PREPARATION AND REACTIONS OF ALPHA-CYANOALKYL BENZENESULFONATES

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PREPARATION AND REACTIONS OP O^-CYANOALKYL BENZENESULFONATES

A Tiiesis Submitted to the Fac ul ty of the Graduate School of the University of Minnesota

by Karry W. Turner

In Partial Fulfillment of the Requirements for the Degree

of Doctor of Philosophy

September,

19i?l

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ACKNOWLEDGMENT

The author wishes to express his appreciation to Professor R. M. Dodson for the privilege of working under his guidance and for his

aid in the prepca'ation

of this manuscript. Grateful thanks are due to the General Mills Company for their grant of a pre-doct©ral fellowship during the school yoa r 1950-^1 .

Harry W. Turner

ii

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DEDICATION

Dedicated to my wife, a constant source of encouragement; the embodiment of cooperation.

iii

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TABLE OP CONTENTS

Page INTRODUCTION

....................................

PART I: THE SYNTHESIS OP CX-CYANOALKYL BENZENESULPONATES AND THEIR REACTION WITH THIOUREA .

1 2

Introduction ................................

3

Historical ..................................

5

D i s c u s s i o n ..................................

11

Preparation of (X-Cyanoalkyl Benzenes u l f o n a t e s ..............................

11

Preparation of 2,l|.-Diamino-5-substituted T h i a z o l e s .........................

ll|-

Miscellaneous Reactions

20

...............

E xp er i m e n t a l.................. ; .

...

23

Preparation of O^-Cyanobenzyl Benzenesulfonate (II; R = C £ ) H £ ) .................

23

Reaction of O^-Cyanobenzyl Benzenesulfonate (II; R=C£)H^) with Ethanol .. . .

2lj_

Preparation of £^-Cyano-/3 -phenylethyl Benzenesulfonate ( X I ) ...................

26

Preparation of cX.-Cyano- X -phenyl-npropyl Benzenesulfonate(XII) ............

27

Preparation of 2,Ij.-Diamino-5-phenylthiazole Benzenesulfonate(XV) . . . . .

28

Preparation of 2 ,lj.-Diamino-5>-ph.enyl~ thiazole ( X V A ) .........................

28

Preparation of 2,l|.-Diacetamido-5>phenylthiazole .........................

29

Preparation of 2-Amino~5-phenyl-Ij.(5)thiazolone (XVII) .......................

30

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V

Page Preparation of 2 -Acetamido-l^-ace toxy............... 5-phenylthiazole (XVIII)

30

Isolation of cX-Cyanobenzyl Phenyl Sulfone (XXXIIIA) from a Preparation of 2,l|.-Diamino-5-phenylthiazole.........

31

Preparation of 2, lj.-Diamino-5-benzylthiazole Benzenesulfonate (XXI) .........

32

Preparation of 2,1}.-Dian ino-5- ( -phenylethyl)-thiazole Benzene sulfonate ( X X I I ) ................................ 33 Preparation of 2-Arnino-5-benzyl-lf (5) thiazolone (XXIII) ......................

3^

Preparation of 2 -Amino-5-(/3 -phenylethyl)lp(5) - thiazolone ( X X I V ) .............. 35 Preparation of 2,5-Diphenyloxazole (XXV).

3&

Preparation of c*.* -Dicyanostilbene ( X X V I ) ............................

37

PART II: THE SYNTHESIS, AND SOME REACTIONS, OP OC-CYANOBENZYL ARYL (ALICYL) S U L F O N E S ....

39

I n t r o d u c t i o n ..............................

1^.0

H i s t o r i c a l ................................

[|_2

Discussion

........................

Synthesis, and Mechanism of Formation, of 0