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Special Synthesis Carlo Joseph M. Moskito BS Chemistry Chemistry 44.1 1L

Chem 44.1 Special Synthesis

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Synthesis of N-acetylanthranilic acid, a triboluminescent material: A Chemistry 44.1 Special Synthesis

Text of Chem 44.1 Special Synthesis

Special Synthesis Carlo Joseph M. Moskito BS Chemistry Chemistry 44.1 1L

OVERVIEW

Synthesis Experiment: Synthesis of N- acetylanthranilic acid, a triboluminescent material Dates Performed: February 21 & 28, 2011

INTRODUCTION

a known compound to exhibit triboluminescene

INTRODUCTION

is the emission of light after has been applied to the crystal. light produced

INTRODUCTION

named in 1895 but reported in 1605 by from the Greek word and Latin which means and respectivelyTriboluminescene Spectroscopy of Common Candies Angelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)

INTRODUCTION

Triboluminescene Spectroscopy of Common Candies Angelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)

INTRODUCTION

Emission occurs due to the by between the surfaces of the fractured crystals and subsequent flourescene. instantaneous charge polarization

INTRODUCTION

Example: Sugar (Sucrose)

INTRODUCTION

Example: Diamond

Triboluminescene of Diamonds. J R Hird, A Chakravarty and A J Walton J. Phys. D: Appl. Phys. 40 (2007) 14641472

INTRODUCTION

Example: Granite

Activities of Triboluminescence at Sample Failure of Granite Itaru Maeda Hokkaido University, Sapporo 060, Japan. Jour. Fac. Sci .. Hokkaido Univ., Ser. VII (Geophysics), Vol. 8, No.1, 65-81, 1986.

INTRODUCTION

H2N

o-toluidine

H2N HO O O O O

MethalqualoneA quinazolone derivative which acts as barbiturates

Production of Methalqualone, a barbiturate.

INTRODUCTION

O

OH

O

O

HO

O

NH2

1. 2. H2O

O

H N

O

/ Heat, refluxOH

andO

General Reaction for the synthesis of N-acetylanthranilic acid.

INTRODUCTION

Mechanism

on Acetic Anhydride; or on Anthranilic Acid

Synthesis of Heterocycles from Anthranilic Acid and its Derivatives Per Wiklund. Karolinksa University Press. Sweden.

INTRODUCTION

MechanismO

tetrahedral intermediateCOOHO O

H CH3 N H O O CH3

OH

ONH2

At neutral conditionsO

COOH HO

+N H O CH3O CH3

INTRODUCTION

MechanismContinuationCOOH HO CH3 O

N H O CH3HO O

OH

andO

H N

O

INTRODUCTION

O

OHO O

NH2O

A CYCLIC INTERMEDIATE

HO

O

OH

H N

O

andO

N-Acetylanthranilic Acid as A Highly Triboluminescent Material. John Erikson. J. Chem. Educ. 49, 688 (1972)

INTRODUCTION

MechanismI. Formation of the cyclic intermediateO OH H N CH3 O OH H N CH3

O

O

OH O O CH3

N H

INTRODUCTION

MechanismI. Formation of the cyclic intermediate, continuationOH O O CH3 O O CH3

N H

N H O H

O

O

N

CH3

INTRODUCTION

MechanismII. Hydrolysis of the cyclic intermediateO O O H O H

+H N CH3

O H O

or -OHN CH3

INTRODUCTION

MechanismII. Hydrolysis of the cyclic intermediate, continuationH O O O H H O

O

H

N

CH3

N

H3C

O

N-acetylanthranilic acid

INTRODUCTION

O

OHO O

O

O

NH2O

N

CH3

2-methylbenzisoxazinone

HO

O

OH

H N

O

andO

N-Acetylanthranilic Acid as A Highly Triboluminescent Material. John Erikson. J. Chem. Educ. 49, 688 (1972)

INTRODUCTION

Formation of 2-methylbenzisoxazinone

a since formation of six-membered rings are favorable.

INTRODUCTION

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.

INTRODUCTION

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)

INTRODUCTION

Conversion of 2-methylbenzisoxazinone:

Dissolve mixture in hot mixture of and (Assumption: 10g intermediate is formed) and allow mixture to stand.

INTRODUCTION

Another Side Product: Acylation of N-acetylanthranilic Acid by Acetic AnhydrideO OH H N CH3 O O O OH

O

N

CH3

O

O

O

INTRODUCTION

MechanismAlkylation of acetic anhydride to form a N-substituted anthranilic acidO OH H N CH3 O OH H N CH3 O O O

O O

O OH H N CH3

O

O

O

O

INTRODUCTION

O

OH H N CH3

O

OH H N CH3 O O

O

O

O

O

O

O

O

OH

N

CH3

O

+O O OH

INTRODUCTION

The alkylation of acetic anhydride to the amino substituted group can also be observed. This alkylation is not favorable since simple alkylation compared to

INTRODUCTION

serves as an Theoretical Melting Point:

:

INTRODUCTION

for (RCOOH) Positive Sign: Evolution of Gas ( ) or

INTRODUCTION

O C R OH + NaHCO3 R

O C O Na + H2O + CO2(g)

bubbling

INTRODUCTION

for (esters, amides, acid halides, acid anhydrides and nitriles) Positive Sign:Complex

INTRODUCTION

O H2NOH C R W R

O C ROH, FeCl3 NHOH O R C N H O 3 Fe + 3HCl

magenta complex

INTRODUCTION

1. to synthesize N-acetylanthranilic acid from anthranilic acid and acetic anhydride;

INTRODUCTION

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

INTRODUCTION

3. to observe triboluminescene in N- acetylanthranilic acid.

REAGENTS

Starting materialO OH

NH2 Other Names: o-amino benzoic acid, vitamin L1, anthraniliteAppearance: White to light tan crystalline powder

Molecular WeightMolecular Formula

137.14 g mol1C7H7NO2

Melting PointFlash Point Density

146148 C>150 C 1.4 g/cm3

REAGENTS

Starting materialO OOther Names: ethanoic anhydride, Ethanoyl ethanoate, Acetic acid anhydride Appearance: clear liquid

O

Molecular WeightMolecular Formula Melting Point

102.09 g mol1C4H6O3 73.1 C

Flash PointDensity

49 C1.082 g/cm , liquid3

REAGENTS

Solvent

O H HOther Names: dihydrogen monoxide Appearance: colorless liquid Molecular Weight Molecular Formula 18.02 g mol1 H2O

Melting PointBoiling Point

0C100 C

Density

1.00 g/cm , liquid

3

REAGENTS

Washing Solvent

H H C H OHOther Names: carbinol, methyl alcohol, wood alcohol Appearance: colorless liquid

Molecular WeightMolecular Formula Melting Point

32.04 g mol1CH3OH 97C

Boiling PointDensity

64.7 C0.7918 g/cm , liquid3

REAGENTS

Reagent for NaHCO3 testONa+ O OHOther Names: sodium hydrogen carbonate, baking soda Appearance: white crystals

Molecular WeightMolecular Formula Melting Point

84.01 g mol1NaHCO3 50 C

Boiling PointDensity

None2.713 g/cm , liquid3

REAGENTS

Reagent for Ferric Hydroxamic Acid TestH N H H O H ClOther Names: Hydroxylammoniumchloride Appearance: white crystalline solid

Molecular WeightMolecular Formula Melting Point

69.44 g mol1HONH2HCl 151- 152 C (decomp)

Boiling PointDensity

None1.67 g/cm , liquid3

REAGENTS

Reagent for Ferric Hydroxamic Acid TestH H O H C C H H HOther Names: ethyl alcohol , methyl carbinol, absolute alcohol, drinking alcohol Appearance: colorless liquid

Molecular WeightMolecular Formula Melting Point

46.07 g mol1HONH2HCl -114.3 C

Boiling PointDensity

78.4 C0.789 g/cm , liquid3

REAGENTS

Reagent for Ferric Hydroxamic Acid Test

Na

+ -

O

HOther Names: Caustic soda, Lye Appearance: White opaque crystals Molecular Weight Molecular Formula 39.99 g mol1 NaOH

Melting PointBoiling Point

318 C1388 C

Density

2.13 g/cm , liquid

3

REAGENTS

Reagent for Ferric Hydroxamic Acid Test

H

Cl

Other Names: Muriatic Acid, chlorane, hydrogen chloride, Acidum Muriaticum Appearance: clear colorless liquid to light yellow liquid

Molecular WeightMolecular Formula

36.46 g mol1HCl

Melting PointBoiling Point Density

-27.32 C110 C 1.18 g/cm , liquid3

REAGENTS

Reagent for Ferric Hydroxamic Acid Test

Fe

3+

Cl

Other Names: Molysite, Iron (III) chloride Appearance: brown solution/ green black in color Molecular Weight 162.2 g mol1

Molecular FormulaMelting Point Boiling Point Density

FeCl3306C 315 C 2.898 g/cm , liquid3

PROCEDURE

O

2g

OH NH2

(reflux set-up)

O

O

10 mLO

Bring mixture slowly to reflux temperature and heat for 15 minutes. A

A Cool Mixture

PROCEDURE

2mL H

O H

Bring to soft boil and cool slowly. Suction filtration with washings of small amount of cold methanol FILTRATE traces of unreacted anthranilic acid, acetic anhydride; methanol and water RESIDUEHO O

H N

O

determine melting point

PROCEDURE

aids the complete conversion of the product by supplying energy to the reaction.

PROCEDURE

PROCEDURE

with the aid of a Bchner Funnel; used to obtain crystals of Nacetylanthranilic acid.

PROCEDURE

Melting Point Determination NaHCO3 Test Ferric Hydroxamic Acid Test

O

O

O

O

O

OH

O

O

H2OCH3 NH

OH

NH2

N

Synthesis of N-acetylanthranilic acidO CH3

DISCUSSION

O

OOH

O

NH2

OLimiting Reagent Excess Reagent

2.0 g anthranilic acid

6.0 mL acetic anhydride

DISCUSSION

Acetate ion, a weak conjugate base is the leaving group from acetic anhydrideCOOH H

COOH H CH3 N H O O CH3

O

O

+N H O CH3O CH3

DISCUSSION

During reflux, the nucleophile (anthranilic acid) attacks the acyl carbon of acetic anhydrideO

OOH

O

ONH2

DISCUSSION

Second reflux, hydrolyzes the intermediate, 2-methylbenzisoxanoneO O

+H N CH3

O H

or -OH

DISCUSSION

Percent Yield of N-acetylanthranilic acid

Parameter Theoretical Yield Experimental Yield Percent Yield

Mass (in g) 2.61 2.148 82.30 %

DISCUSSION

DISCUSSION

Melting Point Determination of N-acetylanthranilic acid

Parameter Theoretical MP Experimental MP Percent Error

Temp (OC) 183 - 185 174 - 180 2.70 - 4.91 %

DISCUSSION

O

O

OH NaHCO3 NH2 NH2

ONa + H2O + CO2(g)

O

O NaHCO3 O Na O H N No Reaction

HO

O

O H N

O

NaHCO3

O + H2O + CO2(g)

DISCUSSION

DISCUSSION

O

OH

H2NOH FeCl3, etOH

No Reaction

NH2 O + OH O O

O

O

H2NOH FeCl3, etOH

FeCl3, etOH NHOH

+ 3HClNHOH3

O

Fe

magenta/burgundyHO O H N

O

H2NOH FeCl3, etOH

No Reaction

DISCUSSION

DISCUSSION

DISCUSSION

Recent theories suggest that the emission of light is due to the highly charged crystal lattice or charge separation of the fractured crystal for electric potential to exist.Triboluminescence and the potential of fracture surfaces Avik Chakravarty and Tacye E Phillipson J. Phys. D: Appl. Phys. 37 (2004) 21752180

DISCUSSION

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 surfaces Avik Chakravarty and Tacye E Phillipson J. Phys. D: Appl. Phys. 37 (2004) 21752180

DISCUSSION

DISCUSSION

DISCUSSION

Other Source of Mechanical Energy:

Triboluminescene Spectroscopy of Common Candies Angelos, Zink and Hardy . J. Chem. Educ. 56, 413 (1979)

DISCUSSION

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 Nalkylation to occur followed by hydrolysis and protonation

Alkylation and acylation of basic salts of anthranilic acid. Wiklund, Bergman .Tetrahedron Letters 45 (2004) 969 972

DISCUSSION

Mechanism of N-acetylanthranilic acid biosynthesis in Aerobacter aerogenes and Escherichia coli

Aerobacter aerogenes

Escherichia coli

Biochim. Biophys. Acta 230 (1971) 451 - 467

APPLICATIONS

Triboluminescent Materials for Smart Optical Damage Sensors for Space Applications M.D. Aggarwal, B.G. Penn, and J. Miller Marshall Space Flight Center, Marshall Space Flight Center, Alabama S. Sadate and A.K. Batra Alabama A&M University, Normal, Alabama May 2008

APPLICATIONS

Triboluminescence in sodiumchloride Srinivasan Arjun Tekalur Michigan State University Journal of Luminescence 130 (2010) 22012206

APPLICATIONS

Newer N-substituted anthranilic acid derivatives as potent anti-inflammatory agentsShalabh Sharma , Virendra Kishor Srivastava, Ashok Kumar

Mefenamic acid and meclofenamates: N-phenylanthranilic acid derivatives,

Eur. J. Med. Chem. 37 (2002) 689697

SUMMARY AND CONCLUSION

The synthesis of N-acetylanthranilic acid from anthranilic acid and acetic anhydride falls under the nucleophilic acyl substitution on acetic anhydride and acylation on anthranilic acid with the aid of the nitrogen lone pairs together with acetic acid as a by product. In the mechanism, anthranilic acid in reaction with acetic anhydride formed the intermediate, 2-methylbenzisoxanone, which is hydrolyzed to form the desired product

From 2.0 g anthranilic acid and 6.0 mL acetic anhydride, 2.148 g out of the 2.61 g theoretical yield. Percent Yield for the synthesis is 82.30%. Side products include 2-methylbenzisoxanone and the acylated N-acetylanthranilic acid. Experimental melting point for the product obtained from the Fisher Johns Melting Point Apparatus was from 174 180 oC compared to theoretical melting point of 183 - 185 oC with percent error of 2.70 to 4.91 %.

SUMMARY AND CONCLUSION

SUMMARY AND CONCLUSION

On the characterization tests, anthranilic acid and the product showed positive results on NaHCO3 test as shown by bubbling and acetic anhydride on the ferric hydroxamic acid test as shown by the formation of a burgundy complex.

SUMMARY AND CONCLUSION

Triboluminescene was observed on N-acetylanthranilic acid as shown by a blue green light emission. This particular emission of light is primarily due to electric discharge on the crystals of the product.

REFERENCES

Angelos, Zink and Hardy. 1979. J. Chem. Educ. 56: 413 414 . Avik Chakravarty and Tacye E Phillipson. 2004. J. Phys. D: Appl. Phys. 37:21752180.

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.