!"#$%&'()*"*$ ,--*.'/0 12&*3$4.

'/ '5
6)'"#7%#&'"

LecLure 8
8#4-*/9:
LxperlmenL 8 of lab manual,
Zubrlck, chapLer 13 (recrysLalllzauon),
SmlLh, chapLer 10.13 (halogenauon of alkenes)
SmlLh, chapLer 29.8 (sLerolds)
2
Llplds are blomolecules LhaL are soluble ln organlc solvenLs.

1he ldenuLy of llplds ls dened on Lhe basls of a physlcal properLy
and noL by Lhe presence of a parucular funcuonal group.

Llplds share many properues wlLh hydrocarbons.
:*(*-7
3
SLerolds are a group of LeLracycllc llplds, many of whlch have
blologlcal acuvlLy.
SLerolds are composed of Lhree slx-membered rlngs and one
ve-membered rlng, LhaL are [olned LogeLher as drawn.
Many sLerolds also have meLhyl groups locaLed aL Lhe Lwo-rlng
[uncuons as shown called angular meLhyl groups.
;%#&'*-7
4
CholesLerol, Lhe mosL promlnenL sLerold, ls synLheslzed ln Lhe
llver and found ln almosL all cell membranes.
CholesLerol has elghL sLereogenlc carbons, so Lhere are
2
8
= 236 posslble sLereolsomers.
ln naLure, however, only Lhe followlng sLereolsomer exlsLs:
6)'"#7%#&'"

6#"" <#=>&4/#7

3
1he baslc unlL of llvlng organlsms ls Lhe cell.
1he cell membrane surrounds Lhe cyLoplasm, Lhe aqueous
medlum lnslde Lhe cell.
1he cell membrane acLs as a barrler Lo sLop Lhe passage of
lons and molecules lnLo or ouL of Lhe cell.
1he oLher [ob of Lhe membrane ls Lo allow nuLrlenLs ln and
wasLe ouL.
ln Lhls way, a cell membrane ls selecuvely permeable.
;%&2$%2&# '5 %)# 6#"" <#=>&4/#
6
7
CholesLerol ls essenual Lo llfe because lL forms an lmporLanL
componenL Lo cell membranes and ls Lhe sLarung maLerlal for all
oLher sLerolds.
6)'"#7%#&'"
8
Pumans do noL have Lo lngesL cholesLerol because lL ls
synLheslzed ln Lhe llver and Lhen LransporLed Lo oLher
ussues.
CholesLerol ls lnsoluble ln Lhe aqueous medlum of blood.
lL ls LransporLed Lhrough Lhe bloodsLream by llpoproLelns,
aggregaLes of phosphollplds and proLelns.
Low-denslLy llpoproLelns (LuLs) LransporL cholesLerol from
Lhe llver Lo Lhe ussues.
Plgh-denslLy llpoproLelns (PuLs) LransporL cholesLerol from
ussues back Lo Lhe llver.
6)#=*7%&? 4/- @*'$)#=*7%&? '5 6)'"#7%#&'"
9
lnLerlor conLalns Lrlacylglycerols and cholesLeryl esLers
(cholesLerol (an alcohol) LhaL has been esLerled wlLh a fauy
acld).
;%&2$%2&# '5 4 :*('(&'%#*/ 14&.$"#
10
LuLs deposlL cholesLerol on Lhe walls of arLerles when Lhey
carry more Lhan ls needed Lo form cell membranes.
1hls forms plaque, whlch resLrlcLs blood ow, Lhus, LuL
cholesLerol ls called bad cholesLerol.
PuLs reduce Lhe level of cholesLerol ln Lhe blood-sLream by
brlnglng excess back Lo Lhe llver, PuL cholesLerol ls called
good cholesLerol.
8ecommended levels are: PuL > 40 mg/dL, LuL < 100 mg/
dL, LoLal serum cholesLerol < 200 mg/dL.
@*'$)#=*7%&? '5 :*('(&'%#*/ 14&.$"#7
11
cross secuon of a clear arLery
wlLh no bulldup of plaque
cross secuon of an arLery LhaL
ls almosL compleLely blocked
by Lhe bulldup of plaque.
1"4A2# @2*"-2(7 */ ,&%#&*#7
12
Biosynthesis of Cholesterol
13
- 1he characLerlsuc reacuon of alkenes ls addluon-Lhe ! bond ls broken
and Lwo new " bonds are formed.
,--*.'/ 8#4$.'/7
- 8ecause alkenes are elecLron rlch, Lhey reacL wlLh elecLrophlles.
14
- Palogenauon ls Lhe addluon of x
2
(x = Cl or 8r) Lo an alkene Lo form a
vlclnal dlhallde.
Someumes used as proof of Lhe exlsLence of a
C=C group (see uehydrauon of Cyclohexanol)
B4"'9#/4.'/ C !"#$%&'()*"*$ ,--*.'/
'5 B4"'9#/
13
- Palogens add Lo ! bonds because halogens are polarlzable.

- 1he elecLron-rlch double bond lnduces a dlpole ln an approachlng
halogen molecule, maklng one halogen aLom elecLron declenL and
Lhe oLher elecLron rlch (x
#+
-x
#-
).
- 1he elecLrophlllc halogen aLom ls Lhen auracLed Lo Lhe nucleophlllc
double bond, maklng addluon posslble.
- 1wo facLs demonsLraLe LhaL halogenauon follows a dlerenL
mechanlsm from LhaL of hydrohalogenauon or hydrauon.
no rearrangemenLs occur.
Cnly anu addluon of x
2
ls observed.
1hese facLs suggesL LhaL carbocauons are noL lnLermedlaLes.
B4"'9#/4.'/ D#%4*"7
16
B4"'9#/4.'/ <#$)4/*7=
17
- Conslder Lhe chlorlnauon of cyclopenLene Lo aord boLh
enanuomers of !"#$%-1,2-dlchlorocyclopenLane, wlLh no cls
producLs.
- lnlual addluon of Lhe elecLrophlle Cl
+
from (Cl
2
) occurs from elLher
slde of Lhe planar double bond Lo form a brldged chloronlum lon.
;%#&#'$)#=*7%&? '5 B4"'/*2= E'&=4.'/
18
- ln Lhe second sLep, nucleophlllc auack of Cl musL occur from Lhe
backslde.
- Slnce Lhe nucleophlle auacks from below and Lhe leavlng group
deparLs from above, Lhe Lwo Cl aLoms ln Lhe producL are orlenLed
Lrans Lo each oLher.
;%#&#'$)#=*7%&? '5 B4"'/*2= 8*/9 F(#/*/9
:4> %)*7 G##H0 12&*3$4.'/ '5 6)'"#7%#&'"
lmpurlues ln
cholesLerol
8#4$.'/7 %)*7 I##H0
J2#7.'/70
Why does Lhls help purlfy cholesLerol?
WhaL ls Lhe sLereochemlsLry of Lhese reacuons?
Pow do we know Lhls?

20
K)# B4"'9#/4.'/ <#$)4/*7=
21
D#)4"'9#/4.'/ I*%) L/ =#%4"
Axlal leavlng groups are besL...why?
22
G)? 4 (#&*("4/4& 9#'=#%&?M
8ecause Lhe %&
3
" orblLals ln Lhe reacLanL C-P and C-x
bonds musL overlap and become p ! orblLals ln Lhe
alkene producL, Lhere musL also be some 'N#&"4( ln
Lhe Lransluon sLaLe.
;*=*"4&*%? %' ;
O
P &#4$.'/7
Cne can Lhlnk of L2 ellmlnauon reacuons wlLh
perlplanar geomeLry as belng slmllar Lo S
n
2 reacuons
wlLh 180
o
geomeLry.
<#%)'-7 '5 (2&*3$4.'/0
recrysLalllzauon
exLracuon (washlng wlLh sodlum hydroxlde)
drylng Lo remove waLer
<#%)'-7 '5 -#='/7%&4./9 (2&*%?0
color and LexLure of crysLals
melung polnL

<#%)'-7 '5 -#='/7%&4./9 *-#/.%?
melung polnL (compared Lo llLeraLure)
lnfrared specLroscopy

Also posslble, buL we won'L have ume:
nuclear magneuc resonance specLroscopy
mass specLromeLry
23
l8 SpecLrum of CholesLerol
26