Organic chemistry

Review-m-MC.AT
mm

mm

-
 Major Functional Groups
0
19 9
11
C R~H RTRZ
carbonyl Aldehyde "
ketone
" "
" " " " "

oxo - -
al oxoyketo -
-
one

OR -
OR
HOUR
.
.

RTHK RTHK
Acetal Hemiacetal

"

-
R
0 ~
Ñ It

RAKI
H
RAR
-
-

A
'

Amine Amide Imine

jiÉr .
R
-

OH
R
'

ti Alcohol
Aldo /
" "
" "
-01
hydroxy -

Ñ
OH
R%R
I
11

"
R
.

"
pÉo- R '

rÑr .

Carboxylic Acid Amide Ester Anhydride

" "
" "
"
" " " " "

Oic acid alkoxycarbonyl

" " " '

oate
'

carboxy amide alkanoyloxy carbonyl anhydride

-
-
-
- - -

. -
.

É¥0H É+ ,
ɵ .
É¥
Phenol Toluene Aniline Anisol
 Functional Group Nomenclature

Functional Group Prefix Suffix

Carboxylic Acids Carboxy -

-

Oic acid

Anhydrides alkanoyloxycarbonyl -

anhydride

Esters alkoxycarbonyl -
-

oate

Amides carbamoyl -
amide
-

Aldehydes 0×0 -

-
al

ketones oxo or keto one

- -
-

Alcohols hydroxy -

-01

Bonding
Bond Order Single Double Triple
Bond Type 0 0 , IT 0,921T

sp
'

Hybridization
'

sp sp

Angles 109.5° 120° 180°

Example c- c c=c c=c

" " " " " "

alkane alkene alkyne

 Isomers
Absolute Configurations
(Z)and(E)_ofa1kenes_
•

( Z) if highest priority substituents

are on the same side of the

double bond .

•
(E) if they are on
opposite sides .

(R)and(s)ofstereocen-
when the lowest is EBA
priority
•

group
→ clockwise is s
→ Counterclockwise is R

when the lowest -1111

priority is
•

group
→ clockwise is R
→ Counterclockwise is 5

yyyyygg@LmyMq.g
cis-trans El =

groups differ
•

about
⇐
in position
an inn .ua , , , won ,

confignrationalIS.com#NewmanProjections-
Enantiomer v. s .
Diastereomer
non super imposable, non mirror images
• • -

mirror images
•
every chiral •
different at some ,

carbon has opposite but all chiral

centers
stereochemistry

•
Same chemical / •
different chemical/

Physical properties Physical properties

Totally
Gauche except rotation of
Eclipsed Anti
-

Eclipsed plane polarized

-

lights
rxns in chiral environments

* A note about stability and isomers :

The major (more favored) Product will be
the more stable one . . .

→
has less strain
→
Conjugated (alternating singlet dbl bonds) products
are more stable
?⃝
 Basic concepts
SNI
2
Reactions
I
Snz Reactions

step 1) LG leaves; carbocation is left step 1) Nuc attacks as the LG leaves

"3
CH ]
{
§i #
EH } Hsc ""
I 1 '
at> - c
-
Br f- C+ + Bi Nu
-

+
c- ✗ → . . . . . -

→ Nu - E + X
-

/
{ Hs
, ,
¥ 1- µ
da ,
Hsc
H
H
µ

* only 1 step !

Step 2) Nucleophile attacks the carbocation

CHS CHS

{
I
E-Nu +
-

Ftse -
C -

Nu

H3C
/
\cH ]
I
CH ]

•
SNZ reactions flip the stereochemistry
•
racemic produces •
option, aa.ues.we.ee , produces

Strong nucleophile not needed Favored w/ strong nucleophile

• •

•
Favorable under increased steric hindrance •

Not favorable under steric hindrance

→
especially w/ 3° carbons •
favored w/ Polar , aprotic solvents
•
favored w/ polar aprotic solvents
,

Leaving Groups
T.N-ncteph.es nucleus loving
-

:
.
. .

want a) The best LG's

•
are able to stabilize
the extra

Electrophiles : want
electrons to it
electron -

loving . -
.
given

f) • The most common LG 's :

-

weak bases

large w/ resonance

T-mportmceofcarbon-IGroupsi-larg.ee groups
-

groups w/
electron-withdrawing atoms

5J
the
0
•

oxygen is

electron-withdrawing
so the A group's pKa < environment pH Deprotonation
•
=
carbon is

left ( )
partially t

OH •
so it is vulnerable A group's pKa > environment pH =
Protonation
to
nucleophilic attacks!

5,1O,l5,20rule:_ "

R¥r
"

o-H.FI
.

R
Rho -

H
H
carboxylic Acid Phenol Alcohol d-
Hydrogen
pKa=5 pKa 10 phat 15
pKaxZ0
 Alcohols
Overview :

Synthesise
properti.es#
higher boiling bonding Aldehyde / pt . due to H -
•
ketone with NABH -1 or
LiAlHy (reduction)
•
weakly acidic hydroxyl Hydrogen
•
Ester /Carboxylic Acid with LiAlH4
•
Polar; more soluble in Hzo •
Snl t
S~2 reactions

RedoxReacti

÷÷÷÷÷÷"~:#
* PCC is a
relatively weak oxidizer

a) PCC turns 1° alcohol

→

b) a Jone 's Reagent Kmnoy , *Jone's Reagent :Crr0s_

°Z°
or an alkali dichromate
turns 2° alcohol into % * A 2° alcohol + Pcc
Hz 504 would also oxidize into
ketones or turns 1° ketone
,
a
.

alcohols into carboxylic .

acids

c) 3° alcohols are
generally
not oxidized any further .

ReductionReact.vn#NaBHytLiAlH4
a) LIAIHY or NABHY can
reducing agents
LiA÷
are

convert a ketone into ,

an alcohol NaBH4

Mesylatestlosylates Quinonestltydroxyqu.no#
•
Acohols can convert to Mes> laces C- so > CHS) •

Treating a
phenol w/ an
oxidizing agent
or Tos> tales C- 5036611-4 CHS) to turn the results in a
quinone
alcohol into a better LG for Nucleophilic substitution
OH
rxns .

É
•
Alcohols can protect for carbonyls ¥ Hzsoy

to
→
Carbonyl +
di alcohol =
unreactive acetal OH

→ the acetal can be removed by an aqueous acid

Can further
ftp.tectedthe-abn-i ! get oxidized into
•
even a
g-

Ñ~~oµt7 ~oµ hydroxy quinone

activity ( i.e
which have significant biological

1T¥
.

Ubiquinone ,
AKA COQ )
OH

¥
 Aldehydes / ketones
Overview :
s¥Proti_ Synthesis
•
Relatively high boiling pt . due
•
oxidation of 1° alcohols # aldehyde
but oxidation € ketone
dipole of 2° alcohols
•
to moment not as ,

high as alcohols (lack of H -

bonding)
•
Ozonolysis of alkenes

NcleoPhilicAddition_ "

H
if no
fit
Hydration : in presence of water
,
aid /Ket forms a
gemi.nald.io#
Ñ'S "
#
co¥ ?
→
" → it>
,
Hz

Hemiacetailltemiketal : Snl mechanism

; addition of nucleophilic ROH to form a
Hemiacetal

É *won , , ye hem;ke+a ,

REH
It
→

p- +→ .

OR
if
to
we

a
added

ketone #
the ROH

Acetallketal simply :
add another equivalent to the above rxn

aldehyde
R¥H°¥R R°¥? acetals

R
HOYER RWR
ketalcondensationRxnsi-add.it
ketone a

ion of N -

groups form imines w/ loss of Hzo

0-7 Foltz
R¥§ÉR
+
Nitz NH * Can undergo
→
R
+
R
R&R → RAR _
RAR + H2O tautomerration
form
to

enam~ife-yr-r-r-rcyanohyd.info#a-ion
NH } Hz an

addition of HCN yields stable

cyanohydrins
:
a

#
-

Ht Ht 1-
-

+ CN + → + →

✓ CN CN

Alcoholt-ormaqt.io#ViaLiAlHyorNaBH4( aldehyde / ketone )

to reduce an to an alcohol

É a

txkeepinmin Aldehydes :
are
slightly
more acidic than ketones b/c

aldehydes have less steric hindrance .

?⃝
 OH

Tautomerizat.io#formsane-no-hasac--c and OH . . .

In
"

and
"

I
"
*
☒ =
veto enol

a) mic-hae-dditi-n.ae Carbanion from a base attacks an d

,
B -

unsaturated carbonyl compound

r☒Ér→r%
r¥¥
It Base
-
→
rÑÉr
Her
b) Enamin
^

as mentioned earlier, imine enamine

YH

R~ir-R~RAIdolcondensationreact.io#s- ep)Ana1-d
is formed .

* This

§t¥ µ+~µ→µ~Ñ¥ÉÉ
basicenvironment.tt
works in a

1
Putting
HÉÉcHs after the
it in

1st
an

step
acidic

would
environment

prevent
the 2nd step .
*

Step Aldol is dehydrated .

*
H
→ µÑ+ Hzo

a) Retro-AldolRea.fi#-. aldol

baseandheatchea-jtriiinir.FI?rIi++Kr
reverse of condensation via addition of a

.
 Carboxylic Acids
*A more stable conjugate

①Verview:- base
an acid
-_
more

it
acidic

is
of

synthesise
properties
rsÉnÉ
very acidic due to •
oxidation of 10 alcohol or aldehyde by a

Polar
strong Kcmo> Cros
•
oxidizer such as : Kmnou, ,

Highly oxidized •

Hydrolysis of Nitriles

Even
higher boiling than alcohols due Cannot be formed by 2° 3° alcohols
•

pt
•
.
or

to ability to form two H -

bonds

NUCleophilicAcylsnbstit.tn# Nucleophile attacks, LG is eliminated, t the carbonyl is reformed .

is
-
-

o o

RFoH
→
R
-

Nu
f- OH
R€¥HÉ Nu
-
nu
Nu
-

H
A) If 11° am
'

formed R
nucleophile is an amine or ammonia
,
an amide is . +
IN -
R
'

→
R µ Hzo RY -
¥
-

'
H
under

b) If (%%¥%ns)
~oH→~ÑoÉÉ
nucleophile is an alcohol ,
an es is formed
+
*

C) If formed ①
,+→Ñ~o~"%
nucleophile is another carboxylic acid
,
an
anhydride is
+
OH No
Reduction: Can get reduced to a 1° alcohol via LIAIHY
"

-9
O

R
# OH É R TH
H

Decarboxylation complete loss of a

carboxyl group as coz ; replaced w/ a
Hydrogen -

results in an enol

r~H →rÉ
- H
o "
o
Ñ
R~i-KE.e-a.ie
'
¥0 * May go its more
→
me + . ,
stable keto form *
If
Saponification long-chain carboxylic acid w/ Na or KOH forms a salt known as soap
•

Soaps have a
long nonpolar tail
,
and a
polar head
A
longer tail is hydrophobic making it better soap
•
more a .

R-eactii-iesotder-iat.es CyclicEs-_

RI II %
° o

R¥R
foramidesg)
11 11 11
,
R^oR Rho - lactam is

acyl chloride anhydride ester amide

carboxylate

most
--mmY least cyclicAM-id.es :

reactive reactive
 + Phosphorus Compounds
Nitrogen
-

synthesisofAminoAC.it#AA'sarezwitterionicN- Containing compounds

a) strecuersyn-thes.rs :

•
Combine the following : •
aldehyde ( R group is an AA -

R group)
•
ammonium chloride CNHYCI ) -

•
Potassium cyanide CKCN )

b) babriels-nthes.is#
•
Combine the following : •
Potassium Pthalamide
•
diethyl bromomalonate

P-containingcompoundI.AT P t DNA are P -

based

a) Phosphoric Acid is a
phosphate group / inorganic phosphate ( Pi )
→ at
physiological pH, Pi is made up of hydrogen phosphate (HPQT)
and dihydrogen phosphate (Hzpoui )

b) pyrophosphate ( PPI) ( ROF)

,µeÉo'§
,
or
,
is released when '

* Ppi 's
forming phosphodeister bonds in DNA .

am
→
Ppi is unstable in
aqueous solution
,
and so is
hydrolyzed
to form two molecules of Pi .

c) Nucleotides w/ phosphate groups ( i.e .

ATP ,
GTP ,
t those in DNA),
are called organophosphates .
 Purification Methods
Extraction :
Filtration :
•

Separation of Compounds based •

Separation of solid from liquid w/ a filter
* can w/ filtration
"
on solubility .

"
speed up vacuum

* like dissolves like

Organiclayer

aqueous
taxer

Chromatography : Distillation
•
Uses a
stationary phase
•

Separation of liquids based on

boiling pt .

*
and a mobile phase to separate Boiling Pt. is
heavily dependent on intermolecular forces #

Compounds by polarity and size

* The mobile phase will elute A)simpledis-illat.io# Use if boiling pts . are:< 150°C

More
quickly when it has the 225°C apart
same polarity as the elnent
*
Larger compounds elute slower b) VacunmDistiHatio Use if boiling pts . are : > 150°

c) Fractionalbis-illat.in# Use if
boiling pts .
are :< 25°C
apart

Recrystallization Electrophoresis :
•

Separation of solids based •

Separation of macromolecules
on their different solubility at based on size and/or charge
varying temperatures
 Spectroscopy
Ifhspectroscopy
•
Gives us information about functional * Yes IR Peaks generally point downward !
groups present
,

•
Tells us the progress of a reaction

a) Peaks to memorize

Tokhtamysh
:

→ O -

H ( broad ,
around 3300cm "
)
→
N -
H ( sharp ,
around 3300cm
-

1)
→ c=o (Sharp ,
around 1750cm " )

UVSpectrosco#
•
Useful for giving us information about
conjugated systems -
Shifts in absorbance spectrum ,
double bonds heteroatoms
created by compounds containing or with lone pairs
•
An increase in
conjugation
=
increase in wavelength
Absorbing red causes to
green
•
color appear .

•
Useful for determining complexes of transition metals

NMRSpectrosc.co# :

A technique used to
gain insight into the chemical composition of a molecule
•
Benchmark numbers indicate shifts for specific chemical bonds .

a) Benchmark Numbers to memorize :

's
Hydrogens on
Sp carbons : 0-3 ppm

Hydrogens 4.6-6.0
'

on
Sp Carbons : ppm

Hydrogens on
Sp carbons : Z 3
-

ppm

Aldehyde hydrogens : 9- 10 ppm

Carboxylic Acid hydrogens : 10.5 -12 ppm

Aromatic hydrogens : 6 -8.5

ppm

b) when analyzing NMR spectroscopy ,

look for . -
.

Downfield
upfield
1) # of Protons = # of peaks

2) Position of Peaks : more down tied ( left ) means more de shielded,

meaning more electron-withdrawing groups

3) Integration of Peaks :
larger integration (height) means more protons
(corresponds to area under the curve )

4) Splitting hydrogens: on
adjacent carbons will
split into

the
"

n-# Sub peaks the # of hydrogens

"

n is on
-

adjacent carbon

( i.e rh )
"
if n=l then 1+1=2
"

,
doublet
(i.e .

if n=2, then 2+1=3

"

triplet
"

Mn )

" "

Leftward direction Downfield

deshielding
• -_ = more
"
"

Rightward direction upfield more

shielding
• -_ =