Preface v

PART - I

1. Use of Water as a Solvent for Organic Reaction 1.11. Introduction 1.1

2. Reactions in Aqueous Phase 1.32.1 Pericyclic reactions 1.3

3. Conclusion 1.83

2. Organic Reactions in Super Critical Water or in Near Water (NCW) Region 2.11. Introduction 2.12. Organic Reactions in SC - H20 2.1

3. Organic Reactions in Near-critical Water (NCW) Region 2.43.1 Conversion of aryl halides into phenols 2.43.2 Claisen rearrangement 2.43.3 Pinacol-pinacolone rearrangement 2.4

3.4 Hydration of alkenes: synthesis of carvacrol from carvone 2.43.5 Diels-alder cycloaddition reaction 2.53.6 Fischer indole synthesis 2.53.7 Hydrolysis of esters and amides 2.63.8 Decarboxylation 2.63.9 Autocatalysis 2.7

4. Miscellaneous Reactions 2.85. Conclusion 2.9

3. Microwave Assisted Organic Reactions in Water 3.11. Introduction 3.12. Synthesis of Heterocycles 3.1

viii Con tents

.--

,_.--.-_.,L.

3.2

3.3

3.3

3.4

3.4

3.5

3.6

3.6

3.6

3.8

3.8

3.9

3.9

3.10

3.10

3.10

3.11

.11

.I­

.I-

3.1

.1

14

15

.1

.1

.1

.1_. I

_.1

3. N-Alky1ation of Nitrogen Heterocycles

4. Biginelli Reaction

5. 1,3-Dioxanes

6. Heterocyclic Hydrazones

7. Aza-Michae1 Reaction

8. Trost's y-Addition

9. Synthesis of Azides, Thiocyanates and Su1fones

10. Coupling Reactions

10.1 Suzuki reaction

10.2 Heck reaction

10.3 Sonogashira reaction

10.4 Hiyama reaction

11. Synthesis of Spiro 2, 5-Diketopiperazines

12. Synthesis of Diazepine

13. Synthesis ofTrizine and Tetrazole

14. Aminocarbonylation Reaction

15. Krohnke Reaction

16. Deprotection of cetal and Ketal

17. Nucleophilic ub tltution of 6-Chloropurine

18. Stille Reaction

19. Cyanation Reacti n

20. ynthe I of Ket ne fr m Amine

21. Chemo electi e Hydrog nati n f (X, (X- n aturat d arb n I mp und

22. Hydroph phmylatl n. of Pr pargyl I h I and thyn I t r I

23. -Acylation

24. -Alkylati n

25. -Arylati n

2 . William on other

27 ynth e'ofH t r

27.1 I -m mber d

27.2 -memb red

27.3 I -m mb red

27.4 I -m m er d -h tr""""

2 Manni h R a ti n

29 u Ie phIlI ub tituti n

30 ptd Rm 1 op nm RatIOn

1 Di I - Ider loaddcti n

32. Mi cellaneou ppli ation

32.1 Hofmann limination

3.....2 Synthe i of deferiprone

32.3 Hydroly i of benzyl chlorid

32.4 Hydroloy i ofbenzamide

32.5 Hydrolysi ofN-phenyl benzamide

32.6 Hydrolysis of methyl benzoate to benzoic acid ( aponification)

32.7 Oxidation of toluene

32.8 Coupling of amines with halide

32.9 N-Heterocyclisations

33. Conclusion

4. Organic Synthesis using Biocatalysts1. Introduction

2. Biochemical (Microbial) Oxidations

3. Biochemical (Microbial) Reductions

4. Enzymes Catalysed Hydrolytic Processes

4.1 Enantioselective hydrolysis of meso diesters

4.2 Hydrolysis ofN-acylamino acids

4.3 Miscellaneous applications of enzymes

5. Conclusion

PART - II

Content •I

3.30

3.30

3.30

3.30

3.30

3.31

3.31

3.32

3.32

3.32

3.32

4.14.1

4.3

4.9

4.14

4.14

4.15

4.16

4.18

5. Organic Synthesis in Super Critical Carbon Dioxide 5.11. Historical Development 5.1

2. Use of Super Critical Carbon Dioxide (Sc CO2) for Extracting Natural Products 5.2

3. Use of Super Critical Carbon Dioxide (Sc CO2) for Dry Cleaning 5.4

4. Use of Supercritical Carbon Dioxide (SC CO2) as Solvent for Organic Reactions 5.6

4.1 Asymmetric catalyst using super critical carbon dioxide 5.6

4.2 Supercritical polymerisations 5.7

4.3 Free Radical brornination 5.7

4.4 Hydrocarbon functionalization 5.7

4.5 Diets-Alder reaction 5.9

4.6 Kolbe-Schmitt synthesis 5.12

4.7 Brornination: displacement of a chlorinated aromatics 5.13

4.8 Freidel-Crafts reaction 5.13

4.10 Hydrogenation in SC - CO2 5.14

4.11 Hydrofonnylation in SC-C02 5.18

x Contents

4.12 Oxidations in SC - CO2

4.13 Radical reactions in SC - CO2

4.14 Acid-catalysed reactions

4.15 Coupling reactions

4.16 Stereochemical control in reactions using SC - CO2

4.17 Photochemical reactions in SC - CO2

4.18 Formation of silica nanoparticles using SC - CO2 and water in oilmicroemulsions

4.19 Miscellaneous applications

5. Conclusion

6. Organic Synthesis using Carbon Dioxide1. Introduction

2. Synthetic Application of Carbon Dioxide

2.1 Synthe i of dimethyl carbonate

2.2 Synthetic of cyclic carbonate

2.3 Alternating polyrnen ation of 0 irane and CO2

2.4 Synthe i of urea and urethane den at! e

2.5 Synthe i of carbo ylic a id

2.6 Synthe i of e ter

2.7 ynthe I of lactone

2.8 Hydroforrnylati n

2.9 Homologatl n

2.10 U e of carb nJ id a Id alaI z d h dr 1 1 f ketal .

epo Ide

3. nclu i n

PART - III

tal and

5.19

5.22

5.23

5.24

5.27

5.30

5.30

5.31

5.37

6.16.1

6.1

6.1

6.2

6.3

6.

6.

6.

.10

.11

.11

.11

6.L

.1

.1

.-

.-

.4

.4

.4

.4

.4

Contents xi

3.7 Chiral ionic liquid 13 7.5

3.8 Halogeno and alkylhalogenoaluminate ionic liquids (binary ionic liquids) 7.6

3.9 Microwave assisted solvent free preparation of ionic liquids 7.6

3.10 Ionic liquids with fluorine-containing anions 7.73.11 Typical preparation routes for ionic liquids 7.7

4. Selection of a Suitable Ionic Liquid for a Particular Reaction 7.7

4.1 Formation ofN-heterocyclic carbenes 7.8

4.2 The Baylis-Hillman reaction in ionic liquids 7.9

4.3 The knoevenagel condensation 7.12

4.4 Claisen-Schmidt condensation 7.124.5 The Homer-Wadsworth-Emmons reaction in ionic liquids 7.13

5. Synthetic Applications 7.14

5.1 Alkylation 7.14

5.2 Allylation 7.15

5.3 Hydroformylation 7.15

5.4 Alkoxycarbonylation 7.16

5.5 Oxidations 7.16

5.6 Hydrogenations 7.19

5.7 Carbon-carbon bond forming reactions 7.21

6. Task-specific Ionic Liquids (TSILs) 7.28

6.1 Brensted acidic ionic liquids 7.286.2 Brensted-basic ionic liquids 7.31

7. Other Application of ionic liquids 7.32

7.1 Conversion of epoxies to halohydrins 7.32

7.2 Conversion of oxiranes (epoxides) into thiiranes 7.33

7.3 Thiocyanation of alkyl halides 7.33

7.4 Synthesis of cyclic carbonates 7.337.5 Biginelli reaction 7.34

7.6 Synthesis of 3-acetyl-5-[(z)-arylmethylidene] 1, 3-thiazolidine-2, 4-diones 7.34

7.7 Synthesis of symmetric urea derivatives 7.34

7.8 Synthesis ofhomoallylic amines 7.35

7.9 Conjugate addition ofthiols to <X, ~-unsaturated ketones 7.35

7.10 Nucleophilic displacement reactions 7.357.11 Bromination of alkynes 7.35

7.12 Alkene metathesis 7.36

7.13 Electrophilic nitration of aromatics 7.37

7.14 Carbon-o ygen bond formation 7.37

xii Con ten ts

7.15 Synthesis of l-acetylnaphtholene

7.16 Synthesis of tonalid and traseolide

7.17 Selective hydrogenation of aromatic compounds

7.18 Alkylation of indole and 2-naphthol

7.19 Methylene insertion reactions

7.20 Synthesis of pravadoline

7.21 Synthesis of cyclotriveratylene (CTV) and tris-(O-allyl) CTV

7.22 Cycloaddition of carbon dioxide to propylene oxide cataly ed byionic liquids

7.23 Epoxidation of electrophilic alkene in ionic liquids

7.24 Oxidation of benzylic alcohol to carbonyl compound withKMn04 in ionic liquids

8. Biotran formation in Ionic Liquid

8.1 Synthe i of Z-a partarne

8.2 Conver ion of I, 3-dicyanobenzene to 3-c anobenzamide and3-cyanobenzoic acid

8.3 Tran e teritication ration

8.4 Ammomoly i of carb Ii aCid

8.5 ynthe I of ep Ide

.6 Tran e t nticat) n f hiral ub trat

.7 I f g ran I a et te

t rificati n glu and -a rbi id

9 ti h dr I I f pr ~hiral m 1 111 e t r

.10 Kin ti r luti n f -a ctyl-a-amin J Id t r•

.11 •nantl J ti c h dr 1 ' i m th 1phcn 1gl 10 t andnapr en mdh I stC! and _- 4- hi r phen .. ) p rp IIll e t r

8. L nantros 1 'ti I cst riti ati n f ibupr fen and 2-. ub tlnll d 1 r pan i a id

R.13 nanti clccti c amin 1 I f m th 1man I t

9. pph alion of I ni I iquid a 1 cnt lor P 1 m rizati e

J O. n Iusl n

PART - IV

7.37

7.38

7.38

7.39

7.39

7.40

7.40

.41

7.41

7.42

7.42

.43

.43

.4

.4

44-

A.4

.4

A

.4

A

-

• P I,' tho I n ,1. 01 nd it luti n .

1. Inlrc u ti n

2. hara't Ii 1I s (t PI' ,

3. in rank R a ti n

1.1 ul titution r .1 li)Jl

:\.2 id-1ti n I a li)Jl

.. Rl: iu II nIl lion

r n R ti n 1 dium f utur .1.1

•1

.-

...

.4

sa PT

a PT

ia PEG-Supported l-Amin carbonyl

em ttll t

4. Peg a' Pha -Tran. t r tal t (PT )

4.1 illiam on ether nthe i'

4.2 ub titution ration u 'ing P

4.3 idati n rea tion u ing P

4.4 R duction u ing P a PT

5. L-Prolin atal ed mm tri Id I Rea ti n

6. L-Proline Catal ed yrnmetri Tran fl r Idol Rea ti n

7. yrnmetric Dih dro ylation of 1 fin

8. Regio electi e Heck Reaction

9. Baylis-Hillman Reaction

10. Synthesis of 2-Thiazol-4-0ne1 2-Diaza-I,3-Butadiene

11. Catalytic Transfer Hydrogenation Reaction (CTH) to PEG-bound ub trate

12. Suzuki Cros -Coupling Reaction in PEG

13. Synthesis of Azo Compound U ing PEG

14. Oxidation of Cyclohexene to Adipic Acid in Polyethylene Glycol Sa edAqueous Siphasic System Using Sodium Tungstate and Hydrogen Peroxide

15. Enzymatic Reactions

16. Synthesis of2-Amino-2-Chromenes

17. Decarboxylation of Cinnamic Acid

18. Conclusion

PART - V

9. Organic Synthesis using Fluorous Phase Techniques1. Introduction

2. Characterstics of Perfluorous Liquids

3. Phase Switching

4. Perfluorinated Catalysts

5. Some Application of Fluorous Phase Techniques

6. Conclusion

Index

•••111

x..6

.6

.9.10

X. 11

.12

.14

.15

8.16

.1

.20

.21

8.23

8.24

8.24

8.25

8.26

9.19.1

9.2

9.3

9.4

9.5

9.9

/.1