ORGANIC CHEMISTRY

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Common Functional Groups

Alcohols: Structure and Physical Properties

An organic compound containing a hydroxyl group attached to an alkyl group Alcohols have the general formula R-OH

Physical Properties
R-O-H has a structure similar to that of water Hydroxyl group is very polar Hydrogen bonds can form readily

12.1 Structure and Physical Properties

Alcohol Boiling Points

Alcohols have abnormally high boiling points relative to their molecular weights due to their ability to hydrogen bond
12.1 Structure and Physical Properties

Hydrogen bonds in Ethane

CH2 H O CH3CH H Hydrogen bonds 2O H O CH2 CH3

CH3

Solubility
Low molecular weight alcohols (up to 5-6 carbons) are soluble in water
12.1 Structure and Physical Properties

Very polar Hydrogen bond with the water molecule

CH3CH2OH very soluble CH3OCH3 barely soluble

CH3CH2CH2CH2OH, 7 g per 100 mL

HOCH2CH2CH2CH2OH is very soluble (two OH groups)

High Molecular Weight Alcohol Solubility

As molecular weight increases, alcohols become insoluble in water
12.1 Structure and Physical Properties

Still polar Ratio of hydroxyl groups to carbons in the chain determines solubility
Diols and triols are more soluble than those with only a single hydroxyl group

Medically Important Alcohols

Methanol
Colorless and odorless liquid Used as a solvent Toxic, can cause blindness and death if ingested Can be used as a fuel

Ethanol
An odorless and colorless liquid Widely used as a solvent The alcohol in alcoholic beverages
12.3 Medically Important Alcohols

Derived from fermentation of carbohydrates Beverage produced varies with the starting material and the fermentation process

2-Propanol

12.3 Medically Important Alcohols

Colorless, but has a slight odor Commonly called rubbing alcohol Toxic when ingested Used as a: Disinfectant Astringent Industrial solvent

1,2-Ethanediol
Used as automobile antifreeze Has a sweet taste, but is extremely poisonous Added to water Lowers the freezing point Raises the boiling point

12.3 Medically Important Alcohols

HO CH2CH2OH
ethylene glycol (antifreeze)

1,2,3-Propanetriol
Very viscous, thick Has a sweet taste OH Non-toxic H O CH CH CH OH 2 2 Highly water soluble glycerol Used in: (in fats, a moisturizer) Cosmetics Pharmaceuticals Lubricants Obtained as a by-product of fat hydrolysis

12.3 Medically Important Alcohols

Phenol
Phenols are compounds in which the hydroxyl group is attached to a benzene ring
Polar compounds due to the hydroxyl group Simpler phenols are somewhat water soluble Components of flavorings and fragrances

Phenols have the formula Ar-OH

Ar must be an aromatic ring (e.g., Benzene)

Phenol Derivatives
Widely used in healthcare as:
Germicides Antiseptics Disinfectants

12.7 Phenols

Ethers
Ethers have the formula R-O-R
R can be aliphatic or aromatic

Ethers are slightly polar due to the polar C=O bond Do not hydrogen bond to one another as there are no OH groups

Ether Physical Properties

Ethers have much lower boiling points than alcohols due to the lack of hydrogen bonding

12.8 Ethers

Medical Uses of Ethers

Ethers are often used as anesthetics Accumulate in the lipid material of nerve cells interfering with nerve impulse transmission Today halogenated ethers are used routinely as general anesthetics Less flammable Safer to store and to work with

CH3 CH2O CH2 CH3 CH3O C C

12.8 Ethers

F Cl H F Cl

Diethyl ether First successful general anesthetic

Penthrane

Thiols
Thiols have the formula R-SH Similar in structure to alcohols with S replacing O Disulfides have the formula R-S-S-R
R may be aliphatic or aromatic

Name is based on longest alkane chain with the suffix thiol position indicated by number

CH3 CH3 CH CH2 CH2 SH

3-methy-1-butanethiol

Thiols and Scent

Thiols, as many other sulfur-containing compounds can have nauseating aromas
Defensive spray of North American striped skunk Onions and garlic

Compare with pleasant scents below

12.9 Thiols

Carbonyl Compounds
Contain the carbonyl group

C=O Aldehydes: R may be hydrogen, usually a carbon containing group Ketones: R contains carbon

Short forms

O R C H RCHO

O RC R

RCOR

Structure and Physical Properties

Aldehydes and ketones are polar compounds The carbonyl group is polar
The oxygen end is electronegative Can hydrogen bond to water Cannot form intermolecular hydrogen bond

Hydrogen bond

O C +

O C

H O H

Hydrogen Bonding in Carbonyls

13.1 Structure and Physical Properties

Bonding with H2O

Intermolecular

Physical Properties
Carbonyls boil at Higher temperatures than:
Hydrocarbons Ethers

Lower temperatures than:

Alcohols

Important Aldehydes and Ketones

Methanal (b.p. 21oC) is a gas used in aqueous solutions as formalin to preserve tissue Ethanal is produced from ethanol in the liver causing hangover symptoms Propanone (Acetone) is the simplest possible ketone
Miscible with water Flammable Both acetone methyl ethyl ketone (MEK or butanone) are very versatile solvents

Important Uses of Carbonyl Compounds

Used in many industries
Food chemicals
13.3 Important Aldehydes and Ketone

Natural food additives Artificial additives

CH3O HO
Vanillin
Vanilla beans

O CH

Fragrance chemicals Medicines Agricultural chemicals

O CH3 CH2 5 C CH3

2-octanone
Mushroom flavor

13.3 Important Aldehydes and Ketone

Other Important Carbonyls

13.3 Important Aldehydes and Ketone

Other Important Carbonyls

Carboxylic Acid and Esters

Carboxylic Acids

Structure
Carboxylic acid groups consist of two very polar functional groups
Carbonyl group Hydroxyl group

Carboxylic acid groups are very polar

Carboxylic acid propanoic acid

Ester methyl ethanoate

Physical Properties
Low molecular weight carboxylic acids
Sharp, sour taste Unpleasant aromas

High molecular weight carboxylic acids

Fatty acids important in biochemistry

Low molecular weight carboxylic acids are water soluble due to hydrogen bonding with:
14.1 Carboxylic Acids

Water Each other

Physical Properties
Due to carboxylic acids forming intermolecular hydrogen bonds boiling points are at higher temperatures than those of any other functional group studied

14.1 Carboxylic Acids

Some Important Carboxylic Acids

O CH3 CH2 16C OH

Stearic acid
found in beef fat

14.1 Carboxylic Acids

Esters
Structure and physical properties Esters are mildly polar, somewhat water soluble Frequently found in natural foodstuffs Many have pleasant aromas
Isoamyl acetate = banana oil 3-methylbutyl ethanoate Ethyl butanoate = pineapple aroma Ethyl butanoate Isobutyl formate = raspberry aroma Isobutyl methanoate

Boil at approximately the same temperature as carbonyls with comparable molecular weight

Saponification
Saponification (soap-making) is:
Base-catalyzed hydrolysis of fats (glycerol triesters)

Simplified Action of Soap

14.2 Esters

Amines
Amines are derivatives of ammonia Most important type of organic base found in nature Consider as if substituted ammonia:
RNH2 R2NH R3N R can be either aliphatic or aromatic

Comparison of NH3 to Amines

15.1 Amines

Physical Properties
Amines form hydrogen bonds but not as strongly as alcohols
Nitrogen is less electronegative than oxygen

Tertiary amines cannot hydrogen bond to each other

15.1 Amines

Boiling Points
Amines have boiling points between alkanes and alcohols

Tertiary amines boil lower then 1o or 2o of similar molecular weight

15.1 Amines

Solubility
All amines can form hydrogen bonds with water Amines up to 6 carbons long are water soluble due to this hydrogen bonding Water solubility decreases as the length of the hydrocarbon portion of the molecule increases

H H CH3N H O H O H

15.1 Amines

Medically Important Amines

Amphetamines stimulate the central nervous system
Analgesics (pain relievers) and anesthetics (pain
blockers)

15.1 Amines

Medically Important Amines

Decongestants shrink the membranes lining the nasal passages
Sulfa drugs (first chemicals used to fight infections) are also made from amines

15.1 Amines

Amides
Amides are formed in a reaction between a carboxylic acid derivative and an amine or ammonia The amide bond is the bond formed between:
Carbonyl group from the carboxylic acid Amino group from the amine or ammonia

Physical Properties
Most amides are solids at room temperature due to internal hydrogen bonding They are not bases A resonance structure shows why the N lone pair is unavailable to accept a proton

15.1 Amines

Amide Hydrogen Bonding

Strong intermolecular hydrogen bonding between the N-H bond of one amide and the C=O bond of another Very high boiling points Simple amides are quite soluble in water
15.1 Amines

Preview of Amino Acids, Proteins, and Protein Synthesis

A protein is a polymer of amino acids linked by the amide bonds As the amino group and the carboxyl group link, water is lost