Ch 14.

Alcohols, Phenols and Ethers

Fundamentals of General, organic and Biological chemistry; McMurry et al., 5ed, Prentice Hall

Alcohol and Phenols have OH group (hydroxyl functionality). Polar. The presence of the hydroxyl group makes them miscible with water The OH group participates in H-bonding Alcohols up to C5 are very soluble in water. After that solubility decreases with increasing number of Carbon atoms

Alcohols

Naming alcohols
Start with the parent chain and replace the hydrocarbon e ending with ol Number the hydrocarbon chain. The carbon containing the OH group should have the lowest number Number the position of the OH group Number and name other side chains or functionalities using IUPAC rules

1-butanol

2-methyl-1-propanol

Primary /secondary/tertiary

2-butanol A 2o alcohol (secondary)

2-methyl-2-propanol A 3o alcohol (tertiary)

1-propanol (1o alcohol)

Distinguish the difference between 1o, 2o and 3o structures

Nomenclature contd.

In a cyclic alcohol, it is understood that the OH group is on C-1

Alcohols

What are the identitifying groups of this molecule?

2-isopropyl-5-methylcyclohexanol

Menthol

Alcohols (diols, triols)

-diols or triols mean two or three hydroxy groups in the molecule Number the hydroxy group carbons with the lowest possible numbers Prefix uses the full parent name, i.e butane Ethane-1,2-diol (ethylene glycol)
,

Propane-1,2,3-triol (glycerol)

Properties of alcohols
Alcohols are polar compounds because the OH group participates in H-bonding Smaller straight chain alcohols are usually liquids Alcohols such as 1-heptanol (C8) tends to act more like alkanes Diols and triols have higher b.ps and are more water soluble

Reactions of alcohols Dehydration: Loss of water to form an alkene. Occurs in presence of acid catalyst. Oxidation: Gets oxidized to carbonyl compounds in presence of an oxidizing agent.

Dehydration reaction
Removal of H and OH group from adjacent carbon atoms produce an Alkene.

Fundamentals of General, organic and Biological chemistry; McMurry et al., 5ed, Prentice Hall

Dehydration of alcohols

What is the major reaction product in these reactions?

Dehydration of alcohols
Predict the starting alcohol in the following:

Write all possible structures then keep the most substituted ones!

Oxidation of Alcohols

*Note- Depending upon the alcohol and reaction conditions a different types and mixtures of carbonyl products may be formed

Oxidation of alcohols

Secondary alcohols get converted to ketones upon oxidation but no further

Q: What is oxidation reaction for a tertiary alcohol

Image Adapted from http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch15/ch15-4-6.html

Oxidation of alcohols

Hydroxybenzene (a.k.a Phenol)

Have been used as an antiseptic

Many OTC sore throat medications contain substituted phenols Most phenols are somewhat water soluble BHA and BHT are often used as food preservatives

BHA

BHT

Phenols
Methanol and Ethanols are as acidic as water, i.e weak acids, Ka = 10-15 Their anion (alkoxide ion) is a strong base, similar to the hydroxide ion Phenols are more acidic than alcohols Phenolic Ka is 1.0X 10-10

Acidity of phenols
Alcohols and Phenols are weakly acidic They dissociate in water to give the alkoxide or the phenoxide anion

Ethers
Ethers, compounds with two organic groups bonded to the same O atom, are named by identifying the two organic groups and adding the word ether.

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Compounds that contain the oxygen atom in a ring are classified as cyclic ethers and are often given common names.

Alkoxy groups
An OR group is referred to as an alkoxy group; -OCH3 is a methoxy group, -OCH2CH3 is an ethoxy group, and so on. These names are used when the ether functional group is present in a compound that also has other functional groups.

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Careful!! These are NOT Ethers.why?

Thiols
Thiols, or mercaptans, are sulfur analogs of alcohols. Skunk scent is caused by the two thiols shown below center and right. The systematic name of a thiol is formed by adding -thiol to the parent name.

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Thiols
Thiols (R-SH) react with mild oxidizing agents to yield a disulfide (R-SS-R). The reverse reaction (R-S-S-R 2R-SH) occurs when a disulfide is treated with a reducing agent. Hair protein is rich in S-S and SH groups. When hair is permed, some disulfide bonds are broken and new ones are formed, giving hair a different shape.

Halogen containing compounds

Any organic compound that contains a halogen atom can be considered a halide. Alkyl halides are organic compounds of the type R-X, containing an alkyl group R covalently bonded to a halogen X. Chlorofluorocarbons (CFC) are compounds containing chlorine, fluorine and carbon only, i.e they contain no hydrogen.

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Halogenated organic compounds have a variety of medical and industrial uses: -Anesthetics -Solvents, propellants, degreasing agents -Fire extinguishers -Herbicides, fungicides, insecticides Despite the enormous benefits of halogenated organic compounds, their use has been restricted, and sometimes banned altogether because: -They persist in the environment and are not broken down rapidly. -They accumulate in some animals to harmful levels. -They can damage the ozone layer.

Adapted from Pearson Prentice Hall Inc. 2007

Chlorofluorocarbons (CFCs)
CFCs-Prohibited/Restricted use because of their role in Ozone Depletion Hydrochlorofluorocarbons (HCFCs) are of a class of haloalkanes where notall hydrogen has been replaced by chlorine or fluorine. They are used primarily as chlorofluorocarbon (CFC) substitutes, as the ozone depleting effects are only about 10% of the CFCs. Hydrofluoro compounds (HFCs) : They contain no chlorine. Lower global warming potential than the HCFCs because of no known effects on the Ozone layer. They do have activity on other realms of greenhouse gases, which also contribute to global warming.

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Thyroxine

Tyrosine (amino acid)

Triiodothyronine (T3)

(T4)

Production of Thyroid Hormones

T3 has three iodine atoms and T4 (Thyroxine) contains 4 iodine atoms Via a thyroperoxidase enzyme, Iodine molecules are covalently bound To Tyrosine residues These Tyrosine residues are known as DiIodoThyronine and MonoIodoThyronine Linking of these DIT and MIT residues forms T3 (Triiodothyronine) And T4 Thyroxine

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Practice questions

The compound shown below is

1. 2. 3. 4.

an alcohol. an ether. a hydroxide. a phenol.

Give the IUPAC name for the alcohol shown below and classify it as primary, secondary, or tertiary.

1.

1,1,1-trimethylmethanol, primary 2. 1,1,1-trimethylmethanol, tertiary 3. 2-methyl-2-propanol, secondary 4. 2-methyl-2-propanol, tertiary

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Which of the following compounds has the highest boiling point? 1. 2. 3. 4. CH3CH2CH2CH3 CH3CH2OCH2CH3 CH3CH2CH2CH2OH HOCH2CH2CH2CH2OH

Which of the following compounds is most soluble in water? 1. 2. 3. 4. CH3CH2CH2CH2CH3 CH3OCH2CH3 CH3CH2CH2OH CH3CH2CH2CH2CH2OH

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Dehydration of the alcohol shown below will result in the formation of which alkene as a major product?

1. only (CH3)2CH2CH2CH=CH2 2. only (CH3)2CH2CH=CHCH3 3. only (CH3)2CH=CHCH2CH3 4. (CH3)2CH=CHCH2CH3 and (CH3)2CH2CH=CHCH3

The addition of a stoichiometric amount of an oxidizing agent to the alcohol shown below will result in

1. 2. 3. 4.

the formation of an aldehyde. the formation of a carboxylic acid. the formation of a ketone. no reaction.

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Which of the following compounds is most acidic? 1. 2. 3. 4. C6H5NH2 C6H10NH2 C6H5OH C6H10OH

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