (11.1 _ H) '] - _SO~; ~ nd [(M - M ~)" J .., l ~~:':' Iou< H m.. """" '" nlmos l C.,lu,ively from the melhyl alOUp. ,\ 1> [ ~1~ )1 ~ ro u l'
J..nu"J"'''';''.''
(I ii ' S,.',n.,,,,, ',, H~ I~, 10 ~ ", p",) ion, ele. ". Kt Of a com""," Of t ho: ' ..... n proou cu fh.!I.. ~"",n' "fl"......1 ionil~l.cn ont'l:)' (I F.. T.hle
cte... od Il:qu;m oo 8,5) 1"' '' in" 'J' ienl j" dir~' ,h~' lI# ,,~rnlX'[i,ioll,
"
.,- _. _.... .....
'"
~ . .. .... '
-'!'- ~
:
~" ~:tH
..
0
-
~
-
"'
,, ;,O., . V
"'
"'0.'
A 100"':'
" ~ .,
'.
0
-
"'
e "'e,
(8.3)
~H
=
A ;' is b \'ored to ' CIUlU II>< "h~r~c and h' b~ Sl~\'en ."" '. R ulo yo u d o not n...d I(> t \'31u.llC p , odl1Cl Leal > of la tlnal;" " , ,i nc " Ih o"" 0;,0 ",,1 nul for co m plemonlMj' h' n."' loIclitl al 1"'1l <cu ~ (Rowe" nod Wdh.am, 19110; Sd,,,,"tI IQR I; '\fortO ll 1nl: I Q~ ~, Bowen 19911. T hi. 1< L...pctld 1M l· bul. ... io n ond (lOQua!ion ~.\I ~ "R a n d om N41l'lln ll\=llllc ,,, FE ' io ", . Qf "J diu",,-,I pn:d;':t i". ' all", i, a propo '-li by fleWl ( l ~nl , nn'p1ifiod by /kno.'e n .., " I ( I 'P SI TI.;. r.,i nl, om lite ..""~'1!" "td"omhili' y ~I' ji)m JI" y "• ~ t1~ I",,' I'' '>too ,.g i>W ~. (PAl in / (.·H. (1'4 - 5.7 oVl i. fdn"r.d 1 or 1M uJl£.... um.cd lil'- i ons. R- OC= U · . K - l~ U ' , K - US::":'U ' . ""d k -O' ---'-C H" or ~".I imem al ene' lti~ ' he Ios;es (>/ CO, IPA _ 1.':" . " LCO (1) 2l SO , (I> I>L . "d {}--{"H , (1."L TC'flCdiYl;t)., . ..., ,,hl .IM" &"'-n:>t'" ",i, I> m· ItIptUti. c , 1>0 "-> '.~ ,-" I"""
,,,act,,,,,,,
'i""'" ,1'>,
"
".
- _. .... .. .......... -.. ...,
•
"
..,
(~ .1 4)
C, ,,,' • O·-'"I;H.,
dlte.tly u",ful fur PfM ic pro t" " atl.odx4 IQ pbm " l l l' " '" g,5 eVi " r butadiene (pA ~ ~,4 . V~ At [" ",,,r lOl" ta ' lattle i" " ' i lhe IKUt,."mes even mo.., l" O' '''''n.:eJ (M tl' \' 'nei 'U '" ,..;1...... me bo.n found \0 = o K " cl ~I\d ll" rll" e!lYIl 1\l7\1~ '/ h" . Ihore i!; ~ qu"liu,'i .," in " ...", "'lalio""llip bet",..,,, S"'"""",m'. ' '''' Il''\eo ''i,,~ O.E " dec(>Mp,,,,tionl ~nd lllu.l:: ror ".t.d""n mp"';\io n, (1'''ble ,\,3~ w>t h , lr ocluI'e gen' l', lly . 1fe s ;. O ~ as ' ''''''d lor rnO't'holi~. , thtomof ploolit>e. nnd 1,4 ' l h io , ~D(" IUl1 rin,ty atld C~ m l',ma 1984).
:",', ,,,,nl-pro.m,,,
[l"du.~· ion ,ta~i h"" li o n a; a ...;1Cfion-d ri"mr f",c" . • m"r.·,l~b k n ,,,,,,,, i< t ~e u t u ,,,,,,,,," ol,ng flI'a ~ , a ", 0,,1 lmP
,.It,,,,,,,
-~ 1tIC '
"
,/"
_..
",
R'.O".. ~
I\'(O ' '''~
=
, -~
• ,.
..• .,
I~- I ~ )
~
nll" I; I)' of Ihe lea ,j,,!\ ~",up (";d,, .'·" fWd), .. ,h ic~ on ~ha'gt mieratioll lorml Lhe
,..,,,,•• 1 1',,,.,1 ,,,,1. How ever. hom ol ~ l ic bend d e.a\'38" Inrm , I"' '' ood- eleetfoll 1" 00' '''' '' and 30 ," "" II;' 'elJu,"", m",t. ~lO" eneri'o ~~ted alcohol" "kkh~ .Jo; ~.1I'n,;.. ." 1" ' " chlor iUc..., . lId ' ~'Il n id>:s (re' "," ,e,o nd , Iep. I:! G u ~ti "n l' 1910=....-.1 100 40 w 4,J -eV ,'a ll,•• nr C;- H ;,,,n,l, (fin-t " ''P) ill ' ....... lral a ll.lb<S A.h T hi! impl~, thaI h~·d roi.n tra m rcr rcar raOl"'m"nl. ffUm "" .... m . " m.. III O . Cl. '" CN t o )' ieW do. ,j""""iI: radical ion ' N ¥ " H e", ofu.-n exolhermio. onerV llcally fH" r; n ~ t"" ", p",h..a )•. Further. , e,n ; C- OH , ' ., C Ol l k· < C NIl , ' (M" lI un, 1 9~2; Rein.., Han i.. " , l "' l\4~
n.b.,
,,,,,,Ie
8.3 &"'.Ie facto,s
Alt h«"l>;li'...... uf proooc" Md inlcrmediatC$ ." ," ~ ..., imro" "nt fa. mr< ;n ~erm; nill" ion . bundancc, . _'1" 1,, a h,,, affect lbe I"" l nen '~t; un k;'ICll< rn ,~ e n n ' l ~ n l rn, a gi. m rnx' " \..'" I l~ ua li on 7.1\ "e!,",nds 0 p,, >d"prI;;r k... lrum , hoP F.f. ' ion n-C , H ,, - CH OH + IO f1T~ fT"'" (n-C, n II ), C II O II ,K u.. cr 3nd 'Ocll>! 1~7 6~ fJllcrc>l ingly. 1M - H , 0 1" r...,m "-C"H ,, OH --; \ I,,"ntd ...;' h 1~·~ 1.4- "",1 63 ~';, 1,5-elimins tlon: h"",e,·e.". m"c h of Ihi> ~r pca '" t" "" d ,,,, to I" Mhe' kosb of ( ·, H. lrom lile 1.4_prodnct. "' (M C, 1f,DOt oMM U ~ ' :47 for 4-
....n_" "._"''' ~ I '" _ mi,
is
1-.,) ,,"• •" " ".. . if16~
.... ... " '..""
'" •"" " ro ., " • "c r
m',
,.
••" •"" J'"
"" " ""
..
..••
"
"
'"1 t
••
,• ••
•
., ,. ,m
.... . . .'... ."
'"
"
,
,. """
'" ""~."
1ll'J
,'"''". •• ,. .., ~
'" ".., " '
.
J.
ol io' .... , ......,""
199JJj In (he\e di...,...,~ 'i ~n" tl'" pliula r)' i" " ~ n ~ ll\..." ral rr:.V"onh do n e li , - 1(; I",w " w , here the """" ",..tile I ~ H" _ O.~ .Vj PhOH ' ,. r,.. ""',1 , h' {t\'lIh on i on ·ltlol~o ul< Ull" n ,,< d ;~ le ( If lho 3· ~.'l~mj do ~roup IEqu al;"" ~,2 1 ). the mokCLlIo o( N.m~l hyf.1a:tamid~ ,~p~m l.
"",Is
-r
I I •
I
(~.1 1 )
w
J
,.i J "':>-\i '0. , H, C
fr'" lOCI
CM I ",roam, lit 1"" "" Ill;I) of tho ion and mo,.,. Hcm .. lhc "'~ roj d , o: e ~ t on to f",n, . 'I~b i "z( d h ~ d . ~", )- I-" , m l ""m1'k' with the 2!l-am;" u "",up. T h~, r"e" wall)' d;•.....,j. l'.. hf ,...lca"" g~ 10 form the Inn "I ",:c !O3. ~"t" Ih~l "the, r a 1h"'"J ' to bli n~ me r......liu.....t Il!OU!", 1"8eltd (he r1!UiJ ,r.ckt nn DI' tD cl< h C ...· '·..1..1 c..:--< CH O grCl UI' in the prnw""tcd ",-...~.ld""l'd. of l:l """ ily on Ill< >paiial pro.,,,,ity or tile . c~plor ~ roll f' "" d Ihe h}.Jw l'P' ....>10 t>el!ljl tr4 n>rerred. In the molecuhu inn of tr ~ ~I.4-Iuly ~rlo "'"""c l. lh< I, t li" , y hr 1l ..1e. citati on {...0.5 •V) i'\ compo, abk 10 Ibe "-jl,,al ."". .., for Ih. 10;, or waler IG=n rr "I. I Q7~). /';"1. tha t til< !erti • • y.H" n" l .. ,~ ilo,t>le fo, direct [ransle. "ia a . i._ mcmbtred t r~ n oi. tion , Ia,e in t lot .-rH . otmr; lh ls I>mlCN b y chemical ionilali.on '" mulrifunctlo nal ooffil' " uIKI, . Th i. ",lte llOlty I'CfUII, I,,,,,, l...n ~ . I.fi l i, .....1efk e" , (i) I tll.btlilal,on of M H' by inl, a-
molu" J;,r prolan elldation. ~nd (ii) nelg llborln g g rc>~ p pa rticipa tion in the d>mlll;llioo of , mall mol;" l ~d] stllbilllg. n or
w~,"r
I g . 2~1
M. j or stereochemical df"eu oro 015.0 " u5.c "tid 1k In dlU;ngut... rtgio- a nd. ' I• ..,.,;"".... ric o:yclC'l('mltllnnt phtl Mad d",," {Fqua. li<m R.ll'll HCdd-tW ble MH + ioo ( I ~J "U~ 10 1"WtI ~bdalion between I'" " ' ~ S"TI turlCliolllo. The MH ~ from the cxo-i""""", (11.., peak nl Ihr S~1n ( [ u mo nt it ..1. 1ol,,· r~nQi ~ , limin;olrU 'd "' ''''' 1f:<j u. I'" '' RJ I , Mc........touITcr lU,d BIlI "" - 19l191_
(8.31)
.Ch il'3.lily ....... n " l1 tn:n .h",..,. '" .n""l Ihe 1""" . 11••" "r "" >1om -hound . om of o ptic.dl}- ' >ume no; """k>culos Ih lt$ a nd \~' ri lOh , 19n ; W i n ~1< , ,, al l "~ li Suming d tJ. I'llt(,. :"l il
t.o." "" of the' ta dieol amd 'h arl o, relative tn eac h OlMr, i $ reacno n I ~i l , .t " ", on "", ....., he p1" ,;....-.1 l h~t the ' "31"' '' high.!}' ,t" bili"",,," (Tom er , r "I. I~~ ~ : CO",,,, l'IU i.
," o;n
R~latj "~ implJrl ancc of po>.ilok ..,~. , r OI a moJecule """ amlni r.On l n l~ la~ li!lll functlo n" l grou p>. lbe li" l \I,,,.~ ) ">niu,i"" ono' BY (IE) Ll, ua lly " ,,"e. p.:lnds I" the value d\~fl.e1eri>l. ic c t Ih. fun" ' ''''''''1 g, ,,up ~f tM low"'t I E voluc, Th" " illu~p, bul 11lc chari " ~ ~ n theh a u~cJ by I hf"" II:h ~p.> p~ fl~ ~melll ~W_>n , The mu,t ~bul1d.ult I011i uf \11l}fu ortwnal molP'I rcMl1)' becau>e ,o>oondary d..."mj)O!oiuo," of
tho hi~hc:r"""""g:> C H, YU I,CH,CH
NH, ' yield,
~ddit .:", oJ
CH •r - (:H, '
",,"'N~ Jkfl1 ••, .'h.!:.....';t~ ;,.ili~';'m . The in itial cbarge 'lite ;n t/l~ ",,""'uJar ion 11M, ;" ll"ocral, th o "'0,1 fa--orabk m "lI vnmro l f" r .-abdiza.tion lor t ~ I"" ili, o . t.o.b>ltz'l"on ;." r,., plOOt'" ch,,' go. Olto n thi, i, ai, ,, In.: . ilO vi upll",,,m ion, f:>.. nr ing reaction' in which t!>e J"."' ti,~ ~h ~ , I!"-' W>L1I n"r move, For O F. ' Ir>l" , uch cha L'go -'~tont iDn = for"" Uln.. dtr~ l ion 01p"",ibl. oJ..om,,,, . ;. lion 1',.. hYt'~~" ami th.i••el lliting proou~ . l.. hil" .... . ,,d0 po ,n' om, r ' , he ioci· ,k". e .. ill. l E' I "'..ell I.:......,. tllUl t!\at .,ith U le' ""' •. '110.po.>nl~e ~I=";ve ",a rra" actnil Uin ~ 1M c h ar ~ e al ~ f~n1 ~ ~ rtl~ li . ~l~ . ",,,11 a",(>ullt (0, 3 u ~ ov). Tho .._mhi,,,I, M l h ~l e h. lero ~lom . Of lho r.· OI' b L I ~1l (If 11,0 lril'l~ hu n4 ~ I ~ cJ",c ,n cn~'1!)' Ie ' ''~ hi ~hc: " ",,,-,,,picd ..-rl>il ~b oI 1~ ~ I k y l groups: th," alh"" rOf considerable orbitll mixin, in the ca llon ,, rule thaI ' fa "o r ~b, lit y lor jcmil 81ion ~ n ... ,II ; i, in Iho o roe r " • .:: It· -: ,,-~I.~tro" " ' I , Th",," clic
n.
"
_",
.... .. .... . .4.
_
,"
UU 91
• 1', 00",," ( W~ nde l boe n aI. 1'181j. 1Iert am 'peI t uw I..:lomatom, ~ , O . DOO f . om", lhc cone:< f'Ondln~ ,,,,linn< " re oith'" uIlltable (RO' , R,N ' ) n, h;t..n "''''''I1~ ,,""'in(OH ' . "' H , • , F'). Compound. coQ{,1lninll hen"itc rn,toro "-,,,,, ,,, IS. CL B•. I) "un si ,' ~ ie"" co n·o. pon ~ in! to .. -bo nd . .. ~~. age wi'h oh"b" n:":nli" n h~ ll", h" l" l'Oatom, Alth(,\lih l,. gmn lts like HS ' IlJl !\O, ' . AlIh,,,,gh flr ' i"", "all gi," ,"ellappm, ,; gnat, or " Il " ~"d C,H.' 1,>, ' ' 8'" dolU Uon oJi , "'" un p.o ifeld elect",n tn In.... " ...... I""'d to ,n .d,acont l2' OI" m (far = Tr"~ em.n t •• SCanl IhtO" ..h 1..-1 Br > H j, ~cncraHy the im'orSCHRr. :~CH·-"l. CH--SH, 5: ;;'C=O. 50; >CH SCH" 100; ::OCH OCH,I OO; :>C(-·OCH,CH,O ) (elhylene kelal), 500; ::OCH-NH" 1,000; and >CH-NWH,j" 2,{)(Xl Unknown 8,4 is complicated, because it de>e' not coot";n" molecular ion, 11
""'1N ' cmorittHtfll r>! • 0""'_'" , S<JC'c lion or ...... ...illm....- t.. R' ... -Y. lbu, l ~il ch~ lg.-mi S'" ti,," "...ct io n , .<j ui",. de1"""'" ~"ci " ~ '" ,,,,,kiI* negli" hIc th~r kmnation of 11 ; , he i,. " m ' 1flag ""'''''' IOon< ar" d l l~u ,oele M M 'ha l i' fort!> lh. ,_ .1 lo.; "'·il1~ lor effieienl , urfac. b oppin~ h . glve p. o' l>o'h the ,fira:t 01' " .Ii, ,, "'....'i"'. ~OO II>:: lW()..'IC ~ ~ath"'a\,, A lth o u~h Ihe Ia"", u. . ....rgr".nUy 1= favor able I b~' o. ). o. ~ , Ill ,ho,n i, . n_ _I"1' "" " nl"r . pen. in EQuauon 8.46 'h. ,,.o-, tep ]XI\ h , hould a1." bt im1"". tant, teeau•• a . """ anli" l r""",i,.,,. f \11dw::tJ;, n.... inool"ed io"i ,,,t;",, in the , ing, . " eh .. of the ,,-eJect,on, in cyd ohe.,,,,. (I" I,,,,li,,,, 4.10). n.elll. U .
~ , C - ,," -
MoCH- NM. ' CH, _ CH""' , '
....,C- W>l-r. ~ C =ff,< · ·
- c:He _ CH ~ .- '
..-.
__.:::,-.:::,,-,.::::::-,,-::,-__ ~,
;.
CHCH- C- "" ' "
d
4,8), T no '1'aC(;\ln is usually a I W"-'~l' (no n-c unccrtcd! ('1undancc, CII = CH . " , ! F, - ~ .4 ,V, "cCll unti,,~ {or til. bi>.c P':"'l m It" Hta ,.,; "(J
••
• R _ H ' mlz . 2, ' iIiI'I'o R _CH,
mlz 10,
I~
,~
..........,-' -_.. . . .._"" ,
'M
,.
'001
I 00 I
,,
..
-.
r_ u .
• •
•
I
h ,-'
00
•
"
I
i
..
"(5
00
j "
,-
I
M;»> l poeirp m ~I 3.3.5 t rimclhyk ydohe" n<J-Akl"r (RDA) li (~_64)
a oJi,wnic fadieul ion similar to tho first steps in Equarions 8.57 and 8,58. Tbe ,"cond l 'ca fl an~omcn l" ,.'ie-IM :lnd Ga umann I ~ ~J, Au"''''' ... ~I. 197 5 ~ In Eq ualMm ~_65 lh • •c....,nd "~ d ,, '8,~ , ,e " fl ~ Llg . n_ t le~ d, 10 mO rln. li nn nr [he ~nd compc k" "1(" a -d eavab'" 1,,,, "r ~l k~1 (E<j uatl ~;.el d a bicydi . i",n
"r
... 0"""""'0'" of .... l~ _
.
"
",
Exampl... In Figurc 8,1 the addition of" double bond apP" "red '0 chan!," 'he 'pedrum dramatically. [-,'" 'he (JI..'+ ha;e peak; in bo'h spectra are 'hose expected (Equa,ion" 8,48. 8,50) from a cydohexalle,/-cne ring sub,tlwtcd by an ammo group, a powerful initi"lor "r radical-,ile me"h""i"", 1J::'!uat;on, 8.68 a"d 8.69).
,
~-
~
CH,N~
--
".:z 96 •
r~
CH'N~ m', 125
m/2fH
OH
.. 18,69)
When the pe'ticide DOE. CI2C-C()J-C6H~O), i, irradiated in '\lr, a compnL1Tld i, f"'mod wh"", m"" spoc . """&,......-,-,~ ... •
•.
- -
,... ... "', I "knuwn S,9
,
•
....
_....
~
-
...,...
'"
'. "u
t} .,
~ .
......
~
"
. ,,
\ ""
""
*
'1 • A
~
" D ,,'"
'/
y ' ~
, ( U {ll
"), • "---..
(8.1 11
,/--,
; fIl.ra lleh bet",,,,,,, the NQr ri,h 1"yl'" II realT" ngem elll (If kctn n.:: . ~"d \ooit Uln.. . pootnL Md e",,_ (19.16. 1959\ d=ti~d lll. bwad int"pr"t 'I,~
.lln-
;U,
utillly 01, uch mecnani' ms lor a "" de variJ rr ~ ntfl M nt \, b ke cyclic "'(l m~n 1..";",,
1m "
,I.
i a "" r~ fU. ' hI:'«: 1)'["'" 0110111. T he pmdl>ct ot b<j.... I)'-'t1 $..70 ;. !,~ e r«nn ~n " c · , " bJ liZll':: ·(e H , ). , ch ., ~ c -m ig to l ' '' n ,,"'d uel l" - ~ or 4) i!; fJ'()~ if fin ~ d " , ~' e ~~ . .. tbe eM,..'rlldi.. jI. c % .c1.~ VOl'< \If,",,''''1 CH j ~ O ·II . ne w ~ f~ l I E .. 1.6 c \'. an d 1M - H, O ' - ; lktli n ~ Ihe 2.J-<e\' dllkrm.. ,n I" IF;, ,,", 1,3) i' l!W WIIe""1« in nUll'.,.1 ooDd -U'~',', T he llnp "i, e ~ electron nf the OF' pm,l"cl inn prnd " ced by ,urr ~nge m e n l can also induce a fnrlh" rearrangement. For example, thi' i' p,,,, iblo in the onoli, DE" ions produced fro m alkanones
Ir ,!,,",; ,,"
R . 7~) .
I~ ' [Eq uQ1io n t hr'l o~h Q "d j, p1 acement ,u ct j",," (s.,;, j" " 8.11). Suclt a
s.n ,
-
.
m RunnlJ~."'. u,,·
nl Ih..., oj or thil s.-1l" 'L
Tkrrr MNd_ ' d~lI ..d. , \> "t.,.:n N jor , ~, l ; , c.....pvund dto:"mp:':l;,i" no, lt~d 1 l> ~." f.ar'fa, ~. , ,,",, ' . ..., .~ • •, .. ,hi' d b-"U}' 'C,! i t Ll ~ n " no lMe ca, .~ .. , I~ , '" the funC1 ionali (~' [th o ,'. H ,'ca,nn~.nl ind.. ~\~, 111fcr ,n I' quatiol1 ~ . 7~ (ni" h.NIl",..... 1M en. 'l!~ " f , h ~ m te rmedi ate ~ ,,(\ lllllllCOCla bila y "'III ai>o facdll"'C H lJ ..... &:" U! IC (}--- HI is lc. Fo r ,h i-< = ,c!i<m h},l ro\1m "'\ -, H
.1
CH,
H,
i C,H 7' ~ CH,OH ,~
I
11
"
! C ~'\.. ce,!
s«,
II····
"
ce
1",
\ e,
II
~ ce,
d" be,
--
•
"
"
'\",
C,Ho
~
CH,oH, ~.
e
ce,-If
h &"
be, (8.8' )
'""
• I
D" ...., .......
"'.m. or ''''' f"""",_""
are determined by lhe relalive prolon affinities of the donor ,nd acc, un,~(uraled, The strength of lhi, new bond I{ Y I H i, thu, a m.a;" ..e of lhe ,ile recepli I'!ty. Thi, fa"Or> " tramle, lhat incr.a.,", lho "oordinaliun n<Jmber al ele"lronegalive "10m,; lhc homc'lylic bond di""ci"tiun energie, of Table .'\.,3 ,how RC~N+ Il > RIo" It> R(iJO)C-O- u, R{ROIC-O~
H
;>
RiH)O+
H
;>
R,C-O+
H
RO-
H
RH,N' -H > R,O'-H > R,HN' -H > R(HJ~'-H, ~.~ eV --+ ,J.~ c\'. Thll3 transfer> to all of the", ,ites musl be considered [or mo,t 'lerically allowed H at'HTlchan~ bel""ee" 1100 hydroA)'l group and tbe hydl'Oc:ll'bon moiety be[O[. lo,ing W"leI (Ward and William, 196~: Turecek el ai, 1981; Bulovil> and Budlikicwin 1~~JI, Under fayorable ,leric """dilion, Ihe high hydrogen .Jli"ily o[ uAygen-"omaininl\ J'WlClional group' c"n induce unu,u"l byrJrogcn-lmmli:r coaelium, Fur eumplc. ()-hydrogen lmnslel' is opemlive in the dimination of i,obulene [rom ex,"",,,-!b~lyla(lamanl,mnnc, which prou:cd, through a ""e,,-rnember h ~d",t''''' lI~n.rttl''-';>;'' \...0 rorm" Hy ""h .. ~ l.l p.lJh ;" ",ado po.sibl" on 311 lO1I · m~ k ~'U k m mpJex Wllh iUl el"",t!"aIM ~ nI ", 1 C- C
'" bond IWendcl bool: ... "/ . I~. roaoptor
""rl
1 ' ~ U l h ~l
Wd ., n, ;olll effect. ~ ,. :l-_ mh.:" ,d lram iliUll .lale" but 4-mon,bcrcd 0.... 8'" renerall, en..fuvor. d (Wf i' kt and Schwan, In3). The ].,n"",bered lr1l Dloi!ion ily i~
the tr an, ition . laI c ( M "" ,J, ~ , R' j (CHI,P ()1I ' ""'i, ~~), .. id,Y\("'h ~·I ",!C.. (II> R C H,U,X>hould tlt due to F.~ ,,~t i o n< ~ . ~ 4 .nd 8.» ~. m ~ I; ""IJ; f", (CM,j,e =O H ' aa. Ha.rilo n I ~M 3j, ome that "",h w.el"'''' h~ ,e II() Analollle:; in the c!le",;,-
f'I'Ck""'"''
)') .1,.
"'''eT
.,1.
tr y nl d""""I· , hoil ",,,inn, in , ,,Iulinn. Th;, H ' 'm mf~T tn """"~t"" (~ 1100 ~in> ~.2, lI,(O~ A I&d of I'U< l.iYC .." n" ", ill all i"o r~ul11 III hi ~h , rill,al C'IC,,~jfi (0' tbe dis><x....I.i"". ' ha l u.., tol e pI..oox. and m,,'" ""m""ti li ~e r~le. Ior I.... l"'m\lk plior . Itd ooooo""... n. ""'' ' d gt"",n il , POlenhftl-eMrS)' 'U • • al'unes. ;no;lu dinp thn'e .u ~ Oli t U l "d wilh h"l"g" n, "y' M, .nd nilro y o " l"' , n o.; ,!"-'C L. ,,m "r (CH , 1 ,r~ H , how, a C, H, ' ion, and th. 1of O '::I, FG-':'-' ,F' sh"",. :I CO, " ion; 1m . ""ak , "" more ahundant, I",,,,",'or, in Ihe >pec t,. of n-< ,,'e m,i, 27 ate due to the 1= nfe t h ~ len ~ li m ,;,. ) and of methyl (2 ~~ ~) : a lthongh the r'>rmcr to Il>·ed ion.. ~ 1 .2-mi ~ratioI' of t l>< protonatod "llbo x~l ~,oop " n,1 (u"~cr 1-2. a",1 IA..H mi~"di",,,, clT,:rti "d~' ..,,,-mn~c ....rhl" pmit;", .. 2- .r.d "- a nd. [0 a 1"' 0
"_,,,Ie
,,, yield. 42':~ I:M - (;, H. )' at 70 ~ \' . bul This il ll1 . b o.K pc . k 1 ' he "f"'Clru m at 11.V (M:~ccoll and M ' \l1e" I ~~~).
,
.
'
.. ~~
+.
/
-
'/
C>i.- { • ••
CoH
- - ,
>~
"
•
•
'\: j
•
•
"/'-.
...
;
/S,Iil6j
8o.;au, • • uch a ...i& ra ",. f in tern al eI", r~, •• I:. 15 e \' ) is. dep""" C(l ln mo!ecu, 1, ,,,, t" n nc'f Ih. atom. is m Ol>-
\ alent, a major ... .
D i'rlOLeeme nl .. action> io '''hing h)-.lrogen mig,.';"" c•.n h.: im,," fl4" . Ie"",. r, ~ ' ''' li " n ~ .n~ b " l amo nalhe mo. l \It , ~n n g example, of r d r""eli,," • • re . h",,"
ill" Ol" ing Ihe mono\ 'm O lL cl,~,~·,, " d, ~" i l\e and b, omi ne ("""Iio" . ~ ~ 2 . nd R.i 03. y . Cl Bfl to )"lCld lhe Ita b," 7fL' Iti.", m4ju. p" ab ~ t·i ~u.-e 3.24 and I lnk D"'. " R ,l ~ Equation ~,1O:1 reo,em!llts lh. H ·""'" a ngc" "'" L in pr ima, )' cblo""",)hn,.. t hr" Ll~h • r." C~ rllembeJ ed- ril1' U . ""'h.... "al. (Section ~ . I IIl. Inc ..... l )· T bsh tll1 iun at ""lural cd cadx'll l U (~ · . adt cal oh, mil'l')', and invok-e in" " '" ~ r conr.gurat ion ~t the c........n au "dr.d, Solution-.tl')' ...... ..... ...""h ," " "e i ~ hb "r i n~ ~r(,)up !"'-fl;ora tion~ or - andJimC ~ a, -p ) ........ di. pl """"' ~n l " sij' h 5lu eo, peci!ie f'~F m.,;ntd · Ii"", are treated in So.olion ~ , l . 4 t", in d ...... p" rallel lo , ,,lutio n ehem.... ,.. lltt oIi' rl accm~"' l 1".. of Dr· lroPl 2 · phcnylethylbroPlld~ ("nn , tho olhyJ.:ncl>t:l>l.J!lII_ ium CPhcnonium'"j l ~ u"l i",n 8,107; K" ppel and M ct.ffm j ' 19'i6~ f ...... tion X.1 0X(Loo. ""n t'l W. 1\177) w;o, , h ",. ~ 10 involve o;yc hl ~ ti ~ n t" oilro""" flOl (I~ ~ll""; note lhal a . illl lic ho,>rod IS d,av. d, The prolimilYof IWO 3rom;tlil: n nll' 1<e.IJ> \ crl 'Y1ic ,,~rbull {C",. ulu"1 " I. I ~I ), U, u~ ll,Y lM EE ' prccu"or i , bifunctional, " , that the . it. of the c h ~ri' moy e. ( Ly u~ Liun ~ .J 12, Seilcr and H~"o I'l6K,I . The ,h~.~c\eli.li u",k:r~ " ,hi. type " f """'1i,,"
r,om
,.G) V'N
(~ ,
-, . .•
0 )"
'y~ ,
.s.:
0
•
o. ,
(~
11 2)
'" I
-f,
~
",
.:c• •,
f i
!
]
e
,
,
•
a
-"'
i
-s
e
E
>-.: ,;~
, !
•
,
-
•
•
,
a
• ,, ,
• _.....•_... ,
,,
••
j
«;
(8.1 I.1)
U"k"ow", 8.13. F ormul~(c a di,plu"fficnl rearraogement which will rationalize an abundanl iun in
lh~
rna" 'pectrurn of {J imlOn., l: nknmm 4.13. {For th.
am"", '"0 Equalion 9.29,j
E/iminat;an " aclimt. with gm"l' migration". Th.
gon~ml
mochani,tic
f"rmlll~_
(ion AHCD+ {OE+- or EC-j -+ AD+ + BC (equation 8.106) would include hydrogen ,..arrangement' for compound, with A ~ H. Three classes of non-H elimination ccacti"m will he di",u."cd here: ""me Iype'
or,~
gro up' exhihit a
high tendency for migralion, ,mall stable neutrals a" common!}' eliminated a, Be. and the new ,\D+ ion can show a substantial in~rcar;e in ,tability ovcr the ,.\,BCD+ precursorR"~rrang"mcnl of u"ygcn function"lil;., is relatively common (Le'-,cD "oJ Schwan; 19~.1l with mctho,yl migration probably beim; the be,l du~umenled nUII-H rcarl'arll.\c"'e"l. Tlli, ha, bt:t:n ruuml in a ",ide "atiety ur pulymcthoxy compound;, ;och a, d"rival",ed "Ild olhcr aliqcli" compound, IlJuiliibewicL d al. 1% 7: Winkler and UI'litzmacher InOI. In eycJoalkanes with lhree ur more molhuxygroups, Equaliou 8.114 ~i,'e, rise to a major po"" in Ihe 'peetrum. Trim elhyl,ilyl g;ruup mig;ratioru; arc common, allhough the,e u,ually ''''''UT thmugh five- l" eighl-member-ring lran,ition "ate, (Iltooh 1979~ the lene, can migrate, ,uch as: CHOH Ihroul\h the eyclopropa.o.e iUlormodiale in E4uation ~.1l6 (McAdou .1 "I. 1ngJ.
"'gil"
CH,O)
1-'/--;
. (CH,I.-,-6 H"":"';:CH,),
(H.114)
,
C H=OCH,
CH,o-~cH=6cH, m'z75
EE· ion. . ' SY",. Cl'm mo " ly 1.....' from M ' I.hrmlgh hyd rog I",,~ il ca o ">rnc,lrnes ,>ccur by ellmlnalloo from acyclic po, lll m", despile tho hillh enlN py rc ~ u i rc lIl
'\
d
(8.112)
1
oP
•
H '~M' ,llk"n ~I' eiim,na" their 2,J-c «ho"", ., (" H. (12'l Wllion ~ .9 m a, ~ "'.. i... l..,,},r cyallid< IBw ~. lma ", 01 e ,een by ""mpa, inj!. !he IIrh3l 01 t ~lel l .. , '~ l~ " l of either kctonci he I"".nd j Q the , ......., . 1;,0d ucls, T h~ . lhe lone ;mpoflanl (bo lh 4~{; l f"\;' mi. 238 and ! ~ ((',,11, " ,,00 C , .H.. ·1 ill an alb "" ' po.>.1 ' um 1 .,. I . nd" + II' +- I,· "f R, R', C 5lw 'u iJ be ~ +-~' + I an d" + 2.'- +- I; of R,R'C . h" uld be In -j. 1 " nd I n ... "' + I; ot R ,H C'I CIl ,)~ C H R , , ~,, " k1 be 2" + I and ) ~ ... III F 2:· "" d of R ,C(("H, l"CR, Ih Quld Ix; ,In -j. ,
f".
f"""
""" n
".i ...
~ nd S ~, ... , 2. ,\ ~ ~i n, IIR'CHCH" RR'C(C II , l, . ~n d R, R-CC H , ,.-ill ..I", yo.:ld I.." "", j ,~ 11!>1 - R' I__IM RHJ' peak. , h ~ t ",(1110.: ~ niza bl e il l"";' M ' ~ nd.'or 1M C H , l ' peak, can f>c hkn tlf~. UnkllOlOIl S.7"'.-. It, ~"I"". of 10 ~ nd 1.1; r", II, II'CH_lhdn + I pair would Ii, onl Y", - n, yiclJinp . _ 6; f" " n " + ~ . + 1 _ 10, ll' _ 3, indicating I( :';H .. l,
., .
,,"
V ,..." I"....' ''t tllip~tlt;c lIy Jr""..,.iHm,-. T he ad ditio" of a double bo nd to an alkane IDefOasn the " t>undaDOe of the C. H .,._, • ",ld C. H _,. + - ion """"" a~ . howo in tho , pcoll um I·dod""," " (I,'igu t\: _u ~ ' ''IC incr"". ing importa nce of Ih. C,H " . , • J lk~'l iO Il SHI. ' ar 10'. ... ' rna-=. Ahl. Cis and ITtBIS il;OTJJCTl; u.u alJ ~ h~ \ " very , i",i1 . r m..., ' I""'lra Alke". ;('Ill ' . ' hihi! all ~'Iinl. riU Illrough m' grnn" n of 11>0 double b<md. I hi, j,
t""
"r
.
CHR _
=
.
C~ H==C 1-lR
rs.» e'!'CC; all}' I' '''' (",
all ",.. "'·'th ..
1""',~ .m .. ll'C"'ar· ""'~llhl
~
0 often sh_
an d 'll'lligh' och. ;" a lke" ... B, ancl>td
specifIC al1l lic-clel1 oa¥" or ,""m oog. ment
""""nlpo"n" ,,, a. rc,"""kd h) C"l~';''' a;.b.:li"ll ..ud.... l "1af'l"es d at. 19~4~ ' he rna" ""'..... .. ,...l' . nn and ' ''I''" ia ll) roJ,.ene'>. len d 10 be indotpt"nd em Dr dDubl¢.bo,od po n th al [.,It!.
.hlll~n. i"c, ~TC rda li,,-ely j~dcfl"no!~l of douhk -hond po , iti,m; ,n if" or tllc d" uhl.; bond to inner pt";!.i01\i lA~bltizc M ' -. ill!el'llal hTa"d, lfl$. a t the """bl. bond jl p al ti ~ ul .f ( ~- eITecti"" 10. '~ d ud ng . p. c;llo di"".. Ci. !iOll b}- lhe l'hyd rogea re"'T. nl!Cnl ~ lIl rEq ni\li.... 9.6. R-- > H ), ,\, di"",,<ed
..
.-
"~
:D, "
.
•
,J
..
in Secl;"n S.2, an electron..u"u l"'3 all)'l iroup al R- .UlliliU! lh. charge; PA(C'H, C H C H" CH,C1I= CHCH.) '" n c \'. hul p.' r.CH, I:C CH, . (C H, j,C=CiKH , l = 8.5c,," . Th e C. H, , · - abll nd'l>CC'; ;n the ....... lrn "f l · aad 2-1> 1 ", il l! o lhtr C.H••' .., t< , ub"anl;all)' red ut:llail'lIt hyd'aloir>• • ",1 1',,,lcT 1 9 R5 ~ leddm g apparent l}' to cydic FE ' l' '''d ....1 i,.... To ,";Icta lc. eo ml' af i,otl of 'pectra of aU a~.IL lb " ,,,-,,,,,,,, i:; ncl/l tt lhe C,H, , ' ""r ic... Cnlli , iolla l aCII~at ion , tudic> (In ' u"'Li, ..",d rm initially J· alb no lO W;, Alkyl. ,ub,I;\uoed ~ }'d " rr " l' an ", ut,.urgo fa" and u .'t "'hIc ring.''fI''Tli n ~ (Zatkin and M,ka y" l~MJ; cyclopropane SlIuct,,,.. h" . c """" ~"n,ion skeleton provide, a classic case. For c,am· pIe. in the mass spectrnffi of 5-~-pregnanc (Figure 9.3~ Lhc (M - CH,l- arises from the 10"' ufthe angul~r melhyl !,'T'>Up' (mainly C191. Loss ofCoH, by the noqdic fragmenlation of the 17-20 bond is neg~glble heeau,e of fa"ored 1:;17 dem'age of the D ring produ~-;ng the ,tahle leniary carhenium iotL Radical,ite reaction< of lhi, ,pee;e< ean pmceed e;lher througb rociprocal hydrogen transfer (Equallon 9,SI and 14 15 ol.,'''"gc to yidd Lhe charactcri'tic OE-' miz 21S ion. or Ihmugh cleClmn donalion to lhe neighhorlng bond. resulting in Ihe miz 232 reak lhrousb 15-16 eleavage (Equation 9.91. A ,ubstmlial part of the
i - - ., ,-
,, ,
-
l"
••
,- , , ,• -" j ! •
,- -
.,
-~ ~
.
.
• , ,- - a ,-
,,
,-:
--
.,- -
-s
) \
\
\
\
(9,91
~, .
r, ~
",".ocJ m" inl)' "r . jn~. /I amI II. bioni.... t rn. a , do a >an ef'!' of C , H, u l1lu« rin ll" + do uble bo ndsl lSOlUCrS and O1h... com",,""'" "il ~ a hi!!h dq;rn: vi u"""tu'1l. " d hyd r" ""r . bo,.. (C,o" ... 1"'0 rmg' - 0,1" .."", hOl,d,) con....inm" a ""-d" h"'..... lin!! a nd an eueriOl double bond eUti b" spc<TIa ....hleb a rc consis.l.nr -.mh iu,ri., 1 " ",n...r i",,';,m I" a cydoh1 ......1" ..... plu' 0'''''' . ClI ...-~ n!!'........I.... ~ ...... a' rncTb)'l n,igral'ou , Cydohc, ene d. "'..." ..... on Ihe orher ha nd. can uDderic peak can be rationalized by a h}d rOfll"\ abstracllo o " '''''ha niwl tun.· lcr nIlll the unpaired el=on to an an~llC rndlCl.l ,,'" I f q.... rlOn 9. IQI fun_ cd bJ.' me th yl I"",. 'I'be- o.i""ir."",nt odd--ele"'ron ion of m.. .~ 'j.t. ..'hieh at..... through a rcl ro- [);eh-.'old. r f in ", ,,,,y .iI'n~ -c l oa va g. ami h ldrog~ n · rean"n b'l--mcn l ~ . c· ~ ; "" .. 1M pnx illch com...." for the po, il;YC d 'larte- Ten " hyJ ",cannab ;nol pro !t:llrlio"...
[I" ~...,
In k
ArM'4 tiIt'''' ~hu"""',,t (I S~;.). Arom,lliell" of p/len~l "lane< am "" ••:".. in Fill",e 3.7 al ma"e~ corrt ' l'0 nJing '" C:. H,tC H , I.· emf; n , 91. IO~, 119,. _,): lh. ~hUll d1lJlc ~ , 01the individual ion. I re llluch nr",,, k n l o n tI•• " roolure of lhe nrnl eC ol~ tMl n Ih" "" ,>I the I"""'·m. ,, i".. ... ie<md, In n ' pmre r>f II>",. " lhal 5-, 6-, a n d 7· n,,,,,, h.-red -rinll l l'\ln ll· lion . late, Can be in..., h,-d (We\demJOli, er aJ. 19171
" (9.1S) Note !h t Lhc SdHIn alilie, (E qllmions 4.33 . nd 4 .14 ~ Soomelimes the rat;" .of Ih..... ,,"m pct;n~ t' c.......,. ......" to ,he ~ lkyl- s u bst,tu,· n t ..,.. hanci njl: 1I-leu t angcrnc TI ( (Oeenl o",i.. 1 964.~ The R~n~TI g"rnefll j , unfn-o",ble ",hen .'; , hol ,he ~. or tbo o ,, ~ "·~ t ; on, ~ 'C ,,' mrlecel)' snb' titutO
... il"D
l~ o; pt ; ' "y
or. t~ric
of ~ n , ,,b,, il" Ie-c~ rl>()n i, d ue [" ""m hOM !i' tn Md eJeC!loJll;C facm" IK lICk 1989t
(''-11)
l'ol._,1-" I"~"yrli.' .._ I;" , ~>. The t>c h~' IN of ~ i !hct 4" 'malic hyd roca.rooo> can he ""- .1 ~. ~n C"T~ ('Iloli"n 1M! ,Il' , Ikylbenzenel de'mpuli l i"n ' n LIl . u.....furatoJ ~ystem 15 ""b]"';1 ' 0 """,TC Io fd w f"" ~,....t .~tlet a l tJ" mJrns C Al> o r mcl~ 'table ion prod llC1 {Sed~ ,he ,m p,
..c, onl)' H ' .l ~ "arran~.rnem of hydro~n to the carbon atom oft~ e oxonium do uble oond to elitninate C. H,. (Fu ll.ti on Y,9 S1 .;,n ~Ctrs of I-hnatkcooo.>l ~ ...I J _"", ~ Jctt "" (lJ nl "" wn. ~. 9 ~nd ~ , 1 0J , T he promiocm c ,H,. ,~. C. II ",,' ,and C) l ' ._j, ion ,. rie, of l , ,,lk,,,,ol. (wnieb "" uld ari,c in p.l n di...-JI) from \t ' I C.IIl S;,'C c"idcncc tor h'~"eh i,,~ 01 Olhel structu ral roah' R.. ,0( ,IJC e. ' '''m , k .icto ,~ this ImgnJtnl J tion boh" " ior g.n.n~l} rol1o", ~ ~ha t ""tlined ro, Ih. co, rnpondiog hldroc" rbo n,.
t""'"
1fT""',,,".
",i""
t·~h m. ~,~
J' M , e,-Jew "g ain II}' Unknown' 4,19,
5.~ ,
5,9, 8,) . an'z
•
CJH,.
71
(9.20)
..
,
I I
Of _ ,
Co_""" C
..
.r, ,
lh;;; and the aualogou,ly r"",,oo 2."'''th lheunal ",oil al$.o. conl rihul c 1" ...... \0 ' nell as mi: 44 and 58, II, in th" m" " 'f'C'..1n o f = ydied to .1. 4, and 5; Ir."''''' ,,( 4· H lI'q ual;.m K ~I\) in,'ol vo" ,-i. --m0 chlmeter istie OF" i o ~ at 1M .. lX) ' io lhi, from the 10M , ,( tho: bel1zylio'ndll.nee. fo r , he ......" MOO /'l.il>k fur 'he I""wl. net ion or l q wth, m. " .23 000 ., 24 C~ n ~ "" olillle these ('o)~ 13t ;"'" for t !nko"",.. '1.2?
_ _
u
. 0
..""
m"
" " " """ m m n. " " ,n
," '" ,"
n
•
....
~
~
..
'" '" '" ". '"
..
'"'
,.,., "" ,n '"
"
,ro
"" '"'" """ n, " m ""
"" "" "" ""
on
"
'. •.
'-
~"
'"' "n "" • ••• •• ", "" ., " " •" ,"". ,."" " • ," , " ,. " as
M M
~
" ".
'OO ~
••,
•• ".
j
••
,
,, ,,
"
"
"
,,
"I .
..jh~
"
J"
, , , ' , r -''" ' 00
"
,.
,.
'" '"
,m
,m
~
9.3 Aldehydes and keton es
AliphQtic IIld, hpJ, _. Illtd Ii f l oM .' . The m"" , »O. UII at !Qlln, ,]dehyde, 3-1>0010oon. , 3-methyl-2-!>u lano"". 4-melllyl-2-pcnlan()nC, ~.m "l h y l .2 .pc n l"n """, lind
2.3-hut'lllcdinnc bu,'. b. en ~i\'.n '" Un known' 1.9. 4,9,4.10, 4.16, 4.1 7, and ~,2; those of 2- and ~-d odecanone a,.. Figuro> .uc an d .1. I I, lh,"'" "r 2 .., [h y l h ~ . ~n ~l, 6-mcthyl-2-heptanone. and 6 -met h)'1·~ - b eplene · 2 ·o ne ore . hown ;n fi gu~ 9.R to 9.111
.oo
elm., dw ", of I"" « ' r1l:>po ooi nll ollpb;u" akoho li, Th. lnQ!e. u!ar ;
n..
v,
O,H,-
"(".' )1 ,j ,
C, H, " '" - •--'--
m'z l~ a
"'-(1. .. '
.
,~ '
-
•
~ _ CH,.
19.271
/JR.,aluraleli keto""."
I r (he ?_hyurogcn is vin yl;", (hi, can Jm (Equation 9.5). doubl.bond i,omerizalion "pparently h,,, not occurred in "11 M' ; the mi. 69 ion. whlch would be the pmduel of allylie dea,'age, i, more abundant than lhe .,-cleavage miz 83 ion (Dia, eI aJ. 1972). The rearrangem.nt 10'" of the .i-alkyl C l h~I ')do ho; UIl Oll< (F i~\l l~ illu, l..-alL" major tildilianal rru rmcnlal ~>n I'"" h",,"\ , ~ '\lnd ' 1'" ,,
- -----
IC, >Hu') _
C-nHon " · , C, H, , .,·
~ =
(9 31)
ij .
·ui
•
F'
, ,
,
-!
,
,• ,•• ~
~
,i
•-.
• ,~
.-
--; !
i ., • " , • , , •
r;;
••
r '' ~
--.
•
I
".
(93 21 ( ~,n "'aoch Ln8 (F igure 9, t I) p" >. oo mi' 101 then indicat", R"- CIICH, -
CH , -(:( IOCH, . b., ~ .q iii! :"", , """. T h ~ m,*,-'Ut" T ion peak of Re O OR' g~u ~ rall y bocom., lban blllyl ( Fi ~uT
u
m'z 1l6
-,"
M I . "" ~~
-"-
)
•
"" A
l"'- z 6Ol
) »:
~, y
';;,...
•
~
f ·)l ...-,'; 1
(B t l
".
• 1M...
'po_
of
Commo, eo ...., .. C"....
For the formor reaction, aiken. iOIl formation prodominates for propyl and high", ester'z116
".
CH,CO=HCH,
miz87
o ~(C-O) ~ ~
".
ICH,CO=CHC,H,j mizlOl
c,Hi miz57 (~,35)
actually ""n also he pnx!"ce<J by an a,:;c ""n "" . ....~ oyri "' d h, ~ h u nda n l douhlel' of (M _ OR)O ~nd ( '-4 - HO RI' ·, anJ f"'sment_ du e 10 , ubIt,.'; 74 4fld ~ 7 i,m, chara d c ri, {lc of "" Ihyl al k3Da1n, ah hoogh in k", c-r ~ hu nd~ """ Alk.noate; gell'r. U)' gi,'. ",.ak ""'kt:..... r ~ m ..; , h. 'peali\·n (Aoden on ~r " I. I ~Ul and ion ltenle re.>c" linn. IFerrer-Correia '" al. I ~7S ; lJ <JtlLi~ 19115; EiuIlo rn Iff trL 19115.>.b) ar" clkc1.i", ,,~y' to diff, umiat. ber...·c. n ~o ll bl e· bo nd 1" '''0"... (..,..;c w. and ern" 1987), .k~-Allenoat.. ,ho ..· t .... ' I'pia l ........ "r tl-- alkyl groop" similar to lhitt in cnnnc, (E ,ncrea.ing "" okc.-..l..r "'d gh, for .... lk~noio: acids above C, . ln poly_ ca mu. yh< m" tc0: M H ' i.... fo rm «1 by In ion ·~,u~ reaction,
p«t,.
.4/ipMt~ -J.-pht1l} I ~ ropi "" ioc acid e~ n . t>ow, a hydrol yl , roup rnrr 'lftgnncnl in lhe oJecom posilion of lhe (M _ Br)~ ion p;. , . lId i"~ Ihf mrl ltoX)-l rea rra"te"""" of R""cli.... Il. ll 4. Fmm~l">n ,>f (M - H, O)O' in acid 'I"Xtr ~ ~pea ... ' 0 be impon ant h In mrt hyl cond llio m oolti..,.j c'lo",. Tho I"" ". en , i. otI en round to . 1It spect ra of diearl> a dominant (M _ H, O r peak by the ' onho" olIt"hk primary "nh",,_ lion ""ed in organ ic s)'JItlle"Sis to pro-
0,1 . " . ..
'"
(9 . 3~ )
tat ",h 1" c!) II.e hydrox}' gr oup; J < lu..!" It, the lcln'~ l dld c.n ,0, - (m,'" 81) io..... Ind uctive , *.. ,a.~ in the latter give< ri ~ 1 an inlr:Il'0 villyl other ions formed arc o'e1)' ..uhlc (.... So: ~ eV} For rho.>n I"'",'ide" a powerful reae honiniliating si," . Tbe ", ilic,,1 e....-. gy r.". ~-.deavage, R-- ·CHIOR'), · .... R'O C H OR ' .... II·O-= C II - O R. iU llbot;lfltiotlly lowcr",l hy the re' ona nce m bilt""-lioll of lilt prod"'" ioo. Unf ylsulfJ dc, 800m. of lhe ",,""
•,
r
.
'~ll i li yields tho l3.'F" C. H,.. , S- pe~k (ion ..."TiI.... 47, 61, 7S, " . ~ b" l ,*", age ~l olher . h in r"5il'''~ ' to )'i.1d thes)0,:" ,,1, the main n orpti"n, ~ lnll t he a d ~ iti""" l (omw i" .. 01 (M - 5 .- ', 1M - SH" , an <J l\( - C , H, l" ' ...~ k..
r".
Su/JIJ~•. Altl" ugh th.; ma.. ,••"rtcum of C H, SC H , C H.C HO ltl>< *ooiOJDY. ""'l ly" od>>r rlQfll p.-,U01Oft.: WAllt r ' 972, p. 716) n hllm••ub:! tu li. 1 M · · l3 ~~·;) ~Dll .",l e po~ n to ....:Ie.o vagc J'l'odu ;on ahern;Olive .",ode r" nn al;oo of lhe /IIi z 1~ ptak. In ro",ras.t 10 ' ''' ]>f0M l pfthe rtltn , " .'ery ' ma li (po " ibiy o",m~ ' 0 the comJl"lllion of Eq u"liou 4.37), altho u~h lh. l;om poni01\ prod uI'l C, H , ' is ~llil . 11. ba'" reak P h~ n )1 ~I.y l iu ll"Jd.. ..!\derto n:.,.;lions l~ pi
,.octi""
i"",
Stndi., on indole , ~ k" loid d.ri"Hi ve' indi. ~le 'hl ~ualernary niuogen compund' (K .. H) d<eomp<Jsc thw nally on heatinll in the rna", ,poctrometer by IwO prlDCipa l p;,th, lead;ulllO dilfenont leni ",y am ;n
R·
+
~ V
(9.45)
• , M... . ..... of C....... C_ _ C1o..-
""tlo;,:, thilt ,,{ the ~on l'p('fldJni f""-1 ed, t .... n in the ' p«tn III ' !Ie an'"'-'!!'.... ",,--i;0... l'C" k in ....·butyl ,,,cta~ Figure 9,12), The no rma lly unb oro•• bk C -N bnnd €ita,'age " ilh char~e retention on N, ,ueh .,;n lh. _..-md" 'Y am ide !Figure 9,2(1. " ,i: 72\. I' mcreased suh' tanlially in tlte ter tiary alolde ( Fill",e 3,20. mi' l 5til
The I«lOla ,i"n enII" n,o"",ol on . k . lron i mp~et (Sectio n 8 6). T ho basic rules or roo d....mp.-.,;Ii"n iOPJ>COlr 10 ~ I." applicable 10 nilr ik. than 10 . IIY1I1hef oimpk """"",,und fInss. fo r the Ionization eoerl1io, ol YCH , • 'r _ eN hu the hit besl value of lhe .o mmon ru n" tio n~l it i", li, led in T:>hic m ~" Sf'I'drum of dod~1 cy.nid~ i. givon in Fi~urc 125. I.. nv.ra ll appearall"" j . u.........l by ma "" ' ~ la l ,t ~nd a rd , ; il rc",m bico an ~ · a) k . "" Qr .:Ik.....pectrurn tFiK" rQ ,\.2 and ). ~, in h. lact 01 specillcity, bu t it II"" al>ul' w nl f'l':'h a, higlM'r .... ~ and ....i" or .illD lfi e ~o t peak> ",pa~ onl)' 0... mao. uni!. Th ~ 1Cl-l, i.C-'; · <eric, (41J), 54, 68, ~ 2, __ . , dominat.. It>< uppe r pollio-'Il vi lh. "!,",-1 run,, the hyd, ogen ' Nlalrangen", nt .. rio, oomi....l1 y ""Itt· 'f" ,nd;n~ 10 C. II , . _jN" (41, 55, 69, ~ 3, , .. ) i, uf ..,.,m!"l'"abk imponaoq lor ,, _ 3 to 6. Th. ~lrgest pc;!\;o in ll>c r" rmer " M are (CII, l, CN' aod \("H,laC N ' r""" lh. displac<meot reacrion Equ ati on 3.103. Cbain I>nonchinJl does incru ,,", the ab"nd,ln. os oh he appropri" te i ~n. in , r.i. ...."Ii.... bill .uch data mu.r he u",d wIth cautloo fOl , truelUr< ,lcl eTmin ~litln . T1>e C.H " , N' odly lhese ions ",e for med by h~dr o~cn .e"'T~"gcm"" . ..llh oIc1ln loti: RoJ ( 1 96~ ) hil' ,hown I", 4-mcl~ylrmt ~non"riJe that lhe abundam C, H. N " i,'n arise. from ~-h}'drogell migr" tion (0110 «1 t>y ]'-("l...... gc. ,\ furt!oeT u ual ""'tllre 01' 1"" spectra of ,~kyl cYiOni,j",; . lhat [(M - It] > [ M- l LouolJ ICN ' a n o to
, I .._
. .......
Co""".' c.... . ,.. c" ....
soa bil= !he l, tile
om' . b u\ th~ .... ~ n d r-i.o mc!~ lield (M
- 0 )" .
T h< followi,,, rn,,'" o.roear a 01 hlogona tN U>D1l",und, are IU,,>lnliw:: 11et,
CHIllr, 2,2,: 00. , a e. CO F" 2,S ; l.~-(-, ll ,O], H, e, HU " z 1.\: c , el F" 35 ; C ~ ,CN. s.u, I· bm m"hexane, ~ .l > l-(~hl"'''''''''lh y l} Unln"'.. a 2 1.C"-,F.
l. ~:
""rca"., ~.I ): aDdeeant , sman (n. t X ) m l",,,I:.. ioa poOh a rc
"'i' no .r>
.
,
, I M...
"PO
i, "ften ncglib~blc ror pc,h"logcnatcd compound, unl"" they aro unsaturated, The presence and number of chlorine or bromine alom, in an inn j, u,ually rccogni'''bk lrnm it, charaoteristic Dr > L For bromine and iodine thi, reaction is negligible for an but low-molecular-weight componnd" and for ~hlorine thi, "aeli"n i., of impTtan~e mainly for IC'Ttiary chl"ride,. Alpha_ cleavage does give unusually abundam (M - nt ions for lower-molecularweight fluorides. p"mJleliug the I:>eha"ior of alkyl cymlides (Sectiou g.6), The weak C.H,.X- ion 'erie' found fDr many alkyl halidc' i' '-luile chancteri'tic aud thus useful for general identillcmion, The second ,,,,,,ce of C. H ,.X· ions i, tbe di,placement re"ction (Section ~.I I: Equalion 4.42). TlIi, lead, to an unu,ual1~ abundant C 4H. C1 · or C 4H, Br· ion in the speetra of !I-alkyl chlorides or bromides eontaiuing more than Ii"e carbon alom' (Figure, 3.B and .1.24 and lJnk nown ~.I). The ahundance, of ,he,e ion' are greatl}' lowered by chain branching and are negligible for flnorides and iodides. I'he" are ,ull'lantial dilTerentt' in alkyl balide 'pectra in regard to tbe pro_ portions of (M - nXj" and (M - Xl" ions formed b}' C-X cleavage; the former is accompanied by seeondary ions ch'm'etcri,tic "f an olefin. while the (M ions characteristieolly decompose further by losses of C.lI ' .' A promineut DE·' ion from the loss "fHX i' observod for fluorides and primary (lower ror n_alk )'1) ,md secondary ~hlori,lc, (Figur", 3.23 and Y.1l ,. Bond-dissociatioll energie, (Table '>",3) account for snch behavior: lhe RF- - II anJ Rei H bonJ, (fiDE ~ 5,6 and 4,6 eV!) "re ,tronger than the C-H bonds 14,3 e'v") in alkanes. making the hydrogen transfer H-CRX·· .... ·CRX· H energelically fa"orable, The formation of 1M - nxj" can be 'lmn gly innuence,l by (he prese"ce of olher fnnctionalities that "nect the C- H DDE's 01' introduce labile hydrogen alom, (see Hydrogen labiHly-, Seclion 8.10). 1,2-Remraugement of fluorine has also been identified (Morton e, "" 1989, 19901. For tertiary and aetivated (for example, allylic) chloride' and for bromide' IFigure 9.22) and iodide" the formalion "f(M - X)' and In","cT C.H,•• ,' IOn< generally is dominant. Electron bombardment can abo produce R- ions of unu,u"lly low "ppear:mce energy by "ion pair"' processes: R X -, R· + X-.
xt
.. 00-_.. . .
'"
!\!thoug b C) I..._, - ,p n, .~ 01, ign ifical1 t a flundance for lo w·mo'"" ln ·....,. hl of thi, tyl"'. ' M y cvmmoaty Jme by 10'" ofHX from C. H,.X· I"n. ([qua· Ii"" 4.45l Perhalo",naled aompIl.
~ ,.i
aI. 1992. C.... ,. m;n.n.'"
~ ,nolltos, .lld pc l r olcu m ~ I n U"",aJ such , )'stems a,t ald. to the ;nf" prncr. "oo ", ill I-.: much .... ,~ ~i l ua~ 10 you J1 you ha,-." good \>• •;0 und er' l.nding of tbe imcrprdahon p' ''"'''' ~ri l><
=
ph."""","" ,
avnilah lt Ill;,! it i, 'ol ' u" gly nnnnll>
..
,
10 .1 The 1llaU.1>.o. . 01 "le r• ...,. EI masa .pectta
The capabi lit;'. of a "'lrie>al algorithm depend dllrob . ... lbe q ual'ly aud ",,,,, p:rchentI,im wo rldwide. anI! there are no , igni"ca nl L~'I ""~ ins of ooe plOpllc la ry 'P'-",i ra no l included III In;', da lab . "". u..c..u ,", rhew m=II .......enl. "" •• !lttn made using a wide " aricl) of instr ument, ,,00 e ~pcrimL"JlI.1 ", ", di lion ~ the abundance valuc ' can ,'u y by m o r ~ th n an nNn- or ..... ~n ;l udc. To aId "'-;th thi, pm bltnt, all availa ble 'Jl"lCll a "r lh. .. me oon ,pouod ale ' ncl",kJ ; ~ lhe data ba,e; thi, has bcc~ hmd 10 rfilooe Ihe mil'a! .. n mg ,,~ 42~~ (Mcl.Wel1< w" ~ reca lled wit h lhe N [:" d. ,.. ba..e '..... us 36/~ ",ilh the Regisl ry, despne t be f. 2., lioles u mny p<J""ihle wrong aoswer. iMcLuflcrty f' "I. IW I h~
""".u,
Sati,,[:>ctor y ntJO.d"nl of all " " k n """ n and a .clen"""e 'J'>«'t 'urn co ns Tit ut es the fin ll1 proof of moJecuLo. ........ (;l ~ (Section 5.5). Howeve r, eva ln.'ll ion of l!lc Ic loobl~ ly (It such a n ioc.. ' i[ou'i oo mUst also con sid er th e Jimi(ati" n. rna.. <poe• •romeuy, p"ak-abtlnol) , m;oll num. ber I>f ~ ,'ai la b l e refe, ence comiJOurnk t.elrc lhrir c" ",,,,,rioon i, feas ible
"r
i"""".-.. ..
o~pertment a lly ,
raMin"I>rp"ra ,os ' he unique fe8 1 ~ m .;T com ponent> eM e.'.a!u:>I<J n alisticall)' tt> find out lhe ,..1u a l lel'a\JIlity 01 till,. ~ O
C. ... ,.tk 10.2 (Lon aod ~k l. a. lTcrty 199\). T lx""" repr-t'S Y 4~;' reliability bel. tho numbor ofincor roct m rirg,m;'; eom po~ nd . ~o nla i ni n g the common _Iement ' . II, C, N. 0 , ~ ,S,. r. s. Cl, Dr, and,im I, ~nd no ot h~rs. 1'" u'"' the infor mallon pm~iJcd b} lhe STl Rl> iy.lc-m. "ne . xamines lhe compo~"d, or the hc. t-malcll!ut """"""" . pn 1l;1 Ic uud for each dal" ~la .. .....J idcmif... tMir cOmmon . IT!Jc it> time requirom"'llI u e only ,.,.:c,n"" il 'h.; 1. t.-.r::~ "'lali .... to l he ohun _ dan.,,, or I"" I'..k, ... ± O_2?_~ rt!ath'e 10 lhe a""" d.""" of tho la rgest pea k ill tl>e ~pooct Nm. Pea kl or Imoll a bullda noc tb . t "' ere tbou i bt to be inoollscqumtial I" l he ""lul;' .n ,,( ,IIi. includ "" unimport ant pU b belo,", 1% I reIa,, ~ 10 t~e m""t abuooant pea k) a t rt... lo.. end 01 ~ v .... r ,,( ""~ ~ . or uni, In . . . ,. " ",. . I;'.n, ' " ,,' I~. I" ..'_m" " end or "f'OClrum I I Tn;, •• Ihe mil .. opectru" , of "'ater, If any re' " in Ihe sptcrru m W rTe,po,xh lO the man of ,be IIWJ"'UIe (thlt i:s. ,ool...ul,,, .... tim pal< murt be
'--ma.,
t""
;,,,'1-
~
". the ODe of b ighL"' l m,o " . T illi sp«:tr um, \110'«10. an d 20 ~ pr e se n t mon,," \om;" ~nJ .... u l>ly e ha , god 'l'\lL'k.." If" r c u mrJe. miz "' !iJ = 20), The r-:~h ~\ m/~ 11 u d 18 Me due t o} 'u ' " (Un k""wn I .I ~ m~" 44 i' di' cu, ,,,,d in Unk""", " 1.5, [l'l'" oll,;n, '''la, n. ~ r",n, ""'11:' ] 1 5 If lho ;solopie peah of rn a' .... 4.~ and % a. c iJlflorod, Ihe ba,e (1.\l a••I) I"'~L in tM "ll"lrum indicates a molerolar ..~'th1 '" 44, The major r-:al l 31 12 a nd II> inc hi" .. In In. le~t .hou ld lnd 10 lhoc " hocrn tion in T~hle 2.1 01 1M J!J ahu ndan", 11.1'0 ,of Ih ~ nalt" " l obk>n ... ' IOt OjX'!l, rna".. 35 and. 37, n..... lht spectrum i. ~ ",i"." ,, 01 H" O 811d H '''C~ in proportions CI). m.pood.ing I" the i",\o pic abunride 1
A,"
,11,.,
1"""''''''' ....
«>o'.,n
rna,,,,,
Ia,,.
2.2. lhe pc;\b a' m ~ ",ute O.Z"/, 10 lh~ proh bili(y 01an i'otopic "'it 66 pc" k. or wil h ~, a tOlal of 4. g~~ ap"~eiBl: ",011 "'i lll the o b'erved 5.00::';' Th< ma,,· :n dilTe"nc. between M · a nd " !> mig ht al' o be al silrned (0 CH . O . ~u t las wiDbe di""", ,,,,d in ~, ion ~) , llu . wouid c,m"" a 1.1 % oon lributioo I ~,/ . 6~ . whicn woo ld .... k~ Il ~ p1edictcd ~b u nd a n" . much too lu ",. ['Sulfur
»c
"c
Ji ,, ~l de]
f'C'l k ",.•~ due 10 C, H ,O" til< b\oe r\'fll ' ali" ratio would he ~-;. h om Ill. two \ """....(.o..(b nlor~ cl~ly I" lhat l"mdk led for tim'" ",,-[ boo atom" ' uch U in the iOll fo""ula ( ""H, ' How.v"" one should " lw"Y" he a", art 01 l h~ po6$ible oon lri .... ci"n rtom "b a "ky o u n d~ in the ;n' lr umenl" wbieh is much mo,e lild)' 10 a hiGh ("0' low; whi l) indicatio n Dr the Dumk l cl caTbo n alomo, O n tbe other hand, ;f an ' ''l~ en alom i' p"""nl in , he "l;·• •.H i" n. the.. ,hould br a o.2~,~ ~"ntTi t>uti atl to Ihe mi z 45 pea k due In C , H, " 0, unfort una tely. thi, i. j U'1 " " th" iimit of the ,,""',lule ~rro, a0;;", ..-ill be ."',cel hoe p robabilit y lh al 0""' o f lbe llSens of the mo lecule .. u " '0. Thus. 'wm T abk 2.2 the mi, 7{·'?2 ral;O _!KIllld be 004~.'; + ~ I,noes Q.2U:',.. ", l).44~_~ eh, eklng the O, j ~,~ fotlnJ The moJ~ c"J u r fOlmuh. un d .""", " f Ihe WA ... 1 ~ clementi i, ...1f...·."... J, I!'~...I tha ' these must be "l'P't".im. te:d hefore a calculatIOn for o. yI!"" "" n be made, T ile [mi. 1~ :\lI mi: 181J val of I ~. e ; indica,es C !J to C" (Ihe . ta red ""or limi' of ± 11:1;,; lneI> ' ha l •• 1 tile fan ge D,6 to 1 6 . 6~", m" ot be co lllid"t~d ), T he intcm ily ••1.... p<ediclN fot mil 1H4 fOT C ,, ---c .. :>.Ie 0.8, 0.9, 1. 1. and 1.3, respect;, ,,I, . if no " X),V"" i. pre.em , Experimmtally, ' hc ..I"" of [mit 184]'l P1!lr 1 ~ !] """ be (1.1) to \. 45, ;' lJo",i " g Inc fo rmulas C 12 0 "_" C" o,, _1. ( ',. 0.. ".nd C". How",,,,, (' ,,0, (ma.. 1 ~2~ c oo, {rna" 1SS), and C ..O lll1an 18 The uullkdy m" lccu.:" for mula C " II, (182 - 15 x 12 = 2). A,>ignill~ ~ ... " ckmcn", lhe remaining po,sibilitic, ~r" c.:" H, oN" C "B,. , C , .IH , f'. e n H ,~O. a nd C.. H ". Improved "'I',,,i",,-"1ll~1 acc" rAC)' or compmi--lion informa tion born 11.;, ' f'\:..1.I.1 pea h would be U""",.;u y 10 l .:tIt""l th;.
ltn rurtocL LC" H,oN., C" II ,., C,.H, F. C, ., H '00. C,. H..] 2.11. InlenK p,,,h fcllmc" b~ lhe 1o" of H , a re UUl\ ""'~ the " bM-1K'C or ~ n 1\1 - 3.1+ .."ulc J'C'l1< . .,."" ,,~>ence Ilf on. or mOle ,.'" .. r clemen.. •t..,ulI/r)Y', r . H.N··, .../z 7 1: C." . NO" m/: 86; C, H,Clflr ' . m"", ltlJ; C. H.OS · , "'.'z 124; C" r ,. ", ", it 1469; H,O I • m/: 19; and C, H.S;O · , rn,/' &9. 3.2, C 'QH" O · is an C1o' . '1.
O . Tbe rallo [mh W I![ m'; 97] i$ m lJundalUlO (1 3.6 0 ,8 - 1!J = 4,9) lS ron5lSlen. with ofld 10 )10:1-[)od-. AkIcr ~ "' ~ lor . - - *"'I'C'''' " Tt T1Ic 10. 11l"lbl..-.'t "'ir 16-1 • , lot 1l'Co>noi ' pecTnlIn ..
~,
~".
_
. . ""... ..
-"'-
0
00
4·Mel tl ~J- 2- pen l a ~ (Jne :
)
•
(ll.13)
4, J7, '-methyl.-
' '0
.J.-.-
. ,N
-"'-
0
II
•
~
{I I. H l
.,n
4./11. Tht " Wl'.."l moleculnr ion a t ...,'~ Dol (omaw. no "/I + r den'lt nl. (e"""p. ol~,. n h nJ I() or 11 c:lIl:>on . Il"",. wnml.lll witM C IoH ,.. Tilt W I ~·
' I"'ndlng r + dl> , al u. 014 i' Ihal e,pooled ror p/I. n~" : [hi. .. . uPf'l'ted I>y Ihe C, H, and C,H, m,illnment' for mi: 91 and 92.altd by 1M «a ro ma lic ion saiesw (So"' i,,,, .S.2), ,,,,,,,"Sling lh l Ih" mol:;,,\c i> a t :. H. C"H. ... omer_ v .... should lIa" e marked "'it 92, C,H" ... an important odd -deC]
(11.1 5)
4./ 9 MaSin 4 ~. 13, and 87 prob.,b1y M \'r 1-..0. fo al l?l, . 00 five .arbo n ..tom , ",,,,I>, "lid \h" , Ill ";1 In . "The '00 lC lon lSo" ;on S,2j ",i. -'1, 4 S, 59. n , 117 ... ~ l l a hk A ·f'I1 I h~1 an ~"'"H , ; lilt lad 01 1M _ l ~l · Rnd 1M - 29t ion! iodle" l"" Iha l 1lteIe IS no cha in hranch mg, (A o extra cllK ;. the l"et~'I ..bl" io n or mi. ~h.S ; .... Section 6.4. Fo' II.e lJam'; li" n "'/. I:\()_ I I 2 a metan ab k! would be exf"'CIed 31 mi" %.4; "..,", 129 ---0 112 -..oukl appear at mi; 97.0, bot would in"",I" e Ihe uDllkriy 1_ of 17 am ll,) [4-OctanolJ 4,20. AJpha-lh mi: 105 and 123 appear 10 contain , eyeD carbon atom. ,
"",nd>.
..
,
" , ....
_. -
" ""'-CI'~,---i.i-l-eM' 6H, ,
rrl z
+'"
y C-Jlt
'"
rri z sa
~, ~
Tbc Mi : 122 i , ,,[
~.
~n
que, ti ~na.bIt l. .. ell a. mi. 77 C.H , ' . T he abundance 0{ mi: I ~2 a >lahle molttular ion, in keeping with r + db '" 9, NoI iee th t the", ill a defuoi'$ m:emblance bet"" u n the . po.lra or u ~ ~ n"",·o, ~. I and 5.l; the pe.al« a l 39, SI, /)). ~o " n "'~I,'I.." t arn ma tle character. From The simpllcit y or Ihc "I'C'-'lJ"....... t he mulecu le ,h ould be generally nable, wil h o n~ 'If a fc,," hnds of mllch !li ~ h e r b bllit". T he "ompo,iti" m " f lhe majM fragment" C." , · and C, H,O ' , ... lKon "..mbin6 re-k, COllu in """ n lind ""en C atoms. consi, teo! wit h the f{lfm ""'" C, H.UO and C, H,ClO" (r + db = 5,5 an_I S ~ KO< C,H , - C HlC,ll. ,-, roltp. bu l lbLS '" rrnJu" im pro bable by th. low ah~ndan"e oi lM _ C, H. t ; lhat n . tile II" A.I» 11•• 1 tho ",n ..'ieo 11, 9 1, 105, 119, 133, 147, >nd 16 1 ' Cf'•..-:n'. y - (0 1, 1, ~ Ik .",", ouch a. Im ty acid , (Fi~uIe ~.YJ. [Oclyl""n,one] '.9. $.10. ~ im por lanl ou - ,o rio, C.H , , · · in Ih, \lllf"-T flMI 01 bolh ' p"111 W\l.IlC' h (T a hle , 5.1, A.6) thai the UnkOO....ni " Ie C.:'H ,. , .. C. H boll Y m o1t_ ....1.... ""Le lhe.. ,or io, in FiguIe, 3,5. ~. K, .1 14. . nd 3.21. 'I1>c: OIoJ): real di rkI.n"" is !he prese nce OJ';1 .. -t 4 in dox" """. in Unkoo",n 5.9 wm.,rn.;nll'" jz ~ L 45, 59, 73. aD «II odd nllm""" ..! n it , o~en atom,. The ab undam ion. of nell ....... . w:b ~. 102 9!l, and 78 co uld In Ihll ",.. y be "'en_cleotr",, ion o, T he ~ il!h ."" ndl noe of th,. postubled mo leeul", ;ll n ,"" \lId 01", be lelll ",il h lhe J rOO" UIC·In:>c ltm ....-ric•. Agoin, ,ovora l j, onte n a~ po."bk: of doc formu la C. H .N I" " " ph.. d "u ~1c ~ , nd, 7), and roforell ~ lpoctra w"Jd " " , ~ mure """,Ii ,. idtllllrlc,llLCIl. [1s oq " i n o~n e ] j .l 1. lbe-r, un: ",w T..1 . ign, tha I this com po und i. q"ile .NT" renl r",m lhe p,«>:d i,,!! 1m.,.,. .\1a, ,,",, 76, 69, 50, 3I, a ud 26 lmvc a "", Sll io,)n C . R 100 lor m ..... 14ll "" Ih" moJ""" la, iOD, AbLlnJanl pt~h oo r"",pondlDS I" (101 - C,H , l' I. "d 1M - CH ,t-1r . uU e' l Ill' , u b S lrt"~tu rc (; , H. -C_CII , O , fOl which a Iv;i""l ", ,,k'.;~ ,,, would be (C , H , ), C{~ H , Cl . H" " ,,ver, tile fOIDl Ir(M C , H, )' ] + [C,H, ' l~ St.'·. llSOn', Ruk O(>prJo ri incon, isl"nl with Iho "h, "r..o:d a bundances, sinu Ihe i"n i ,~ti"n or an alk yl radi. al , h"\lld be lo d by U ........it.. ' ioD. 1I0w",'. r, bot h C.H. ' " "d C, H, • ean be Ionn. d at 1:>1 """"ndary docompo. i· tio n.. aod t"c i""" ' ( H(C',II, lCH , CI "nd ' C HIC. H.\C.ll,C'l can un derS" I,....a. ill HC I and C', H , CI (' en""" b"""' lon ~ C, ".0' p"at indic,'.' th.u " , ) Il"n i , " l( a ~h o d to th. M g.1bo 1....1 Ihlt (M - ClIoCW i, m lll;" \.o, !",," IM O (M _ C11' is indi "",i "" Iobil< m . C'I il' 0u p; d C]'oll: a bl",d. ace, of Ih.l ~r ge pco.ks indiQtc lhe ekmcnlaJ "am· ""';1;' _ CI-I. N, C,H,!'!, C: , H" N, altd C. H ..N . Th_ .re consi' tent "..ith
i"""
"""'fry
n.c
. I)~ 11>e1. -.b,mld be ethyl and m elhy~ but 110 la'llet alkyl, aroup' on the ca rbon alOJIJl ' ) alph a 1 tho:; nil ro ~.n " lorn, H,,", c'-cr , m any ; '''mcTj~ C, H 1, N .min... til Ih... de""riplion . Th. lh,.. metastable ion peaks co, er, pon d to the decompo.iri un. 5 ~ I _ 3lJ' • 100' .• S ~ ·. and H6 ' --. 5H' _The m o.t "omm nn palh ",. ) C.H,. Io u from _ "h h un.. l« !ro n ions is l h. charge-sile rea,rang"mou! leOm On 4.44 in\'C)l~lll& c l .n~n 8 . ufth< C N b on d. Thu, the (M - C H , l' _ 4M_ C H ._ C , H.l' tn e!;on indi cate, lh. ,lnlclure CH , --C_ N __C , H" oIIxl 1M valh"", )'
r",
(1'.1
C, H, )' _ (M
C, H" -C , H.l ' in
N- C , H'" T he o nly C, H L , N i, o rner roDl llining bo th of Iht$e sII MINe"'.... ;. 1,NCII, CH,CH,. [ DiethyIprO(lyiantiDo]
tc.n,
6.1. (AI R, - K, - H, Y - II , ; (111 R, _ CH ,O. R, '" ca ; \' = HJ ; IC) R, _ CII ,O, R, _ CH" Y = 0; see Ilinnann 1% 2, p. .'OY, Th ~ peal< al
(M
~ ~J ' ;n A _nd H. a n'" 1M - 421' in C
", v
"
"''""
r:
J/
(
y
I,
~
-v
"
can t>r ~'rJ aintd "" 11 17.
_ rn H,~~V 11 1.17l
8.1. A , da li.d) abulldam (M _ 2)+ io n i, uu us ual iu moo, spoelra., SO lhe 164 /1 66 sho uld be cheeked 0111 a, Mp ploo. bly Ihu (M + I) ' ion (McLa fferty 1957b) and .. a pl'lo. imalcly ( ' , ,, flo{ ,. (In,." 1791 ,ncn co nlain, an odd nwn ba .>fni " ....g L"Tl .. ,om.. T h• ...iz 12(1 aoo 88 peab lon e ,'alues of 8 and 1, ""'l""'livdy. for lhei. mlU imulll number of c,u lxm atom,. Lo w-m"", peah ind ,cate 1M pl_n~ 01 ato mMOc ;,. ",I';llur ~..., J am ine (mi z 30) and oxygenaled r"l" 3 1.45) funOllt, nahtici. ... met hyl estel, - CO- OCH" i, a proba ble ~au ", tT . ble A,5) 01 the pea.. H;p,c'l(;nl;n s (M - 3 1)', (M - 321' , and (M - 59)',
-... _. ...._-_.
.....
'" mi.
I .... of , he IIl,,*"SI pe.Jb in lh. , peclrum.
~~
"nd 9l . cctlld arioe Ifom ctu""fe 01 ,he ""me "' ,nd (~ 8 + 91 _ 179); Iho mi: QI < a .c1< . ,~ "" p,od UcTS {OIl' 88 '" 12) t h",..g h hyd ro l!'"D ""alfao",m" D' I( q ualion 4.44t thi' would not "" l'O" ible wllb tM I"rtlary amino>; " and e. h .>G~ ' HC H I G H , 1,
,"
+-Y>"===CHGl6. (""" "' )
-
(1l,20J 1".-, 301
I h~, " ' honid giw weal< tIIi ; .lOand « pc. h . The ",/ lo r , h• • b undll nl >It/t 31, 45. Jnd 75 io ns, re,pc"ti ...~ y, T il....
m.l, 75 m""t ronl"'-D (" '0 fulKllon.:J ~ roup" ; tll«. i, no odd_eleot"'.. (M - IS)" ion w ind icale lha l ei1 l>cr" a "l'dr~ ,} sroup, The abundant CH , " . ,,"""" a C H,O moic1 y; ,d ali, " i,,,, 'lahiblies predict a low abundallCe ro. C H . " u..less il i. auached 10 an de c1 ron-J l traCl1n ~ ~w u p. Tho C H,O gro up ;'; prob:>b!j au"elled 10 CH , • • in"" il OaMol be par! 0( a C H , (X:HICH , l- VI C H , OCl C H., ), ..- gro up. If tm"e groupo \li . ~ r< . ~m.. tile aIIunJ,o....", OF lhe "'/: ~ 01 13 ioos, respectivd y, would he m..,-fI 8..... ler til. .. ;,; obsn" cd. J h. few ,,""" danl ;0", in lhe spectrum suU".;t . simpk mol ha , e se,,,,, carboo atom, afid two ,"Yt"" ato m,. '0 it eould be C~ II.O : , T1fip·p1Il6·d.....l:>lc-txm d' .alue _ 5, The ../: . )04 i,m J'O"i bly ha' ""von calOOo a\orn.. u J 1\ .ts tha llh. mole,uk con t~im an ndd numbtI " f nitroi en atoms. conli , ten! WIth th. C. H. N a,,;gurnenl of m,i: 54 (EE- . r + db _ 2~ Bt:cau.. "'iz 59 . <mla;n. ox)'g.n (c E ' , r + db = OJ.lhe moM lolli, a] as"1I1lffiem lor m,i: 84 is C. H.NO (EE' , ' + db .. 2~ and lh"" C , H, N O 10' M " ' rhe , ignifi, ant rna". 31 , 4.\ ,,00 j9 ;'1nl , uU ,,.,1 ( h ble A.N an ak" b"l m elt", lunc\lonM>ly, For "'i: 54 Table: A.6 lu,~lt l C,H.CN. an d the pre..""" of a nimle grou p would . 1", e' rlain the unu. uaJ (M - J)' anJ [M - 17)' ;0_ n.c "'i: -59 i"" il most likel, H OC(CH sl. - , CH ,OClI (C1I, )---. or C, H,OCH , - , in ~gl" " r (1.1 - I ~ l ' .. (M - 2'W . The ""IJ of 11J
". """,ma l•• mi. 177 a, the mol«ulu i<m, C , H, , NO, S. O ther odd ~ I" U ions au diffICult to idfmif)' \>" in m""I 11 6 T he 1M _. 731' i, expcelN (Eq u t,OI' 11 . 2~J far K_ CO OC , II , ....hen
-,.
l r*l,
R--c~ ,
1l.. .:t H:::.-cOClCA
R ' i••,. hili.red, " och .. ,"'cu,,,
(Dr
.. . ~
11 U ~)
" "I ,mno m;i ,h (Tab le A.S), The ,,~hle
It - al$O . """ uuh for Ibe lack of the e.p.",lc'\l (M - C,H . t · Mnd (M - C ,II ,,- ,
,Ii,
mu'JI h. w: a ma"$ of 177 102 _ 75. 3nd mu,1 "DOl "i n R_· CHi'; H,CO OC CH.,SCH, - , lt candidat, I'm , he M " . Compou~,l, , uel1 a, HOCII , C H, Oould beC ~ H . NOF " r ... db _ I. The unlll ua ltM - 211' ~' n mu. t be d ue III , he 1, .... of C , H, . nnt HCN , '" .. - I; Table A.5 ru U "'lO tllat an eth yl amide ,,,'uld """'...." I" , (~ - le radical ,pecic"~
\ (lUI)
(lUll
",'r 99
". ""i[h~r
of which " In abstract II byd",!!,," t tl give "',/: Y'I (C , H_O, ' ) l>y m"' i.._ Equ~l; "n Y.42. f or 1M I?·h lo d.ri" l flve. bo..." ',,r, .>-d ..... '. . or loc ","ake"l "" nd It ad' 10 lIIi: 99. 9,5, The i' N " p!C alm nJ ano;e, "I ll.e "', Z 1 ~ 4 ",d ICa l.. Ihe wmp indi ca, .. thal ;rn alkyl mo iet y i' al"" a\\,••:I...'" pt».iu""- is indiQl~ l>~ Ihe p;~l ~l ",i. 121,
ni,m, , imlla. to
•
•
(M - C H , - 11, 0 1- . The mfz 98 ,,1M!. pJ ."ti m~I:>I) , '17 l""ak lltjU,onlaill . ul!ur, and Ihus appd r~otlJ ...-c(M - (', H. - CO)" and (M C , R, C H()j' , con· -';, 1