CHEM 31.

1 JK-1L

Exercise 13 Amines Submitted by Rhoda Mae B. Pableo

Group members Maybelle Fortaleza Katia Charmaine Ponce

Submitted to Dominica DM. Dacera, Ph.D.

ABSTRACT Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkylor aryl group. Amines are classified into 3 different classes which are primary, secondary, and tertiary amines. They were differentiated and characterized in this experiment were different tests were done such as solubility test and Hinsbergs test. All of these classes can form hydrogen bonds with water thus low molecular weights are soluble in water. However, amines with six carbon atoms may reach borderline solubility. Diethylamine was found out to be the only one which is soluble in water and it is a secondary amine. In the Hinsbergs test, aniline yielded crystals which were dissolved in NaOH which makes it a primary amine. Diethylamine was clear and evident of crystal formation which is a characteristic of secondary amines and on the other hand, N-N dimethylaniline did not yield any crystal either dissolved or undissolved which is a characteristic of tertiary amines.

INTRODUCTION Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an alkylor aryl group. Important amines include amino acids, biogenic amines, trimethylamine, and aniline. Inorganic derivatives of ammonia are also called amines, such as chloramine (NClH2). Compounds with the nitrogen atom attached to a carbonyl of the structure R-C(=O)NR'R'' are called amides and have different chemical properties from amines. Amines are weak organic bases that form salts with strong acids. Amine salts are usually highly dissociated ions and are water soluble. These salts may be converted back into amine by making the solution alkaline (en.wikipedia. org). In amines, the central atom is a nitrogen atom. Amines are derivatives of ammonia, NH3, in which carbon atoms replace one, two, or three of the hydrogen atoms (Timberlake, 2008). Amines fall into different classes depending on how many of the hydrogen atoms are replaced. In primary amines, only one of the hydrogen atoms in the ammonia molecule has been replaced. That means that the formula of the primary amine will be RNH 2 where "R" is an alkyl group. In a secondary amine, two of the hydrogens in an ammonia molecule have been replaced by hydrocarbon groups. At this level, you are only likely to come across simple ones where both of

the hydrocarbon groups are alkyl groups and both are the same. n a tertiary amine, all of the hydrogens in an ammonia molecule have been replaced by hydrocarbon groups. Again, you are only likely to come across simple ones where all three of the hydrocarbon groups are alkyl groups and all three are the same. The small amines of all types are very soluble in water. In fact, the ones that would normally be found as gases at room temperature are normally sold as solutions in water - in much the same way that ammonia is usually supplied as ammonia solution. All of the amines can form hydrogen bonds with water - even the tertiary ones. Although the tertiary amines don't have a hydrogen atom attached to the nitrogen and so can't form hydrogen bonds with themselves, they can form hydrogen bonds with water molecules just using the lone pair on the nitrogen. Solubility falls off as the hydrocarbon chains get longer - noticeably so after about 6 carbons. The hydrocarbon chains have to force their way between water molecules, breaking hydrogen bonds between water molecules. However, they don't replace them by anything as strong, and so the process of forming a solution becomes less and less energetically feasible as chain length grows (www.chemguide.co.uk). An electrophilic reagent, benzenesulfonyl chloride, reacts with amines in a fashion that provides a useful test for distinguishing primary, secondary and tertiary amines (the Hinsberg test). As shown in the following equations, 1 and 2-amines react to give sulfonamide derivatives with loss of HCl, whereas 3-amines do not give any isolable products other than the starting amine. In the latter case a quaternary "onium" salt may be formed as an intermediate, but this rapidly breaks down in water to liberate the original 3-amine (lower right equation).

The Hinsberg test is conducted in aqueous base (NaOH or KOH), and the benzenesulfonyl chloride reagent is present as an insoluble oil. Because of the heterogeneous nature of this system, the rate at which the sulfonyl chloride reagent is hydrolyzed to its sulfonate salt in the absence of amines is relatively slow. The amine dissolves in the reagent phase, and

immediately reacts (if it is 1 or 2), with the resulting HCl being neutralized by the base. The sulfonamide derivative from 2-amines is usually an insoluble solid. However, the sulfonamide derivative from 1-amines is acidic and dissolves in the aqueous base. Acidification of this solution then precipitates the sulfonamide of the 1-amine (www2.chemistry.msu.edu).

OBJECTIVES This study, objectively aims to discover and study the characteristics and properties of amines. On the other hand, this experiment specifically aims to accomplish the following objectives: To characterize amines and their functional group To be able to perform and understand tests which can describe the behavior of amines To know and examine its properties based on its structure

METHODOLOGY
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Please refer to Exercise 9 in lab manual entitled Chemistry 31.1 Organic Chemistry

Laboratory. The procedure can be found in page 84 of the said manual. PRESENTATION OF RESULTS Table 1. Solubility, Acidity and reaction of amines to concentrated HCl. Test Compound Aniline Solubility Insoluble Acidity Neutral Observation after addn of HCl There was emission of white gas; aniline mixed with water Oily solution/layer spread but no further essential changes More evolution of gas

N-N dimethylaniline

Insoluble; formation of brown layer (top) Soluble: homogenous colorless solution

Red

Diethylamine

basic

Table 2. Hinsberg test on primary, secondary, and tertiary amines Test Conpounds Aniline Observations There were crystals dissolved in NaOH; primary

N-N dimethylaniline Diethylamine

No crystals formed; tertiary There was crystal formation; secondary

DISCUSSION OF RESULTS In Table 1, the solubility, acidity and reaction with concentrated hydrochloric acid of three representative organic compounds of the classes of amines. It was shown that aniline and N-N dimethylaniline are insoluble and water and diethylamine on the other hand is soluble. The small amines of all types are very soluble in water. In fact, the ones that would normally be found as gases at room temperature are normally sold as solutions in water - in much the same way that ammonia is usually supplied as ammonia solution. All of the amines can form hydrogen bonds with water - even the tertiary ones. Although the tertiary amines don't have a hydrogen atom attached to the nitrogen and so can't form hydrogen bonds with themselves, they can form hydrogen bonds with water molecules just using the lone pair on the nitrogen. Solubility falls off as the hydrocarbon chains get longer - noticeably so after about 6 carbons. The hydrocarbon chains have to force their way between water molecules, breaking hydrogen bonds between water molecules. However, they don't replace them by anything as strong, and so the process of forming a solution becomes less and less energetically feasible as chain length grows (www.chemguide.co.uk). In the second part of the experiment, Hinsberg test was performed in order to identify and characterize primary, secondary, and tertiary amines from each other. Table 2 exhibits the results that were obtained. It was found out that aniline is a primary amine and diethylamine is a secondary amine, while N-N dimethylaniline is a tertiary amine. Primary and secondary amines, due to the presence of hydrogen atoms attached to nitrogen can be acylated into amides. Tertiary amines do not undergo such reaction. Such reaction is used to explain the Hinsbergs test. The amine to be tested is reacted with benzenesulfonyl chloride and alkali. After which, the solution is acidified. Primary amines react to form sulfonamide, which are soluble in alkaline reaction but precipitates after acidification. Secondary amines react to form precipitate of sulfonamide in alkaline solution. After acidification, ni change occurs. Tertiary amines do not react with benzenesulfonyl chloride in alkali solution. The amine however, dissolves when acidified due to the formation of salt. Aniline yielded crystals which were dissolve in NaOH which makes it a primary amine. Diethylamine was clear and evident of crystal formation which is a characteristic of secondary amines and on the other hand, N-N dimethylaniline did not yield any crystal either dissolved or undissolved which is a characteristic of tertiary amines.

CONCLUSION In this experiment, the solubility of amines and its different classes were determined and characterized in Table 1. The small amines of all types are very soluble in water. In fact, the ones that would normally be found as gases at room temperature are normally sold as solutions in water - in much the same way that ammonia is usually supplied as ammonia solution. All of the amines can form hydrogen bonds with water - even the tertiary ones. Although the tertiary amines don't have a hydrogen atom attached to the nitrogen and so can't form hydrogen bonds with themselves, they can form hydrogen bonds with water molecules just using the lone pair on the nitrogen. Solubility falls off as the hydrocarbon chains get longer - noticeably so after about 6 carbons. The hydrocarbon chains have to force their way between water molecules, breaking hydrogen bonds between water molecules. However, they don't replace them by anything as strong, and so the process of forming a solution becomes less and less energetically feasible as chain length grows (www.chemguide.co.uk). This experiment also determined what characterizes the classes of amines and how they are classified which were specifically primary, secondary, and tertiary. This was done and properly observed through the Hinsbergs test in which the results are found in Table 2. Aniline yielded crystals which were dissolve in NaOH which makes it a primary amine. Diethylamine was clear and evident of crystal formation which is a characteristic of secondary amines and on the other hand, N-N dimethylaniline did not yield any crystal either dissolved or undissolved which is a characteristic of tertiary amines.

ANSWERS TO QUESTIONS Pre-Laboratory Questions: N/A Post-Laboratory Questions: 1. Using structures, explain solubility of amines in water. Primary amine Secondary amine

Tertiary amine

The small amines of all types are very soluble in water. In fact, the ones that would normally be found as gases at room temperature are normally sold as solutions in water - in much the same way that ammonia is usually supplied as ammonia solution. All of the amines can form hydrogen bonds with water - even the tertiary ones. Although the tertiary amines don't have a hydrogen atom attached to the nitrogen and so can't form hydrogen bonds with themselves, they can form hydrogen bonds with water molecules just using the lone pair on the nitrogen. Solubility falls off as the hydrocarbon chains get longer - noticeably so after about 6 carbons. The hydrocarbon chains have to force their way between water molecules, breaking hydrogen bonds between water molecules. However, they don't replace them by anything as strong, and so the process of forming a solution becomes less and less energetically feasible as chain length grows (www.chemguide.co.uk). 2. Using equations, a. Write the equation of diethylamine with HCl, then followed by the treatment of NaOH to the product formed

OHCH3CH2NHCH2CH3 + HCl

NaOH or H+ NH(CH3CH2)2 no reaction

b. Show the reaction of Hinsberg test to each test compound

c. Which of the sulfonamides was soluble in alkali and why? The sulfonamide which was formed by primary amines through reaction with benzenesulfonyl chloride was soluble in alkali. It is soluble in alkali but precipitates when acidified. In this reaction, it was soluble in alkali since the hydrogen ion form HCl is neutralized by the base.

REFERENCES Book Reference(s): Timberlake, K.C. 2007. General, Organic, and Biological Chemistry Structures of Life 2 nd ed. Singapore: Pearson Education, Inc. p. 433. On-line Articles: Amines. Accessed on September 26, 2011. Accessed from http://www.chemguide.co.uk/organicprops/amines/background.html Amines. Accessed on September 26, 2011. Accessed from http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/amine1.htm Amines. Accessed on September 26, 2011. Accessed from http://en.wikipedia.org/wiki/Amine