Intramolecular ortho group participation

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INTRAMOLECULAR

^ortho

GROUP PARTICIPATION

BY

SUNIL KUMAR JAIN

A THESIS SUBMITTED

IN FULFILMENT FOR THE REQUIREMENTS OF THE DEGREE OF DOCTOR OF PHILOSOPHY

TO THE

Department of Chemistry

INDIAN INSTITUTE OF TECHNOLOGY, DELHI

October, 1983

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DEDICATED TO

MY PARENTS

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200

B 10-DATA

*lam o S un i 1 Kumar Jam Fa ther' s Shri T1. K. ja in Dat-_=, o i--;i_rth December 5, 1957.

Z t 0 n;-) 1 Q t ion s -

7.,s soca un^iversity year o Div.1.. Sian 3-2a

pre .-e(-.1 ica 1 Kuru;:shetra univ.. 1975 ',:, irsL E H ruksh etrc..i .

B .Sc. urukshetre un iv. , 1977 First K,u ruksh et ra .

.Sc. uh Ivo rsity o Roorkee, 1979 First Roorkee

Resc..irch Folia:shiP

JF I.I.T.,Delhi. Aug. 1979 to July 1981 P

S F I • I •T • Delhi Aug. 1901 to present

r-

Tft-mq

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ACKNOWLEDGEI&?.\ITS

The author wishes to express his profound gratitute.

La Dr. Raj Kumar nans11, Assistant professor, Department of Chemistry, Indian Institute of Technology, Delhi, for his

invaluable c!uidance, help and encouragement during the course of this work. But for his help, this thesis would not have at:ained this stage.

Tt is a great pleasure to thank professor „lha, De)artment of Chemistry, for providing the necessary

A debt of gratitute is due to professor F. T;achelor, Deartment of Chemistry, university of Calgary, CaL::ary,

Alberta, Canada, for the mass spectral analysis.

is special thanks are also due to Dr. P. L. Dhar, As::.i':.tiant Director, Regional Research Laboratory, Jammu Tawi and to Dr. C. R. Jagoa, IrT711\1Er', Indian Institute of Technology

T.)4,311i, for the mass spectral analysis of some samples.

The author also takes this opportunity to c:( -)ress his dcti.p .se: :3e. of cfratitute to his family members anu: frinnds for their constant

worc3 of a ^17: 1.Lticin 13 due to r/s ^{Durna P}ingh and f,or theif ^t^•-_,:^;:-^;^(-²⁽³ in run,lin(i; tie !7,7 and IR

(StYrf TL ...;.1 -R

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ABSTRACT

The thesis entitled l'intramolecular ortho-Group T)articiation," has been divided into five chapters.

The first chant :r rives an upto-date survey of the literature on the work regarding a discussion on neinhbouring group 2articipation. Various methods, namely, kinetic measure-

dsolation of products, trapping of intermediates, sereochemieal evidence, spectroscopic methods, etc., whid may he employed to assess participation by a nucleophilic

substituent, have been described in detail with apropriatc

The .second chapter deals with the solvolysis of substituted benzhydryi. bromides. Isomeric ortho- and para- carbuh'anoxy and ortho- and pares- carbeeLhoybehydryi

bruri,iucs were prepared and solvolyzed in aqueOus acetone and aueolin dioxane. The intramolecular participation capacity of caropc:noxy- and carboetho;(1,- groups, when placed at the orthQ- ,7)(Daif-,icrn to thc, reaction site in this sys,i1Els been comarc,ci. An atmLi-, was made to bfominate cnzoic acid to obtain o-carb4)•yin.Znycir;)1 brom]de, i..ui L ,±! product:

ined was 3-1 henyihthalide. The effect of ajing silver nitrate to the reaction medium, on the solvoly rates, was

Iso stuied. The thermodynamic constants were also calCulatcd.

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he third chapter consists of a study on the

selvolysis of isomeric ortho-, meta- and para- nitrobenzal c:iloriOcs one unsubstituted benzal chloride. These nitro- beural chlorides were i.:repared and solvolyzed in aqueous ethanol in order to see if ortho- nitro group would function as an intramolecular nucleophils. The sovelysls was also carcie:, out in the piscence of silver nitrate in order to

effect on the solvolvsis rates.

hc fourth chapter gives an account of the hydrazonc- and ox.i..H.ino- groups as intramolecular nucleophile:',. A ^series oi eleven o-aruylbenzoic acids was prepared and ',:reated

seTar,-2.tely under :juang-hinlon modification of Wolf;.-Kishner recluct.ion and with hydroxylamine hydrochloride respectively.

:-,-;:.:1-11zinoneF: in the first case and the lactones in the

:;eceni case were isolated and characterized by their ^elemental ana siTcc-Lzal analyses. Appropriate mechanisms for their

10;7Mu'ci011 were also po:.;tulated. The fragmentLtion patterns Th:.:usilai./sluonc-c under electron impact were also e:;,..!Tlined.

The last chapter drain with the solvolysi; of

;1 ituLui ch r,ulan c arias. Lnthaiani c cUb, with LJIch as nitc0-, n10Lnv)-, ci,for()-, 1.(..e.c..e6 in the pciLa-po5itiL.. 0 of aniline L inj, ^OCSC

cnc! LAA_v()1y2,c6 in aclueju::, dio::une at Cr ion c s',:cenytll of i.12 p and an apLarent Pi of 6.C.) in orciez to

c;27 thO cmarli.L.:C 65%

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an intramolecular !:,articipant. A Hammett plot was drawn aria a robable mechanism for the reaction was suggested.

Thermodynamic constants were also calculated

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CONTENTS

Page CI-TAT.-TER I

INTP.ODuCTIOm

1.1 vethods of Studying Participation 15

1.1.1 Kinetic Measurements 15

1.1.2 Evidence from product Isolation 25 1.1.3 Isolation or Trapping of Intermediates 29

1.1.4 Stereochemical Evidence 32

1.1.5 Spectroscopic Investigation of Intermediates 36 38

CI IAJ TE R 3.3.

SOLVOLIZSIS OF SUBSTITUTED BENZI-IYDRYL BROMIDES

2.1 INTRODUCTION 47

2.2 EXPERI:-ENTAL 52

o-Eenzoylbenzoic acid (I) 52

p-Nethylbenzophenone (II) 53 p-senzoylbenzoic acid (II3.) 54

o-Denzylbenzoic acid (IV) 55

ID-Benzylbenzoie acid (v) 55

Phenyl o-benzylbenzoate (VI) 56 Phenyl p-benzylbenzoatc (viT) 57 Lthyl o-benzylbenzoate (vI3j) 57 Ethyl p-bcnzylbenzoate (1.;(.) 58

Diphenylmethane (x) 58

romjnation of Diphenylmethane and substituted 59 Diphenylmethanes (General procedure)

3c.,,,n2Thydry/ bromid6., (x.r1 59

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page

(XII) 60

(XIII 60

(XIV) 60

(XV) 60

o.,,carbophenoxybenzhydryl bromide D-Carbophenoxybenzhydryl bromide o-carboethoxybenzhydryl bromide

P-Carboethoxybenzhydryl bromide

12-Carboxybenzhydryl bromide (xvI) 60

3-phenylphtha3.ide (XVII) 61

p-Renzoylthiobenzoate (XVIII) 61

o-Denzoyithiobenzoate 62

o-Benzoylbenzoyl chloride (XXI) 63 Reaction of Acid Chloride with Thiophenol 63 in !pyridine

Reaction of o-Benzoylbenzoic acid with 64 Thiophenol in Denzene

Reaction of Acid Chloride (0(I) with 64 Thiophenol in Benzene

Reaction of Normal Ester (XIX) with 64 Thiophenol in pyridine

Purification of Acetone 64

purification of Dioxane 65

2.2.1 Kinetic Heasurcments 65

2.3 RESULTS Ai'TD 69

REFF:Fr.:„ 90

C7--,ATTER ITT

SOLVOLYS.IS OF ISO■ERIC NITP,01-3EIZAL CHLORIDES ---•-_.--,---•- _.--'-_-_.--___•- -..---•-

3.1 TNTRODuCTIOil 93

3.2 ExpE 95

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Page

0-Nitrobenzaldehyde• (I) 95

P-Nitrobenzaldehyde 96

m-Nitroben z a ldehyde ) 97

Benzal chloride (IV) 98

o-:itrobenzal chloride (V) 98

m-Nitrobenzal chloride (VI) 98

P-Nitrobenzal chloride (VII) 98

Benzyl chloride (VII3) 99

Purification of Ethanol 99

3.2.1 Kinetic mea:-.;urements 100

3.3 PL'SuLTs DISCuSSTMT 103

3.3.1 The Thermodynamic con ^Ant' 113

RE ]E S 117

CHAPTER Iv

I YD RAZO:' 'I — AND C'XI I NC — C P.0 UPS AS INTRA NO LE CU Lz-.1-1 UC LE O Pci I i_E S

4.1 INTRODUCTION 119

4.2 E XrE RI C,ENTAL 121

Ethylbenzene (I) 121

n-propylbenzene 121

iso-Duty.Lbenzene 122

4.2.1 General Procedure for the Preparation 122 of o-Arcylbenzoic Acids

o-Denzoylbenzoic acid (IV) 123

o-(p-methylbenzoyl)benzoic acid (v) 124

• 0-(3,4-Dirnethylbenzov3.)benzoic acid (VI) 124 o-( 2,5-Dimethylbenzoy3.)benzoic acid _(vi):) ₁₂₄

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Page o-(p-Ethylbehzoyl)benzoic acid (VIII) 124 o-[p-(n-propyl)benzoyl]benzoic acid (IX) 125 L o-[^p- (iso-Propyl)benzoyllbenzoic acid (x) ¹²⁵

L_

o- Fp- (iso-F3 utyl)benzoyll benzoic acid ^(XI) 125 1-

o-(p-siphenyloyl)benzoic acid (XII ) 125 o- (cr -Naphthoyl)benzoic acid (XIII ) 126 o- (

5

--Naphthoynbenzoic acid (XIV) 126 4.2.2 General Procedure for the preparation 126

of Substituted Phthalazinones

il-;Theny1-1(21-1)phthalazinone ( ./.7) 127 4-(p-Toly1)-1(2H)phthalazinone ^(XVI)¹²⁷ 4-(3,4-Dimethylpheny1)-1(2H)phthalazinone (XVI1) 127 4- ( p-E thylphen yl) -1 (21-! ) phtha lazinone (Xv111) 128 4_ 1rp- (n-7ropyl) phenyl.] -1(2H ) phthalazinone (XIX) 128

- -

4- rp-(iso-prooy3_)pheny13 -1(2H )phthalazinone (XX) 129 L-

4- [L)-( if.;o-Eutyl)phenyl] -1(2H )phthalazinone (xxi) 129 4-(p-Biphenyly1) -1( 21-I )phthalazinone (7,X11 ) 129 4- ( oc -Naphth y 1 ) -1 ( ) ph tha la z inone ) 130

•

4-( -Naphthy 1 ) -1( 21-1) phtha lazinone (xxlv ) 130

4.2.3 General T,roccdure for the preparation of 131 o- (2, 5-Dimethylbenzyl)benzoic acid (KV./ )

cubstitnted penzoxazones

1-rheny1-2,3-benzoxaz-l-One (XXVI) 131 1- (p-Tolyl ) -2, 3-henzoxaz- 1-one ) 132 (2.,4-Diphenylmetl)yl) -2, 3-benzoxaz-1-ono 132

(XXV13j) 4-(2,5-Dimethylpheny1)-2,3-benzoxa7-1-one

(;;IX)

132

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V

page 4- ( p-E thylpheny1)-2,3-benzoxaz-1-one (x:(7,)

4- rp- (n -Fropyl )phen -2,3-ben zoxaz-1-one (XXXI).

4- p-( iso-propyl) phenyl] -2, 3-benzoxaz-1-one (xXXII)

4-{

- p-(iso-Rutyl)pheny1]-2,3-benzexaz-1-one (XXXII].)

4- ( p-Biphenyly1 )2,3-benzoxaz-l-one (xx:<iv) 134 4:- (cc -qiaph th y 1 ) -2, 3-ben zoxaz 1-on e ) 134 /1-( -Naphthy1)-2,3-benzoxaz-1-one (xxxvi) 135

4.3 RESULTS AND DISCUSS:LC0 136

REFER Nos 145

at A ITE V

hYDROLYSIS OF SUBSTITUTED PHTHALANILIC ACIDS

5.1 INTRODUCTION 117

5.2 1:-.X.FE RI;,:ENTAL 151

5.2.1 General Procedure for the preparation of 151 Phthalan ilic and substituted Phthalanilic Acids

o' -;,lethylphthalanilic acid ( I) 152

phthalanilic acid (n ) 152

-Chloronhthalanilic acid (II]) 152 p1 -1litrophthJA.anilic acid ( iv ) 152

5.2.2 The ;Jnetic 153

5.2.3 Prep:!rat ion of si-substituted Ph tha 154 5.2.4 The Product , o f 1ydrclysis of p' -Eubstituteci 155

itythalanilic acids

5.3 RE:.)ULTS AND DISCUSS:IC/I: 157

133 133 133 134

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Page 5.3.1 Linear Free Energy Relationship 160 5. 3. 2 Thermodynamic Constants 16 3 5.3.3 I.c.echanism of the Hydrolysis of phthalanilic 163

Acids

Pd-7 NCES 16 7

IX 16 9

LIST OF 1.11BLICATIONS- 199

IC -DATA 200