Organic Chemistry Functional Groups 221160
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Transcript of Organic Chemistry Functional Groups 221160
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Organic Chemistry I
From atoms to molecules and beyond Functional rou!s
"onding and #olecular $tructure
%esonance and &somers
&ntermolecular interactions
'ydrocarbons
$ubstitution and Elimination %eactions()ygen Containing Com!ounds
*mines
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Lewis Dot Structures
%ules +or ,riting Find total - valence e.
1 e. !air / 1 bond0 *rrange remaining e. !er octet rules E)ce!t eriod 3 can have e)!anded octet vacant d orbital
reuired +or hybridi5ation6
Formal Charge - valence e. isolated atom6 - valence e. le,is structure6
$um o+ +ormal charge +or each atom is the total charge onthe molecule
*C* charge distribution de!ends on electronegativity
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?
Functional Groups
List #1- Critical for the MC!
*l=ane CC *l=ene C/C *l=yne CC
*lcohol %(' Ether %(% *mine %
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A
Functional Groups
List #"- lso seful
*l=yl $alogen emdihalide Bic dihalide
'ydro)yl *l=o)y 'emiacetal 'emi=etal #esyl grou! osyl grou!
Car%onyl *cetal *cyl
*nhydride *ryl &en'yl (henyl 'ydra5ine 'ydra5one Binyl Binylic *llyl
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&on)s
y!es &onic
Covalent Coordinate covalent
olar covalent
'ydrogen "onds
com!lete trans+er o+ electrons
shared electrons
(ne atom !rovides both electrons in ashared !air.
uneual sharing o+ electrons
bonds bet,een !olar molecules
containing ' and O* +* or F
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Co,alent &on)s
$igma σ "et,een s orbitals
$mall strong lots o+ rotation
i Π "et,een ! orbitals
:iscreet structure ,ea=er than sigma no rotation
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Co,alent &on)s
1D1D
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&on)s
&n the !i bond o+ an al=ene the electron !air have
*. 33 ! character and are at a lo,er energy level
than the electron !air in the σ bond.
". 33 ! character and are at a higher energy levelthan the electron !air in the σ bond.
C. 1DD ! character and are at a lo,er energy level
than the electron !air in the σ bond.
:. 1DD ! character and are at a higher energy level
than the electron !air in the σ bond.
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$y%ri)i'ation
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$y%ri)i'ation
%emember *ll !i bonds are bet,een orbitals
e+toverG and $ orbitals hybridi5e
!artici!ate in sigma bonds
E) '2C/C'2
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$y%ri) &on)s
$u++i) C bonds 'ybridi5ation
ercent
$
"ond *ngle
"ondength
"ond$trength
ane
ene
yne
yl
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1?
$y%ri) &on)s
$u++i) C bonds 'ybridi5ation
ercent
$
"ond *ngleo
"ondength
!m6
"ond$trength
=HImol6
ane CC s!3 2?7? 1D9.? 1?4 34A
ene C/C s!2 33AA 12D 134 A12
yne C/C s! ?D?D 18D 12D 83?
yl $idechain
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1A
Special Cases O an) +
>no, ty!ical bonding +or C
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*6 s!2 s!2
"6 s!2 s!3
C6 s!3 s!3
:6 s!3 s!2
For the molecule 1*. penta)iene* what
type of hy%ri)i'ation is present incar%ons # 1 an) # / respecti,ely0
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S2(34 molecular geometry
valance shell electron !air re!ulsion
E(#E%J / #inimi5e electron re!ulsion
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molecule Lewis structure Shape molecule Lewis structure Shape
&eCl" Linear* sp
SF. $eesa, SO/
!rigonalplanar* sp"
ICl/ sha!ed +O"
- &ent
C$. !etrahe)ral* sp
/ +$/
!rigonal
(yrami)al
(Cl5
!rigonal%ipyrami)al*
)sp/SF
6
Octahe)ral*)"sp/
IF5 $uare yramidal ICl.
- $uarelanar
S2(31. :ra, the e,is dot structure
2. lace electron !airs as +ar a!art as !ossible
then large atoms then small atoms
3.
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+O7 L2!8S MO2 S!FF 3O+D9
KeLve seen static !ro!erties o+ atoms and moleculesM
2D
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Delocali'e) e- an) 3esonance%esonance +orms di++er only in location o+ e.
o be a signi+icant resonance +orm must be sta%le
%emember octet rule and consider +ormal charge
%eal structure / blend o+ !ossible resonance
structures resonance hybridG
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3esonance4 ci)s an) &ases
Con;ugate stabili5ed by %E$(
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Stereochemistry
&somers same molecular +ormula di++erent
s!atial arrangements
:i++erent s!atial arrangements
di++erent !hysical and chemical !ro!ertiesO
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Stereochemistry4 Isomers
C(
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Stereochemistry4 Isomers
%(*&(<
Conformational isomers :i++erent s!atial
arrangement o+ same molecule but doesnLt reuirebond brea=ing to interconvertO rotationalG isomers Chair vs. boat $taggered vs Ecli!sed auche vs *nti
:(E$ reuire bond brea=ing to interconvert
configurational isomers2?
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Stereochemistry4 Isomers
:("E "(
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Stereochemistry4 Isomers
Khat =ind o+ isomers are the t,o com!ounds belo,P
= :iastereomers
&= Enantiomers
C= Constitutional isomersD= eometric &somers
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http://en.wikipedia.org/wiki/Image:L-tartaric_acid.pnghttp://en.wikipedia.org/wiki/Image:D-tartaric_acid.pnghttp://en.wikipedia.org/wiki/Image:D-tartaric_acid.pnghttp://en.wikipedia.org/wiki/Image:L-tartaric_acid.png
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Enantiomers di++er in rotation o+ !lane!olari5ed light E)cess o+ one enantiomer causes rotation %ight cloc=,ise de)trarotary d6 or N e+t countercloc=,ise levarotary l6 or Q
$!eci+ic rotation RaS / a I lTd6
%acemic ?D?D mi)t o+ enantiomers
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Stereochemistry4 Chirality
% and $
1. *ssign !riority by atomic number &+ attachments are the same loo= at the β atoms
2. (rient lo,est !riority -46 a,ay +rom the observer
3. :ra, a circular arro, +rom 1 to 2 to 3 % / cloc=,ise $ / countercloc=,ise
E and U :i++erent than cis and trans U/ same side o+ high !riority grou!s E/o!!osite side o+ high !riority grou!s
3D3D
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7$! &O! &2!722+ MOL2CL2S0
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Intermolecular interactions
:ue to :&(E #(#E
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Intermolecular interactions
ondon :is!ersion Forces "et,een 2 instantaneous di!oles
:i!oledi!ole interactions :i!oledi!ole or di!oleinduced di!ole
'ydrogen "onds
$trongest di!oledi!ole interaction
33
7hen al%uterol is )issol,e) in water* which of the
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7hen al%uterol is )issol,e) in water* which of the
following hy)rogen-%on)e) structures )oes +O!
contri%ute to its water solu%ility0
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$>D3OC3&O+S
he +irst and sim!lest class o+ molecules ,e
need to get +riendly ,ith +or est :ay
3?
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3A
I(C +aming Con,entions
I(C 3ules for l?ane +omenclature
1= Find N name the longest continuous carbon chain.
"= &denti+y and name grou!s attached to this chain.
/=
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l?anes
hysical ro!erties $traight chains # and " increase ,ith length "ranched chains
" decreases less sur+ace area v:K +orces6
# Q a little more com!licated due to crystal structure Khen com!ared to the straight chain analog the straight
chain ,ill have a higher # than the branched molecule." amongst branched molecules the greater thebranching the higher the #.
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l?anes Important 3eactions
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4D
l?anes-Important 3eactions(retty Darn nreacti,e
Com%ustion *l=ane N ()ygen N 'igh energy in!ut +ire6 roducts '2( C(2 'eat
$alogenation &nitiation ,ith B light
'omolytic cleavage o+ diatomic halogen
Jields a +ree radical
ro!agation chain reaction mechanisms6 'alogen radical removes ' +rom al=yl Jields an al=yl radical ,hich can ma=e more radicals
ermination %adical bonds to another radical
%eactivity o+ halogens F V Cl V "r VVV &
$electivity o+ halogens 'o, selective is the halogen in choosing a !osition on an al=ane6 & V "r V Cl V F
more electronegative means less selective
$tability o+ +ree radicals more substituted / more stable so halogenation @ most su%8) C
arylVVVal=eneV 3o
V 2o
V 1o
Vmethyl
4D
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Cycloal?anes
eneral +ormula C'26n or Cn'2n
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Cycloal?anes
Cyclohe)ane E)ist as chairG and boatG con+ormations Chair con+ormation !re+erred because it is at the lo,est
energy. K'JP6
$ubstituents can occu!y a)ial and euatorial !ositions. *)ia A6 !er!endicular to the ringEuatorial A6 roughly in the !lane o+ the ring "ig substituents !re+er to be euatorial Q less cro,dingGO
Khen the ring reverses its con+ormation substituentsreverse their relative !osition
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Cyclohe
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32C!IO+S99
hings start getting more e)citing once ,e start substituting ' +or
more interesting +unctional grou!sM so letLs get ready +or some
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4?
Su%stitutions
$ubstitution
one +unctional grou! re!laces another
Electro!hile ,ants electrons has !artial N charge
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4A
2liminations
Elimination
+unctional grou! lost double bond made
(+ten a e,is base is res!onsible +or ta=ing 'leaving behind an e)tra !air o+ e. +or the /
he o!!osite o+ elimination is a))ition
4A
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Su%stitution an) 2limination
E1 elimination unimolecular #echanism t,oste!
1. s!ontaneous +ormation o+ carbocation $(K6 2. "ase abstracts beta '
>inetics rate de!ends only on the substrate %/=RreactantS Favored ,ith good stable carbocation ,ea= base
rotic solvents stabili5e carbocation Can see carbocation rearrangement
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7hich of the following
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g
car%ocations is the most sta%le0
=C'3C'2C'2C'2
&=C'3C'2C'2C'C'3
C
= C'363C
D=C'3 49
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?D
Su%stitution an) 2limination
$
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?1
Su%stitution an) 2limination
E2 elimination bimolecular #echanism C(inetics rate de!ends on substrateNbase %/=RsubstrateSR"S Favored ,ith strong bul=y base
&+ you see 'E* thin= Elimination E2 reactions o+ten run in solvent o+ con;ugate acid K'JP6
?1
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?2
&en'ene
* s!ecial molecule a s!ecial case o+ substitutionO *ctually itLs addition and then elimination.
*romatic molecule $tabili5ed by resonance ndergoes net su%stitution not addition K'JP6
$ubstituents determine subseuent reactivity Electron donating grou!s activate the ring and are ortho!ara directors Electron ,ithdra,ing grou!s deactivate the ring and are meta directors $alogens are electron ,ithdra,ing " are ortho!ara directors
?2
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?3
&en'ene4 Su%stituent 2ffects
?3
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&n ,hat order ,ere the substituents addedP
'o, can you tellP
?4
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OA>G2+-CO+!I+I+G COM(O+DS
*nother class o+ molecules ,e need to be +amiliar ,ith
??
O C t i i C )
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?A
Oetones
Carbo)ylic *cids
*cid :erivatives *cid Chlorides
*nhydrides
*mides >eto *cids and Esters
?A
l h l
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?7
lcohols
(ne o+ the most common reactions o+ alcohols isnucleo!hilic substitution. Khich o+ the +ollo,ingare %E in regards to $
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?8
lcohols
hysical ro!erties olar 'igh # and " K'JP6 #ore substituted / less acidic
C'363C(' !>a / 18.DD C'3C'2(' !>a / 1A.DD C'3(' !>a / 1?.?4
Electron ,ithdra,ing substituents stabili5e al=o)ide ion and lo,er !>a. ertbutyl alcohol !>a / 18.DD a / ?.4
eneral !rinci!les ' bonding *cidity ,ea= relative to other ( containing com!ounds
?8
lcohols
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?9
+aming
$elect longest C chain containing the hydro)yl
grou! and derive the !arent name by
replacing –e en)ing of the correspon)ing
al?ane with –ol =
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lcohols-O
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A1
Common o)idi5ing and reducing agents
enerally +or the #C* ()idi5ing agents have lots o+ o)ygens
%educing agents have lots o+ hydrogens
O#n(4
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A2
synthesis
*ldehydes =etones esters and acetates can bereduced to alcohols , strong reducing agents suchas
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A3
,ia a strong aci) catalyst
%(' N 'Cl %Cl N '2D
(' is converted to a much better leaving grou!,hen !rotonated by a strong acid
For tertiary alcohols 'Cl or '"r rimaryIsecondary alcohols are harder need $(Cl2 or
"r 3
A3
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A4
&n the reaction above i+ the reagents in the+irst ste! ,ere re!laced ,ith i*l'4 ,hat
!roduct ,ould resultP
a6 c6
b6 d6
A4
('
('
('
(
('
('
(''(
Car%onylsC % ) %l % ) ) t O
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A?
Car%on )ou%le %on)e) to Oetones nucleo!hilic addition6Carbo)ylic *cids nucleo!hilic substitution6
*mides
A?
l)ehy)es an) etones
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AA
l)ehy)es an) etones
hysical !ro!erties Carbonyl grou! is !olar 'igher " and # than al=anes K'JP6 #ore ,ater soluble than al=anes K'JP6
rigonal !lanar geometry reduction yields racemic mi)tures
eneral !rinci!les E++ects o+ substituents on reactivity o+ C/( e ,ithdra,ing increase
the carbocation nature and ma=e the C/( more reactive
$teric hindrance =etones are less reactive than aldehydes *cidity o+ al!ha hydrogen carbanions α β unsaturated carbonyls resonance structures
AA
l)ehy)es an) etones+aming lalala it8s the same rules9
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A7
+aming lalala it s the same rules9
+aming l)ehy)es %e!lace terminal –e o+ corres!onding al=ane ,ith –al =
arent chain must contain the QC'( grou!
he QC'( carbon is C1
Khen QC'( is attached to a ring ,e say carbaldehydeG
+aming etones %e!lace terminal –e o+ corres!onding al=ane ,ith –one.
arent chain is longest chain containing =etone
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l)ehy)es an) etones
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A9
l)ehy)es an) etones
>etoenol automerism >eto tautomer is !re+erred alcohols are more
acidic than aldehydes and =etones6.
A9
Guanine* the %ase portion of guanosine* e
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7D
7hich of the following structures represents the
enol form of guanine0
7D
l)ehy)es an) etones-
reactions at a)acent positions
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reactions at a)acent positions
*ldol aldehyde + alcohol 6 condensation (ccurs at the al!ha carbon
i electrons in enol act as nucleo!hile
"ase cataly5ed condensation removal o+ '2(6
Can use mi)tures o+ di++erent aldehydes and =etones
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l)ehy)es an) etones
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l)ehy)es an) etones
(rganometallic reagents
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Car%o
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Car%o
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7A
+aming
Carbo)ylic acids derived +rom o!en chainal=anes are systematically named by
re!lacing the terminal –e o+ the
corres!onding al=ane name ,ith –oic acid . Com!ounds that have a QC(2' grou!
bonded to a ring are named using the su++i)
Qcarbo)ylic acid. he QC(2' grou! is attached to C -1 and is not
itsel+ numbered in the system.
7A
Car%o
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77
Carbo)yl grou! reactions etones undergo a))ition K'JP6
#ust contain a good leaving grou! or a substituent
that can be converted to a good leaving grou!.
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Car%o
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78
%eduction Form a !rimary alcohol
i*l'4 is the reducing agent
C'3C'26AC((' C'3C'26AC'2('i*l'4
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Car%o
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79
Carbo)yl grou! reactions :ecarbo)ylation =no, that it ha!!ens C(26
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Car%o
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8D
Fischer Esteri+ication %eaction *lcohol N Carbo)ylic *cid Ester N Kater *cid Cataly5ed !rotonates Q(' to '2( e)cellent
leaving grou!6 *lcohol !er+orms nucleo!hilic attac= on carbonyl
carbon
hese bonds are
bro=en
'N
8D
Car%o
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p
$ubstitution reactions =eto reactions sho,n
consider enol reactions
To make->
SOCl2
or PCl3
Heat, -H2O
R'OH, heat,
H+-
R 2NH
heatHO-
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Car%o
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82
'alogenation enol tautomer undergoeshalogenation
82
ci) Deri,ati,es+aming
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83
*cid 'alides %C(Y6 oyl halideG instead o+ oic acidG e) ethanoyl chlori)e
*cid *nhydrides %C(2C(%L6 Hust re!lace the ,ord acid ,ith anhydride.
2 acetic acid acetic anhy)ri)e nsymmetrical anhydrides are named by citing the t,o acids al!habetically.
*cetic acid N ben5oic acid acetic %en'oic anhy)ri)e Esters %C(2%L6
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8?
ci) Deri,ati,es- 3eactions ofDeri,ati,es
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8A
Z'ydrolysis N,ater carbo)ylic acidZ *lcoholysis Nalcohol ester Z *minolysis Nammonia or amine amideZ%eduction N ' aldehyde or alcoholZrignard N (rganometallic =etone or alcohol
8A
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