Alcohols

1) Alcohols:
Defination: Alcohols. Dihydric Alcohols: Method of Formation of Ethylene Glycol-industrial method and From Alkene using OsO4, Chemical Reactions of Ethylene Glycol-nitration, Acylation, Oxidation ( Using Pb(OAc)4 without Mechanism Pinacol-Pinacolone rearrangement, Trihydric Alcohols: Preparation of Glycerol from propane, Reactions of Glycerol. 6 Hrs. Monohydric Alcohols: Methods of Formation by reduction of Aldehydes,

Ketones, Carboxylic Acids and Esters (One eg.each) Acidic Nature, Reactions of

Alcohols are hydroxy-derivatives of alkanes, alkenes, or alkynes in which a hydroxyl group is bound to a saturated carbon. The general formula for alcohols is ROH (CnH2n+1OH for saturated alcohols), where the R group can represent the alkyl, alkenyl, or alkynal groups. In the case of substitution on alkenes and alkynes, only saturated carbons may be substituted. For example, the following compounds are all alcohols:

If the hydroxyl group were substituted for hydrogen on an unsaturated carbon, an alcohol would not form. For example, substituting the hydroxyl group for terminal hydrogen of 1-propene gives an unstable enol that tautomerizes to a ketone.

Classification of Monohydric Alcohols

Alcohols are classified By the number of alkyl groups attached to the carbon bonded to the hydroxyl.

As primary (1), secondary (2), or tertiary (3).

primary (1),

secondary (2),

tertiary (3)

Nomenclature
Both the common and the IUPAC systems are used to name alcohols. In the common system, you name an alcohol by listing the alkyl group and adding the word alcohol. Following are some examples of alcohols and their common names:

In the IUPAC system, use the following series of rules to name alcohols:
1. Pick out the longest continuous chain to which the hydroxyl group is directly attached. The parent name of the alcohol comes from the alkane name for the same chain length. Drop the -e ending and add -ol. 2. Number the parent chain so that the carbon bearing the hydroxyl group has the lowest possible number. Place the number in front of the parent name. 3. Locate and name substituents other than the hydroxyl group.

The rules for IUPAC nomenclature system can be summarized in the following table.1

Step 1 Select the longest carbon chain that contains the -OH group. Step 2 Number from the end nearest to -OH group. Step 3 Change the ending of parent alkane from -e to -ol. Use the number to show the location of -OH. Step 4 Give the location and name of each substituent (alphabetical order) as a prefix to the name of the main chain.

Physical properties
Alcohol show a gradation with the increase in their molecular weight belonging to the homologous series. Alcohols contain both a polar OH group and a nonpolar alkyl group. As a result of this composition, alcohols that have small alkyl chains tend to be water soluble. As alkyl chain length increases, water solubility decreases. Through the OH group, alcohols are capable of forming hydrogen bonds to themselves, other alcohols, neutral molecules, and anions. This bond formation leads to abnormally high boiling points compared to other organic molecules of similar carbon chain length. The presence of the hydrogen bonding between alcohol molecule as a result of the higher boiling point than the alkanes or ethers having same molecular weitht.

Alcohols are acidic in nature.

StructuralFormula CH3OH CH3CH3 CH3CH2 OH CH3CH2 CH3 CH3CH2 CH2OH CH3CH2 CH2CH3 CH3CH2 CH2CH2OH CH3CH2 CH2CH2CH3

Name methanol ethane ethanol propane 1propanol butane 1butanol pentane

Molecular Weight 32 30 46 44 60 58 74 72

bp (C) 65 89 78 42 97 0 117 36

Solubility inWater infinite insoluble infinite insoluble infinite insoluble 8g/100g insoluble

Preparation of Alcohols
Alcohols can be prepared by the hydration of alkenes or by the reduction of aldehydes, ketones, acids, and esters.

Reduction of aldehydes and ketones

The carbonyl compounds can be reduced to alcohol by using various reducing agents, such as: - Zn / H+ , Zn / HCl , Na / alcohol -H2 / Pt or Pd or Ni, - Li Al H4 /dry ether ( for ald., or ket.) ( for all C=O compounds) ( for all C=O compounds)

Apart from the above reducing agents complex metal hydrides, such as lithium aluminum hydride (LiAlH4) or sodium borohydride (NaBH4) are also used for reduction.

A.

Aldehydes can be reduced to primary alcohols with i) sodium amalgam and very dilute HCl or H2SO4 or ii) Zndust and acetic acid.

The reduction can also be carried by using i) Pt or Pd and H2 or ii) Platinium oxide in the presence of ferrous salt. a) Reduction using sodium amalgam (Na-Hg) in water Aldehydes and/or ketones can be converted into primary and secondary alcohols by reduction using sodium amalgam in water. b) By catalytic reduction: Hydrogen gas on passing into a solution of aldehydes and/or ketones in the presence of catalyst (Ni or Pt) at 413K undergo reduction of carbonyl group to give primary and/or secondary alcohol respectively.

c) Reduction using Sodium borohydride:

Sodium borohydride is a best and mild reducing agent for the reduction of aldehydes and ketones. It is preferably used in most laboratory scale reductions. Into a solution of aldehydes and/or ketones in methanol or water, sodium borohydride is added at room temp. gives primary and/or secondary alcohol respectively.

d) Lithium aluminium hydride (LiAlH4) in 1947 is used for the

reduction of carbonyl compounds to alcohols

O R-C-H O CH3-C-H

1) Li Al H4 / dry ether or NaBH4 1) H3O 1) Li Al H4 / dry ether or NaBH4 1) H3O

OH R-CH2

CH3-CH2OH

Lithium aluminum hydride is a very strong reducing agent that will reduce many functional groups in addition to aldehydes and ketones. Sodium borohydride is a much weaker reducing agent that basically will reduce only aldehydes and ketones to alcohols.

Reduction of carboxylic acids

The reduction of carboxylic acid requires a very strong reducing agent, and lithium aluminum hydride is the standard choice.

Catalytic hydrogenation gives very poor yields or does not undergo reduction of carboxylic acids.

Reduction of esters
Esters, like carboxylic acids, are normally reduced with lithium aluminum hydride. In these reactions, two alcohols are formed. An example is the reduction of methyl benzoate to benzyl alcohol and methanol.

Some of the methods of preparation of alcohols is summarized in the following diagram.

Acidity of Alcohols
Alcohols are only slightly weaker acids than water, with a Ka value of approximately 1 1016. The acidity of alcohols decreases while going from primary to secondary to tertiary. This decrease in acidity is due to two factors: an increase of electron density on the oxygen atom of the more highly-substituted alcohol, and steric hindrance (because of the alkyl groups, which inhibit solvation of the resulting alkoxide ion). Both of these situations increase the activation energy for proton removal. The basicity of alkoxide ions increases while going from primary to tertiary. This increase in basicity occurs because the conjugate base of a weak acid is strong. The weaker the acid, the stronger the conjugate base.

Reactions of Alcohols
Alcohols are capable of being converted to metal salts, alkyl halides, esters, aldehydes, ketones, and carboxylic acids.

Metal salt formation

The reaction of ethanol with sodium metal (a base) produces sodium ethoxide and hydrogen gas.

This reaction is identical to the reaction of sodium metal with water.

However, the latter reaction occurs faster because of the increased acidity of water (Ka value of 1 1015) than alcohol Alcohols (Ka value of approximately 1 1016). Likewise, similar reactions occur with potassium metal.

Alkyl halide formation

Alcohols are converted to alkyl halides by SN1 and SN2 reactions with halogen acids.

Primary alcohols favor SN2 substitutions while SN1 substitutions occur mainly with tertiary alcohols. A more efficient method of preparing alkyl halides from alcohols involves reactions with thionyl chloride (SOCl2).

This reaction is rapid and produces few side reaction products. In addition, the sulfur dioxide and hydrogen chloride formed as byproducts are gasses and therefore easily removed from the reaction. Mechanistically, the alcohol initially reacts to form an inorganic ester.

The chloride ion produced by this reaction, acting as a nucleophile, attacks the ester in an SN2 fashion to yield molecules of sulfur dioxide, hydrogen chloride, and an alkyl halide.

Because the reaction proceeds mainly by an SN2 mechanism,

the alkyl halide produced from an optically active alcohol will have the opposite relative configuration from the alcohol from which it was formed. Because thionyl bromide is relatively unstable, alkyl bromides are normally prepared by reacting the alcohol with phosphorous tribromide (PBr3).

This reaction proceeds via a two-step mechanism. In the first step, the alcohol reacts with the phosphorous tribromide.

The second step is an SN1 or SN2 substitution in which the bromide ion displaces the dibromophosphorous group.

In a similar manner, alkyl iodides are prepared by reacting an alcohol with phosphorous triiodide.

Ester formation
Esters are compounds that are commonly formed by the reaction of oxygencontaining acids with alcohols. The ester functional group is

Alcohols can be converted to esters by means of the Fischer Esterification Process. In this method, an alcohol is reacted with a carboxylic acid in the presence of an inorganic acid catalyst. Because the reaction is an equilibrium reaction, in order to receive a good yield, one of the products must be removed as it forms. Doing this drives the equilibrium to the product side.

The mechanism for this type of reaction takes place in seven steps: 1. The mechanism begins with the protonation of the acetic acid.

2.

The electrons of the carboxyl group,

, migrate to pick up

the positive charge.

3.

The oxygen of the alcohol molecule attacks the carbocation.

4.

The oxonium ion that forms loses a proton.

5.

One of the hydroxyl groups is protonated to form an oxonium ion.

6.

An unshared pair of electrons on another hydroxy group

reestablishes the carbonyl group, with the loss of a water molecule.

7.

The oxonium ion loses a proton, which leads to the production of

the ester.

Following are several examples of the oxidation of primary alcohols:

Because ketones are more resistant to further oxidation than aldehydes, you may employ stronger oxidizing agents and higher temperatures. Secondary alcohols are normally converted to ketones by reaction with potassium dichromate (K2Cr2O7), potassium permanganate (KMnO4), or chromium trioxide in acetic acid (CrO3/CH3COOH). Following are several examples of the oxidation of secondary alcohols:

Carboxylic acid formation. Upon oxidation with strong oxidizing agents and high temperatures, primary alcohols completely oxidize to form carboxylic acids. The common oxidizing agents used for these conversions are concentrated potassium permanganate or concentrated potassium dichromate. Following are several examples of this type of oxidation: