MACROCYCLIC SYNTHESIS: HEME ANALOG

Samir Mohandes Instructor: Sanhita Sanharay CHEM 243B-018 February 21, 2012 Experiment performed on February 14, 2012

ABSTRACT In this experiment, the aromatic molecule tetraphenylporphyrin was synthesized. Its characteristic bright color is responsible for its high molar absorptivity, which made UV/Vis spectroscopy an effective detection method; peaks at 414 nm were recorded both before and after metal complexation, suggesting that perhaps the complexation procedure failed. The tetraphenylporphyrin was synthesized with 11.43% yield, and its corresponding metal complex was derived at 31.06% yield.

RESULTS Table 1. UV/Visible spectrum peaks for the tetraphenylporphyrin product. max Abs 414 nm 2.200 515 nm 0.243 550 nm 0.221 591 nm 0.221 647 nm 0.200

Table 2. Theoretical, actual, and percent yields for the tetraphenylporphyrin product. Theoretical Yield .945 g Actual Yield .108 g % Yield 11.43%

Table 3. UV/Visible spectrum peaks for the tetraphenylporphyrin copper complex. max Abs 414 nm 0.640

Table 4. Theoretical, actual, and percent yields for the tetraphenylporphyrin copper complex. Theoretical Yield 108.5 mg Actual Yield 33.7 mg % Yield 31.06%

DISCUSSION In this experiment, the porphyrin derivative tetraphenylporphyrin was synthesized by refluxing propanoic acid at its boiling point. Acidic conditions are necessary for the synthesis of porphyrins. Propanoic acid specifically is one of the preferred acidic solvents because it is highly polar. A polar solvent is necessary because it will separate easily from the TPP product, which is mostly nonpolar. Furthermore, propanoic acids high boiling point allows the reaction to be carried at a high temperature while connected to a reflux apparatus. A reflux-based procedure was used in the synthesis so that the reaction could proceed at a high temperaturein this case, the boiling point of the propanoic acid solvent. The elevated

temperature increases the reaction rate by adding kinetic energy to the molecules, causing them to collide more often. By maintaining the solvent in reflux, this temperature can be maintained while avoiding the problem of the reaction mixture boiling off all of the solvent, halting the reaction. Careful management of the propionic acid concentration is essential because enough propanoic acid must be used to maximize yield, while too much will result in impurities: longer reaction times in propionic acid do not appreciably improve the yield, but actually decrease the purity of the products.1 Addition of pyrrole and benzaldehyde provided the reagents necessary for the synthesis of the tetraphenylporphyrin to proceed according to the following chemical equation: 4(C4H4NH) + C6H5CHO + CH3CH2COOH C44H30N4

Rinsing the tetraphenylporphyrin product in methanol served to increase the purity of the yield. Because the methanol is polar, it can be used to dissolve and wash away polar impurities such as the propanoic acid solvent. Tetraphenylporphyrins stability is derived from its aromaticity. It is a planar molecule, as a result of the trigonal planar molecular geometry arising from its double bonds. A max shift is expected after the tetraphenylporphyrin undergoes complexation with the copper (II) acetate; however, the UV/Vis spectra data indicates that such a shift did not occur, with max remaining constant at 414 nm both before and after complexation (Table 1, Table 3). Such a shift is the result of * electron orbital shifts; the excited state

appears as a peak of a shorter wavelength on the UV/Vis spectra. TPP is insoluble in propanoic acid at room temperature; as a result, when the reaction mixture is cooled, TPP precipitates. 108 mg were recovered after precipitation for an 11.43% yield (Table 2). Metal complexation with the copper (II) acetate gave a 31.06% yield (Table 4).

A. D. Adler, F. R. Longo, J. D. Finarelli, J. Goldmacher, J. Assour and L. Korsakoff (1967). "A simplified synthesis for mesotetraphenylporphine". J. Org. Chem. 32 (2): 476476.