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Electrochemical Analyses and Reactions of Malononitrile Derivatives and Phenyl Azide a Research Paper Submitted to the Graduate

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Electrochemical Analyses and Reactions of Malononitrile Derivatives and Phenyl Azide a Research Paper Submitted to the Graduate ELECTROCHEMICAL ANALYSES AND REACTIONS OF MALONONITRILE DERIVATIVES AND PHENYL AZIDE A RESEARCH PAPER SUBMITTED TO THE GRADUATE SCHOOL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE MASTERS OF ART BY JINYU LIU DR. CHONG ‐ ADVISOR BALL STATE UNIVERSITY MUNCIE, INDIANA JULY 2013 CONTENT Abstract 1 Introduction 1 Material 3 4-methoxybenzalmalonoitrile 3 Phenyl azide: 4 Set up 6 Experiment 6 1. 4-methoxybenzalmalonoitrile 6 a. Low concentration experiment to check and determine the potential of 4-methoxybenzalmalononitrile. 6 b. High concentration experiment to confirm the reaction and the product. 8 c. Product isolation. 10 2. Electronic effect for different substituted group 12 3. Phenyl azide reaction. 15 Result 16 Acknowledgement 18 Reference 19 Abstract: The versatile and relatively inexpensive (low energy cost) synthesis of new organic molecules is important for pharmaceutical production, polymerization, and other industrially applicable facets of chemistry. Electrochemical reduction of unsaturated organic compounds at room temperature to new organic products offers a benign and ambient method for the production of such molecules. The compounds, (p-methoxybenzal)malononitrile, 1 , Epc = 0/+ -1.64 V vs. Ferrocene/Ferrocenium (Cp2Fe ), its derivatives and phenyl azide, 2 , Epc = 0/+ -2.43 V vs. Cp2Fe , were investigated for their redox activities with and without alkylation agents, R-X, via scanning and pulse voltammetric techniques in acetonitrile, acetonitrile/water and tetrahydrofuran as solvents, using 0.1 M [NBu4][PF6] as the supporting electrolyte. The redox potentials were measured at glassy carbon and platinum disk 0/+ electrodes. Controlled potential electrolysis (CPE) of 1 at Eappl = -1.75 V vs. Cp2Fe was 0/+ yielding p-methoxybenzaldehyde (> 90%). CPE of 2 at Eappl = -2.54 V vs. Cp2Fe in air gave aniline in good yield. Bulk cathodic electrolyses of 1 and 2 were exhausted in < 0.5 - 1 h, following the passage of 1 F/mol of analyte. Upon completing bulk reductions at each applied potential, products were characterized by 1H-NMR and GC-MS data analyses. Introduction: Nowadays, the C-C bonds cleavage and the C-C bonds coupling are top prior in the organic field. However, in the traditional way, the synthesis of aldehyde from olefin is an oxidation reaction. In the presence of PdCl2 (MeCN) 2, 1, 4-benzoquinone, and t-BuOH, aryl-substituted olefins can selectively be oxidized to aldehydes. The reaction was as followed. [1] 1 The use of PhI(OAc)2 in dichloromethane enables a clean oxidative cleavage of 1,2-diols to aldehydes. Using OsO4 as catalyst, NMO and 2,6-lutidine, olefinic bonds can be cleaved in acetone/water to yield the corresponding carbonyl compounds. [2] Based on the both catalytic reaction, in the reaction, expensive catalyst was used. One reaction is in the high temperament and another one need a long time to get a good yield. Also, the hydration can be the first step, and followed by the oxidation to get the aldehyde from olefin. The olefin was hydrated to alcohol. Then the alcohol was oxidized to aldehyde. + H + H2O OH [O] OH O From the above reaction mechanism, after hydration of olefin, only ketone produced, and it could not cleave the C=C double bond. Depend on the traditional organic synthesis reaction, it will spends lots of time and energy especially in the conjugated structures, like the compound in this project, the olefin double bonds conjugated with the phenyl group which stabilized the C=C bond. In the previous research, to make the 2 p-methoxybenzalmalononitrile, p-methoxybenzaldehyde and malononitrile are reactants, but no research shows the inverse reactions. However, after checking the potential of p-methoxybenzaldehyde, one cathodic peak is shown in the cyclic voltammetry graph that means some reduction reactions can happen on this compound by using bulk electrolysis on Pt electrode under the room temperature with less than 1h. There is no previous research to indicate the cathodic reduction induced hydration of olefin. Based on the reaction of hydration of benzalmalononitrile, the CS-gas which is in the similar family can be easy to decompose into nontoxic compounds. In the organic synthesis, it is an important reaction to reducing azide to amines. The methods for converting the azide to amines contain catalytic hydrogenation [3], the phosphine-based Staudinger reduction [4] and the metal hydride reduction [5]. However, for these methods, they have significant limitation. [6] In electrochemistry, voltammetries are important tools to show the nature of the compound based on different solvents. The solvent effect can affect the behavior of compounds depended on the donor number and the dielectric constant. [7] The voltammetries can be related to the thermodynamic and kinetic properties of the compounds. Bulky electrolysis is a normal tool in electrochemistry to make the reaction happen. Materials: 4-methoxybenzalmalonoitrile: Light yellow solid 0.0745g; b.p. less than 220 oC IR (acetonitrile, cm-1) 3621 (w, hydrocarbon), 2225 (s, nitrile), 1514(s, aromatic double 3 bond), 1038 (m, C-O group) 1H-NMR (400MHz, acetonitrile) δ 7.95 (singlet, 1H [A]), 7.94 (doublet, 1H [B], J=8.8Hz), 7.10 (doublet, 1H [C], J= 9.16), 3.88 (singlet, 3H [D]) [M+1]=185. B C H H NC D CN H3CO H A B C H H It is a family member as the malononitrile, which also has the cyanocarbon group. It can be synthesized by the Knoevenagel condensation. [8] Take the CS gas as an example: The reaction is catalysed with weak base like piperidine or pyridine. The production method has not changed since the substance was discovered by Corson and Stoughton. Other bases, solvent free methods and microwave promotion have been suggested to improve the production of the substance. Phenyl azide: It is an organic compound with the formula C6H5N3. It is one of the prototypical 4 organic azide. It has a pungent odor. The structure consists of a linear azide substituent bound to a phenyl group. Molecular formula C6H5N3 Molar mass 119.12 g/mol Appearance Pale yellow, oily liquid Boiling point 49 °C at 5mm Hg Main hazards Explosive N3 Fig 1: MS spectrum for phenyl azide. [9] 5 Setup: The photo above is a sample of the e-chem cell which had been set up. Working electrode as 2mm Pt or 2mm glassy carbon electrode was placed in the middle which was C, the reference as Ag/ AgCl was placed in part A, and the counter electrode as Pt was placed in part B. Though the change of the potential and current by using the potentialstat, it shows the graph for the voltammetry to get and check the potential of the analysts and using that potential to do the electrolysis to make some unknown reaction in the e-chem cell. Experiment： 1. 4-methoxybenzalmalonoitrile reaction. a. Low concentration experiment to check and determine the potential of 6 4-methoxybenzalmalononitrile. a E pc = -1.70V 5μA i ca background pre-electrolysis i an post-electrolysis b 2 1 0 -1 -2 -3 +/0 E (V vs Cp2Fe ) Fig2. CV scan for 2m M of 1 in acetonitrile with 0.1M [NBu4][PF6] as electrolyte at room temperature, the scan rate was 200mV/s on 2mmPt electrode. From a which is pre-electrolysis, it showed the peak potential of sample was 1.7V vs ferrocene on Pt electrode which has a huge peak, and post-electrolysis (b), when it ran in the same potential range, the huge peak disappeared, which may mean the starting material was reacted during the bulk electrolysis. i ca post-electrolysis i ca i an 2μA 0.5 0 -0.5 +/0 -1 -1.5 E (V vs Cp2Fe ) 7 Fig3. CV scan for 2mM 1 post-electrolysis at room temperature in acetonitrile with 0.1M [NBu4][PF6] as electrolyte, the scan rate was 200 mV/s on 2mm Pt electrode. Post electrolysis, two new peaks showed up at -0.33V vs. ferrocene and 0.107V vs. ferrocene that it did not show up in the pre-electrolysis graph. It means that some unknown reaction happened and some new stuff came up. If all of the product can dissolve in the acetonitrile, it may two products there. Also, after electrolysis, the color of the solution in the working electrode turned to orange like the honey. SWV 1μA Half Width=130mV -1 -1.2 -1.4 -1.6 -1.8 -2 -2.2 -2.4 +/0 E (V vs Cp2Fe ) Fig4. Square wave voltammetry for 2mM 1 at room temperature with 0.1M [TBA][PF6] as electrolyte on 2mm Pt electrode. This graph showed that the half potential of the sample was -1.65V vs. ferrocene, and by calculating the half width of the peak, it indicated that the reaction in the cell was one-electron transfer reaction whose half width was larger than 90mV. Seeing the SWV, it is found that the half width was 90mV, it is likely a one-electron transfer reaction. b. High concentration experiment to confirm the reaction and the product. 8 50 μA background ca i molanonitrile post-electrolysis i an 2 1 0 -1 -2 -3 0/+ E (V vs Cp2Fe ) Fig5: 30mM 1 with 0.109M [TBA][PF6] in acetonitrile in the room temperature on 2mm Pt electrode. The scan rate was 200mV/s. For the high concentration, a little difference appeared by comparing the low concentration, at the end of range (about 1V vs. ferrocene) a reversible peak showed up. So the concentration may have some unknown effect on the reaction. And also at -2.5V vs. ferrocene, there was a new peak there. Also the two old peaks were at the simile place, because of the high concentration, the peak potential shifted a little.
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