Alma Lipnica Pabilane Michael Angelo Ronquillo

Can be used to distinguish among

primary, secondary and tertiary amines. The reagents used were Benzenesulfonyl chloride, 10% NaOH, and HCl

5 ml test tube 20 drops 10% NaOH +5 drops methylamine +5 drops benzenesulfonyl chloride

The tube was covered w/ cork, and shaken for 5 mins. Then, tested w/ red litmus paper.
If the soln wasnt basic, 10% NaOH was added until red litmus turned blue.

If precipitate formed, 40 drops of water was added. The mixture was shaken.

3M HCl was added dropwise to the resulting mixture of the above procedure.

The procedure was repeated with dimethylamine, trimethylamine, aniline and N-methylaniline.

Test Samples

NaOH, benzenesulfonyl chloride

HCl

methylamine

Curdy mixture

Mixture became more cury (curdier?) , precipitate formed

No reaction; precipitate not dissolved N/A;Theoretically: precipitate will dissolve Mixture became more curdy Precipipitate undissolved; layers formed

dimethylamine trimethylamine aniline N-methylamine

Formation of precipitate (yellowish) N/A; Theoretically: precipitate will form Formation of brown precipitate (brown) Formation of precipitate (black)

Benzenesulfonyl chloride undergoes reaction with primary amines in basic solution to form sodium salts of the sulfonamide. These salts are soluble in the basic solution.

RNH2 + C6H5SO2Cl + 2NaOH 1 amine benzenesulfonyl chloride C6H5SO2NR-Na+ + NaCl + 2H2O (soluble) | HCl

C6H5SO2NHR sulfonamide (insoluble)

 Secondary amines, when treated with

benzenesulfonyl chloride, yield the sulfonamides, which precipitate from the solution. Acidification of the solution does not dissolve the sulfonamide.

R2NH
secondary amine

C6H5SO2Cl
benzenesulfonyl chloride

NaOH

C6H5SO2NR2 + NaCl + H2O

sulfonamide (insoluble)

HCl No Reaction

 TERTIARY AMINES undergo reaction

with benzenesulfonyl chloride to produce quaternary ammonium sulfonate salts, which yield sodium sulfonates and insoluble tertiary amines in basic solution. ACIDIFICATION of the reaction mixture results in the formation of sulfonic acids and soluble amine salts.

+
R3N + C6H5SO2Cl
Tertiary amine benzene sulfonyl chloride

C6H5SO2NR3Cl
+ 2NaOH

C6H5SO3-Na+ + NR3
(soluble)

+ NaCl + H2O

(insoluble) 2HCl

C6H5SO3H + R3N+HCl- + 2NaCl

(soluble)

REAGENTS USED

TEST FOR

POSITIVE RESULTS
Soluble in base and insoluble in acid Insoluble in both base and acid Insoluble in base and soluble in acid

1. Benzenesulfo Primary amine nyl chloride 2. Sodium Secondary amine Hydroxide 3. Hydrochloric Tertiary amine Acid

 Nitrous Acid Test is useful in classifying amines

not only as primary, secondary, or tertiary amines but also as aliphatic or aromatic.

Nitrous Acid is unstable; it is prepared by

reacting sodium nitrite (NaNO2) with an acid (in the experiment, HCl was used) in 0-5 oC

10 ml test tube 3 drops methylamine +40 drops 2M HCl. The soln was cooled to 0-5oC in ice bath. 5drops cold 20% NaNO2. Temp was maintained 0-5oC . Repeated with dimethylamine, trimethylamine, aniline, Nmethylaniline.

If no evolution of gas nor formation of yellow to orange color, half of the soln was warmed to room temp.

Ice cold solution of 50 mg b-naphthol in 2ml of 2M NaOH was added dropwise.

TEST Samples HCl, NaNO2 Methylamine Evolution of gas; clear solution

B-naphthol in NaOH

Dimethylamine Formation of yellow oily liquid/ppt Trimethylamine N/A; theoretically : the amine will dissolve Aniline Nmethylaniline No observable evolution of gas; clear solution Formation of yellow oily liquid/ppt Orange coloration; evolution of gas

 Primary aliphatic amines react with nitrous

acid to form an intermediate diazonium salt, which is highly unstable and degradates into a carbocation that is capable of reaction with any nucleophile in solution.

Primary aromatic amines react with nitrous

acid to form diazonium salts which are stable at 0C but decompose to nitrogen gas at room temperature.

 Therefore, reacting primary amines with nitrous

acid leads to a mixture of alcohol, alkenes, and alkyl halides. Nitrogen gas is released. RNH2 + HONO + 2HCl [RN2+Cl-]
1o aliphatic Amine nitrous acid
H2O

0-5oC diazonium salt unstable

[RN2+Cl-]

N2(g) + ROH + RCl + ROR + alkene

spontaneous

 Primary aromatic amine - forming

stable diazonium salts at 0 degree Celcius

 Secondary amines (both aliphatic and

aromatic) undergo a reaction with nitrous acid to form N-nitrosoamines, which are usually yellow solids or oil.

The nitrosoamines formed from secondary amines are the ones responsible for the yellow precipitate. These are carcinogenic and are not useful as intermediates for subsequent reactions.

 Tertiary aliphatic amines do not react with

nitrous acid, but they form a soluble salt. The reaction mixture gives an immediate positive test on the starch-iodide paper for nitrous acid.

3o aliphatic Amine

R3N

+ H+

R3NH+
soluble

 Tertiary aromatic amines treated w/ nitrous

acid will yield a dark orange-red solution or an orange crystalline precipitate resulting from the formation of the hydrochloride of Cnitrosamine.

Treating the solution with base liberates the

blue or green C-nitrosoamine.

REAGENTS
1. Sodium nitrite (NaNO2) 2. HCl

TEST FOR
PRIMARY ALIPHATIC amines PRIMARY AROMATIC amines SECONDARY aliphatic and aromatic amines TERTIARY ALIPHATIC amines TERTIARY AROMATIC amines

POSITIVE RESULTS
Evolution of N2 gas Evolution of N2 gas Yellow oil or solid precipitate Dissolution of amine (clear solution) Colored precipitate

EXPERIMENT 8B-H

Pabilane, Alma L. Ronquillo, Michael Angelo A. CHEM 31.1 SAD Sir Alphius Mendoza

In a 10-ml test tube, a pinch of salicylic acid and 20 drops of methanol were mixed. 5 drops of conc. H2SO4 was added.
Acid catalyst

The mixture then was heated in a water bath for 5 mins.

Test sample

Result

Structure/formul a of compound responsible

Salicylic acid

Minty smell

Methyl salicylate

Also known as Fischer esterification, esters (RCOOR) are produced when carboxylic acids (RCOOH) are heated with alcohols (ROH) in the presence of an acid catalyst, usually concentrated sulfuric acid. Methyl salicylate, oil of wintergreen, gives a sweet menthol odor. This reaction involves nucleophilic acyl substitution, the electrophilic nature of the acid substrate increases, making it very susceptible to a nucleophilic attack by an alcohol.

20 drops H2O and 10 drops CH3CH2OH were mixed in a 5-ml test tube. 5 drops benzoylchloride was carefully added. The tube was covered with cork and was shaked gently.

20 drops 25% NaOH was added while mixing.

Test sample

Visible Result/ Odor

Structure/formul a of compound responsible

Benzoylchloride

Rubber-like smell; Clear sticky solution with white precipitate

Ethyl benzoate

The reaction between an acylhalide (benzoyl chloride) with an alcohol (ethanol) will form a solution of ester (ethyl benzoate) with white precipitate and raspberry-like odor The cleavage of a bond with alcohol is called alcoholysis.

The organic reagents combine in the organic phase, forming an ester, while acidbase neutralization occurs in the inorganic phase.

ROH

OR

A pinch of benzamide and 20 drops 10% NaOH were placed in a 5ml test tube. A piece of moist red litmus paper was held over the mouth of the test tube while heating the mixture. The change in color and odor of the litmus paper were noted.

Test sample

Visible Result/ Odor

Structure/formul a of compound responsible

Benzamide

Blue to litmus ammonia- smelling

NH3
Ammonia

Hydrolysis of benzamide yields benzoic acid plus ammonia (NH3) upon heating in 10% NaOH solution. The overall transformation was a typical nucleophilic acyl substitution of OH for NH2. Benzamide is a primary aromatic amide, capable of being hydrolyzed in heat with a dilute solution (10%) of a strong base, like NaOH. When amides are hydrolyzed, they yield carboxylic acid salts and ammonia or amine. In the experiment, Benzamide evolved a gas that turned red litmus paper to blue. The gas had the smell of ammonia.

20 drops of ethylacetate and 5 drops 25% NaOH solution were placed in a 5ml test tube. The test tube was loosely covered with a cork and it was heated in a water bath for 15 minutes. A molar of HCl was added dropwise until the solution became neutral to the litmus paper. Change in the odor of the mixture was noted.

Test sample

Result

Structure/formul a of compound responsible

Ethylacetate

Clear liquid with yellow precipitate and a sweet odor Sodium carboxylate

Esters can be hydrolyzed using water in the presence a dilute strong acid as catalyst. This reaction is the reverse of forming esters from carboxylic acid and alcohol.

 In the experiment, the ester was hydrolyzed with

a dilute strong base, NaOH. This has two advantages than using acid, 1. the reaction is one-way rather than reversible and 2. the products are easier to separate. The products of this reaction are alcohol and the sodium salt instead of the carboxylic acid itself.

 A positive result for this is a clear solution with a

yellow precipitate and a sweet smell. Notice that in alkaline conditions the carboxylate ion is formed. The addition of a strong acid, such as dilute hydrochloric acid, is required to free the carboxylic acid molecule.

+ HX

+ NaX

Esterification is a slow and reversible reaction, and is therefore subject to Le Chateliers principle. When a carboxylate ester reacts with a strong base, the metal cation and the carboxylate will form a salt via electrophilic substitution, leaving the alkyl group and the hydroxide anion to form an alcohol. Adding an acid will cause the carboxylate anion to be protonated, thus forming a carboxylic acid.

20 drops water and a piece of both red and blue litmus papers were placed in a 5ml test tube 20 drops of acetic anhydride was carefully added to the mixture. The test tube was gently shook. Change in temperature of the solution was noted.

Test sample

Result

Structure/formul a of compound responsible

Acetic Anhydride

Vinegar- smelling Red to litmus

CH3COOH Acetic acid

Acetic anhydride hydrolyses to give acetic acid, indicated by the increase in temperature of the solution. When water reacts with acid anhydrides, the carboxylic acid of the derivative will form, together with the evolution of heat. A positive test for this reaction is evident when the test tube where the reaction took place feels warm. Also, since the carboxylic acid of the derivative is formed, the resulting solution must be acidic, and can be tested with a blue litmus paper. And also change in odor should be noted.

METHODOLOGY
5 drops of ethylacetate and 20 drops of 7% methanolic hydroxalamine HCl solution were placed in a 5ml test tube. 10% methanolic KOH was added until the red litmus paper turns blue. Then 10 drops more were added.

The solution was heated to boiling in a water bath and was allowed to cool slightly.

10 drops of 3% FeCl3 solution were added to the mixture.

The procedure was repeated using benzamide, acetic anhydride and benzoyl chloride.

Test sample

Visible Result/ Odor Yellowish mixture yellowish mixture w/ white ppt., less dense liquid layer lessened Clear white mixture with small white ppt. brown mixture w/ white & brown ppt. Clear white mixture w/ small white ppt. orange soln w/ white ppt. Cloudy w/ white ppt. red soln w/ white ppt.

Structure/ formula of the compound responsible ROH

Ethylacetate

Benzamide

NH4Cl

Acetic Anhydride

RCO2H

Benzoylchloride

HX

Esters characteristically have a sweet fruity smell. Esters react with hydroxylamine to yield an alcohol and hydroxamic acid. They will be converted into a hydroxamic acid (HOHNC=O), this will then give a positive result for ferric chloride test. This positive test will be exhibited by a burgundy or magenta color from the ferric hydroxamate complex.

Aliphatic amides react with hydroxylamine hydrochloride to form hydroxamic acid. Similarly, aromatic primary amides react with hydrogen peroxide to produce hydroxamic acid .The hydroxamic acid then reacts with ferric chloride to form the ferric hydroxamate, which has a characteristic magenta color.

Anhydrides reacting with hydroxilamineHCl soln yields carboxylic acid and hydroxamic acid which reacted with Ferric chloride to form the complex, (burgundymagenta color).

The acyl halide undergoes reaction with the hydroxylamine to form a hydroxamic acid, which is then treated with ferric chloride to form the magenta-colored ferric hydroxamate complex. Benzoylchloride with ferric hydroxamate complex will create an orange layer on top and a dark reddish brown color on the bottom.

 Bruice, P.(2006).Essential Organic Chemistry. Pearson

Education South Asia Pte Ltd. Furniss B., Hannaford, A., Smith, P., Tatchell, A.(1989). Vogels Textbook of Practical Organic Chemistry 5th Ed. Longman Group UK Ltd. Shriner, R., Hermann, C., Morrill, T., Curtin, D., Fuson R.(2004).The Systematic Identification of Organic Compounds 8th ed. John Wiley & Sons, Inc. http://www.cliffsnotes.com/ http://jchemed.chem.wisc.edu http://www2.chemistry.msu.edu http://www.chemguide.co.uk http://www.transtutors.com http://www.chemistry.ccsu.edu http://wwwchem.uwimona.edu.jm

The LORD is my Shepherd; I shall lack nothing. Ps.23:1