Special reactions/tests for Urea, Formamide, Oxamide, Salicylamide, Succinimide, Phthalimide

Urea

Urea nitrate and oxalate: Take a concentrated solution of urea, to one portion, add a few drops of con. HNO₃: the white crystalline urea nitrate (m.p. is 163°) is precipitated; to another portion, add con. Oxalic acid solution and scratch with a glass rod. White crystals of urea oxalate (m.p. is 171°) are separated. In an excess of water both salts dissolve.

Biurate reaction: Take 0-2 g of urea into a dry test-tube and heat gently above the melting point. NH₃ is evolved. After 2 minutes the liquid rapidly solidifies with the formation of biuret.

2NH₂CONH₂à NH₂CONHCONH₂ + NH₃

Dissolve the solid residue in a few ml. of warm 10% NaOH solution. Stand it to cool and add 1 drop of dil. CuSO₄ solution. A purple coloration is obtained. A pink/purple coloration is due to containing two -CONH- groups attached to one another, or to the same carbon atom or nitrogen atom. Therefore the same colouration is also given by malonamide, oxamide and by proteins/peptides.

Urease test: Urease enzymes can hydrolys Urea to Ammonium carbonate. The reaction is specific. It is used for solutions of urea to which the biuret test cannot be applied.

Action of hypobromite: Add sodium hypobromite solution to a solution of urea. The brisk effervescence is given.

NH₂CONH₂ + 3NaOBr à N₂ + CO2 + 3NaBr + 2H₂O

Formamide

Boil 1 ml of formamide in a test-tube. NH₃is evolved from it.  CO is produced, but cannot be ignited in the presence of the NH₃.

Oxamide

Biuret test: Oxamide does not need any preliminary treatment to proceed with the test. Shake 1 g of oxamide with 1ml of 10% NaOH solution. Add 1 drop of very dilute CuSO₄ solution to it and mix well. A pink coloration is produced.

Sulphuric acid test: Heat 0-3 g of Oxamide with con. H₂SO₄. CO and CO₂ are evolved.

Salicylamide

FeCl₃ coloration: Take the solid into a test tube. Add FeCl₃ solution and shake. An intense violet coloration is produced as the Phenolic groups are present.

Succinimide

Reduction: Take about 1 g of succinimide and an equal amount of Zn dust into a dry hard-glass test tube and mix well. Heat strongly. Soak a pinewood splinter in con.HCl and place it in the mouth of the tube. The splinter is turned red by the vapour of pyrrole which is formed by reduction.

Fluorescein reaction: Take about 1 g of Succinimide, 1 g of resorcinol and 2 drops of con. H₂SO₄ into a dry test tube and fuse all of it together. Cool and add water. Then add NaOH solution in excess. A green fluorescent solution is produced.

Phthalimide

Phthalein reaction: Take about 1 g of Phthalimide, 1 g of phenol and 2 drops of con. H₂SO₄ into a dry test-tube and fuse all together very gently. Let it cool and add water. Then add NaOH solution in excess. A red coloration is produced which is decolorized by acids.

Fluorescein reaction: Repeat the above test, using resorcinol instead of phenol. A green fluorescent solution is produced on the addition of NaOH solution.

Physical properties of common organic compounds (In brief)

One of the easiest ways to get an idea about an unknown organic substance is to check for its physical properties first. Physical properties are appearance, state, odour, colour, solubility in water etc. Below are some general physical properties of common organic substances.

Odour

Fruity odour: Esters, ethers.

Odour of almonds: Benzaldehyde, Nitrobenzene, Benzonitrile,

Pungent odour: Pyridine, Formic acid, Acetic acid, Benzoyl chloride, Benzyl chloride, Acetyl chloride.

Many phenols give a unique Phenolic odour. Also some derivatives of salicylic acid such as Salicylaldehyde.

Colour

Orange: Ortho-Nitro-aniline, Alizarin.

Yellow:  Quinones, m-nitroaniline, o-nitrophenol, and many other nitro-compounds. Also Iodoform.

Red: i,2-Naphthoquinone.

Blue: Commonly Copper salts.

Solubility in water

Soluble in cold water: Lower aliphatic alcohols, lower aliphatic aldehydes & ketones, lower aliphatic nitriles, lower aliphatic acid chlorides, aliphatic amines, pyridine, salts of amines, glycine, some phenols, aliphatic acids, sulphonic acids, ammonium salts and alkali salts of all acids, methyl esters of certain acids such as  formic, oxalic, succinic and tartaric. Also some aliphatic amides and imides, such as succinimide.

Almost insoluble in cold water: Higher ketones, most esters, ethers, higher alcohols, higher phenols, Benzyl alcohol, metaformaldehyde, Aromatic aldehydes, aromatic acids, aromatic amides, aromatic imides, aromatic amines, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonamides, sulphonyl chlorides, starch, anilides, uric acid, hydrocarbons.

Hydrolysed with water: Acids, esters can hydrolyse easily. Acid anhydrides, acid chlorides, salts of amines and nitrophenols.

Using  litmus-paper on a solution

Weakly acidic: Phenols. Except for nitrated phenols, phenols do not liberate CO₂ from Na₂CO₃ solution.

Weakly alkaline: Alkali salts of some weak acids and pyridine.

Preparation of solid derivatives of Carbonyl compounds (aldehydes & ketones) :- 2, 4- Dintrophenylhydrazones, Semicarbazones

The systematic procedure that involves several steps and preparations is carried out to identify unknown compounds to some extent. The preparation of derivatives usually establishes the identification of the unknown with certainty. Here the term derivative is simply referred to a compound prepared from an unknown, in order to identify the unknown compound. An ideal derivative should be a crystalline, easily purified solid with a sharp melting point, which can be prepared readily from the unknown in one direct and unambiguous step.

Many carbonyl compounds can be synthesized from the esterification reaction. There are excellent and conveniently prepared derivatives which use to identify carbonyl compounds. Oximes, Phenyl hydrazones, 2, 4-dinitrophenylhydrazones and semicarbazones are some of the best derivatives of aldehydes and ketones. In the preparation of each of these types of derivatives, the elimination of a water molecule between a molecule of the carbonyl compound and a molecule of the reagent is involved.

Dinitrophenylhydrazine is relatively sensitive to shock and friction. It is a red to orange solid usually supplied wet to reduce its explosive hazard. This is often used as a qualitative test for carbonyl groups, associated with aldehydes and ketones. The hydrazone derivatives can be used as evidence toward the identity of the original compound. These are usually yellow-red colour crystals. Crystals of different hydrazones have characteristic melting and boiling points allowing the identification of the unknown substance.

Semicarbazone is one of the most commonly used derivatives to identify aldehydes and ketones. It is a derivative of an aldehyde or ketone formed by a condensation reaction between a ketone or aldehyde and the reagent; semicarbazide. As semicarbazides are not very stable in the free form, they are usually stored in the laboratory in the form of their hydrochloride salts. Many semicarbazones are off white, crystalline solids, useful for the identification of the parent carbonyl group by melting point analysis.

Nitration of acetanilide (Lab report)

Introduction

Nitration is a type of chemical reaction which a nitro group is added to/substituted in a molecule. Basically it can be carried out by a mixture of concentrated nitric acid and sulphuric acid. Mixture is useful to obtain the active nitronium ion. Electrophilic aromatic substitution is a method used when a functional group is needed to be substituted on to an aromatic compound. In the nitration, nitronium ion acts as the electrophile that involves the attack of the electron-rich Benzene ring. In this experiment nitration is carried out using acetanilide.

Theory

Acetanilide displays moderately reactivity in electrophilic aromatic substitution. Also another advantage is, it’s not oxidized by nitric acid. Principally, acetanilide gives Ortho and Para mono nitroacetanilides. This position of nitronium ion is directed by the –NHCOCH₃ group attached to the benzene ring. This is due to the resonance delocalizing the benzene ring by nitrogen lone pair. Therefore Ortho and Para positions are more resonance stabilized than the Meta. Acetanilide undergoes ready nitration giving mainly the colourless P-nitroacetanilide, mixed with much smaller proportion of the yellow colour O-nitroacetanilide.

Procedure

·         About 2g of powdered acetanilide and 2mL of Glacial acetic acid were mixed well in a 100mL beaker.  4mL of con.H₂SO₄ was added to the mixture.

·         The beaker was placed in crushed ice until the temperature of the mixture was dropped down to 0-5⁰C.

·         4mL of con.H₂SO₄ was added drop wisely while stirring the viscous mixture continuously keeping the temperature below 10⁰C.

·         Afterwards the beaker was removed from the freezing conditions and allowed to stand 30 minutes at room temperature.

·         The mixture was poured onto about 20g of crushed ice and stirred to obtain crystals. The beaker was rinsed with 10mL of water containing few fragments of ice and the solution was added to the main bulk of the product.

·         It was allowed to stand for about 20minutes.

·         Later it was filtered at the pump and washed thoroughly with cold water.

·         Afterwards the crude product was recrystalized with water.

·         Finally the melting point of the product was determined.

Observations

·         Acetanilide powder was white in colour.

·         Glacial acitic acid, H₂SO₄ and acetanilide mixture was initially in pale yellow colour.

·         In cold condition, white colour crystals were formed.

·         Final purified crystals were also white.

·         The determined melting point range was 150-152⁰C.

Conclusion

The initial compounds used were known. Therefore according to those the final product should be nitroacetanilide. As the colour of the product was white, it should be Para nitroacetanilide.  

Discussion

Through the use of electrophilic aromatic substitution, acetanilide is nitrated to nitroacetanilide. There are several key steps involved in the nitration. The first step of the reaction involved in the donation of an electron pair by the acetanilide to the eletrophile, the nitronium ion. This nitronium ion was formed by the reaction of sulfuric and nitric acids. Basically the whole mechanism undergoes as below; (Benzene is shown here instead of acetanilide )

Image via en.wikipedia.org

To prevent dinitration of the acetanilide, the nitrating mixture of concentratred nitric acid and sulfuric acids were added in small portions to the acetanilide solution, so that the concentration of the nitrating agent is kept at minimum.

Also the addition of nitric acid is exothermic. Therefore the mixture would get too hot exceeding the temperature range suitable for the nitration. To avoid this, the addition of HNO₃ acid should be done very slowly, dropwisely.

Cold temperatures were used to slowdown the reaction rate and help to avoid over nitration.

Glacial acetic acid is used because it is a polar solvent capable of dissolving acetanilide and the acetate ion is a poor nucleophile, so no substitution is possible.

At the end, traces of acid should be removed because hydrogen ions catalyze the hydrolysis of the amide to p-nitroaniline. Acid is removed by pouring the mixture onto ice and water and filtering.

The melting point is determined to characterize the product. Theoretical melting point of the Para nitroacetanilide is found to be 214-216⁰C. The observed value was 150-152⁰C and it is much lower than the theoretical values and can be accounted for impurities in the product. Some impurities might be Ortho and Meta directing substances. Also there can be some experimental errors occurred during the experiment such as not controlling the exact temperatures mentioned for the reactions.

Test for primary aromatic amines (Benzoylation):- Anilene, O.toluidene, P.toluidene, M.toluidene

Benzoylation

Procedure	Observation
1ml of the compound, 20ml of 10% NaOH solution and 1.5ml of Benzoyl chloride were mixed together in Stoppered conical flask. Mixture was vigorously shaken.	Aniline: White semi-solid O.toluidene: Pale pink semi-solid M.toluidene: Pale brown semi-solid P.toluidene: Dark brown semi-solid

Tests for Phenols - Discussion

Phenol

Catechol

Resorcinol

2-napthol

Solubility

Some phenols (Ex: Phenol,catechol,resorcinol) are soluble in water and others are sparingly soluble or insoluble in water because of the increasing molecular weight and hydrophobic nature. But all the phenols are capable of reacting with NaOH solution and dissolve.

C₆H₅OH + NaOH ----> C₆H₅ONa + H₂O

Reaction with Sodium carbonate

Phenols give no reaction with sodium carbonate but as the aqueous solution of it was used,phenols dissolved in it giving the same colourations given when testing the solubility in water.As Phenols do not produce gas from sodium carbonate it should be a very weak acid.

Benzoylation

To react with benzoyl chloride, phenol should be modified to make the reaction possible.the -COCl group is bounded directly to the benzene ring. Therefore it's less reactive.phenol is first dissolved in NaOH in order to get the phenoxide. Later it's reacted with the Benzoyl chloride.

Tests for Carboxylic acid - Discussion

Acetic acid

Benzoic acid

Salicylic acid

 Cinnamic acid

Solubility
Acetic acid is soluble in water but Benzoic acid,salicylic acid and cinnamic acid are insoluble due to their heavy molecular weight and increased hydrophobic nature. Carboxylic acids are acidic therefore they can dissolve in bases such as ethanol and sodium hydroxide forming the carboxylate ion/salt.


Reaction with Sodium carbonate
Reacts with sodium carbonate liberating carbon dioxide

Esterification
Acetic acid----> Medicinal or strong odour of apples
Benzoic acid----> Fruity odour
Salicylic acid----> Medicinal odour
Reaction with Ferric chloride
Higher acidity can interfere the final results. Therefore it's important to use neutral ferric chloride neutralized by sodium hydroxide.
FeCl₃ + C₆H₅COO^-   -------->     Fe ( OOC₆H₅)₃
FeCl₃ + CH₃COO^-   -------->     Fe ( OOCH₃)₃
Cinnamic acid with KMnO4
This will give out Benzaldehyde and acetic acid. Almond odour was given due to the formation of benzaldehyde.