Test # 2

Capital 04

a estmctura tridimensional de una Molina se denomina estereoquimica

Conformations
•

de
•
rotation oeuvre entk enlaces seniillos entre dos carbons
akanosaciuisos
↳ esto causa los otwiatomo , enlaiados cambilnde orientation
que
las conformations diterentes los atoms rotacion
•
de causa dos por la
son
arreglos entre

or

enlaces
Tiposdearreqos

•
enlaces

eclipsed a
Caborn
de un enuuntan direct a Mente Aline ados all carbon 0
adyaunte
•
se con cos
§

:I • al wtar los enlace de un carbon 6o°

,
se wnvievte en Altetnada

:5 A
'n9YYinedral
g

¥ altevnada
•

• 101 enlace de un carbon bid can el

ahgulo de enlau del otw

Las
proylccionls newman
reagan
los 3
grupo
I enlaiados a Ioc 2 carbon Os particulars
↳
siempre solo se consider a Un enlace C -
c

Lal el Miano estabilidad

contumacious no
computers grado de

↳ las conformations aitevnadad estables

tienen Menor
energia y
son mad
que as eaipsadas

Las repulsions electionelectro 's

-

son mayor es entre los enlace de una conformation eclipsed A

↳ Mma
energia
Cada enlace la 4.0
c- H eclipsado aumenta por

La tension
angular es I ailment en
energia causado por
las interactions eclipsadas
↳ tension aumento
esta result a en an de
energia

solo enlace
eswgl
•
se un cc

Contumacious deal ( anos con

Usitan 600
•

6 a
Mas de un enlace c- c
M 6 rotacionel de para hegav a

Conform acio 's original

estos ningunas la conformations

en
iguale
de
•

cases ,
1 son

•
Altemada anti →
Ma 's mention 180
los
gwpos grandes seen a entre si

••

's estin Si
°

Ahemada until
grandy
60
gauche los
grupo
a
→ Ma
 La tension estinica es un Alimento en energia que result a Wando losdtomos estain fovzados a estaraka

↳ Es
por es to que general
Mente ,
las contumacious Gauche son
mayor es en
energia

'

catambiin
'

la tension este ni atecta a lat wntovmacione Gauche

Ej cuando los Mais grandee eclipsan

-

se
-

guipos
.

ahemadas
energia Is

[
contumacious se enwentran en Menor
-

§
g.
qq.ca .
-
intevacciones estihicas no favorable s aumentan energia
a

- -
-
- .
- -

Angulo Dihedral

La difevencia 's
en
energia until las contumacious on
mayor y Menor
energia se llama la
barrera de rotacio

tipode Interaction Increment en

Energia
KJ / mol

Hitt 4
eclipsada
6
H , CH } eaipsada
CHs ,CH3 lclipsada
"

gauche CH 3 3.8

indicator conformation a menor

energia

Introduction a
°

las wntormaciones de cidoakanos son ate Hadas por

la tension angular
CKIOAKANOS ↳
elahgulo tetrahedral sedesvia
'

la tension aumenta Wando enlace 10950

angular de an de

Baeyer strain Theory

asume los cicloalcanos anillos pianos dngulo ia

-

que son el enlace del tamano Anil 10

y que de depend del

anillos oinguws enlace difeventes tetrahedral estah tension sumamente reactive

de
bajo
-

al aha
con
yson

's molecular
Rlsu Ha que los cicloalcanos con ma de 3 cavbonos no son planaj
 CICLOHEXANO

•
Tamaro de anillo Ma
's comin en wmpuestos de ocuwencia natural

sielaclohexano these mowiula tendriademanada tension

una
planar ; angular 4 torsional
•

Cklohexano conformation MAE

•

de Silla la
adopt a una Wal es estabw

up

down
] Eli Mina toda la tension
angular ya que
todos 105
Cingular de 105 lnlallf c- c- c son de 109.5°

Aggregate Hidrogenot axialls local izadol above and below elanillo

-

Hidhglnos eulatonales -

local izados en el Mano all Anil Io

Ring Flippin 9 •
ciclohexano no
permanece en una sola contovmacio 's Sino
que
los enlaces

se doblan

(
:
Mororraba.se U
aka
n

U soo
reasons
Silla bote Silla

los Cavbonos de Amba converter carbons de

en
Abajo vice versa
-

se
y

los
hidngenos axidusse converters eulatonau
-

in nice versa
y

k
Ymol
'

las tension este hica

wntovmaciones
angular
silk 30
de son Ma 's estabus que la de bote oebido a la y

•
la position ecuatonal time ma 's espacio que la axial

Cidoakanos
↳ estah
swbstituyentes de mayor tamari Ma 's estate en la position ecuatonal
Substitutions
after ring flipping los
sustituyentes se
que dam hacia U mismo lado lo
que cambia axial oecuatonal
.

es
;

up
-
axial

down em atonal
FI
-

up -
ecuatohal

down - axial

Ambas conformations sonditerentes Asi estabilidad Vania '

que su
porque it
sustituyente esta placed differently

Sustituyentes axiales
grande , cream interactions diaxiales 1,3 no favorable que de -

estabilizanuciclohexano

tilnln isomers
•

cis trans
y
Cicloakanos

Disubstituidos trans Cis

tea . ,
111111 sea .
*aosI

: th
sustituyentes
up Or down
 chapter 5
-
-

stereochemistry

Gases Principals lsdmuos son diferentes compuestos con ia msmatovmula molecular

de lsdmeros

Exisan dos uasls principals

Constitutionals estereoisimeros
Ditilren en la cone ctividad solo difilren en la Manera en la

de is atoms cual ios atoms estin oientados

Tienen end espacio
•
Diferentes hombres IUPAC Tienln

Gmpostuncionaus variants Nombres WPAC idinticos prefijos

•

con
•

piferentespnpiedadesfisicas Cis trans

•
o

•
Diferentes propiedadesquimicas •
Mismos
grupostuncionalu
Difieren en
configuration
•

Quival VS Lo important es si la
imagen de
espejo
es identical odiferente de a Moda
Aquiral

iniagen
una molecular some
QVIRAL puedesobreponer la de
que no se

( No identical
espejo son

AQVIRAL una Molina que se

puede sobreponer some
suimdgende
espejo 1 son idinticas )

*
Carbon osenlaiados a ouatw atoms diferentts son
qui vales *

↳ centos eotereogeniws

'
•
Las Molinas auivaws son enantio meal

↳ '

de
espejo
no se some
ima genes que pueden part

Generalmente Molina estereogehiws

•

,
si una no time Antos es
aquiral
•
Si la Moldova time un Centro estereoginiw tetrahedral siempre es qwiral
si time +
centres estereoginiws puedl set
quival 0
aquiral
•
2

Un plan simetvia alla Mita d reflex ioh

'

o de aorta una mole la ambos ladot sean una

por para que
↳ maiailas simetna
las qwivaksno tiemn Manos de
 Antos Cualquilr ditlrenhtsenlaiados
•

carbon
quips
o con cuatro aet a un
,

Esteveogdniws centro estereogeiniw tetrahedral

6 se considerer atodos los atoms en an unidad

grupo
como una

Carbons sp y spa no son centos esteveoginicos tetrahedral

Dtbujar maiwlawnun
Ehantiomlto
una antpoestereogeniw tetrahedral exist comoun parole
enantiomlns

CHZ at 3

° C
H It

. .
OH
CHZCHH OH CHZLH 2

minor

identifier
Para centres estereogehiws en anillo ,
dibujael
•

an se
centre
Estlreoginiwsm amino plan amente
y se began los carbons enlaiadls a man
compuestosuidiws
gwposditerentes

Wando
lossultituythtes dflientes aebewmpararkd
•
son se
;

atoms que son equidistantly all dtomo en Westin

Example

time carbon tetrahedral qwival to hau exist

an
que que Como an

Par de enantidmuos

or
•
+
H
 in utilize enantiomlnt
Configured se
para distinguir entre
•

R S ↳ a send hombre
Wii
lizard R NPAL
0
prydjo
0

est se hau
asignando una priori dad Cada
gupo enlazado
al onto
•
a

estereoginiw
↳ dll narrow atomiw
llguipo
* la
pvionidadseasigna order
de en

mend prioridad ↳ el mayor Minero atomiw time la Mayor prionidad

↳ si atoms
time
que
esta dos en mango
esterloginiw son
igualls ;
hacia atra
's se
asigna la plionidadbasado enlos atoms lnlazados
↳ sisl isotopes Order
usan dos ; se a
sign an laspvioridadls en de

decreasing mass number ( mass # ma 's Alto =

Ma 's pnionaad )
↳
doble enlaces se divider

'
"
Diasteroiso Maximo
'

Menos Para n Antos estereoginiws ,

elnu men de estereoisimens es 2

Paso s
-

a
Dibiyia un e stereoisomer
Q la
Dibuja imdgln de
espejo
a Cambia las poniiones de dos

Sterling
gwpos
a
Dibuja laimagen de espejo

Dia estueoisdmuos de
son
que
no son
imagines espejo

Compuestosmeso Un wmpuesto aquiral que time centos estereogehiws tetrahedrons

↳ linen simetuia
plan de

Rosen
Configuration •
Cuando unwmpuerto time Ma 's de un centre ester
eoginiw, sedlbe

Compuestos an 20 aoh a cada uno

asignar configure
antws esterwginicos
's
ma

Compuestos idintiwstienen as Minas Rys mcada cento

designations

Enantidmerostienen Rys quests

Diastuoisomuostienen identical una

opullt
designation
•

una y
AUOAKANOS Rewerda ailoalcano disubstituido tenet isomers 's
ytanl
que an puede u

Disubstituidos W
LD
Dibujavdiastenisomuos cisyvans son estereoisomuospnnf
[ 21 de Cada de
Dibuja la
images de
espejo who
y imageries espejo
determine st se
puedln sodeponer ✓
[ 3 ] sisl
pueden sobleponlr y tienlnplanos de son diastetoismens
simetua ; es
med
[ 4 ] Si se
pruden
no
sobllponlt ; son

enantiomeros

Resumed :
lsdmeros

Wmpulstosditerentes con la misma formulae molecular

constitutionals Estereoisdmuos
varian tridimensional
varian en wnectinaad end
aneglo

Ehantidmeros Diastenisomeros

imdglnls de
espejo no son
imagines de

espejo
 Pwpiedades Fisicas de Estero is O' mews

las pnpiedadesfisicas yquimicas de doslnantidmeros son idinticas except al interaction con

substances guide

Actividad Optic a sosenantiomenstienenpropiedadestisicas idinticas except en la Manera en la cud

interaction an
bajo una luz pdaniada

## YI: una

eawz
luz polarized a
sense
reiuja
es

en
aquella que
an Mano
es posada por Un filth de Manera que

Con compuertos aquiraks , lawz pumaneuigual use dice que son

dptkamente inactive

Con
wmpuestos qui raw I
plano de la
luz polarized a cambia
↳ al ambio se llama la wtacion obslhada
elahgulo [

se did I wmpuesto es iptilamente actin

que

Diana rotation puedeser law contra del vuoj

a 0 en

v ✓

bexrotatono lewrotatono
d / Ct I l / C- )

Dos enantioimeroswtan divecci ones opuesta

iguaemente in

'
Mezda Race mica time la misma cantidad de cada enantiomen y es opticamente inactiva
Parque
las rotations guests se canaan

Rotaoion lantana 's Obsorvadadlplnde del mimeo de medullas quirks interaction

e specific a que
Con la kkpdaniada
y
constants
concentration 4 all tube
Depende de ea del
largo

Rotation =

Ytaciohobservadadm
) 91mi )
Especifica (
 Ehantiomeriw enantiomuo
'

Exleso Wando Mada mica

•

no es an
puro o una race

pureza jplica exusoenantiomenw =

%
enantiomuo ,
- % enantiomena

'

Not dill want de an lnantiomen esta en ex Uso an relation Alameda race mica

t.li/Usoenantiimenw
'
-

100% =
mud a race Mica

.
'

data = Cuarto nay de Cada Manlio Men

"
2

Uso t %
enantidmelo =
% total del enantiomen A

-
%
total de enantiomen A -
100% = %
total all enantidmln B

ex Uso = a- x 100

enantiomehiw [ a ] enantiomln pub

Pnpiedadls Fish AS
'

pwpiedadl diterentlt
:
Como no son ima ( de tienln
•

gene espejo ,
master isomers ✓

la rotation optic a
incwye
•

Debi do a
que
dosenantilimuos tienen ,
las mismas propiedadls final
no pueden sew slparadol por teinilas de separation fisica
↳ '

Por an diastehiso isomers constitutional

, los
lado nude pueden
set
separados por tetnicas de separation tibias
 Chapter 13 -
-

E spectrometric de Mas as
y E spectroscopic de Intra
vrojo

E spectroscopic •
usada
para me dir el
peso molecular y determiner la formula molecular

de Mas a

la Moldova de e-
es
vaporizada eionizada por medio de un bombard 0

formdndose Asi cation's

'
↳ est ha la mole una pierda election radical
u
que un un
+
[ m
.

→
elma 's alt K denomina base time
pico y a

Mayor abundance

→
plniltimo se denomma pho Padre
=
MM

Mt
→
=

isotopes

La masa ion molecular la Misha del Compuesto ; pores to de utilizar

all es u espeuw masa se
piled
ventre compuestos wn
propiedades titicas similarly pero Mas as mdaresdiferenty
para distingue

Complies to
que contienln C , H 40 simple ten drain in valor de masa de an ninon par

de
Para
pioponer Formulas an
# impair indicator
[ is
MY = # Cmax
present al an dtomo
12
Nitrogen
[a]
foimula G
¥
an # cmax

µ
una Modula an an # impair de M

[ 3 ] 10 =
City atoms de N ,
tendroi una Mara molav impa ✓

Chlorine and Bromine have 2 isotopes

d a
35 79

Cl Br
37 81
a Br

a s
3 :L ratio I :L ratio
 Espectoswpia de la fuente de
energia es radiation
electromagnetic a

lntrarrojo
energia con
radiantde
propiedads onda 4 particular Gul
*

caractenia por ea Onda

ytiecuencia
↳
Haman to tones
las particular y
Cada uno tienela energia de un
quantum

× distance twm
point adjacent
=
one
point on a wave to the same on the wave

Frecuencia =
ncimew de ondas por unidad all tempo

Velocidad de = X . V

vadiacioh
electromagnetic a

6.63×10-34 )
lnltgia fotoh 9.
V ( s
de
.

Un =

Absorption of
light causes
changes in the vibration motions a a molecule
••
•

Bonds stretch and bend under

light
can IR

112 characteristics

:-

§ +
-
caaa
piw correspond a un enlace difetentl y
Cada
tip de enlace
± c

E in cavactenstica
foot trewencia
Owe a una
s
§ §
§
× + Region de Grupo E I
tuncionalls
±
El IR depend
lugar seabsovbe enlace
particular U
-

donde un in

de la fortaleza del enlace

y
la MASA del atom

Wavenumblt ↳ enlaces MAJ fuertes se absorber a wave number Ma

's altos
,

↳ dtomos linanos se absorber a Wave number mall Alto

H
refujan
C H 0 H N se al EHKMO izquierdo
-
- -

⇐ c ⇐ c c .

c
Cabonoswn triple email se
vetljanmds hacia la
izquierdo milntras que
los enlaiados Sevilla Mente se muenen haoia laderecha
↳
fingerprint region

functional group region are due to bond stretching

 .

Para enlace sea absorb ido a I r el moment dipolar

que un en
,
debe haber un combo en

aurante lavibracio 's

# in Satu radio's = # C -

(
# H +

#z
x t # N
) + 1
 Chapter # 14

Nuclear Magnetic Resonance spectroscopy

NMR is tool for it to

the most
powerful characterizing organic molecules because can be Used
identity
carbon framework
the
hydrogen
-

'

}
HNMR -

Determine the # and type of A in both interacts with a

"
,
energy
GNMR Determine the
type of carbons Molecule
-

the source of in NMR is radio waves that the nuclear spins of elements
energy change some

G she one with odd atom R numbers

Two variables NMR

Affllt
↳ 1 )
applied magnetic field the stronger the
larger energy difference
↳ of radiation
frequency

the number ot NMR

signal equals the number
•

Saman of
different type of protons in a Compound
↳
equivalent protons give the same

µ
NMR
NMR
signal
console workstation

equivalent if they
•
two proton are are u 's or

trans
conducting
magnet
•
where A particular photon absorbs depends on its environment

protons near
electronegative
atoms are deslnilldld
and absorb downfield

downfieldfield
•
Photons on
Benzene Rings , carbon -
Carbon double bonds and absorb

•
Carbon
-

Cabon triple bonds absorb

up -

the area under an NMR

signal is
••
proportional to me number
of absorbing protons

•
carbons around it +
splitting
= I
 Test # 3

chapter
-

@
-

Reactions
Understanding Organic

Reactions are at the heart of chemistry

organic
↳ All few basic
together by
chemical reactions are woven a memes

Equations
for Reaction
writing Organic

drawn with reaction between material and product [ ]

starting
a
usually
arrow
•

single

[ ]
sometimes drawn side the equation above / below ×

left
the the arrow
reagent is On of the
•

or

the solvent and temperature may be added above or below the arrow
"

hv and A used for reactions that require light heat

•

is or

without [ Yas
]
reactions
drawing
when two carried out
•

numbered
intermediates ; steps
are are

↳ this
that the
reagents are added in sequence
signifies

kinds reactions
of organic

a. SVBSTITVCION
Un atom veempeaiado povotn
0 un
apupodeatomos es
.

se vllaci On A los enla US 6

-

↳ enlace 6 se otw 6 forma I MHMO carbon

un wmpl enlace se en o
y

Z
Y

+ Y + 2

Z =
A or hetero atom

b. EHMINAUON
" "
elements material lost formed
of
starting are and a it bond is
-

the

Y
reagent
+ + x -

X Y

two × and Y are removed from a

starting material
groups
G two 0 bonds are broken and OM I bond is formed
 To determine the
type of Reaction
Addition and Elimination

with
complex materials
are opposites starting ; tours
functional that
on
groups change

a ADDITION
elements materials
starting
are added to
-

+ X -

×
Y

I bond is broken And two bond 1 Are

6
formed
-

Bond
Breaking and
Bond
Making

↳ A reaction mechanism is detailed description of how bonds and

a are broken
formed af a
starting
material is converted to a product

↳ relative and rate bond and formation

Describes the order of
cleavage

↳
explains everything about a reaction and accounts for all products

One Two reaction

step reaction step
& d

concerted reaction stepwise reaction

A -
B A →
unstable are active intermediate →
B

cleavage
When bond is
a broken , the electrons in a bond can be divided equally Or
unequally between the

two atoms of the bond

equally dividing the electrons between two atoms is called 1

homouysis homolytic cleavage
A- B A B
•

+
•

unequally dividing electrons between two atoms is called hetero

wpislhetewlytil cleavage
•

At
-

+ B :

A -
B
-

+
A :
+ B

Electrons normally end up On

the most electronegative atoms

 reactive intermediates with unpaired electrons
Homolysis uncharged
•
=

Hetewwsis intermediates
•

charged
=

radicals ,
carbocations and earbanions

•
Curved arrow notation can be used to represent cleavage

HOMOHSIS
AFB
✓
→ A .

+ .
B To illustrate movement of a
single
election ; use a halt -

headed

aimed arrow

HETEROMSIS At → at + B :
.

A intermediate radical
single unpaired
reactive with a election is a

↳ unstable intermediates in radical reactions

highly ,
no
charge ,

Hetenwsis can
generate carbonation or ( avbanions

polar reactions occur when a

electro phills nuluophies nuueophill reacts with an

electro phiw

both Are unstable and reactive

band
formation
↳ releases
always energy

Bond formation two

ways
can own

[ it two radicals can each donate an electron to form a two -

election bond

nn
A +.
•

B →
A -

[ 2)
two with both electrons
ions can come together the
negative ion
donating

~
At
-

+ B : A -

B
 arrows

Curved arrows specially Important because show what electrons involved in

•

are they are a

reaction in and reaction via

,
how
they move
forming breaking
bonds and
if a
proceeds radical
or
polar pathway

between material and

-
starting products

-7
equilibrium
e-
resonance

~ movement of electron pair

~ movement of
single election

Bond Dissociation
Energy
↳

energy
needed To hemolytic ally cleave a covalent bond

°
is Absorbed endothermic
H AH
energy
=
=

Alto
enthalpy change heat of reaction
= '

is released exothermic
° =

,
=
, *
energy
.

↳ indicates bond strength

°
•
Homann 's has a HAH and is endothermic
• Bond formation has a Hato and is exothermic

the stronger the bond the dissociation

higher
•

, energy
•
Bond dissociation Decrease down a column
energies
↳ valence e- in
bonding
are
farther from nucleus

•
Bond dissociation is and to calculate AH°
energy
↳ AH
°

indicative of bonds broken and

formed
is of the
strength

H ) A Ho move is needed to break than is released in the formation

energy
=

in
starting material bonds are
stronger than products

is in bonds than is needed break them

released
forming
C- into more to
energy
=

bonds are than materials

formed stronger starting
 1- )
°

sum Of DH t sum of AHO

AH
°
=

all broken bonds all bonds formed

Bond dissociation has two limitations

energy
[ D overall
present changes in
energy
↳ reveal nothing about mechanisms or
speed
[ a ] reactions
Only for in the
gas phase
↳
carried out solvent
most
organic reactions one in a
liquid

thermodynamics Describes
energy
and
equilibrium
equilibrium
must favor products
and the speed reasonable
kinetics Describes reaction rates

Equilibrium constant and Free Energy change

Equilibrium constant Keq relates the amount of reactants and products at

equilibrium

[ Products ] favors
Keg when K > l
equilibrium products
=

-
;
[ reactants ]
when Kc 1

; equilibrium fawn reactants

determined relative reactants and product

Keg is
by the energies of

↳ the tree of molecule is called its Gibbs free

energy a
energy
( Ci )

D6°
in the between and product
change energy reactants
↳ Determines direction of equilibrium

keg
when > I

/ ldlal
CA and boot )
log Keg
D6°
Model 47
2.30312T
logkeq equilibrium fawn
= -

\ when Keg
< 1

Keg c- ) and Ault )

log
veauantl
equilibrium favors
D6° depends on the
log Keq

↳ A small change in
energy corresponds to a
large difference in the amounts

of reactant and product at

equilibrium
 Equilibrium the
products when they stable than
starting Materials
•

favors are more

Energy Changes and Conformational Analysis

•
the past equations can be used for any processes with two States in equilibrium
allows
the
energy difference between two
conformations as to calculate
•

knowing
the amount
of each at
equilibrium

enthalpy and
entropy
s s
AH
° °

DS

measure of randomness
the disorder the
more
entropy
, more

for example ; gas molecules move more

freely
and are
therefore higher
in
entropy
•

molecules lower in
cyclic
•

are
entropy
°

AS and
is in amount disorder between reactants products
•

the
change of

↳ Ct ) when products are more disordered

a when reactants Are more disordered

Reactions increase of favored

entropy
•

in are
resulting
an

AG° AN T As tells the

as tha
energy depends on
= -

T; Kelvin
enthalpy and entropy

In reactions that not carried out in

high temp ; toss be
are can
neglected
so the is estimated by
energy
A6°
°
I
AH

AH
°
C- ) products tawvld AH oh ) reactants Favored

•
a material forms two products entropy increases
when
starting ;
decreases
when an acyclic compound forms a
ring entropy
•

;
 energy diagrams
↳ turned
representation of
energy changes
that take place al reactants are to products

Indicates how how

readily a reaction
proceeds ,
many steps and how
energies compare

€
transition state

Ea =

Energy of activation
between reactants and Transition
energy difference state
•

Fame
minimum
tao.tn?emenugmdedaofoermfaaeubonosinreauam
•

Is
→

reactants
reactants
°

AH lower than =
exothermic
A Ho
Alto than reactants endothermic
higher
=

products
°

Reaction coordinate Ea and DH are

independent of each other

↳
a reaction
progress of

the unstable maximum is called transition slate

energy
↳ and
bonds are
partially broken partially formed
↳ transition state can never be isolated

draw a transition state

structure is between
the the
starting material and
product

Bonds partially broken or formed are

represented by
partial 0
Atom that
gains
or loses a
charge contains a
charge
-

Drawn between brackets [ ]

±
Supperscript double
dagger
-

[ E)
of
±

. - .

B- . .
 for
Energy Diagram a Two -

Step Reaction Mechanism

Reaction Occurs by a
stepwise pathway
↳

breaking
bond bond
occurs
before making
[ ]
clearing
↳ endothermic -

products at
higher energy

To draw must draw each combine them

energy diagram
an we an and
,
energy diagram for step
↳
Each step has its own barrier and transition state
energy

the step the transition state is

with highest energy
•

called the rate -

determining step

A A( µ
transition state at maxima
•
are
energy
=
+
0
AH
Reactive intermediates are at minima
•
an
.
-
energy

Each step has its Own Att and Ea

•

There Overall
is
different
•

an
energy

Las reaccionei de Adidas son exoteirmicas

porqul los enlaces 0 tornados en los

mis enlace
products son fuertes que el
0 IT en los reacting
y
 Chapter 10

Alquenos
-

Because easily addition

alkenes
alkynes undergo
•
IT bonds are broken and
,

variety ot addition reactions

euctwphyui
with in
react a
reagents

alkenes

alkenes
Terminal have the double bond at the end the carbon chain
of
•

•
Internal alkenes have at least one carbon atom bonded to each end the double bond
of

Ailoalquenos linen doble enlace

•
an en un anillo

El doble time enlace

enlace
)
•
un or uno it
y
ll whale IT ls 's
Ma dibil
Cada spa y ( ;
Carlson
tvigonal planar )
boo
•

o es

por estoparttiipan en mis machines

lose olcanos
que
Tienen rotation da
resting
•

Wando alqueno
un time
gwposdipuntb final enlace
•

does al de an E o
;
dos diastenisomeros son
posiblej
Cis trans
y
•
trans son 's e stable is
Aequenoi Ma
que
ha estahdlidad Minero
de aumenta propauionalmentl el de
•
an alquemo con

R el ⇐ c
grupo
in

Alloalcanos
•
8 tienln as
con Menos de carbons
geometrid

lnsaturaci ones

formula molecular de Cn Han

•

up alquenotilnl una

↳ Cada ⇐ c saca dos atoms de H

4 Causa una insatuvaltoh

Grades de =
( al +2 ) -

H -
Xt N
In saturation 2
 -

Weak Van der Waals forces

low
melting points 4 boiling points
physical
-

↳ increase as the number of carbons increases

because of surface area

properties -

soluble
inorganic
solvents not soluble in water
A as Aken is more polar than trans when it a
slightly
-

giving
a
,

night boiling point and

more
it
making soluble in
polar solvents

Introduction to Addition Reactions

-
the C- C IT bond is weaker
-

the characteristic reaction of alkenes is ADDITION

F bond is broken and two 6 bonds are formed

+ X -

×
Y

Alkali Are election rich

-

↳ rich is concentrated bond

e
region and below plane of
the molecule the #
-

above the exposing

rich ; react with ueetophiles

-

Because alkenes they

-

are e

stereochemistry is important in
delineating mechanisms
-

↳
Are × and Y added to the same or
opposite sides

Anti
Syn

I \
×
Y Y

placed the side

placed opposite sides
on same on
 Result a en la adidois de Haluns ( H X ) para forma r
hidnakanos

It

i. se
romper dos enlaces 1
enlace IT del aiqueno el enlace A X )
y
-

+ H -

X -

Br & forman dos enlaces ( Uno a H yno a X )

×
y

•
U enlace HX esta
polarized d+ et H
wncarga
en

↳ electronica atraida es 's electronica

parte es al doble enlace
y por eso una Aaicio

UUW
footedness
A cido -

Base Lewis ) Mecanismo consisted dos

Paseos
cation
+
[ D Adicioh de H forma run Carbo
para
[ ] nucllofilico X
-

Ataqul de
2

M
A H
M : ijr :

izir +0
;rI
is
:
H -

slow + :
@ @
. -

MAKOWNIKOV

Con an
alqueno asimethio ,
la R/ entre Hx y el doble enlace pile de real Haven dos isomers
constitutionals

•
Eh a adkio 's de HX a un aiqwno asimethiw Udtomo de H se enlaza con el carbon metros
;
substituted 0

↳ Carbon el nci men de H

o con
mayor

Estereoquimica

Atmos iguaipnbabilidad
•

reaccionan de directories
tvigonaustdanaves dos con

Reacting aquirales forman products aauivalls

•

•
A vecessetovman news centos esteveogenkos y
el
product exist Como una mezdaracdmica
6
cantidaa = aezenantiomens

0am Aaicio 's anti

•

syn y
 Obtenlr U product Antimakovvnikov ( H )
utilizan pgoxidos ( R ) para 202
•

se -

o_O -
R

Haiogeno et carbon sustituido

•

en Menos

H Br
H

←
-

Br

OR

IUSUHA la adiciin de haer alcohol

en
Agua para un

HZO dcido debit puedl pootonav anode Has 04

•

es an que no un alqvlno ; por eso se

•
Adicioh electronica

.io
a
HM
*

M j.0.tt
@
.

- @
o
H
Q Hz Hz §
Hip
-

+
→ - + H 30 :

- .

slow

se utiliza a de Makownikov
regla
•

•
Ocuwe anti
syn y
del cavbocatio's
puedl owmivreaweglo
•

* Alcohols anadlp a
alquenol para areas tovmav etlt
 Result la adicion Xz alaulnotormando dihalun
en de an halogen 0 a an an vecinal

( a / Br )

+
' 5
•

Halogens add to T bonds because they Are polanizabw ( X -

X )
↳ × nucleophilic double bond
the electwphilic is attracted to the

No occur
rearrangements
Only • ANTI

intermediaries
•

Cavbocationes no son

Cite
di
to

.x
*
"

*.
:

¥
: :

-
-
V
0 y
'
'
' ,

g :
.
:

:
. .

10h de Hal Ohio

ls instable albedo tension
a ia
angular

Esteveoquimica
• enantiomers in a raumic mixture

trans Cis
•
or

✓
Xt
Addition of forms an unstable bridged halonium ion

✓
Backside attack of X Occurs to form trans products
-

✓
Resulting anti addition across the double bond
•
stereo specific
 Treatment of an alone with Xz and HAO forms a halohydnin by addition ot X and OH
[ I '
Addition of X
+
to form a
bridged haonium ion

[ 2 ] Nuueophilil attack by H20

[ 3 ] For macioh de Halohidnha and H3O+

MA :Xii.

C %#
"

go x x
:O
:

Ynh
"
-
"
.

- + :* - -
+ not
O'
'
O
µ
' '

\
'
.

Hao

+00
: OH
Had H
~
.

Hao
:
Estereoquimica
•
Anti y trans
•
Xt bonded to less substituted carbon
•

Hao on more substituted carbon

No
rearrangements
•

Two reaction sequence that

step converts an alhenl to an alcohol

product anti Makownikov de hidratacioh .

•
Hidnoboracio's es la Adicioh de BH3 a un alqueho
↳ atomo de
regiosekctiw ; e B se enlaia al carbon memos substituted
•

Oxidacioh wnnirte el enlace c- B in uno c- 0

nonaureanegw
[ ] '
Aaiion H enlace all
alqulno
de BH 2 al IT
y
[ ] a substitution del enlace C
-

B
por C- 0

W Aaioioh
syn
-

Haoa HO

f. ,+T ( )±
,
- -

Is
' •

*
'
I 'bµ
.
H BH H OH
+ 2
 chapter
11

Aquino
-

Alquinos son
wmpuestos que wntienen enlace triple C- C
•
an

Formula de Cn Han
general
•
a
-

↳ tilnen 4 H Menos 12 grades de insaturaci ones

↳
( Ada carbon de un
tuple enlace Here nibridacion sp ,
tienen form a linear
ydngulos de 1800
↳
triple email consist de 2 enlaces IT
y uno 6

•
Both IT bonds of a C
-

C triple bond are weaker than a C -

C 6 bond

•
Aquino are more
polanzable that alquenos because e- in the T bond are move loosely held

•
Cicloalqwinos con anillos
pequerios son in stable
↳ La Cadena de Cabo no deed set losufililntmente
largos para wnectavloc extremis del Aquino
sin tension angular
↳ a ciaoalquino Ma 's pequeno es aclooctino

PROP 18 DAOES
FISICAS
✓
melting and that increase of carbons increases
low
boiling points as the number
•
soluble en solvents
organics e insoluble s en Agua

alkyhe px

acidic
occur because they contain easily broken IT bonds oh an
sp hybridized C- H bond
•

addition
undergo
•

•
electron rich and react with
nuueophiles
spmbiidized C- H bond more acidic and
get depwtonattd with Bronsted Lowry base
•
are
strong
-

↳
pka > 25
 Adiciin de HX ( x =D ,
Br ,
1)

•
se usan dos equivalents de HX

↳ Adidas clean mol forma Un vinyl halide

↳ Adicio 's de an mol forma germinal di halide

segundo an

With two equivalents HX both H atoms bond to the same Carbon

•

of
,

•
With a terminal Alleyne ; both H atoms bond to the terminal carbon
↳ Makorvnikov
follows

often Here
:&

TEE net
in
:
:
:b: :

:b :
.
:@

Add Xa ( X =
a or Br )

Add to In much add

alkynes they to alkenes
•

the same way

✓ Addition of One mole forms a trans di halide

✓ Addition ot a second more
yield I a tetra halide

addition
Each
bridged halonium intermediate
of Xa with
•

involves a two step process a ion

= go
÷F
(
.4?
"

III. :
:
:*
:c:

'll
:

fcoi
@ 0
g @

0 D
'

):c!
:
:

ii.
i.
"
: :
:c! :c :
: : :
:
.
.

:@
.

:#
 't
•
In the presence A a
strong avid or Hg He elements ot Hao aadtolhe triple bond but the initial addition
, ,

product is an end that is unstable so it

rearranges to a product containing a

↳ alkenlt alcohol

terminal yield methyl

•

alkynes require the presence of an additional Hg2+ to Ketone

by Manownikov addition of Hao

tautamee constitutional
"

{am
c)
W
isomers that

)
o 0

differ in the location of a double bond and

equilibrium favors the Keto
= *

a atom form because a o_0 is

hydrogen
bonehead

ketone
OH toakneatoac
⇐ c co
-
H
stronger than a ⇐

Tdutomenzacioh

+07
M
:O
. .

:
%H
G
:O

- H -

? Hz
- GOH e- Hid - H t H30+
.
H H
TO

6 tautomeniacioh cambia unenol a una utond

Hidrataciobde an alquino intern wnunduido fuerte forma end tautomenia lautona Ma's estate
qulwlgo
un se a

Adkiin HZO para fovmar end

ftp.
H

¥!Hz
pit A

+0
€0 :
:O

U
@
it bit

+ H3O+
- - -

end

Tautomenizacion

.pt#
"€| M
H :iH to :#
U ÷
Hid - + Hot
-
@ - .
 two step
reaction that converts an alkyne to a carbonyl

H BHZ H OH
µ
H 0

R R BH3_ tho -

Hidwbomcioh
-

oxidaciin tautomenizacioh
R R R
R R R

Overall result is the addition of HN to a triple bond

Hidwboracioh -
oxidation de an aquino intern forma una letona
•

Hidwboracioh -
oxidation de an
alquino terminal ariadl el bow al carbon terminal Menos sustituido
G Oxidaoio's tautomeniacion aldehido
Despite's de la del end jla real Ha en Un
 •
Aquino terminals & wnvilrtln en anions de autiluw al reaccionav con base fuertes ( NANHZINAH )
↳ Reaccionan wn electro 'fil0s wmohaluws deal Kilo expsxidos
y

:O
to
nn ~
R CEC

:C
H + :B R ⇐ C E
-

c=c
-

R
-

+
-
-

- -

electro 'filo

•
Anions de autiluro reaccionan wn haluns de alhilo
para format products de substitution nudeotilila

•
the mechanism of nucleophilic substitution is SNZ and the reaction is fastest with CHs X and halun ] aealkilo

•
Substitution nuueotilila wn anions de autiluw forman nuevo enlaces t C

R -

X +
0
= c -
R # R -

C= C -

R
+ × :O

Anions deautiluw nuulotilos turtles habien anillos epoxidos SNZ

•

son
que por an mecanismo
•

Result en la formation de un enlace carbon -

carbon

I lado sustituido
•

Menos
Ataque own en

: it :O i. OH

Poe -
Ha 0
-

.
H -

C= C :@

H H

in
tint
. .

0 "
'

o ; :c = C -

H HZO
"

- - +
" "

. .
It
 Synthesis
-
-

TO plan synthesis of more than one step of veto synthetic analysis

•

a we use the
process
,

⇒
synthesis backwards from product to the
starting material
•

To write a the use

working
the
product of a synthesis is often called
target compound
•
the

when synthesis divide reactions into

designing a two
categories
[ D for C -
C bonds

C 2 ] interwnvert functional into another

one
group

STEPS
annum

[ "
Compare carbon skeletons of the
starting material and products
[ 2)
Concentrate on the functional
groups
 Chapter # 16

conjugation , Resonance a ypienol

Occurs whenever orbitals can overlap On three or more

adjacent atoms
Conjugation p
↳ dimes and Carbo cations
common
conjugated systems are 43
allylic

to

1,3 Dienes
contain carbon Carbon double bonds bond
joined by a 6
•

two
single
-
.

carbon is spa hybridized has orbital containing

-

each I
•

and one an e

•
orbitals Overlap and elections delocalize
p
↳ e density is spread out over a
larger volume
-

Isolated Dienes
↳
density in IT bond is localized between two C atoms
-

e each

all ilyc Carbo Cations

of
example conjugated system
•
a

three orbitals if one the Orbitals is empty make

on three
adjacent atoms even of p
•

p the ,

the awl cabocation conjugated

↳ stabilizes the amyl carbonation because Overlap of the the

Adjacent orbitals delocalize the e

density 3 atoms
-

p s Over the

resonance and all ylic Carbo cations

↳
↳
the resonance structures
differ on the placement of I bonds and non bonded e-

resonance structures be causations

Can drawn for aelylic

Dinos Conjugaaos
↳ tiemn ties esterevisomens posibus

R
R
R
R R

ambos trans ambos u 's Uno a 's y Uno trans

Four features Distinguish Conjugated Diehl

joining
an
C- C 0 bond the two double bonds is short

stable
conjugated
as
aim are more

ate
reactions of different
some
conjugated aims are

a. absorb
dienes
conjugated larger wavelengths

ekctnpnilic ADDITION

112 VS .
I
,
4

Gelectnphylic addition in
conjugated dines
gives a mixture of products
↳
conjugated undergo a unique reaction

from addition Ot HBR across two Carbon atoms

112 Addition results Makomikov the
adjacent

44 ADDITION results from addition Ot HBR to the two end carbons

~⇒
Br

-
+
t.fr
: :
-

ftp.s.r
:
*
*

:@
.iq
; -
Be

H
H

Kinetic vs .

Thermodynamic Product

major product formed

6 the is by Addition
At low temp ;
112

↳
high temp is formed by Addition
At ; the
major product 114

•
the more stable product is formed Slowly

faster reaction rate =

Kinetic product
lower
energy
=
thermodynamic product
 Diels -

al Der
Reaction between a 1,3 dine and a dilmphill to form a new six numbered ring

The following in common

at
initiated by heat
Has
form six member d
rings
* three IT bonds break and two 0 bonds and One I bond form

. concerted =
all bond are broken and formed in a single step

on

RUKS
•

the dine can Only react in the s -

as conformation

e-
withdrawing in the dienophile increase reaction rate
•

group
stereochemistry of the dilnophie is retained in the product
.

endo product is
prlffllld
•

↳ position longer bridge

of 2 closer to the
 Chapter IF
Benzene and Aromatic compounds

Aromatic compounds are highly unsaturated hydrocarbon that dont undergo addition reactions
•

Blnzlm is the simplest aromatic hydrocarbon

6 cuatro
grade de insaturation

Kekule