The Reaction of Some Ketones and Aldehydes with Dioxane Sulfotrioxide

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PU R D U E UNIVERSITY

T H IS IS TO C E R T IF Y TH A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS IO N

B Y ______________

C harles C, f t l f i e r l _______ _______________ _____

e n t i t l e d __________ T O -B S A G J I ON OF

SOME KETONES

AND

ALDEHYDES-__

__________________ WITH DIOXANE SULFOTRIOXIDE________________

C O M P L IE S W IT H T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D IS A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FOR THE DEG REE OF

____________________ Doctor o f Philosophy_______________________

v

V L /G C /C j& j

P

H

June /

r o f e s s o r in

ead o f

S

Charge

chool or

D

of

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e s is

epartm ent

19 50

TO T H E L IB R A R IA N :---T H IS T H E S IS IS N O T TO B E R E G A R D E D A S C O N F ID E N T IA L .

P R O F E SSO R IX CHARGE

G B A D , S C H O O L F O R M 9 —3 - 4 9 —1M

THE REACTION OF SOME KETONES AND ALDEHYDES WITH DIOXANE SULFOTRIOXIDE A T h esis Submitted t o th e F a cu lty of Purdue U n iv e r sity by C harles C. A l f i e r i In P a r t ia l F u lfillm e n t o f th e Requirements f o r th e Degree of D octor o f P hilosophy June, 1950

ProQuest Number: 27712249

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ACKNOWLEDGMENT

The author w ish es t o exp ress h is g r a titu d e t o D r, W illiam E, Truce under whose guidance t h i s work was conducted.

He i s a ls o in d eb ted to t h e Purdue R esearch

Foundation and t h e R esearch Corporation f o r th e f in a n c i a l support o f t h i s in v e s t ig a t io n .

TABLE OF CONTENTS Page ABSTRACT S u lfo n a tio n o f K etones.

I.

A ryl Methyl K e t o n e s ............................i

S u lfo n a tio n o f Ketones and Aldehydes I I ...................... INTRODUCTION

ix

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

1

DISCUSSION........................................................................................................................ 3 Mechanism o f R e a c t i o n ...............................................................................

6

EXPERIMENTAL S u lfo n a tio n o f Acetophenone

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

8

P reparation of S-Benaylthiuronium S a l t s ........................................... 10 S u lfo n a tio n o f 2 -A c e to th ie n o n e ............................................................. . 1 0 S u lfo n a tio n of

^ -A c e to n a p th o n e ......................................................... * 1 1

S u lfo n a tio n o f A c e to m e s ity le n e .....................

. . . 1 3

P reparation o f Sodium- u ) -K e to n e su lfo n a tes by th e Displacem ent R eaction ........................... . . . . . . . . . . . . 1 5 S u lfo n a tio n o f P i n a c o l o n e ................................................ M odified Procedure fo r S u lfo n a tio n o f Acetone

........................... 1?

M odified Procedure f o r S u lfo n a tio n o f Cyclohexanone S u lfo n a tio n o f P rop iop h en on e.....................

15

. . . .

18 .1 9

S u lfo n a tio n o f I s o b u ty r o p h e n o n e .......................................................... 2 1 S u lfo n a tio n of Phenylacetaldehyde S u lfo n a tio n o f Isobutyraldéhyde S u lfo n a tio n o f Heptaldehyde

. . . . . . . . . . . . . 2 2 .................................... . . . . . 2 3 .........................................................25

Cleavage o f Sodium Aldehyde- oL - S u l f o n a t e s ....................................... 26 S u lfo n a tio n o f g -T o ly l Methyl Su lfon e

............................................. 27

S u lfo n a tio n o f Pivalophenone .................. . . . . . . . . . . . 2 8

TABLE OF CONTENTS (con tin u ed ) Page MISCELLANEOUS S u lfo n a tio n o f Camphor.............................

29

S u lfo n a tio n o f Camphorquinone

30

.

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

S u lfo n a tio n o f B e n z a la c e t o n e ...................................................................... 31 S u lfo n a tio n o f T h io p h en e ................................................................

32

Attempted S u lfo n a tio n o f 2-N itroth iop h en e . . . . . . . . .

3h

Cleimnensen R eduction o f Sodium AcetophenoneAttempted S y n th e sis o f

Ç -K e to su lfo n e s

.

-S u lfo n a te

.

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

SUMMARY................................................................................................ BIBLIOGRAPHY VITA

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

35 36 37 38

AN ABSTRACT (C on trib u tion from th e Department o f Chem istry, Purdue U n iv e r s ity ) S u lfo n a tio n o f K etones, I . A ryl Methyl Ketones by W illiam E . Truce and C. C, A lf ie r i^

(l)

This work i s taken from th e t h e s i s t o b e subm itted i n p a r t ia l f u lf illm e n t o f th e requirem ents f o r t h e Doctor o f P hilosophy d eg ree. This paper was p resen ted b e fo re th e D iv is io n o f Organic Chemistry a t th e 116 th M eeting o f th e American Chemical S o c ie t y , A tla n tic C ity , September, 19h9« T his paper r e p o r ts on t h e r e a c tio n o f dioxane s u lf o t r io x id e

w ith a r y l m ethyl k etones lea d in g to th e form ation o f a c id s .

P -k e to s u lfo n ic

Analogous r e a c tio n s have b een observed i n a few is o l a t e d

c a ses p r e v io u s ly .

Acetophenone-

iP - s u lf o n ic a c id has been obtained

by t r e a tin g a s o lu tio n o f acetophenone in a c e t ic anhydride and e th er w ith 1$% oleum a t 0 °.^

(2 )

The a c tio n o f c h lo r o s u lf o n ic a c id

Doering and B erin ger, This Journal, 71, 2221(19k 9).

on acetophenone has produced th e 2 , U? - d is u lf o n y l c h lo r id e , w h ile acetop h en on e-U -su lfon ic a cid w ith c h lo r o s u lfo n ic a c id has probably formed t h e It, CD - d is u lf o n y l c h lo r id e .^

(3 )

The su lfo n a tio n o f

Weston and S u te r , i b i d . , 6 l , 389 (1 9 3 3 ).

acetophenone w ith

oleum a t tem peratures which do n o t cause

clea vage ( t o a c e t ic a c id and benzene s u l f o n i c a c id ^ ), has y ie ld e d

(it)

K rek eler, B er. , 1 9 , 676 , 2627 (1 8 8 6 ).

a m ixture o f ortho and meta acetop h en on esu lfon ic a c id s . Acetophenone, 2-a c e to th ie n o n e , and a c e to m e sity le n e were converted to th e corresponding sodium u )-k e to n e s u lfo n a te s i n approxim ately 70% y i e l d s ( r e c r y s t a lliz e d ) b y treatm en t w ith dioxane s u lf o t r io x id e fo llo w e d by n e u t r a liz a tio n . y ie ld e d a m ixture o f p roducts.

(5 -A cetonapthone

One o f t h e s e products was shown

to b e th e expected sodium P -aceton ap th on e- ^ - s u l f o n a t e , w h ile another product was a d is u lf o n a t e .

Presumably th e second s u lfo n ic

acid group entered th e n o n -su b stitu te d r in g i n th e n u c le u s. The str u c tu r e s o f t h e s e a c id s were proved b y preparing t h e ir S-benzy Ith iu r o n iu m s a l t s and comparing th an w ith s im ila r s a l t s obtained from a u th en tic samples o f th e s e a c id s .

The a u th e n tic

samples were prepared by t r e a t in g th e corresponding U? -bromoketones w ith sodium s u l f i t e .

The str u c tu r e s o f sodium u )-a c e to p h e n o n e su lfo n a te

and sodium 2 -a ee to th ie n o n e —(X?—s u l f onate were fu r th e r proved by treatm ent w ith sodium iy p o io d it e s o lu t io n .

N eith er one gave

iodoform; however, b en zo ic acid and 2-th io p h e n e c a r b o x y lie a c id were recovered from th e r e a c tio n m ix tu res.

Sodium h y p o io d ite

s o lu tio n d id n ot c le a v e sodium u )-a c e to m e s ity le n e s u lf onate.'*

(5 )

Johnson and Fuson, This Journal, 5 7 , 919 (1 9 3 5 ).

B o ilin g sodium Q -a c e to m e s ity le n e s u lfo n a te f o r fo u r te e n hours n it h 20 ^ sodium hydroxide s o lu tio n produced no c le a v a g e of th e compound

to th e expected sodium m esito a te and sodium m ethanesulf o n a t e ^ th u s

( 6 ) S u te r , Evans and K ie fe r , i b i d . , 60, 538 (1 9 3 8 ).

fu r th e r dem onstrating th a t th e carbonyl group i n t h is compound i s so s t e r i c a l l y hindered as t o b e p r a c t ic a lly immune t o a tta c k by rea g en ts which must f i r s t add t o th e carbonyl carbon

(7)

Kohler and B a lt z ly , i b i d . , 5U, U015 (1 9 3 2 ).

(8 )

Lock and Schreckeneder, B er. , 72B, 511 (1939)♦

(9 )

Kadesch, This Journal, 6 6 , 1207 (19UU).

a t o m

.

The b e s t method o f p rep arin g sodium (X? -a c e to m e s ity le n e s u lfo n a te i s by th e d ir e c t s u lfo n a tio n o f a c e to m e sity le n e w ith dioxane s u l f o t r i oxide as describ ed h e r e in .

D isplacem ent o f th e bromine atom i n

Ia7 -brom oacetom esitylene by sodium s u l f i t e d id n o t proceed s a t i s ­ f a c t o r i l y even a t r e f lu x tem peratures.

Although th e n u c le o p h ilic

displacem ent i s ta k in g p la c e on th e carbon atom ad jacen t t o th e carbonyl group, apparently th e r e i s s t i l l s u f f i c i e n t s t e r i c in t e r ­ fe r e n c e a t t h i s p o s it io n to a f f e c t the r a te of r e a c tio n and reduce th e y i e l d . The course of t h i s r e a c tio n appears t o b e sim ila r t o th e

mechanism "which has been proposed fo r th e a c id —c a ta ly z ed brom ination o f k e to n e s . 10

(10)

This would in v o lv e an e n o la te -ty p e s tr u c tu r e as

Hammett, 11P h y sic a l Organic Chem istiy", McGraw-Hill, New York, N .I ., I W , p . 96.

an in te r m ed ia te. ArC0CH3

A

4

ArC-CH^

SO-rSf

ArOCHo ÔA” #

-4

A+

ArCOCHgSO^-

-4

ArCOCHgSO^H

B

4

Dioxane s u l f 0 t r i 02d.de r e a g e n t.

"A" may be SO^ or H* MBrt may b e OC^HgO, ArCOCH^ or -5 0 ^ . Support f o r t h i s h y p o th esis i s o ffe r e d by th e f a c t th a t methyl g - t o l y l su lfo n e i s i n e r t toward t h i s r e a g e n t.

Apparently an

analogous e n o la te -ty p e s tr u c tu r e cannot farm s in c e i t would in v o lv e expansion o f th e s u lfu r v a le n c e s h e ll from e ig h t to t e n e le c t r o n s , ■> T

Su lfu r i s r e lu c ta n t to undergo such a change.

TO

9

Furthermore,

(1 1 )

Z ie g le r and Conner, This Jou rn al, 6 2 , 2596 ( 191*0).

(1 2 )

Kohler and T is h le r , T h is Journal, 57* 218 (1 9 3 5 ).

pivalophenone, which c o n ta in s no alpha hydrogen atoms and th e r e fo r e i s in cap ab le o f forming an e n o la te -ty p e s tr u c tu r e , i s a ls o in e r t toward t h i s r e a g e n t.

V

Acknowledgment.

-

The authors w ish t o thank th e Purdue Research

Foundation and t h e R esearch Corporation f o r p rovid in g funds which made t h i s work p o s s ib le .

Preparation o f Dioxane S u lf 0 t r i 02d.de R eagent. - E x a c tly 0 .3 5 mole o f dioxane s u lf o t r io x id e reagen t was prepared accord ing

t o d ir e c t io n s given i n th e l i t e r a t u r e . ^

(1 3 ) B ordw ell and R ondestvedt, T his Journal, 70, 2lt29 (I9 lt8 ).

S u lfo n a tio n o f Acetophenone. - The p rev io u sly -p rep a red dioxane s u lf o t r io x id e was allow ed t o reach room tem perature and 0.35 mole (li2 g . ) o f acetophenone was added a t a r a te such th a t th e tem perature o f th e r e a c t io n m ixture never exceeded 3 5 ° .

A ll

th e acetophenone was added w ith in an hour; th e m ixture was s tir r e d fo r two more hours and then hydrolyzed b y pouring in to 300 m l. of w ater.

The organic la y e r was sep arated , washed w ith w ater, d r ie d ,

and th e eth ylen e c h lo r id e s o lv e n t was evaporated.

About 1 g. o f a

p a le y e llo w s o li d remained; i t was r e c r y s t a ll iz e d from e th y le n e c h lo r id e and i t m elted a t 158 ° . A nal.

Found:

C, 6 3 .6 ; H, U.60; S, 1 1 .1 $ .

The aqueous la y e r was n e u tr a liz e d t o a pH o f 7 w ith c o ld sodium hydroxide s o lu tio n .

The aqueous la y e r was then evaporated

to dryness by blowing a stream o f a i r over i t .

The s o l i d mass

vi

which remained was e x tr a c te d w ith a b o ilin g 60 $> a lco h o l-w a te r m ixtu re.

Upon c o o lin g t h e a lco h o l-w a te r s o lu t io n , c r y s t a ls o f

sodium u? -a ceto p h en o n esu lf onate se p a r a te d .

The y i e l d was 5h

grams which rep resen ted a 70$ con version f o r t h i s r e a c t io n .

A

s im ila r procedure was u sed i n th e s u lfo n a tio n o f 2 -a c e to th ie n o n e , a ceto m esity len e and

@ -acetonaphthone.

A nalyses of sodium s a l t s : 1.

Sodium

-a ceto p h en o n esu lf onate : Ha, 1 0 .3 6 .

A nal. C alcd. f o r CgHnO^SKa: Found: Ha, 10.57> 1 0 .oO.

2.

Sodium 2 -a ce to th ie n o n e - ^ - s u lf o n a t e : A nal. Calcd. f o r C^Hc;0 ),S^Ha: Ha, 1 0 .1 0 . Found: Ha, 1 0 .3 8 , 1 0 .3 8 .

3.

Sodium tO -a c eto m esity le n e s u lf on ate: A nal. C alcd. fo r Ha, 8 .7 1 . FoundT" Ha, 8 .7 0 , 8 .6 0 .

I4 .

Sodium Q - acetonaphthone- s u lf o n a t e : A nal. Calcd. f o r O^gHnOkSNa: Ha, 8.U 5. A n al. Calcd. fo r ci 2 H807S2^a2 : 1 2 .3 0 .

SNa:

Found: Ha, 1 1 .U, 11*ll.

P reparation o f S-Benzylthiuronium S a l t s . - Approxim ately 0 .2 g . o f th e sodium s u lfo n a te was d is s o lv e d i n 5 m l. o f w ater.

In another

t e s t tube 0 .2 g. of S-bensylthiuronium c h lo r id e was d is s o lv e d i n 5 m l. of w ater.

The two s o lu tio n s were m ixed, th e p r e c ip it a t e was

f i l t e r e d and r e c r y s t a lliz e d from 25 m l. o f w ater which con tain ed one drop o f 10$ hyd roch loric a c id .

In some c a s e s i t was n ecessa ry t o

blow a stream o f a i r over th e s o lu tio n i n order t o induce th e s a l t t o p r e c ip it a te ; however, once a few c r y s t a ls had form ed, th e remainder o f t h e s a l t c r y s t a lliz e d upon c o o lin g th e s o lu t io n . S-Benzylthiuronium s a l t s : 1.

S-Benzylthiuronium -a ceto p h en o n esu lfo n a te: M.P. 1 5 2 °. A nal. Calcd. f o r : H, 7 .6 7 . Found H, 7 .5 7 , 7*52.

2.

S-Benzylthiuronium 2 -a c e to th ie n o n e - (a7 -s u lfo n a te : M.P. ll|0 o . A nal. Calcd. fo r N, 7 .5 3 . Found: N, 7.1)6.

3.

S-Benzylthiuronium u ô -a c e to m e s ity le n e s u lfo n a te : M.P. 1 6 0 °. A nal. Calcd. f o r C^pHg^O^SgNg: N, 6 . 8 6 . Found: N, 6 . 8 3 .

I4.

S-Benzylthiuronium P -aceton ap th on e- U ^ -su lfo n a te: A nal. Calcd. f o r CgoHgQOkSgHg: N, 6 .7 3 A nal. Calcd. f o r C^gHmC^Si.Ni, : N, 8 .I 1.6

FSSd:

N, 8.11, SZIii.

M.P. 2 0 6°.

4 4

P reparation o f th e Sodium & -K e to n e su lfo n a tes b y t h e D isp la c e ­ ment R eaction . -

Sodium cD -aceto p h en o n esu lfo n a te was prepared as

d escrib ed i n th e l i t e r a t u r e . ^

( ill)

Sodium 2- u ^ -a c e to th ien o n e su lfo n a te

Parkes and T in s le y , J. Chem. S o c ., l 86 l (I93i+).

was prepared as f o llo w s :

To 0 .2 mole (I4I g .) o f 2- tà -brom oaceto-

th ien o n e, th e re was added a s o lu t io n o f 25 g . of sodium s u l f i t e i n 100 m l. o f w ater. o v ern ig h t.

The r e a c tio n f la s k was p la c ed on th e steam b ath

The n ex t morning th e h o t s o lu tio n was f i l t e r e d and th e

sodium s a lt o f the acid c r y s t a lliz e d from th e c h i l l e d f i l t r a t e . same procedure was used t o prepare sodium

The

W -a c e to m e sity le n e ­

s u l f o n a te, th e only d iffe r e n c e b ein g th a t t h i s s o lu t io n was r e flu x e d . The s o lu tio n was th en evaporated t o dryn ess and th e r e s u lt in g mass was e x tr a c te d w ith a b o i li n g 60$ a lco h o l-w a ter m ixtu re. water s o lu tio n was c o o le d and a few c r y s t a ls o f sodium s it y le n e s u lf onate p r e c ip it a te d .

^ -acetom e­

2- tO —Brom oacetothienone was

prepared b y th e method o f B ru n sw ig;^

(15)

The a lc o h o l-

Brunswig, B e r ., 1 9 , 2890 (1 8 8 6 ).

u? -brom oacetom esitylene

was prepared in an analogous manner. SUMMARY 1. and

Four k e to n e s, acetophenone, 2 -a c e to th ie n o n e , a c e to m e sity le n e , P -a ceto n a p th o n e, have been su lfo n a te d u sin g d ioxane s u lf o ­

t r io x id e .

For th e f i r s t th r e e k e to n e s, th e corresponding sodium

(4) -k e to n e su lfo n a te s have b een is o la t e d a s the p r in c ip a l products in approxim ately 70$ y i e l d s ( r e c r y s t a l li z e d ) .

In th e c a s e o f

F -aceton ap th on e, a m ixture o f s u lfo n a te s was ob tain ed . 2.

A mechanism has been proposed f o r th e course o f t h i s r e a c t io n .

L a fa y e tte , Indiana

AN ABSTRACT (C on trib u tion from th e Department of Chemistry, Purdue U n iv e r sity ) S u lfo n a tio n o f Ketones and A ldehydes.

II

by W illiam E. Truce and C. C. A lf ie r i^

(l)

This work i s taken from Mr. A l f i e r i *s Ph.D. t h e s i s .

Dioxane s u lfo t r io x id e r e a c t s w ith a r y l m ethyl keton es t o form

(2 )

^ - k e t o s u lf o n ic a c id s , i . e . , ArCOCHgSO^H.^

This r e a c tio n

Truce and A l f i e r i , This J ou rn al,72, 0000 (1 9 5 0 ).

has now been extended t o se v e r a l oth er keton es and s e v e r a l aldehydes P in acolon e, propiophenone and isobutyrophenone were converted in approxim ately 70% y i e l d s by th e p r e v io u sly d e scrib ed procedure^ to th e corresponding c r y s t a llin e sodium k e to n e su lfo n a te s , i . e . , (CH3 ) 3 C0 CH2 S03 Na, C^COCHfCH^SOÿîa and C^COCCCH^SO^Ta, r e s p e c t iv e ly .

S im ila r r e s u lt s were ob tain ed w ith aceton e and

cyclohexanone ; however, i t was more d i f f i c u l t t o o b ta in a pure product in th e se c a s e s . The d ir e c t s u lfo n a tio n o f an a lip h a t ic aldehyde has not been p r e v io u sly rep o rted .

Dioxane s u lf o t r io x id e was found to

r e a c t w ith p h enylacetaldehyde, heptaldehyde and isob u tyrald éh yd e to fo r a th e corresponding sodium aldehyde- 6 - d is u lf o n ic a cid a t l 60 ° . 3- p o s it io n .

3 -Methylcoumarin a lso formed

6 -N itrocoum arin su lfo n a te d i n th e

li-M et]^ l-,i 4, 7- d im e th y l- , 3 , L , 7 ,-tr im e t]g r l-, and lt-m ethyl-

7 -methoxycoumarin a l l su lfo n a te d in th e 6- p o s it io n , w h ile U,6 -

dimethylcoumarin gave th e 8- s u lf o n i e acid ( 5 ) . An in v e s t ig a tio n c a r rie d ou t on a d ia r y l k e to n e , which was o f i n t e r e s t to th e p resen t work, was the s u lfo n a tio n o f p h eryl ketone w ith 95% s u lfu r ic a c id a t 2 0 °.

q C -n a p h tb y l-

At 160-170° h y d r o ly sis

occurred to b en zoic a c id and napthalene d is u lf o n ic a c id s ( 6 ) . In view o f the v ariou s r e s u lt s obtained i n th e s u lfo n a tio n o f k eto n es, depending on th e co n d itio n s and s u lfo n a tin g agents employed, and on th e s tr u c tu r e o f th e k eto n e, fu r th e r s tu d ie s i n t h is f i e l d appeared t o be in order.

The d ir e c t s u lfo n a tio n o f an a lip h a tic

aldehyde has n o t been rep o rted .

This t h e s i s rep o rts on th e r e a c tio n

o f dioxane s u lf o t r io x id e w ith ketones and aldehydes le a d in g t o the form ation o f k eton e- and a ld e h y d e -su lfo n ic a c id s .

3

DISCUSSION Âcetophenone, 2 -a c e to th ie n o n e , and a c e to m e sity le n e were converted to th e corresponding sodium u) -k eto n esu lfo n a b e s in approxim ately 70% y i e l d s ( r e c r y s t a lliz e d ) *

Sodium

-acetophenone-

su lfo n a te has been p r e v io u sly reported ( 7 ) , w h ile th e l a t t e r two compounds have to our know ledge, not been p r e v io u sly reported* The s tr u c tu r e s o f th e s e s u lfo n a te s were proved b y preparing t h e ir S-benzylthiuronium s a l t s and comparing them w ith th e Sbenzylthiuronium s a l t s obtain ed from a u th en tic samples o f th e se s u lfo n a te s . corresponding

The a u th e n tic samples were prepared by tr e a tin g the u)-brom oketones w ith sodium s u l f i t e .

The str u c tu r e s

o f sodium lO -acetop h en on esu lfon ate and sodium 2 -a c e to th ie n o n e - (x) su lfo n a te were fu r th e r proved by t r e a t in g th e se s a l t s w ith a lk a lin e sodium h y p o io d ite s o lu tio n .

N either one gave iodoform; however, th e

a lk a lin e r e a c tio n m ixture was a c id if ie d and e x tr a c te d w ith e th er and th e corresponding b enzoic acid and 2-th io p h en eca rb o x y lic a cid were recovered from the e th er e x tr a c t s .

With sodium iO -a c e to m e s ity le n e -

s u lfo n a te , s t e r i c hindrance apparently prevented th e iodoform r e a c tio n from occu rrin g ( 8 ) .

L ik ew ise, b o ilin g sodium

U)-acetom e-

s it y le n e s u lf o n a te fo r fo u r te e n hours w ith 20% sodium hydroxide s o lu tio n produced no clea v a g e o f th e compound to th e exp ected sodium m esito a te and sodium m ethanesulfonate ( 9 ) , thus fu r th e r dem onstrating th a t th e carbonyl group i n t h i s compound was so s t e r i c a l l y hindered as to b e p r a c t ic a lly immune to a tta c k by rea g en ts w hich must f i r s t add to th e carbonyl carbon atom (1 0 ) ( 1 1 ) ( 1 2 ) .

h

The b e s t method o f preparing sodium U )-a c e to m e sity le n e su lfo n a te i s by th e d ir e c t s u lfo n a tio n o f a c e to m e sity le n e w ith dioxane s u lf o t r io x id e as d escrib ed herein. bromine atom i n

D isplacem ent of the

oO-brom oacetom esitylene by sodium s u l f i t e d id n ot

proceed s a t i s f a c t o r i l y even a t r e flu x tem p eratu res.

The in d ic a tio n

was th a t although th e n u c le o p h ilic d isp lacem en t was ta k in g p la c e on th e carbon atom adjacent to th e carbonyl group, th e r e was s t i l l s u f f i c i e n t s t e r i c in te r fe r e n c e a t t h i s carbon atom t o a f f e c t th e r a te o f r e a c tio n and th u s reduce t h e y i e l d . Another in t e r e s t in g fe a tu r e o f t h is s u lfo n a tio n r e a c tio n was th a t although 2-a c e to th ie n o n e and a c e to m e sity le n e had p o s itio n s i n th e nucleus which were s t i l l com p aratively s u s c e p tib le t o a tta c k , the p r in c ip a l p o in t of attack was th e m ethyl group. con n ection , when

In t h i s

Ç -acetonapthone was s u lfo n a te d w ith dioxane

s u lfo t r io x id e , a m ixture o f products was ob tain ed . products was shown t o b e th e expected sodium

One o f th e s e

Ç -a ce to n a p th o n e -^ -

s u lfo n a te , w h ile another product was a d is u lf o n a t e .

Presumably

the second s u lfo n ic a c id group en tered th e n on -su b stitu b ed r in g in th e nucleu sj however, th e p o s it io n o f t h i s group has n o t been e s ta b lis h e d . P in acolon e, propiophenone and isobutyrophenone were converted in approxim ately 70% y i e l d s t o th e corresponding c r y s t a llin e sodium k e to n e su lfo n a te s , i . e . , ( CH^^COCHgSOÿîa, C^H^COGHCGH^)S0^Na and C^H^COCCCHj^SOjHa, r e s p e c t iv e ly .

S im ila r r e s u lt s were ob tain ed

w ith acetone and cyclohexanonej however, i t was more d i f f i c u l t to ob tain a pure product i n th e se c a s e s .

5

The d ir e c t s u lfo n a tio n o f an a lip h a tic aldehyde has n o t been p r e v io u sly r e p o r te d .

Dioxane s u lf o t r io x id e was found to r e a c t

w ith p h en ylacetald eb yd e, heptaldehyde and isob u tyrald éh yd e to form th e corresponding sodium a l d e h y d e - - s u l f o n a t e s in f a i r y i e l d s . The s tr u c tu r e s o f sodium p in a co lo n e- o f - s u lf o n a t e , sodium propiophenone- oC - s u lf o n a t e , and sodium isobutyrophenone- çC s u lfo n a te were proved by preparing t h e ir S-benzylthiuronium s a l t s and comparing them w ith sim ila r s a lt s obtained from a u th e n tic samples o f th e s e s u lf o n a t e s .

The au th en tic samples were prepared

by t r e a t in g th e corresponding

-bromoketones w ith sodium s u l f i t e ( 1 3 ) .

(With oC -bromopropiophenone and oC -brom oisobutyrophenone, th e y i e l d s obtained by th e displacem en t r e a c tio n were p oor, and th e r e a c tio n took p la c e v e r y s lo w ly . )

Furthermore, on t r e a t in g sodium

p in a co lo n e- o C -su lfo n a te w ith sodium h y p o io d ite s o lu tio n no iodoform was obtained; however, p iv a lic acid ( id e n t i f i e d through i t s a n ilid e ) was recovered from th e r e a c tio n m ixture. propiophenone-

Sodium

- s u lf o n a t e and sodium isob u tyrop h en on e- (X -

s u lfo n a te were o x id iz e d w ith a lk a lin e permanganate t o ben zoic a c id , thus fu r th e r dem onstrating th a t su lfo n a tio n had occurred on th e s id e ch a in . The str u c tu r e o f sodium a ceto n e su lfo n a te was proved by clea v a g e w ith 20% sodium hydroxide s o lu tio n ( 9 ) aixl subsequent i d e n t i f ic a t io n of th e cleavage p rod u cts. o f sodium phen ylaeetald eh yd e-

S im ila r ly , th e str u c tu r e s

- s u lf o n a t e and sodium heptald eh yde-

oC - s u lf o n a t e were proved by cleavage w ith 20% sodium hydroxide

6

s o lu t io n .

The clea v a g e products in t h is case were form ic a c id

and th e corresponding sodium a lk a n e s u lfo n a te s , i d e n t i f ie d through i t s

Formic a c id was

£ -bromophenacyl e s t e r w h ile sodium - i J -

to lu e n e s u lfo n a te and sodium hexane- 1 - s u lf o n a t e r e s p e c t iv e ly were i d e n t i f ie d b y preparing t h e ir S-benzylthiuronium s a l t s and comparing them, w ith sim ila r s a l t s obtain ed from a u th e n tic samples o f th e s e s u lfo n a t e s .

Sodium phenylac e t aldehyde- ol - s u lf o n a t e

was a lso o x id ized w ith a lk a lin e permanganate to b en zoic a c id , in d ic a tin g th a t su lfo n a tio n had occurred on the s id e c h a in . F in a lly , th e sodium aldehyde-

- s u lf o n a t e s a l l gave p o s it iv e

S c h i f f ’ s and T o lle n s ' t e s t s f o r th e p resen ce o f an aldehyde group. The s tr u c tu r e s of sodium eyclohexanone- e8°. Anal. Found:

C, 6 3 .6 3 H, U.60; S , 11.U 9.

The aqueous la y e r was n e u tr a liz e d t o a pH of 7 w ith co ld hydroxide s o lu t io n .

The aqueous la y e r was th en evaporated t o dryness

by blow ing a stream o f a i r over i t .

The s o li d mass w hich remained

was ex tr a c ted w ith a b o ilin g 60% a lco h o l-w a ter m ixture, le a v in g Ik g . o f sodium s u lfa t e as a r e sid u e .

Upon c o o lin g t h e a lc o h o l-

w ater s o lu t io n , c r y s t a ls o f sodium Ut2 -acetop h en on esu lfon ate sep arated .

The y i e l d was $k grams which rep resen ted a 70% con­

v e r sio n fo r t h i s r e a c tio n . The stru ctu re o f t h i s compound was proved by o x id a tio n to b enzoic a c id w ith sodium h y p o io d ite .

The S-b e n z y lth iu r onium s a l t s

o f t h i s compound and an a u th en tic sample o f sodium

U ?-acetophenone­

su lfo n a te were prepared and th e y m elted a t 152 ° and l 5 0 ° r e s p e c t iv e ly . A mixed m eltin g p o in t o f th e s e s a l t s was not depressed (m .p. 15>0°). The sodium ü) -acetop h en on esu lfon ate prepared from t h i s r e a c tio n m elted w ith decom position a t 260 ° which i s i n agreement w ith th e v a lu e reported i n th e l it e r a t u r e ( 7 ) . A n alysis o f sodium s a l t : Sodium W -acetop h en on esu lfon ate: Na, 1 0 .3 6 .

Found:

A nal. Calcd. fo r CgHyOj^SNa:

Na, 1 0 .5 7 , 1 0 .6 0 .

A n alysis o f S-B e n z y lth iu r onium s a l t : S-Benzylthiuronium i P -a ceto p h en o n esu lfo n a te: A nal. Calcd. fo r C^H^yO^SgHg: N, 7 .5 7 , 7 .5 2 .

M.P. 152°

N, 7 .6 7 .

Found:

10

Preparation of S-Benzylthiuroniom S a l t s . - Approxim ately 0 .2 g . o f th e sodium s u lfo n a te was d is s o lv e d in 5 m l. o f w ater.

In another t e s t tube 0 .2 g . o f S-benzylthiuronium c h lo r id e was d is so lv e d in 5 m l. o f w ater.

The two s o lu tio n s were m ixed, th e

p r e c ip it a te was f i l t e r e d and r e c r y s t a lliz e d from

25 m l. of w ater

which contained one drop of 10% h ydrochloric a c id .

In some c a ses

i t was n ecessa ry to blow a stream o f a ir over th e s o lu t io n i n order to induce th e s a l t to p r e c ip it a te ; however, once a few c r y s t a ls had formed, t h e remainder o f th e s a l t c r y s t a l li z e d upon c o o lin g th e s o lu tio n . S u lfo n a tio n o f 2 -A cetoth ien on e: - E xactly 0.325 mole o f dioxane s u lfo t r io x id e was prepared.

The reagen t was allow ed to

reach room tem perature and lj.0^95 ( 0 .3 2 5 mole) o f 2 -a c e to th ie n o n e was added a t a r a te such t h a t th e tem perature o f th e r e a c tio n m ixture never exceeded 3 5 °•

S t ir r in g was continued fo r two hours a f t e r th e

l a s t a d d itio n of k eton e.

A fter th e i n i t i a l r e a c tio n occurred, th e r e

was s t i l l a p r e c ip it a te in th e r e a c tio n f l a s k .

At f i r s t i t was

thought th a t t h i s p r e c ip it a t e was unreacted dioxane s u lf o t r io x id e which i s a ls o a s o lid ; however, t h is s o li d d id n ot behave l i k e th e rea g en t.

I t was com p letely hydrolyzed by water and ap p aren tly i t

was a coord in ation compound o f th e s u lfo n ic a c id , formed in t h i s r e a c tio n , w ith dioxane.

The r e a c tio n m ixture, c o n ta in in g t h i s

s o l i d , was hydrolyzed by pouring i t in to 300 c c . o f w ater.

The

organic la y e r was sep arated , washed w ith w ater, and d r ie d .

E thylene

c h lo rid e was d i s t i l l e d o f f and 11 g . o f unreacted 2-a c e to th ie n o n e

11

■was recovered .

The aqueous la y e r was n e u tr a liz e d to pH 7 w ith a

c o ld sodium hydroxide s o lu tio n .

The aqueous la y e r was then

evaporated t o dryness by blow ing a stream of a i r over i t .

The

s o li d mass which remained was ex tr a c ted w ith a b o ilin g a lc o h o lwater m ixture, le a v in g 20 g . of sodium s u lf a t e as a r e s id u e .

Upon

c o o lin g the a lco h o l-w a ter s o lu t io n , c r y s t a ls o f sodium 2-acetoth ien on eu ) -s u lf o n a te sep arated .

The y i e l d o f sodium 2 -a ce to th ie n o n e - oO -

s u lfo n a te based on th e amount of 2 -a ce to th ie n o n e which rea cted was 38 g . or 70$.

The str u c tu r e o f t h i s compound was proved by o x id a tio n to 2 -th iop h en ecarb oxylic a c id (M.P. 12 9 °) u sin g a lk a lin e sodium h y p o io d ite .

No p o s it iv e iodoform t e s t was g iv en by t h is compound.

The S-benzylthiuronium s a l t o f t h i s compound was prepared and i t was checked w ith th e S-benzylthiuronium s a l t o f an a u th e n tic sample o f t h i s compound prepared by an independent s y n t h e s is . There was no d ep ression o f m eltin g p o in t (M.P. II4.O 0 ) . Sodium 2 - a c e t o th ie n o n e - u ) -s u lfo n a te : c6% °iiS2Na:

Na> 1 0 *1 0 -

A nal. Calcd. f o r

Found:

Na, 1 0 .3 8 , 1 0 . 3 8 .

S-Benzylthiuronium 2 -a ce to th ie n o n e - w ? -s u lfo n a te : A n al. Calcd. fo r cij 4Hi 6 °l4^3^ 2 : Found: S u lfo n a tio n of

^

M.P. IJ4O0 .

7»5>3«

N, 7 . It6 .

P -A cetonapthone.

dioxane s u lf o t r io x id e was prepared.

- E xactly 0 .1 5 mole o f

The reagen t was allow ed t o reach

room tem perature and a s o lu tio n of 2 5 .5 g. (0 .1 5 m ole) of

P -

12

acetonapthone d is s o lv e d i n 75 c c . o f e th y le n e c h lo r id e was added at a r a te such th a t t h e tem perature o f th e r e a c t io n m ixture n ever exceeded 3 5 °.

The r e a c tio n proceeded sm oothly and r a p id ly and

s t ir r in g was continued f o r two hours a f t e r th e l a s t a d d itio n o f k eton e.

In t h i s experim ent, as in th e 2-a ceto th ien o n e experim ent,

a coord in ation complex was formed between dioxane and th e s u lfo n ic a cid which was b ein g prepared.

This complex p r e c ip ita te d in the

r e a c tio n f la s k and gave th e appearance o f unreacted rea g en t; however, i t was com p letely hydrolyzed when th e r e a c tio n mixture was poured in to w a ter.

A fter h y d r o ly s is , th e organ ic la y e r was sep a ra ted ,

washed w ith w ater, d r ie d , and th e e th y le n e c h lo r id e s o lv e n t was evaporated.

Seven grams o f unreacted ketone was recovered from

th e organic la y e r .

The aqueous la y e r was n e u tr a liz e d to pH 7

w ith a c o ld sodium hydroxide s o lu tio n , le a v in g 9 .5 g . of sodium s u lf a t e as a r e s id u e .

The n e u tr a liz e d s o lu tio n was evaporated to

dryness by blow ing a ir over i t . an a lco h o l-w a ter m ixtu re. th e s o lu tio n .

The s o lid mass was e x tr a c te d w ith

Upon c o o lin g , c r y s t a l s sep arated from

These c r y s ta ls were f i l t e r e d and d r ie d .

The y i e l d

was 21.5 g . o f sodium s u lfo n a te or 77 $j based on th e amount o f ketone which a c tu a lly r e a cte d . A sodium a n a ly s is on t h i s m a te r ia l gave th e fo llo w in g r e s u lt s : A nal. Calcd.

for C-^H^O^SNa: Na, 8,1*5.

Anal. C alcd. fo r C-^HgOySgNag:

11 . 1*, 1 1 . 1*.

Na, 1 2 .3 0 .

Found:

Na,

13

The S-benzylthiuronium s a lt of t h is m aterial was prepared. A c r y s t a l li n e s a l t which m elted at 206° was obtain ed a f t e r two r e c r y s t a ll iz a t io n s .

A n a ly sis of t h i s s a l t gave th e fo llo w in g

r e s u lt s : Anal. Calcd. fo r OgQHgQO^SgNg*

6 .7 3

A nal. Calcd. fo r GggH^QOyS^N^:

N, 8 .1*6

Found:

N, 8.U 1, 8 .I4I

An iodoform t e s t was perforaed on t h i s compound. t e s t was o b tain ed .

No p o s it iv e

The iodoform t e s t s o lu tio n was a c id if ie d and

ex tr a c ted w ith e th e r .

ft -N apthoic acid (M.P. I 8I40 was ob tain ed

from th e e th er e x tr a c t; t h i s a c id was id e n t if ie d through i t s amide (M.P. 1 9 5 ° ).

I t was concluded from th o se r e s u lt s th a t a m ixture

o f su lfo n a te s was p r e s e n t. S u lfo n a tio n of A ceto m esity len e. - The aceto m esity len e used in t h i s experim ent was prepared according to the lit e r a t u r e ( 2 6 ) . E x a ctly 0 .3 0 mole o f dioxane s u lfo t r io x id e was prepared.

The

reagen t was allow ed to reach room temperature and I4.8 .6 g. ( 0 .3 0 m ole) o f a ceto m esity len e was added a t a r a te such th a t th e tem perature o f th e r e a c tio n m ixture never exceeded 3 5 °.

The r e a c tio n m ixture

was s tir r e d fo r two hours a f t e r th e l a s t a d d itio n of k eton e.

The

m ixture was hydrolyzed, th e organic la y e r was sep arated , washed w ith w ater, d r ie d , and th e eth ylen e c h lo r id e so lv e n t was evaporated. Seven and o n e -h a lf grams o f aceto m esity len e was recovered from th e organ ic Ig y e r .

Ik

The aqueous la y e r was n e u tr a liz e d to pH 7 w ith a co ld sodium hydroxide s o lu t io n .

The n e u tr a liz e d s o lu tio n was evaporated

t o dryness by blow ing a ir over i t .

The s o lid mass was e x tr a c ted

w ith an a lco h o l-w a ter m ixtu re, le a v in g 15 g. o f sodium s u l f a t e as a r e s id u e .

Upon c o o lin g th e s o lu t io n , c r y s t a ls sep arated o u t.

The c r y s t a ls were f i l t e r e d and d r ie d .

The y i e l d was Î4.7 g . o f

sodium u) -a c e to m e s ity le n e s u lfo n a te or 70.1% based on th e amount o f a ceto m esity len e which a c tu a lly r e a c te d .

A sodium a n a ly s is on

t h i s m a teria l gave th e fo llo w in g r e s u lt s : A nal. Calcd. f o r C^H^O^SNa: Found:

Na, 8 .7 1 .

Na, 8 .7 0 , 8 .6 0 .

The S-benzylthiuronium s a l t o f t h is m a teria l was prepared and a s o lid c r y s t a llin e s a l t which m elted a t l 60 ° was ob tain ed a f t e r two r e c r y s t a ll iz a t io n s .

An a n a ly s is of t h i s s a l t gave th e fo llo w ­

in g r e s u lt s : Anal. Calcd. fo r

N, 6 .8 6 , Found:

M, 6 . 8 3 .

The str u c tu r e o f t h is compound was proved by sy n th e siz in g sodium u) -a c e to m e s ity le n e s u lfo n a te independently from U? -bromo­ a ceto m esity len e (18) and sodium s u l f i t e . gave v e r y low y i e l d s .

This displacem en t r e a c tio n

The S-b e n z y lth iu r onium s a l t o f the a u th en tic

su lfo n a te checked w ith th a t obtained from t h e above experim ent.

The

mixed m eltin g p o in t was l6 0 ° . As was t o b e expected t h i s compound d id not g iv e an iodoform t e s t ( 8 ) , nor was i t cleaved by r e flu x in g w ith 20% sodium hydroxide (10) ( 11) ( 12) .

15

Preparation o f

u)-Brom oarylm ethyl K etones. -

bromide was r e a d ily a v a ila b le .

Phenacyl

2 - $ -Brom oacetothienone was

prepared by th e method o f Brunswig (1 8 );

CÙ -brom oacetom esitylene

was prepared in an analogous manner. P reparation o f th e Sodium

-K e to n e su lfo n a tes b y th e

D isplacem ent R e a c tio n . - Sodium (0 -aceto p h en o n esu lfo n a te was prepared from phenacyl bromide and sodium s u l f i t e as d escrib ed i n th e l it e r a t u r e ( 7 ) . prepared a s fo llo w s :

Sodium 2 -a c e to th ie n o n e -

- s u lf o n a t e was

To 0 .2 mole (U l g . ) of 2- lO -brom oacetothienone,

th e r e was added a s o lu tio n o f 25 g. o f sodium s u l f i t e i n 1 0 0 m l. o f w ater.

The r e a c tio n f l a s k was p la c ed on th e steam b a th o v e r n ig h t.

The next morning th e hot s o lu tio n was f i l t e r e d and th e sodium s a l t o f th e a c id c r y s t a lliz e d from th e c h ille d f i l t r a t e .

The same

procedure was used to prepare sodium 6*) - a c e to m e sity le n e su lf o n a te , th e on ly d iffe r e n c e b e in g th a t t h i s s o lu tio n was r e flu x e d .

The

s o lu tio n was th e n evaporated t o dryness and t h e r e s u lt in g mass was ex tr a c ted w ith a b o ilin g 60% a lco h o l-w a ter m ixture.

The

a lco h o l-w a ter s o lu tio n was cooled and a few c r y s t a ls o f sodium LÎ> -a c e to m e sity le n e su lfo n a te p r e c ip it a te d .

The y i e l d was very poor

in t h is experim ent. S u lfo n a tio n o f P in acolon e. s u lfo t r io x id e was prepared.

E xactly 0.225 mole o f dioxane

The reagen t was allow ed to reach room

tem perature and 2 2 .5 g . (0 .2 2 5 m ole) o f p in a co lo n e was added. pin acolon e was added a t a r a te such t h a t the tem perature o f th e

The

16

r e a c tio n m ixture never exceeded 3 5 ° •

The m ixture was s t ir r e d f o r

two hours a f t e r th e l a s t a d d itio n of k eton e.

At th e end o f t h is

tim e th e m ixture was hydrolyzed by pouring i t in to 250 c c . o f w ater.

The org a n ic la y e r was sep arated , washed w ith w ater, d r ie d ,

and t h e eth y len e c h lo r id e so lv e n t was evaporated. r e sid u e in th e organic l^ r e r .

There was no

The aqueous la y e r was n e u tr a liz e d

to pH 7 w ith a c o ld sodium hydroxide s o lu t io n .

The n e u tr a liz e d

s o lu tio n was evaporated to dryness by b lo w in g a i r over i t .

The

s o li d mass was ex tr a c ted w ith an a lco h o l-w a ter m ixtu re, le a v in g U.5 g* o f sodium s u l f a t e as a r e s id u e .

Upon c o o lin g and p a r t ia l

evaporation o f th e a lco h o l-w a ter m ixture, w h ite c r y s t a ls o f sodium p i n a c o l o n e - - s u l f o n a t e p r e c ip it a te d .

The c r y s ta ls were washed

w ith co ld 95% eth an ol and d r ied in a d e s s ic a t o r . 3 8 .5 g . or B»k%*

The y i e l d was

A sodium a n a ly s is on t h i s m a teria l gave th e

fo llo w in g r e s u lt s : A nal. Calcd. f o r C^H-QO^SNa:

Na, 1 1 .3 9 .

Found:

Na, 1 1 .2 7 .

The S-benzylthiuronium s a l t of t h i s m a te r ia l was prepared. A c r y s t a llin e s a l t which m elted a t 162° was ob tain ed a f t e r two r e c r y s t a lliz a t io n s .

A n a ly sis of t h i s s a l t gave th e fo llo w in g

r e s u lts : A nal. Calcd. fo r

N, 8 .0 9 .

Found:

N, 8 .0 6 .

The S-benzylthiuronium s a l t o f an a u th e n tic sample o f t h i s s u lfo n a te was prepared and i t d id not depress th e m eltin g p o in t o f th e above s a lt.

17

An iodoform, t e s t was performed on t h i s compound. t e s t was o b ta in ed .

No p o s i t i v e

The iodoform t e s t s o lu tio n was a c id if ie d and

ex tra cted w ith e th e r .

P iv a lic acid was ob tain ed form th e eth er

e x tr a c t; t h i s acid was i d e n t i f ie d through i t s a n ilid e (M.P. 1 2 9 ° ). M odified Procedure f o r S u lfo n a tio n o f A cetone. - E x a ctly 0.225 mole o f dioxane s u lf o t r io x id e reagen t was p rep ared .

The

reagen t was allow ed t o reach room tem perature and 10 c c . more of dioxane was added t o d is s o lv e a l l o f th e r e a g e n t.

This s o lu tio n

was added dropYd.se and w ith s t ir r in g to 130.5 g. ( 2 ,5 0 m oles) o f aceton e.

The tem perature was m aintained below 3 5 °.

A fter th e

l a s t a d d itio n o f th e r e a g e n t, th e m ixture was s t ir r e d f o r th r e e hours and then hydrolyzed by pouring i t in to 300 c c . o f w ater. The organic la y e r was sep arated , washed w ith w ater, d r ie d , and the ethylene c h lo rid e was d i s t i l l e d o f f .

Ten grams o f m e s ity l

oxide ( 2 ,lj.-dinitrophenylhydrazone, M.P. 203°) was ob tain ed from th e s t i l l p o t.

The aqueous la y e r was n e u tr a liz e d to pH 7 w ith a co ld

sodium hydroxide s o lu tio n .

The n e u tr a liz e d s o lu t io n Y/as evaporated

to dryness by blow ing a ir over i t .

The r e sid u e Y/as ex tra cted w ith

9$% eth a n o l, lea v in g 10 g . of sodium s u l f a t e .

On co n cen tra tin g

and c o o lin g the eth anol e x tr a c t a heavy o i l separated which s o l i d i f i e d in a vacuum d e s s ic a t o r . 25 g . f a ile d .

The y i e l d o f t h i s hygroscopic m a te r ia l was

Attempts to prepare a c r y s t a l li n e S-benzylthiuronium s a l t The str u c tu r e o f t h i s s u lfo n a te was proved b y c le a v a g e

w ith 20 % sodium hydroxide, as d escrib ed in th e l i t e r a t u r e ( 9 ) .

18

A n alysis o f th e sodium s a l t : Sodium a c e to n e su lf onate: Ha, l l i . 3 8 .

A nal. Calcd for C^H^O^SNa:

Found:

Na, 13.1*r0 .

M odified Procedure fo r S u lfo n a tio n of Qyclohexanone. E x a ctly 0 .25 m ole of dioxane s u lfo t r io x id e reagent was prepared. The reagent was allow ed t o reach room temperature and 10 c c . more o f dioxane was added to d is s o lv e a l l of the reagen t.

This s o lu tio n

was added dropwise and w ith s t ir r in g to 21*5 g. ( 2 .5 m oles) o f eyclohexanone.

The tem perature was m aintained below 3 5 °.

A fter

th e l a s t a d d itio n o f th e r e a g en t, the m ixture was s t ir r e d f o r th r e e hours and then hydrolyzed b y pouring i t in to 300 c c . o f w ater.

The

organic la y e r was sep arated , washed w ith w ater, d r ie d , and th e eth y len e c h lo r id e was d i s t i l l e d o f f .

One hundred and f i f t y grams

of eyclohexanone was recovered from t h is la y e r w hile 20 g . of a h igh b o ilin g v isc o u s liq u id formed th e s t i l l p o t r e s id u e .

This

liq u id was probably a condensation product o f eyclohexanone s im ila r to th e m e s ity l oxid e formed in th e a ceton e experim ent.

The aqueous

la y e r was n e u tr a liz e d t o pH 7 w ith a cold sodium hydroxide s o lu t io n . The n e u tr a liz e d s o lu tio n was evaporated t o d iy n e s s by blow ing a ir over i t .

The r e sid u e was ex tra cted w ith hot 95% e th a n o l, lea v in g

2h g. o f sodium s u l f a t e .

Upon con cen tratin g and co o lin g th e eth an ol

e x tr a c t , 19 g . o f sodium eyclohexanone-

- s u lf o n a t e was o b tain ed .

This rep resen ted a 38 % con version fo r th e r e a c t io n .

A n alysis o f

sodium eyclohexanone- c< - s u lf o n a t e gave the fo llo w in g r e s u lt s :

19

A nal. Calcd. fo r C^H^O^SNat

Na, 1 1 .5 .

Found:

Na, 1 0 .1 .

The S-b e n z y lth iu r onium s a l t o f sodium eyclohexanonesu lfo n a te was prepared and i t m elted a t 160°.

-

A n a ly sis of

S-benzylthiuronium eyclohexanone- o< - s u lf o n a t e gave th e fo llo w in g r e s u lt s : Anal. Calcd. f o r C^N^O^S^N^:

N, 8.11t.

Found:

N, 8 .1 9 .

The s tr u c tu r e o f t h i s compound could not be r e a d ily e s ta b lis h e d . S u lfo n a tio n o f Propiophenone. - E xactly G.ij.75 mole o f dioxane s u lfo t r io x id e reagen t was prepared.

The reagen t was

allow ed t o reach room tem perature and 0.^ 7 5 mole ( 6 3 .7 g. ) of propiophenone was added a t a r a te such th a t the tem perature o f th e r e a c tio n m ixture did not exceed 3 5 ° . a black c o lo r .

The m ixture s lo w ly assumed

I t was s t ir r e d fo r th r e e hours a f t e r th e l a s t

a d d itio n o f ketone; a t th e end of t h i s tim e th e m ixture was hydro­ ly ze d by pouring i t in to 300 c c . o f w ater.

The organic la y e r was

sep arated , washed w ith w ater, d r ie d , and d i s t i l l e d .

The eth y len e

c h lo r id e so lv e n t was recovered and 10 g. o f unreacted propio­ phenone formed th e r e sid u e from t h i s la y e r .

The aqueous la y e r was

n e u tr a liz e d to pH 7 w ith a cold sodium hydroxide s o lu tio n .

The

n e u tr a liz e d s o lu tio n was evaporated t o dryness by blow ing a ir over it.

The s o li d mass was e x tr a c ted w ith an a lco h o l-w a te r mixture and

15 g. o f sodium s u lf a t e remained as a r e sid u e ♦

The a lco h o l-w a te r

m ixture was con centrated and allow ed to c r y s t a l l i z e . c r y s t a llin e s a l t , sodium propiophenoneThe y i e l d was 85 g . or 90%,

A w hite

- s u lf o n a t e , was ob ta in ed .

The s a l t appeared to have a stron g

20

tendency t o be hygroscopic j however i t m aintained i t s cry s t a l l in e form very w e ll even when exposed to th e atmosphere for two w eeks. A n a ly sis of sodium propiophenone- 0* - s u lf o n a t e gave th e fo llo w in g r e s u lts : A nal. Calcd. fo r C^O^SNa:

Na, 9 .7 5 .

Found:

Na, 9 .8 6 .

The S-benzylthiuronium s a l t of t h is s u lfo n a te was prepared. I t was a w h ite c r y s t a l li n e s o li d m eltin g a t 1 2 6 °. S-benzylthiuronium propiophenone-

A n a ly sis of

- s u lf o n a t e gave t h e fo llo w in g

r e s u lt s : A nal. Calcd f o r C]_7^I2o%^2IÎ2 :

^

7 .3 7 .

Found :

N, 7 .3 6 .

The S-benzylthiuronium s a l t o f an a u th e n tic sample o f t h is s u lfo n a te was prepared and i t d id n o t dep ress th e m eltin g p o in t o f th e above s a lt. Preparation o f Iso b u ty r y l C hloride. - Iso b u ty r y l c h lo r id e was prepared from is o b u ty r ic a cid and th io n y l c h lo rid e a ccord in g t o th e method o f Shriner and Fuson (3 1 ). P reparation o f Isobutyrophenone. - Isobutyrophenone was prepared by th e F r ie d e l-C r a fts r e a c tio n in th e fo llo w in g manner: 1 .7 2 m oles (182 g . ) of iso b u ty r y l c h lo r id e was added t o 5 moles (390 g. ) o f benzene; to t h i s m ixture th e re was added i n p o rtio n s 3 .5 m oles (U53 g. ) of aluminum c h lo r id e .

The m ixture was r e flu x e d

fo r two hours a t th e end o f which tim e i t was poured over two l i t e r s o f cracked i c e .

The benzene la y e r was sep arated , d r ie d and d i s t i l l e d .

The benzene s o lv e n t was strip p ed o f f a t atmospheric pressu re; th e

21

p ressu re was then reduced t o lU mm. and isobutyrophenone d i s t i l l e d over a t 92 o .

The y i e l d o f ketone was 170 g. or 70%,

S u lfo n a tio n of Isobutyrophenone; - E x a ctly 0 .1 3 8 mole of dioxane s u lfo t r io x id e was prepared.

The reagen t was allow ed to

reach room tem perature and 0 .1 3 8 mole ( 2 0 .14 g .) o f isobutyrophenone was added a t a r a te such th a t t h e tem perature o f th e r e a c tio n m ixture d id n o t exceed 3 5 °.

The m ixture assumed a dark y e llo w

c o lo r and i t was s t ir r e d f o r th r e e hours a f t e r th e l a s t a d d itio n o f k eton e.

At th e end of t h i s tim e t h e m ixture was hydrolyzed by

pouring i t in to 200 c c . o f w ater.

The organ ic la y e r was sep a ra ted ,

washed w ith w ater, d r ie d , and d i s t i l l e d .

The e th y le n e c h lo r id e

so lv e n t was recovered; l e s s than a gram of unreacted isobutyrophenone formed t h e r e s id u e .

The aqueous la y e r was n e u tr a liz e d t o pH 7 w ith

a cold sodium hydroxide s o lu tio n .

The n e u tr a liz e d s o lu tio n was

evaporated t o dryness by blow ing a ir over i t .

The s o li d mass was

ex tra cted w ith an a lco h o l-w a te r m ixture and 3 g* of sodium s u lf a t e remained as a r e sid u e .

The a lco h o l-w a te r s o lu tio n was c o o le d and

18 g. o f a w h ite c r y s t a llin e s o l i d , sodium isobutyrophenone- oL -

s u lfo n a te , p r e c ip it a te d .

Further co n cen tra tio n o f t h e s o lu tio n with

subsequent c o o lin g produced an a d d itio n a l 12 g . of s o l i d .

This

second crop o f c r y s t a ls was i d e n t ic a l w ith th e f i r s t crop. t o t a l y ie ld was 30 g . or 87%.

The

A n alysis of sodium isobutyrophenone-

oC -s u lf o n a t e gave th e fo llo w in g r e s u lt s : A nal. Calcd. f o r C^^H-^O^SNa:

Na, 9 .2 0 .

Found:

Na, 9 .2 5 .

22

The S-b e n z y lth iu r oniran s a l t of t h i s s u lfo n a te was prepared and i t was a w h ite c r y s t a llin e s o li d m eltin g a t l60°* S-b e n z y lth iu r onium isobutyrophenone-

A n a ly sis o f

- s u lf o n a t e gave th e fo llo w in g

r e s u lt s : Anal. Calcd. fo r

^

7 .1 1 Found:

N, 7♦12.

The S-benzylthiuronj.um s a l t of an a u th en tic sample o f t h i s s u lfo n a te was prepared and i t d id n ot d epress th e m eltin g p oin t o f th e above s a lt. O xidation o f the Sodium S u lfo n a te s Obtained from Propiophenone and Isobutyrophenone t o Benzoic A cid . - One gram samples o f sodium propiophenone-

- s u lf o n a t e and sodium isobutyrophenone- X - s u lf o n a t e

were o x id ized w ith a lk a lin e permanganate accord ing to th e method o f Shriner and Fuson (3 2 ).

Both su lfo n a te s o x id ized to benzoic acid

(M.P. 121°) showing t h a t su lfo n a tio n had occurred on th e s id e ch a in . The y i e l d o f b en zo ic acid obtained from th e sodium isobutyrophenone- s u lf o n a t e was low as should be expected from branched hydrocarbon chains o f t h i s type ( 3 0 ) . S u lfo n a tio n o f P henylaeetaldehyde. - E xactly 0.363 mole of dioxane s u lf o t r io x id e reagen t was prepared.

The reagent was allow ed

to reach room tem perature and U3 .6 g. ( 0 .3 6 3 m ole) of phenylaeetaldehyde was added a t a r a te such th a t th e tem perature o f th e r e a c tio n m ixture did not exceed I4O0 .

The r e a c tio n m ixture slo w ly turned b la c k .

The

m ixture was s t ir r e d f o r one hour a f t e r th e l a s t a d d itio n o f aldehyde, and then i t was hydrolyzed by p ou iin g i t in to 300 c c . o f w ater.

The

organic la y e r was sep arated , washed w ith w ater, d r ied , and th e eth y len e c h lo r id e was d i s t i l l e d o f f . formed th e r e s id u e .

Ten grams o f ta rr y m a teria l

The aqueous la y e r was n e u tr a liz e d to pH 7

w ith a c o ld sodium hydroxide s o lu tio n .

Upon n e u t r a liz a tio n 5 g .

o f a p a le y e llo w s o li d separated; t h i s was f i l t e r e d o f f and r e c r y s t a lliz e d from a m ixture o f benzene and petroleum e th e r . This s o li d m elted a t 9U°«

Anal. Found:

C, 83.1*; H, 5 .7 5 .

m a teria l farmed a phenylhydrazone w hich m elted a t 1 2 0 °. N, 9 .3 0 .

This

A nal. Found

The remainder o f th e aqueous la y e r was evaporated t o

dryness by blow ing a ir over i t .

The r e sid u e was e x tr a c te d w ith

95$ eth anol le a v in g 30 g . o f sodium s u l f a t e .

The eth anol e x tr a c t

was evaporated t o dryness and t h i s r e sid u e was washed re p e a te d ly w ith acetone and e th e r .

This r e s u lte d in th e i s o l a t i o n o f a w h ite

c r y s t a llin e s a l t , sodium phenylaeetaldehyde- ^ - s u l f o n a t e .

The

y ie ld was 33 g. which rep resen ted a 1*1 . 3 $ conversion fo r t h i s r e a c tio n . The a id eh yd esu lfon ate f a il e d to form an S-benzylthiuronium s a lt.

Attempts to form th e oxime

and th e phenylhydrazone o f the

aldehyd e s u lf onate a ls o f a i l e d . A n alysis o f the sodium s a l t : Sodium phenylaeetaldehyde- of -s u lf o n a t e :

A nal. Calcd.

fo r CgHyO^SHa:

Na, 10.36; C, 1*3.3; H, 3 .1 5 .

Found:

Na, 10.05; C, 1*1*.2; H, 3 .2 9 .

S u lfo n a tio n o f Isobutyraldéhyd e. - E x a ctly 0.375 mole o f dioxane s u lfo t r io x id e reagent was prepared.

The rea g en t was

2h

allow ed t o reach room tem perature and 27 g« (0,375 m ole) of i sobutyr a ld e­ hyde was added a t a r a te such t h a t th e tem perature o f th e r e a c tio n m ixture d id not exceed 3 5 ° .

The r e a c tio n m ixture assumed a darker

c o lo r as th e r e a c tio n proceeded.

The m ixture was s t ir r e d a t room

tem perature f o r one hour a f t e r th e l a s t a d d itio n o f aldehyde.

At

th e end o f t h i s tim e , th e m ixture was hydrolysed by pouring i t in to 300 c c . o f w ater.

The organic la y e r was separated, washed w ith w ater,

d r ie d , and d i s t i l l e d .

The e th y le n e c h lo r id e s o lv e n t was recovered

and 10 g. of ta r r y m a teria l formed the r e sid u e o f t h is la y e r .

The

aqueous la y e r was n e u tr a liz e d to pH 7 w ith a cold sodium hydroxide s o lu tio n .

The n e u tr a liz e d s o lu tio n was evaporated to dryness by

blow ing a ir over i t .

The s o lid mass which remained was e x tr a c ted

w ith 95% eth anol and 30 g . o f sodium s u l f a t e formed the re sid u e from th e e x tr a c tio n .

The a lc o h o l e x tr a c t was con centrated and c o o le d

but th e ald eb yd esu lf onate would n ot p r e c ip it a t e .

F in a lly , th e

a lc o h o l e x tr a c t was evaporated t o dryness and th e organic im p u r itie s were washed f r e e from th e s o li d w ith a c e to n e .

This r e s u lt e d i n th e

i s o l a t io n o f a w h ite c r y s t a llin e s a l t which gave n e g a tiv e t e s t s fo r any p o s s ib le contam inating io n s . - s u lf o n a t e .

This s a l t was sodium iso b u ty ra ld eh y d e-

This s a l t gave a p o s it iv e T o lle n s 1 t e s t in d ic a tin g

th a t an aldehyde group was s t i l l p r e s e n t. form an S-benzylthiuronium s a l t .

The compound did n ot

The y ie ld o f sodium isob u tyrald eh yd e-

c< - s u lf o n a t e was 26 g . which rep resen ted a k0% con version fo r t h i s r e a c tio n .

An a n a ly s is o f t h i s s a l t gave the fo llo w in g r e s u lt s :

25

A nal. Calcd. fo r C^HyO^SNa:

Na, 1 3 .2 2 ; C, 2 7 .6 ; H, it.02.

Foundi

Na, 13.1 6 ; C, 2 7 . 6 ; H, Lt.Q5.

S u lfo n a tio n o f H eptaldehyde. - E x a ctly 0.2 2 5 mole o f dioxane s u lfo t r io x id e reagen t was prepared.

The reagen t was allow ed t o

reach room tem perature and 2 5 .6 g . ( 0 .2 2 5 mole) of heptaldehyde was added a t a r a te such th a t th e tem perature o f t h e r e a c tio n m ixture d id n o t exceed 3 5 °.

The r e a c tio n m ixture s lo w ly darkened.

The

m ixture was s tir r e d a t room tem perature fo r one hour a f t e r the l a s t a d d itio n o f aldehyde and then i t was hydrolyzed by pouring i t in to 300 c c . of w a ter.

The organic la y er was sep arated , washed w ith

w ater, d r ie d , and d i s t i l l e d .

The eth ylen e c h lo r id e s o lv e n t was

recovered and approxim ately 10 g . o f ta rr y m aterial formed the r e sid u e o f t h i s la y e r . or o x id a tio n product.

T his t a r was probably an aldehyde polymer The aqueous la y er was n e u tr a liz e d to pH 7

w ith a c o ld sodium hydroxide s o lu t io n .

The n e u tr a liz e d s o lu t io n

was evaporated to d iy n e ss by blow ing a ir over i t .

The s o li d mass

which remained was ex tr a c ted w ith hot 35% eth an ol and 19 g . of sodium s u l f a t e formed th e r e sid u e from th e e x tr a c tio n .

The a lc o h o l

e x tr a c t was concen trated and co o led b ut th e aid ehydesulf on ate would n ot p r e c ip it a t e .

F in a lly , th e a lc o h o l e x tr a c t was evaporated to

dryness and th e organic im p u r itie s were washed f r e e from the s o l i d w ith a ceto n e.

This r e s u lte d in th e i s o l a t io n o f a s l i g h t l y co lo red

c r y s t a llin e s a l t which gave n e g a tiv e t e s t s fo r any p o s s ib le contam inat­ in g io n s .

This s a l t was sodium h ep tald eh yd e-ct-~~s u lfo n a t e .

This

s a l t gave a p o s it iv e S c h i f f ’s t e s t in d ic a tin g th a t an aldehyde group

26

was s t i l l p r e s e n t. s a lt.

The compound d id n o t form an S-benzylthiuronium

The y i e l d of t h is compound was 19 g. which rep resen ted a

\\0% con version fo r t h i s r e a c t io n .

An a n a ly s is on t h i s compound

gave t h e fo llo w in g r e s u lt s : A nal. Calcd. f o r CyH^O^SNa: Na,

1 0 .6 5 ; C, 3 8 .9 ; H, 6 .0 2 .

Found: Na,

1 0 .6 2 ; C, 3 8 .7 ; H, 6 .1 2 .

Cleavage o f Sodium Phenylaeetaldehyde-

- s u lf o n a t e . -

Two grams o f sodium p h en ylaeetaldehyde- -1olylm eth yl s u lf id e t o th e su lfo n e (M.P. 89°) proceeded i n 90% y ie ld .

S u l f o n a t i o n o f ]> -T o ly l M e th y l S u l f o n e . - The s u l f o n a t i o n o f t h i s s u l f o n e w as a tte m p te d u s in g d io x a n e s u l f o t r i o x i d e .

E x a c t ly

0.3375 m o le o f d io x a n e s u l f o t r i o x i d e was r e a c t e d w it h 57 «U g . (0.3375 m ole) of th e s u lfo n e .

The procedure employed fo r th e

su lfo n a tio n of ketones was used and th e products were i s o la t e d in th e u su al manner.

From th e organic la y er th e r e was recovered 5 6 .0

g. o f unreacted su lfo n e which rep resen ted 97*6% o f th e s t a r t in g m a te r ia l.

This in d ic a te d th a t th e su lfo n e was p r a c t ic a lly imaune

to atta ck b y dioxane s u lf o t r io x id e .

T his experiment supported our

h y p o th esis th a t t h i s r e a c tio n took p la c e through an m o l a te type o f s tr u c tu r e .

For th e su lfo n e to e n o liz e would r e q u ire an expansion

o f th e su lfu r v a len ce s h e l l from e ig h t t o te n e le c t r o n s .

S u lfu r

e x h ib ite d a great r e lu c ta n c e t o expand i t s s h e ll as has been p r e v io u sly noted i n th e lit e r a t u r e ( 1 5 ) ( 1 6 ) , hence one would n ot expect a r y l m ethyl s u lfo n e s t o undergo r e a c tio n w ith dioxane s u lfo t r io x id e i f our hyp oth esis were c o r r e c t.

P r e p a r a t io n o f P iv a lo p h e n o n e . - P iv a lo p h e n o n e w a s p r e p a r e d b y t h e r e a c t i o n o f p h en y lm a g n esiu m b r o m id e w i t h p i v a l y l c h l o r i d e a t lo w te m p e r a t u r e s a s r e p o r t e d in t h e l i t e r a t u r e ( 2 0 ).

T he y i e l d

in t h i s r e a c t io n co rresp o n d ed w ith th a t r ec o rd ed in th e l it e r a t u r e (67%).

28

S u lfo n a tio n o f Pivalophenone. - E xactly 0,167 mole o f dioxane s u lfo t r io x id e reagen t was prepared.

The reagen t was

allow ed t o reach room tem perature and 27 g. ( 0 . 16 ? m ole} o f pivalophenone was added.

The k eton e was added slo w ly at f i r s t

but a s th e r e was no in c r e a se i n tem perature, th e r a te o f a d d itio n was in c r e a s e d .

The tem perature o f t h i s r e a c tio n m ixture never

exceeded room tem perature.

The m ixture was th en s t ir r e d fo r three

hours a f te r the l a s t a d d itio n of ketone; a t the end o f t h i s tim e , th e m ixture was hydrolyzed by pouring i t in t o 300 c c . o f w a ter. The organic la y er was sep arated , washed w ith w ater, d r ie d , and d is tille d .

The eth ylen e c h lo r id e so lv e n t was recovered and 26 g .

o f unreacted pivalophenone formed th e r e sid u e from t h i s la y e r . This showed th a t th e pivalophenone was recovered 9 6 .5 $ unreacted from th e r e a c tio n m ixture.

The aqueous la y er was n e u tr a liz e d t o

pH 7 w ith a cold sodium hydroxide s o lu t io n . s o lu tio n was evaporated to d ryn ess.

The n e u tr a liz e d

The s o lid mass was ex tr a c ted

w ith an a lco h o l-w a ter m ixture, but no organic sodium su lfo n a te was obtained from t h i s e x tr a c tio n .

The bulk o f th e r e s id u e

c o n siste d of sodium s u lfa t e and ig n it io n o f a sm all sample f a i l e d to r e v e a l th e presen ce of even a tr a c e o f an organic s a l t .

This

was to b e expected s in c e th e high recovery of pivalophenone in d i­ cated t h a t no s u lfo n a tio n had occurred in t h i s in s ta n c e .

T his

experim ent rath er c o n c lu siv e ly dem onstrated th a t ketones co n ta in in g no alpha hydrogen atoms w i l l not s u lfo n a te under th e se c o n d itio n s . This experim ent a ls o was a good p ie c e o f evidence i n support o f th e mechanism which has been proposed fo r t h is s u lfo n a tio n r e a c tio n .

29

MISCELIMBOUS S u lfo n a tio n o f Camphor. - E x a ctly 0.1875 mole of d ioxan e s u lfo t r io x id e was prepared.

The reagen t was allow ed t o reach

room tem perature and a s o lu tio n o f 2 8 ,5 g . ( 0 .1 8 7 5 m ole) of camphor d is so lv e d i n 75 c c . o f dry eth y len e c h lo rid e was added. m ixture d id not heat up n o tic e a b ly .

The r e a c tio n

The m ixture was s t ir r e d f o r

s i x hours a f te r th e l a s t a d d itio n o f ketone and then i t was heated to lt0° fo r two more hours w ith continu ed s t i r r in g .

At th e end o f

t h is tim e th e m ixture was hydrolyzed by pouring i t in to 200 c c . o f w a ter.

The organic la y e r was sep arated , washed w ith w a ter, d r ie d ,

and th e e th y le n e c h lo r id e so lv e n t was evaporated.

S ix te e n grams

o f unreacted camphor was recovered from th e organic la y e r .

The

aqueous la y e r was n e u tr a liz e d to pH 7 w ith a co ld sodium hydroxide s o lu tio n .

The n e u tr a liz e d s o lu tio n was evaporated t o d ryn ess by

blow ing a ir over i t . water m ixtu re. c r y s ta lliz e .

The s o lid mass was e x tr a c te d w ith an a le oho 1 -

Upon c o o lin g an o i l sep arated .

This o i l would not

The a lc o h o l was evaporated and th e r e s id u a l o i l was

p laced i n a vacuum d e s s ic a t o r .

The s o lv e n t was pumped o f f and th e

r e sid u a l s o li d was e x tr a c te d w ith a b so lu te a lc o h o l.

The f i l t r a t e

from th e e x tr a c tio n y ie ld e d 1 9 ,5 g . o f sodium caraphorsulfonates which could not be obtained in good c r y s t a l li n e form .

About lu 5

g . o f a c r y s t a llin e sodium cam phorsulfonate was r e ta in e d on th e f ilte r .

A sample o f t h is s u lfo n a te was o x id iz e d w ith a lk a lin e

permanganate and camphoric a cid (M.P. 202 - 3 0 ) was o b ta in ed . showed t h a t some su lfo n a tio n occurred i n th e 3 - p o s it io n .

An

This

30

S -b e n z y lth ittr o n iu r a s a i t o f t h e c r y s t a l l i n e s u l f o n a t e w as p r e p a r e d b u t a n a l y s i s sh ow ed i t t o b e im p u r e . s a l t w as lo w .

T h e y i e l d o f S - b e n z y lt h iu r o n it u n

The im p u re so d iu m cam phor s u l f o n a t e s o b t a in e d fr o m

t h i s e x p e r im e n t w e r e e x t r e m e ly h y g r o s c o p ic . P reparation o f Camphorquinone. - Camphorquinone was prepared according t o th e l it e r a t u r e (2?) (2 8 ) ( 2 9 ) .

B r ie f ly th e s y n th e sis

c o n siste d o f tr e a tin g an eth er s o lu tio n o f camphor w ith sodium and amyl n i t r i t e ; t h i s r e a c tio n produced i s onitrosocamphor which was hydrolyzed t o the ketone by treatm ent w ith form alin and con cen trated ty d r o c h lo r ic a c id .

The r e s u lt in g camphorquinone was steam d i s t i l l e d

from th e r e a c tio n m ixture.

The y i e l d from t h i s sequence o f r e a c tio n s

was n o t v e r y good. S u lfo n a tio n o f Camphorquinone. - E x a ctly 0.08Ui| mole o f dioxane s u lfo t r io x id e was prepared.

The reagen t was allow ed t o

reach room tem perature and a s o lu tio n of 13 g . (O.OSUU mole ) o f camphorquinone d is s o lv e d in 5>0 c c . o f dry e th y le n e c h lo r id e was added.

The r e a c tio n m ixture d id n ot heat up n o tic e a b ly .

The m ixture was s t ir r e d f o r fo u r hours a f t e r th e l a s t a d d itio n o f ketone and th e n i t was heated to U0 ° fo r two more hours w ith continued s t i r r in g .

At th e end of t h is tim e th e m ixture was

hydrolyzed b y pouring i t in to 200 c c . o f w a ter.

The organ ic la y er

was sep arated , washed w ith w ater, d r ie d , and th e e th y le n e c h lo r id e s o lv e n t was evaporated.

Seven grams o f unreacted camphorquinone

was recovered from th e organic la y e r .

The aqueous la y e r was

31

n e u tr a liz e d t o pH 7 m t h a c o ld sodium hydroxide s o lu t io n .

The

n e u tr a liz e d s o lu tio n was evaporated t o dryness by b low in g a i r over it.

F ive grams o f a very h ygroscop ic r e sid u e was o b ta in ed .

The

r e sid u e was p la ced i n a vacuum d e s s ic a to r and w ater was removed. The l i g h t brown c r y s t a ls which were ob tain ed im m ediately took on m oisture when th ey were exposed to th e atmosphere.

No attem pt

was made to i s o l a t e and p u r ify th e products which were a m ixture o f sodium s u l f a t e and sodium camphorqinLnonesulfonates. S u lfo n a tio n o f B en zalaceton e. - E x a ctly 0.1875 mole o f dioxane s u lf o tr io x id e was prepared.

The reagen t was allow ed t o

reach room tem perature and a s o lu t io n o f 27 . U g . o f b en zalaceton e d is s o lv e d i n 50 c c . o f dry eth y len e c h lo r id e was added a t a r a te such th a t th e tem perature o f the r e a c t io n m ixture d id not exceed 3 5 °.

The m ixture turned a dark red and i t was s tir r e d f o r th r e e

hours a f t e r th e l a s t a d d itio n o f k eto n e.

At th e end o f t h i s tim e

th e m ixture was hydrolyzed by pouring i t in to 200 c c . o f w a te r . The organic la y e r was sep arated , washed w ith w a ter, d r ie d , and th e eth y len e c h lo r id e s o lv e n t was evap orated . contained no r e s id u e .

The organ ic la y e r

The aqueous la y e r was n e u tr a liz e d to pH 7 w ith

a c o ld sodium hydroxide s o lu tio n .

The n e u tr a liz e d s o lu tio n was

evaporated t o dryness by blow ing a ir over i t .

The s o l i d mass was

e x tr a c ted w ith an a l cohol-w ater m ixture and 5 .5 g. o f sodium s u lf a t e remained a s a r e s id u e .

Seven grams o f a y e llo w s o l i d sep arated

from th e a lco h o l-w a ter m ixture.

This compound formed no S -b e n z y l-

thiuronium d e r iv a t iv e , and i t burned w ith d i f f i c u l t y .

The remainder

32

o f t h e a lco h o l-w a ter e x tr a c t was concentrated and 30 g. o f a dark red o i l was ob tain ed .

This o i l would not c r y s t a lliz e ^ i t

apparently was a m ixture o f s u lfo n a t e s .

This o i l seemed t o have

e x c e lle n t d eterg en t p r o p e r tie s as i t formed copious suds when in c o n ta ct w ith tap w ater.

Since t h is problem in v o lv ed th e sep a ra tio n

o f a rath er complex m ixture o f s u lfo n a te s , work on i t was suspended. S u lfo n a tio n o f Thiophene. - O ne-half mole (U2 g .) o f thiophene was added to th e p r e v io u sly prepared dioxane s u lf o t r io x id e .

The

tem perature o f th e r e a c tio n m ixture was m aintained a t l5 -2 0 °C . A fter th e a d d itio n o f th iop h en e was com plete, th e r e a c tio n m ixture was s t ir r e d f o r one hour and th e n the r e a c tio n f la s k was allow ed to stand overn igh t a t room tem perature.

The fo llo w in g morning

th e r e a c tio n m ixture was hydrolyzed by pouring i t in to 500 c c . o f d i s t i l l e d w ater. then sep arated .

The water and eth y le n e c h lo r id e la y e r s were

The e th y le n e c h lo r id e la y e r was evaporated to

dryness, le a v in g only a tr a c e o f r e s id u e .

The aqueous la y e r was

n e u tr a liz e d w ith a satu rated s o lu tio n o f barium hydroxide.

A

sm all amount o f barium s u lf a t e p r e c ip ita te d and t h i s was f i l t e r e d o ff.

The n e u tr a l aqueous la y e r was th en evaporated t o dryness

and th e barium s a l t o f th io p h e n e su lfo n ic a cid was ob ta in ed .

The

c r y s t a ls were washed w ith c o ld a lc o h o l in which they w ere s l i g h t l y s o lu b le .

The w eigh t o f pure s a l t was 72 g.

The a lc o h o l w ashings

were combined and evaporated to d ry n ess, and an a d d itio n a l 29 g . o f impure s a l t was ob tain ed .

The t o t a l w eight o f barium s a l t recovered

33

rep resen ted a con version o f 87/3 f o r t h is r e a c tio n .

To determ ine

whether mono or d i su lfo n a tio n occurred, a barium a n a ly s is was performed on th e s a l t . Anal. Calcd, f o r CgH^O^S^Ba:

Ba, 29*1%.

Found:

Ba, 28%.

P reparation of t h e Sodium S a lt o f T h ioph en esulfonic

A cid . -

T h irty grams o f th e barium s a l t o f th io p h e n e su lfo n ic a c id was d is s o lv e d in 200 m l. o f d i s t i l l e d water and 9 .2 g . o f sodium s u lf a t e was d is s o lv e d i n 100 c c . of d i s t i l l e d w ater.

The two s o lu tio n s

were mixed and th e barium s u lf a t e which p r e c ip ita te d was f i l t e r e d o ff.

The c le a r s o lu tio n was evaporated t o dryness and 2b g* o f

sodium 2 -th io p h e n e su lfo n a te was o b ta in ed .

T h is r e p r ese n ts a quanti­

t a t i v e con version . P reparation o f 2-T hiophenesulfonyl C hloride^ - E ig h t grams o f th e sodium s a l t o f 2-th io p h e n e su lfo n ic acid was tr e a te d w ith 5 grams o f phosphorus o x y c h lo rid e .

The m ixture was h eated under

r e flu x f o r f i v e hours and ex tr a c ted w ith warm benzene. zene la y e r was washed w ith w ater and d r ie d .

The ben­

Upon evaporation o f

th e benzene about 2 g . o f an o i l remained; t h i s o i l was 2- t h i o p h en esu lfon yl c h lo r id e (M.P. 2 9 ° ) .

No attem pt was made to p u r ify

th e o i l and i t was used f o r th e n ex t experim ent. Preparation o f 2-Thiophenesulfonam ide. - To th e 2 g. o f 2- th io p h e n e s u lfo r y l c h lo r id e , th e r e was added 15 c c . o f liq u id

ammonia.

The liq u id ammonia was allow ed t o evaporate slo w ly and

th e rem aining s o li d was r e c r y s t a lliz e d from w a ter.

A fter two

r e c r y s t a lliz a t io n s th e sulfonam ide m elted a t II4.O0 , which i s i n agreement w ith the v a lu e rep orted i n th e l it e r a t u r e . Preparation o f S-B enzylthiuronium 2-T h iop h en esu Ifon ate. Four grams o f the sodium s u lfo n a te was d is s o lv e d in 20 c c . o f w ater. Four grams of S-benzylthiuronium c h lo r id e was d is s o lv e d in 20 c c . o f hot w ater.

The two s o lu tio n s were mixed and c h i l l e d .

The

s a l t which p r e c ip ita te d was r e c r y s t a lliz e d from water co n ta in in g a tr a c e o f a c id .

This s a l t m elted a t 1 3 8 °.

The d e r iv a tiv e can

a lso be prepared d i r e c t ly from th e barium s u lfo n a te in th e same manner. A nal. Calcd. fo r C1 pH^O.^Np:

N, 8 .I16 .

Found:

N, 8.L 5, 8 .

Attempted S u lfo n a tio n o f 2-N itro th io p h en e. - E x a ctly 0.li75 mole o f dioxane s u lfo t r io x id e reagen t was prepared.

To th e reagen t

th e re was added 6 l «8 g . ( 0.^ 7 5 m ole) o f 2-n itr o th io p h en e which was d is s o lv e d in 150 c c . o f eth y len e c h lo r id e .

The s o lu tio n

con tain in g the 2 -n itro th io p h en e was added slo w ly a t 10 ° .

S ince

no r e a c tio n appeared to be ta k in g p la c e , the m ixture was allow ed to reach room tem perature and then th e remainder o f the 2- n it r o ­ thiophene s o lu tio n was added slo w ly .

There s t i l l was no ap p reciab le

h ea t evolved and th e r e appeared to b e no r e a c tio n .

The m ixture was

allow ed to stand o v ern ig h t and th e fo llo w in g morning th e r e was s t i l l a con sid erab le amount of reagent in th e f l a s k .

The m ixture

was g e n tly heated to I4.O0 and allow ed t o stand f o r fo u r more hours. At th e end o f t h is tim e, th e m ixture was hydrolyzed by pouring i t

35

in to 500 c c . o f m t e r . sep arated , and d r ie d . 11

The organic la y e r m s washed w ith w ater, Evaporation o f th e organic la y e r y ie ld e d

g. o f a re sin o u s m a te r ia l which was in s o lu b le i n 9$% a lc o h o l,

a b so lu te a lc o h o l, e th y le n e c h lo r id e , carbon t e t r a c h lo r id e , aceto n e, chloroform , e th e r , petroleum eth er and benzene.

A lso from t h e

organic la y e r th e re was recovered 30 g . of 2-n itr o th io p h e n e ( r e c r y s t a l li z e d ) .

The aqueous la y e r was n e u tr a liz e d w ith a

satu rated s o lu tio n o f barium hydroxide. p r e c ip ita te d was f i l t e r e d and d r ie d .

The barium s u lf a t e which

The w eigh t o f barium s u lf a t e

recovered from th e n e u tr a liz e d s o lu tio n was 101 g . which in d ic a te d th a t 91% o f th e a v a ila b le s u lfu r t r io x id e in the reagen t d id not r e a c t w ith th e 2 -n itr o th io p h en e.

Evaporation o f t h e n e u tr a liz e d

aqueous la y er f a i l e d t o produce any s u lfo n a t e s , th u s confirm ing our o r ig in a l ob servation th a t e s s e n t i a l l y no s u lfo n a tio n of 2 -n itr o th io p h en e had taken p la c e .

This la ck o f r e a c t iv i t y may b e

due to t h e d e a c tiv a tin g in flu e n c e o f th e n itr o group on th e thiophene n u cleu s. Clemmensen R ed u ction o f Sodium A ceto p h e n o n e -U ? -su lfo n a te . The Clemmensen red u ction was ca rried ou t on sodium acetophenone-L^ su lfo n a te accord in g t o th e procedure o u tlin e d i n “Organic R eactions" ( 3 3 ).

Twenty grams o f sodium acetophenone- txX s u lf onate was used

and th e r e a c tio n m ixture was r e flu x e d u n t i l a l l th e zin c disap p eared . The r e a c tio n m ixture was then n e u tr a liz e d w ith sodium carbonate. Zinc carbonate, which p r e c ip ita te d , was f i l t e r e d , and th e remainder o f th e s o lu tio n was evaporated t o d ryn ess.

The s o l i d mass which

remained was ex tra cted w ith two 150 m l. p o r tio n s o f hot e th a n o l.

36

The r e sid u e tris a. m ixture o f inorganic s a lt s #

The eth anol e x tr a c t

was concen trated and c o o le d , b u t a heavy o i l was ob tain ed .

This

o i l was tr e a te d w ith aceto n e t o remove organic im p u r itie s .

A fte r

repeated washings w ith acetone and e th a n o l, U g . o f a s l i g h t l y colored s a l t was o b ta in ed .

This compound r e a d ily formed an S-

benzylthiuronium d e r iv a tiv e which m elted a t 230°. was b e lie v e d to b e sodium

This compound

Ç -phenyl ethane s u lf o n a te.

The y i e l d i n t h i s r e a c t io n rep resen ted a 20% con version of sodium acetophenone-

- s u lf o n a t e to th e reduced p roduct.

I t was

very d i f f i c u l t to sep arate th e product which was formed in t h is r e a c tio n from th e la r g e q u a n titie s o f in organ ic s a l t s which were a lso p r e se n t.

This procedure showed promise o f p rovid in g another

method f o r the prep aration o f a lip h a tic -a r o m a tic s u lfo n ic a c id s once th e sep a ra tio n problem has been so lv e d . Attempt to S y n th esize

P -k e to s u lfo n e s by th e Condensation

o f a Ketone w ith M ethanesulfonic A cid. - One hundred m i l l i l i t e r s o f anhydrous e th e r , 26 g . of a c e t ic anhydride, 26 g. of m eth an esu lfon ic a c id , and 29 g. o f acetophenone were p laced in a th ree-n eck f la s k f i t t e d w ith a thermometer, s t i r r e r , and condenser.

The m ixture was

s t ir r e d f o r two days a t room tem perature, and th en i t was heated fo r a few hours on th e steam b a th .

The m ixture assumed a darker

c o lo r during the course o f th e r e a c t io n . m ixture was poured in to i c e w ater.

A fter h e a tin g , th e

The e th er la y e r was sep a ra ted ,

washed w ith water se v e r a l tim e s , d r ied , and th e e th e r was evaporated. A heavy b la ck o i l formed the r e s id u e . p u r ify t h i s o i l ended in f a i l u r e .

Attempts t o c r y s t a l l i s e and

37

SUMMARY

1.

Acetophenone, 2 -a ce to th ie n o n e , a c e to m e sity le n e , and P ace t onapthone, have been su lfo n a te d u sin g dioxane s u lf o t r io x id e . For th e f i r s t th r e e k e to n e s, th e corresponding sodium u ) k e to n e su lfo n a tes have been is o la t e d a s th e p r in c ip a l products i n approxim ately 70$ y i e l d s ( r e c r y s t a l li z e d ) .

In th e c a se o f

P -

acetonapthone, a m ixture o f s u lfo n a te s was ob tain ed . 2.

P in acolon e, a c eto n e, cyclohexanone, propiophenone, and isobutyrophenone have been su lfo n a te d w ith dioxane s u lf o t r io x id e to th e corresponding sodium k eton e- 0*-- s u lf o n a t e s .

3.

Phenylacetaldehyde, isob u tyrald éh yd e, and heptaldehyde have been su lfo n a te d w ith dioxane s u lf o t r io x id e to th e corresponding sodium aldehyde- *4 - s u lf o n a t e s .

In

g -T o ly l methyl s u l f one and pivalophenone d id n ot r e a c t w ith dioxane s u lf o t r io x id e .

3.

A mechanism has been proposed fo r th e cou rse o f t h i s r e a c tio n .

38

BIBLIOGRAPHY (1 )

K rekeler, B e r 19, 6 7 6 , 2627 (1 8 8 6 ),

(2 )

Weston and S u ter, J . Am. Chem. Soc>^ 6 1 , 389 (1 9 3 8 ).

(3 )

Doering and B erin ger, i b i d . , 71, 2221 (19U 9).

(U)

S u te r , nOrganic Chemistry o f S u lfn r ." , John W iley and Sons, I n c ., New York, N. Y ., 19UU, p . 139.

(5 )

I b i d ., p . 316.

(6)

I o f f e and Naumova, J . G en. C hem ., 9 , 1121 (1939),* C.A. , 33, 8605 (1 9 3 9 ).

(7 )

Parkes and T in s le y , J. Chem. Soc. , 1861 (193U ).

(8 )

Johnson and Fuson, J . Am. Chem. S oc. , 5 7 , 919 (1 9 3 5 ).

(9 )

S u ter, Evans and K ie fe r , i b i d . , 60, 538 (1 9 3 8 ).

(10) K o h ler and B a l t z l y , i b id . , 5U, U0l5 (1 9 3 2 ). (11) Kadesch, i b id . , 66, 1207 (19kL). (12) Lock and Schreckenëder, B er. , 72B, 511 (1 9 3 9 ). (13) Z u ffa n ti, J . Am. Chem. Soc. , 62, lOUU (1 9 ii0 ).

(lit) Hammett, "P hysical Organic Chemistry", McGraw-Hill, New York, N. Y ., 19lt0, p . 96. (15) Z ie g le r and Conner, J. Am. Chem. Soc. , 62, 2596 (19U 0). (1 6 ) Kohler and T is h le r , i b i d . , 5 7 , 218 (1 9 3 5 ). (17) Bordwell and R ondestvedt, i b i d . , 70, 2^.29 (19U 8). (18) Brunswig, Ber. , 19, 2890 (1 8 8 6 ). (19) Gilman and Beaber, J. Am. Chem. Soc. , l|.7, llt50 (1 9 2 5 ). (20) Ford, Thompson and M arvel, i b i d . , 5 7 , 2619 (1 9 3 5 ). (21) Brown, i b id , 6 0 , 1325 (1 9 3 8 ). (22) K otz, Ann., 338, 195 (1 9 0 8 ).

Campaign and S u ter, J . Am. Chem. S o c ., 61;, 30i;0 ( 19l;2) . V e ib e l, i b i d . , 6 7 , 1867 (19U 5). Shriner and Fuson, "The S ystem atic I d e n t if ic a t io n o f Organic Compounds," 3rd e d ., John W iley and Sons, I n c ., New York, N. Y ., 19lt8. Meyer and Molz, Ber. , 30, 1271 (1 8 9 7 ). C la isen and Manasse, Ann. , 27U, 73 (1 8 9 3 ). Rupe and S p littg e r b e r , B er. , lj.0, 1;313 (1 9 0 7 ). Lapworth, J . Chem. Soc. , 91, 113U (1 9 0 7 ). Legge, J. Am. Chem. S oc. , 6 9 , 2079 (19U7) . Shriner and Fuson, "The System atic I d e n t if ic a t io n o f Organic Compounds," 2nd e d ., John W iley and Sons, I n c ., New York, N. Y ., 19i;0, p . 132. I b id . , p . 161;. Adams, "Organic R eaction s" , V o l. I , John W iley and Sons, I n c . New York, N. Y ., 19l;2, p . 161;.

VITA

Charles C. A l f i e r i was b o m Ju ly 1 9 , 1922, a t Groton, C onnecticut, th e son o f Mr* and Mrs. James A l f i e r i .

He atten d ed

Groton H eights grammar sc h o o l and Robert E, F itc h h ig h s c h o o l, graduating from th e l a t t e r i n 191+0*

In 191+3 he was granted th e

S c.B . degree cum laude from Brown U n iv e r s ity , P rovidence, Rhode I s la n d ,

A fter working s i x months fo r th e S h e ll O il Company,

Houston, Texas, and th r e e months f o r Ansco, Binghamton, New York, he was e n lis t e d in th e U nited S ta te s Navy and served th e r e in from June 191+U through June 191+6* to Ansco*

Upon le a v in g th e Navy, he returned

In February 191+7, he e n r o lle d i n the graduate sc h o o l

o f Purdue U n iv e r sity where he was employed as a graduate te a c h in g a s s is ta n t*

He was awarded a Purdue Research Foundation fe llo w s h ip

In September 191+8*

He i s a member o f th e American Chemical

S o c ie ty , Phi Lambda U p silon , and Signa X i,

He was granted t h e

degree o f Doctor o f P hilosophy from Purdue U n iv e r s ity , L a fa y e tte , Indiana, i n June 1950*