Lab # 8 A. Crossed Aldol Condensation B.

Haloform Reaction Darimi Johari, 6024045, CHM 2123, Section D TA: Soghra Jalil Pour Partner: Mohamad Kebbe Due date: November 24, 2011 1 Introduction Carbonyl reactions allow for the formation of a variety of compounds. This is caused by the resonance that influences the acidity of the alpha carbon and the oxygen double bond. Aldol Condensation In the case of crossed condensation reaction, 2 carbonyl compounds will react and form one product; one becoming an electrophile while the other becomes a nucleophile.

Self Condensation

To make the crossed condensation preparation useful, it is important to have only one of the compounds capable of forming the enolate (and so have the other compound not have an alpha hydrogen), and the other compound to not self condense rapidly. This can be achieved knowing that aldehydes self condense faster than ketones. This reaction can be seen with a bensaldehyde and an acetophenone, those that are used in this lab. With the given parameters, benzelacetophenone is able to be produced.

Haloform Reaction The haloform reaction occurs when a methyl ketone reacts with a halogen in a basic solution. This produces multiple halogenations at the carbon of the methyl group because the alpha hydrogens become more acidic as the electron withdrawing halogens are added. This is also partially determined by the inductive effect. The reaction results in a product known as a trihaloketone, a very strong electrophile. Nucleophilic attacks by a hydroxide can then occur on the carbon of the carbonyl to then produce a carboxylate anion and a haloform.

Trihaloketone is not formed during the lab because the trihaloketone intermediate is immediately attacked by OH which kicks out the CX3 for the carboxylate.

Formation of trihaloketone with a carboxylate product

2 Table of Reagents A. Crossed Aldol Condensation Compound Molar mass Quantity (g/mol) Acetophenone 120.16 1.0 mL Benzaldehyde 106.13 1.0 mL Ethanol 46.07 5.0 mL NaOH 39.9971 4.0 mL B. Haloform Reaction Compound Molar mass (g/mol) Acetophenone 120.16 NaOCl 74.44 Acetone 58.08 HCl 34.4606 3 Experimental procedure Refer to pages 74-76 of the CHM2123 Lab Manual, University of Ottawa. 4 Observations A. Crossed Aldol Condensation Steps Addition of EtOH, NaOH, and acetophenone Addition of benzaldehyde After 45 minutes Crystallization Crystals after being dissolved in boiling ethanol Re-crystallization B. Haloform Reaction Steps Addition of NaOCl and acetophenone Observations Highly viscous liquid, translucent, yellow Yellow liquid, opaque Peach colour with red precipitate on the bottom, opaque Red and orangish, After filtration and drying, became completely red Orange liquid Red coloured crystals Quantity 1.0 mL 1.0 mL 5.0 mL Density (g/mL) 1.028 1.0415 0.789 1.515 Density (g/mL) 1.028 12.06 0.79 1.2 mmol 8.56 9.81 85.63 3.788 mmol 8.56 16.2 68.0 Equivalents 2.26 259 22.61 1.00 Equivalents 1.00 1.89 7.94 -

Observations White liquid formed, opaque. After about 30 minutes, become transparent with bubbles liquid, transparent, Lots of bubbles, foamy, white liquid White crystals, powdery

Addition of acetone Addition of HCl Filtration

5 Results A. Crossed Aldol Condensation Experimental melting point: 50-52 C Mass obtained: 1.6 g Yield: 88.89% B. Haloform Reaction Experimental melting point: 119-120 C Mass obtained: 0.98 g Yield: 98% 6 Discussion The product of the first part of the lab was benzalacetophenone. Its appearance was that of red solid crystals with a melting point of approximately 51C. The yield of the product came to be about 89%. The yield was calculated by dividing the experimental mass by the theoretical mass. The results indicated a fairly accurate product based on the theoretical values. The loss in yield could be a result from dissolving the crude product in ethanol, and so cause the desired product to be too soluble in the solvent, making it harder to recrystallize. The product of the second part of the lab was benzoic acid. The appearance was a white powder with a melting point of around 120C, fairly close to the theoretical melting point of 121 to 125C. This slight difference in values can be attributed to the presence of impurities in the final product. The yield was fairly accurate at 98%. The addition of too much or too little HCl may have caused this slight disparity. Inaccuracies and mistakes during the lab can be attributed to a variety of sources of error. A few examples could have been from slight mistakes in measuring quantities, contamination on the given glassware, inefficient swirling of the reactions, and loss of product from filtration. These errors can be alleviated to an extent through better equipment and experience, proper cleaning of the tools, and continuous rewashing and multiple filtrations. 7 Questions Written on a separate paper.