Reactions of Aldehydes and Ketones
Introduction
In this experiment, many tests were performed on an unknown to determine its identity. The tests that were used include: Tollens Test, Iodoform Test, and the preparation of solid derivatives with the use of both 2,4 – dinitrophenylhydrazone and semicarbazone1. The reactivity of the carbonyl group is utilized in this experiment. The structure of a carbonyl group and the differences between an aldehyde and a ketone are as shown in Figure1:
Figure 1: In organic chemistry, carbonyl groups (as shown in the aldehyde and ketone above) are the birthplace of many reactions1.
In addition, Figure 2 shows the mechanism of how a carbonyl group utilizes polarity to make the carbon into an electrophile1. The polarity of the double bond between the carbon and oxygen results in a positive charge on the carbon and a partial negative charge on the oxygen1.
Figure 2: Polarity is what makes the carbonyl group so easy to react with1.
Figure 3 shows the next step in the SN2 reaction where the nucleophile attacks the electrophile1. The hydrogens on the carbon directly attached to the carbonyl group are acidic due to the resonance that stabilizes the negative charge on the oxygen1.
Figure 3: The SN2 mechanism for creating an alcohol from a ketone.
As shown in Figure 4, the basic hydrogens can be removed in the presence of a base to form an enolate anion that can act as a nucleophile and attack an electrophile1. This experiment will use all the chemical properties of carbonyl groups to perform the tests and form the solid derivatives to determine the melting point of the solid derivatives and ultimately the identity of the unknown.
Figure 4: The acidic hydrogens can be removed in the presence of a base, forming an enolate anion that can act as a nucleophile1.
Tollens Test:
Bernhard Tollens helped to discover/modify the Tollens reagent as he did some work with carbohydrates and their structures1. The Tollens reagent tests for the presence of aldehydes in chemical compounds2. The reagent is formed using the chemical equations in Figures 5 and 61. Once the reagent is formed, it can be used to test for an aldehyde group2. If an aldehyde group is present, the reaction in Figure 7 will occur, and Ag1+ will be reduced to a metal or form a silver mirror-like film on the inner wall of the test tube2.
Figure 5: Step 1 of preparation of the Tollens reagent1.
Figure 6: Step 2 of preparation of the Tollens reagent1.
Figure 7: Reaction that occurs when Tollens reagent is added to a compound with an aldehyde group.
Iodoform Test:
The iodoform test shows if there are any methyl ketones in the unknown compound or not. The methyl ketones produce HCI3 (Iodoform), and the compounds that lack methyl ketones do not produce HCI33. Iodoform is characterized by its yellow color and solidity3. Figure 8 shows the mechanism of the acidic hydrogens being removed from the ketone by a base to form an enolate anion1. Then, in Figure 9, the enolate (nucleophile) is attacking the iodine (electrophile)1. Figure 10 shows that the acidic hydrogens can be removed by the base until there are not any of the remaining1. In addition, the enolate anion can also attack the iodine until there are not any more enolates able to be formed by the removal of acidic hydrogens as shown in Figure 101. Lastly, the carbonyl carbon is attacked by base, as in Figure 11, and is turned into an alcohol with CI3 as the leaving group1. CI3, then attacks the hydrogen on the hydroxyl group, forming the iodoform1.
Figure 8: Iodoform test begins due to acidic hydrogen being removed by the base.
Figure 9: The enolate anion that is formed when the acidic hydrogens are removed by the base acts as a nucleophile.
Figure 10: The carbon becomes a nucleophile and attacks iodine.
Figure 11: The carbonyl carbon is attacked by the base and the CI3 leaves as the leaving group.
Preparation of Solid Derivatives:
The solid derivatives of the unknown are formed using the reactivity of carbonyl groups. In Figure 12, the two derivatives formed in this lab are shown. Both derivatives are formed from a ketone.
Figure 12: The two solid derivatives formed in the experiment.
The above tests and preparations were completed in this lab using the compounds listed in Table 1: Table of Reagents. Lastly, the melting point of the solid derivatives of the unknown compound, listed in Table 2: Melting points of Aldehyde & Ketone Derivatives, were used to determine the identity of the unknown compound.
**SOURCES**
Table 1: Table of Reagents
Compound
Molecular Weight (g/mol)
Boiling Point (C)
Melting Point (C)
Density (g/cm3)
AgNO3
169.870
440.00
212.00
4.350
NaOH
39.997
1,388.00
604.40
2.130
Ag2O
35.040
24.70
-91.50
0.880
H2O
18.015
100.00
0.00
1.000
CH3OH
32.040
64.70
-97.60
0.792
CH3CH2OH
46.068
78.37
-114.10
0.789
2,4 – dinitrophenylhydrazine (2,4 – DNP)
198.140
378.60
198-202
1.700
Semicarbazide
75.080
N/A
96.00
1.300
Semicarbazide Hydrochloride
111.529
253.30
175-177
1.286
C2H3NaO2
82.034
881.40
324.00
1.528
I2
126.904
184.40
113.70
4.930
Table 2: Melting Points of Aldehyde & Ketone Derivatives (C)
Compound
2,4 – DNP
Acetone
126
190
Acetophenone
240
203
237
222
Butanal
122
95
2 – Butanone
116
146
2 – Butenal
190
199
Cinnamaldehyde
255
216
Heptanal
106
109
Hexanal
104
106
2 – Hexanone
106
122
3 – Hexanone
130
112
2 – Methylcyclohexanone
136
191
2 – Methylpropanal
182
125
2 – Pentanone
144
110
3 – Pentanone
156
138
Propanal
148
89
Para – Tolualdehyde
234
215
Cyclohexanone
160
166
Cyclopentanone
142
205
Experimental
The Tollens test was performed first. First, the test tubes were rinsed with 10% NaOH solution. 1 mL of 0.3 M AgNO3 was obtained in a test tube, then 0.5 of 3M NaOH was added to the test tube of AgNO3. A brown precipitate formed after this mixture.Next, 2M aqueous NH4OH was added drop by drop while constantly shaking. NH4OH kept being added until the brown precipitate that was formed dissolved. One drop of the unknown #166 was added, then. The test tube was shaken and left to sit at room temperature for 10 minutes. After 10 minutes, no black precipitate was observed, therefore, the test tube was placed in a warm water bath (45˚C) for 5 minutes. After five minutes, there was still no black precipitate formed, therefore the results for the Tollens test were negative.
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The second test that was done was the Iodoform test. The unknown was used again. A large test tube was obtained, and 0.5 mL of water was added to this test tube, and then 2 drops of the unknown were added to this test tube. In addition, 0.5 mL of 3M NaOH was also added to the same test tube. After this, basic iodine solution was made by mixing 0.5 g of I2, 1.009 g of KI, and 4 mL of H2O. This 0.75 mL mixture of basic iodine was added to the test tube slowly, drop by drop while shaking until the brown iodine color stayed. If a bright yellow precipitate forms, the test is positive, since there was no yellow precipitate formed, the Iodoform test was negative.
To find the identity of the unknown, two other steps were taken: both including the formation of solid derivatives. First, a test tube was obtained. Then, 10 drops of the unknown #166 was added in 2 mL 95% ethanol. This solution was then added via pipette to 2 mL of the 2,4-dinitrophyenylhdrazine solution. A solid derivative was formed. This solid in the test tube was then placed in an ice bath to cool so that crystallization was maximized. Next, vacuum filtration was used to isolate and filter the solid. After the product was filtered, the product was placed in the oven for 10 minutes to dry even more due to it being more of a clay-like consistency. After it was dried, the melting point was obtained and determined.
The last part was the second preparation of derivatives. Semicarbazide was prepared by combining: 0.251 g of Semicarbazide hydrochloride, 0.351 g sodium acetate, and 2 mL of water in a test tube. The test tube mixture was shaken gently to allow the mixture to dissolve. The unknown was obtained again, and 0.5 mL of the unknown was added to the mixture in the test tube. The test tube was shaken again for a minute and then placed in a hot water bath for 5 minutes. The test tube was then allowed to cool at room temperature before placing it in an ice bath for 15 minutes to crystallize further. Vacuum filtration was then used to filter the product. Once dried, the melting point was obtained.
Results
Table 3: Results for the Tollens and Iodoform Tests and Semicarbazone and 2,4-DNP Solid Derivatives
Tollens Test
Iodoform Test
Semicarbazone
2,4-DNP
Results
Negative
Positive
MP: 218-221 C
MP: 235-237 C
Discussion
The identity of the unknown #133 was found based on the negative results of the Tollens test the positive results of the Iodoform test in addition to the melting points of the solid derivatives – semicarbazone and 2,4 – DNP. The results of the Tollens test were interpreted to be negative based on the formation of the silver mirror or black precipitate did not occur. The iodoform test was said to be positive, because a yellow precipitate formed. The melting point range of the solid derivative, 2,4 – DNP, was from 235-237 C. By comparing the temperature range with the values in Table 2, the unknown could have a few possible identities due to possible sources of error. One example of a possible error being that the sample used to take the melting point may have contained traces of water, which can ultimately affect the melting point.
The other melting point, with a range of 218-221 C was determined from the solid derivative, semicarbazone. This melting point helped us to determine the identity of the unknown more effectively than that derived from the 2,4 – DNP derivative, because it was closer to the value in the chart than the other melting point was. Using both the melting point from 2,4 – dinitrophenylhydrazone and the semicarbazone, the identity of the unknown was determined to be Benzaldehyde which has a 2,4 – DNP melting point of 237 C and a semicarbazone melting point of 222 C.
**QUESTIONS?**
Conclusion:
In this experiment, unknown bottle #166 was determined to be 3-pentanone. The melting point of the solid derivative composed of 2,4- dinitrophenylhydrazone was about 20 degrees lower than the melting point due to the solid not being dried enough. The melting point taken of the solid derivative composed of semicarbazide was used to determine the identity of bottle number 166. A way to improve this experiment is to dry the product completely through vacuum filtration or possibly even in an oven.
References
University of Alabama at Birmingham. Reactions of Aldehydes and Ketones Handout. Accessed 20 June 2018.
North Carolina State University – Department of Chemistry. Tollen’s Test (Silver Mirror). Accessed 23 June 2018. https://projects.ncsu.edu/project/chemistrydemos/Organic/TollensTest.pdf
Jasperse. Minnesota State University. Carbonyl Unknowns. Accessed 23 June 2018. http://web.mnstate.edu/jasperse/Chem365/Carbonyl%20Unknown.pdf
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