Benzoyl Hydrazone Synthesis Essay

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Synthesis of Salicylaldehyde benzoyl hydrazone with a metal complex and spectroscopic investigation of the metal complex Introduction Schiff bases which are compounds containing a double bond between an aryl or alkyl nitrogen and a carbon (-CH=N-) are versatile ligands consisting of important biological significance that have been investigated extensively due to their bonding potentiality with various metal complexes (School of Chemistry 2015) . The Schiff base known as salicylaldehyde benzoyl hydrazone (SBH) is formed by the reaction of saliclaldehyde and benzhydazide. The SBH is then used to form a copper (II) complex in the form of; ( ) ( ) ] . The Jobs plot in this experiment is used to determine the binding ratio the reaction stoichiometry through the use of UV visible spectrometry, investigating the metal complexes of SBH (School of Chemistry 2015) . The purpose of this experiment is to determine the binding stoichiometry from the absorbance data collected from the UV spectroscopic investigation and also to observe the relationship of absorbance and colour of ligand, metal and ligand-metal complexes. Method Benzhydrazide (1.0 g, 7.3 mmol) was dissolved in water (40 mL). Salicylaldehyde (1.6 mL) was dissolved in ethanol (15 mL) and this was mixed with benzhydrazide. The solution was filtered and washed with cold ethanol (5.0 mL) twice followed by recrystallization with hot ethanol (5.0 mL). The mass of the SBH solid products were recorded. Copper chloride (0.40 g, 3.0 mmol) was dissolved in ethanol (5.0 mL). To the SBH (0.70 g, 2.9 mmol) above, ethanol (20 mL) was added and heated. The copper chloride solution was added to SBH solution to allow precipitation. The precipitate was filtered and washed with cold water (10 mL). The mass of the metal-SBH complex was recorded. SBH (0.024 g, 1 mM) was mixed with methanol as solution 1. (1 mM, 1 mL) of the stock was mixed with methanol as solution 2. The metal-SBH complex (0.031 g, 0.090 mmol) was mixed with methanol as solution 3. Solutions 1, 2 and 3 were used to obtain a UV-visible spectrum (200-600nm) of the three solutions. A visible spectrum (400nm) was obtained for each of the solutions to measure the absorbance of each and the data were recorded on a table (School of Chemistry 2015) . Results Through the synthesis of salicylaldehyde benzoyl hydrazone (SBH) from the salicylaldehyde and benzhydrazide, gave white/cream coloured powder when it was crystallised. Figure 1. Formation of salicylaldehyde benzoyl hydrazone from benzhydrazide and salicylaldehyde (Fryatt & Christie 2002). The reacting with SBH led to the formation of the copper complex of SBH according ( ) ( to following equation, ) ] , which was dried to obtain a green/lime powder. According the above equation, the yield of copper complex of SBH was calculated according to following; 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢𝐶𝑙 = 0.40 g 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢𝐶𝑙 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢𝐶𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢(𝑆𝐵𝐻) 𝑚𝑎𝑠𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢(𝑆𝐵𝐻) 1 4 45 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢(𝑆𝐵𝐻) 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢(𝑆𝐵𝐻) ( ) 𝑚𝑎𝑠𝑠 𝑀 𝑤𝑒𝑖𝑔 𝑡 0 40 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢𝐶𝑙 The molar ratio of should produce ( ) 𝑔 and ( 3 8 8 ) should be 1:1 hence the moles of moles of ( ) . Therefore theoretical mass of 3 8 Therefore theoretical yield = ℎ The reaction between salicylaldehyde and benzhydrazide yielding salicylaldehyde benzoyl hydrazone(SBH) have the following chemical equation; 14 𝑚𝑎𝑠𝑠 𝑜𝑓𝐶 𝐻6𝑂 = 1.8 g 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓𝐶 𝐻6 𝑂 𝑚𝑎𝑠𝑠 𝑜𝑓𝐶 𝐻8𝑁 𝑂 = 1.0 g 𝑚𝑎𝑠𝑠 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓𝐶 𝐻6 𝑂 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻6 𝑂 1 1 1 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻6 𝑂 1 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻6 𝑂 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻6 𝑂 𝑚𝑎𝑠𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 1 1 15 3 Hence benzhyrazide is the limiting reagent in this reaction. 𝑚𝑎𝑠𝑠 𝑜𝑓𝐶 4 𝐻 𝑁 𝑂 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓𝐶 4 𝐻 𝑁 𝑂 = 0.99 g 𝑚𝑎𝑠𝑠 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 0 99 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 4𝐻 𝑁 𝑂 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 4 𝐻 𝑁 𝑂 40 4 The molar ratio of and of should produce 3 mass of 14 1 14 1 14 1 should be 1:1 hence the 3 moles moles of 14 1 . Therefore theoretical 3 4 6 Therefore theoretical yield = ℎ The absorption spectra of the Cu (II) metal and SBH and the Cu (II)-SBH complex was measured and illustrated as following. Figure 2: Absorption spectra of SBH, metal salt (Cu II) and meal-SBH complex shown through Sol 1, Sol 2 and Sol3 respectively. The following table indicates the colour of ligand SBH, Fe (III) and Cu (II) as well as both metal complexes also including their maximum absorption wavelength and the corresponding absorbance. Table 1: Colour, maximum absorption wavelength and absorbance at maximum wavelength for the ligand, both metals (Cu (II) and Fe (III)) and for both metal complexes involving SBH are shown. Solution Colour SBH Fe(III) Cu(II) Fe(III)-SBH complex Cu(II)-SBH complex White Yellow Green Black Green/lime ( 280 300 250 288 220 ) Absorbance at 0.567 0.096 0.065 0.573 0.560 Solutions 1 and 2 along with methanol were used to measure the absorbance and the mole fraction of ligand (SBH) at a correct wavelength of 400nm for SBH + Cu (II). The data were tabulated in the table below. Table 2: mole fraction of ligand (SBH) and the absorbance of solution 1 and solution 2 each containing SBH and the metal salt respectively, with 1.8 mL of methanol making up the volume to 3 mL. Vol. Solution 1 (mL) 0 0.075 0.15 0.23 0.30 0.35 0.40 0.45 0.50 0.55 0.6 Vol. Solution 2 (mL) 0.60 0.53 0.45 0.38 0.30 0.25 0.20 0.15 0.10 0.05 0 Vol. methanol (mL) 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Mole Fraction Absorption ligand ( ) (nm) 0 0.53 0.13 0.63 0.25 0.85 0.38 0.91 0.50 0.98 0.58 1.00 0.66 1.11 0.75 0.93 0.83 0.86 0.96 0.80 0 0.78 From the data collected from table 2, a job’s plot was created using the values for absorbance against mole fraction to determine the nature of the binding between Cu (II) and the ligand SBH. Figure 3: Job’s plot of mole fraction against absorbance at 400 nm measuring the binding strength of metal to its ligand where a maximum absorbance occurring at a ligand mole fraction of 0.66 According to figure 3, the intersection of the two lines represents a stoichiometric mixing of the metal and its ligand. The maximum absorbance occurs at a ligand mole fraction of 0.66 and this corresponds to a metal : ligand ratio of 1:2 when the values are matched with table 2. The stoichiometry of the metal complex is determined by following the ligand mole fraction at the highest absorption on the jobs plot and following that value with the values on table 2. And the binding ratio is the volume of solution 1 over solution 2 as equated below; Ligand mole fraction ≈ 0.66 ( ( ) ) 4 The table below summarise the stoichiometries of the Fe (III)-SBH complex and Cu (II)-SBH complex calculated as above. Table 3: Binding ratio of metal to its ligand for both Fe (III)-SBH complex and Cu (II)-SBH complex Complex SBH : Fe(III) SBH : Cu(II) Binding ratio 1:2 2:1 Discussion: According to the theoretical yield of the product salicylaldehyde benzoyl hydrazone (SBH), only 57% was obtained when reacting salicylaldehyde with benzhydrazide. This could be due to the loss of product during filtration process where not all solid were scraped off from the filter paper while some escaped through the filter paper into the filtrate. The main advantage of undertaking the recrystallization process is to purify the solid that was form through the reaction in making SBH. Through the alternative use of hot and icecold ethanol made sure that the solid was soluble when it’s hot and insoluble when it’s cold. In this way the product can separated from the impurities as they removed when filtering with hot ethanol. Through the experiment, before the recrystallising process, the crude solid had excess moisture and impurities which were all removed evidently by the recrystallization (School of Chemistry 2015) . The binding stoichiometry of Cu (II) was found to be 2:1 with two SBH ligands bound to one Cu(II) metal in the structure as depicted below (Fryatt & Christie 2002). Figure 4: Stoichiometric binding of Cu (II) with the ligand SBH to the ratio of 2:1 for ligand: metal Compared to this, Fe (III) was found to bind ligand: metal ratio of 1:2 with two Fe (III) metals ions binding to SBH. This strength of binding vastly depends on the presence of nitrogen in SBH, and there is a greater attraction towards Cu (II) with nitrogen as Fe (III) eventually reduces to Fe (II). The binding strength is also affected by the strength of ionic radius which is greater for Cu (II) than for Fe (III) (Fryatt & Christie 2002). The relationship between observed colour of the compound and its UV-visible spectrum is that the observed colour of a compound is the colour of a specific wavelength that is reflected while all the other colours are absorbed. The UV-spectrum indicates as shown below all the colours that are in the ultraviolet-visible spectral region (UV-visible absorption spectra 2010) . Table 4: colours of the UV-visible spectrum correspond to their specific wavelengths. However, from the results on table 1, the colour of the metal complex, Cu-SBH was recorded as green/lime does not correspond to the wavelength on table 4. This is because, figure 2 suggests the maximum absorbance of the metal complex occurred at a wavelength of 220 nm. The reason for difference in actual wavelength of the metal complex (520nm – 565 nm) to the experimental wavelength (220 nm) could be that the solution was more dilute than what it supposed to be, or the addition of excess methanol that was due to not rinsing the cuvettes due to lack of time. Conclusion In this experiment, salicylaldehyde benzoyl hydrazone (SBH) was prepared using salicylaldehyde and benzhydrazide. The yield SBH, was then used to synthesis a metal-ligand complex using Cu (II). The solutions involving SBH, metal salt and metal-SBH were observed under a UV-visible spectrometer, to observe the maximum absorbance wavelength and its intensity. The solutions were also used to produce a job’s plot to determine the stoichiometry of the metal complex. From the results it’s evident that SBH coordinates with Cu (II) to a 1:2 ratio with metal to ligand. The UV spectrum of the metal complex gave a different wavelength to the colour observed. References Fryatt, R & Christie, SD 2002, ‘Applications of stoichiometric transition metal complexes in organi c synthesis’. Journal of the chemical society, vol 4, pp 447-458. School of Chemisty 2015, CHEM2401 molecular reactivity and spectroscopy, practical manual, University of Sydney, Australia, pp- 29-33. UV-visible absorption spectra. UV-visible absorption spectra 2010, viewed 27 March 2015,


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