Orgo 2 Lab Review

Nick Merrill
Thursday, May 3
rd
8 pm LC !"
# hope $his helps a%d bes$ o& luck''
Make sure you k%ow all o& $he sa&e$y rules a%d regula$io%s o%
page 8()8*+
Experiment 7: Sn1 and Sn2 Rxns:
Make sure you u%ders$a%d $he basics behi%d ,% a%d ,%2
reac$io%s
# would $ry a%d skim over $he sugges$ed readi%gs as # ca%
see him aski%g -ues$io%s &rom $hem+
Mai% purpose o& $his lab was $o s$udy $he rela$io%ship o&
s$ruc$ure a%d reac$ivi$y i% %ucleophilic subs$i$u$io% reac$io%s
by $es$i%g reac$ivi$y+
#% $hese reac$io%s a nucleophile is used $o displace a
leaving group+
#% ge%eral.
R)/ 0 Nu
)
1 R)Nu 0 /
)
2lkyl halide reac$iva$es depe%d o% bo$h reac$io%
co%di$io%s a%d subs$ra$e s$ruc$ure
,%2 is a o%e s$ep direc$ displaceme%$ process whos ra$e
o& reac$io% depe%ds o& bo$h co%c o& alkyl halide a%d
%ucleophile+
,% is a $wo s$ep process wi$h a carboca$io% i%$ermedia$e
whos reac$io% ra$e o%ly depe%ds o& co%c o& carbo ca$io%
&ormed+
Order o& reac$ivi$y.
,%. 3323
o
,%2. 3233
o
Sn2: 4se ace$o%e because i$ is a %o%)pro$ic a%d rela$ively %o%)
polar solve%$ a%d #odi%e is a% e5celle%$ %ucleophile+
The #odo sal$ is soluble, bu$ whe% a subs$i$u$io% occurs,
$he resul$i%g bromo or chloro sal$s are %o$ soluble+
Sn1: 4se silver %i$ra$e a%d e$ha%ol+ 6$O7 is a pro$ic a%d
modera$ely io%i8i%g solve%$ a%d $he %i$ra$e io% is a poor
%ucleophile+
Look over $he reac$io%s o% pg 89+
2roma$ic compou%ds like a%d are
u%reac$ive &or bo$h ,% a%d ,%2 r5%s+
Co%:uga$ed molecules such as or
reac$ &as &or ,% a%d ,%2 r5%s+
The precipi$a$io% o& a produc$ &rom solu$io% will drive $he
reac$io% $oward $he produc$s a%d also serves a a visual
i%dica$io% o& $he reac$io% a%d i$s ra$e+
Exp 8: The Diels-Alder Reaction
;asic reac$io%.
<!02= co%cer$ed cycloaddi$io% reac$io%
The reac$io% is s$ereospeci&ic
#$>s a peri)cyclic reac$io%, where i$ is a reac$io% $ha$ i%volves a
cyclic rearra%geme%$ o& bo%di%g elec$ro%s+ ;o%ds are broke%
a%d &ormed simul$a%eously+
O%e s$ep reac$io%
This is why $he reac$io% is s$ereospeci&ic, $he subs$i$ue%$s do%>$
have $ime $o swi$ch arou%d+
The <!02= is $hermally allowed, $ha$ a ! elec$ro%s o& o%e ca%
reac$ wi$h 2 elec$ro%s o& a%o$her
2 <202= is &orbidde%
This reac$io% is.
2)3 drops o& a-u 7Cl ac$s as a ca$alys$ i% $he hydrolysis o& $he
cyclic a%hydride+ ,eco%d s$ep o& $he r5%+
No$e. 7ydrolysis ca% also $ake place i% prese%ce o& base as
ca$alys$+ #% $his case a&$er hydrolysis you %eed $o acidi&y $he
produc$ $o ob$ai% $he acid+
Look a$ $he #R spec$rums care&ully a%d %o$e wha$ peaks
sig%i&ies $he produc$+ ?%ow how $o $ell $he di&&ere%ce be$wee%
$he a%hydride a%d $he &i%al diacid produc$+ @ou ca% see a
di&&ere%ce is $he carbo%yl peak+ #$ will shi&$ &rom abou$ *93
cm) &or $he es$er a%d A9 &or $he carbo5 acid+ @ou will also
see a carbo5 O7 peak+
Exp : The E1 Reaction
Two mai% pa$hways e5is$ $o prepare alke%es by elimi%a$io%
r5%s+
B dehydra$io% o& a% alcohol
2B Cehydrohaloge%a$io%
Cehydra$io% o& a% alcohol occurs i% highly acidic medium
Cehydrohaloge%a$io% occurs i% alkali%e co%di$io%s+
?%ow $he mecha%ism o& how each works+
6 D&irs$ orderB or 62 Dseco%d orderB
6 is a u%imolecularD2 s$epB elimi%a$io% o& wa$er will give a%
alkyl ca$io%, $ha$ elimi%a$ies a pro$o%
62 is a bimolecular D s$epB reac$io% where wa$er ac$s as a
base abs$rac$io% a ;)hydroge%+
;o$h &orm a% alke%e
Ee used a s$ro%g acid $o &avor $he 6 reac$io%
Our lab.
Cehydra$io%. 6limi%a$io% o& wa$er
Curi%g workup, Na
2
CO
3
washi%g, removes a%y e5cess acid le&$+
Fai$sev>s rule applies whe% u%symme$ric produc$s possible+
Grese%ce o& e5$e%ded co%:uga$io% &avors dehydra$io%.
65
reac$s &as$er $ha%
Look a$ $he #R o& cyclohe5e%e care&ully a%d also $he NMR+
Ehy use a mi5$ure o& acidsH
2%y s$ro%g acid ca% be used $o ca$aly8e $he reac$io%, bu$
co%ce%$ra$ed sul&uric acid alo%e causes bo$h o5ida$io% a%d
polymeri8a$io% o& $he produc$ alke%e a%d gives rise $o ,O
2
Ghosphoric acid is $oo slow so use a mi5$ure
Resi%s ca% be used a%d recovered $o reuse+
Ehy dis$ill $he produc$H
7as a lower ;G $ha% $he side produc$ wa$er a%d by
removi%g $he produc$, you shi&$ $he e- $o &ormi%g more
produc$+
Exp 1!: "itration o# $eth%l &en'oate
Groduc$io% o& $he Ni$ro%ium io%
Our reac$io%.
2roma$ic compou%ds are surrou%ded by pi elec$ro% clouds
which makes $hem very u%reac$ive $o %ucleophiles,
elec$rophiles are be$$er+
COOMe is a me$a direc$or, as see% &rom $he reso%a%ce
s$ruc$ures+ D or$ho a%d para posi$io%s have a posi$ive chargeB
7,O
!
)
removes $he pro$o% &rom $he me$a posi$io% allowi%g $he
aroma$ic ri%g $o re&orm+
Cold me$ha%ol wash makes sure you do %o$ dissolve much o&
your produc$+ D MeO7 is your recrys$alli8i%g solve%$B
Look a$ $he #R a%d NMR &or impor$a%$ peaks+
Exp 11a(: )ischer Esteri#ication:
Ie%eral r5%.
2 reversible reac$io% a%d is se%si$ive $o e5cess wa$er+ The
posi$io% o& $he e-uilibrium is de$ermi%ed by $hermody%amics+
2cid ca$aly8ed
Compou%ds are o&$e% used i% &ood as &lavori%gs a%d smells+
To push $he reac$io%, add e5cess reage%$s or comple5 wa$er
&rom produc$s+
Eashi%g wi$h Na
2
CO
3
removes e5cess acids
Look a$ #R a%d NMR &or $he produc$ a%d k%ow impor$a%$ peaks
4l$ramicro ;G
?%ow how $o se$ i$ up
7ardes$ par$ is ge$$i%g sample i%$o capillary cell
Gu$ i% bell
Trapped air e5pa%ds as $empera$ure rises
@ou see bubbles comi%g &rom $he bell
Ehe% $he bubbles are comi%g ou$ a$ a &as$ ra$e $ha$ you ca% %o$
cou%$ $hem, i$ is almos$ a$ ;G
O%ce all $he bubbles are ou$, $ha$ is $he ;G
2$ $his poi%$, $he JG i%side $he bell e-uals $ha$ o& ou$side $he
bell
4po% cooli%g, $he JG i%side $he bell decreases pulli%g li-uid
back i%$o $he bell
Re&rac$ive #%de5
#$ is a ra$io a%d does %o$ have u%i$s a%d is co%s$a%$ &or a
subs$a%ce
Ceriva$ive
This is used $o ide%$i&y $he alcohol par$ o& your es$er
Exp 12: *))
Ee do a 2 s$ep reac$io%
B sy%$hesis o& acid chloride
2B 2mide bo%d &orma$io%
65cess base is used $o reac$ wi$h e5cess 7Cl &ormed
Cirec$ addi$io% o& acid wi$h base gives a ammo%ium sal$ which
%eeds $o be hea$ed a$ high $emp $o ge$ a% amide so i$s %o$
co%ve%ie%$ &or lab sy%$hesis
Name o& produc$ is C66T. N,N)die$hyl m)$oluamide Dm1 me$aB
K
NaO7 washi%g remove a%y e5cess acid le&$
7Cl washi%g removes a%y e5cess ami%e as ammo%ium sal$
Colum% puri&ies produc$ C66T &rom a%y polar impuri$y
?%ow how $o make $he colum%
Ilass wool scave%ges 7Cl vapors
?%ow how $o calcula$e $he molar e5cesses
Look a$ #R a%d look &or $he di&&ere%ces be$wee% $he s$ar$i%g
ma$erial, acid chloride a%d C66T, $he amide carbo%yl
?%ow why you use a molar e5cess o& your reage%$s
,i%ce o%ce e-uivale%$ o& 7Cl reac$s wi$h o%e e-uivale%$ o&
ami%e, a%d a% e-uivale%$ o& 7Cl is produced per reac$io%, a 3
mol e5cess is %eeded $o keep $he reac$io% goi%g+
Exp 1+: The ,rignard Reaction:
Maki%g $he reage%$.
Irig%ard reage%$s belo%g $o a class o& compou%ds called
orga%ome$allic compou%ds $ha$ co%$ai% a carbo% bo%ded $o a
me$al
6$her s$abili8es $he reage%$ by salva$io%, see page !"
The C)Mg bo%d is polar wi$h mos$ e de%si$y $oward $he carbo%
;ecause o& $his, $he Irig%ard reage%$ is a s$ro%g %ucleophile
a%d a s$ro%g Lewis base
The reage%$ reac$s wi$h highly acidic pro$o%s like o%es i%
wa$er, alcohols a%d carbo5 acids
,$ar$i%g ma$erials mus$ %o$ co%$ai% acidic pro$o%s a%d
every$hi%g mus$ be comple$ely dry
,ee mecha%ism o% page !
Lorms biproduc$s.
a%d
puri&y by reac$i%g reac$io% mi5$ure wi$h NaO7 which $ur%s $he
acid i%$o a sal$, which is soluble i% $he a-ueous layer leavi%g
$he $wo side produc$s soluble i% $he orga%ic layer
you $he% add 7Cl $o $he a-ueous layer $o pro$o%a$e $he sal$ a%d
i$ will precipi$a$e &rom solu$io%
$hree ways $o Mkick s$ar$N $he reac$io% i& i$ wo%$ s$ar$.
B Crush $he Mg
2B 2dd iodi%e
3B ,$eal some o& your %eighbors worki%g reac$io%
Look a$ #R a%d NMR o& your produc$ a%d u%ders$a%d $he
impor$a%$ peaks $ha$ $ell you $ha$ you made your acid
Exp 1-: Aldol .ondensation
#$ $akes adva%$age o& $he carbo%yl &u%c$io%ali$y
The carbo%yl has dipolar charac$er
;ecause o& $he large e%eg o& o5yge%, i$ pulls e)de%si$y a%d
makes $he alpha hydroge%s more acidic due $o
B i%duc$ively $he hydroge%s will be more acidic because
o& $he par$ial posi$ive charge o% $he carbo%yl carbo%
2B $he co%:uga$e base a&$er depro$o%a$io% will be
s$abili8ed by reso%a%ce $o $he e%ola$e a%io%
The i%i$ially &ormed aldol produc$ will some$imes
spo%$a%eously dehydra$e
Cehydra$io% is more &avored i& $he produc$ &ormed has
e5$e%ded co%:uga$io% a%dOor i& $he dehydra$io% produc$
precipi$a$es &rom solu$io%
Two $ypes o& aldol co%de%sa$io%s
B Mi5ed) $wo di&&ere%$ carbo%yl compou%ds are $he
reac$a%$s+ This will lead $o a mi5$ure o& produc$s u%less
$here are %o alpha hydroge%s
2B Couble) &ormed &rom a symme$ric ke$o%e will be able
$o reac$ wi$h $wo molecules o& a%o$her carbo%yl
compou%d u%der alkali%e co%di$io%s
Ee did $he double
Reac$io% $akes place i% prese%ce o& e5cess base, i$ abs$rac$s $he
alpha hydroge% &rom $he ke$o%e $o &rom a% a%io%
Look over $he s$eps o& how $o pick a good recrys$alli8a$io%
solve%$
Glace abou$ (" mg o& sample i% small $ube
2dd abou$ "+( mL o& a solve%$ $o sample a%d s$ir a$ RT
#& sample dissolves, $he% sample is $oo polar a%d use a less
polar solve%$
#& sample does %o$ dissolve, $he% hea$ a%d add mL o& solve%$
#& sample does %o$ dissolve, use a more polar solve%$
#& sample does dissolve, cool i% ice $o see i& crys$als &orm+ #&
$hey do you have &ou%d a good solve%$
65 reac$io% be$wee% be%8aldehyde a%d ace$o%e
look a$ pos$ lab -ues$io% *+ #& you have a%y -ues$io%s abou$ $he
produc$s :us$ se%d me a% email
Exp 1/: *xidative .leavage
Maki%g adipic acid by o5ida$ive cleavage o& $he C1C bo%d i%
cyclohe5e%e
2dipic acid is used $o make %ylo%)*,*
Mos$ i%dus$rial produc$io% me$hods use %i$ric acid o5ida$io% o&
compou%ds $ha$ are sy%$hesi8ed &rom be%8e%e
This leads $o $he emissio% o& %i$ric o5ide $ha$ is a gree% house
gas
The reac$io% we did is.
$his reac$io% is a 2 phase reac$io% where you mus$ s$ir $he
reac$a%$s &or $hem $o mi5 a%d reac$++ This will leave you wi$h
$wo $hree phases i% your reac$io% vessel
o%e layer is $he 2li-ua$ 33* $ha$ coa$s $he bo$$om, middle
a-ueous produc$, $op u%reac$ed orga%ics
?7,O
!
mai%$ai%s a par$icular p7 o& $he a-ueous phase+ #$ ac$s
as a bu&&er
2li-ua$ 33* is a phase $ra%s&er ca$alys$ $ha$ ca% be reused
Look a$ #R a%d eve% $hough$ # did%>$ re-uire a% NMR, look a$
$ha$ also+
Look a$ &igure ()2 o% page (9 $o see how $he phase $ra%s&er
ca$alys$ works
4%ders$a%d $he pos$ lab -ues$io% &or $his lab a%d k%ow why
$his is a Mgree%N reac$io%
6%d %o$e.
Make sure you go $hrough $he pos$ lab -ues$io%s a%d -ui88es+
@ou %eed $o u%ders$a%d how $o do P yield calcula$io%s D.
s$oichiome$ry a%d 2. s$oichiome$ry reac$io%sB+ @ou also %eed
$o u%ders$a%d $he di&&ere%ce be$wee% P yield a%d P recovery+
Le$s say you have a $heore$ical yield o& "+*(* g+ Ehe% you
weighed your crude produc$, you produced "+!3* g+ 2&$er
puri&yi%g a recrys$alli8i%g you recovered "+3!8 g+ ,o $hey
would be.
P yield. "+!3*O"+*(* Q ""
P recovery. "+3!8O"+!3* Q ""
#& you have a%y -ues$io%s abou$ a%y$hi%g please email me'
;es$ o& luck wi$h your &i%als a%d # will see you o% $he 3
rd
a$ 8pm
i% LC !"'''