Organic compounds containing

oxygen

Matej Kohutiar

http://www.wellesley.edu/Chemistry/chem227/lipids/transport.htm

Organic compounds containing

oxygen

• Alcohols and phenols

• Carbonyl compounds

• Carboxylic acids and derivatives

• Ethers

Electron configuration of oxygen

1s2 2s2 2p4

In organic molecule oxygen is attached covalently

O

O

Electronic effects in molecules

Inductive effect

H3Cδ δ+ →CH2

δ+ → Cl δ-

Hydroxy derivatives

• Alcohols (Csp3-OH)

• Phenols (Car-OH)

• Ethers (R-O-R)

Alcohols

‌

-Cδ+→O δ -←H‌δ+

‌

Alcohols

• In 1o alcohol, only one carbon atom is attached to the

carbon carrying the -OH group (primary carbon)

• In 2o alcohol two carbon atoms are attached to the

carbon carrying the -OH group (secondary carbon)

• In 3o alcohol three other carbon atoms are attached to

the carbon atom carrying the -OH group (tertiary

carbon)

Alcohols

The number of hydroxyl groups, there are:

• Monohydroxyderivatives

• Polyhydroxy alcohols

Diols (dihydroxyderivatives,)

Triols (trihydroxyderivatives)

Tetrols (tetrahydroxyderivatives)

• Phenols -OH attached primary to aromatic ring

Acidity and alkalinity

CH3

OH

NaNH2CH3

O Na

CH3

OH

NaOH CH3

ONa

Acidity and alkalinity

OH2OH

-

CH3

OH

CH3

CH3

OH

CH3

CH3

OHCH3

CH3

O-

CH3

O-

CH3

CH3

O-

CH3 CH3

acidity

alkalinity

Nucleophilic substitution

CH3

OH

H+

CH3

OH2

+

CH3

Nu

Nu

Nucleophilic substitution

CH3

CH3

OH ClHCl

CH3

CH3

CH3

CH3

OH

CH3

CH3

BrPBr3

Elimination

CH3

OH

CH3H3PO4

OH

CH3

H2SO4

CH3

Oxidation of alcohols

CH3

CH2OH

CH3

CH O

CH3

C O

OH

KMnO4KMnO4

CH3

CH CH3

OH

CH3

C CH3

O

KMnO4

C OH

CH3

CH3 CH3

KMnO4

Biological effects of alcohols

• Drugs often contain OH group

• Increase of polarity and solubility in water

• Hypnotic activity decreases from tertiary to primary

alcohol

• Natural structures – steroids, hormones etc.

• Methanol

• Ethanol

• Glycerol

PHENOLS

Phenols

OH O-

Reactions of phenols

OH OH

N+

O-

O

OH

N+

O-

O

N+

O-

O

HNO3

H2SO4

ONa

CO2

OH

C

O

OH

Reactions of phenols

OH

OHC

C

O

O

OH

OH

C

C

O

O

K2Cr2O7

K2Cr2O7

Biological effects of phenols

• Reactive group of acidic properties

• Phenol

• Resorcine

• Salicylic acid

• Acetylsalicylic acid

CARBONYL COMPOUNDS

O

CH3

muscone

CH3

CH3

CH3

O

citral

O

OH

O

CH3

vanil in

O

cinnamaldehyde

Reactivity

C O

R1

R1

+ -

Nucleophilic addition

O

R

R1

Nu-

O-

R

R1

NuH

+

OH

R

R1

Nu

Nucleophilic addition

5 4

OH OH

CH+

1OH

4

O1

CH3

OH

OH OH

O

H+

5

4

OH OH

CH+

1OH

1

4

O

5

OH

OH

Nucleophilic addition

CH3 C

CH3

ONH2-CH3

CH3

CCH3

NH

CH3

OH

CH3

C

CH3

NH

CH3

OH -H2OCH3 C

CH3

N

CH3

Aldol condensation

C

R2

R1

H

O

+

-

Aldol condensation

CH3 CH

O+ CH3

CH OCH3

CH

O

OH

Biological effects of carbonyl

containing molecules

• Very reactive group

• Formaldehyde

• Benzaldehyde

• Acetone

• Steroid hormones

CH3

OCCH3

N

CH3

CH3

NH

CH3

O

O

NN

CH3

CH3NCH3

CH3

O

glutethimid

aminophenazone

methadone

CARBOXYLIC ACIDS

Carboxylic acids

C3+

C3+

C

O H

R

O.

.

. .C

O

O H

R

+

-

+

-

Nucleophilic substitution

esterification

CH3 C

O

OH

C2H5OH+ CH3

C O

O

CH3

Carboxylic Acid Derivatives

Functional derivatives

CR

X

ONu

CR

Nu

O

CR

Cl

O

CR

OCOR

O

CR

OR

O

CR

O

NH2

CR

OH

O

Substitutional derivatives

CH3

C O

OH

Br

C O

OH

OH

CH3 C

C O

OH

O

C

O

NH2

OHCH3C

O

NH2

CH3OH

Examples of Polyfunctional Carboxylic Acids

HOOC-COOH – oxalic acid HOOC-CH2-COOH – malonic acid

HOOC-CH2-CH2-COOH – succinic acid (citric cycle) HCCO-CH2-CH2-CH2-COOH – glutaric acid

lactic acid

malic acid

citric acid

Dicarboxylic acids

-OH group containing acids

Maleic acid and fumaric acid are geometric isomers

pyruvic oxaloacetic acid

Unsaturated acids

a-ketoglutaric acid

Ketoacids

Errata

By mistake I wrote wrong formula for resorcinol. Please, find right formula for this

structure below:

BR,

M.K.

OH

OH

OH

OH

resorcinolpyrocatechol