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Finishing Chapter 21 Chapter 16 - Intro to Carbonyls Chapter 15 - Highlights Grignard and Gilman reagents

Lecture 11 Sessler 310N

Recommended Problems CHs 20; 21 20.4, 20.6, 20.7-20.10, 20.16, 20.17, 20.19-20.32, 20.43, 20.46-20.48

21.2, 21.4, 21.5, 21.7-21.9, 21.11, 21.14-21.22, 21.24-21.26, 21.30-21.43

Exam I will cover spectroscopy (MS, IR, NMR, UV-Vis) and Aromaticity (Chapts. 12-14; part of 23; 20 and 21.1-21.2)

NOTE: NO OFFICE HOURS TOMORROW (SORRY). However, There is a review session Tonight (5 pm; Wel 2.122)

Di- and Polysubstitution


z

Existing groups on a benzene ring influence further substitution in both orientation and rate Orientation:
certain substituents direct preferentially to ortho & para positions; others direct preferentially to meta positions substituents are classified as either

ortho-para directing or meta directing

Di- and Polysubstitution


z

Rate:
certain substituents cause the rate of a second substitution to be greater than that for benzene itself; others cause the rate to be lower substituents are classified as

activating toward further substitution, or deactivating preventing or slowing further substitution

Di- and Polysubstitution


z

-OCH3 is ortho-para directing and activating.

MECHANISTIC EXPLANATION ACCOUNTING FOR THIS OBSERVATION WAS PRESENTED IN CLASS THURS.

zTHE

OCH3
B r2 CH 3 CO 2 H anisole

OCH3
Br +

OCH3
+ HBr Br

o-bromoanisole (4%)

p-bromoanisole (96%)

Di- and Polysubstitution


z

-NO2 is meta directing and deactivating!


NO 2 + HNO 3 Nitrobenzene NO 2 m-Dinitrobenzene (93%) o-Dinitrobenzene NO 2 p-Dinitrobenzene H 2 SO 4 NO 2 + NO 2 NO 2 + NO 2

Less than 7% combined

MECHANISTIC EXPLANATION ACCOUNTING FOR THIS OBSERVATION WAS PRESENTED IN CLASS THURS.

zTHE

Methyl Group
CH3

Toluene undergoes nitration 1000 times faster than benzene. A methyl group is an activating substituent.

MECHANISTIC EXPLANATION ACCOUNTING FOR THIS OBSERVATION WAS PRESENTED IN CLASS THURS.

zTHE

Relative rates of Nitration


OH H Cl NO2

1000

1.0 Reactivity

0.033

6x10-8

Halogen Substituents
Cl

Chlorobenzene undergoes nitration ca. 30 times more slowly than benzene . Halogens are deactivating substituents. But, they are o,p directors!

How can this be???

Back to

Theory of Directing Effects


Sowhats going on here???? The rate of EAS is limited by the slowest step in the mechanismduh For EAS, the rate-limiting step is attack of E+ on the aromatic ring to form a resonance-stabilized cation intermediate The more stable this cation intermediate, the faster the ratelimiting step and the faster the overall reaction In the case of halogen, competing effects are at work!

Use this Table to Practice and Review

Real Fast Pretty fast Kinda slow Pretty slow Slow Real Slow

To Review: Effect on Regioselectivity


Ortho-para directors direct an incoming electrophile to positions ortho and/or para to themselves. Meta directors direct an incoming electrophile to positions meta to themselves. All meta directors are deactivating All ortho-para directors are activating except halogen

Polysubstitution--General Rules
z

Where more than one substituent exists on a benzene ring, look to see if one is significantly more activating than the other. If this is the case and open ortho and/or para site(s) are available, the incoming electrophile will substitute at these latter sites. Groups such as -OR and -NR2 dominate over more weakly activating groups, such as alkyl groups, and halogens If groups are similarly activating or deactivating and they are not oriented to direct towards the same position (s), such as in the case of 1,3-dinitrobenzene, horrible mixtures can result.

Plan your synthesis to avoid mixtures!

The wrong way.


CH3 Na2Cr2O7 H2SO4 NO2 NO2 CO2H HNO3 H2SO4 NO2 NO2 CO2H NO2 + NO2 CO2H

The right way


CH3 HNO3 H2SO4 NO2 NO2 CH3 NO2 Na Cr O 2 2 7 H2SO4 NO2 CO2H NO2

Explain this with mechanism(s)!


Chemistry 310N

And one last minimum expectation review problem:

ortho Nitration of Toluene


CH3 H + H H
Practice going from your list of structures to a coherent argument about which products will be formed in preference and why.

NO2 H H
Be sure you can write the remaining resonance structures and then do the same for meta and for para attack.

End of Material That will be Covered on Exam I

Note how Sect. 21.3, Nucleophilic Aromatic Substitution, is not going to be on the Exam or, in fact, covered in the course.

Chemistry 310N

Lecture 10 Cont. Carbonyl Chemistry I

Suggested Homework Problems (for this lecture)


15.13, 15.14a 16.4, 16.15, 16.16, 16.19-16.23

O C

O
C

The Carbonyl Group


z

Over the course of several chapters we will study the physical and chemical properties of classes of compounds containing the carbonyl group, C=O
aldehydes and ketones (Chapter 16 (+15.1)) carboxylic acids (Chapter 17) acid halides, acid anhydrides, esters, amides (Chapter 18) enolate anions (Chapter 19)

Resonance Description of Carbonyl Group


O C

O C +

nucleophiles attack carbon; electrophiles attack oxygen

The Carbonyl Group


z

The carbonyl group consists of


one sigma bond formed by the overlap of sp2 hybrid orbitals, and one pi bond formed by the overlap of parallel 2p orbitals

C O

Structure of Formaldehyde

The molecule is planar bond angles: close to 120 C=O bond distance: 1.22

Bonding in Formaldehyde

Carbon and oxygen are sp2 hybridized

Bonding in Formaldehyde

The p orbitals on carbon and oxygen overlap to form a bond

Nomenclature-Aldehydes
z

IUPAC names: select as the parent alkane the longest chain of carbon atoms that contains the carbonyl group..subtract e and add al
because the carbonyl group of the aldehyde must be on carbon 1, there is no need to give it a number

For unsaturated aldehydes, show the presence of the C=C by changing -an- to -en the location of the suffix determines the numbering pattern

Nomenclature-Aldehydes
O
1 CH 3 CH 2 CH 2 CH 2 CH 5 4 3 2 4

CH 3

3 2 1 CH 3 CHCH 2 CH

Pentane O
3 2 1

Pentanal

3-Methylbutanal O

7 8 6

5 4

3 2

CH 2 =CHCH 2-Propenal (Acrolein)

(2E)-3,7-Dimethyl-2,6-octadienal (Geranial)

Nomenclature of Aldehydes
O H 4,4-dimethylpentanal O O 5-hexenal O H

HCCHCH 2-phenylpropanedial

Nomenclature of Aldehydes
O when named as a substituent this is a formyl group C H when named as a suffix it is carbaldehyde carboxaldehyde

Nomenclature-Aldehydes
z

For cyclic molecules in which the -CHO group is attached to the ring, the name is derived by adding the suffix -carbaldehyde to the name of the ring
1

CHO

CHO
1 2 3

CH 3 2 CH 3 2,2-Dimethylcyclohexanecarbaldehyde

2-Cyclopentenecarbaldehyde

Many aldehydes and ketones occur naturally


O

2-heptanone (component of alarm pheromone of bees)

trans-2-hexenal (alarm pheromone of myrmicine ant)

Structure of Ketones
z

The functional group of a ketone is a carbonyl group bonded to two carbon atoms
O Cyclohexanone

O CH3 -C-CH 3 Propanone (Acetone)

Trivial Nomenclature of Ketones


O CH3CH2CCH2CH2CH3 ethyl propyl ketone benzyl ethyl ketone O CH2CCH2CH3

O divinyl ketone H2C CHC CH CH2

IUPAC Nomenclature-Ketones
z

IUPAC names:
select as the parent alkane the longest chain that contains the carbonyl group, number to give C=O the smaller number and then subtract e and add one
7 1

O CH 3 CCH 3 Propanone (Acetone)


1 2

O
3 4

CH 3
5 6 5

6 4

O
2 3

CH 3 CH 2 CCH 2 CHCH 3 5-Methyl-3-hexanone

Bicyclo[2.2.1]-2heptanone

IUPAC Nomenclature-Ketones
O
1

CCH 2 CH 2 CH 2 CH 3

1-Phenyl-1-pentanone
z

Even the IUPAC system retains the common names acetone, acetophenone, and benzophenone

O CH 3 CCH 3 Acetone

O CCH 3 Acetophenone

O CBenzophenone

IUPAC Nomenclature of Ketones


O O CH3CH2CCH2CH2CH3 3-hexanone O CH3CH2CCH2CH2CH3 ethyl propyl ketone
O

CH3CHCH2CCH3 CH3 4-methyl-2-pentanone


O H

4-oxohexanal

Order of Precedence
(Pecking order)
z

For compounds that contain more than one functional group indicated by a suffix
Functional Group Precedene -CO 2 H -CHO C=O -OH -NH 2 -SH Suffix if Higher Prefix if Lower in Precedence in Precedence -oic acid -al -one -ol -amine -thiol oxooxohydroxyaminomercapto-

Synthesis of Aldehydes and Ketones


A number of reactions already studied provide efficient synthetic routes to aldehydes and ketones.
Review these after the exam since they are expected knowledge.

from alkenes
by ozonolysis

from alkynes
by hydration (via enol)

from arenes
via Friedel-Crafts acylation

from alcohols by oxidation

Reactions of Carbonyls
z

We will cover quite a number, including early on ones where carbon acts as an electrophile and the oxygen acts as a nucleophile or, more commonly, base. But first, oxidation chemistry of aldehydes:
O H O [oxidant]
H2O

OH oxidant = Cr(VI), Mn(VII), Ag(I), etc.

We had this last semester. Review the material and mech!

Okay, Lets Stop Here For Today!

Read up on organometallic chemistry after the exam. And, as importantly, good luck with it!!

Chemistry 310N