[PDF] Alkylation of Salicylic Acids Andrew David Feilden

Chapter 5 The Reactions of the Esters of Salicylic Acid 5 Introduction The general mechanism for the alkylation of an aromatic, using an alkyl halide, forming

Thus, salicylic acid can react with nucleophilic molecules like methanol in addition to reacting with electrophilic molecules like acetic anhydride For example, many of the flavors that wines develop are formed when alcohols and carboxylic acids in the wine combine to form esters

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Aspirin: some background ▫ Patented by Bayer in 1893 O OH HO O O acetyl salicylic acid (aspirin) Organic background Esterification mechanism R 1

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Mechanism (In class) 7 Conclusion Introduction Esters are produced by the reaction between alcohols and carboxylic acids For example, reacting ethanol with acetic acid to give ethyl acetate is shown below → + + In the case of ethyl

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the esterification of salicylic acid with methanol in the presence of a solution- diffusion mechanism which consists three consecutive steps: 1) selective sorption

[PDF] 8-Synthesis of Aspirin

The phenol group on the salicylic acid forms an ester with the carboxyl group on the acetic acid However, this reaction is slow and has a relatively low yield If

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To prepare aspirin, salicylic acid is reacted with an excess of acetic anhydride A small amount of a strong acid is used as a catalyst which speeds up the reaction

[PDF] Alkylation of Salicylic Acids Andrew David Feilden - White Rose

Chapter 5 The Reactions of the Esters of Salicylic Acid 5 Introduction The general mechanism for the alkylation of an aromatic, using an alkyl halide, forming

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AlkylationofSalicylicAcids

AndrewDavidFeilden

AthesissubmittedtotheUniversityofYork

forthedegreeofDoctorofPhilosophy

DepartmentofChemistry

UniversityofYork

February1997

Abstract

eightcarbonatomsisexploredinChapter3. thescale-upofthereaction. ii

TableofContentsiii

Acknowledgementsxi

Chapter1Introduction

I.Introduction2

1.2.CompositionofanEngineOil.4

1.3.1.LubricatingOils5

1.3.2.OverbasedDetergents5

1.3.3.Dispersants5

1.3.4.Anti-WearAdditives..7

1.3.5.FrictionModifiers..~8

1.3.6.ViscosityIndex(VI)Improvers8

1.3.7.Anti-oxidants..8

1.3.8.FoamInhibitors10

1.4.1.Salicylates14

1.4.2.Phenates.14

1.4.3.SulfonatesandPhosphonates15

1.5.AlkylationofAromaticRings17

1.5.2.AromaticSubstrate19

1.6.Acylation21

1.7.1.Catalysts..23

iii

1.7.2.AlkylatingAgents25

1.7.3.1CarbocationRearrangements28

1.8.1.Polyalkylations..30

1.8.3.RearrangementoftheAlkylChain..32

1.10.SulfurChemistry..34

1.10.1.ReactionsofSulfur.34

1.11.Aims..35

Chapter2TheAlkylationofSalicylicAcid

2.Introduction..37

2.4.AnalysisoftheAlkylsalicylicAcids..44

WeightAlkylatingSubstrates.

3.Introduction47

3.1.AlkylationUsingLongChainEthers..47

3.3.AlkylationUsingLongChainAlcohols..52

3.3.1AlkylationUsingTertiaryAlcohols52

3.3.1.1.2-Methyl-2-hexanol.52

3.3.1.2.2-Methyl-2-undecanol.56

3.3.2.1.1-,2-and3-Hexanols58

3.3.2.2.2-0ctanol.63

3.4.1.TertiaryAlkenes..66

3.4.1.1.2-Methyl-l-pentene66

3.4.1.2.2-Methyl-l-undecene..67

3.4.l.3.3,3-Dimethyl-l-butene..69

3.4.1.4.2,4,4-Trimethylpentenes72

3.4.1.5.Cyc1ohexene73

3.4.2.1.l-Hexene..75

3.4.2.2.l-Octene75

3.4.2.3.l-Dodecene..76

3.5.GCCalibration78

3.5.3.PurificationbyExtraction..81

3.5.4.PurificationbyDistillation81

3.6.Conclusions82

4.Introduction..85

4.1.1.1.SulfuricAcid86

4.1.1.2.OrthophosphoricAcid88

4.1.1.3.PolyphosphoricAcid89

4.1.1.4.p-ToluenesulfonicAcid90

4.1.2.SolidAcidCatalysts..90

4.1.2.1.Fulcat.90

4.1.2.2.Amberlyst15..99

4.1.2.3.Nafion-IO100

4.5.Conclusions114

5.Introduction................118

5.2.2.TheReactionsofSecondaryEsters125

5.4.FutureWork130

6.Introduction.133

LackStearicAcid.142

6.7.Conclusions146

Chapter7TheSulfurisationofAlkylphenols

7.Introduction.148

7.1.2.4-IsopropylphenolandSulfur151

7.2.ReactionsUsingSulfurMonochloride.156

160

7.3.DisulfideSynthesis164

Mixture.170

7.4.ConclusionsandFutureWork.172

Chapter8Experimental

8.1.General.176

8.1.1.GasChromatography176

8.1.3.NMRSpectroscopy177

8.1.5.ChemicalReagents.177

8.2.l.1.Reactionoft-Butylmethylether.178

8.2.1.2.Reactionoft-Butanol.179

179

8.2.3.SynthesisofDiazomethane.180

8.3.2.1.Reactionof2-Methyl-2-hexanol.183

8.3.3.1.Reactionsof1-,2-and3-Hexanol.185

8.3.4.2.Reactionof2-Methyl-l-undecene189

pentene.191

8.3.4.5.ReactionofCyclohexene191

8.3.5.1.Reactionofl-Hexene192

8.3.5.2.Reactionofl-Octene..193

8.3.5.3.Reactionofl-Dodecene..193

8.3.6.GCCalibration..194

8.3.6.2.Purificationby(HPLC)195

8.3.6.3.PurificationbyExtraction196

8.3.7.4.PurificationbyDistillation196

Vlll.

8.4.1.AqueousSolutionsofAcids.197

8.4.2.SolidAcidCatalysts.199

8.4.2.2.ReactionsUsingNafion-IO203

butylsalicylicacid207

8.6.1.ScaleupReactions..215

8.6.1.3.ReactionofPolyisobutene(pm)216

8.6.2.1.Containingstearicacid..217

8.6.3.MolecularModeling218

8.7.1.StandardIndustrialSynthesis219

8.7.2.SimplifiedIndustrialSynthesis219

8.7.3.ReactionsUsingSodiumPerborate223

.........................224

9.References225

10.Appendix231

Acknowledgements

wouldhavegroundtoahalt. Xl

Abbreviations

s broad(NMR)

ChemicalIonisation

doublet(NMR) doubletofdoublets(NMR)

ElectronImpact

FlameIonisationDetector

GasChromatography

GasChromatographylMassSpecrometry

HighPerformanceLiquidChromatography

absorptionmaximum multiplet(NMR) meta

NuclearMagneticResonance

para

Polyisobutene

partspermillion poundspersquareinch quartet(NMR) singlet(NMR)

SulfurisedAlkylPhenol

SpecificIonMonitoring

triplet(NMR)

TotalBaseNumber

triethylbenzylammoniumbromide)

ThinLayerChromatography

Tetramethylsilane

VariabletemperatureprobeMS

Zincdialkyl(ordiaryl)dithiophosphatebr

Cl d dd El FID GC GCIMS HPLC NMR p- PIB ppm pSI q SAP SIMS t TBN TEBAB TLC TMS VTPMS ZDDP Xli

Chapter1

Introduction

1.Introduction.

offunctions". discussedinmoredetail. 2 processesthattakeplace.

OrganicAcids------

/0.S.N.species.....

Oxidation/I

DegradationIWater

InorganicACids______

Corrosion

WearFuelCombustion-----

Lbri.(uncatJOI14Solubleand

---DispersedProductsViscosity

Increase

Wear

IronInsolubles---Varnish

Sludge

thelifeoftheengine. 3

1.2.CompositionofanEngineOil.

followingcompositionbyweight"t-

71.5-96.2%

Lubricatingoil

2-10%

Overbaseddetergents

1-9%

Ashlessdispersants

0.1-3.0%

Anti-wearadditives

upto5%Viscosityindex(VI)improvers

0.1-2.0%

Anti-oxidants

0.1-3.0%

FrictionModifiers

2-15ppmFoaminhibitors

0.5-3.0%

Anti-rust/corrosioninhibitors

haveapolarendgroupandahydrocarbontail. 4

HydrocarbonTail

OleophilicGroup

SolublizerPolarHead

1.3.1.LubricatingOils.

Lubricants".

1.3.2.OyerbasedDetergents.

1.3.3.Dispersants.

5 typesofdispersants

SludgeDispersion

Sludge

DispersantSludgeMicelle

II__PIB-CH'C-O-(CH)-OHI2n

CH'C-O-(CH)-OH2112n

oSuccinateEsterSimpleSuccinateEster PIBSA +HO-(CHz)OHn

PolyisobutenylPolyol

SuccinicAnhydride

MannichBaseDispersant

2¢+2CH,O+H,N-(CH,l,t'H,

AlkylphenolFormaldehydePolyamine

PhosphorousDispersant

water

SIIPIB-P-OHIOHPIB

Poly- isobutene+ P 2 S 5

Phosphorous

pentasulfidetreatmentOHOH qCH,-NH-(CH,l-NH-CH,¢ RR

MannichBase

PropYl~ne

OXIdeSCJ..fIII~'3

PIB-P-(OCH2CH'OH)2

1.3.4.Anti-WearAdditives.

muchbetteranti-wearcharacteristics. (withthemetalsurfacetypicallybeingsteel)

Cohesion

Iron

Stearate

1.3.5.FrictionModifiers.

1.3.6.ViscosityIndex(VI)Improyers.

1.3.7.Anti-oxidants.

Scheme1.1

Initiation:

RH+°2H02'+R(1)

Propagation:

+°2RO'(2)R2 RO' +RHROOH+R(3) 2 ROOH ..RO"+'OH(4) RO" +RHROH+R(5) 'OH +RH~O+R(6)

Termination:

~02+02(7)2HO'2 2R0'

ROOR+0

2(8)2 RO' +RROOR(9)2 2R

R-R(10)

Scheme1.2

quotesdbs_dbs17.pdfusesText_23

[PDF] [PDF] Alkylation of Salicylic Acids Andrew David Feilden - White Rose