CHE 211-03 Qualitative Unknown (Unknown 15-30) Report

E.J. Icatar
Introduction: Para-aminobenzoic acid (PABA), or 4-aminobenzoic acid, is an
Carboxylic acid proton undetected due to extreme intra and inter molecular hydrogen
organic compound with the molecular formula of C7H7NO2. It is normally prepared
bonding.16
through the reduction of 4-nitrobenzoic acid, as well as the Hoffman rearrangement of
Derivative (4-(benzoylamino)-benzoic acid): melting point 284.5C-285.6C (lit.
the primary amide derivative of terepthalic acid (C6H4(CO2H)2). Biologically, PABA
278C, exp. 284C, 287C)8,13,14
is synthesized by bacteria, plants, and fungi and it is combined with pteridine and
FTIR (chloroform):
glutamic acid to form folic acid, and is classified as a Vitamin B complex member.
Peak
Shape/Intensity
Assignment
Because of its ability to absorb UVB light throughout the entire UVB spectrum, it is
3332.42
Spike/moderate
NH
also widely used as an active ingredient in sunscreens. Medically, PABA is orally
2500-3200
Very broad/strong
Carboxylic Acid
prescribed for the treatment of scleroderma, dermatomyositis, and Peyronies disease. 1
1680.60
Spike/strong
Carbonyl
Discussion: The substance appeared as a fine white powder of white crystals, which
1650.34
Spike/strong
Carbonyl of COOH
clumped together. The substance had no apparent odor. The MSDS indicated that the
1524.59-1594.43
Sharp/moderate
Aromatic alkene
1
substance causes slight irritation to the respiratory system and decomposes to nitrogen
H NMR (400 MHz): MeOH
and carbon oxides under fire. The substance was soluble in water at elevated
Peak (ppm)
Splitting
J Value
Integration
Assignment
temperatures and formed white crystals when cooled to room temperature. It was
12.7312
Singlet
--1H
NH
readily soluble in alcohols, and barely soluble in chloroform. Several TLC tests were
10.5372
Singlet
--1H
COOH
needed to find an appropriate solvent ratio. An analysis using
7.9309
Multiplet
--6H
Aromatic CH
50:50::methanol:hexanes (Rf=0.73) and 40:60::methanol:hexanes (R f=0.274) indicated
7.6173
Triplet
8.7 Hz
1H
Aromatic CH
that the substance was pure. UV analysis of the TLC plates were positive, indicating
7.5989
Multiplet
--1H
Aromatic CH
conjugated double bonds, while iodine stained the substance with a brownish-red spot,
7.5669
Multiplet
--1H
Aromatic CH
indicating and unsaturated or aromatic, organic compound.2 A ninhydrin stain stained
Structures:
3
the TLC plate bright red, indicating the presence of an amino group. The melting
point of the substance was measured to be 182.0C-183.0C (lit. 187C). 4 While
performing a combustion test,5 the substance emitted a yellow flame with white
smoke, which is false-negative result for the absence of an aromatic compound. Very
little residue was left, and the remaining residue had a neutral pH indicating the lack
of any metal ions. In the sodium fusion test6 the solution produced a Prussian blue
product for the nitrogen test confirming the presence of nitrogen, and no black
precipitate for the sulfur test, negating the presence of sulfur. Halogens were tested for
twice, since the first test produced a white emulsion after adding AgNO3, an
inconclusive result since halogens produce a solid precipitate. The second test for
halogens produced no precipitate, indicating the absence of a halogen. The molecular
weight of the substance was determined to be 130 grams per mole by the RAST
method. Six classification tests for functional groups were run including a sodium
Para-aminobenzoic acid, 4-(benzoylamino)-benzoic acid, and
bicarbonate test,7 two versions of the Hinsberg test,7,8 an aromaticity test,9 an acetyl
methyl 4-aminobenzoate17
chloride test for amines,7 and a nitrous acid test for amines.7 The sodium bicarbonate
References:
test produced carbon dioxide bubbles, indicating the presence of a carboxylic acid.
1
Bolton, E.; Wang, Y.; Thiessen P. A.; Bryant S. H. Integrated Platform of Small
The aromaticity test was not completed since the substance was virtually insoluble in
Molecules and Biological Activities. Annu Rep in Computat Chem, Vol. 4.
7
chloroform. In the first Hinsberg test (using pyridine) a purple color was observed
2008. 217-240. http://pubchem.ncbi.nlm.nih.gov/compound/4after adding two drops of benzenesulfonyl chloride to the amine-NaOH-pyridine
aminobenzoic_acid (accessed Mar 17, 2015).
solution, indicating the presence of a 3 amine. The second Hinsberg test (using only
2
Henry, W. et al. Spot Tests. Paper Conservation Catalog. Washington, D.C.:
benzenesulfonyl chloride)8 was positive for a 2 amine as a residue formed that was
American Institute for Conservation Book and Paper Group. 1990.
insoluble in acid, which is indicative of a 2 reacting with benzenesulfonyl chloride
http://cool.conservation-us.org/coolaic/sg/bpg/pcc/10_spot-tests.pdf (accessed
and precipitating an insoluble sulfonamide. Since an IR spectrum of the substance
Feb 05, 2015).
showed two medium peaks at 3360.57 cm-1, which indicates a 1 amine, additional
3
Andronov, A., Stains for Developing TLC Plates
confirmation tests were run. The substance was extremely reactive with acetyl
www.chemistry.mcmaster.ca/adronov/resources/Stains_for_Developing_TLC_
chloride and the resulting vapors were very acidic confirming the presence of a 1
Plates.pdf (accessed Feb 05, 2015).
amine. During the nitrous acid test, the substance produced a vibrant red-azo dye
4
4-Aminobenzoic acid Material Safety Data Sheet, Sigma-Aldrich Corporation. 2015.
precipitate confirming the presence of a 1 aromatic amine. Two derivatives, methyl
http://www.sigmaaldrich.com/MSDS/MSDS/PleaseWaitMSDSPage.do?langua
4-aminobenzoate and 4-(benzoylamino)-benzoic acid, were produced.10,8 The ester
ge=&country=US&brand=SIGMA&productNumber=A9878&PageToGoToUR
was much less soluble in alcohols comparatively, and no melting point was measured
L=http://www.sigmaaldrich.com/catalog/product/sigma/a9878?lang=en&region
since a recrystallization was not performed. The known literature value of the ester
=US (accessed Mar 17, 2015).
derivative, methyl 4-aminobenzoate, is 110C-111C11 and was experimentally
5
Robertson, F. Qualitative Unknown Organic Laboratory. WCSU Organic Chemistry
determined to be 111C-113C.12 The benzamide product was a light pink solid that
2015.
was barely soluble in chloroform or 40:60::ethanol:hexanes, but was readily soluble in
6
Robertson, F. Qualitative Unknown Organic Laboratory Sodium Fusion. WCSU
methanol. The benzamide decomposed between 284.5C-285.6C (lit. 278C)13,8
Organic Chemistry 2015.
which is comparable to experimental results from Chattopadhyay (284C) and Gould
7
Pavia, D.L.; Lampman, G.M. Eds. Chemical Tests for Functional Groups. A Small
(287C).13,14 An IR and 1H NMR spectroscopy was obtained for the benzamide
Scale Approach to Organic Laboratory Techniques, 3rd ed.; Belmont, CA:
produced a unique spectra compared to the original substance.
Brooks/Cole Cengage Learning. 1976.
Experimental: % composition 61.31% carbon, 5.15% hydrogen, 10.21% nitrogen,
8
Shriner, R. L.; Hermann, C. K. F.; Morrill, T. C.; Curtin, D. Y.; Fuson, R. C.
23.33% oxygen; degrees of unsaturation 5; molecular weight (RAST method) 130
Chemical Tests for Functional Groups. The Systematic Identification of Organic
grams per mole ( 10%); melting point 182.0C-183.0C (lit. 187C, exp. 184C)4,15
Compounds, 8th Ed.; New York: Wiley. 2004.
FTIR (MeOH):
9
Cheronis,
N.; Entriken, J.; Hodett, E. Chemical Tests for Functional Groups.
Peak (cm-1)
Shape/Intensity
Assignment
Semimicro Qualitative Organic Analysis; New York: Wiley. 1965.
3458.13
Sharp/moderate
OH of COOH
10
Hosangadi, B. H.; Dave, R. H. An Efficient General Method for the Esterification of
3360.57
2 Spikes/moderate
NH2
Aromatic Carboxylic Acids. Tetrahedron Lett. 1996, 37, 6375-6378.
3229.18
Sharp/weak
General CH (sp2)
11
Methyl 4-aminobenzoate Material Safety Data Sheet, Sigma-Aldrich Corporation.
2200-3100
Very broad/strong
Carboxylic Acid
2014.
1660.02
Spike/strong
COOH carbonyl
http://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=U
1521.81-1598.90
Sharp/moderate
Aromatic alkene
S&language=en&productNumber=274186&brand=ALDRICH&PageToGoToU
13
C NMR (100 MHz): Acetone
RL=http%3A%2F%2Fwww.sigmaaldrich.com%2Fcatalog%2Fproduct%2Faldr
Peak (ppm)
Assignment
ich%2F274186%3Flang%3Den (accessed Feb 02, 2015).
206.3828
Acetone
12
Sharma, S.; Kumar, M.; Kumar, V.; Kumar, N., Metal-Free Transfer Hydrogenation
168.1773
Carboxylic Acid
of Nitroarenes in Water with Vasicine: Revelation of Organocatalytic Facet of
113.8350
sp2 aromatic carbon
an Abundant Alkaloid. J Org Chem, 2014, 79, 9433.
2
118.6681
sp aromatic carbon
13
Chattopadhyay, G.; Chakraborty, S.; Saha, C. Brine-Mediated Efficient
2
132.4422
sp aromatic carbon
Benzoylation of Primary Amines and Amino Acids. Synthetic Commun. 2008,
153.9668
sp2 aromatic carbon
38, 4068-4075.
29.2636-30.4176
Acetone
14
Gould, S.; Laufer, D. A. Carbon-13 Nuclear Magnetic Resonance Spectra of p1
H NMR (400 MHz): Acetone
Aminobenzoic Acid Oligomers: Range Dependence of Additive Substituent
Peak (ppm)
Splitting
J Value
Integration
Assignment
Effects. J. Magn Reson. 1979, 34, 37-54.
7.7833
Doublet
8.7 Hz
2H
H-2
15
Farah, B. S.; Gilbert, E. E.; Sibilia, J. P. Perhalo Ketones. V.1 The Reaction of
6.7076
Doublet
11.6 Hz
2H
H-3
Perhaloacetones with Aromatic Hydrocarbons. J. Org. Chem. 1965, 30, 10065.4134
Singlet
--1H
NH (H-4)
1007.
3.0966
Singlet
--1H
NH (H-5)
16
Robertson, F. Personal Interview. February 6, 2015.
17

Reaxys https://www.reaxys.com/reaxys (accessed Mar 23, 2015).