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Section ____________________
Stoichiometric Data (For any reactants that are part of the balanced equation, base on the amounts measured in lab)
* HNO3
1 mol63.01 g x 1.41 gml x 6 ml= 0.13 mol
* H2SO4
mol98.08 g x 1.84 gml x 6 ml = 0.11 mol
* Phenylacetonitrile
mol117.15 g x 1.015 gml x 2 ml = 0.017 mol
*p-nitrobenzyl cyanide
162.15 gmol x 0.257 mol = 41.7 g
*1.2 g 41.7 g x 100 = 2.9%
* production Mass = 1.2 g
mol 162.15 g x 1.2 g = 0.007 mol
0.007mol0.257 mol x 100 = 11.2 %
Product Structure (correlated to**)
End Product p-nitrobenzyl cyanide
DISCUSSION
Nitration is a well studied process because it has a lot of industrial applications such as making pesticides, pharmaceuticals, explosives and for organic synthesis processes. (Olah et al., 1982, p. 4487) Electrophilic nitration is the most common mechanism in aromatic nitrations (using compounds composed of benzene rings.)
Nitration accomplishes an electrophilic substitution via the nitronium ion (NO+2). (Olah et al., 1982, p. 4490) A proton is removed and replaced with a nitrogen to form the product. In 1969 Ingold hypothesized that two steps were taking place where the first step controlled rate and was the step that determined substrate selectivity. The second step determines the positional selectivity. After a decade of progress in better instrumentation and development of methodology it has been found that is not the rate controlling step so “the Ingold scheme must be amended.” (Olah et al., 1982) Figure 1shows the process of the Phenylacetonitrile explosed to H+ (acid) reacts to become the anilinium ion. The nitrating solvents nitric acid and sulfuric acid initiate the substitution of a Carbon with NO2. The substitution uses the proton from NH3+ so that m-nitroaniline is formed. The reaction is stabilized with the addition of aqueous sodium hydroxide. Figure 2 is a schematic which shows how “the nitrations were found to take place via a nucleophilic displacement pathway involving the N-nitropyridinium ions themselves and not by the free nitronium ion” (Olah et al., 1982, p. 4490)
Figure 1. Nitration ions to product
Source: Rarh, V. “Organic Compounds containing Nitrogen” Organic Chemistry.30 May 2007. Web. 4 April 2013. http://nsdl.niscair.res.in/bitstream/123456789/796/1/Revised+organic+compounds+containing+Nitrogen.pdf
Figure 2. N substition
Source: Olah, G.A., Narang, S.C., Olah, J.and K. Lammertsma. “Recent aspects of nitration: New preparative methods and mechanistic studies (A Review)” Proc. Natl. Acad. Sci.79, (1982): 4487-4494. n.d. Web. 5 April 2013. http://www.pnas.org/content/79/14/4487.full.pdf
References
Doleib D. M. and Y. Iskander. “The influence of the nitro-group upon side-chain reactivity. Part IV. The inhibition of α-proton extraction from 4-nitrobenzyl chloride by the steric effect of methyl groups in the 3- and 5-positions.” J. Chem. Soc. B., 1967: 1154-1158. Available at http://pubs.rsc.org/en/content/articlelanding/1967/j2/j29670001154
Hibbert F. and F.A. Long. “Proton transfer from cyanocarbon acids, IV. Kinetic ionization behavior o p-nitrobenzyl cyanide and bromomalononitrile.” Journal of the American Chemical Society, 94 (1972): 2647-2651. Available at http://pubs.acs.org/doi/abs/10.1021/ja00741a001
“Organic Syntheses” Coll. 1 (1941): 396; 2 (1922) : 57. Web. 5 April 2013. Available at http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0396
Rarh, V. “Organic Compounds containing Nitrogen” Organic Chemistry.30 May 2007. Web. 4 April 2013. http://nsdl.niscair.res.in/bitstream/123456789/796/1/Revised+organic+compounds+containing+Nitrogen.pdf
Appendices
Appendix A
Experimental
Appendix B
Experimental
Appendix C
Published NIST
http://webbook.nist.gov/cgi/cbook.cgi?ID=C555215&Units=SI&Type=IR-SPEC
Appendix D
Published NIST http://webbook.nist.gov/cgi/cbook.cgi?ID=C555215&Units=SI&Mask=200#Mass-Spec
