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Synthesis of N-acetylanthranilic acid, a triboluminescent material: A Chemistry 44.1 Special Synthesis
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Special Synthesis Carlo Joseph M. MoskitoBS ChemistryChemistry 44.1 – 1L
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W Synthesis Experiment:Synthesis of N- acetylanthranilicacid, a triboluminescent material
Dates Performed:February 21 & 28, 2011
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a known compound to exhibit triboluminescene
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is the emission of light after has been
applied to the crystal. light produced
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named in 1895 but reported in 1605 by from the Greek word and Latin which means and respectively
Triboluminescene Spectroscopy of Common CandiesAngelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)
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Triboluminescene Spectroscopy of Common CandiesAngelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)
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Emission occurs due to the by
between the surfaces of the fractured crystals and subsequent flourescene. instantaneous charge polarization
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ION Example:
Sugar (Sucrose)
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ION Example:
Diamond
Triboluminescene of Diamonds.J R Hird, A Chakravarty and A J Walton
J. Phys. D: Appl. Phys. 40 (2007) 1464–1472
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ION Example:
Granite
Activities of Triboluminescence at Sample Failure of GraniteItaru Maeda Hokkaido University, Sapporo 060, Japan.
Jour. Fac. Sci .. Hokkaido Univ., Ser. VII (Geophysics), Vol. 8, No.1, 65-81, 1986.
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H2N
O
HO
OO
O
H2N
o-toluidine
MethalqualoneA quinazolone
derivative which acts as
barbiturates
Production of Methalqualone, a barbiturate.
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NH2
O OH OO
O1.2. H2O
∆ / Heat, reflux
HN
OHO
O
O
OH
and
General Reaction for the synthesis of N-acetylanthranilic acid.
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Mechanism
on Acetic Anhydride; or on Anthranilic Acid
Synthesis of Heterocycles from Anthranilic Acid and its DerivativesPer Wiklund. Karolinksa University Press. Sweden.
OH
O
NH2
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ION Mechanism
OO
O
COOH
N
H
H
O
CH3
O
CH3
O
COOH
N
H
H
O
CH3
+
O CH3
O
tetrahedral intermediate
At neutral conditions
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ION Mechanism
COOH
N
H
H
O
CH3
O CH3
O
HN
OHO
O
O
OH
and
Continuation
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ION
NH2
O OH
OO
O
∆
HN
OHO
O
O
OH
and
N-Acetylanthranilic Acid as A Highly Triboluminescent Material. John Erikson. J. Chem. Educ. 49, 688 (1972)
A CYCLIC INTERMEDIATE
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ION Mechanism
I. Formation of the cyclic intermediate
N
O OH
CH3
H
O
N
O OH
CH3
H
O
N
O O
OH
CH3
H
N
OO CH3
H
O H
N
O
O
CH3
N
O O
OH
CH3
H
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ION Mechanism
I. Formation of the cyclic intermediate, continuation
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ION Mechanism
II. Hydrolysis of the cyclic intermediate
N
O
O
CH3
+H
O
H
N
O
O O
CH3
H
H
or -OH
O
O
H
H
N
H3C O
N
O
O O
CH3
H
H
N-acetylanthranilic acid
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ION Mechanism
II. Hydrolysis of the cyclic intermediate, continuation
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ION
NH2
O OH
OO
O
∆ N
O
O
CH3
2-methylbenzisoxazinone
N-Acetylanthranilic Acid as A Highly Triboluminescent Material. John Erikson. J. Chem. Educ. 49, 688 (1972)
HN
OHO
O
O
OH
and
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ION Formation of
2-methylbenzisoxazinone
a since formation of six-membered rings are favorable.
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ION Formation of
2-methylbenzisoxazinone
since it will be hydrolyzed to form the product
water is produced in the reaction completely hydrolyzed thru the addition of water in the second reflux.
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ION Conversion of
2-methylbenzisoxazinone
provides a scheme in the hydrolysis of the intermediate to produce the product
N-Acetylanthranilic Acid as A Highly Triboluminescent Material. John Erikson. J. Chem. Educ. 49, 688 (1972)
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ION Conversion of
2-methylbenzisoxazinone:
Dissolve mixture in hot mixture of and
(Assumption: 10g intermediate is formed) and allow mixture to stand.
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ION Another Side Product: Acylation
of N-acetylanthranilic Acid by Acetic Anhydride
N
O OH
CH3
H
O
OO
ON
O OH
CH3
O O
N
O OH
CH3
H
O
N
O OH
CH3
H
O
OO
O
N
O OH
CH3
H
O O
O O
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ION Mechanism
Alkylation of acetic anhydride to form a N-substituted anthranilic acid
N
O OH
CH3
H
O O
O
O
N
O OH
CH3
H
O O
O O
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N
O OH
CH3
O OOH
O
+
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The alkylation of acetic anhydride to the amino substituted group can also be observed. This alkylation is not favorable since
compared to simple alkylation
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: serves as an
Theoretical Melting Point:
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for (RCOOH)
Positive Sign:Evolution of Gas ( ) or
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R
C
OH
O
+ NaHCO3
R
C
O
O
Na
+ H2O + CO2(g)
bubbling
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for (esters, amides,
acid halides, acid anhydrides and nitriles)
Positive Sign:
Complex
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R
C
W
O
R
C
NHOH
O
H2NOH ROH, FeCl3
R C
O
NH
O
Fe
3
+ 3HCl
magenta complex
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1. to synthesize N-acetylanthranilicacid from anthranilic acid and acetic anhydride;
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2. to characterize the product and the starting material thru physico-chemical tests such as MP determination, NaHCO3 test and ferric hydroxamic acid test; and
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3. to observe triboluminescene in N- acetylanthranilic acid.
RE
AG
EN
TS
Starting material
NH2
O OH
Other Names: o-amino benzoic acid, vitamin L1, anthranilite
Appearance: White to light tan crystallinepowder
Molecular Weight 137.14 g mol−1
Molecular Formula C7H7NO2
Melting Point 146–148 °C
Flash Point >150 °C
Density 1.4 g/cm3
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AG
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TS
Starting material
OO
O
Other Names: ethanoic anhydride, Ethanoyl ethanoate, Acetic acid anhydride
Appearance: clear liquid
Molecular Weight 102.09 g mol−1
Molecular Formula C4H6O3
Melting Point −73.1 °C
Flash Point 49 °C
Density 1.082 g/cm3, liquid
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H
O
H
Solvent
Other Names: dihydrogen monoxide
Appearance: colorless liquid
Molecular Weight 18.02 g mol−1
Molecular Formula H2O
Melting Point 0°C
Boiling Point 100 °C
Density 1.00 g/cm3, liquid
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Washing Solvent
Other Names: carbinol, methyl alcohol, wood alcohol
Appearance: colorless liquid
Molecular Weight 32.04 g mol−1
Molecular Formula CH3OH
Melting Point −97°C
Boiling Point 64.7 °C
Density 0.7918 g/cm3, liquid
C
H
H
H
OH
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TS
Reagent for NaHCO3 test
Other Names: sodium hydrogen carbonate, baking soda
Appearance: white crystals
Molecular Weight 84.01 g mol−1
Molecular Formula NaHCO3
Melting Point 50 °C
Boiling Point None
Density 2.713 g/cm3, liquid
Na+
OHO
O-
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TS
Reagent for Ferric Hydroxamic Acid Test
Other Names: Hydroxylammoniumchloride
Appearance: white crystalline solid
Molecular Weight 69.44 g mol−1
Molecular Formula HONH2·HCl
Melting Point 151- 152 °C (decomp)
Boiling Point None
Density 1.67 g/cm3, liquid
N
O
Cl-
HH
H
H
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TS
Reagent for Ferric Hydroxamic Acid Test
Other Names: ethyl alcohol , methyl carbinol, absolute alcohol, drinking alcohol
Appearance: colorless liquid
Molecular Weight 46.07 g mol−1
Molecular Formula HONH2·HCl
Melting Point -114.3 °C
Boiling Point 78.4 °C
Density 0.789 g/cm3, liquid
C
CO
H H
H
H
H
H
RE
AG
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TS
Reagent for Ferric Hydroxamic Acid Test
Other Names: Caustic soda, Lye
Appearance: White opaque crystals
Molecular Weight 39.99 g mol−1
Molecular Formula NaOH
Melting Point 318 °C
Boiling Point 1388 °C
Density 2.13 g/cm3, liquid
Na+ -O H
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TS
Reagent for Ferric Hydroxamic Acid Test
Other Names: Muriatic Acid, chlorane, hydrogen chloride, Acidum Muriaticum
Appearance: clear colorless liquid to light yellow liquid
Molecular Weight 36.46 g mol−1
Molecular Formula HCl
Melting Point -27.32 °C
Boiling Point 110 °C
Density 1.18 g/cm3, liquid
H Cl
RE
AG
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TS
Reagent for Ferric Hydroxamic Acid Test
Other Names: Molysite, Iron (III) chloride
Appearance: brown solution/ green black in color
Molecular Weight 162.2 g mol−1
Molecular Formula FeCl3
Melting Point 306°C
Boiling Point 315 °C
Density 2.898 g/cm3, liquid
Fe3+ Cl-
PR
OC
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UR
E
NH2
O
OH2 g
(reflux set-up)
OO
O
10 mL
A
Bring mixture slowly to reflux temperature and heat for 15 minutes.
Suction filtration with washings of small amount of cold methanol
PR
OC
ED
UR
E
A
Cool Mixture
2mL H
O
H
Bring to soft boil and cool slowly.
FILTRATE RESIDUE
traces of unreactedanthranilic acid, acetic
anhydride; methanol and water
HN
OHO
O
determine melting point
aids the complete conversion of the product by supplying energy to the reaction.
PR
OC
ED
UR
E
PR
OC
ED
UR
E
PR
OC
ED
UR
E
with the aid of a Büchner Funnel; used to obtain crystals of N-acetylanthranilic acid.
PR
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E
Melting Point Determination NaHCO3 Test Ferric Hydroxamic Acid Test
OH
O
NH2
OO
O
N
O
O
CH3
H2O OH
O
NH
O CH3
Synthesis of N-acetylanthranilic acid
DIS
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ION
2.0 g anthranilic acid Limiting Reagent
6.0 mL acetic anhydrideExcess Reagent
OH
O
NH2
OO
O
DIS
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ION Acetate ion, a
weak conjugate base is the leaving group from acetic
anhydride
COOH
N
H
H
O
CH3
O
CH3
O
COOH
N
H
H
O
CH3
+
O CH3
O
OH
O
NH2
DIS
CU
SS
ION During reflux, the
nucleophile (anthranilic acid) attacks the acyl carbon of acetic
anhydride
OO
O
DIS
CU
SS
ION
N
O
O
CH3
+H
O
H
or -OH
Second reflux, hydrolyzes the intermediate,
2-methylbenzisoxanone
DIS
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ION
Parameter Mass (in g)
Theoretical Yield 2.61
Experimental Yield 2.148
Percent Yield 82.30 %
Percent Yield of N-acetylanthranilic acid
DIS
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DIS
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ION
Parameter Temp (OC)
Theoretical MP 183 - 185
Experimental MP 174 - 180
Percent Error 2.70 - 4.91 %
Melting Point Determination of N-acetylanthranilic acid
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ION
OH
O
NH2
NaHCO3
O
O
NH2
+ H2O + CO2(g)
Na
OO
O
NaHCO3No Reaction
HN
OHO
O NaHCO3
HN
OO
O
+ H2O + CO2(g)
Na
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ION
DIS
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ION
OH
O
NH2
H2NOH
FeCl3, etOHNo Reaction
OO
O
H2NOH
FeCl3, etOH
O
OH
+
O
NHOH
FeCl3, etOH
HN
OHO
O H2NOH
FeCl3, etOHNo Reaction
O
NHOH3 Fe
+ 3HCl
magenta/burgundy
DIS
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ION
DIS
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SS
ION
DIS
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ION
Recent theories suggest that the emission of light is due to the “highly charged” crystal latticeor charge separation of the fractured crystal for electric potential to exist.
Triboluminescence and the potential of fracture surfacesAvik Chakravarty and Tacye E Phillipson
J. Phys. D: Appl. Phys. 37 (2004) 2175–2180
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This in return, when crystal lattice returns to its neutral state or charges recombine, the electric discharge ionizes the surrounding air, releasing a blue green sparks.
Triboluminescence and the potential of fracture surfacesAvik Chakravarty and Tacye E Phillipson
J. Phys. D: Appl. Phys. 37 (2004) 2175–2180
DIS
CU
SS
ION
DIS
CU
SS
ION
DIS
CU
SS
ION
Other Source of Mechanical Energy:
Triboluminescene Spectroscopy of Common CandiesAngelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)
DIS
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ION
Alkylation and acylation of basic salts of anthranilic acid.Wiklund, Bergman .Tetrahedron Letters 45 (2004) 969 – 972
Other ways of synthesizing N-acetylanthranilic acid includes the conversion of anthranilic acid to sodium anthranilate in a slight excess of NaOH in water followed by addition of acetic anhydride. Wiklund and Bergman (2004) that basic salts of anthranilic acid and its N-substituted derivatives undergo O-alkylation when reacting with alkylating agents. Excess alkylating agent will cause the N-alkylation to occur followed by hydrolysis and protonation
DIS
CU
SS
ION
Biochim. Biophys. Acta 230 (1971) 451 - 467
Mechanism of N-acetylanthranilic acid biosynthesis in Aerobacteraerogenes and Escherichia coli
Escherichia coli
Aerobacter aerogenes
AP
PLIC
AT
IO
NS
Triboluminescent Materials for Smart OpticalDamage Sensors for Space ApplicationsM.D. Aggarwal, B.G. Penn, and J. Miller
Marshall Space Flight Center, Marshall Space Flight Center, AlabamaS. Sadate and A.K. Batra
Alabama A&M University, Normal, AlabamaMay 2008
AP
PLIC
AT
IO
NS
Triboluminescence in sodiumchlorideSrinivasan Arjun Tekalur
Michigan State UniversityJournal of Luminescence 130 (2010) 2201–2206
AP
PLIC
AT
IO
NS
Newer N-substituted anthranilicacid derivatives as potentanti-inflammatory agentsShalabh Sharma , Virendra Kishor Srivastava, Ashok Kumar
Mefenamic acid and meclofenamates: N-phenylanthranilic acid derivatives,
Eur. J. Med. Chem. 37 (2002) 689–697
SU
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Y A
ND
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NC
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SIO
N The synthesis of N-acetylanthranilicacid from anthranilic acid and aceticanhydride falls under the nucleophilicacyl substitution on acetic anhydride andacylation on anthranilic acid with the aidof the nitrogen lone pairs together withacetic acid as a by product. In themechanism, anthranilic acid in reaction withacetic anhydride formed the intermediate,2-methylbenzisoxanone, which ishydrolyzed to form the desired product
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CO
NC
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NFrom 2.0 g anthranilic acid and 6.0
mL acetic anhydride, 2.148 g out of the2.61 g theoretical yield. Percent Yield forthe synthesis is 82.30%. Side productsinclude 2-methylbenzisoxanone and theacylated N-acetylanthranilic acid.Experimental melting point for the productobtained from the Fisher Johns MeltingPoint Apparatus was from 174 – 180 oCcompared to theoretical melting point of183 - 185 oC with percent error of 2.70to 4.91 %.
On the characterization tests,anthranilic acid and the productshowed positive results on NaHCO3
test as shown by bubbling andacetic anhydride on the ferrichydroxamic acid test as shown bythe formation of a burgundy complex.
SU
MM
AR
Y A
ND
CO
NC
LU
SIO
N
Triboluminescene wasobserved on N-acetylanthranilic acidas shown by a blue green lightemission. This particular emission oflight is primarily due to electricdischarge on the crystals of theproduct.
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Y A
ND
CO
NC
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SIO
N
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NC
ES Angelos, Zink and Hardy. 1979. J. Chem. Educ. 56: 413 – 414 .
Avik Chakravarty and Tacye E Phillipson. 2004. J. Phys. D: Appl. Phys. 37:2175–2180.
Erikson, John. 1972. J. Chem. Educ. 49: 688.
Shriner, RL, Herman, CF et al. 1998. The Systematic Identification of Organic Compounds. 7th ed. John Wiley and Sons, Inc.
United Nations Office on Drugs and Crime. 2010. Recommended methods for the identification and analysis of methaqualone/mecloqualone. United Nations.
Wiklund, Per and Bergman, Jan. 2004. Tetrahderon. 45: 969 – 972.
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