3.

1MassSpect
roscopy
Whenexposedt
osuf
fi
cientener
gy,amol
ecul
emayl
oseanel
ect
ront
ofor
ma
cat
ion-
radi
cal
,whi
ch t
hen may under
go f
ragment
ati
on of bonds.These
pr
ocessesmakemassspect
roscopy(
MS)ausef
ult
oolf
orst
ruct
urepr
oof
.Ver
y
smal
lconcent
rat
ionsoft
hepar
entmol
ecul
es(
R:S)
,int
hev
aporst
ate,
arei
oni
zed
byabeam ofener
get
icel
ect
ronse-.

andanumberofpar
entcat
ion-
radi
cal
s(R.S+)mayt
henf
ragmentt
ogi
veot
her
cat
ionsandneut
ral
speci
es.Fr
agmenti
onscanunder
gof
urt
herbond-
cleav
aget
o
gi
veev
ensmal
l
ercat
ionsandneut
ralspeci
es.I
namassspect
rogr
am,shar
p
peaksappearatt
hev
aluesofm/
e(t
hemass-
to-
char
ger
ati
o)f
ort
hev
ari
ous
cat
ions.The r
elat
ive hei
ght
s(i
ntensi
ti
es)oft
he peaks r
epr
esentr
elat
ive
abundancesoft
hecat
ions.Mostcat
ionshav
eachar
geof+1,andt
her
efor
e
mostpeaksr
ecor
dthemassesoft
hecat
ions.Fr
agment
ati
ont
endst
ogi
vet
he
mor
est
abl
ecat
ions.Themostabundantcat
ionsar
ethemostst
abl
eones.

Thest
andar
dagai
nstwhi
chal
lpeaki
ntensi
ti
esi
nagi
venmassspect
rogr
am ar
e
measur
edi
sthemosti
ntensepeak,cal
l
edt
hebasepeak,whi
chi
sar
bit
rar
il
y
assi
gned t
he v
alue 100.I
ffew par
entmol
ecul
es f
ragment
— nota t
ypi
cal
si
tuat
ion—t
hepar
entcat
ionwi
l
lfur
nisht
hebasepeak.

Unl
essal
lthepar
enti
onsf
ragment
,whi
chr
arel
yhappens,t
hel
argestobser
ved
m/
eval
ue i
sthe mol
ecul
ar wei
ght of t
he par
ent (
RS) mol
ecul
e.Thi
s
gener
ali
zat
ion ov
erl
ookst
hepr
esenceofnat
ural
l
yoccur
ri
ng i
sot
opesi
nthe
par
ent
.Thus,
thechancesoff
i nga13Cat
ndi om i
nanor
gani
cmol
ecul
ear
e1.
11%;
t
hechancesoff
indi
ngt
woar
enegl
i
gibl
e.Ther
efor
e,t
hei
nst
rumentdet
ect
sa
lpeakatmRS+1,
smal owi
ngt
othe13C-
cont
aini
ngpar
ent
.Thechancesoff
indi
ng
2Hi
namol
ecul
ear
enegl
i
gibl
e.
Themassesandpossi
blest
ruct
uresoff
ragmentcat
ions,especi
all
ythemor
e
st
abl
e ones,ar
e cl
ues t
othe st
ruct
ure oft
he or
igi
nalmol
ecul
e.Howev
er,
r
ear
rangementofcat
ionscompl
i
cat
est
hei
nter
pret
ati
on.Massspect
ra,
li
keot
her
spect
ra,
areuni
quepr
oper
ti
esusedt
oident
if
yknownandunknowncompounds.

Pr
obl
emsf
orMassSpect
romet
ry

1.Acompoundwi
thmol
ecul
arf
ormul
aC4H8Ohasast
rongI
Rabsor
pti
onat1730
cm-1.I
tsmassspect
rum i udeskeypeaksatm/
ncl z44(
thebasepeak)andm/
z
29.Pr
oposeast
ruct
uref
ort
hecompoundandwr
it
efr
agment
ati
onequat
ions
showi
nghowpeakshav
i hesem/
ngt zval
uesar
ise.

2.I
nthemassspect
rum of2,
6-di
met
hyl
-4-
hept
anolt
her
ear
epr
omi
nentpeaksat
m/
z87,
111,
and126.Pr
oposer
easonabl
est
ruct
uresf
ort
hesef
ragmenti
ons.

3.I
nthemassspect
rum of4-
met
hyl
-2-
pent
anoneaMcLaf
fer
tyr
ear
rangement
and t
wo ot
hermaj
orf
ragment
ati
on pat
hway
s occur
.Pr
opose r
easonabl
e
st
ruct
uresf
ort
hesef
ragmenti
onsandspeci
f hem/
yt zval
uef
oreach.

4.Whatar
ethemassesandst
ruct
uresoft
hei
onspr
oducedi
nthef
oll
owi
ng
cl
eav
agepat
hway
s?

(
a)a-
cleav
ageof2-
met
hyl
-3-
hexanone(
twopat
hway
s)

(
b)dehy
drat
ionofcy
clopent
anol

(
c)McLaf
fer
tyr
ear
rangementof4-
met
hyl
-2-
oct
anone(
twopat
hway
s)

1
5.Pr
edi
ctt
hemassesandr
elat
ivei
ntensi
ti
esoft
hepeaksi
nthemol
ecul
ari
on
r
egi
onf
ort
hef
oll
owi
ngcompound.

6.Et
hylbr
omi
deandmet
hoxy
benzene(
shownbel
ow)hav
ethesamenomi
nal
mol
ecul
arwei
ght
s,di
spl
ayi
ngasi
gni
fcantpeakatm/
i z108.Regar
dingt
hei
r
mol
ecul
ari
ons,whatot
herf
eat
ureswoul
d al
l
ow t
het
wo compoundst
o be
di
sti
ngui
shedont
hebasi
soft
hei
rmassspect
ra?

7.Thehomol
ogousser
iesofpr
imar
yami
nes,CH3(
CH2)
nNH2,f
rom CH3NH2 t
o
CH3(
CH2)
13NH2 al
lhav
ethei
rbase(
lar )peakatm/
gest z30.Whati
ondoest
his
peakr
epr
esent
,andhowi
sitf
ormed?

8.Whi
choft
hesei
sat
ruest
atementconcer
ningmassspect
romet
ry?(
Ther
e
maybemor
ethanone.
)
a)TheM+peaki
( sal
way
sthemostpr
omi
nent(
l gestm/
ar z).
(
b)Onl
yli
qui
dscanbeanal
yzedbyMS.
(
c)Unl
i
keI
RandNMR,
MSi
sadest
ruct
ivemet
hodofanal
ysi
s.
(
d)Themol
ecul
ari
oni
sassi
gnedav
alueof100ont
hev
ert
ical
scal
e.
(
e)Thei
nit
ial
eventi
nthedet
ermi
nat
ionofamassspect
rum i
ntheEImodei
sthe
f
ormat
ionofar
adi
cal
cat
ion.

9.Whati
sthest
ruct
ureofacompoundC5H12whi
chexhi
bit
sapr
omi
nentMS
peakatm/
z57?

2
10.A l
ow-
resol
uti
on mass spect
rum oft
he al
kal
oid Vobt
usi
ne showed t
he
mol
ecul
arwei
ghtt
obe718.Thi
smol
ecul
arwei
ghti
scor
rectf
ort
hemol
ecul
ar
f
ormul
asC43H50N4O6andC42H46N4O7.Ahi
gh-
resol
uti
onmassspect
rum pr
ovi
ded
amol
ecul
arwei
ghtof718.
3743.Whi
choft
hepossi
blemol
ecul
arf
ormul
asi
sthe
cor
rectonef
orv
obt
usi
ne?

11.At
etr
amet
hyl
tr
iacet
ylder
ivat
iveofOr
egoni
n,adi
ary
lhept
anoi
dxy
losi
def
ound
i
nredal
der
,wasf
oundbyl
ow-
resol
uti
onmassspect
romet
ryt
ohav
eamol
ecul
ar
wei
ghtof660.Possi
ble mol
ecul
arf
ormul
as i
ncl
ude C32H36O15,C33H40O14,
C34H44O13, C35H48O12, C32H52O14, and C33H56O13. Hi
gh-
resol
uti
on mass
spect
romet
ryi
ndi
cat
edt
hatt
hepr
eci
semol
ecul
arwei
ghtwas660.
278.Whati
s
t
hecor
rectmol
ecul
arf
ormul
afort
hisder
ivat
iveofor
egoni
n?

12.Anunknownsubst
anceshowsamol
ecul
ari
onpeakatm/
z=170wi
tha
r
elat
ivei
ntensi
tyof100.TheM +1peakhasani
ntensi
tyof13.
2,andt
heM +2
peakhasani
ntensi
tyof1.
00.Whati
sthemol
ecul
arf
ormul
aoft
heunknown?

13.Anunknownhy
drocar
bonhasamol
ecul onpeakatm/
ari z=84,wi
tha
r
elat
ivei
ntensi
t 3.TheM +1peakhasar
yof31. elat
ivei
ntensi
tyof2.
06,andt
he
M +2peakhasar
elat
ivei
ntensi
tyof0.
08.Whati
sthemol
ecul
arf
ormul
afort
his
subst
ance?

14.Anunknownsubst
ancehasamol
ecul
ari
onpeakatm/
z=107,
wit
har
elat
ive
i
ntensi
tyof100.Ther
elat
ivei
ntensi
tyoft
heM +1peaki
s8.
00,andt
her
elat
ive
i
ntensi
tyoft
heM +2peaki
s0.
30.Whati
sthemol
ecul
arf
ormul
afort
his
unknown?

15.Themassspect
rum ofanunknownl
i
qui
dshowsamol
ecul
ari
onpeakatm/
z
=78,
wit
har
elat
ivei
ntensi
tyof23.
6.Ther
elat
ivei
ntensi
ti
esoft
hei
sot
opi
cpeaks
ar
easf
oll
ows:

m/
z=79 Rel
ati
vei
ntensi
ty=0.
79

3
7.
55 80

0.
25 81

Whati
sthemol
ecul
arf
ormul
aoft
hisunknown?

16.Assi
gn ast
ruct
uret
hatwoul
d beexpect
ed t
o gi
ver
iset
o each oft
he
f
oll
owi
ngmassspect
ra.

Exampl
e:Anunknowncompoundhast
hemassspect
rum shown.Thei
nfr
ared
spect
rum oft
heunknownshowssi
gni
fi
cantpeaksat(
3102,3087,3062,3030,
1688,1598,1583,1460,1449,1353,1221,952,746,691cm−1)
.Ther
eisal
soa
bandf
rom al
i
phat
icC-
Hst
ret
chi
ngf
r o2979cm−1.
om 2879t

Sol
uti
ont
oExampl
e:

1.Themol
ecul
ari satan m/
onappear zval
ueof134.Appl
yi
ngt
heRul
eof
Thi
rt
eengi
vest
hef
oll
owi
ngpossi
blemol
ecul
arf
ormul
as: C10H14 U=4
C9H10O U=5

.
2 Thei
nfr
aredspect
rum showsaC=Opeakat1688cm-1.Theposi
ti
onoft
his
peak,
alongwi
tht
heC-
Hst
ret
chi
ngpeaksi
nthe3030–3102cm-1r
angeandC=C
st
ret
chi
ngpeaksi
nthe1449–1598cm-1 r
ange,suggest
saket
onei
nwhi
cht
he
car
bony
lgr
oupi
sconj
ugat
edwi
thabenzener
ing.Suchast
ruct
urewoul
dbe
consi
stentwi
tht
hesecondmol
ecul
arf
ormul
aandwi
tht
hei
ndexofhy
drogen
def
ici
ency
.

3.Thebasepeaki
nthemassspect
r satm/
um appear z=105.Thi
speaki
sli
kel
y

4
duet
othef
ormat
ionofabenzoy
lcat
ion. Subt
ract
ingt
hemassoft
he
benzoy
lion f
rom t
he massoft
he mol
ecul
ari
on gi
vesa di
ff
erence of29,
suggest
ingt
hatanet
hylgr
oupi
sat
tachedt
othecar
bony
lcar
bon.Thepeak

appear
ingatm/
z=77ar
isesf
rom t
hepheny
lcat
ion.

4.I
fweassembl
eal
loft
he“
pieces”suggest
edi
nthedat
a,asdescr
ibedabov
e,
weconcl
udet
hatt
heunknowncompoundmusthav
ebeenpr
opi
ophenone(
1-

pheny
l-
1-pr .
opanone)

Probl
em 16(
conti
nued)Assi
gnast
ruct
uret
hatwoul
dbeexpect
edt
ogi
ver
iset
o
eachoft
hefoll
owi
ngmassspectr
a.

(
a)The i
nfr
ared spect
rum hasno i
nter
est
ing f
eat
uresexceptal
i
phat
icC‫ـ‬
‫ـ‬
H
st
ret
chi
ngandbendi
ng.

(
b)Thei
nfr
aredspect
rum hasamedi
um-
int
ensi
typeakatabout1650cm−1.
Ther
eisal
soaC‫ـ‬
‫ـ‬
Hout
-of
-pl ngpeaknear880cm−1.
anebendi

5
(
c)Thei
nfr
aredspect
rum oft
hisunknownhasapr
omi
nent
,br
oadpeakat3370
cm−1.Ther
eisal
soast
rongpeakat1159cm−1.Themassspect
rum oft
his
unknowndoesnotshow amol
ecul
ari
onpeak.Youwi
l
lhav
etodeducet
he
mol
ecul
arwei
ghtoft
hisunknownf
rom t
heheav
iestf
ragmenti
onpeak,whi
ch
ar
isesf
rom t
hel
ossofamet
hyl
groupf
rom t
hemol
ecul
ari
on.

(d)Thisunknowncontai
nsox
ygen,buti
tdoesnotshowanysi
gni
fi
canti
nfr
ared
-
1
absorpti
onpeaksabov
e3000cm .

6
(
e)Thei
nfr
aredspect
rum oft
hisunknownshowsast
rongpeaknear1725cm−1.

-
1
(
f)Thei
nfr
aredspect
rum oft
hisunknownshowsast
rongpeaknear1715cm .

7
(g)Theinfr
aredspectrum ofthi
scompoundl acksanysi
gni
fi
cantabsor
pti
on
−1
above3000cm .Ther eisaprominentpeaknear1740cm−1andanot
herstr
ong
−1
peaknear1200cm .

(h)Theinf
rar
edspectrum ofthissubst
anceshowsav er
ystr
ong,br
oadpeakin
−1
therangeof2500–3000cm , aswellasastr
ong,somewhatbr
oadenedpeakat
−1
about1710cm .

(
i)The13CNMRspect
rum oft
hisunknownshowsonl
yfourpeaksi
nther
egi
on
125–145ppm.Thei
nfr
aredspect
rum showsav
eryst
rong,
broadpeakext
endi
ng
f
r o3500cm−1,
om 2500t aswel
last
rongandsomewhatbr
oadenedpeakat1680
cm−1.

8
(
J)Not
etheoddv
alueofmassf
ort
hemol
ecul
ari
oni
nthi
ssubst
ance.

(
k)Not
icet
heM +2peaki
nthemassspect
rum.

(
l)Thei
nfr
aredspect
rum oft
hisunknownshowst
wost
rongpeaks,onenear
1350cm−1andt hernear1550cm−1.Not
heot icet
hatt
hemassoft
hemol
ecul
ar

9
i
oni
sodd.

(m)Thereisasharppeakofmedi
um i
ntensi
tynear2250cm−1 i
nthei
nfr
ared
spect
rum oft
hiscompound.

(
n)Consi
derthefr onsatm/
agmenti z=127and128.Fr
om whati
onsmi
ght
t
hesepeaksari
se?

10
(
o)

(
p)

(
q)

11
(
r)

(
s)Thei
nfr
aredspect
rum oft
hi ppeakat3087cm−1and
sunknownshowsashar
p peakat1612 cm−1 i
ashar n addi
ti
on t
o ot
herabsor
pti
ons.Theunknown
cont
ainschl
ori
neat
oms,
butsomeoft
hei
sot
opi M +n)ar
cpeaks( etooweakt
o
beseen.

12
I
ntegr
atedpr
obl
ems

13
14
15
16
17
18
19
Appendi
xA:
Conceptmapf
orOr
gani
cfunct
iongr
oupsandI
nfr
aredspect
roscopy

20
Appendi
xB:
Conceptmapf
or1HNMRspect
roscopy

Appendi
xC:
Conceptmapf
or13CNMRspect
roscopy

21
Exer
cise:
Nomencl
atur
ePr
obl
emsf
orhet
erocy
cli
cCompounds
Expl
ainhowcany
ounamet
hef
oll
owi
nghet
erocy
cles?
1. ………………………………………………………………………………
………………………………………………………………………………

2. ………………………………………………………………………………
………………………………………………………………………………

3- ………………………………………………………………………………
…………………………
4- ………………………………………………………………………………
………………………………………………………………………………

5- ………………………………………………………………………………
………………………………………………………………………………

6- ………………………………………………………………………………
………………………………………………………………………………

7- ………………………………………………………………………………
…………………………

8- ………………………………………………………………………………
…………………………

9- ………………………………………………………………………………
…………………………

22
10- ………………………………………………………………………………
………………………………………………………………………………

11- ………………………………………………………………………………
………………………………………………………………………………

12- ………………………………………………………………………………
…………………………

13- ………………………………………………………………………………
…………………………

14- ………………………………………………………………………………
………………………………………………………………………………

15- ………………………………………………………………………………
………………………………………………………………………………

16- ………………………………………………………………………………
………………………………………………………………………………

17- ………………………………………………………………………………
………………………………………………………………………………

18- ………………………………………………………………………………
………………………………………………………………………………

19- ………………………………………………………………………………
…………………………

23
20- ………………………………………………………………………………
………………………………………………………………………………

21- ………………………………………………………………………………
…………………………

22- ………………………………………………………………………………
…………………………

23- ………………………………………………………………………………
…………………………
24- ………………………………………………………………………………
………………………………………………………………………………

25- ………………………………………………………………………………
…………………………

26- ………………………………………………………………………………
………………………………………………………………………………

27- ………………………………………………………………………………
…………………………

28- ………………………………………………………………………………
…………………………

29- ………………………………………………………………………………
…………………………

30- ………………………………………………………………………………
…………………………

24
31- ………………………………………………………………………………
…………………………

32- ………………………………………………………………………………
…………………………
33- ………………………………………………………………………………
………………………………………………………………………………

34- ………………………………………………………………………………
…………………………

35- ………………………………………………………………………………
…………………………

36- ………………………………………………………………………………
…………………………

37- ………………………………………………………………………………
………………………………………………………………………………

38- ………………………………………………………………………………
………………………………………………………………………………

39 ………………………………………………………………………………
…………………………

40 ………………………………………………………………………………
…………………………

41- 4H-
Imi
dazo[
4, d]
5- t
hiazol
e

42- 4H-
3,1-
Benzoxazi
ne

43- b]
Benzo[ f
uran

25
44- 5H-
Pyr
ido[
2, d]
3- o-
- ox
azi
ne

45- Thi
eno[
2, b]
3- f
uran

46 1-Et
hyl-
1,4-
dihydro-
7-met
hyl
-4-
oxo-
1,8-
naphthyr
idi
ne-3-car
boxyl
i
cacid

REFERENCES

1.Wi
l
li ownandThomasPoon,I
am H.Br ntr
oduct
iont
oOr
gani
cChemi
str
y,6th
edn,
JohnWi
l
ey&SonsI
nc.
,NewJer
sey
,2016.

2.Gr
aham Sol
omons,Cr
aigB.Fr
yhl
e,andScot
tA.Sny ,Or
der gani
cChemi
str
y,
11thedn,
JohnWi
l
ey&SonsI
nc.
,NewJer
sey
,2013.

3.Pav
ia,Lampman,Kr
iz,andVy
vyan,I
ntr
oduct
iont
oSpect
r ,5th edn,
oscopy
2010.

4.Her
ber
t Mei
sli
ch, Howar
d Nechamki
n, Jacob Shar
efki
n, and Geor
ge
Pr
Hademenos, obl
em Sol
vedOr
gani
cChemi
str
y,4thedn,
Schaum I
nc.
,2013.

5.Dav
id Kl
ein,Or
gani
cChemi
str
yasa second l
anguage,second semest
er
t
opi 4thedn,
cs, JohnWi
l
ey&SonsI
nc.
,NewJer
sey
,2016.

26