UNIVERSITI PUTRA MALAYSIA

THE SYNTHESIS OF QUATERNARY AMMONIUM SALTS WITH

CARBONYL FUNCTIONALITY AND STUDIES OF THEIR PHYSICAL PROPERTIES

WONG CHAN HOONG

FSAS 2002 40

THE SYNTHESIS OF QUATERNARY AMMONIU M SALTS WITH CARBONYL FUNCTIONALITY AND STUDIES OF THEIR PHYSICAL

PROPERTIES

By

WONG CHAN HOONG

Thesis Submitted to the School of Graduate Studies, UniH'rsiti Putra l\lala} �ia, in Fulfilment of Hequirement for the Degree of Master of Science

July 2002

Abstract of thesis presented to the Senate ofUniversiti Putra Malaysia in fulfilment of the requirement for the degree of Master of Science

THE SYNTHESIS OF QUATERNARY AMMONIUM SALTS WITH CARBONYL FUNCTIONALITY AND STUDIES OF THEIR PHYSICAL

PROPERTIES

By

\VONG CHAN HOONG

July 2002

Chairman: Associate Professor Karen Badri, Ph.D.

Faculty: Science and Environmental Studies

This study is mainly focused on the synthesis of compounds of quaternary

ammonium compounds. Iodoacetone has been produced through a simple method by

reacting crystalline iodine and acetone in aqueous medium without adding any acid or

base catalyst. Iodoacetone has been shown to react with various types of amines to

produce tertiary and quarternary ammonium salts . For example, the reaction between

pyridine and iodoacetone produced N-acetonyl pyridinium iodide. lodoacetone reacts

with triethylamine to produce N-acetonyl triethylammonium iodide and it reacts with

triethanolamine to produce N-acetonyl triethanolamonium iodide. The reaction has been

shown to be a general one. In many cases, single crystal x-ray analysis was used to solve

the structure of the salts. We have found that the crystal system for N-

acetonyltrimethylammonium iodide, N-acetonyltriethylammonium iodide, N-

acetonylpyridinium iodide, 1-( l -ethyl-2-oxo-propyl)-pyridinium iodide and 2-hydroxy-

11

4,4-bis-(2-hydroxy-ethyl)-2-methyl-morpholin-4-ium iodide were monoclinic. Whereas

N-acetonyltributylammonium iodide was tetragonal and N-acetonyltripropylammonium

iodide was orthorhombic. The benefit in choosing crystalline iodine instead of other

halogens as the reactant is mainly related to its low toxicity compared to chlorine and

bromine. Surface tension measurements showed that for most of the salts synthesized

performance as surface lowering agents were not very good. Nevertheless, N­

acetonyltridodecylammonium iodide and N-acetonyltrihexyl-amonium iodide showed

very low critical micelle concentration. Antibacterial and antifungal activity tests were

also carried out on the quaternary ammonium compounds. We found that N­

acetonyltrihexylammonium iodide was active against four types of bacteria namely

Bacillus subtilis mutant, Bacillus subtilis wild type, Methicillin ressistant

StaphylococclIs, and Pseudomonas aeruginosa. The antifungal assay tested on three

types of fungi; Saccaromyces ceciricaee (2034 J), Candida albicans (CA), and

A.spergillus ochraceous (398). Only N-acetonyl tributhylamonium iodide and N­

acetonyltrihexylamonium iodide were active against the fungi.

111

Abstrak tesis yang dikemukakan kepada Senat Universiti Putra Malaysia sebagai memenuhi keperluan untuk ijazah Master Sains

SINTESIS GARAM KUATERNARI AMONIUM YANG MENGANDUNGI KUlVIPULAN BERFUNGSI KARBONIL DAN KAJLt\N KE ATAS CIRI-CIRl

FIZIKAL SEBA TIAN

Oleh

\VONG CHAN HOONG

Julai 2002

Pengerusi : Profesor Madya Karen Badri, Ph.D.

Fakulti : Sains dan Pengajian Alam Sekitar

Kajian ini adalah terutamanya memberi tumpuan ke atas penghasilan sebatian

kuaternari ammonium. Iodoaseton telah dihasilkan melalui kaedah yang senang dengan

rnenindakbalaskan hablur iodine dengan aseton dalam larutan akuas tanpa penambahan

sebarang asid atau bes sabagai mangkin . Iodoaseton telah ditunjukkan clapat

bertindakbalas clengan pelbagai jenis amina untuk menghasilkan garam kuaternari

amonium. Sebagai contoh, tindak balas di antara piridin dan iodoaseton dapat

menghasilkan N-asetonil piridinium iodida. Iodoaseton dapat bertindakbalas dengan

trietilamina untuk menghasilkan N-asetonil trietilamonium iodida. Tindakbalas ini boleh

dikatakan berlaku secara umum. Dalam banyak kes, analisis sinaran-X hablur telah

digunakan untuk menyelesaikan strukur molekul untuk sebatian-sebatian itu, Kami telah

mendapati bahawa sistem hablur untuk N-asetoniltrimetilamonium iodida, N-

acetoniltrietilamonium iodida, N-asetonilpiridinium iodida, 1-( l -etil-2-okso-propil)-

IV

pll ldmlUI11 lodlda dan 2-hldlOksl-4,4-blS-(2-hldl ok�l-etil)-2-111etil-11101 f<JIIIl-4-llllll I()cilcid

dci,lldh 1110110klll11k Namun begltu, lvr-asetoniltl lbutilamonlu111 Iud Ide! ddalclh tetl dgllllcli

dcll1 N-e!�etoniltllplOpilamotllul11 lodlda adalah otoroll1bil\. Kebdlkclll dalcl1l1 pelllllli1cll1

i1dblur 10dll1 dan bukannya halogen yang lam sebagdl ree!ktal1 berkaltan ter utd1l1al1\ a

dcngcl11 ketok:-'lkan yang rendah berbandmgkan dengal1 klol1l1 dan bl omm Pel1'vukatan

It'gclIlgd11 pel mukaan memll1]ukkan bahawa kebanYdkan gard111 yang dlha"i1Ll11

lllcnul1]ukkan pel anan sebagar aJen 111erendahkan tegang,lI1 pel111ukaan yang sedel iJdna

\\ dlau baga l111anapun, N-asetomItndodesllamol11um loclida dan \-

,hetoniltl lheksilamotllum lodlda teIah menul1]ukkan mlal kepekatan kntlkal I11I"el

(C \ IC) \dng �clngat rendah U]lan aktlvltl antlbclkteI Ia dan antItungl ]Ugcl dlJalanLl11 ke

dU" gal dill kUdtel nar I amotllum Kaml mendapatl b,li1dVvd ;\-,betol11lhek,,!IdIl1011111111

iodlda adalah aktlf clalam per encatan ter hadap pelbagal len]:' bacter la contohm a

I!U/J!Il!()( ()( (11\ eLm P')clldo/llo17{/\ 4el11gl1lo\u UJlcll1 antrfungl telah cllJaIankan kt ,H,\'­

tlgd jerm fUI1g1 ,\Cf(UI10177)W\ cec11lulec (20141) CU1lclILiu ulhlu!m (CA) cleli1

I \/)e; g;III/\ ()ch; c/vCOIl\ (398) Hanya N-acetolllltnbutllamOI1IUI11 rodrdc1 cLm \-

(,,,('tol1lltr Ihek"Ild111011lUm roclicia adalclh aktrf daIam merencat peItumbuiJan fungi

A CKNOWLEDG EMENTS

I would l ike to express my s ll1cere and deepest appreciation to my superviso r r\SSOC

Prof Dr. Karen Sadri for her inte l lectual advice, suggest ions and guidance thro llghll ll t

the course of this p roject and for reviewing th is thes is with construct ive crit ic isms IVI)'

sincere thanks and deepest grat i tude is also extended to Pro f Dr Sadri [\luhallll1lad

being t h e master m ind of this p roject . H is invaluable suggest ions and ad\ices \\ ere

indeed the main factor fo r t he Sllccess i n my research. I'm a lso indebted to Assoc PIlli'

Dr Mel Aspo l lah Hj. Sukari and P rof Bohari Yam in, UKM for the i r invaluable

guidance. F inancial support fro m IRPA p rogram (63 500, jo int p roject with U P[\J) is also

great ly appreciated

1 abo \\' ish to thank my l ab mate Lee Yean Kee for h is help and advice t h ro ughout the

cou rse of my research, 1 am also grateful to En. Zainal Zahari fClr assist ance with N;vLR

spcdra and Puan Rus llani Amiruddin fo r ass istance with lR spectra

Last but not le ast, I am indebted to my parents, sisters and friends \v!Juse

Cllcll u ragement and support have contributed towards the success of this project

\'1

I certify that an Examination Committee met on 17th July 2002 to conduct the final examination.of Wong Chan Hoong on his Master of Science thesis entitled "Synthesis of Quaternary Ammonium Salts with Carbonyl Functionality and Studies of Their Physical Properties" in accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and Universiti Pertanian Malaysia (Higher Degree) regulations 1981. The Committee recommends that the candidate be awarded the relevant degree. Members of the Examination Committee are as follows:

ANUAR KASSIM, Ph.D.�cr-_, Associate Professor Faculty of Science and Envir UnIversity Putra Malaysia (Chairman)

KAREN BADRI, Ph.D. Associate Professor Faculty of Science and Environmental St Universiti Putra Malaysia (Member)

BADRI MUHAl\<lMAD, Ph.D. Professor

,L� 100 Faculty of Science and Environmental Studies Universiti Putra Malaysia (Member)

IHD. ASPOLLAH IIJ. SUKARl, Ph.D. Associate Professor Faculty of Science and Environmental Studies Universiti Putra Malaysia (Member)

�A.MSHER lVIOHAMAD RAlVLADILI, Ph.D.

ProfessorlDeputy Dean School of Graduate Studies Universiti Putra Malaysia

Date: 1 7 OCT 2002

Vll

This thesis submitted to the Senate of Universiti Putra Malaysia has been accepted as fulfilment of the requirements for the degree of Master of Science. The members of the Supervisory Committee are as follows:

KAREN BADRI, Ph.D. Associate Professor Faculty of Science and Environmental Studies Universiti Putra Malaysia ( Chairperson)

BADRI MUHAMMAD, Ph.D. Professor Faculty of Science and Environmental Studies Universiti Putra Malaysia (Member)

MD. ASPOLLAH HJ. SUKARI, Ph.D. Associate Professor Faculty of Science and Environmental Studies Universiti Putra Malaysia (Member)

AINI IDERIS, Ph.D. Professor! Dean School of Graduate Studies, Universiti Putra Malaysia.

Vlll

DECLARATION

I hereby declare that the thesis is based on my original work excepl I'or quolatioll,> alld cil�llion:-. that have been duly acknowledged. J also declare that it ha:-. nol heell prcy iUlI,>ly OJ concurrently submitlecl for any other at UPM or other institution:-..

- -�-----

Wong Chan Hoong

Date:

\\

TABLE OF CONTENTS

ABSTRACT ABSTRAK ACKNOWLEDGEMENTS APPROVAL SHEETS DECLARATION FORM LIST OF TABLES LIST OF FIGURES LIST OF ABBREVIATIONS

CHAPTER

1 INTRODUCTION Halogenated Organic Compounds

a,-Iodoketones Iodination of Acetone Halogenation of Ketones The Physlcal Properties of Iodine Quaternary Ammonium Compounds Properties of Quaternary Ammonium Compounds Biological Properties Phase Transfer Catalyst Preparation of Quaternary Ammonium Compound Cationic Surfactants Surfactant Solubility Micelles and Critical Micelle Concentration (CMC) Carbonyl Functionality Objectives

2 MATERlALS AND METHODS Chemicals Physical Measurements and Elemental Analyses

CHN Elemental Analysis Infrared Spectra (IR) Nuclear Magnetic Resonance CHNMR) Gas Chromatography and Mass Spectra (GCMS) X-ray Structure Analysis Surface Tension Measurement Thin Layer Chromatography (TLC)

Page

11 IV Vi

VII IX

Xlll XVll

XiX

1 1 7 7

10 11 12 14 15 16 17 18 20 21 22 ') " _.J

24 24 26 26 26 26 26 27 27 27

X

Iodination of Acetone 28 Iodination of 2-pentanone and 3-pentanone 28 General Method in Producing Quaternary Ammonium Compounds 29 Preparation of Other Quaternary Ammonium Compounds 30

N-Acetonylpyridinium Iodide 30 N-Acetonyltributylammonium Iodide 30 2-Hydroxy-4,4-bis-(2-hydroxy-ethyl)-2-methyl-

morpholin-4-ium Iodide 30 General Procedure in Surface Tension Measurement 3 1 Surface Tension Measurement 31

N-Acetonyltrihexylammonium Iodide 3 1 N-Acetonyltridodecylammonium Iodide "7 .J...,

Antimicrobial Activity "7 .J� Preparation of Nutrient Broth Culture 33 Procedures of Gro\\ring Microbes "" .J.J Quantitative Antimicrobial Assay 34

3 RESULTS Iodoacetone 35 3-lodo,pentan-2-one and 2-iodo,pentan-3-one 36 Characterization of Quaternary Ammonium Compounds 39

N-Acetonyltrimethylammonium Iodide 39 N-Acetonyltriethylammonium Iodide 42 N-Acetonyltripropylammonium Iodide 45 N-Acetonyltributylammonium Iodide 48 N-Acetonyltrihexylammonium Iodide 5 1 N-Acetonyltridodecylammonium Iodide 54 2-Hydroxy-4,4-bis-(2-hydroxy-ethyl)-2-methyl-

morpholi n-4-ium Iodide 57 1-(1-Ethyl-2-oxo-propyl)-pyridinium Iodide 59 N-Acetonylpyridinium Iodide 60

Surface Tension Measurements 63 N-Acetonyltrimethylammonium Iodide 64 N-Acetonyltriethylammonium Iodide 66 N-Acetonyltripropylammoniurn Iodide 68 N-Acetonyltributylammonium Iodide 70 N-Acetonyltrihexylammonium Iodide 72 N-Acetonyltridodecylammonium Iodide 74 2-Hydroxy-4,4-bis-(2-hydroxy-ethyl)-2 -

methyl-morpholin-4-ium Iodide 76 N-Acetonylpyridinium Iodide 78 1-( l-Ethyl-2-oxo-propyl)-pyridinium Iodide 80

Q ualitative and Quantitative Antimicrobial Assays 82

4 DISCUSSION 84 Hemiacetal 90

Xl

Intramolecular Hemiacetal 90 . X-ray Structure Analyses 93

N-Acetonyltrimethylammonium Iodide 93 N-Acetonyltriethylammonium Iodide 96 N-Acetony 1 propy lammoni urn Iodide 100 N-Acetonyltributylammonium Iodide 104 2-Hydroxy-4,4-bis-(2-hydroxy-ethyl)-2-methyl-

morpholin-4-ium Iodide 108 N-Acetonylpyridinium Iodide 112 1-( l-Ethyl-2-oxo-propyl)-pyridinium Iodide 116

Antimicrobial Activity 125

5 CONCLUSION 127

REFERENCES 129

APPENDICES 133

VITA 148

xu

LIST OF TABLES

Table Page

1 .1 Summary of Substitution and Elimination Reactions of Alkyl Halides 2

1 .2 Dissociation Energies of Halogenation Molecules 11

1.3 Ionization Potential and Electron Affinity of Halogens 13

1 .4 Properties of Quaternaries and Chain Length 1 5

3. 1 lH NMR (400, CDC13) Assignments for ATMAI 40

3.2 lH NMR (400, CDC13) Assignments for ATEAI 43

3.3 lH NMR (400, CDCI3) Assignments for ATPAl 46

3.4 1H NMR (400, CDCl3) Assignments for ATBAI 49

3.5 lH NMR (400, CDC13) Assignments for ATHAI 52

3.6 lH N1vlR (400, CDC13) Assignments for ATDAI 55

3.7 Elemental Analysis of Quaternary Ammonium Salts 62

3.8 Surface Tension of ATMAI 64

3 .9 Surface Tension of ATEAl 66

3 . 1 0 Surface Tension of AT PAl 68

3 . 11 Surface Tension of ATBAl 70

3.12 Surface Tension of ATHAI 72

3.13 Surface Tension of ATDAI 74

3.14 Surface Tension of HEMI 76

3 . 15 Surface Tension of API 7 8

3. 16 Surface Tension ofEOPPI 80

Xlll

3.17 Diameter Inhibition Zone (mm) of the QAC p ( -

3.1 X Minimum Inhibitory Concentration (MIC) X" ( .'

.1 . 1 Crvstal data and structure refinement of A TMAI l)4

4.:2 Bond lengths and angles for A TMAI 95

... u Crystal data and structure refinement of A TEAl 97

.1. -+ Bond lengths and angles for A TEAl 98

-+.5 Crystal data and structure refinement of ATPAI 10]

-+.6 Bond lengths and angles for A TP AI 102

4.7 Crystal data and structure refinement of A TBAI 105

-+.8 Bond lengths and angles for A TBAl 1U6

·t () Crystal data and structure refinement of HEMI 109

-+.10 Bond lengths and angles for HEMl 110

-+. I 1 Crys tal data and structure refinement of API 113

-f 1 � Bond lengths and angles for API 11-+

·+.13 Crystal data and structure refinement EOPP! 117

-+.]-+ Bond lengths and angles for EOPPl 118

.'\ ] ElMS c1ata of iocloacetone ] "" .' J

\:2 ElMS clata of 3-iodopentan-2-one 1"-' .' .'

\ � ElMS data of:2-iodopenta-3-one 1 "" .'.'

. \4 Atomic coordinates and equivalent isotropic displaccmcnt parameters of A TMAl 13-+

, \5 Ilydrogen coordinates and isotropic displacement Paranlcters of ATMAI 134

,\() Anisotropic displacement parameters of A TMAI 135

\ I \'

\7

, \�

,\ 9

\10

\ 11

/\ 1 .2

. \ 13

.\1-+

A 1 5

\ J()

,\ 17

\1�

\19

\2U

\.21

\.2.2

\2�

\::-+

Atomic coordinates and equivalent isotropic displacement Parameters of ATEAI

Hydrogen coordinates and isotropic displacement Parameters of A TEAl

Anisotropic displacement parameters of A TEAl

Atomic coordinates and equivalent isotropic displacement Parameters of A TP Al

Hydrogen coordinates and isotropic displacement Parameters of ATPAI

Al1lsotropic displacement parameters of A TP AI

Atomic coordinates and equivalent isotropic displacement Parameters of A TBAl

Hydrogen coordinates and isotropic displacement Parameters of A TBAI

Anisotropic displacement parameters of A TBAI

Torsion angles of ATDAI

Atomic coordinates and eqUIvalent isotropic displacement Parameters of HEMI

llydrogcn coordinates and isotropic displacement Parameters of HEMI

Anisotropic displacement parameters of HEMl

Tors1On angles of HEMI

Atomic coordinates and equivalent isotropic displacement Parameters of API

Hydrogen coordinates and isotropic displacement Pardl11cters of API

Anisotropic displacement parameters of API

T llr:,ion angles of API

135

136

137

137

1 30

130

130

140

140

1-+ 1

1 -� 1

1-+2

1-+2

143

1-+3

14-+

144

I-� :;

\\

\25

,\27

Atomic coordinates and equivalent isotropic displacemcnt Parameters of EOPPI

II) drogen coordinates and isotropic di�placell1ent Parametcrs of EOPPI

Anisotropic displacement parameters of EOPPI

Torsion angles of EOPPI

1-+5

1.+6

1.+7

\ \1

, LIST OF FIGURES

Figure Page

1.1 Mechanism of the Acid-Catalyzed Halogenation of Ketones 10

1.2 Synthesis of Cationic Cleavable Surfactant 19

3.1 ElMS Spectrum of Iodoacetone 35

.... ') :J._ IR Spectrum of 3-iodopentan-2-one 37

.... .... IR Spectrum of 2-iodopentan-3�one 37 .).J

3.4 EIMS Spectrum of 3�iodo,pentan-2�one 38

3.5 ElMS Spectrum of 2-iodo,pentan-3�one 38

3.6 IR Spectrum of ATMAI 40

3.7 IH NMR spectrum of AT MAl (400 MHz, CDCh) 41

3.8 lR Spectrum of A TEAl 43

3. 9 IH NMR spectrum of ATE AI (400 MHz, CDCh) 44

3.10 IR Spectrum of AT PAT 46

3.11 IH NMR spectrum of AT PAl (400 MHz, CDCh) 47

3.12 IR Spectrum of ATBAI 49

3.13 lH NMR spectrum of ATBAl (400 MHz, CDCh) 50

3.14 lR Spectrum of ATHAI 52

3. 15 IH NMR spectrum of ATHAl (400 MHz, CDCh) 53

3.16 IR Spectrum of ATDAI 55

3.17 IH NMR spectrum of ATDAI (400 MHz, CDCI3) 56

3.18 IR Spectrum of HEM I 58

XVll

�. 1 C) IR Spectrum of EOPPI 60

�.:2() IR Spectrum of API () 1

.1.21 The Surface Tension Versus Logarithm Molarity or ,AlMAI ()5

1.=2 The Surbce Tension Versus Logarithm Molarity or A ["LAI h7

�.23 The Surface Tension Versus Logarithm Molarity or ATP 1\1 69

� 24 The Surface Tension Versus Logarithm Molarity of AlBAl 7 1

�.2� The Surface Tension Versus Logarithm Molarity or ATHAI 73

3.26 The Surface Tension Versus Logarithm Molarity of A TDAI 75

�.27 The Surface Tension Versus Logarithm Molarity orHEMI 79

�.28 The Surface Tension Versus Logarithm Molarity orArl 77

.1 .2l) The Suri�lce Tension Versus Logarithm Molarity or l-:OPPI 8 1

-u 1 H NivfR spectrum of HEr-Ill (400 MHz. CDCb) 89

1 " I.l. lH NMR spectrum of API (400 MHz. CDCb) 92

-I. � ORTEP diagram of ATMAI 95

-1. -I ORTEP diagram of ATEAl 99

4.5 ORTEP diagram of AT PAl 1()3

-L6 ORTEP d iagram of ATBAI 107

·L7 ORTEP diagram of HEMI 11 1

4.8 ORTEP diagram of API 115

.-1. () ORTEP diagram of EOPPI I 10

'\ \ iii

ATMAI

ATEAI

ATPAI

ATBAI

ATHAI

ATDAI

API

CHN

CMC

8

d

EIMS

EOPPI

FTIR

HEMI

Hz

J

mi

m.p.

MIC

MPOB

LIST OF ABBREVIATIONS

- N-Acetonyltrimethylammonium Iodide

- N-Acetonyltriethylammonium Iodide

- N-Acetonyltripropylammonium Iodide

- N-Acetonyltributylammonium Iodide

- N-Acetonyltrihexylammonium Iodide

- N-Acetonyltridodecylammonium Iodide

- N-Acetonylpyridinium Iodide

- degree in Celsius

- Carbon, Hydrogen, Nitrogen Analyses

- Critical Micelles Concentration

- chemical shift in ppm

- doublet

- Electron Impact-Mass Spectroscopy

-1-(] -Ethyl-2-oxo-propyJ)-pyridinium Iodide

- Fourier Transfer Infra-Red

- 2-Hydroxy-4,4-bis-(2-hydroxy-ethyl)-2-methyl-morpholin-4-ium Iodide

- Hertz

- Coupling constant in Hz

- mililitre

- melting point

- Minimum Inhibition Concentration

- Malaysian Palm Oil Board

XIX

ORTEP

QAS

NMR

s

TLC

)..tg

QAC

m

- Oak Ridge Thermal Ellipsoid Plot (from the program for Crystal Structure Illustration)

- Quaternary Ammonium Salt

- Nuclear Magnetic Resonance

- singlet

- thin layer chromatography

- mIcrogram

- Quaternary Ammonium Compounds

- multiplet

xx

CHAPTE R I

INTRODUCTION

Halogenated O rganic Compoul\(h

Hctiogenated ol gal11c chemicals are Important not onl) In thell 1�el\;e" a" filll"hed

pi odUCb such as o rganoch lo rofluorocarbons, 01 pi ecur� ors to fit1Ished pI Oducts, �uch a�

poh \ IIlvlchlol Ide, but also as IIltermedIates for downstream products In the lattel Cd�e

thl� IS so because a halogenated orgal11c compound can undergo \al I OU� reactIon" �uch

Nuc1eopllllic substitution

DehydrohalogemtIon

PI epm atlon of GI 19nard Reagents

Reduction

There m C many methods a\ allable fOI syntheslZlng alkyl halide,> II1 the labol atol \;

\lo�t of t he�e methods p rodu ce good YIelds of sll1gle pI OduCb For e\.dJllple

hdlllgenated hydI O cal bons ale generally produced from the COIl \ CI:-lon of akohol" fhl"

ledlllOI1 h geneldl l) �dtIsfactory tor the p repaIdtlOI1 of blon1J(le� and lodlcle� Fle:-tel r.::f

uf 1961)

R OH [ I ]

HCllogenated hydrocarbons can also be plOduced frolll alkane� ll::.mg free-! ddlcal

halogenation

X2, heat or light R-X + H-X [2]

Addition of hydrogen halides to alkenes will also produce halogenated

hyd! ocarbons

HX \ / -C-C-

H x [3]

(Wade, 1987)

Alkyl halides are versatile organic compounds, easily cO l l \'erted to most uf the

llth�1 functional groups The most important prope!iy of alkyl halides is the ability uf the

h alogen atom to leave with its bonding pair of electrons to form a stable halide Ion

['dany of the reactions of alkyl halides can be classified as eillninations 01 as

llucleophIlic substitutions Some of these rea:ctions are summarized in Table J I

'I clbk I I Summary of Substitution and Elimination ReactIons of AI\,::) I Haltde:-

Nllcleopllllr:

R-X T - OH R-X T - OR' R-X + - i'\J-l3 R-X + -:C=C-R R-X + -:C=N R-X + R'-COO -

------

Prodllct

R-OH R-OR R-NH

+3X- ,

R-C=C-R

R,-C=N R -COO-R

------ - --

('1m \ (Jj;)roc/It( I

alkohol ether amine

alkyne nitrile ester

- - -�--

I o d inat ion of palmit ic acid, PA, has been carried out in several so lvent systems

The two p hase sys tem composed of d ic hloroethanel acetone/ water was found to he the

p referred so Ivent (1'vl uhammad eI al., 2000). Acetone was used to fac i l i t ate the reactiu n

het weell iod ine and pa lmi t ic acid . Iodoacetone was obta i ned as a s i de pro duct or perhaps

\\ as an essent ia l in termediate. This compound was also found to be h ighly react i \'e \ \ i th

tert iary amines forming q uaternary ammonium sal ts

Therefore it was wise to focus on the react ion between acetone and iod i ne i l l an

at tempt to impro ve upon its synthes is . Several react ion condit ions have been modifi ed to

obta in a better y ie ld Once an easy route to iod inated acetone \vas found, the techn ique

\\ as appl ied to other ketones Com pared to cOl1\entional quaternary ammon iu lll

compounds , the newly synthes ized prod ucts with carbonyl functio na l i ty were consider'ed

CIS 1I11iquc and perhaps possess several specia l propert ies

I n an i nvest igat ion of t he reaction of compounds conta in i ng a reacti\ 'e hyc.lrugcll

atom \\ ith iod ine in t he p resence of a base, King e t ul. ( 1 944 and 1 946) attempted to

make some aryl methyl ketones react with iod ine and pyridine . They were able to

p repare t he substituted � -ketoalkylpyr id inium iod ides such as l -p henacylpyridll l i u l11

iodide ( I ), 1 -( I -naphthoylmet hyl)-pyrid in ium iod ide ( 1 1 ). 1-( I-anthroylmethyl)­

P\ I icii n i um iod ide ( I l l), and 1 -( a -methylphenacyl)-pyrid in iu l11 iod ide ( 1\') These

products were accompanied by some h ydro iod ide of the base as shown in react ion l.:) J 1 n

each of the react ions s tud ied, approx imately ha lf of t he iod ine LIsee! appeared a� py r id iJ1 e

hydroiodide. Each of the substituted f3-ketoalkylpyridinium iodides produced by the

above reaction gave characteristic hydroxy acids when cleaved by means of aqueous

alkali (5] (King et at., ] 945).

O'{<J (1)

& r NO Ij � -- 0

(III)

NO o �I

(II) <Y(NO Ij � -

- 0

(IV)

4