Organic Synthesis part 1

Combustion Analysis
Combustion analysis is the method used to work out the composition of an organic compound. The
percentages that you see in empirical formula questions, for example:

C 26.7% H 2.2% O 71.1%

These values are found by doing combustion analysis. This involves burning (combusting) the organic
molecule and trapping the CO2 and H2O that is formed.

CO2 is trapped by passing it through solid Ca(OH)2 and measuring the increase in mass.

H2O is trapped by passing it through solid MgSO4 or CaCl2 and measuring the increase in mass.

The masses obtained allow you to calculate the amount of carbon and hydrogen in the original sample.
From there, the amount of oxygen can be obtained.

Example

An organic compound weighing 3.60g was burned completely in oxygen. 3.60g of H2O and 8.80g of CO2
were obtained. Calculate the empirical formula.

Step 1 calculate the moles of CO2 and H2O obtained

Moles CO2 = 8.8/44 = 0.2 moles

Moles H2O = 3.6/44 0.2 moles

Step 2 calculate the moles of hydrogen and carbon

Moles of carbon also = 0.2 as there is only one carbon atom in CO2

Moles of hydrogen = 2 x 0.2 = 0.4 as there are two hydrogen atoms

Step 3 calculate the mass of hydrogen and carbon

Mass of carbon = 0.2 x 12 = 2.4g

Mass of hydrogen = 0.4 x 1 = 0.4g

Step 4 calculate the mass of oxygen

The total mass of the compound = 3.6g (sum of C + H + O)

3.6 = 2.4 + 0.4 + O

Therefore mass of O = 0.8g

Step 5 use the moles empirical formula

C 0.2 H 0.4 O 0.8/16 = 0.05

Divide everything by 0.05 C 4 H 8 O 1 C4H8O

Grignard Reagents
Grignard reagents can be thought of as carbon nucleophiles. This is unusual and is another method
(along with nitriles) to extend the carbon chain.

Preparation
Halogenoalkane + Mg Grignard Reagent

CH3CH2Br + Mg CH3CH2MgBr

think of the CH2 in this example as having a - charge and the Mg having a + charge.

Reactions
Grignards will react with an aldehyde, ketone or CO2. Think of it like the nucleophilic addition
mechanism. The Grignard is the nucleophile and attacks the C=O.

Grignard

+ CO2
+ aldehyde + ketone

carboxylic acid
primary or tertiary alcohol
secondary alcohol
 the reaction must be done in dry ether as the solvent. Grignards do not like water. In presence of
water the Grignard alkane!

Example

Reaction of Grignard with CO2

This is typical of a Grignard reaction. The OMgBr product is formed first and is then hydrolysed with acid
to form the product. Note the Mg(OH)Br side product.

Comparison with nitriles

As was mentioned above Grignards along with nitriles are methods to increase the length of the carbon
chain.

Nitriles: extend the carbon by 1 carbon only. Can make carboxylic acids or amines from the nitrile.

Grignard reagents: much more versatile than nitriles. We can make alcohols and carboxylic acids and
increase the carbon chain by however many carbons we choose.