1-1 Chemistry 121, Winter 2015, LA Tech Introduction to Organic Chemistry and Biochemistry...

1-1Chemistry 121, Winter 2015, LA Tech

Introduction to Organic Chemistry and Biochemistry

Instructor Dr. Upali Siriwardane (Ph.D. Ohio State)

E-mail: [email protected]

Office: 311 Carson Taylor Hall ; Phone: 318-257-4941;

Office Hours: MTW 8:00 - 10:00 am;

ThF 9:00 - 10:00 am 1:00 - 2:00 pm.

December 19, 2014: Test 1 (Chapters 12-13)

January 26 , 2015: Test 2 (Chapters 14-16)

February 13, 2015: Test 3 (Chapters 17-19)

March 2, 2015: Test 4 (Chapters 20-22)

March 3 , 2015: Make Up Exam: Chapters 12-22)

Bring Scantron Sheet 882-E

Chemistry 121(001) Winter 2015

1


Chapter 15: Aldehyde and Ketones

15.1 The Carbonyl Group, 469

15.2 Compounds Containing a Carbonyl Group, 470

15.3 The Aldehyde and Ketone Functional Groups, 471

15.4 Nomenclature for Aldehydes, 472

15.5 Nomenclature for Ketones, 474

15.6 Isomerism for Aldehydes and Ketones, 476

15.7 Selected Common Aldehydes and Ketones, 476

15.8 Physical Properties of Aldehydes and Ketones, 479

15.9 Preparation of Aldehydes and Ketones, 481

15.10 Oxidation and Reduction of Aldehydes and Ketones, 482

15.11 Reaction of Aldehydes and Ketones with Alcohols, 486

15.12 Formaldehyde-Based Polymers, 491

15.13 Sulfur-Containing Carbonyl Groups, 492

http://instructors.coursesmart.com/9781133103943/469














Carbonyl Group


Simplest Aldehyde


Common Names of Aldehyde and Ketones

Aldehydes: Fomaldehyde: HCHO

Acetaldehyde: CH3CHO

Propionaldehyde: CH3CH2CHO

Butyraldehyde: CH3CH2CH2CHO

Valeraldehyde: CH3CH2CH2CH2CHO Ketones:

Acetone: CH3COCH3

Methyl ethyl ketone CH3CH2COCH3

Butyl propyl ketone CH3CH2CH2CH2COCH2CH2CH3


IUPAC Nomenclature of Aldehyde and Ketones

The IUPAC system deals with functional groups two different ways.

Modification of the hydrocarbon name to indicate the presence of a functional group.

aldehyde, -CHO use -al ending.

Ketones -RCOR’ use -one ending.


IUPAC Nomenclature of Aldehyde and Ketones

The IUPAC system deals with functional groups two different ways.

Modification of the hydrocarbon name to indicate the presence of a functional group.

aldehyde, -CHO use -al ending.

Ketones -RCOR’ use -one ending.


Example

C - C - C - C - CHO

Base contains 5 carbon

- aldehyde name is pentane

- remove -e and add -al

C - C - C - C - CO-C-C

Base contains 7 carbon

- aldehyde name is heptane

- remove -e and add -one

3-heptanone


Physical Properties of Aldehydes and ketones

Aldehyde and ketones can only make dipole-dipole attraction.

BP and MP are lower than alcohols ,

higher than hydrocarbons and ether

with comparable carbon numbers


Bonding Characteristics of Aldehydes Ketones

Both aldehydes and ketones contain a carbonyl

functional group. A carbonyl group is an carbon atom

double-bonded to an oxygen atom. The structural

representation for a carbonyl group is

Carbon-oxygen (C=O) and carbon-carbon (C=C) double

bonds differ in a major way. A carbon oxygen double

bond is more polar


Physical properties of aldehydes and ketones.


Nomenclature

HCOOH

O

COOHO

COOHHO

OHHS

COOHNH2

-al oxo-

Ketone -one oxo-

Alcohol -ol hydroxy-

Amino -amine amino-

3-Oxopropanoic acid

3-Oxobutanoic acid

4-Hydroxybutanoic acid

3-Aminobutanoic acid

Example of When the FunctionalGroup Has a Lower Priority

Sulfhydryl -thiol mercapto- 2-Mercaptoethanol

Functional Group Suffix Prefix

Carboxyl -oic acid

Aldehyde


Name the Aldehyde

2,4-dimethylpentanal


1. Assign the type of organic compound with following general

condensed (structural formula.


2. Names (common/IUPAC)of following aldehydes and

ketones.

a) ____________ b) _______________ c) __________________

d) ____________ e) _______________ f) __________________

g) ____________ h) __________________


Nomenclature

CHO HO CHO

Cyclopentane-carbaldehyde

trans-4-Hydroxycyclo-hexanecarbaldehyde

14

3-Methylbutanal 2-Propenal(Acrolein)

H

O

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

1

2

3

4

5

6

7

8

11

223

3

4H

O

H

O

2-Methyl-cyclohexanone

5-Methyl-3-hexanone

Benzophenone Acetophenone

OO

O O


3. Draw the condensed formula of

following aldehydes and ketones:

a) acetaldehyde/ ethanal

b) ethyl methyl ketone

c) 3-methyl-2- pentanone

d) isopropyl methyl ketone

e) 2-methylbutanal

f) 5-methyl-3- hexanone

g) benzophenone

h) acetophenone


Addition reactions of als & onesHemiacetal or hemiketal formation


Hemiacetal form of cyclic sugars


4. Identify each of the following compounds as a hemiacetal, hemiketal,

acetal, or ketal:

a) ____________ b) _______________ c) __________________

d) ____________ e) _______________ f) __________________


Important AldehydesMethanal or formaldehyde

Ethanal or acetaldehyde

2-Propanone or acetone

2-Butanone or methyl ethyl ketone

Oil of almonds or benzaldehyde

Oil of Cinnamon or cinnamaldehyde

Oil of vanilla beans or vanillin

Mushroom flavoring or 2-octanone

Oil of lemongrass or citral:


Bakelite


Preparation of Aldehydes:

Partial oxidation of primary alcohols with H2CrO4:


Preapration of ketones:

Oxidation of secondary alcohols with KMnO4, or H2CrO4


Oxidation of alcohol


Oxidation of Alcohols

• to oxidize a 1° alcohol to an aldehyde, use PCC

• PCC oxidation of geraniol gives geranial

Tertiary alcohols are not oxidized by either of these reagents; they are resistant to oxidation

CrO3 HClN N

H

CrO3Cl-

Pyridinium chlorochromate (PCC)

Pyridine

+ ++

OHPCCCH2Cl2

H

O

Geraniol Geranial


Oxidation of alcohol


5) Which alcohol would you oxidize to produce each of the

following compounds?

a)

b)

c)

d)


6) Preparation of adehydes and ketones

a) Control oxidation of 1ry alcohol

b) Complete oxidation of 1ry

alcohol


6) Preparation of adehydes and ketones

c) Oxidation of 2ry

alcohol

d) Oxidation of 3ry

alcohol

No Reaction


Chemical Reactions of Aldehydes and Ketone

1) Combustion: Alkenes are very flammable and the combustion products are carbon dioxide and water.

2) Addition Reactions: Atoms or group of atoms are added to each a carbon oxygen double bond. Two different

reactants are involved.

a) hemi-acetal or hemi-ketal formation: Addition of Alcohols: -OR group of the R-OH is added to the C atom and H of the

ROH is added to O atom.

b) Aacetal or ketal formation : Another or second ROH is reacted in a substitution reaction to replace the H atom of the -OH

group of the hemi-acetal or hemi-ketal and water molecule is produced.

O: both reactants (H-X (X= Cl, OH)) and the alkene need to be asymmetric

3) Oxidation Reactions: only aldehydes are oxidized to carboxylic acids.

4) Reduction Reactions: both aldehydes and ketones are reduced to alcohols by taking H from the reducing agents.


Chemical Reactions of Aldehydes and Ketone

a) hemi-acetal or hemi-ketal formation: Addition of Alcohols: -OR group of the R-OH is added to the C atom and H of the

ROH is added to O atom.

b) Aacetal or ketal formation : Another or second ROH is reacted in a substitution reaction to replace the H atom of the -OH

group of the hemi-acetal or hemi-ketal and water molecule is produced.

O: both reactants (H-X (X= Cl, OH)) and the alkene need to be asymmetric


Reduction of als & ones compounds to alcohols:


Redox Reactions Reduction Reactions: both aldehydes and ketones

are reduced to alcohols by taking H from the reducing agents.

a) LiAlH4

b) NaBH4

c) H2/Ni or Pt catalysts

Oxidation Reactions: only aldehydes are oxidized to carboxylic acids.

d) Jone’s Reagent

e) AgNO3/NH4OH (silver mirror test)

f) CuSO4/Na2CO3/Citrate (Benedict’s reagent)


Aldehyde and Ketone Reduction: To alcohols

H2, Ni

NaBH4 or LiAlH4

then H+

C

OC

OH

H


7) Complete the following reductions of aldehyde and ketones and identify the type of alcohols (1ry, 2ry

and 3ry) produced.

d)


Reduction of als & ones compounds to alcohols:








Formation of Acetals and Ketals.


8) Complete the following formation reactions hemiacetal, hemiketal, acetal, or ketal:


Redox Reactions Reduction Reactions: both aldehydes and ketones

are reduced to alcohols by taking H from the reducing agents.

a) LiAlH4

b) NaBH4

c) H2/Ni or Pt catalysts

Oxidation Reactions: only aldehydes are oxidized to carboxylic acids.

d) Jone’s Reagent

e) AgNO3/NH4OH (silver mirror test)

f) CuSO4/Na2CO3/Citrate (Benedict’s reagent)


Chemical Reactions

Oxidation of aldehyde.

Benedict's Test for aldehydes:


Test for Urine Glucose: Benedict’s Test


Oxidation of aldehyde.

The commercial manufacture of silver mirrors uses a similar process.

Tollen's Test:


9) Complete reactions of following aldehydes

and ketones

a) Tollen’s Reagent: Silver mirror test:

b) Benedict's test:


9) Complete reactions of following aldehydes

and ketones

c) Oxidation of aldehyde

d) Cyclic hemi-acetal formation


Addition of HCN and H2O


Aldol Condensation

In biological systems this reaction is catalysed by an enzyme named aldolase.


Keto & Enol tautomers

keto form enol from


Keto & Enol tautomers in sugars

aldehyde enol ketone




Formation of Acetals and Ketals.



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