Chemistry!

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Elementary Organic -
Chemistry
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,
-

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 introduction
I.
! ! ! ! , c. 4 !! ! .

! ! ! !

D covalent bonding D Octet Rule

D D Electron Dot structure

hybridization Lewis

D valence bond theory

organic
! ! chemistry
!
! !! ! f ! ! ! ! ! ! ! ! ! ! ! !
d p

atomic models
! !
!! !
! !
*
! ! ! ! ! ! ! ! -
-

! ! !
L, study of carbon containing compounds .
g
B

IMPORTANCE OF CARBON the solid sphere Model ( 1803 )

99 l
-

.
. of more than 37 million known compounds -

proposed by John Dalton

contain carbon →
naturally occurring or not r

adopted atomism by Democritus

↳
" "

atom 05
unique property halogens Chia, indestructible
- -

I ( F. ( 1,1 ,
etc .

" "

tetra valence property ( H O N s.pt X ) Gold sheet -

when you tear gold sheet into small
C
, ,

(
- -
,

can occupy a maximum of 4 bonds pieces ,

there is a single material you
1

form long chains and ring structures

cannot destroy
nm
not all are stable in
long chains e- t recognizes that atoms differ
rings from
-

Dalton ; mode ,

bonding and hybridization ) element to element

electron config
: Is
'
252ps
'

! ex . Fluorine Nitrogen

N
- = =
single , double , triple bon

N N

NuclearAtom atoms are not indivisible

TTY
-

matter : that t" debunked to

ANYTHING "" P "" due

space and has mass

subatomkpartiu&
→
basic unit is atom the Plum pudding Model ( 1904 )

with subatomic .

proposed by J ) .
. Thompson 1979.9.7.fi?nasa
notice mya na na

Part '"" '

" " over " " electron due

cathode ray tube

to cathode ray
#
experiment theorized that
#

components Of

PROTON (pt In"arae%%:S

""

charged
"
: Ct ) and equal with the Z) termed
-

atomic number electron as

- -

"corpu
'

I II:mm"In:"me
" -

ex .
IX .

NEUTRON : no charge and the sum of proton and neutron f 3 Raisin Bread Model

defines the atomic mass ( A -

-

pt t no )
-

whole bread is It ) , raisins are f 7

-

ELECTRON : t) charged and arranged into orbitals ( electron config ) t recognized electron as component of atom

W J
→ mass of electron is highly negligible no nucleus
-
 atomic
!! ! orbitals
! ! !! ! ! ! ! ! ! ! ! !
! !

The Nuclear Model ( 1911 ) ↳ a region in

space around the nucleus where the e-
-

/ y
-

proposed by Rutherford are likely to be found

gold foil experiment passed 4 Kinds of Orbitals

through

D
.
atom contains a 1 .
S -
orbital : spherical and can only

;D
-
÷÷÷÷÷÷÷÷÷÷÷÷÷÷÷ : ::::÷:÷::÷
man . "

+
. . . "" "

..

r
+ realized that the positive and canholdceelectrons

www.II.IIIITD
Charge is localized in the 3 .
d -
orbital : cloverleaf and can

t.anotexmamwn.ee#ronsareiiiii'
'

or . . " "

and canhotd
The Planetary Model ( 1913) klelectrons
.

proposed by Neils Bohr * carbon has only s and p orbitals ,

which has nodal points

electrons orbit the nucleus at specific energy levels

.
theorized the quantization
-
of electrons -

electron
!! ! ! ! ! configuration
!! !
! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! -

G there is a specific amount of energy Aufbau Principle : lowest energy orbitals are filled First

mm
popularized since there were space explorations certain order

t÷÷÷÷÷:÷÷÷÷:÷OLD
-
→ may

!!!

¥+5
must memorize

etheeray
"

quantized

collapse to the nucleus Pauli 's Exclusion Principle : only 2 electrons with opposite spins are

(
⑥
remains questionable Placed in each orbital
same energy
#
Hund 's Rule : if orbitals are degenerate ,
electrons must be

Home
the Quantum Model ( 1926 )
¥÷÷÷i÷a in the same spin until the orbitals are

proposed by Erwin Schrodinger half -

filled before pairing

MYI
.
electrons does not move in path

but waves ( particulate / wave )

Bd
.

the location can 't be exact but can only use probability

wave function → orbitals are the probabilities where e- resides

Hlttlvltl ) -
iihatlvltl) ✓

+ widely -

accepted model
1- chemical
!!
! ! bonding
!
! ! ! ! !
!
!! ! !
! ! ! !
! ! !
! #

ofLf
Valence electron : found outermost of elements
are on the s and p orbital of the outermost energy level ; the group number

mhm
( group A only ) dictate its valence electron →
easily attached/ removed

{wwf
# of electrons ex .
Group IA O -

sodium ( NA )
,
Fe =
152546353 p 3d
. ↳ valence electrons =D

÷:*
-

"
"""
"" " "" ""

Ii:÷÷ :p:
'
::
. ..
" "
.
.

.ee ..

* inner energy levels are harder to remove since they are closer to the nucleus

HISTORY

:÷i ÷ ÷ ÷ ÷ ÷ ÷ :÷ ÷ ÷ :÷ ÷ ÷ ÷ ÷ :÷÷÷÷÷"
Types of Bonding
-

electrostatic force bonds them together

-

-
interaction between a metal and non -
metal

-
formation of salt ( product )

V
COVALENT -
shared electrons

covalent interactions

non metal to non metal interaction

- -
-

formation of molecules

valence shell electron pair repulsion theory (VSEPR)

/ /
"
the best arrangement of a given number of electron domains is

"
the one that minimizes the repulsions among them .

* when electrons are bonded to a carbon -

center , it will find

e, " na way , m.mme.ep.no .

gym ,
,

l l l l

#
f-
hybridization
!
!
! !
!
!
!
! ! ! !
! ! ! ! ! ! ! !

VI - - - - - -
- - - - - -

sp
'

fi
-
- - -

'

I sp

p l
- - -

,
l
l
l
'
l
- - -
- - - - - - -

valence bond theory

-

hybridization is a major player in this

approach to bonding

there are two ways orbitals can overlap

foggy Overlap and Bonding
form bonds between atoms

⑧Bqt
types of bonds

: ÷:÷ ÷ ÷ ÷ ÷ ÷ ÷
.
electron density above
::::

and below the

¥
.

internuclear axis

)
E ↳
only p d
, ,
and t

Wvu÷÷÷÷÷:
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b- itof covalent bonds

Tiff
I

{ E
www.u-u-w-w-nvw-v
-
-

A
or B
* SB

T.m.mo.MN
ft g
-

H -

H → same
electronegativity H -

Cl → Cl has higher electronegativity

( property of atoms to 47 creates non equal

"" "" " " " "

{ f.y.a.m.w.am#.. . . .yg.. gg.. . ,.

ex CC 14 polar bond (CI

/
bonds towards itself )
- -

pulls e
.
=

} LT
molecule

gonna II. rare

=

opposite so they cancel out

:÷÷÷÷÷÷:÷÷÷÷÷:

C-
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condensed structure lewis structure
( Hz COOH or Cz Hy O ,
→ bonds are represented
by dots

( only elements and Its no ,

are written

cons : cannot identify the type of attachment

of the elements

kekulé structure skeletal structure

↳ don't usually present carbons

it is a notion that at every joint / junction

there is a carbon present

it is also tetravalent
assumed that the carbons are

functional
! !! ! ! ! "oups
!! ! ! ! ! ! ! ! ! ! ! ! ! !

i÷÷÷
÷
,
.

group of atoms in a molecule that defines its properties ; makes it possible to classify organic compounds

into families

* R -

any carbon structure /constituent

quiz

4 .
I mine

5 . Thiol
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!
! ! ew
! !
mor! e ! ! ! ! !

:÷÷i÷÷÷
! !
* atoms are neutral or have partial charges ,
no fun charges

D covalent bonding bonds 2e shared

-

* represent that are

D hybridization Cle covalent Alzsz Ionic

D valence bond theory NaBr ionic H2O covalent

D Octet Rule Ck H2O

D lcN
'

Electron Dot structure O

'

Lewis
-

iii. ii

covalent bond
:
I

!
(
:c =
:c
.si :

I n

! I
H H
electrons are shared ,
between a non -

metals :c :

H
.

H H
•

ex .
-

Na
.
.

:c! :
Nya!
→
ionic bonds
valence electrons
O
nonpolar polar "
:!⑧
'
I .it Fi
-

H -

it - -
sua .me
" . . . .

equal sharing unequal sharing \ 2 core e

-

7
-

e
Of
-

e
if polarized
molecule

electronegativity ⑤ -

difference
.
→ 3 valence e

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÷÷÷÷÷÷÷÷÷÷
d-
a.
Na -

Fao -7 Ionic bond V H 2 3 4 5 6

i 7 He

)
most polar ? 4 Be B C F Ne
N O

a N F P F or As F ? Na Ma Al Si s Cl Ar 8
p
-
- -

,
.

least N -
F
c NTI k ca Ga Ge As Se Br Kr
T

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F p I

m0sF As
5! total e
-

=
agree
-

t rate
-

?
-

b .
C -
F N -

F .
O -
F 53 =
core e t 7
,

~
F
-

C N O F core e = 46
a

N -
F ✓
least O F -
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!
! ! ew
! !
mor! e ! ! ! ! !

:÷ ÷ i÷ ÷ ÷
! ! ① '
methane a -

isp o

⑦
o ←
l
t

⑥ covalent bonding ④ f ④ - -

Its

D hybridization p④ oh o

D valence bond theory ethylene

Hy /④ T

OHO "

:& !!
"

D octet rule
④⑥
HI spa'④ → 0*0=0*0
D Lewis Electron Dot structure ↳ unhybridlzed
- =

①
-

acetylene H 2 →
sp

hybridization
-
-

c→④p=④
( O 4 's
water → sp

combining atomic orbitals HOT THO

4→sp3
'
sp =
stptptp ammonium
,

sp2 =
stptp
OH ④ s -1

sp

sp =
Stp ""

d2sp
' =
dtdtstptptp ④ 5-1 dsp
's

s p :O 4-1 Sps
Pz O
O
8¥ ¥ ⑤
.

x
Q '
-
⑤
S 6-1 d2sp3
④ '
⑤

Hybrid ed
- O bonds ( stronger ) O > IT A
I
:÷i÷÷:÷÷÷÷÷÷:÷ ÷ ÷
→ localized
jo !
: why ! 'IYto%9
.
'
.

. .
0 It

Unhybridized
-

IT bonds
noagta.bonnedsa.rs H -

② -
-

① H -

⑥ -
N
,
-

① sp
'

H
y ,
TH at I → s 4 →
'
sp I t④ amine tf ④ amide

µ
IC FCK
g
f
H 70
a →
sp 5 → dsp
'
4→sp3
-

: :
spa
I t
H
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6162
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g → sp 6→d2gp H -
C = N
l
delocalized H
localized

% X
'
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CE
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e
H -

" s "
.

+
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( Hz -

CHI -

COCHZCOOH 1ST
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÷i÷ ÷:÷ ÷ ÷
! !

⑥ covalent bonding 2 .

⑥ hybridization H -

⑥=c -
H ,
C -
H sp
-
s

D bond theory s "p st CEC sp sp

valence
-

D Octet Rule Ct sp otp =2sp

DLewhEleutronD0tstrVktU#

valence bond #eory 00¥

÷÷÷÷÷÷÷÷÷¥÷÷÷÷¥÷
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it it :
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. " -

Hora . "

Worf
Bond
J f
-

e t →

q t
f →
coeiectron )

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octet rule
④
.

O ⑦
'
H → Is t →

2
I
( Ha
-

C →
15252ps
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YL

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i:*:÷÷: .

C. →
sp
's C#

C-' sp
'
zspz
0=001+0
stptp
=

TP
-

TP
-

- D

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" ' no

" :::::n : : :* .

3 bonds
Nitrogen -

carbon -
4 bonds

* bonds are made of electrons → not permanent

"
*
"

nature is made from chemicals

→
Gilenya calculate formal ch!ge
Zohnza ( Bfd )
→
FC Ve
= -

• 0

→ vancomycin
ex . R -
N -
H
O A

N Fc
orbital how orbit 5 ( 4)
-

e =
2 t
=
I
- - -

s e- p
-

Hill Hzot
• ot 't
d transition metals
H
H O
Ofc 6 (3+2) It
-

-
-
= -
=

t -

rare elements
H
b 6

S Sfc = A -

( o ta ) = It
•
.

+ y
0 .

Mendeleev did not know e- .

.
:O .

Opc = 6 -

(21-4)=0
•

Ofc = 6 -

(11-6)=-1
rds Tsz

t.lt#I. .iA-EAi--kekulE
x
x

Rxn

( Hy ( H2 ( ( Hz )zCHz0H
CHZCHZCCCH 372GHz ( HCl CHZCFG
H ft
l ft ft ft H
l
H
C C C C C
H CH3 It .
H H F
H C H
- -
- -

o l l l
-
-
-

l
-

l l
,

t't 't it if it if H C c C c c c
-
- -

e
-

c
- -
- -

l l l
l l l l
l
H H ( Hy H Cl F
CH 's CHBRCHZCCCH , } H

H Br H CH 's
l
l
l l

H - C -

C -
C -
C -
CH ,
l l l
l
H H H
CHS

CHS CH ( ( Hz ) ( H2 CH ( OH
)z
CH3 H OH
It l l l
C C OH
H f C
- -
-
-
-

l l
l
H H
H H
synchronous meeting
september 18 +
(4)

f
NH , -
D 5T I -

lets =
8

ELECTRONIC CONFIGURATION 't -

ni -
H

is → sphere 0 HYBRIDIZATION
VBT bonds are formed when orbitals overlap
N 15252ps
-

's
Cz Ha
tf ft c c →
sp

¥
-

I I ↳ sp
' -

sp
'

µ -

c ,
-

c, -
H

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THERMODYNAMICS
(
" I
II! :]
-

Mg t → mgclz spontaneity

/ \
p

kinetics -
D
speed

COVALENT BOND He tf Oz → H2O spontaneous

diatomic
-

H ,
O N.CI
, ,
Br ,
I ,
F 4, kinetically inert

Fz
: :
F -

F -

DG -
o spontaneous

tag "kntr0Py
"
→
randomness
DG = OH -

t t exothermic
TRIP
Oz Gibb 's enthalpy TRIP
endothermic
=

8 8
Universe → TS

÷i÷÷÷÷÷
KEKUIE -

each atom follows octet rule

( Ha -
D 4 t ( 114=8 CO2 → 4 t 216 ) =
16

* it
H
.
:
 S block

block
p

d block

1 IUPAC Periodic Table of the Elements 18

1 2

Is
H He
hydrogen helium
1.008
[1.0078, 1.0082] 2 Key: 13 14 15 16 17 4.0026

3 4 atomic number 5 6 7 8 9 10

25
Li Be Symbol B C N O F Ne 2p
lithium beryllium name boron carbon nitrogen oxygen fluorine neon
6.94 conventional atomic weight 10.81 12.011 14.007 15.999
[6.938, 6.997] 9.0122 standard atomic weight [10.806, 10.821] [12.009, 12.012] [14.006, 14.008] [15.999, 16.000] 18.998 20.180

I
11 12 13 14 15 16 17 18
Is Na Mg Al Si P S Cl Ar 3p
sodium magnesium aluminium silicon phosphorus sulfur chlorine argon
24.305 28.085 32.06 35.45
22.990 [24.304, 24.307] 3 4 5 6 7 8 9 10 11 12 26.982 [28.084, 28.086] 30.974 [32.059, 32.076] [35.446, 35.457] 39.948

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
45 K Ca Sc
ydscandium
Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4p
potassium calcium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton
79.904
39.098 40.078(4) 44.956 47.867 50.942 51.996 54.938 55.845(2) 58.933 58.693 63.546(3) 65.38(2) 69.723 72.630(8) 74.922 78.971(8) [79.901, 79.907] 83.798(2)

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

↳
" Rb Sr "d
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe "
rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon
85.468 87.62 88.906 91.224(2) 92.906 95.95 101.07(2) 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60(3) 126.90 131.29

55 56 57-71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86

Ces
Cs Ba lanthanoids
Hf
5A hafnium
Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Gp
caesium barium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon
204.38
132.91 137.33 178.49(2) 180.95 183.84 186.21 190.23(3) 192.22 195.08 196.97 200.59 [204.38, 204.39] 207.2 208.98

87 88 89-103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118

7- s Fr Ra actinoids Ced Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og 7p
francium radium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium copernicium nihonium flerovium moscovium livermorium tennessine oganesson

57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 4f
lanthanum cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium
138.91 140.12 140.91 144.24 150.36(2) 151.96 157.25(3) 158.93 162.50 164.93 167.26 168.93 173.05 174.97

89 90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 5f
actinium thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium
232.04 231.04 238.03

For notes and updates to this table, see www.iupac.org. This version is dated 28 November 2016.
Copyright © 2016 IUPAC, the International Union of Pure and Applied Chemistry.
 B

organic reactions and mechanisms

*

! ! ! ! !
ee ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! ! !
! ! ! ! ! ! ! !
!
!
! ! ! !
? ! !
!
? as

!
!

I
•
Definition of terms :

Organic Reaction
"

a chemical involving carbon containing compounds

-

rxn -

Reaction Mechanism step by step sequence of elementary ( step detailed )

'

a rxns to describe is
-

overall rxn every

Types of Organic Reactions substitution Addition Eliminations and Rearrangements

-

-
.
,

substitution elimination
usually undergone by saturated compounds ( ex alkanes ) removal of small from a large
' '

.
groups molecule

common with to form smaller species

aromatic compounds
'

used
saturated all single bonds in preparation of alkene and
- -

alkynes
-

into
↳ C H -

is at maximum ex .
dehydrogenation
f H2O

X # o -
ex .

~ -
or dehydration
-

SH H H H
i :3 2A H H
IB la heat
l

[saturated
l

H KOH ( alcoholic) C C H t k Br t H2O

C H t H =
D
C
- -
-
- -
-

↳
unsaturated l l ethene

H Br

* explains why margarine solid and butter melts Bromo ethane

is at room temp
H H coned Hzsoy H H
l ,
one grouplspecies replaced by another group ( species I 1
-

is 180°C
H C C H C =
C
HOH
-

-
-

t
-

l
¥ ILLIT)
l l excess l
CHL, t Cl , GHz It byproduct H OH acid H H water

ethanol ethylene
"
pot alkene →
alkyne halide
v
VHA

CHzlH2 It KOI cag , → CH3CHz OH

rearrangement
alkene halide → alcohol
'

reorganization of a constituent parts by action of

addition other factors

Usually occurs on compounds w/ multiple bonds formation of structural of the

'

isomers original molecule

-

O - OH O
H N 11
( ex .
alkenes ) Ip unsaturated compounds ex . A NHZOH It Hasa, TN -
H

l l →
a → l l
X l l I
combination of 2 X
'

Or more molecules to form

cyclohexane ne cyclohexane oxime cupro lactam
H "
H "
bigger products

¥ !
i r

⑤ f
?}
H

µT
- -

usually occurs in breaking doublet triple bond

'

a
reversible

used in alkane preparations

-

H H
ex .

I / p
c C Br
Tyr
-
-

t
-

H/ethene Bromine

H H
H
H '
' '
'
-
H -

C -
C -
H
H -
C -

C -
H t Br →
l l
l to
Br Br
Br

Bromide
carbocation 1.2 -

di bromo ethane
10h
intermediate
bondTbreaking
-
-

(nrrwnww
LEWIS DEFINITION
acid
-

e pair acceptor
-

HONIOLYSIS base -
e
-

pair donor

:
-

bonds break and each sharing species take one electron importance widens definition of acidity I basicity
g•
-

creation of radicals → similar EN uses electron makes others qualified

ex .

Bfg ( no Ht )
n . .

Ch :C! 2 Clo →
radical accepts electron ↳
q! → acid
:
-

→ still an

Tp unpaired electron

very reactive
( Hy OH t BF 's

M t
transfer le
-

only

HETEROLYSIS "tout # a.

species take both leaving the other

-

bond breaks and one e

with an empty orbital CHZOCHZ t Bt's

TEI Htt
-

H → :c ,

"

acid and bases

⇐E±o
-

elemental effects

BRONSTED LOWRY DEFINITION

→
-

T electronegativity t acidity
-

I -
H -
n
.
-

H -
o -

H " -
e

acid -

proton donor T size ( mass ) T acidity H -

F H -

Cl H -
Br H -

base -

proton acceptor '

resonance effect

conjugate acid -

base pairs the more stable resonance structure T acid strength

,

/
acid donates -1 form conjugate base CHZCHZO -
H →
CHZCHZ : acetic acid → T resonance structure

A B CB CA
CH 3GHz OH → CH 's COOH ethanol acid → no delocalization
H2 504 t H2O T HS Oj t Hz Ot
'

hybridization effect

S P E C T A T O R l O N S T s -

character of a bond to H , the T acidity

' '
species that plays part acid sp
-

no in the -

base rxn sp sp

l 't
25g 33g
-

l 't
L
50g
'

known counter
.

ions
'

as
Nat
-

Spectator ions Cl H
ND
niatottdinaiiitittiii"aiii→
more
CH ' p
Hzc HEH
-

+ Hao sit ,
audio

↳
y
T T goes to a

strong base strong completion neutralization

-

Inductive effect
acid

↳ dissociate produce
completely
→ salt and water weaken OH bond -
induced → effect come from other parts
in H2O

pull e Yung mas EN

fffedbngfe÷ Lo mas madan napapamigay si H

autoionization of water
④
-

and Kw
④ O 0
l
TD dissociate
I 11 → l,
on its own
④ -
C
l
-

C -
OH
④ -

C -

c
-

OH
l
acidic
H
f ④
more

⑤
L
O
11
l

⑤ -
C
,
-
c -

OH

acidic
⑤ most
 :÷ mf÷ ÷ ÷ ÷
movement of arrows
electrophiles
( electron pushing )
! ! ! ! ! ! -
t
! ! ! ! !
! ! ! ? t an
A fish hook -

movement of one electron Br Br-

r
'

species that seek e

-

/
"

electron loving
" A normal -
movement of 2 electrons H -

Br

all lewis acids are electrophiles → t 8

'
Note :
charges
.

or

nucleophilic
(
( Ha
'

from tall to head

"÷
CH } It 0

i:÷÷÷÷÷i÷÷: ÷÷÷÷÷÷÷:÷÷
"
" '

nucleophiles
"

¥34
species that seek positive center ( e. G. )

Jo:L
a carbocation
-

lat
-

→ pjr BE , -7
-

BB
all lewis bases
-

JIE )
3 :

YN :#
important trends
: it :
Yt
→ -

I nucleophilic tty increases as the charge on the

n
c=Tj
.
"
becomes negative c'
'

Ct
'

more N'
'

H : = H → :O E c H
H -
: → -
= -
-

INNIT
H2O Hzot

dia"ams and
7 7

energy
QQ.my#N
2 nucleophilic Hy increases with basicity
✓~#~
,

mechanisms
.

.oµ
-

, µ, , , ,

3 nucleophilic tty increases with polarizability ( size )

④ -

Br 7
-

Cl 7
-

F H
\ /
H H H addition

:/
1 ,
C =
C →
reaction

g
t Br , H c H
-

OH
-

7 SH 7
- -
-

l l
l
H H
Br Br

CARBOCATION
-

electron deficient

€y 777! ! :[it
nucleophile

:÷÷÷:
to
l l
-

example of a lewis acid H H electrophile

'

'
i' i'in :÷: ' '

"÷÷÷ :: .in

my
bond breaking and
forming rate determining step

electron rich TS , : HI 1H 4 slowest step →

step I
C C
l l \ ↳ highest Ea
example of lewis base H H
-

a -

' 4 formation of the Ct

'
Br - - -

Br H
: H
l l I
f less EN
IA -
l l
t
!
t
-

C -

z -
C -

z → -
C :
-
t z Tsz : it t
' -

C -
c -
H
l t
H -

C -

C H
↳
-

l l l l Br
carbanion s l
,

Br
Br
 I → x → N

addition

M
Molton

X H

II. ¥: ÷÷ aaamon

④
Ny ¥04 my
elimination

④
'
'

LD

~i④ substitution

→
rearrangement

¥i.÷¥*iiiii
¥t
:
mechanism

NAH Fi →
y
-

por
-

→
Br

word" rp reducing agent puueoph

" 't

"I÷÷
" a
"

i .

:
mechanism
Nat

pj
""

ii.
"

B -

it it -
is:÷¥ .

it →
→
2. O 2 l -

→ nucleophilic

i. It
 → the rearrangements

secondary carbocation →

÷÷
"

. . → i
④ :

ly ¥1
mechanism
XX
→
ii : → A
⑤→ elimination

÷
"m
substitution

-x

Ez
" "
"
→ →

L
OH
XX
↳
Br L Nott lift "
BI'D
N ly
°

1¥
↳ second order t

!
nucleophilic I hv
.

, , Br

FBI :
-7 a
:i÷
.

!!
B :
→ Nt H -

Br

AE BI t
:
→
-

Br
 hydroc!b
! ! ! !
! ! on! !
! ! ! !
! ! !
! !

alkanes -

Physical state

I -4C exist
example of hydrocarbon ( composed of H and C only ) as gases
- -

saturated = no double bonds

-
5- 17C exist as liquids

can be long chain or cyclic I -

18 and above C exist as solid

Intermolecular Forces
-

aliphatic
-
T # of C TMM TIMEA →
, , of Attraction

T LDF London
-

general formula for an unbranched alkane :

→
,=or7EPer" On → weakest IMFA

( n Hantz -

Density

ex butane less dense than water

octane
-

" "
weak IMFA that loose packing
-

results in

HYBRIDIZATION of molecules Iman volumes

tetravalent carbon

sp
'

hybridized BOILING POINT

-

valence configuration :
25215 -

general trend :
larger molecule equals higher BP
stronger
r,

Tl Tl T t →
large molecules have larger sur thus T IMFA
red ,

Is 25 2p× 2py 2Pa

COMMON SOURCES
.

plants

solid long chain

forms cuticle to protect plants

Animals
-

cows producing methane

-

male himalayan musk deer

-

Fossil
'

natural gas

petroleum
-

PHYSICAL PROPERTIES
Solubility
.

insoluble in polar solvents

-

soluble in non
-

polar solvents ( e.g ether Cla )

.

,
-

like dissolves like :

alkanes are non -

polar
REACTION OF ALKANES
"
also known paraffin s from
"
little affinity
-

as param affinis meaning

chemically inert to most organic reagents

-

can only undergo combustion and free radical

-

substitution

COMBUSTION
rxn of hydrocarbons oxygen
-

in

2 TYPES :

I complete

good of
-

source oxygen

alkanet Oz → CO2 t H2O

2 Incomplete

Insufficient oxygen

alkanet Oz → CO
or
t H2O
c

FREE RADICAL SUBSTITUTION

rxn where halogens Ill Br ) replaces hydrogen
-

or one

product is an alkyl halide

occurs the presence of heat or light polar solvents

in in non or in gas phase rxns
-
-

Stability of Radicals :
307207107 methyl radical

mechanism :
excess
heat 1119 ht
µ
if there is still
H H µ
H
l D
XS
I
l

H -
C -

H t Cl -

C l H - -
Cl → H C -
-
Cl
l l l

H H Cl

① Initiation step ③ Termination Step

X H
Cl -
Cl → 2cL .
l

H C -
°
Clo
② Propagation step It
H H

Act
l l
l

Cl Mou Cl
f;
H -
c → H -

t H -

Cl →
-

Cl

H
H H H H
2
N MA
' ' l l

H -
co Cl -

Cl → H
-
C
l
-

Cl t Cl .
H -
C MCI
-

→ H -
c -

Cl
, l ,

H H H H
H H
3 '

H -
in ?
C .
°

C -
H → Hz C -
C Hy
l
l

H H
 aldehydes and ketones
-

carbonyl group
COMMON TYPES OF NUCLEOPHILE
O O Nitrogen Nu
11 found in found oxygen Nu
11 -
-

RAH
→
extrlmltles RNR , → Internally
IVH ,
only only
H - § .
-
H
R -

aldehyde ketone . .

R -

Ni -

H
p
- ? -
H l

R,

COMMON USE phyanaeiiti , ponanardreaaent

13101091cal testosterone ( hormones ) Hydrogen Nu carbon Nu

'

o -
-

As H H
-

Flavor ants vanillin H

R
I l Max
-
-

o l l
-
-

Al B
HO H H H H
:c
-

µ
- -

=
-

atleast
OC Hz l l
3C
go
solvents Acetone H H
-
-

° •

at least
,
.

preservatives -

Formaldehyde ' c

µ µ

oxygen nucleophiles (hydrate formation)

REACTION ( NUCLEOPHILIC ADDITION
Nu riaeminal
n
"

gi÷÷ di 's
"m
-

carbonyl groups can form resonance ( electrophilic in nature )

.

( attached to
. .no .

the same carbon

by
can be done acidic ( basic condition
-

in

a
Mechanism : aaaumeamm

[O
'

carbonyl C H H OH
nucleophilic attack
'

is prone to
- -

ft
:O → 11 oxonium

#
→
:L H
8- O
AH
"
:O : a
fly
, -
-
tho
It
H -
o -
H .

it
'
? -
HI
St
£
OH
aldehydes
'

#
are more reactive than ketones I
more
Gerold O nababawasan ang pagka
→ t
Hz Ot

if ftp..ee#onnaei:itie:ii:i:iom::i::itmi:
" '

elections
on .

attack
Group ( EDG ,

reaction proceeds under "

-

audio basic condition

÷
'

t Hzsoy →

µ ,
-

nucleophilic attacks carbonyl group and break f- O bond µ *

GENERAL MECHANISM : mech

-y①
:
nucleophilic attack basic medium

②
joy:p to if H Hsoii
'

protonation
-

, # , →

BASIC

✓
'

NU ( the
'

: more t'
nucleophile is stronger )
H - '
H H

pnoreuiiatioeate
① o ②
Htt 't :O H
- .
. . . -

:÷
"

t :O .
.

Nui Nu NU
→ I OH

"o ,
→

H '
it
#H t Hzsoy
'

Acidic Nu H Ht
of
J
-
→ lots '
It

② ① :O
(O OH
H
:O
-

Ht → →
f- →
4- + Ht

H
+
NU -

H Ny
protonation activates

the carbonyl group U

'
 I
RO OH RO OR oxygen nucleophiles (acetal formation)
I
'

X X '

riot XO
" "

I Rott as Nu

( Hemiacetallhemlketal )
( acetal lketal )
hemiacetal acetal
OH
O no # on mech :

T.io X it # " A:
'

OH

→ →
Ho -
r
mech :
H
15 A :
-

HI
-

Iii
t

i. Hit OH
#
'

→ "
→
^ % →

€
'
:* →
-
H hemiacetal .

# Ir
OH
-

:O'H :

4 X !!
→

f-
→
→
→ t Hoot r
. t HA

rt ? -

it
?
: -

J
e x e r c i s e s :

1)
H2O
hydrogen nucleophiles (reduction)
N) →
OH
11 O
NABHY
O
Hype
FAITH HIR

0
2) " NaBH4 -

weak reducing agent

XTH →
Heo

I I Hzsoy
-
reduce aldehydes / ketones but not carboxylic acids
×
HAI Hy -

strong reducing agent

" AH )
z, can reduce carbonyls and carboxylic derivatives
-

# H2O
OH

lol )
→
O I
CHI
→ AH
H
10 OH

→
20 OH

:
mechanism

:O :
C 11
:O :
H >H -
f -
y
6-
AHIR H 't ' →

4-
✓
-
A -

H AIR
it H
At Hz

O -

4-
work up
→

H2O AIR
H
e x e r c l s e :

"

it
t"

2) Tt O
H x

¥0
It

3) LAH
# →
11 11
O O

cannizzaro reaction
2 of ( NaOH )
benzaldehyde the of base
'

moles in presence a

I will be oxidized → acid

a It
÷% I
OH t OH
I will be reduced → alcohol

benzoic acid benzyl alcohol

mechanism :

- '

:-. : i

,¥t
i

,T÷
H -
in H
l l
"t
t 't t
→ → I
it
carbon nucleophiles (Grignard reagent)
°
H
R
'
-

Max
Ott
aldehyde → 20 OH
0

X
N Ma Br
!/
# HIR
- .

AHIR H2O ketone -130 OH R:

'
R -

÷
" "

it "t
it

# #
→ .. ..
.
AIR → HIR
'
R '
R

grignard structure :

when bond breaks , carbon is less electronegative

R
MI, × SO when heterolysis occurs electrons move to
× Mg ,
-
-

a
halogen →
making the carbon become
A
Hz C carbocation
ex .
-
X → Hz Ct
-

↳ Use 919 hard if you want it to be a

Hz X → inser t my
carbanion

A + I -

Hsc -

Mg -
Cl → Hzc ?
↳ non metal
↳
-

cation ,
metal

C X e r e i s e :

"
-

M9Br
m
11 →
H2O
O

2) 14 D- Mg
Br

XX H
→

I l H2O

÷ #H
11
Ph Ma Br

l l -

Hao
Kwun Evonne Verano

Chem 31 -

FI

"
Maior
f
Y' at
' '
Fo
It A
X

workup

Af
→ , →
°
I
-
'

'

Q: p '

t"
U µ
,
y,

Iit

"
Nt
i÷÷o
"

#
no:

It
Cto H
: -

" it → →
A
^ -

H rft -
H

t
o
Ift
.

→
M
#
t thot

no:
acetal / ketal formation
O OR OR
tea ROH OR OH
X
.

'
Thot Hoot

mechanism :

✓ OH
'

't -0 OH

ft n H ,
-

o
ion In →
: - -'

→ → A
n
"
y A I
U
R- Hz OR
-
H - Ot ,
R

T
'
H H2O t
i. ER
OR OR
IH Hy ?
-
1
✓
A
'
you "
-

→
T
.

it
.

kick out
( R -

ft -
H
t "

OR R -

I -
H
He
→ H t Hzot

OR

nitrogen nucleophiles
general to amines 2
°
amines 30 amines 40 amines

R
Ii N
• o

- -

R -
N -

H R -
ii -

R R -
-

R at
R -
N - R
l l l
l l
H H R
R

N' Ha )
'

"
l amines ( R -

-
→ Ht

N' Ho
"

'
'

mildly acidic condition ,

it high → R -
→ R -

NH ,

imine formation / SCHIFF base

in -
R
R N' Hz
-

O
H
x -
Hz Ot
n
imine ( C -
-
N )

In 02 nucleophile ,

I → hemiacetall
hemlketal
→
acetal

ketal
,

In 10 Imine
,

→ carblnolamine → imine
 :
mechanism

'

"" :-O -
it '

:O It
EH
-

H I

:mH →

U
→
R
IN
'
'

Hf
→
4-
carbinoiamne

Nj RN OH
-

f Hit X
"
'

R N' Ha R H
M
-

- -

.
.

M
oxyonnum.io
'

H
H
' H
→

H
Nt
ij
-

v
+ R - -

H
R

f- In
H
-
-

H →
→ I →
t Hoot
R -

H
.
-

H
R -

!H iminium

10h

2° amines
-

mildly acidic
-

enamine formation

±i÷¥ enamine

intermediate : OH

tr
.

!!
-
R
carblnolamine

mechanism :

H2O :O'H
II
"
EY
It
:
-
it
→ →
, →

# # t Hzot

R -

N -
R R -
NER '

R -
N :
carbinolamine
I I
I
.
.

'

O
R
H H .

:O.IR, Hzot H ft H H2O

Nt
- -

R R ii
U g R R
' - - -
-

t '
→

tf →
HsH → A
thot
N B
R - :
R -
N : B
H
l
'
l HB -
H
R pi
d -

contains functional group

B elimination ( remove B H )
alkenes → Zaitsev rule
-

HB carbon is same ,
either -

side is
okay 't not the alkene with the more substituted
)
,

product will be the major product

(
ex .
N
o
all regio selective → has 2 paths
p

µ
of "
ortho: X
H H
L major minor

I eliminate HX
.
→ substituted
R
→ / .

#
.
L

N N HL tri substituted
R
t R major product
ye xx
# R'
°
→
o

Hz monosubstituded
-
minor product
P r a c t c t :
i e s e

"t
" ×,

in -
Hzot
O

"

Eat
"

I
if
to
# ,

protecting
species

¥÷oi i ÷÷÷:÷÷÷÷ .

¥
.
c!boxylic
! !
!
! ! acids
!
and! its
! !
derivatives
!
! ! !
!
! ! ! ! ! ! ! ! !
! !
!
! ! ! ! ! ! ! ! ! !
!
! ! ! ! !

:O :

compounds containing the COOH groups 11

'

-
C '

R H
undergoes Nucleophilic Acyl substitution hydroxyl
-

O
O
I
11 →

C f
NU

structure and physical property

t .
exists as Dimers due to H -
bond

I
always exist in pairs

additional dipole
2 .
higher boiling point than
corresponding Alcohol
HOAC
exhibit more IMF
Eto H
' stronger ,

H bonds -1
IMF → It interacts n
O j
t
due to
-

F
O H O Presence Il .
-

F
,N
- - -

¢
-

with F, o →
.

\ A
.
.

Ot carbonyl
.
-

R OH
-

dipole
O -

H - - -
OAR -

t 118°C
acetic acid acetic acid Bps : 78°C

not a true bond but

→ forces of Interaction To physical T IMF T Bp
has similar strength
a property → IMF thus

acidity
contains mildly Ht
'

acidic

.
can react w/ strong base ( NaOH ) to form salts

°
Weaker acid compared to inorganic acids but strong compared to organic acids

higher acidity than alcohols

'

°
Ionizable proton ' delocalized
f
carboxylate ion

:O : Nat salt form of carboxylic and is more soluble in

o y
" resonance I

Rao
→ '→ salt

of ,+
.

:
r r .
.
water compared to Its carboxylic form

ethanol ethanol acid propanol C acid benzoic acid

acetic
cannot delocalize 0
° ° "
the e
Xx
-

since are ( aliphatic ) "

benzene ring

to
H

H .

H . o .

H Y ( cyclic )
-

electron rich ( want e- )

§
(
pKa 's 16 4.76 4.87 4.19

benzoic acid stronger ?

'

↳
strong acids resonance effect does not have enough why is

have , ma , can form resonance e. + open , toward , , many , .ee#eu

.

→
pm , o, e. toward ,

itself
structures caused by ring

I cannot resonate

*
hybridization effect -

weak

-
proton is attached directly to the bond
reduction reaction
"
Strong RA
WH
#

Y
reduction OH ( LAH )

alcohol

at
o alcohol aldehyde COOH
( DIBAL H ) most oxidized form
µ
-

weak RA
aldehyde susceptible to IH

selective to COOH :
use BH , -

THE

BHS THF -

-
O I

11 to
# OH
H I N
LAH H l
I → x

\
no
selectivity
)
To no
OH

NABHA
→ ⇐

carboxylic derivatives
ayy
O O O

H H H
# OH XX # OR
R
'
R R ( alkyl group )

O
carboxylic acid acid halide ester
11
#2
R

i
O
""

iron :
'

c
::::::i
form
.
" . "x r -

en

amide nitriles
acid anhydride
-
,
Carbon attached to 3 hetero atoms
t

t
,
anon highly electronegative
p on *

N ,
O ,
X
 If compound IS acyl halides

§
more reactive ,

can convert to

other derivatives

,
,

ftp.#--------------------I-------TEr!¥→
Izo
nucleophilic acyl substitution : reaction
" """

. "
in .
General Mechanism :

I ..
+ a
.

↳ be good LG (
can a
leaving group )

common reactions acyl halide

11 Hydrolysis rxn with H2O to yield COOH

-

2) Alcohol ysls -

rxn with ROH to yield esters anhydride

3) Amino lysis -

ran with NH } or amines to

yield amides

41 Reduction -

rxn with hydrides to yield alcohol coat

5) Reaction w/ Grignard Reagent ( carbon nucleophile )

CONVERSION OF COOH TO ACYL HALIDE

t soil
r on.

, c,

mech :

A 9
'

→ '

V
i :c .
-

→
eras . →
¥
c
. . .

HYDROLYSIS
amide to COOH
-

"
In ..
rino .
'
-

N 't '

mech :

iiiiiinii
O good leaving
-

"
t
't -

÷
r

:
o. . . "

Ot is a good leaving group

SAPONIFICATION HASE HYDROLYSIS )

R
'

t -
OH
r o wat
.

op r -

t
ester salt alcohol
strong
base
mech :
.
no protonation acidic
,
r

iii. .to#iiii-:::.o.:::::s
( basic ) O

÷
-
or
.

r "

salt
soap

ALCOHOL.US/StFtSHED ESTERIFICATION )
t H2O
r on .
r op ,

Este

i¥÷÷.÷n÷÷÷ii
'
mech : t good LG
n
"
"
f A
-
M H - to -
H

¥:*
C
→ - .

in

~
In
'

R -
.

A
-
→
Hiro .
→
,
t H2O
, p
.
r or

AMINO LYSIS
-

ester to amide

OH
'

t R -

R or
.
R NH ,

mech :

iii. or
.
-
i

.
-
r
i. → rin ..
+ "o -

REDUCTION
H
a strong RA
It
µ c,
# OH
aldehyde intermediate
mech : p cannot isolate

"it
iii. iii.i→÷÷* i' iii.
"
"
- -
"

Is hydride nucleophile
REDUCTION
amide to
-

amines

" lightly acidic )

r NH , , ,

mech :

pl A

i !÷:
→

mi - it .
.

in Iain
.

it Hz

R
X H
H

REACTION WITH GRIGNARD

M"r
"
' Br "
r R
r
.

or r
..

mech :

iii.
"
"
- - -

iii.
"
r .

"
s

.
i:
it -

.i÷ .
"

exercises
 stereochemistry

chiral center / asymmetric achiral

y -

carbon that has 4 diff groups

2h stereoisomers
por Br
→
por Br
H
q
=

I
-

- c

'
n -1 chiral center
# NT
citzutzcth CH 's
\ , a stereoisomers Enantiomers
chiral

-
potential OH
↳ similar images
3°C
an
1¥ 23 8
1 stereochemistry
=

'
to R R R s s
s

R R S S R
s

R S R S R S

R S S S R R

N City
-

CH z
GHz -

CH
, → achiral
1

chiral
F
→
OH

417 Identical

t¥:m
"

÷:÷:÷÷÷
.mn/%B4ijchiraiI → enantiomers

Yt counterclockwise Bri
l

!
HH C Cl
-

it! ;
"
,
=
S ⑤ " " "
a
out ,
Br
1 ( highest atm not

IDR
'

in
szt ④
"

y
Emc
,
-
Br
,
a
it R

( Hy
4
 Cl

.%÷÷ il !
'

Is
or " '

.
i ;

I Br
4 5C

Mitt
g€ ,
glitz
25 -

Bromo pentane

' F H

!!
3 2 IN
R
-

chloro -
ar -

fluoro octane
H
Cl
I 4
organohalides
! !
i.
! ! !
!
! ! ! ! ! ! ! ! ! ! ! ?

compounds with
-

one or more halogens

found in algae and marine

'

organisms

'

used as solvents ,
inhaled anesthetics , refrigerants and food additive ,
insecticide Freon
Pyrethrold

TYPES
alkyne
NBR
alkyne) 1=1 Br
= Br
H
y
/
aromatic ring
Br

Alkyl Halide Vinyl Halide Alky nut Halide Aryl Halide

-

TD On the =
bond

allyl
-

next to =
bond

Br

-
y
•

o
alkyl halides T

S t r u c t u r e

' d C the
halogen →
where
-

bonded to a saturated sp hybridized carbon

'
-

1-
-

tetrahedral in shape functional group

Br
g. × bona ,, paan ; a , ,, neuro ,,n , ,, ,
§y ,, apamea
,
.

B -

carbon feels inductive effect caused by X

'

Nu : a carbon
attacks
f
C l a s s i t l C a t l O n B hydrogen
AC B B

BA
Br B
X O

Br
# B
Br

primary secondary tertiary

-
AC is attached -

attached to -

attached to

to another carbon 2 B carbons 3 BC

p r o p e r t i e s nonpolar

Nl
- Polar
low solubility water soluble most organic solvents
'
'

in ,
in

Boiling pt is higher than corresponding alkane NL NV

d , d,
-

LDF
Increase
TBP
°
Bp , larger alkyl groups
decreases
°
low Bp ,
Increase in branching ( surface area increases )

R -

F L R -

Cl L R -

Br L R -

I
r e a C T l O n ( preparation of Grignard Reagent )
°

any Orqanohahde reacted with Mg metal Br t

✓ M$-7
/ MAYR
-

:
°
R -

Mg :
essentially covalent but with high degree of ionic character

Rt)
THF or Ether
•
Ma -
X : essentially ionic Rt Br

s v b s t i t u t t O n 1 Reactions )
OH
Br
[ )
substitution
one group exchanged for another I
-

is
-
-

removal of a leaving group

I &
elimination
X

9enexaregooa
-
R
Lo
µ
t
substitution
eliminate

NUCLEOPHILIC SUBSTITUTION
possible mechanism :

undergoes nucleophilic attack and loss of a leaving group

.
can be concerted or stepwise ( Snl or sn2 ) → Edward Hughes and Christopher Ingold

sn , concerted :

↳
)
'

→ Nn t Lo :
simultaneously
-

Nu :

stepwise :
y#
Sn ,
> )
-

→ a -
→ -
Nu t LG :
+ .nu

carbocation
Intermediate

S 2 mechanism
N

K i n e t i c s s t e r e o c h e m
prate constant [I -

molar concentration
rate KC substrate ] ( nucleophile ] change conformation It the C chiral
'

x
'

=
→ amount of the substrate and In -

Is
- -
-

alkyl halide the nucleophile is affecting 's

2nd
when carbon is sp
Order
WAN
-

the
-

rate of the reaction hybridized and

attached to 4 d 't .

When the attacks the x carbon

nucleophile
-

bimolecular the groups

leaving group will cleave

From s product becomes an R

concerted
,
'

why does it happen ?

dah "
satay hangyayari ,
the Nu uses

backside attack Csahkoaaatake ,

TRANSITION gfqfe

finn ]
a carbon is

:i÷÷÷: mriiiii:
"

* backside attack
-

attack directly
opposite the LG
 s t r u c t u r e o f s u b s t r a t e

methyl 110720 30
: Nu attack
reactivity 20
→
'
is more susceptible to
>

since concerted Nu : will experience steric hindrance

*
-

leaving group
-

•
Nu :

due to LG are expelled as negatively charged best LG are the ones

producing stable anions
-

TP Pag amahs Kasama Sl i

-

OHL NHZC ORK Fc Clc Brc l

poor

example :

GHB
" "
→
t Hao

"

Mc ±,
l l
,

S 1 mechanism
N

K i n e t t C S s t e r e o c h e m

limiting step : formation of Ct

rate k ( substrate ] * rate
since there Ct either side attacked
- -

=
is a ,
can be
-

loss of LG

first order mixture of Rand S products

fig
. '

rxn

'

Uni molecular

.
not affected by amount of Nui

s t r u c t u r e o f s u b s t r a t e

steric hindrance is not an issue

'

carbocation stability #
'

methyl
-
l
primary c secondary (
tertiary
hyper conjugation most stable

more susceptible
ELIMINATION
B elimination
HII
-

B '
'

removal of a leaving group and a small substrate

(
7- a
usually HI to produce an alkene / alkyne

)
-

regio selective : production of mixture it unsymmetrical

(

&

Zaitsev Rule
•
'

B B
-
L R

i
r
-

proposed by Alexander Zaitsev 11875 )

vary in other
-
reactions -

production of a more substituted alkene

mechanisms :
°
possible
Hana

:(
'
Ez cleavage of the C C
-

simultaneous H and X bond C

Cy
- - -

Gx
Ei the C X bond cleaves first ; giving carbocation IB
'

µfNu
-

a
-
-
: :

strong base
'
-

subsequent base attraction of H

c -

c
,

" " ×
E. CB -

conjugate base

-
base attraction of It first ; production of carbanion

predominates In biological systems

E mechanism
2

bimolecular
B:
-

J
-

alkyl halide is treated with a strong base ( OH OR )

,

concerted w/o intermediate preter H

Mh

E mechanism
I

×
stb .

same mechanism as Snl but subsequent removal of A rather than

-
¥0 substitution

-
E, and Snl occurs together

usually uses hydroxy lil solvent and non -

basic Nu
-
-

have ionizable proton neutral Nu -

E cB mechanism
I

Occurs usually with acidified H

°

a poor LG like Colt ) or

due to resonance w/ C -
O

2 carbons away
LG
from
carbonyl
conjugate base

- -

acidic due to

resonance
SUMMARY
°
I RXIROH Snl if Nu
strong nucleophile but weak base ( Eg I Br : NH , )
-

is a .

Ez if Nu is a strong base and strong nucleophile ( OH OR ) ,

E. CB if the LG is 2 carbons away from a carbonyl group

IHO C -
-

CH -

C
-
-
O)

2.
°
RXIROH Snl base ( Eg
if Nu
strong nucleophile but weak I Br : NH , )
-

is a .

Ez if Nu is a strong base and strong nucleophile ( OH OR ) ,

E. CB if the LG is 2 carbons away from a carbonyl group

IHO C -
-

CH -

C
-
-
O)

3° RXIROH Ez if Nu is a strong base and strong nucleophile ( OH OR ) ,

Ei and Snl if neutral and acidic conditions ( weak base and weak Nu )

E. CB if the LG is 2 carbons away from a carbonyl group

IHO C -
-

CH -

C
-
-
O)

exercises
"
" b""

y ÷%¥
1) Cl
-
elimination ( Ez mechanism)
20
B

"
" "

!
"

get
substitution isnt mechanism ,

NaN ,
3) # Br
Ether NN 's

41
N KOH
I →

Cl Ethanol

"

Lyter
6)

it EH
⑦ OH Ether
alcohols
!! ! !and
! phenols
! ! ! !!
!
!
! ! !
! ! ! !
!
!
! !
! ! !

f.etnI .BY/e !:Iai tieue.sowentanaJ

A l C O h O l s Applications
'
-

OH
group is bonded to a saturated sp
-

hybridized carbon (C -

OH )
-

Industrial ,
Pharmaceutical ,

Fit !onae! . an maturing car -

on

alcohol derivatives where O is replaced by S ( R -

SH )
.

phenol -

general disinfectant

PROPERTIES ether
mono , phenol
-

organic derivatives of H -

O -
H ( R -

O -

H ,
Ar -
O -
H . R -

O -

R )
'

and property '

O
'
-

almost same geometry with water →

tetrahedral H H

solubility : at most 4C alcohol are highly soluble in water

alcohol has dipole -

dipole
( esp t -

butanol for 4 carbons ) F'OH TOH

-

r -

boiling point :
higher Bp than corresponding alkane

( formation of T # Of C 's T Bp T branching t Bp

H -
bond ) , ,

Io alcohols have TBD TLDF t surface area → ewasattffttabekeodmebbsow.ae

acidity
-

amphoteric species → It can act as acid l base

'

can act as weak base ( formation of OXOMUM 10h )

-

O has 2 lone pairs ( electron pair donor )

can act as weak acid ( formation of alkoxide 10h ) -

due to proton 12 able H ( proton donor )

acidity trend :
tertiary s
secondary c Primary as Phenol

as base : as acid :

" "
~ E. of Not -
H
I-
µ ~ H H
TI:
-
→ →
, →
§ it
.

-
I ✓
H
.

H
OXONIUM 10h Alkoxide 10h

NO -

// / phenol
-

the oxygen is attached to an aromatic ring ( electron rich group )

→
tendency of

¢ electron is to go to the ring

→
O
-

H bond weakens →
It is easily given oft

→ To:
No -

H
O H broken since H cleaves
is
-

primary
-

A It
1-
→
OH +
stability of
OH
-

tertiary the O cleaves OH carbocation stable OH given oft

→
more
-
→ is is
p r e p a r a t t O n ( From carbonyl compounds )

Gen mech : basic

Reduction OT carbonyl group a
• .

H2O

y
-

!
'

9ft
:
From aldehydes product is " alcohol
→

µ H
.

From ketones :
product is 20 alcohol
,

*
use Nabha in water lallohol solution

From aldehyde :
From ketone :

O NABHC, HO O HO
NABHA
→
Hit X
-
, la
H H

p r e p a r a t t O n ( From carboxylic And I Esters )

yields primary alcohol ( due to addition of 2h ; using stronger reducing agent )

-

use of 4AlH4
-

O O HO

11 or 11 t, ITH
TOH XOR ' H

and ester to alcohol

carboxylic

p r e p a r a t t O n ( Rxn of Grignard Rat with 1=0 )

addition of alkyl nucleophile ( R :-) mechanism :

" alcohol
produce EY
'
From formaldehyde Br
:
Ma
-

→ →
µ H it
t,
From any aldehyde :
produce 20 alcohol

From ketone produce 30 alcohol

:

From formaldehyde :
From aldehyde :
From ketone :

II I Mei II
O " O
Hye Mg Br
- OH ''

X. X.
-

* " . x.
R CH z
CH 3

examples
r e a c t i o n s

dehydration
elimination of water to an alkene '
-

produce "
'

'
t

: :O :O : :: 'm :c:::i: :::c: ::: 'm .

major minor
:
mechanism

"
" I:* - t.io -
"t
-
→
'
'

+ not

oxydation
°
(A) I OH oxidation ( depends OA )
yields aldehyde , then carboxylic acid It continuous on

( B) 20 OH yields ketone

K) 30 OH does not react

II
''' waiaka "

II
"" " nana

I
"" -'

II. I Io Nr
Proton Ra ble H
. .

For 10 OH :

"
'

use Des -

Martin Period inane for aldehyde product NH →

DMP ~
I 11
0
( weak oxidizing agent : expensive for large scale rxns ) OH
KMn04 hot
, ,
acidic

'

use cross or Naz Cho , for carboxylic acid product NH Of OH

DMP /
OH 0
( can 't Isolate aldehyde )

For 20 OH :

OH O
period inane for sensitive
use rxns
Periodlnane,
'

y , y
use Nazcrzo , for large scale
'

conversion to ethers
.
rxn of Ott with alkyl halides

.
Williamson Ether synthesis :
uses strong base ,
NAH

-
SN 2 mechanism ( for lo alkyl halides since Ez will occur with more substituted substrate )

A
a- I H

]
-

I
→ → out Naor
-

H :

acts as 110 alkyl halide )

( from NAH ) alkoxy
acid

For unsymmetrical ether products : product Possible reactants

( 30 )
+ OH Act ✓

|-O
t
use more hindered alkoxide with /
-

less hindered halide 110 halide ) fo , t Nott X

reaction of phenols
can 't be dehydrated using acid
-

°"

f Hoot ,
Benzine :
unstable and reactive

can 't be converted to halide using HX

EI
" "

EI

electrophilic aromatic substitution (eas)

most common reaction of phenol due to aromaticity
'

-
ortho and para products since OH is an EDG

EI
"

te.EE
"

para

conversion to ethers (using K2 ( 03 )

EI?
"
+ ~

oxidation of phenols: production of quinones

-

does not oxidize same with aliphatic OH since there is no H in the hydroxyl
-

bearing carbon

EI EI
"
'
#

f s÷!o
"t

Bemoan none at
e#ers and epoxides
e#ers
-

contains the R -

O -
R
'
structure → least reactive form hindered by R -

groups

derivative of water Ioa go

( )
.

structure and properties Bolllngtolnt

'
hybridized / \
I-
-

sp -

- g Toit
nearly tetrahedral geometry ca Hao C2H60
-

240C 78.73°C
lower Bp than corresponding alcohol
-

preparation
acid catalyzed dehydration ( Snl )
'
-

- H
- O H H2O

T.o.tt
' H
V'
it Al

t.o-H-s-y.to to:X
→

\
→

l - I
H -
H n
Tio
' .

-
H
.

williamson ether synthesis ( Snl)

OF alcohol Other Preps :
Alkoxymer curation
-

Demerol ration
strong base
-

rxn with a

-5 Reagents :

T.ci?HHu →
→ -
÷
11 Hg COACH ,
ROH

2) NABHA

reaction of ethers
acidic cleavage
-

R
'
O R X R
'

R t X
- - -
-

→ A t

In H Cl
it:c ,
-

✓ →
✓
0 -
→
- IH t
Hac -

Cl
,
H

with Xs HX
=
H

✓?
HIT → Hac - Ot → " 3C -

Cl t H2O
It
q:c ,
-
epoxides
cyclic derivatives of ethers very reactive due to ring strain
- -

special names : .

simplest oxlrane :
ethylene oxide

D U H

# " H
X

Langa Yar
nomenclature
H
oxirane oxetane oxolane
X
strain ring
% most reactive since ring strain is very strong → prone to
ring breakage

0 is
highly electronegative because of ring structure

↳ does not want ring bln C O bond which has 2 carbons

only
-

preparation
'

alkene with Per oxy Acid ( MCPBA -

meta
-

chloro per oxy benzoic acid )

( )
X X o
"

tmuz
"

① ton O t
, o t r
= t MCPBA →

,
.

carboxylic

from halohydrin
x x

÷! "÷l:i:* ::o
mechanism :

'

' in
:÷÷n:c:
'

"
.ru .am .me . .

:*.
-
→

only when C is chiral

reaction of epoxide (ring opening - basic or acidic)

b a s i c
OH

① '
-
OH
SN 2
H2O

mechanism :

TH - In ,
U
'

work-up
:

In '
→ ,

Ton .
OH
i.
EH ~, basic medium

nucleophile
A C l d l C

Sn 2
D
OH

mechanism :

H2O as nucleophile

÷
''

-
.
. .

ROH as nucleophile

'

"" " → - '

' "-
.
.

e x a m p l e

'

÷
:
"
nona . .

"

unsymmetrical epoxides (stereochem)

H

't
fo Nu
OH hindered carbon
↳ 1-
( → less
.

Nu

µ ¥
""
→ Partial carbocation

Inn I
character ( no carbocation )

I
"

it
.

iii.
÷:: -

e L men . .
I
,
e x a m p l e

÷÷÷ ÷
-

. .
. . .