211 F'l {) INTIIAI-S L Multiple Choice Questions: (30 pts, I pt each) Mark the correct ans$'er in the box

provided.
Linda Wrldman
1.

Chemistr"\,

Alcohol oxygen atoms are a) Arrhenius b) Bronsted-Lowf c)

Lewis

d) none ofthc above

2. Ifmolecule A has a greater waveleDgtfi ofabsorytion than moleculc B with the same molecular fbrmula in the UV-VIS spectluIn. which onc has more conjugated double bonds'l a) Molecule b) Moleculc c) Both are equally conjugated d) It is impossible to te11.

3. Which compound is not afl'ected bl spin splitting? a) isopropinol b) 1,2-dichloroethane c) Benzeniring. cl) cth-vlbc#ene
,1.

$l-icl- olrhe

r'1,

arC.H.

Br'\

lou irg ,Jompounds ha.

or(.ll : ot oll,O. /dra.H

lllD-!L4:-.o. have?

5. I !o*. many neighboring H does a hydrogen b) c),1 d) s

a;t2 3

*ith a triplet

6. Which compou[ds

will give a molecular ion having nr/z a)CH;CH:NH: b)CHTCLITOH c)CII3CO:I{

w
d) (cH:):NCII:C=N

an odd number?

rH NMR spectra? 7. Which compounds u,ouid be expected to show spin-spi[ splitting in their a) (CHI):COCH; b) (CHrrCqOCFlr c) BrCl l:Cll:Cll:Bt d) BICII:CIl:Br.
8.

@,, D

A compound is either cyclononane or cycloclecane. Which ol the following is the most

usef'ul

a) IR

spectroscopy

--.-,"-

i'

b)

mass spectrometrl,

r c; lH N\l[R d) ilc NlvlR

\

9. What is the multiplicity ofthe methylene h"vdrogens indicated in tbllowing cornpound? a) singiet

fie proton NMR ol

the

!lqge{!+ c) pentet\ 'i)iiplet oftriplets

r

g-*'i'"O
a

e) doublet of doublets

g u
t-Ft

fe),t l-

lo.What are the approximate intensities ofthe four lines in the quartet tom the ploton NMR ol diethyl ether, (CHTCH:):O? (Assume distofiiluiiLcqrurtet is ninirml.)

.r l:l:l I

br l:l:2

c, 2:J:.r2 Ldt- I i:,il /

lrl

11. The proton

NMR spectrum ofa compolrnd gives a singlet at 5 2.10 and 6 2.56 in Which compound beiow is the best match lbr the spectrum?

ratio of3:2, rcspcctlvcly.

z-4
a)
cH.rocH2ctl2ocHj
/..

-l r) b) clt:ccI:cH:ccl
ri

r)

b
t.r

lt -' c) CH3OCCH2CH2COCH:r
I

..

1/'

d)

*0'o ? CI t1CHzC CCH2CH]

Linda Waldman INITIALS Chemistry 211 F'10 protor 12. Which comoound bel below firs the lbllouing NMR data? Triplet 5 1.22 (3H) L) OCH, I Singlet 6 1.98 (3H) CH.CH.COCH, b) H2C:C Quartet 6 4.07 (2H)

cHr

),'

-)

d) CH3aoCH2CH3 rH NMR 01'a compour4 -gtrtocio, has the lollowiid peaks. 13. fhc Which I u11d belo$,best fits the data? broad singlet

r c)

'-?.:..
HO\
CH

CHrCClll2OCI Ir

()

'j
,cHroH l
CH,CH,OH

6 2.,11

(1H)

CH,CH,C a

,-CH3

b)

c)

triplet triplet
doublet doublet
1,1.

6 2.7s

(2H)

5 3.69 (2H)

5 7.02 (2H)

d 7.50 .-u

'r. ' It
(2Hl

D,'.:,

,., ,

,1r ,

Which ot'the 1bl1ou,ing describcs the spili-spin splitting oI lhe indicated H rH in the NMR ofthe compound shown belou,?

HO
H

:L.llslqL
O CI13

i --c) _dlqblel triplet

b)

of doublet!/

d)

doublet

oft

plets

-------

LH-IH spin-spin splilting is common. 15. ln proton NMR , \\ h\ i< hcrc no cnmparrhle iC-l'C .pin^p'n <pliring .n

l'C ha. a nuulcar ul'zeru. "; "pin b) The probability ol'two rlC nuclei being close to each other in a compound is very 1or'. c) The coupling constant is very small - too small to be obsened. d) There is IrC-rrC spin-spin splitting but because ofthe complcx splitting patterns
decoupling techdqucs are used to suppress

l't \VR.

o ]. ( a -^16. Which one of thc fbllou,ing isomeric CsH rs compounds has 1i\.e p.uf,,
in its NMR spectrum? a) octane b) 2-methylheptane

it-><

rlc

c) 3-methylhcptanc

1'd) 4-mcth-vlhcptane

17. what is the mulliplicity of the indicatcd carbon in nn off-resolancc dccouplcd L'( 1lr,'ff- <.onanc< decoupled spe. tra. dirccL - H couplir5 i. oh.er eJ.
r

rrC

NMR spectrum'l

H]C

i
CH-CH2_CH2OII
CH:

a) b) c) d) e)

singlct_ doublet / quartet multiplet jt is impossible to tell

Page 3

Linda Chemistrv 211 F''10 1lC 18. Which onc ofthc folloni comoounds fits the NMR

Waldman

INI'IIALS
cctrum shorn bclow?

a)

b)

c)
ltt

d)

e)

fl
None

ol

\ b')
t_ ,/
19.

these

(,

Ho$

man_v

(CHr2CHCH2CH(CH3)2 a) onc b)

U ;. i;: A

monochlorination products do you expect in the tbllo\.ving reaction?

two fE::i
C

C12

heat

--

------>

d)

four
,H

e) nvc

20. Which ofthe met-hods belou,would be most usei'u] in dislinguishing betueen the fbllowing two compounds?

lt
C_C
H

CLl3

t)J
and

HIC
C-C

III

a)

NMR

,'CH:

b)

HH

ll{

''c

Nun (, :

'., ,.

,-'

spectroscopy mass spectlomctrv

spectru1n?

Vl,.-

21. Wlich se es matches each steroid

belo\ \r,ilh its ltui, in its Uv-\,isible

(2)

a) 209 nm

b)

241

241 rr284 mn 206 nm

c) 284 mr
d),284 nm

.2Q[nm ' - ! 206 nm. ;;.',', r

284 nm

241 nm

Linda Waldman Chemistry 211 F'i0 22. Which ofthe lbllowing is the most stable radicai?

INITIAI,S
CH2CH2CH(CH1)2

cHrcH2c(c}lr)2 (H3CH.TCHCH) CHICHCH(CH3)2

aaao

q)-'

B, I to cH.
b)

||
t

Dr

wl

23. What is the dihedral bond angle ofthe ceniml carbon iElhe /e/t-butyl carbocation?

a)

60"

eo'

c) 10e.5"

{rf),

,i.ir),.,

24. Studies indicale that the methyl radical is trigonaLplanar. Based on this. u'hich oi'the 1b11o*ing bcst descrihes the rnelhvl radical? a) The carbonis sp2 h1'bridized ancl thc unpaired electron occupies an spz orbital. br lh< carbon i. +r hlbridi,,;d urd rhe unprired elecrro.r occLrp,es fl 'p nrb:rd'. "c1 I l^e carb,n i' sp h) bridi,,(d -nJ,he unpait'eo clccr-orr ncc.rpic. ar .n' orhiral. d) The carbon is sp3 hybridizcd and the unpaired electron occupies a 2p orbital.
25. \\''hich of the

lbllouing is the key inten]]edlate in the chlorination reaction belor'?

c,vclopcntane

f,

+ Cl2 - '->

heat

H
H

cldorocyclopenlane :

cr

i),
i,;,,r

)6 Which ofthe follouing mechanistically depicls the protonation of tcrt-but) I irl(ohol by hydrogen bromide?

rl

\( H

)rC-O:

..\ H-Br n-:

b) (

Hi)i(

-O:

..^\H:Br: f..

l A-l

c)

(cHr)rc

,11 (CH3);C-O:
H

l-. \\ .rat is .he IHD o. d conrJgllno u rth the nrolecular

a,

.l

ht

-l

/-t rl

d,

e,

-))' :rt: -__/ lornruta CoHl \Ol o8 s, o h) 10 i) 11 j)

-!

12

28. An isomer ofbutane is brominated and only one product is lbrmed, this product has only a singlet at 2.0 ppm in a rH NMR iment. Which comoound was brominated?

H:c-\u
CH2 CH3

2 fi'' i'
i..t

It is impossible lo lell liom the infomatlon

),i

ti )',,t,t.1,,
PJge 5

'

INITIALS Linda Chemistn 211 29. A compound has a molecul:r lbrmula, C4H802 (IHD=l), iahich sfuclure shown belo$,is colisistcnt with the lbllowing IR spectrum?

Waldman

F'10

'i)
3000

.')
1000

2oo0

,1500

."A-^""
a)

b)
has a molecular formuia, C,1H8O2

c)

d)

c)

30.

A compound

(IHD:1), $,lich structurc shown below is consistent

with the lbllowing NMR spectur?

3H

sjnglet singiet

Eingle:

!_/
11 'tt'rri 10 3 8 7 6 5 .+ l 3 2 1
l

f)

..,i
;c'-a)

ll

\o--b)

\",t, \c,
c)

*+
d)
e)

II

211 I'10 INfIIALS Matching: (10 pts, I pt each) Mark the corect ans\\.'er on the line provided.
Linda Waldman
1. ,^. researcher

Chemistry

rrc did the NMR ofthe tfuee compounds given be1ow, but forgot to 1abel the spectra, identify the conect compound to match thc ilfolmation providcd by thc spect1um.

NMR

L
A

a) reveals the presence or signals the absence

ofkey l'unctional groups.

b) gives the molecular weight and fornrula. both ofthe molecule itself and va ous stlLctural Lrnits within it.
c) gives inlbrmation on carbon skeleton and environments ofthe h),drogens attached to il.

MS

D
3. Matoh
a)

d) measures the molecular vibrations and rotations ofbonds in a molecule.

number

the words that best

b)

illtensily

lili

in the blanks. below:

c)

multiplicity
hor.v many

The The

of{signaL,gives an idea

ditlerent kind ofprotons there ffe.

ofa signal tells the relativc mtio ofthe diffcrent kind ofprotons.
/.1

The ;.-.,

ofa signal tells ho\r manv protons

are

vicinal to the one giving the signal.

ll

True/False: (10 pts, 1 pt each) lndicate whether each ofthe following statements is true (T) or t'aise (F) on the line provided.

{ "( -{

a.

lR spectroscopy uses $?velel'rgth or SI units ofliequency.

b. lR spectloscopy identifies the preseDce offunctional groups oforganic struclure.

c. IR spectra can be determined regardless ofthe physical state

rf
a

ofa samplc-

d. ln NMR, thc frequency does not depcnd on the strength ofthe magnetic 1ield.
c. lncrcasing the elccfonegativity ofatom attached to CH3 decreases the shielding ofthe methyl protons.
.

The le.s.\'elded

Lr

protun

i'.

the

l.r*er r\e chenical shih i.. '" "rid io

be dow,n.lel.l

g. The alcohol proton sl'iifts upfield ir, more conccntlated solutions.

.F

". \\'l-en: ploton is.aiJ i.r

b< .lrirloed. it

i. j.

l\4ore reactivc radicals are less selective.

In NMR speclroscop-v deuterium is shifted dou,nfield compared to hydrogen,

T,inda Waldman
1. (3

Chemistrl 211 F'10

INITIALS

lV. Short Answer Questions: (36 points, 3 points each)

pts) A compound $ith the molecular formula CBHI8 is characledzed by aTHNMR spectnurl that consists ofonly one singlet at 0.9 ppm. Draw the compound. lndicate ho$, ric NMR? many peaks do you expect to see in

(1r' +' a': '' t C.' Q-c"

'-

aii.,

c4'?,

2. (3 pts) Consider the follo\ving reaclion (X = C1 or Br). lisht

CHTCH2CHI

+ X2 ----:'-->

CIIICIJCH3

CH3CH2CH2

,x

lltmWhich -

stalement(s) is(arc) correct? Choose all that are correct. a) Statistically the 1-halopropane should be the major isomer.y' .3 I i b) The 2-halopropanc to lialopropane ratio is largest when X:Br.y' c) The 2-halopropanc to 1-halopropane ratio is the largest when X=Cl.

A oB

,1.

(l

pts) What is the complete colaect IUPAC name ofthe comoound beloq,?

cllrc C 2CH2C(CHrl
otT

Ji- l'''o

i:l'd

-2-h<,Yalidi
4 < C<
B

5. (3 pts)

Rank the following three compounds in order ofincreasing boiling point. a) CHTCHTCHT b) CtlrCHrOH c) CH3OCH3 ns in order

ti Z n,;a oftheir increasing stabilitics (lcast stablc first).

d
rearangement.

8.C.
producl that

A
Aom a

ses

8. (3 pts) Calculate the chemical shift ofa pcak that occurs 750.5 Hz downfield tehamethylsilane on a spectum recorded using a 200 MHz spechometer?

of

,-'14"..1 I

)' -')61,-.,,, -:* -/ -'tt )o:,. l0'

3 Y5w^

INITIAI,S Chemistry 21 1 F'10 I-inda Waldnran 9. (3 pts) Calculate the predicted yields for all ofthe uronohalogenatcd prcducts frnduced bLIZCX)"bromination of2.l- dimethylbutane. 1",,

('_ e

''L -

, '" ; -

2': 3o ,s

- t ) Z

--

-,.rodtci5

10. (3 pts)

lte molecular fornrula ol'a compound indicates 1 oxygen and has an lllD of onc. Circle the possible functional groups that are presenl and cross out those that are not possiblc from thc list provided below.
Alkene

alk\{e

befizene

alcohol

cthcr

aldehyde

ketone

ester

carhoxvliC acid l'

'i)
I

1 and 12. (6 pts) Predict the

NMR and coupled rrc NMR spectrum 1'or methyl ethanoate. Be sulc to indicate the relative heights of the split aeaks (i.e. 1 rl for a doublet) and the relative nunber of cquivalent resonances if applicablc.
rH

)o- /'> lndicate the correct answer in the space provided. 1. (9 points) Drarv the chain propag4Ao4-mechanism for the production ofthe major product ol'the light catalyzed reaction between bromine and 2-meth1.lpropane. (You need not sho$, the initiation or temination steps). Be surc to indjcate u,hich position is favored in bromination reaclions, by your predictior o-tl'c rra.i." rrodr!

'3 -,@p/n .:) pp,"\ l-ong Answer Questions: (27 points)

1(0

4o'Go

ilIr

:,8rr ' ,l

:.

t' AL^, ";1_,_CH,

t' Y

,,

-= ll-3r:+ rr
'

rl.

,(:-Ch,
Y
:

ltr, C l'

Cttz z-^\ \,e I ,--.l '; -, l + ',Br- q, f Ll_ C a\.-''3

'ds

\ H '..
,

Cil,
od

cil,

't

!4r1 + "BrI / ;. ;; e/^T

'u

tr,

Page 9

Linda Waldman

Chemistry 21

F'l0

INITIALS

2. (,l polnts)

a)

Choose one ofthe following and explain it. Why do protons in difl'ere11t environments u.ithin a molecule havc dift'crent chemioal shilis?

b)

,,\11

,:l

::" ,%-',"' 2' "*; &i*

,1 *. '4t a .u"la'/ (;tlvl
",^.- /t/,.1
" .*/,h",1
9

:ffi /:i,rf.:ln:'#
''v

{krpt,,,Sd,lL,.,\, ur.,../.rr'i .

carbocations. lll NMR spectrum. once a substiluent is the prolons ofcyclohexane appcar to bc equivalent in the -vet added, the axial and equatodal protons appcar diffcrently iu the spectrum; this is pafticularly pronounced r.rhen the substituent is very large such as t-butyl. What causes dlis difference?

z'/--'/

1.'1

-'t

':!a"i;' --

*t, "n' f6 1 b;f /'r, r.,* lr ' '-'r-4/q J u,,rrn .J ^,i ,-L) /; c-'o"' ,rJ ucz'/,''J , t,l /lo, "--, ('J/t,'
',1

,,," ^' -^c _:/:r,r-ff_"j,,jir7, '{t's -r./a"*rl lz,.tzr z/i"l

"
L^1

u.

k,-a

/i L,:. -v;aa -L)24 -a<' -i/li-' ,,7 l/n '*7-i*?t,r:,.( ft/ * .v*J 0',t- ! '1k14,4 " . t( 0"t'! ry"'* -/ltty,,z -y, 2 2-y,"t( .", ,) -;;r"' .., ,r" 4" ttf :(.' '
(
.

:::i: *:'fi1,.'I.o', tt//4 'zt't '* -/ ,

't
-'
ci

/j; ,,',/'n'!,4'$/A

nlt,, Z'trJtd

tt -"a

fu7

Cra./t1tr/4

- . b,
,2a un

;< '' c;

P"s' ro