Lecture 09 & 10

Formation of Active Species

Carbocation
Carboanion
Radical
Carbene
Nitrene

Lecture 09 & 10
SN-1, E-1 (Monomolecular)
SN-2, E-2 (Bimolecular)
SE and SN on Aromatic
Radical Substitution
Addition on Not Activated Multiple
Bond

Carbocation
Carbocation is ion formed via heterolytic cleavage of
covalent (sigma) bond especially in alkylhalogenide
(R-X) compounds
Formation of Carbocation is reaction rate determining
step
Change of hybridization: from sp3 (tetrahedron) to
sp2 (planar): needs a lot of energy
Unstable and reactive
Planar geometry (SP2 hybridization) enables
nucleophilic attack from both side (top and bottom)

SN-1 Reaction
Reaction rate
determining Step

Fast

Fast

Geometry of Alkylhalogenide

Carbocation

Carbocation

Reactivity of Alkylhalogenide
The reactivity of halo compounds in biological
systems can be predicted to a significant extent on
the basis of their relevant chemical properties such
as alkylating potential and susceptibility to hydrolysis.
Bromo compounds are expected to be more reactive
than chloro compounds; SN1 and SN2
characteristics will determine the nature and the
extent of reactivity towards nucleophiles
Steric factors may also play a part in some cases
David J. Snodin, Genotoxic Impurities: From Structural Alerts to Qualification
Organic Process Research & Development 2010, 14, 960976,

Toxicity of Alkylhalogenide
TD = Tumorigenic Dose
nda = no data available
NP = No Positive Test

David J. Snodin, Genotoxic Impurities: From Structural Alerts to Qualification

Organic Process Research & Development 2010, 14, 960976,

Carboanion
A carboanion is an anion in which carbon has an
unshared pair of electrons and bears a negative
charge usually with three substituents for a total of
eight valence electrons.
This ion has a trigonal pyramidal geometry
Formally, it is the conjugate base of a carbon acid.
A reactive intermediate and is encountered in organic
chemistry for instance in the E1cB elimination
reaction and in organometallic chemistry for instance
a Grignard reaction or in alkyl lithium chemistry

Carboanion

CH-Acidic Compounds
A series of CH-acidic compounds such aldehyd, keton,
carboxylic acid, and ester compounds (compounds with
a hydrogen in -position to carbonyl group, as well
as cyanide and acetylene) have the ability to release hydrogen (dissociation) to form Carboanion

E1cB Reaction
(Monomolecular)
Fast

Carbanion
Conjugated Base (cB)

Leaving Group

The cleavage of C-H bond occurs prior the C-Y bond cleavage

pKa-Value of Some CH-Acidic

Compounds
o
pKa values in water at 25 C
Substance

pKa

Substance

pKa

Methane

50

Malononitril

11.2

Ammonia

36

Piperidiniumion

11.1

Triphenylmethane

33

Ethyl acetate

10.8

Acetylene

26

Cyanoacetic acid-ethylester

10.5

Acetonitrile

25

Nitromethan

10.2

Acetic acid methyl ester

24

Phenol

10

Acetone

20

Cyanide

9,3

Ethanol

18

Ammonium ion

9.3

Methanol

16

Acetyl acetone

9.0

Water

15.7

Malon aldehyd

5.0

Malonic acid -diethylester

12.9

Acetic acid

4.8

Radical
Radical are atoms or molecule with one or more
unpaired electrons
They are formed in a homolytic cleavage of a Bond:

The homolytic cleavage is predominant in the gas

phase and at high reaction temperature

Radical
Polar solvent on the contrary promotes
the heterolytic bond cleavage
(solvatation of formed ions)

Production of Radical
Photochemical cleavage, Photolysis:
Irradiation with Light which is absorbed by the
compound. Ex. UV radiation or sun light

Production of Radical
Thermal cleavage, Thermolysis:
Compounds which is easy to be cleaved at low temperature
(<150 C):

The substitution pattern determines the stability and hence the

cleavage temperature.
The more stable the formed radical, the lower the needed
temperature

At >500 C cleavage of Chlorie molecule

At>600 C The most organic-chemical reactions
undergo radical reactions (Pyrolysis, Crack process).

Radical Starter
Initiator of radical-reaction
Activation at 80-100 C

Benzoylperoxide

Radical Formation Through

Redox Reaction
Under participating of Metal Cations!
Ex.: Fe 2+/3+ Cu +/2+
Application: Sandmeyer-Reaction:
Possible radical reaction mechanism
(Arylradical)
A prim. aromatic Amine is diazotized and
added with a Cu(I)X-Salt
Substitution of Diazonium group through X,
possible Educts: X = Cl, Br, NO2 or CN

Sandmeyer Reaction

Stability of Radicals I
Alkyl Radical
General
Formation Reaction
Stability order

Increasing of Stability due to Hyperconjugation

Radical Stability II:

Hyperconjugation

Radical Stability III

A Special stable Radical is the

Triphenylmethyl radical
The reason for the stability is however steric
shielding of radical function, not dimerization
to hexaphenylethane

Carbene
Carbenes are neutral species containing a
carbon atom with only six valence electrons:
two in each bond and two nonbonding
electrons
Carbenes are extremely reactive species.
Application in the synthesis of alcohols,
cyclopropanes, insertion into CH bonds

Carbene
Clayden, J. Et al., Organic Chemistry, Oxford University
Press, New York, 2001, Chapter 40, page 1053-1077

Stable Carbene
Some very few examples show that certain
carbenes are stable compounds.
An X-ray crystal structure shows the bond
angle at the carbene carbon to be 102

Formation of Carbene
Carbenes from diazo compounds
Carbenes from tosylhydrazones
Carbene formation by elimination

Carbenes from diazo

compounds

Due to explosive nature of diazoalkanes, this

is not a very practical way of generating
carbenes
Instead of that diazocarbonyl compounds
are applied

Carbenes from diazo

compounds

Carbenes from diazo

compounds

Carbenes from diazo

compounds

Carbenes from tosylhydrazones

Good starting materials for these reactions are
tosylhydrazones, which produce transient diazo
compounds by base-catalysed elimination of
toluenesulfinate.
The diazo compound is not normally isolated, and
decomposes to the carbene on heating.

Carbene formation by elimination

One of the best known a elimination reactions occurs
when chloroform is treated with base. This is the
most important way of making dichlorocarbene, :CCl2

Nitrenes
Nitrenes are the nitrogen analogues of carbenes
Nitrenes have two bonds fewer than a normal amine
and has two lone pairs making six electrons in all.

Nitrenes
Nitrenes are also reactive and electrophilic, and undergo
Wolff-style to give an isocyanate.
The substituent R migrates from carbon to the
electrondeficient nitrogen atom of the nitrene to form
isocyanates.
Isocyanates are in turn unstable to hydrolysis: attack by
water on the carbonyl group gives a carbamic acid which
decomposes to an amine.

SN-1 Reaction
Only the Halogen alkane, but not the
Nucleophil (here: H2O), takes part in the
reaction rate-determining step
1. Step: Dissociation to planar
Carbenium-Ion (Carbocation)
2. Step: nucleophilic Attack (here:
Formation of Alkyloxonium-Ions)
3. Step: Deprotonation

SN-1 Reaction
Reaction rate
determining Step

Fast

Fast

Reaction Diagramm of an SN1-Reaction

Transition state of
reaction rate
determining step

Activation
Energy, Ea

Reaction Coordinate

The Influence of Leaving Group on the

Nucleophilic Substitution
The stronger the conjugated acid HX, the
better X functions as leaving group

Stability of Carbocations

SN-2 Reaction

Reaction Diagramm of an SN2-Reaction

Transition State

Activation
Energy
Ea

Reaction Coordinate

Influence of Nucleophilicity on
the SN-2 Reaction
Increasing of base properties:

Increasing of leaving group polarity

1,2 Elimination (E-1)

Slow

The cleavage of C-Y bond occurs prior the C-H bond cleavage
E1: Only one reaction partner determines the reaction rate

1,2 Elimination (E-1)

1,2 Elimination (E-2)

E2: Two reaction partners determine the reaction rate

1,2 Elimination (E-2)

E1cB Reaction
(Monomolecular)
Fast

Carbanion
Conjugated Base (cB)

Leaving Group

The cleavage of C-H bond occurs prior the C-Y bond cleavage

E1cB = Elimination-1 conjugated Base

SN vs E

Slow

Saytzev Product

Saytzev-Rule:
In Elimination reactions the -Proton will be
preferentially eliminated from the carbon
atom, which binds less hydrogen.
High substituted Alkene will be
produced!
Monomolecular Elimination gives mainly
Saytzev-Product.
The Saytzev-Product is thermodynamically
more stable

Hofmann Product
In Hofmann elimination, alkene with less number of alkyl group
on double bond will be produced.
Less substituted alkene will be produced
e.g. Hofmann degradation
E2 mechanism: degradation of quarterner Ammonium Salt

For example: Dehydration of Tertiary Alcohols

1,1-(,)-Elimination
In the case of 1,1-elimination, Carbene or Nitrene
will be produced. It is a short-life very reactive
intermediate

Influence of Substrate Structure on the

Nucleophile Substitution / Elimination
Primary Alkyl compounds:
Bimolecular Reactions: SN2, E2
Tertiary Alkyl compounds:
Monomolecular Reaktionen: SN1, E1

Influence of Nucleophilie on SN2-Reaction

(Experiment)

Chlormethane + HO- (fast)

Chlormethane + Water (very slow)
Pr-O-SO2-CH3 + Cl- (Slow)
Pr-O-SO2-CH3 + Br- (fast)
Pr-O-SO2-CH3 + I- (very fast)

Factors which influence the concurrence of

Substitution and Elimination reactions
Substrate

prim. Alkyl compounds

tert. Alkyl compounds

Reagent

Strong basic reagentt

Solvent

SN-1

SN-2

E-1

E-2

+
-

+
0

No stabilized Carbenium ion

Stabilized Carbenium ion

E2: Abstraction of Protons by the strong

Base
SN2 is also possible if Nucleophilie good
enough and slight room demands

steric unhindered

++

steric hindered

++

Reagent with high Nucleophilie 0

++

Nucleophilic attack decides

Polar protic solvent

SN1 + E1: Stabilization of Carbenium ion

by the polar solvent

SN1: good solvatation of reagent

Nucleophilie of reagent sinks

polar aprotic solvent

E1: Leaving group can be solvated and

hence is stabilized
SN2: slight solvatation of reagent
Nucleophilie of reagent increases
E2: Leaving group can not be solvated
and hence is not stabilized

Miscellaneous

Temperature

Stereochemistry of E2
Ingold-Rule: Bimolecular Eliminations (E2)
will smoothly run, if the Substituents to be
eliminated stand in staggered conformation
(anti-Elimination)

Stereochemistry of E2
Ingold-Rule for Cyclohexane:
Bimolecular Eliminations (E2) in
Cyclohexanes will only smoothly run, if
both Substituents to be eliminated
stand in the axial (a) position. If these
Substituents stand in the equatorial (e)
position (e,e-conformation), the Ring
can however easily turn into a,aconformation

Substitution on Aromatic
Electrophilic Substitution (SE)
Nucleophilic Substitution (SN)

What is an Aromatic ?
Hckel Rule:
Full conjugated, planar cyclopolyene
with (4n+2) -electrons, shows special
stabilities

Aromaticity
Aromaticity is special case of conjugation in olefine.
Conjugated systems are compounds with -bonds
(double bonds) in which each -bonds is separated
through -bond (single bond). In this case, the
interaction of -orbitals over -bond is possible
(delocalization), which leads to reducing of total
energy of molecule.

Electronic Transition

Energy

Anti Bonding
MO

Bonding MO
MO
Ikatan

Colorless Compound

Absorbance
Absorbance

Retinol

Ergocalciferol

Endabsorption
211

265
325

350

300

250

Wave Length
Wavelength

200

(nm)

Colorful Compound
(-Carotene)

Absorbance

Absorbance

Absorbed

Reflected (Vis.
Perception)

0.8
0.6
0.4
0.2

300

400
Wavelength

500

nm

Colorful Compound
(-Carotene)

Absorbance

Absorbance

Absorbed

Reflected (Vis.
Perception)

0.8
0.6
0.4
0.2

300

400
Wavelength

500

nm

Aromaticity
The reducing of energy will be further more
favourable under special structural requirements
(aromatic system).
Hckel-Rule:
It should be a cyclic conjugated system, conjugated
-electrons should form a ring (It is the -electrons,
not the atoms)
The number of -electrons should follow the formula
"4n + 2" in which n = 0, 1, 2 ...
The whole aromatic system should be planar

Electrophilic Substitution
High electron density in aromatic
systems
The attacking agent is a positives ion
(cation) or a positively charged dipol
The leaving group must be cleaved
without electron pair. The most
available leaving group in the aromatic
electrophilic substitution is proton

The Arenium Ion Mechanism

(1) Formation of -complex

(2) Formation of -complex (Arenium-Ion,

Wheland-complex)

(3) Re-aromatization
Stabilization of very reactive Intermediate,
either cleavage of Y or H
Aromatic system will be formed again
A fast reaction step

Orientation and Reactivity

In a monosubstituted Benzene, a new group
can be substituted in ortho, para or meta
positions
The substitution occurs faster or slower than
the reaction of unsubstituted Benzene.
Groups which increase the reaction rate:
activating group. The decreasing group:
deactivating group

Orientation I: The I-Effect

The +I-Effect of Substituent Z leads to a
preferential second substitution in ortho or para
position

Ein bereits vorhandener elektronabgebender +I-Substituent Z kann die positive

Teilladung um so staerker kompensieren, je naeher er ihr steht, also in o- und p-Stellung
staerker als in m-stellung

Orientation II: The M-Effect

The +M-Effect of Substituent Z leads to a
preferential second substitution in ortho or para
position

The Influence of I and M-Effects

An I- and M-Substituent increases the positive partial charge in
o- and p-position more than in m-position

I and M Effects
The activating groups:
Alkyl
-OH -NH2 -NHR -NR2
-O-

Effects
+I
+M -I
+M; +I

The deactivating groups:

-COR, -COOH, -COOR, -CN, -NO2
Halogene
-NR3

-M;
-I
+M -I
-I

Nitration
Aromatic Hydrocarbon can be easily
nitrated
The substitution with nitro group can be
carried out using different reagent
Aromatic nitro compounds are
important products in organic chemistry
since they can be reduced to amines

Preparation of Agent (Nitronium-Ion)

For benzene, simple alkylbenzene and low reactive
compound, nitrous acid is agent of choice:

For activated aromatic structure i.e. amine, phenoles or

pyrroles, milder conditions are possible. The nitration
occurs with concentrated HNO3

Reaction Mechanism

Since nitro group deactivates the aromatic ring: mono

substitution
Activated aromatic: second substitution is possible

Third substitution is only possible under special

conditions (For example: Production of picric acid)

Sulfonation
The Electrophilic agent: SO3, either free or bound to a
carrier
Possibilities: Oleum (SO3 in H2SO4)

Concentration > 80-85% : mainly SO3 as electrophile

Concentration < 80-85% : mainly H3SO4+ as electrophile

Reaction Mechanism

Reversible reaction, either cleavage of SO3H or attack by

other electrophilic agent (Ipso-Attack)

Halogenation
1. Chlor and Brom:
ArH + Br2

ArBr + HBr

Aromatic can be substituted with chlor and brom in the

present of a catalyst, such as: AlCl3, FeCl3, AlBr3, FeBr3
(Lewis Acid)
Cl2 is more reactive than Br2

Halogenation
For active aromatics (ex. phenole,
aniline) no catalysator is needed
Aniline : always multi substitution
Phenol : Stopping the reaction after first
substitution is possible
Another Reagents: HOCl, HOBr, NChloramide, N-Bromamide (NBS),
always in the present of acid

Preparation of Agent
If Lewis acid is used as catalysator,
Br2/Cl2 is the attacking species which
was polarized by the catalyst:

Friedel Crafts Alkylation

Aniline reacts only with alkene and needs
special catalysts
Heterocyclic aromatics (Furan, Thiophene,
Pyrrole) react very difficulty
With desactivated aromatic (ex.
Nitrobenzene): no reaction
Catalysts are nearly always needed
Reactivity: AlBr3 > AlCl3 > FeCl3 > SnCl4 >
BCl3

Friedel Crafts Alkylation

Friedel Crafts Alkylation

Preparation of Agent

Friedel-Crafts-Acylation
The most important method for the
production of Arylketones
Reagents: Acid halogenide, Anhydride,
Ketene, Carboxylic acid
No rearrangement reaction
Due to deactivating Group, no multi
substitution

Preparation of Agent:

Reaction Mechanism:

In this reaction, activated aromatic, in the present of N,Ndisubstituted Formamide and Phosphoroxychloride, is
converted to an aromatic aldehyde

Nucleophilic aromatic
Substitution
Nucleophilic Substitutions in aromatic systems
are possible under following conditions:
1. Aromatic ring is activated by electron
withdrawing Group located in ortho or para
position to leaving group
2. Reactions are catalyzed by very strong
Base and undergo via Arin-Intermediate
4. Reactions, in which nitrogen of a
diazonium salt is substituted by a Nucleophile

Reaction Mechanism

There are different mechanisms. One of them is the

Additions-Eliminations mechanism
The first step is the reaction rate determining step

Tschitschibabin Reaction

Pyridine and another heterocyclic nitrogen compounds

can be substituted with amide in the present of strong
alkali
The substitution occurs in position 2 (ortho), if this
position is blocked, then Position 4 (para)

Schiemann Reaction
Reaction Mechanism:

Preparation:
Diazonium salt are normaly produced (nitrite and HCl). A cold aqueous
solution of NaBF4 or HBF4 or NH4BF4 are then added to the salt
The best way to produce aromatic fluoride

Radical Substitution

Radical
Radical are atoms or molecule with one or more
unpaired electrons
They are formed in a homolytic cleavage of a Bond:

The homolytic cleavage is predominant in the gas

phase and at high reaction temperature

Radical
Polar solvent on the contrary promotes
the heterolytic bond cleavage
(solvatation of formed ions)

Production of Radical
Photochemical cleavage, Photolysis:
Irradiation with Light which is absorbed by the
compound. Ex. UV radiation or sun light

Production of Radical
Thermal cleavage, Thermolysis:
Compounds which is easy to be cleaved at low temperature
(<150 C):

The substitution pattern determines the stability and hence the

cleavage temperature.
The more stable the formed radical, the lower the needed
temperature
At >500 C cleavage of Chlorie molecule
At>600 C The most organic-chemical reactions undergo radical
reactions (Pyrolysis, Crack process).

Radical Starter
Initiator of radical-reaction
Activation at 80-100 C

Benzoylperoxide

Radical Formation Through

Redox Reaction
Under participating of Metal Cations!
Ex.: Fe 2+/3+ Cu +/2+
Application: Sandmeyer-Reaction:
Possible radical reaction mechanism
(Arylradical)
A prim. aromatic Amine is diazotized and
added with a Cu(I)X-Salt
Substitution of Diazonium group through X,
possible Educts: X = Cl, Br, NO2 or CN

Sandmeyer Reaction

Stability of Radicals I

Increasing of Stability due to Hyperconjugation

Radical Stability II:

Hyperconjugation

Radical Stability III

A Special stable Radical is the

Triphenylmethyl radical
The reason for the stability is however steric
shielding of radical function, not dimerization
to hexaphenylethane

Reactions of Radical

Under Loss of Radical properties:

Combination of two Radicals
Disproportionation
Under Transfer of Radical properties:
Degradation
Substitution
Addition at Double bond
Polymerisation
A special reaction in which the C-H bond is attacked
The only weak polarized Bond in alkanes could be
attacked by radicals (on the contrary to nucleophil
and electrophil)

Radical Substitution SR
Chain Reaction:
-Initiation Reaction:
-Propagation Reaction:
(Abstraction-Addition Mechanism)
Abstraction of one H atom
Addition of a Substituent

-Termination Reaction:
Recombination of two Radicals

SR Halogenation I
Differences in the reactivity of Halogen-Radicals
Ground: difference in the enthalpie of chain reactions
Fluor: both steps (Abstraction, Addition) strongly
exotherm (= -389 kJ/mol). consequence: Reaction start
without activation; often: Fragmentation of Molecule
(explosive-like Reaction)
Chlor: both steps are exotherm ( = -100 kJ/mol) Poor
selective; often multi chlorination.
Ex.: Chlorination of methan. Only if Methan-excess =>
CH3Cl as main product. Normally, because of the decrease
in the C-H bond strength (CH2Cl2 => CHCl3 => CCl4), the
next substitution will be easier

SR Halogenation
Brom: only the second step (addition) is
exotherm ( = -25 kJ/mol). More selective on
going: (prim. <) sec. < tert. < Allyl < Benzyl
With N-Brom-Succinimid (NBS) as Brom
supplier (Wohl-Ziegler-Reaktion), selective
Substitution in Allyl position is possible

Iod: first step is strongly endotherm; Energy

equilibrium is positiv ( = +59 kJ/mol)
Normally, no Reaction!

SR Halogenation
Rule for aromatic hyrocarbon:

Ex. Of a Chlorination

Ex. Of chain
reactions (next
products are
possible)

Radical Addition (AR) and

Polymerisation
Addition of Radicals on C-C multi bond:
1. Chain reaction:
By a thermic or photolytic generated
Radical, especially radical starter (Ex. R-R
= Dibenzoyl peroxide)

2. Chain propagation:

Polymerisation: by products

3. Chain stop:
Through Recombination of Radicals or/and
Disproportionation

Ex. Of Addition of HBr

Side Reaction : Polymerisation

Chain growth

Disproportionation
In the absence of other species with which a
radical can react, their life is terminated
largely by dimerisation or disproportionation:

Disproportionation, Ex.: Nifediphine

NO 2
N
H
H3C

H
O
CH
3
O
O CH

H3C

Disproportionation
H
H3C
H3C

H
CH3
O

O H

O
NO2

H3C
CH3

H3C

CH3
O

O
NO

Product of the reaction: Derivative of 4-(2-Nitrosophenyl)pyridine is pharmacologycally not active

CH3

Addition On Not Activated

Multiple Bond

Typical Addition Reaction for C-C

double and Triple Bonds

Orbitals in double Bond

Planar

Properties of Alkene
-Orbital posses richer energy than -Orbital and
hence less stable
Tendency: -Bonds formation
-Bond is easily polarizable
-Orbital is easily accessible
Negative partial charge between C-Atoms (LewisBasicity)
C-atoms are shielded from nucleophilic attack
Increasing of reactivity due to substituents with +Mand +I-effects
Cl-CH=CH2 < H2C=CH2 < R-CH=CH < R-CH=CH-R

Type of Reactions
Nucleophilic Addition AN
Only if DB due to electron attracting
substituents is for AN activated or with strong
Nucleophile
Radical Addition AR
Gas phase or non polar solvents
Light influence
high Temperature
Electrophilic Addition AE
polar solvents
low Temperature
Cycloaddition

Nucleophilic Addition

Radical Addition

Electrophilic Addition

Halogenation

Regioselectivity

Chloronation
Of Propene

Multi steps reaction

mechanism
Control of addition
direction through stability
of carbocation

Hydrohalogenation

Regiospecific

Regioselective

Markovnikov Rule
In the case of electrophilic addition of hydrohalogenic
acid on asymmetric substituted alkene, the hydrogen
atom will be bound to carbon atom which already
binds the most hydrogen atoms

but:

Anti Markovnikov
Product
(under influences of
Light or Peroxides)

Stereo specificity

2
1

Racemic 2,3-Dibromobutane

Stereo specificity

Meso Form of 2,3-Dibromobutane

Hyroboronation

BH3 from diboran (in THF) or NaBH4 in acidic

Solution

Diboran

For low substituted Alcohol

Anti-Markovnikov propduct

Stereoselectivity of Hydroboronation

Epoxidation, trans-Hydroxylation

Cis-Hydroxylation

Advantages:
Selective, high yield
Disadvantages:
Toxic, volatile, expensive

With KMnO4:
Less selective, over
oxidation

Ozonolysis, Glycol Cleavage

The same results like dihydroxylation

and glycol cleavage with Pbtetraacetate or sodium periodate
(Malaprade cleavage)

Catalytic Hydrogenation

Addition of Hydrogen under heterogenic Catalysis

Catalysts: Pt, Pd, Ni, fine distributed:
Due to adsorption on support (Pt/C)
Skeletal Catalyst (Raney-Nickel)
Reduction of oxide (PtO2)
Catalysis due to Chemosorption of Reactants: Syn-Addition

Classified according to participating -electrons:

From carbene to cyclopropane
derivatives

From singulett-O2 to dioxethane, from

aldehyde, ketone to oxethane

1,3-Dipole addition
From diazocompound, azide,
nitriloxide, ozon to different
heterocyclic compounds

Stereo Specificity of Diels-Alder-Reaction

Maleic acid dimethylester

Fumaric acid dimethylester

endo-Rule of Diels-Alder-Reaction

exo-Product
Thermodinamically more stable

endo-Product,
Kinetic reaction control
is needed