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)

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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 e