The synthesis of pure hydrocarbons

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The S y n th e s i s of Pure

c a rb o n s

The work began w ith th e p r e p a r a t i o n of a l i p h a t i c h y d ro c a rb o n s f o r th e m easurem ent o f t h e i r p h y s i c a l p ro p e rtie s .

The h y d ro c a rb o n s p r e p a r e d w e re :*

1)

3 ; 4 -P im.e th y ln o n a n e

2)

4: 5 "Dime th y ln o n a n e

3)

2 :6 - P im e th y lo c ta n e

The p r e p a r a t i o n o f 2 : 4 : 4 -T rim e th y 1hexane was a t t e m p t e d , th e k e to n e 2 : 4 : 4 -T r im e th y lh e x a n * 3~GH6 b e in g th e r e q u i r e d In te rm e d ia te ,

The p r e p a r a t i o n of t h i s was a t te m p te d by

th e r e a c t i o n betw een is o b u ty ra m id e and tejrt-am ylm agne sium b ro m id e .

The p r o d u c t , a t f i r s t th o u g h t t o be th e k e t o n e ,

showed t h a t an i n v e s t i g a t i o n of t h i s r e a c t i o n would prove in te re stin g , A s e r i e s o f r e a c t i o n s was th e n c a r r i e d o u t betw een f i v e a l i p h a t i c a c i d am ides and G rig n a r d r e a g e n t s p r e p a r e d from f i v e a l k y l iia l i d e s *

The r e s u l t s a r e s t a t e d in P a r t V

of th e t h e s i s and d i s c u s s e d in P a r t TV. c o n c l u s i o n s have b een drawn from th e

The f o l l o w i n g

results

obtained:*

1 ) The amide r e a c t s w i t h th e G r ig n a r d r e a g e n t in th e k e t o form and n o t i n th e im i n o - a lc o h o l fo rm , a s s u g g e s te d by p r e v i o u s w o rk e rs . An i o n i c mechanism i s th o u g h t t o summarize most s u c c e s s f u l l y th e r e s u l t s o b t a i n e d , 2 ) The amide c a u s e s th e d e c o m p o s itio n o f th e G rig n a rd re a g e n t.

T h is i s shown by th e volume of g a s e v o lv e d .

th e f a c t t h a t some of t h i s volume i s u n s a t u r a t e d , and th e p re s e n c e of s a t u r a t e d and u n s a t u r a t e d h y d ro c a rb o n s in th e l i q u i d p r o d u c ts * The reactions of acetamide are discussed. product is the condensed nitrile cyanmethine.

Here the

The mechanism is

thought to be similar to that of other amides in the first stage.

T ir

Gi/imwoiG

or

THESIS SUBMITTED FOR THE DEGREE OF PH.D.

by G.M.QV/EH. B.SO.

March, 1950.

ProQuest Number: 10097960

All rights reserved INFORMATION TO ALL U SE R S The quality of this reproduction is d ep endent upon the quality of the copy submitted. In the unlikely event that the author did not sen d a com plete manuscript and there are m issing p a g es, th e se will be noted. Also, if material had to be removed, a note will indicate the deletion.

uest. ProQ uest 10097960 Published by ProQ uest LLC(2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C ode. Microform Edition © ProQ uest LLC. ProQ uest LLC 789 East Eisenhow er Parkway P.O. Box 1346 Ann Arbor, Ml 48106-1346

The a u t h o r w is h e s to th a n k P r o f e s s o r S .E «T u rn er f o r h i s h e l p an d e n c o u ra g e m e n t th r o u g h o u t th e w o rk ,a n d th e In s titu te

of P e tr o le u m f o r f i n a n c i a l a s s i s t a n c e .

HTTRODÜGTIOÏÏ PART T

P r é p a r a t i o n of t h r e e h y d ro c a rb o n s 2 :6 -Dime t h y l o c t a n e , 3 : 4 -Dime th y ln o n a n e and

4 : 5 -Dimeth y ln o n a n e ♦

PART I I

A tte m p te d p r e p a r a t i o n of 2 : 4 :4 -T rlm e th y l‘h exane •

part I II

H i s t o r i c a l I n t r o d u c t i o n to th e work on am ides and G rig n a r d R e a g e n ts .

PART IV

D is c u s s i o n of th e r e s u l t s o b ta in e d from a s e r i e s o f r e a c t i o n s between am ides and G rig n a rd R e a g e n ts .

PART y part

VI

E x p e rim e n ta l. P r e p a r a t i o n of I n t e r m e d i a t e s .

httrootct M

The work f o r t h i s t h e s i s began w i t h th e p r e p a r a t i o n of some p u re h y d ro c a r b o n s f o r t h e measurement of t h e i r p h y s i c a l p ro p e rtie s *

The e x p e rir/ie n ta l d e t a i l s o f th e p r e p a r a t i o n of

t h r e e h y d r o c a r b o n s a r e r e p o r t e d in P a r t T*

They were a l l

p r e p a r e d by th e f o l l o w i n g g e n e r a l m e th o d :R

OH '^ C

\

= 0 + B, 1 CHp MgBr

>

.

CH GHg

^CHOH— ) R CH = CH R, /

r

^

i R C H ^ C H g R]_

The k e to n e r e q u i r e d f o r t h i s s y n t h e s i s was 2 : 4 :4 - t r i m e t h y l h e x a n o n e -3 , and i t s p r e p a r a t i o n was a t t e n ^ t e d by th e r e a c t i o n between is o b u ty ra m id e and t e r t -amylmagneslum

■bromide : CH. ^ CH^

OH. 1 3 CH CO HHp + C.Hp, - C - MgBr 2 2 5 , CH^

CH. 3

CH. I 3 ) CH CO C —CgHp7 ^ , 2 5 CH^ CH^

The r e c o r d e d v a lu e of th e b o i l i n g p o i n t o f th e k e to n e i s 158°«i61®C, an d a p r o d u c t was o b ta in e d b o i l i n g i n t h i s ran ge ($8 o - 6 2 «5 * /22 mm. )

T h is was assumed a t f i r s t to be

th e r e q u i r e d k e to n e (from th e r e s u l t s of r e c e n t work t h i s o p in io n h a s been r e v i s e d ) .

The y i e l d was v e r y low and th e

m ethod was o b v io u s ly of no use f o r th e p r e p a r a t i o n o f any q u a n t i t y o f a p u re h y d r o c a r b o n .

C r y s t a l s were n o te d on

th e s t i l l - h e a d d u r in g t h i s f r a c t i o n a t i o n .

These c o u ld

o n ly be due t o th e p r e s e n c e in th e p r o d u c t o f d i - t e r t -am yl, form ed by the c o u p lin g of th e t e r t -amyl r a d i c a l s , d u rin g th e r e a c t i o n of th e amide and G rig n a r d r e a g e n t . The s tu d y of th e r e a c t i o n betw een am ides and G rig n a rd r e a g e n t s had b een r e p o r t e d l i t t l e

in th e l i t e r a t u r e *

numerous r e a c t i o n s have been c a r r i e d o u t f o r th e p r e p a r a t i o n of a r e q u i r e d k e t o n e , b u t a stu d y of th e c o n d i t i o n s f o r o b t a i n i n g th e maximum y i e l d , and an i n v e s t i g a t i o n o f th e o t h e r p r o d u c t s of th e r e a c t i o n , f o r a s e r i e s of a m id e s , had n o t b een a t t e m p t e d . So ^ s e r i e s of r e a c t i o n s was c a r r i e d o u t b etw een am ides o f a l i p h a t i c c a r b o x y l ic a c i d s and G r ig n a r d r e a g e n t s p r e p a r e d from a l k v l h a l i d e s .

Some a r o m a tic G r ig n a r d r e a g e n t s were

a l s o u s e d , “but th e s tu d y o f a l l th e p r o d u c t s was n o t th e n p o ssib le .

The h y d ro c a rb o n s e v o lv e d a s a g a s when u s in g

a l i p i i a t i c G rig n a r d r e a g e n t s were l i q u i d imhen u s in g a r o m a tic G rig n a r d r e a g e n t s and mixed w ith th e h y d ro c a rb o n form ed by th e d e c o m p o s itio n o f th e e x c e s s G r ig n a r d r e a g e n t .

The

r e s u l t s o f t h i s s e r i e s of r e a c t i o n s i s r e p o r t e d in P a r t V o f t h i s t h e s i s , an d d i s c u s s e d in P a r t TV# The r e a c t i o n betw een G rig n a rd r e a g e n t s and am ides i s m ost s u c c e s s f u l f o r th e p r e p a r a t i o n of k e t o n e s , w hich a r e o f t e n d i f f i c u l t to o b t a i n pure by o t h e r m e th o d s.

Prom

th e r e s u l t s i t can be c o n c lu d e d , t h a t th e g r e a t e r th e c o n c e n t r a t i o n o f G rig n a r d s o l u t i o n combined w ith a s h o r t e r l e n g t h of h e a t i n g tim e , th e g r e a t e r w i l l be th e p u r i t y of th e p r o d u c t .

T h is i s p a r t i c u l a r l y so when th e g ro u p

a t t a c h e d to the c a r b o n y l c a rb o n atom slow s down th e r e q u i r e d re a c tio n .

Prom s t r a i g h t c h a in a c i d am ides and n - a l k y l

G rig n a r d r e a g e n t s h ig h y i e l d s of pure k e to n e can be o b t a i n e d .

PART I PREPARATION OP THREE HYDROCARBmS

The t h r e e h y d ro c a rb o n s p r e p a r e d in t h i s p a r t w e r e ; 1.

2 : 6 “D im e th y lo c ta n e GH 2- O H - GH^' CH^

O H y OH- GH^

2•

GH. GH^ i 3 3 :4 -Dime th y ln o n a n e GH j ' G H g- C H .- G H ' CH^-GH^' G H ^- C H g- GH^

CH3 GH^ 3«

4 : 5 -D im ethylnonane G H y GH^- G R ^ G H -G H ,- GH2~ C H g G H 2 -C H ^

GH^ CH3 As a l r e a d y s t a t e d , th e s e t h r e e h y d ro c a rb o n s were p r e p a r e d by th e a c t i o n o f a k e to n e on a G rig n a r d r e a g e n t , th e d e ­ h y d r a t i o n of th e r e s u l t i n g c a r b i n o l and th e r e d u c t i o n of th e o l e f i n , G a r e f u l f r a c t i o n a t i o n o f th e s t a r t i n g m a t e r i a l s , and th e i n t e r m e d i a t e p r o d u c ts was n e c e s s a r y a s a l l th e r e a c t i o n s u se d p ro d u c e d a m ix tu re of compounds; e . g . from th e r e a c t i o n betw een a k e to n e and a G rig n a r d r e a g e n t f o u r compounds a r e o b ta in e d in v a r y in g p r o p o r t i o n s 1 , K e to n e . 2 * Reduced k e t o n e , 3 . R e q u ire d c a r b i n o l , 4 , Condensed k e to n e * 1 and 2 a r e lo w e r b o i l i n g and 4 h i g h e r b o i l i n g th a n th e r e q u i r e d c a rb in o l. The d i s t i l l a t e was c o l l e c t e d in f r a c t i o n s , and o n ly th o s e w i t h th e same r e f r a c t i v e i n d i c e s were b u lk e d . th e p u r i t y of th e compound i s a s s u r e d th r o u g h o u t .

Thus

r P r e p a r a t i o n o f 2 : 6 -D im e th y lo c ta n e GHjCH-GH^CH^CH^CH-GH^GH^ GH^

GHj

T h is h y d ro c a rb o n was s y n t h e s i z e d a s f o l l o w s : GH

C H ,G O O H gC O O G gH ^

3

2

2 5

G H G H -G H gB r GH / 2 -J______________ > CH^COCHGOOC^H^

^

3

I

2 ^ 0H,

C H „CH oC H

2

r

/O ^

2

^

\C H ^

10^ KOH ^

CH^OHgO-OHgCHgCHgCH CH^

^GH^ J

CgH^MgBr CH^0 OCHgOHgOHgOH ^

^^OHj

^CH^

o l e f i n ----------^ hy dro carb o n * A specim en o f p ure isoam yl a l c o h o l was d i f f i c u l t to o b t a i n , b u t 400 gm* were s u p p l i e d w ith o n ly a s m a ll r o t a t i o n : 5461 C
1» 2 d.cm .

,5780 ^ I oC = -0,08 J 18 T h is a l c o h o l was c o n v e r te d i n t o th e hrom ide and 5^5 gm« of iso am yl hromide were o b t a i n e d , r e p r e s e n t i n g a y i e l d of 7 5 .8 ^ . P re p a ra tio n of iso a m y la c e to a c e tic e s t e r Q.UMTTITIBS A b so lu te a l c o h o l

l $ 6o c . c .

Sodium

71*8 gm.

A c e to a c e tic e s t e r

406 gm#

isoam yl brom ide

51? gm#

The sodium was ad d ed in sm a ll p i e c e s to th e a l c o h o l , t h a t was s t i r r e d c o n t i n u a l l y , a n d , on c o o l i n g , th e a c e t o a c e t i c e s t e r was ru n in*

To th e c o ld s o l u t i o n was

added th e iso a m y l b ro m id e, and th e whole h e a te d f o r 1^ h o u rs*

The a l c o h o l was th e n b o i l e d o f f and when c o l d ,

th e sodium bromide d i s s o l v e d in c o ld w ate r*

The u p p e r ,

e s t e r l a y e r was s e p a r a t e d , d r i e d o v er a n h y d ro u s p o ta s s iu m c a r b o n a te and d i s t i l l e d u n d e r vacuum.

6o c*c* o f a l i q u i d ,

b o i l i n g betw een 3 2 ^ -6 4 ^ /3 0 mm. were c o l l e c t e d i n an a l c o h o l / COg t r a p a t - 7 2° .

T h is was a m ix tu re of a l c o h o l and th e

e t h y l e s t e r of i s o h e p t o i c a c i d .

T h is was form ed by th e

h y d r o l y s i s of th e is o a m y l a c e t o a c e t i c e s t e r : C H v C O -O H -G O O GgHp-

^

I

CH^

CH.

\ h - CHg-

CHg CR g GH

C H ^ O H g- COO

CH. CH.

The r e s i d u e was f r a c t i o n a t e d : 2 0 .5

20

P ressu re

We i g h t 21 gm.

1 .4 1 2 7

1 .4 1 2 9

?R .

Bp.

1

33. 5 " - 3 4 . 2 «

1 mm.

2

3 4 .2 0 -6 4 .5 0

0*8 mm.

4 gm.

1 .4 1 4 4

1 .4 1 4 6

3

6 4 .5 0 -6 5 0

0*8 mm.

8 gm.

1 .43 06

1 .4 3 0 8

4

6 4 .5 0 -6 5 0

0 .8 mm.

117

1 .4 3 1 1

1 .4 3 1 3

5

650

0*8 mm.

135 g32l.

1 .4 3 1 1

1 .4 3 1 3

6

6 5 0 -6 9 ,5 0

0 .8 mm*

1 6 .5 gm. 1 .4 3 2 3

1 .4 32 5

'0

FR.

Bp •

6 9 .5 0 - 9 6 .5 0

7

9 6 .5 0

8 R e sid u e

20 %

2 0 .5

P ressu re

Weight

0 .8 mm.

3*5 gm.

1 .4 38 2

1 .4 3 8 4

0 .8 ram.

2 gm.

1 .4 4 0 0

1 .4 4 0 2

21 gm.

-

-

-

F r a c t i o n s 3-6 i n c l u s i v e were b u lk e d . F r a c t i o n s 7 > 8 and r e s i d u e were th e d i s u b s t i t u t e d e s t e r . Weight of i s o a m y l a c e t o a c e t i c e s t e r * 276 gm. (1 ,3 8 gm. mol) P r e p a r a t i o n o f M ethyl is o h e x y l k eto n e The e s t e r was b o i l e d w ith 4 .1 4 gm. m ol. of p o ta s s iu m h y d ro x id e in 10^ s o l u t i o n .

The s o l u t i o n was s t i r r e d .

The o i l y e s t e r l a y e r g r a d u a l l y d i s a p p e a r e d , b u t on b o i l i n g an u p p e r l a y e r of k e to n e was p ro d u c e d .

The k eto n e was

steam d i s t i l l e d from th e s o l u t i o n , d r i e d o v e r a n h y d ro u s p o ta s s iu m c a r b o n a te and f r a c t i o n a t e d u n d e r vacuum. 18

20

FR.

Bp.

P ressu re

We ig h t

1

-^ 7 0 .3 ^

30 mm.

1 gm.

1 .4 1 3 3

1.4125

“d

2

70.3®

30 mm.

50 gm.

1 .4 1 4 4

1 .4136

3

7 0 .3 °

30 mm.

Ç2 gm.

1 .4 1 4 4

1 .4136

4

7 0 .3 0

30 mm.

50 gm.

1 .4 1 4 4

1 .41 36

-

-

10 gm.

1 .43 98

1 .43 90

R esid ue

F r a c t i o n s 2 -4 i n c l u s i v e were b u lk e d . The r e s i d u e c o n t a in e d u n s a p o n i f i e d e s t e r . Weight o f k e to n e = 1^2 gm.

i . e . 1 .1 9 gm. m o l.

n

P r e p a r a t i o n o f 2 : 6 - D im e th y lo c ta n o l-6 Magnesium

57*9 gm.

(2 ,3 8 gm. mol*)

E t h y l bromide

28 4 .9 gm.

( 2 .3 8 gm, m o l.)

ISo

M ethyl/xhexyl k e to n e E th e r

1$2 gm. ( I . I 9 gm. m o l.)

14^0 c . c .

The magnesium was p la c e d in a 2 l i t r e f l a s k and c o v e re d w i t h 500 c . c . o f sodium d r i e d e t h e r . th e f l a s k were s t i r r e d and a l i t t l e

The c o n t e n t s of e t h y l bromide ru n i n .

The r e a c t i o n s t a r t e d e a s i l y , and th e re m a in in g e t h y l bromide was a d d e d .

The e t h e r was added i n two e q i a .1

volumes d u r in g th e f o rm a tio n o f th e eth ylm ag nesiu m b ro m id e . When c o o le d th e e t h e r s o l u t i o n was f i l t e r e d th r o u g h g l a s s wool to remove any p i e c e s of u n r e a c t e d magnesium. The r e a c t i o n b etw een th e ^ e to n e and ethy lm agn esiu m brom ide was v e ry v i g o r o u s .

A f t e r th e a d d i t i o n o f a l l th e

k e t o n e , th e s o l u t i o n was r e f l u x e d f o r l i a l f an h o u r , c o o le d , and decomposed by p o u r in g oftto i c e ;

th e magnesium h y d ro x id e

was d i s s o l v e d by c o n c e n t r a t e d h y d r o c h l o r i c a c i d and th e w a te r l a y e r e x t r a c t e d tw ic e w i t h e t h e r .

The combined e t h e r

l a y e r s were washed w i t h w a te r , 5^ sodium c a r b o n a te s o l u t i o n , 10^ sodium c h l o r i d e s o l u t i o n , and a g a in w i t h w a t e r . whole was d r i e d o v e r p o ta s s iu m c a r b o n a t e .

The

The e t h e r was

d i s t i l l e d o f f th r o u g h a 1 2 " packed column, and th e r e s i d u e vacuum d i s t i l l e d , 100 c . c . of low b o i l i n g l i q u i d were condensed in an

/JL

a l e olio I/GO2 t r a p - t h i s was a l l e t h e r

The r e s i d u e was

fra c tio n a te d » Bp*

FRo

20

P ressu re

Weight

1

560-58°

2 mm*

1 gm.

“d 1 .4 2 9 8

2

58° - 5 9 . 3°

2 mm*

1 gm.

1 .4326

3

5 9 . 3 ° - 5 9 .5® 2 mm*

11 gm*

1 .43 38

4

5 9 .5 °

2 mm.

32 gm.

1 .4339

5

5 9 . 5“

2 ^mm* ,

36 gm.

1 .43 39

6

59. 9 “

2*2 mm*

38 gm.

1 .4339

7

59. 9“

2 .2 mm*

20 gm*

1 .4340

6 gm#

1 .4 4 6 7

R esid u e

F r a c t i o n s 3«7 i n c l u s i v e were b u lk e d and d e h y d ra te d * P r e p a r a t i o n o f th e o l e f i n The c a r b i n o l was d e h y d r a te d by h e a t i n g i t u n d e r r e f l u x w ith p h t h a l i c a n h y d r id e , in an o i l b a th *

At I34® th e

p h t h a l i c a n h y d rid e a p p e a re d to m elt and im m e d ia te ly c r y s t a l s o f p h t h a l i c a c i d a p p e a r e d on th e b o tto m o f th e f l a s k *

The

whole was k e p t a t 1 $0°0 f o r t e n m in u tes* F r a c t i o n s 3, 4 and 5 were d e h y d r a te d t o g e t h e r and th e n f r a c t i o n s 6 and 7 *

The two volum es were b u lk e d and the

o l e f i n washed w ith 10^ sodium h y d ro x id e s o l u t i o n , and w a te r u n t i l n e u t r a l t o m o is t litm u s * c h l o r i d e and f r a c t i o n a t e d .

I t was d r i e d o v e r c a lc iu m

‘à

20

FR.

B p.

P ressu re

Volume

1

590. 59.2

»

24 mm.

1

2

59,2

»

24 mm.

10

c .c .

1 .4 2 6 9

c.c .

1 .4 2 6 9

3

5 9 .2 » -5 9 .3 °

24 mm.

10

c .c *

1 .4 2 7 0

4

5 9 . 3 ‘’- 5 9 . 4 »

24 mm.

10

c .c .

1 .4 2 7 1

24 mm.

11

c .c .

1 .4 2 7 3

5

59,4

6

60»

25

nim.

11

0 *0

.

1 .4 2 7 3

7

60 0

25

mm.

12

c .c .

1 .4 2 7 4

8

60»

25

mm.

20

c .c .

1 .4 2 7 4

9

60

»

25

mm.

20

c .c .

1 .4 2 7 4

25

mm.

15

c .c .

1 .4 2 7 6

25

mm.

3

c «C.

1 .4 2 8 2

10

®

600-6 0 . 5®

11

6 0 .5 0

F r a c t i o n s 2-11 i n c l u s i v e were b u lk e d . I t was e x p e c te d t h a t d e h y d r a t io n by means of p h t h a l i c a n h y d r id e would g iv e one compound, and n o t a m ix tu re o f iso m ers*

T he p o s s i b l e

/

iso m ers a re : -

OH

CH^-CH-CH2~ GR^ CR^ Ç"CR^ CH3 —^OR^- GR-CH^ CR^,CR»G-GRg- GH3 CH.

GH.

^1

CH,- CH-CH^ C R g CR^ G=CH-CH^ GH^

GHj- CR-GR^ GR^ GH^ G-GR^ GH^ GH.

GH,

GH

/4

The r e f r a c t i v e

in d ic e s of th e o l e f i n

m ix tu re o f iso m ers a re p ro d u c e d .

in d ic a te th a t a

T h i s w as p o s s i b l y due t o

t h e f a c t t h a t d e h y d r a t i o n was c a r r i e d o u t i n two p a r t s . d iffe re n t

A

i s o m e r was p r o d u c e d e a c h t i m e .

The o l e f i n was r e d u c e d in g l a c i a l a c e t i c a c i d u s i n g P tÛ 2 c a t a l y s t ,

and a hydro gen p r e s s u r e

o f Ç0 l b s / s q * i n c h .

A f t e r one r e d u c t i o n , b ro m in e i n c a r b o n t e t r a c h l o r i d e was n o t d e c o l o u r i z e d , b u t to e n s u re c o m p lete r e d u c t i o n ,

th e

h y d r o c a r b o n w as s h a k e n t w i c e w i t h c o n c . s u l p h u r i c a c i d . V e r y s l i g h t c l i a r r i n g o c c u r r e d w i t h t h e f i r s t w a s h in g * was t h e n w a s h e d t h r e e t i m e s w i t h 1 0 ^ so d iu m h y d r o x i d e tio n ,

It so lu ­

s i x tim e s w ith w a te r, and d r ie d over c a lc iu m c h l o r i d e ,

a n d f r a c t i o n a t e d t h r o u g h a 1 2 ” c o lu m n p a c k e d w i t h P e n s k e h e l i c e s and f i t t e d

w ith a h e a te d j a c k e t . 20

FR.

Bp

1

P ressu re

Volume

20 mm.

0 .5

c .c .

1 .4 10 7

2

220

20 mm.

5 c .c .

1 .4 1 1 0

3

240

19 mm.

16 c . c .

1 .4 1 1 0

4

240

19 mm.

15 c . c .

1 .4 1 1 0

5

240

19 mm.

20

c .c .

1 .4 1 1 0

6

54.250

19 mm.

20

c.c.

1 .4 1 1 0

7

540

19 mm.

12

c.c.

1 .4 1 1 0

8

540

19 mm.

6

c.c.

1 .4 1 1 0

F ra c tio n s 2 -8 94

c.c.

i n c l u s i v e w e re b u l k e d .

o f p u r e h y d r o c a r b o n w e re p r o d u c e d w i t h BP*54®/19 mni.

/S

20

and

1 , 4110.

.\HALYSES

M ethyl is o h e x y l k eto n e R e q u ire d

R ound

C

7 5 . 0#

7 5 .2 ^

H

1 2 ,5 #

1 2 . 4%

2 : 6 - d i m e t h y l o c t a n o l ~6 R e q u ire d

Round

0

7 5 . 9#

75.8%

H

1 3 *9^ .

1 4 . 0%

2 : 6 -d ime t h y l o c t a n e R e q u ire d

Round

C

8 4 . 55?

84.6%

H

1 5 .5 ^

1 5 .3 ^

/6

P r e p a r a t i o n of 1 : 4 -Dim ethylnonane CH^- CH-ÇH-CH ' CH - CH^ CH^ CH^ CH^CHj T h is h y d ro c a rb o n was s y n th e s iz e d a s f o llo w s CH^ CH^ CH-MgBr + CHj CQ-CH^ CH" CH^ CK^“ CH^ ------^^3

^OH

\|
B-C

/

% E-H

K-Mg X

lOmg X b) R-C

\

+ Ev R-Mg X

\

R-C

R-Mg X

+ MgO MgX^

c)

Ri

R.

/

R-0 %

+ HpO

------- \

/

R-C

%

R-Mg X

X + Mg

/ \

M ,

OH

The k e to n e was o b t a i n e d by b o i l i n g th e k e t im in e w ith h y d r o c h l o r i c a c id * Rl

Ri

/

%

R-G

b o i l w ith HCl : >

/ R-C^

\

NH

^

+ m . 0

V in c e n t G a rr M eu nier ( 5 ) h a s c a r r i e d o u t a s e r i e s o f r e a c t i o n s on p in a la m id e and h a s sum m arized h i s c o n c l u s i o n s a s to th e c o u r s e of th e r e a c t i o n , i n th e f o l l o w i n g f o u r e q u a tio n s: OH a) R -G ^

Omg X +

RnMg X ------> R - c '^

m

+ R,H m

Omg X b ) R - C '^

+

R.Mg X ------ >R-ChH MgO MgXg + R^H

c ) R-GsH MgCMg Xg + R^Mg X

>R-C=H MgX MgO MgX^ Rl

d ) R-C=H MgX MgO MgXg + 3H0H

»R-C= 0 Rl

+

+ 3Mg(QH)X

The r e a s o n s f o r s u g g e s t i n g th e s e s t a g e s a r e summ arized b e lo w :-

A4

a ) One m o le cu le o f t r l m e t h y l a c e t a m i d e and one m o le c u le of m éthylm agnésium io d id e e v o lv e d one m o le c u le o f m e th a n e # When one m o le c u le of amide was t r e a t e d w ith one m o le c u le of eth y lm a g n e siu m brom ide and th e r e a c t i o n m ix tu re h y d r o l y s e d , t r i m e t h y l a c e t a m i d e was p r e c i p i t a t e d i n good y ie ld . b ) The b a s i s f o r t h i s e q u a t i o n i s th e f o l l o w i n g A Z e r e w i t i n o f f d e t e r m i n a t i o n , w ith two m o le c u le s o f m é th y l­ m agnésium io d id e and one m o lecu le o f t r i m e t h y l a c e t a m i d e , gave two m o le c u le s o f m e th an e .

W ith two m o le c u le s of

e th y lm a g n e sium brom ide and one m o le c u le of a m id e , a s o l i d was fo rm e d . n itrile ,

H y d r o l y s i s of t h i s solid gave t r i m e t h y l a c e t o A s o l i d of s i m i l a r p r o p e r t i e s was o b t a i n e d from

th e r e a c t i o n of t r i m e t h y l a c e t o n i t r i l e , magnesium o x id e and a n h y d ro u s magnesium b ro m id e.

The s t r u c t u r e s o f th e

p r o d u c t s from e q u a t i o n s a ) and b) d i f f e r a s h y d r o l y s i s of a ) g i v e s amide an d b ) th e n i t r i l e , b u t t h e y were n o t in v e s tig a te d th o ro u g h ly . c ) I t i s s u g g e s te d t h a t th e t h i r d m o le c u le of G rig n a r d r e a g e n t a d d s t o th e OsH g r o u p in g . d) T h is e q u a t i o n i s d e r i v e d from th e f a c t t h a t t h r e e m o le c u l e s of etihylm agnesium brom ide and one m o le c u le of t r i m e t h y l a c e t a m i d e gave 78% of e t h y l t e r t - b u t y l k e t o n e . A ls o , th e h y d r o l y s i s of th e com plex fro m th e r e a c t i o n of one m o le c u le o f amide w i t h t e n m o le c u l e s o f m éthylm agnésium

HI

i o d i d e , gave one m o lecu le of ammonia. Some e x p e r im e n ts were c a r r i e d out by Montagne ( 6 ) on t h r e e H - d i s u b s t i t u t e d a m id e s.

They we re : -

OpHf 1 ) C H ^C O ir^

CH. 2 ) CH^CHjCHgCON

P2«5 3 ) GH^GHgGHgCOm \ an d th e G r ig n a r d r e a g e n t s u se d were C2H^MgBr and CgH^Mgl# The f o l l o w i n g r e s u l t s were n o t e d . a l a r g e volume of g a s was e v o lv e d .

In a l l th e r e a c t i o n s Some k e to n e was

p r o d u c e d in th e r e a c t i o n s of 2 ) an d 3)» T^ut th e p r i n c i p l e p r o d u c t was a t e r t i a r y b a s e ; -

G H ,G H pG H ^G — H

where R r e p r e s e n t s th e r a d i c l e of th e G r ig n a r d r e a g e n t and th e r a d i c l e j o i n e d to th e n i t r o g e n atom i n t h e o r i g i n a l d i s u b s t i t u t e d a m id e . The d i s u b s t i t u t e d a c e ta m id e ,

i t was r e p o r t e d , n e i t h e r

gave a k e to n e n o r a compound o f t h i s t y p e .

The p r i n c i p l e

p r o d u c t of th e r e a c t i o n was a /S -k e to n ic d i s u b s t i t u t e d amide ; C2H5 GHjGOGHgOOE G.H 2^5

4r

To a c c o u n t f o r i t s p r o d u c t i o n , t h e f o l l o w i n g mechanism was s u g g e s t e d : a)

GpH^ + CgH^MgBr—

0

I

I

C H ^C -H ^

+ C2H5

1

OMgBr G2H5 to)

0H2-=0-35r

^2^5 >

^ OMgBr

^

H-M gBr

\

GgHj

+

GH^O CHCOH

\:p H r ^

GpHcr / c ) 1 -MgBr

C2H5

OMgBr ^

CpHe + GHpG=.GHGOÎT

I

OMgBr

\

^

GgH^

C2H5 M-H

GHpCOCH^COH'^

/ C2H5

\

G2H^

Many r e a c t i o n s a r e r e p o r t e d in t h e l i t e r a t u r e betw een a l i p h a t i c G r i g n a r d r e a g e n t s a n d a m id e s , f o r t h e s y n t h e s i s o f a c e r t a i n w anted k e t o n e .

These a r e , how eve r, th e o n ly

mechanisms t h a t have been p u t f o r w a r d to a c c o u n t f o r t h e r e s u l t s obtained.

6?

PART IV D i s c u s s i o n of R e s u l t s .

So

D i s c u s s i o n of e a r l i e r t h e o r i e s The e x p l a n a t i o n p u t f o r w a r d hy B e i s ( 2 ) t o a c c o u n t f o r t h e f o r m a t i o n o f a k e t o n e and ammonia from t h e r e a c t i o n betw een a number o f a l i p h a t i c am ides and G r i g n a r d r e a g e n t s , i n v o l v e s a s i m u l t a n e o u s s u b s t i t u t i o n and a d d i t i o n o f t h e G r i g n a r d reagent.

ITo a t t e m p t was made to i s o l a t e t h e i n t e r m e d i a t e

p r o d u c t s - suc h an a t t e m p t would p r o b a b l y have b e e n u n s u c c e s s f u l , a s t h e r e a c t i o n s of the am ides u s e d by him are very ra p id . In a d d i t i o n , t h e volume of g a s g i v e n o f f fro m t h e r e a c t i o n s , a s summarized i n h i s e q u a t i o n ; 0 R -0 ^

+ 2RnM gX

\

>R

QmgX

\ G/ ^

/ \

R^

+ R,H

lIHMgX

i s much l e s s t h a n h a s b een fou n d from a r e p e t i t i o n o f some of h i s e x p e r i m e n t s .

In h i s o r i g i n a l p a p e r on t h i s work,

he d o e s n o t s t a t e t h a t he measured th e volume of g a s g i v e n off. The y i e l d of k e t o n e o b t a i n e d fro m t h e r e a c t i o n s between a c e t a m i d e , p r o p i o n a m i d e , b u ty r a m id e , i s o v a l e rami de and benzamide i s s t a t e d t o be betw e en 20^ and

The f a c t

t h a t o t h e r p r o d u c t s - t h e n i t r i l e and h i g h b o i l i n g n i t r o g e n ) c o n t a i n i n g r e s i d u e - a r e o b t a i n e d fro m t h e s e r e a c t i o n s , i s ig n o red .

A s p e c i a l n o t e i s made of t h e f a c t t h a t a c e t a m i d e does n o t g i v e low y i e l d s of k e t o n e , b u t i t h a s a lw a y s been found t h a t , i f any k e t o n e were p r e s e n t i n t h e p r o d u c t of t h e r e a c t i o n s betw e en a c e ta m id e a n d G r i g n a r d r e a g e n t s , h as been very d i f f i c u l t to d e te c t*

it

The h i g h e s t y i e l d of

6% was o b t a i n e d from t h e p r o d u c t s of t h e r e a c t i o n b e tw e e n

a c e ta m id e and n -butylroagnesium b r o m id e . R a m a r t- L u c a s , Lac10t r e and A n a g n o s t o p o u lo s (3) co n s id e re d the fo rm a tio n of the n i t r i l e d u rin g the r e a c t i o n . They s u g g e s t t h a t t h e amide r e a c t s i n t h e i m i n o - a l c o h o l form and t h a t two gram m o l e c u l e s of g a s a r e g i v e n o f f f o r e v e r y gram m o le c u le o f amide a dde d t o t h e G r i g n a r d r e a g e n t . T h i s , how ever, h a s o n ly been found to be so o c c a s i o n a l l y . U s u a l l y a volume of g a s v a r y i n g between 7 ,4 7 0 c . c . and 14^940 c . c . h a s been e v o l v e d d u r i n g th e r e a c t i o n s . Bruzau (4) d i s c u s s e s a t some l e n g t h th e d i f f i c u l t y i n d e c i d i n g w h e th e r t h e amide r e a c t s i n th e k e t o o r imino*» a l c o h o l f o rm .

I t i s f i n a l l y d ecid ed t h a t the suggested

mechanism o f Ramart -Lucas e t a l ( 4 ) i s c o r r e c t , b u t unfinished.

To a c c o u n t f o r t h e f o r m a t i o n o f t h e i n t e r m e d i ­

a t e compound

C

/

C

X

a f u r t h e r m o l e c u l e o f G r i g n a r d r e a g e n t i s u se d in t h e reactio n .

The q u e s t i o n im m e d ia te l y a r i s e s a s to why t h i s

'fj.

f u r t h e r r e a c t i o n d i d n o t t a k e p l a c e when R a m a r t•L u c a s was working w i t h e x c e s s of G r i g n a r d r e a g e n t .

The p r o p o r t i o n s

used by R a m a rt-L u c a s were tiii*ee m o l e c u l e s of G rigtfa rd r e a g e n t t o one m o le c u le of am ide, a n d i t would be e x p e c t e d t h a t a t l e a s t some of th e i n t e r m e d i a t e complex would have reacted fu rth e r,

i f such a r e a c tio n o cc u rre d .

In a d d i t i o n , t h e f o r m a t i o n of t h e k e t i m i n e f o r which Bruzau i s t r y i n g to a c c o u n t , can be sim ply e x p l a i n e d by assum ing t h a t the organo-magnesium complex o f B e is decomposes in two s t a g e s : R

OMgX

/ \

Rj_

^ MHMgX

R

OH

/ \

+ 2 M g '^

\

X

i

R

\

OH

C=NH

+ H„0

H

\

0=0 + ÎTH

In most c a s e s t h e k e t i m i n e v/ould be u n s t a b l e , and r e a c t i m m e d ia te l y w i t h w a t e r to g i v e t h e k e t o n e and ammonia but t h a t o b t a i n e d by Bruzau was a s t a b l e compound, and had to be b o i l e d w i t h d i l u t e h y d r o c i i l o r i c a c i d b e f o r e th e k e t o n e was formed f ro m i t .

S3

The a c c o u n t o f t h e work o f M e u n i e r ( 5 ) on th e r e a c t i o n s of p i n a l a m i d e w i t h alk y lm a g n e siu m h a l i d e s c o n t a i n s a number of sweeping s t a t e m e n t s t h a t a r e n o t j u s t i f i e d when th e r e s u l t s of a s e r i e s of e x p e r i m e n t s u s i n g am ides o t h e r t h a n pinalam ide are studied»

Again, t h e amide i s assumed to

r e a c t i n t h e i m i n o - a l c o h o l fo rm , and two m o l e c u l e s of g a s a r e assumed t o be g i v e n o f f f o r e v e r y m o le c u le of amide used» T h i s , a s s t a t e d b e f o r e , h a s n o t been fo u n d t o be the c a s e . Jxi

a d d i t i p n , i t h a s been found t h a t v^en p i n a l a m i d e was

added t o n - p ro p y lm a g n e s iu m bromide and the r e a c t i o n m i x t u r e h e a t e d f o r a s lo n g a s t e n h o u r s , t h e k e t o n e o b t a i n e d on d e c o m p o s i t i o n was c o n t a m i n a t e d w i t h h i g h b o i l i n g n i t r o g e n c o n t a i n i n g compounds»

As t h e s e were n o t d e t e c t e d when the

r e a c t i o n m i x t u r e was h e a t e d f o r o n l y t h r e e h o u r s , t h e r e must be a r e a c t i o n t a k i n g p l a c e w hich h a s p r e v i o u s l y been i g n o r e d . I n s u p p o r t o f t h e i n t e r m e d i a t e compound ROE MgOMgBr^ M e u n ier c l a i m s t h a t a s i m i l a r compound was o b t a i n e d by t r e a t i n g t r i m e t h y l a c e t o n i t r i l e w i t h a m i x t u r e of magnesium oxid e a n d a n h y d r o u s magnesium b r o m i d e .

The m i x t u r e of

o x i d e , bromide and b a s i c bromide o b t a i n e d by f u s i n g h y d r a t e d magnesium b r o m id e , was b o i l e d w i t h t r i m e t h y l a c e t o n i t r i l e f o r s i x h o u r s i n e t h e r s o l u t i o n , b u t no : such i n s o l u b l e complex was o b t a i n e d .

ITo a t t e m p t was made by M eunier to s u g g e s t

a p o s s i b l e f o r m u l a f o r t h i s compound. The e x p e r i m e n t s of Montagne (6) on E - d i s u b s t i t u t e d am ides a r e o f i n t e r e s t , p a r t i c u l a r l y , f o r one s t a t e m e n t

J4

t h a t i s made*

I t i s p o i n t e d out t h a t in a l l th e

experim ents b etw een:/ 1)

2«5

CH.con

3

2) CH.CHpCH^COH^

\

3

^

^

C2H5

C2H5 /°2 ^ 5

3) OH^OHgCHgCOn ^ C2H5 and G r i g n a r d r e a g e n t s , a l a r g e volume of g a s was e v o l v e d . The t e r m ”a l a r g e volume" i s i n d e f i n i t e , b u t more t h a n one m o le c u l e of g a s p e r m olecule of amide would be e x p e c t e d But i n t h e mechanism t h a t h a s been p u t f o r w a r d t o e x p l a i n t h e f o r m a t i o n of t h e p r o d u c t s o b t a i n e d , o n ly one m o le c u le of g a s p e r m o le c u l e of amide i s a c c o u n t e d f o r *

I t would

a p p e a r f ro m t h i s t h a t a f a c t o r i s in o p e r a t i o n t h a t h a s been i g n o r e d i n th e e x p l a n a t i o n *

ITo a t t e m p t i s t o be made

h e r e t o s u g g e s t th e s t r u c t u r e o f th e p r o d u c t s from the r e a c t i o n s of H - d i s u b s t i t u t e d am ides w i t h G r i g n a r d r e a g e n t s * These r e a c t i o n s were o n ly c a r r i e d out i n t h e p r e s e n t s e r i e s t o a s c e r t a i n w h e t h e r t h e k e to n e was formed»

The a n a l y s i s

o f the o t h e r p r o d u c t s i s a work a p a r t from th e p r e s e n t considerations*

The r e a c t i o n s a r e however l i n k e d up w i t h

t h o s e of am ides by t h e m e n tio n of th e l a r g e volume of g a s t h a t i s e v o l v e d - a f a c t n o t a c c o u n t e d f o r i n the e x p l a n a ­ t i o n s g iv e n *

S6^

G e n e r a l s u r v e y o f p o s s i b l e r e a c t i o n mechanisms Having d i s c u s s e d t h e Mechanisms t h a t have h ee n p u t f o r w a r d t o e x p l a i n th e r e a c t i o n s between am ides and G rignard r e a g e n ts , i t

i s now p o s s i b l e to s u r v e y th e f a c t s

gene r a l l y . The f i r s t th o u g h t t o e n t e r t h e mind when c o n s i d e r i n g t h e r e a c t i o n o f an amide w i t h a G r i g n a r d r e a g e n t i s t h a t th e amide i s f i r s t d e h y d r a t e d by th e G r i g n a r d r e a g e n t , to form t h e n i t r i l e ;0 H

R -G

/\»

+ R^M gX — >.R -C =H + R ,H

+ Mg

m

/

X

m

A f t e r c a r r y i n g out a few r e a c t i o n s , when t h e n i t r i l e is the p r i n c i p a l p rod uct,

i t i s r e a l i z e d t h a t t h i s sim ple

ex p lan atio n is not p o s s ib le . k e t o n e or n i t r i l e

In a l l r e a c t i o n s , w h e th e r

i s th e main p r o d u c t , an e t h e r i n s o l u b l e

organo-magne sium complex i s formed.

C onsidering the

r e a c t i o n between b u t y r a m i d e and t e r t - b u ty lm a g n esiu m b r o m id e , i f t h e above sim ple e x p l a n a t i o n were c o r r e c t , t h e r e a c t i o n m i x t u r e would c o n s i s t of an e t h e r l a y e r c o n t a i n i n g the n i t r i l e , and a w h ite p r e c i p i t a t e of t h e i n o r g a n i c magnesium compound.

But a l t h o u g h s e p a r a t i o n o f th e e t h e r s o l u b l e

and i n s o l u b l e p a r t s h a s n o t been e a s y , t h e r e s u l t s i n d i c a t e t h a t the n i t r i l e p recip itate.

i s p r o d u c e d from t h e e t h e r i n s o l u b l e

I t i s o b vious from th e c r y s t a l l i n e n a t u r e of

t h i s p r e c i p i t a t e , and i t s immediate r e a c t i o n w i t h w a t e r .

^6

t h a t i t c a n n o t he an i n o r g a n i c compound, suc h a s b a s i c magnesium bromide (Mg

)

I t h a s been n o t i c e d r e p e a t e d l y in t h e s e r e a c t i o n s t i i a t when th e amide i s added t o th e G r i g n a r d r e a g e n t , r e a d i ly , appearing to d i s s o l v e .

it reacts

A fter heating fo r a sh o rt

w h i l e , t h e l e n g t h of time depending on th e amide u s e d , the e th e r insoluble p r e c ip ita te

i s form e d.

I t m ight be a r g u e d

t h a t th e sim ple d e h y d r a t i o n o c c u r r e d , fo rm in g t h e n i t r i l e , and t h i s n i t r i l e

t h e n c o - o r d i n a t e d the magnesium s a l t t o

itse lf :-

Mg ^OH R-CHN

X

---------- > R-C5N:— ^OH

f o rm i n g a compound i n s o l u b l e in e t h e r , t h u s g i v i n g the w h ite c r y s t a l l i n e p r e c i p i t a t e t h a t i s a l w a y s p r o d u c e d . T h i s sim p le e x p l a n a t i o n can a g a i n be shown t o be im possible h e r e .

M eunier s u g g e s t s t h a t th e f i r s t r e a c t i o n

to o c c u r betw een an amide and a G r i g n a r d r e a g e n t i s the follow ing : ^O H R-C

OMgX + R.MgX

>R-C

\m

4 R-H

57

He p o i n t s out t h a t when one gram m o le c u l e of p i n a l a m i d e i s added t o one gram m o le c u le of e th y lm a g n e s iu m bromide ( i n e t h e r s o l u t i o n ) one volume of g a s i s e v o lv e d *

I f th e

r e a c t i o n m i x t u r e i s im m e d ia te l y h y d r o ly z e d » t r i m e t h y l a c e t a m i d e i s p r e c i p i t a t e d i n good y i e l d .

T h i s e x p e r i m e n t h a s been

r e p e a t e d , and a s i m i l a r r e s u l t o b ta in e d * d e h y d r a t i o n o f th e amide to the n i t r i l e

I f a sim ple o c c u r r e d , th e amide

would n o t be o b t a i n e d on h y d r o l y z i n g th e p r o d u c t of t h e reaction* A p o s s i b l e mechanism t o a c c o u n t f o r t h e f o r m a t i o n of n i t r i l e and k e t o n e i n one r e a c t i o h c o u l d be deduced by com bining t h e s u g g e s t e d mechanisms of Be i s (3) and R a m a r t L ucas ( 4 ) .

A b s o r p t i o n m easurements i n d i c a t e t h a t am ides

c o n s i s t of an e q u i l i b r i u m m i x t u r e of two forms:-* 0

Œ

R-C*

R-C 2

I s i t n o t p o s s i b l e t h e n f o r t h e k e t o n e t o be p r o d u c e d from th e k e t o form , a s s u g g e s t e d by B e i s , and t h e n i t r i l e from t h e .l^jaino-alcohol form , a s s u g g e s t e d by R am art-L ucas? A little

t h o u g h t on t h i s p o i n t shows i t to be i m p o s s i b l e ,

a s i t would t h e n be n e c e s s a r y f o r t h e n i t r i l e - p r o d u c i n g r e a c t i o n t o e v o lv e tw ic e a s much g a s a s t h e k e t o n e producing r e a c tio n *

A s t u d y of th e f o l l o w i n g g a s volumes

w i l l show t h i s t o be c o n t r a r y t o e x p e r i m e n t a l f i n d i n g s : -

Y i e l d of Ketone Gas e v o l v e d

REACTION n - B u ty r a m id e + n - B u % B r

70%

1 1 ,2 5 0 c c . 1 0 ,5 0 0 c c .

n - B u ty r a m i d e + sec -BulCgBr n - B u ty r a m id e + n-PrMgBr

66%

1 4 ,9 2 5 c c .

n - B u ty r a m id e + i s o p r o p y l MgBr

^ 3%

15,0 0 0 c c .

P i n a l a m i d e + n-PrMgBr

23%

1 2 ,0 5 0 c c .

P i n a l a m i d e + is o p r.M g B r

neg lig ible

1 2 ,5 0 0 c c .

P ro p io n a m id e + n-PrMgBr

61%

1 4 ,2 5 0 c c .

P ro p io n a m id e + iso p r .M g B r

2,2%

13*500 c c .

P ro p io n a m id e + sec-BuKfeBr

29%

9 ,7 5 0 c c .

Wben a few r e a c t i o n s between p i n a l a m i d e and G r i g n a r d r e a g e n t s had been c a r r i e d o u t , and th e p r o d u c t s a n a l y s e d , i t was q u i t e o b v io u s t h a t the h i g h y i e l d s of k e t o n e o b t a i n e d i n t h e s e r e a c t i o n s by Whitmore, îToll and Meunier ( 7 ) were not being d u p lic a te d .

The r e s u l t s o b t a i n e d , and th o s e

o b t a i n e d by Whitmore a r e t a b u l a t e d b e l o w : Whitmore R eaction

Y i e l d of Ketone

Y i e l d of Ketone

P i n a l a m i d e + nPrMgBr

23%

(>7 %

P i n a l a m i d e + nBuMgBr

26%

68%

P i n a l a m i d e + i s o p r o p y l MgBr

N egligible

20%

The e x p e r i m e n t a l c o n d i t i o n s of % i t m o r e were d i f f e r e n t from t h o s e u s e d d u r i n g t h i s s e r i e s of e x p e r i m e n t s .

The tim e of

h e a t i n g and th e c o n c e n t r a t i o n of t h e G r i g n a r d s o l u t i o n were d i f f e r e n t i n t h e two c a s e s .

Whitmore p r e p a r e d two gram

m o l e c u l e s of t h e G r i g n a r d r e a g e n t $n 7OO c c . o f a n h y d r o u s

e t h e r and h e a t e d f o r 15 h o u r s «

I n t h e p r e s e n t s e r i e s of

e x p e r i m e n t s , one and one t h i r d gram m o l e c u l e s of G r i g n a r d r e a g e n t were p r e p a r e d i n 800 c c . o f a n h y d r o u s e t h e r i . e . t h e e q u i v a l e n t of two gram m o l e c u l e s in 1 , 200. c c .

A few

r e a c t i o n s were c a r r i e d out w i t h p i n a l a m i d e , u s i n g a s o l u t i o n o f t h e same c o n c e n t r a t i o n a s t h a t u s e d by W hitm ore, As o n ly one f a c t o r a t a time was a l t e t e d , th e h e a t i n g time was s t i l l k e p t a t t h r e e h o u r s .

Under t h e s e c o n d i t i o n s th e

h i g h y i e l d s of Whitmore were o b t a i n e d .

T h i s e f f e c t of t h e

c o n c e n t r a t i o n o f th e s o l u t i o n on th e p r o d u c t s of th e r e a c t i o n of b u t y r a m i d e w i t h G r i g n a r d r e a g e n t s was n e x t i n v e s t i g a t e d , b u t i t was found h e r e t h a t c o n c e n t r a t i o n d i d n o t e f f e c t th e y i e l d o f k e t o n e . In t r y i n g t o a r r e s t the p r o g r e s s of th e r e a c t i o n , and d e t e r m i n e th e s t r u c t u r e o f t h e i n t e r m e d i a t e compounds, a n o t h e r d i f f e r e n c e was f o u n d i n t h e r e a c t i o n s of th e b u t y r ­ amide and p i n a l a m i d e .

The amide was added to th e G r i g n a r d

r e a g e n t ( t h e e q u i v a l e n t of m o le c u le of e a c h b e i n g u s e d ) . The a d d i t i o n was c a r r i e d out a s q u i c k l y a s p o s s i b l e , and the r e a c t i o n m i x t u r e t h e n decomposed.

Whereas w i t h p i n a l a m i d e

th e o r i g i n a l amide was o b t a i n e d u n c h a n g e d , b u ty r a m id e gave a m i x t u r e of k e t o n e , n i t r i l e and a m id e .

In t h e c a s e of

p i n a l a m i d e t h e r e had d e f i n i t e l y been a r e a c t i o n , a s t h e e q u i v a l e n t of one gram m o le c u le of g a s was c o l l e c t e d , when one gram m o le c u le o f amide was u s e d .

The r a t e of t h e

éc

r e a c t i o n p r o d u c i n g t h e k e t o n e and n i t r i l e was o b v i o u s l y much g r e a t e r when u s i n g b u ty r a m id e t h a n when u s i n g p i n a l a m i d e , a l t h o u g h th e f i r s t r e a c t i o n was r a p i d in b o t h c a s e s . The f o rm u la e f o r b u ty ram id e ( 1 ) GH^CH2GH2C 01ÏÏÎ2

( l ) and p i n a l a m i d e (2) a r e : GH^

( 2 ) CH^

: G-G01ÏÏÎ.

GHj One o b v io u s d i f f e r e n c e between t h e s e two f o r m u l a e i s th e amount of s t e r i c h i n d r a n c e a ro u n d t h e c a r b i n o l c a r b o n ato m . When c o n s i d e r i n g a p o s s i b l e mechanism f o r th e f i r s t p a r t of t h e r e a c t i o n ,

i t i s n e c e s s a r y t o d e c i d e w h e th e r

t h e amide r e a c t s i n t h e k e t o o r e n o l f o r m . t h e p r e s e n t s e r i e s of r e a c t i o n s ,

A fte r studying

i t h a s been d e c i d e d t h a t

w h e th e r t h e p r o d u c t i s a l l n i t r i l e

or m a i n l y k e t o n e , th e

f i r s t p a r t of t h e r e a c t i o n i s t h e same.

The î T - d i s u b s t i t u t e d

am ides a r e known t o g i v e k e t o n e s i n t h e i r r e a c t i o n s w i t h G rignard re a g e n ts ( i . e . a l l except H - d i s u b s t i t u t e d acetam ide) a l t h o u g h in lo w e r y i e l d s t h a n the u n s u b s t i t u t e d a m id e s .

In

a d d i t i o n , the o r g a n o - m e t a l l i c complex formed i s w h i t e , c r y s t a l l i n e and i n s o l u b l e i n e t h e r , a p p e a r i n g very much l i k e t h e s i m i l a r p r o d u c t from t h e u n s u b s t i t u t e d a m id e s .

In these

I T - d i s u b s t i t u t e d a m id e s, t h e k e t o - i m i n o a l c o h o l ta u to m e r i s m is prevented.

Here t h e n , th e k e t o n e must be o b t a i n e d from

t h e k e t o f o rm , a n d i t i s r e a s o n a b l e t o assume from t h i s t h a t the f i r s t r e a c t i o n of a l l am ides w i t h G r i g n a r d r e a g e n t s

y

t a k e s p l a c e w h ile th e amide i s a l s o in th e k e t o form* The e l e c t r o n i c s h i f t in th e amide m o le cu le i s away from t h e -ITH

group:S0

T h i s l e a v e s t h e n i t r o g e n atom w i t h a s m a l l p o s i t i v e c h a r g e , and the oxygen atom w i t h a s m a ll n e g a t i v e charge#

The

f i r s t p a r t of th e r e a c t i o n between am ides and G r i g n a r d r e a g e n t s can be summarized a s below i n v o l v i n g an i o n i c mechanism : -

R-C m

T T h i s i n t e r m e d i a t e compound has th e same s t r u c t u r e a s t h a t s u g g e s t e d by M e u n i e r . d i f f e r e n t mechanism.

I t Has however been p rodu ced by a The d r i f t of e l e c t r o n s away from

t h e n i t r o g e n atom e n a b l e s the above r e a c t i o n t o t a k e p l a c e e a s i l y , a s a l o o s e n i n g of t h e n i t r o g e n - h y d r o g e n bonds i s brought a b o u t. T h i s i n t e r m e d i a t e compound would, on d e c o m p o s i t i o n , g i v e back th e o r i g i n a l a m i d e : -

OîIgX R-C

\

/

OH + HpO------- ^

/

R-C

+ Mg

\

^ m

j

X

\

m

/

OH

y

^

HH

2

T his a g re e s w ith exp erim en tal ev iden ce. T h i s f i r s t p a r t of t h e r e a c t i o n shows t h a t one m o le c u le of g a s i s e v o l v e d f o r e v e r y m ole cule of amide u s e d .

But

t h e volumes of g a s c o l l e c t e d have alw ays been much g r e a t e r than t h i s .

T h i s f a c t » and the f o r m a t i o n of some u n u s u a l

p r o d u c t s i n th e l i q u i d p h a s e , have l e d t o th e c o n c l u s i o n t h a t th e G r i g n a r d r e a g e n t i s decomposing u n d e r t h e i n f l u e n c e o f t h e a m id e .

When u s i n g t e r t -butylm agne sium b ro m id e , th e

s o l i d h y d r o c a r b o n 2 : 2 : 3 î 3 - t e t r a r a e t h y l b u t a n e was a lw a y s one of t h e p r o d u c t s .

The c l o s e b o i l i n g p o i n t o f t h i s and the

n i t r i l e s p r o d u c e d d u r i n g t h e r e a c t i o n made i t d i f f i c u l t to i s o l a t e t h e p r o d u c t s , e x c e p t i n the r e a c t i o n between a c e t a m i d e and t e r t -b u ty lm a g n esiu m b r o m id e .

Here t h e main

p r o d u c t was t h e co n d e n sed n i t r i l e , much more s o l u b l e i n w a t e r t h a n i n e t h e r , a n d i t was p o s s i b l e t o show t h a t 2 : 2 : 3 : 3 * i - t e t r a m e t h y l b u t a n e and a s m a ll amount of an u n s a t u r a t e d l i q u i d were p r o d u c e d .

The w h ite s o l i d t h a t

was o b t a i n e d on d i s t i l l a t i o n b o i l e d between 1 0 0 ®-1 0 6®C.

It

a p p e a r e d t o be mixed w i t h a s m a ll amount of l i q u i d , and was

63

t e s t e d f o r u n s a t u r a t i o n by a d d i t i o n t o a s o l u t i o n of bromine i n c a r b o n t e t r a c h l o r i d e . im m e d i a t e l y removed.

The c o l o u r was

The o n ly o t h e r p o s s i b l e p r o d u c t s

were u n r e a c t e d t e r t - b u t y l b r o m id e , t h e k e t o n e 3 : 3 ~ & iM e th y lb u ta n -2 -one and a c e t o n i t r i l e .

îTone of t h e s e

i m m e d i a t e l y d e c o l o u r i z e a s o l u t i o n of bromine in c a r b o n tetrach lo rid e

s o l u t i o n , so the d e c o l o u r a t i o n can o n ly have

been b r o u g h t a b o u t by a sm a ll amount of an u n s a t u r a t e d o c t a n e in th e s o l i d h y d r o c a r b o n . An a c c o u n t of some p r e v i o u s work w i l l h e r e a s s i s t i n the argum ent.

An a t t e m p t was made t o p r e p a r e a specim en

o f 2 : 2 : 3 : 3 - t e t r a m e t h y l b u t a n e by th e a d d i t i o n of a n h y d r o u s c o b a l t c h l o r i d e to t e r t - b u t ylmagne sium b r o m id e .

Anhydrous

c o b a l t c h l o r i d e i s th o u g h t t o induce f r e e r a d i c a l s , and from t h e r e a c t i o n m i x t u r e was o b t a i n e d a sm a ll q u a n t i t y of 2 : 2 : 3 : 3 - t e t ramet h y l b u t a n e and a l i t t l e

d i-iso b u ty len e.

By

a n a l o g y , i t would a p p e a r t h a t t h e a d d i t i o n of t h e amide i s h a v i n g t h e same e f f e c t on the t e r t -b u ty lm a g n e siu m bromide as the anhydrous c o b a lt c h l o r i d e . The p r o d u c t s from t h e r e a c t i o n of a c e t a m i d e w i t h s e c - b u t y l m a g n e s i u m bromide a r e a l s o of i n t e r e s t h e r e .

In

e x p e r i m e n t G .4 0 , i s r e c o r d e d t h e f a c t t h a t a few c c , of a l i q u i d were p r o d u c e d b o i l i n g m a i n l y betw een l l 6 ® and llS^G w ith

1 .4 0 7 6 - 1 . 4 0 5 5 *

The p h y s i c a l c o n s t a n t s of th e

r e q u i r e d k e t o n e 3 - m e t h y l p e n t a n o n e -2 a r e : ?0 Bp. 118° ng 1.3994

k-

These v a l u e s a r e c l o s e t o t h o s e o b t a i n e d , b u t no s e m ic a r b a z o n e o r 2 : 4 - d i n i t r o p h e i i y l h y d r a z o n e c o u l d be p r e p a r e d . The s e m lc a rb a z o n e of a s i m i l a r k e t o n e ( P a r t I P a g e 2 6 ) was prepared e a s ily . k e to n ic odour.

In a d d i t i o n t h e l i q u i d d i d n o t have a The p h y s i c a l c o n s t a n t s o f a c e t o n i t r i l e

and s e c - b u t y l bromide a r e d i f f e r e n t from th o s e r e c o r d e d . The o n ly o t h e r p o s s i b i l i t y I s t h a t th e l i q u i d i s a h y d r o ­ c a r b o n form ed by th e d e c o m p o s it io n of th e G r i g n a r d r e a g e n t u n d e r t h e i n f l u e n c e of t h e am id e.

The p h y s i c a l c o n s t a n t s

o f 3 : 4 - d im e t h y lh e x a n e a r e CH0CH0CH-CH-CH5-CH, 3 2| I 2 3 CHjCHj

Bp. 1 1 7 .80c

n

20

D 1 .4 0 4 5

As th e l i q u i d g i v e s an immediate t e s t f o r u n s a t u r a t i o n , some f o rm of un s a t u r a t e d octane must he p r e s e n t .

The

o b s e r v a t i o n t h a t t h e b o i l i n g p o i n t r i s e s and r e f r a c t i v e index f a l l s during the d i s t i l l a t i o n p o i n t s a l s o to t h i s fact.

The v e r y c l o s e p h y s i c a l c h a r a c t e r i s t i c s o f t h e s e

two compounds, k e t o n e and h y d r o c a r b o n , make i t d i f f i c u l t t o d i s t i n g u i s h betw e en them on such sm a ll q u a n t i t i e s . From t h e two e x p e r i m e n t s r e c o r d e d on Page /36 th e p r o d u c t was a n a l y s e d f o r c a r b o n and h y d r o g e n .

The

d i f f i c u l t i e s i n o b t a i n i n g pure such a s m a l l amount of l i q u i d are obvious.

The a n a l y s i s f i g u r e s f o r th e k e t o n e

3 " M e t h y l p e n t a n - 2 ~one, and t h e h y d r o c a r b o n 3 : 4 -Dim ethylhexane are s ta te d below :-

65"

1 ~Ke t~iaylpentaff2 -one

^ -4 -B Ime t hy 1 he xane

0

12 %

8 4 . 2^

H

12^

15.

The a n a l y s i s f i g u r e s f o r th e specim ens from t h e two e x p e r i m e n t s were : -

1) 2)

c

81,2^

H

15.1^

c H

\h-rL

These f i g u r e s , a l t h o u g h n o t c o r r e c t f o r a p ure specim en, i n d i c a t e t h a t t h e l i q u i d i s not th e k e t o n e , th e a n a l y s i s f i g u r e s b e i n g much n e a r e r t h o s e f o r t h e h y d r o c a r b o n ♦

A

s m a l l amount of k e t o n e or w a t e r i n t h e sam ples s e n t f o r a n a l y s i s would b r i n g t h e c a rb on and h y d ro g en a n a l y s i s f i g u r e s down by a sm a ll amount. The p r o d u c t from th e r e a c t i o n betw een a c e ta m id e and n - b u ty lm a g n e s i u m b r o m id e , b o i l e d o v e r a c o n s i d e r a b l e r a n g e . Some k e t o n e was p r o d u c e d , b u t th e lo w e r b o i l i n g f r a c t i o n s of t h i s k e t o n e (FR,1 3 & 1 4 , 0 , 3 8 ) gave an immediate t e s t f o r u n s a t u r a t i o n - a t e s t t o which p ure meti^yl n - b u t y l k e t o n e do^s n o t r e s p o n d .

T here i s h e r e an i n d i c a t i o n ths.,t

6é

an u n s a t u r a t e d l i q u i d i s p r o d u c e d , b e s i d e t h e k e t o n e * Both n - o c t a n e and octene b o i l i n t h i s r a n g e . The f o r m a t i o n o f t h e s e p r o d u c t s i n r e a c t i o n s o t h e r t h a n t h o s e of a c e ta m id e i s d i f f i c u l t t o show, b u t t h e l a c k o f d e f i n i t e , c l e a r c u t , f r a c t i o n s from many f r a c t i o n a t i o n s , h a s been o b s e r v e d e .g *

In e x p e r i m e n t G$30 no d i f f i c u l t y

s h o u ld have been e x p e r i e n c e d i n s e p a r a t i n g t r i m e t h y l a c e t o « n itrile

(Bp. 1 0 5 “6 ®C) and the k e t o n e ( B p . l 6 4 ®C), b u t f o u r

grams of l i q u i d was c o l l e c t e d betw een t h e s e two t e m p e r a t u r e s S o d i u m - f u s i o n showed t h a t n i t r o g e n was not p r e s e n t in th e fraction» The sm a ll volume of h i g h b o i l i n g l i q u i d o b t a i n e d from t h e r e a c t i o n between b u ty r a m id e and t e r t -amylmagnesium bromide gave an immediate t e s t f o r u n s a t u r a t i o n , and must be a form o f u n s a t u r a t e d d e c a n e .

The c r y s t a l s of

3 : 3 s4 : 4 - t e t r a m e t h y l h e x a n e formed on t h e s t i l l - h e a d d u r i n g t h e f r a c t i o n a t i o n of t h e p r o d u c t from t h e r e a c t i o n between i s o b u t y r a m i d e and jte rt-a m y lm a g n e siu m b ro m id e , show t h e r e a c t i o n in t h i s case i s s i m i l a r to t h a t u s i n g t e r t ~ b u t y l G rignard r e a g e n ts . The t e r t i a r y G r i g n a r d r e a g e n t s a r e known to beliave d i f f e r e n t l y fro m o t h e r s , b u t the a n a l y s i s of t h e p r o d u c t s o b t a i n e d from t h e r e a c t i o n s betw een am ides and t h e s e o t h e r G r i g n a r d r e a g e n t s , i n d i c a t e t h a t th e t e r t -alkylme.gnesium b r o m id e s a r e n o t a l o n e in decomposing u n d e r th e i n f l u e n c e

S'}

of th e a m i d e • The f a c t t h a t p a r t of th e g a s t h a t i s e v o l v e d i s u n s a t u r a t e d i s a n o t h e r i n d i c a t i o n of t h e d e c o m p o s i t i o n of the G rignard r e a g e n t.

The p o s s i b i l i t y was c o n s i d e r e d t h a t

t h e s a t u r a t e d g a s was e v o l v e d d u r i n g t h e f o r m a t i o n of one of t h e p r o d u c t s , and t h e u n s a t u r a t e d g a s d u r i n g t h e f o r m a t i o n of t h e o t h e r *

T h i s t h e o r y , was how ever, soon d i s p l a c e d

a s t h e r e was alw ays more t h a n 8 ,0 0 0 cc* of s a t u r a t e d g a s e v o l v e d ( when working w i t h -§-rd gm. m o le c u l e of amide) w h a t e v e r t h e p r o d u c t of th e r e a c t i o n * I t was fo u n d th s.t t h e voluirie of g a s e v o l v e d v a r i e d w i t h tlie tim e of h e a t i n g .

The r e s u l t s of some e x p e r i m e n t s

w i t h b u ty r a m i d e a r e summarized b e l o w : /

H eating R eaction

Volume of g a s

ketone

evolved

Time 3 hours

1 4 ,9 2 5 c c .

n

15 mins*

1 0 ,9 0 0 c c .

H

11 h o u r s

1 5 ,4 2 0 c c .

B utyra m ide & n - P r % B r

Y i e l d of

66%

The % y i e l d of k e t o n e i s n o t a l t e r e d a p p r e c i a b l y . E x p e r im e n t h a s a l s o shown t h a t th e volume of g a s c o l l e c t e d v a r i e s w ith the c o n c e n tr a t io n of the G rignard s o l u t i o n e*g* H e a t i n g Time

R eaction

V o l . of g a s evolved

P i n a l a m i d e & n-PrîJgBr ( d i l ) «

(c o n e )

3 hours •

12,050 c c .

3 hours

1 5,300 c c .

éS^

I f th e second s t a g e of t h e r e a c t i o n were a s d e s c r i b e d by M e u n i e r , the volume of g a s e v o l v e d would be th e same u n d e r a l l c o n d i t i o n s , i f the p e r c e n t a g e y i e l d of k e t o n e were th e same.

In a d d i t i o n t h e g a s c o l l e c t e d would a l l be

saturated. R e t u r n i n g now t o th e mechanism of t h e a c t u a l r e a c t i o n betw een am ides and G r i g n a r d r e a g e n t s , and the c o n s i d e r a t i o n of t h e n e x t s t e p .

I t h a s been p o i n t e d out t h a t b u ty r a m i d e

a nd n - a l k y l h a l i d e s r e a c t v e r y q u i c k l y to g i v e h i g h y i e l d s of k e t o n e , and t h a t th e l e n g t h of h e a t i n g time h a s l i t t l e e f f e c t on t h e p r o d u c t s of t h e r e a c t i o n .

So, where t h e r e

i s no s t e r i c h i n d r a n c e t o slow down t h e r e a c t i o n , t h e n e x t step w ill occur rapidly*

T h is i s a s s e t out b e l o w : -

OMgX /

RiMgX

R-C

-

— ---- >

m

OMgX

^

Hilgx

The s h i f t o f e l e c t r o n s c a u s e d by t h e c o - o r d i n a t i o n of the m o le c u l e of G r i g n a r d r e a g e n t r e s u l t s in a n i n t r a m o l e c u l a r r e a r r a n g e m e n t g i v i n g r i s e t o the organo-magnesium complex

6?

w ith a s tr u c t u r e

s i m i l a r t o t h a t s u g g e s t e d hy B e i s ( 2 ) «

The number of m o le c u l e s of

OMgX

in t h e

s o l u t i o n w i t h a m o le c u l e of G r i g n a r d r e a g e n t c o - o r d i n a t e d to t h e n i t r o g e n atom a t any t i m e , i s t h o u g h t to be sm all* They w i l l be i n dynamic e q u i l i b r i u m w i t h o t h e r u n c o - o r d i n a t e d m o le c u l e s *

I f t h e n e x t s t a g e i s r a p i d , t h e whole r e a c t i o n

w i l l be f i n i s h e d q u i c k l y . When d e a l i n g , h o w ever, w ith a r e a c t i o n t h a t o n ly t a k e s p l a c e s l o w l y b ec au se o f t h e s t e r i c f a c t o r s i n v o l v e d , ( e . g . b u ty r a m i d e and tei^t - b u t ylmagne s i urn bromide o r p i n a l a m i d e and n -p ro p y lm a g n e s iu m bromide) an i n t r a - m o l e c u l a r r e a r r a n g e m e n t w i l l o c c u r , b e f o r e a n y f u r t h e r r e a c t i o n can take place : OMgX

X

R-C ^ %

VR-GsXr-^Mg^ \

^

T h i s i n t e r m e d i a t e would r e a c t a s a n i t r i l e w i t h a G r i g n a r d reagent : R Î MgX""

R-CSlT^-^Mg

\

^ C«lTT-4Mg m

«I

Mgx

I n a l l r e a c t i o n s a w h ite c r y s t a l l i n e e t h e r i n s o l u b l e compound i s p r o d u c e d .

When c o n s i d e r i n g t h e r e a c t i o n

between p i n a l a m i d e and t e r t -buty lm a g n esiu m b r o m id e , t h i s

( a c c o r d i n g t o t h e above t h e o r y ) would b e : X B-CEtîî—

If t h i s fu rth er.

were e n t i r e l y i n s o l u b l e ,

i t would n o t r e a c t

I t must however, be s l i g h t l y s o l u b l e i n b o i l i n g

e t h e r , t h u s e n a b l i n g i t t o r e a c t w i t h a f u r t h e r m o le c u le o f G r i g n a r d r e a g e n t , t o g iv e the k e t o n e fo rm in g com plex. The f a c t t h a t no co**ordination compound between m g n e s i u m compounds an d n i t r i l e s can be o b t a i n e d by b o i l i n g trie two t o g e t h e r i n e t h e r s o l u t i o n d o e s n o t mean t h a t u n d e r t h e c o n d i t i o n s o f th e r e a c t i o n , i t w i l l n o t be f o rm e d . The s u g g e s t e d median ism i s summarized o v e r l e a f : »

Suunraary of su g g ested r e a c t io n mechanism 5->0

QMgX + R.MgS

R-C

^

R-C

\

+ R

i^ T

IT-H R e a c tio n s t h a t take p l a c e more s l o w l y

OMgX

OH

R _ y &+ 6/ R **GslTÎ ^ Mg \

X

R-G=R \1/ R

CEgX

>
Mg

1

MgX

R.

i/H^O R

H^O m

\/ R

\

R

i

>

G=m

R.

R \ R. / R

\

R.

/

c=m

i c=o

R C=0 R/

/

\

X

>2

A r e v i e w of t h i s s u g g e s t e d mechanism and t h e e x p e r i m e n t a l r e s u l t s t h a t have been o b t a i n e d , b r i n g s to l i g h t some i n t e r e s t i n g facts:-* S t e r i c f a c t o r s p l a y a l a r g e p a r t in d e t e r m i n i n g th e y i e l d of k e t o n e from a r e a c t i o n , b u t t h e y c a n n o t be the o n ly f a c t o r s involved.

The y i e l d of k e t o n e i s a lw a y s a p p r e c i a b l y

h i g h e r when u s i n g i s o p r o p y l G r i g n a r d r e a g e n t s t h a n when using .se c-b u ty l G rignard r e a g e n ts .

The s t e r i c f a c t o r s

i n v o l v e d a r e a p p r o x i m a t e l y t h e same .

The h i g h e r y i e l d s

from i s o p r o p y l c o u l d , however, be p r e d i c t e d from o t h e r con sid eratio n s.

I n t h e two i n t e r m e d i a t e s : -

QMgX R -C=mF

, and

Mg

R-CsiT :---- > Mg \

X

OH

% th e c a r b o n i s a c e n t r e of e l e c t r o n d e f i c i e n c y .

The sec -

b u t y l g r o u p i s more e l e c t r o p h i l i c t h a n t h e i s o p r o p y l group i . e . t h e i s o p r o p y l g r o u p w i l l r e a c t more r e a d i l y w i t h a c e n t r e of e l e c t r o n d e f i c i e n c y t h a n t h e s e c - b u t y l g r o u p , thus giving a h ig h er y ie ld . S l i g h t l y h i g h e r y i e l d s have been o b t a i n e d when u s i n g n - b u t y l G r i g n a r d r e a g e n t s , t h a n when u s i n g n - p r o p y l G rignard r e a g e n ts .

On t h e b a s i s of t h i s r e s u l t th e

n - b u t y l g r o u p would be p r e d i c t e d t o be s l i g h t l y l e s s e l e c t r o p h i l i c th a n the n -p ro p y l g ro u p .

T h is i s known t o

be so from o t h e r c o n s i d e r a t i o n s . The e f f e c t of c o n c e n t r a t i o n i s i n t e r e s t i n g t o c o n s i d e r i n t h e l i g h t of t h i s s u g g e s t e d mechanism.

The more c o n c e n t r a t e d

th e e t h e r s o l u t i o n , th e l e s s chance t h e r e i s of th e i n t e r m e d i a t e complex d i s s o l v i n g and r e a c t i n g f u r t h e r .

But

when i t d o e s d i s s o l v e , t h e c o n c e n t r a t i o n of i o n s i s so much g r e a t e r , t h a t r e a c t i o n t a k e s p l a c e more e a s i l y and a h i g h e r y i e l d of k e t o n e i s o b t a i n e d . The r e a c t i o n s of a c e ta m id e The r e a c t i o n b e tw e e n a c eta m id e and a G r i g n a r d r e a g e n t i s o b v i o u s l y d i f f e r e n t from the o t h e r r e a c t i o n s c a r r i e d out*

The, e t h e r s o l u t i o n , alw ays b l a c k from t h e f i n e l y

powdered c a r b o n from the magnesium suspended i n i t ,

r e m a in s

b l a c k d u r i n g a r e a c t i o n such a s t h a t between b u ty r a m id e and a G rignard re a g e n t.

But when a c e ta m id e i s added t o a

G r i g n a r d r e a g e n t , the r e a c t i o n a t f i r s t a p p e a r s t o be the same, b u t a f t e r h e a t i n g f o r h a l f an hour th e c o l o u r changes to a d a r k g r e e n , and much s o l i d i s p r o d u c e d .

When t h i s

s o l i d i s added t o i c e , t h e r e a c t i o n i s v e r y v i g o r o u s and a gas i s evolved.

The p o s s i b i l i t y t h a t t h i s e v o l u t i o n of

g a s was due t o t h e d e c o m p o s i t i o n of G r i g n a r d r e a g e n t , a d h e r i n g t o t h e s o l i d , was c o n s i d e r e d .

But a f t e r washing

w i t h e t h e r and decom posing, t h e e v o l u t i o n of g a s s t i l l to o k p lace. The p r i n c i p l e p r o d u c t from the r e a c t i o n s w%s th e

condensed n i t r i l e

c y a n m e t h in e :

t h i s has t h e f o l l o w i n g

stru ctu re : -

!■ . CH

II

ÎT

I

yC-CH^ II

The d i f f i c u l t i e s i n many*

i s o l a t i n g such a p r o d u c t were

I t i s much more s o l u b l e in w a t e r t h a n e t h e r , and

is stro n g ly b a s ic .

Hence, when th e magnesium compounds

a r e d i s s o l v e d in a c i d , t h e cyanmethine d i s s o l v e s a l s o * The e a s i e s t method of o b t a i n i n g a specimen was t o d e c a n t t h e e t h e r s o l u t i o n from t h e w a t e r l a y e r and e v a p o r a t e o f f t h e ether#

Xf t h e e t h e r s o l u t i o n were washed, th e r e q u i r e d

compound b e i n g s o l u b l e was washed o u t . Lower a l i p h a t i c n i t r i l e s a r e known to p o ly m e r i z e when t h e y r e a c t w i t h G r i g n a r d r e a g e n t s , so the p o i n t t h a t h a s t o be s e t t l e d i s w h e th e r th e a c e t a m i d e r e a c t s a t f i r s t a s o t h e r a m id e s,

or w h e th e r i t i s f i r s t d eh y d rated :-* G rignard

C H .C O H H p

---------------------^

reagent

CH C s H + H pO

^

f o l l o w e d by p o l y m e r i z a t i o n * A r a p i d d e c o m p o s i t i o n of t h e r e a c t i o n p r o d u c t o f a c e t a m i d e and n - p ro p y lm a g n e s lu m bromide was c a r r i e d o u t . A lth o u g h t h e r e had been a r e a c t i o n , a s t h e g a s e v o l v e d had

been c o l l e c t e d , no o t h e r compound t h a n a c e ta m id e c o u l d he d e t e c t e d in t h e p r o d u c t .

(The s o l u b i l i t y of a c e t o n i t r i l e

i s much r e d u c e d i n ammonium c h l o r i d e s o l u t i o n ) . In a d d i t i o n , t h e r e a c t i o n between a c e t o n i t r i l e and n«^propylmagnesium bromide was v i g o r o u s and r a p i d :

con­

d e n s a t i o n , w i t h t h e r e s u l t i n g change in c o l o u r of th e r e a c t i o n m i x t u r e , o c c u r r e d r a p i d l y a f t e r the i n t r o d u c t i o n of t h e n i t r i l e ,

Wiien a c e ta m id e was added t o a b o i l i n g

e t h e r e a l s o l u t i o n of a G r i g n a r d r e a g e n t , r e a c t i o n was immedia.te, b u t t h e c o l o u r change, i n d i c a t i n g condensait i o n , d i d n o t t a k e p l a c e u n t i l the s o l u t i o n had been h e a t e d f o r some t i m e . n itrile ,

I f t h e amide were f i r s t d e h y d r a t e d t o th e

i t would be e x p e c t e d t h a t c o n d e n s a t i o n would o c c u r

a s r a p i d l y a s when working w i t h a c e t o n i t r i l e . I f a c e t a m i d e r e a c t e d a s o t h e r a m id e s , t h e r e a r e two f a c t o r s to e x p l a in .

The m ethyl g ro u p j o i n e d to th e

c a r b o n y l c a r b o n atom d oes n o t cause s t e r i c h i n d r a n c e , and t h e r e a p p e a r s t o be no r e a s o n why t h e i n t e r m e d i a t e p r o d u c t d oes n o t r e a c t im m e d ia te l y w i t h a f u r t h e r m o le c u le of G rignard re a g e n t.

T h i s however d i d n o t t a k e p l a c e .

There

i s no a p p a r e n t r e a s o n why t h e i n t e r m e d i a t e compound should undergo rearrangem ent to the n i t r i l e , b efore r e a c t i o n w ith a f u r t h e r m o le c u le of G r i g n a r d r e a g e n t i s p o s s i b l e . E x p e r i m e n t a l e v i d e n c e i n d i c a t e d th e c o n t r a r y , a s i f t h i s were s o , c o n d e n s a t i o n would have o c c u r r e d r a p i d l y .

76

A f t e r a c o n s i d e r a t i o n of t h e s e p o i n t s i t was d e c i d e d t h a t a c e t a m i d e r e a c t e d f i r s t a s o t h e r amides* and t h e d i f f e r e n c e i n t h e r e a c t i o n from t h e n on* was due to th e p r e s e n c e of t h e a c t i v e m e th y l g r o u p .

The c o u r s e of the

r e a c t i o n i s a s p i c t u r e d helow:*OMgX + R,MgX ----^

1

./

CH,-C

+ R,H

3 %

-L

m St

T

CH2=C

OMgX

/

CH, ' 3 OMgX

c m Fa XMgO - C y m . 2

CH^ )

C-CH^ \ ^ OMgX

Y H

,C / \ ÇHg ÎT-H

H,H-C

C-GH^

/ \ ir/ \ QMgX ^

XMgO

I

1

Rj_MgX

X

A

HC

HoO "2-

H

\ //

I:

^

R,

CH,

\ /

'

Mg

2

.QMgX ^

/

y

/C

\

^-^0

XMgO

/

C-CH,

"X

,H H

/ \

OMgX

The P r o b l em of t h e R e s i d u e In a l l the r e a c tio n s c a r r ie d o u t,

some h i g h b o i l i n g

n i t r o g e n c o n t a i n i n g compounds have b e e n p r o d u c e d *

A ll

a t t e m p t s a t e s t a b l i s h i n g a p o s s i b l e fo rm ulst have so f a r failed * resid u e,

In s tu d y in g the p h y s i c a l p r o p e r t i e s of t h i s it

seems u n l i k e l y t h a t one f o r m u l a c o u l d be a p p l i e d

t o T/diat m u st be a h i g h l y complex m i x t u r e * o f t e n v a r i e s o v e r a s much a s in d ex i s u s u a l l y v e ry high*

The b o i l i n g p o i n t

100® and t h e r e f r a c t i v e The p r e p a r a t i o n o f a s e m i -

c a rb a zo n e and 2 : 4 ~ d in itro p h e n y lh y d ra z o n e h a s been a t t e m p t e d , b u t no s u c h d e r i v a t i v e h a s been o b t a i n e d *

T h is does n o t

n e c e s s a r i l y i n d i c a t e th e absence of a c a rb o n y l g ro u p , a s the

s t r u c t u r e o f t h e compounds would p r o b a b l y make t h e

fo rm a tio n of a d e r i v a t i v e d i f f i c u l t * .When b o i l e d w i t h 10^ c a u s t i c so d a ammonia was e v o l v e d * The l i q u i d d i d n o t h o w ev e r d i s s o l v e a f t e r tw e l v e h o u r s boiling*

The r e s i d u e when s e p a r a t e d f r o m t h e a q u e o u s

l a y e r , w ash e d an d t e s t e d by sodium f u s i o n , was s t i l l f o u n d to c o n ta in n itro g en * T h e r e a r e a f e w p o i n t s of i n t e r e s t c o n c e r n i n g t h i s n itrogenous resid u e ,

t h a t g iv e an i n d i c a t i o n as t o i t s

m e th o d o f f o r m a t i o n : 1) Wlien s u r v e y i n g t h e r e s u l t s of a l l t h e e x p e r i m e n t s , i t is a n otable f a c t th a t there r e s i d u e when t h e r e

i s no n i t r o g e n c o n t a i n i n g

i s no k e t o n e i n t h e p r o d u c t *

T his

7y

i n d i c a t e s t h a t t h e r e s i d u e i s u n l i k e l y t o be t h e p o l y m e r i z e d n itrile . 2 ) W hen w o r k i h g w i t h p i n a l a m i d e ,

t h e y i e l d of h i g h b o i l i n g

residue

is a d e fin ite trim eth y l-

i s very sm all, but th e re

a c e t o n i t r i l e f r a c t i o n c o l l e c t e d from th e f r a c t i o n a t i o n * W i th b u t y r a m i d e and o t h e r s t r a i g h t c h a i n a m i d e s , when t h e p r e s e n c e ofc< h y d r o g e n atom s makes c o n d e n s a t i o n e a s i e r , no d e f i n i t e b u t y r o n i t r i l e f r a c t i o n is obtained*

A ll the

n itr o g e n c o n ta in in g p ro d u cts are high b o ilin g * 3) A s t u d y o f t h e r e a c t i o n s b e tw e e n p i n a l a m i d e and n - p r o p y l m a g n e s i u m b ro m id e f u r n i s h some i n t e r e s t i n g r e s u l t s * The l o n g e r t h e r e a c t i o n i n d i l u t e

s o l u t i o n i s heated* th e

g r e a t e r i s th e y i e l d of k e to n e .

G r e a t e r a ls o ^ however, i s

th e y i e l d of the h ig h b o i l i n g n itr o g e n o u s r e s i d u e .

The

c o m p a r i s o n o f t h e f r a c t i o n a t i o n t a b l e s of G.2 4 and G*27 show th is clearly . 4 ) The w e i g h t o f r e s i d u e from t h e r e a c t i o n s of b u t y r a m i d e d o e s n o t v a r y a p p r e c i a b l y w i t h v a r y i n g l e n g t h of h e a t i n g tim e o 5 ) The y i e l d o f k e t o n e f ro m i s o b u t y r a m i d e i s a l w a y s h i g h , a n d t h e w e i g h t of r e s i d u e l o w .

The c o n d e n s a t i o n o f

i s o b u t y r a m i d e w i l l be more d i f f i c u l t b e c a u s e o f s u b s t i t u t i o n on t h e oC c a r b o n a t o m . w i l l condense a t a l l

The f a c t t h e p r o d u c t s f r o m p i n a l a m i d e shows t h a t c o n d e n s a t i o n ca.n t a k e p l a c e

t h r o u g h one of t h e m e t h y l g r o u p s * The c o n c l u s i o n t h a t c a n be drawn f ro m t h e s e p o i n t s i s t h a t

79

t h e com p lex r e s i d u e

i s fo rm e d by t h e c o n d e n s a t i o n of t h e

k e t o n e f-producing com plex w i t h t h a t p r o d u c i n g t h e n i t r i l e . T h i s c o n d e n s a t i o n d o e s n o t t a k e p l a c e a t t h e tim e o f d e ­ c o m p o s i t i o n * a s t h e l e n g t h o f h e a t i n g tim e would t h e n have no e f f e c t on t h e amount o f c o n d e n s e d p r o d u c t « has proved the co ntrary*

E xperim ent

In a r e a c t i o n s u c h a s t h a t

b e t w e e n p i n a l a m i d e a n d n - p r o p y l m a g n e s i u m brom ide* t h e r e a c t i o n f o r m i n g t h e k e t o n e i s slow e d down by s t e r i c f a c t o r s * The n i t r i l e

form ing co m p lex :-

CH; I ^ / CH^-C - C=H ^ M g

OH

OH^ i s t h e n i n s o l u t i o n f o r a much l o n g e r tim e w i t h t h e k e t o n e f orming c o m p le x : CH; OH I ^ / CH.-C - C=ITHMg

^ I

I I

CH3 R, MgX

\

X

A g r e a t e r ejaount o f c o n d e n s a t i o n i s t h e n p o s s i b l e a n d i s found to o c c u r. VThen c o n s i d e r i n g a r a p i d r e a c t i o n s u c h a s t h a t b e tw e e n b u t y r a m i d e a n d n - p r o p y l m a g n e s i u m brom ide re a c tio n i s very ra p id .

the k eto n e form ing

Hence an y change ; -

OMgX

X

OHjCHgCHgC^------ > CH^OHgCHgCsEi— > m

OH

So

t h a t o c c u r s w i l l be s m a l l ,

A s m a l l amount o f c o n d e n s a t i o n

between : OMgX CH,CHpGHpG ^

/

l\

' m%x ^1

X and

GH,OH«GH.GaFi— >Mg ^

^

^

/

\

OH

w i l l ta k e p la c e quickly* b u t th e r e a c t i o n i s f i n i s h e d in a s h o r t tim e and f u r t h e r h e a t i n g w i l l n o t a f f e c t th e resu lt.

Hence f r o m a l l r a p i d r e a c t i o n s o f b u t y r a m i d e ,

a f a i r l y c o n s ta n t w i g h t of re sid u e

is obtain ed .

m

PART V. EXPERÎMSÎÎTAL

9è

f o l l o w i n g octriPB of e x p é r i m e n t a b e tw e en G r i g n a r d r e a g e n t s and

l i p l i a t i c a m i d e s , have a l l b ee n c a r r i e d o u t

u n d e r t h e sfune e x p e r i m e n t a l c o n d i t i o n s , u n l e s s o t h e r v â s e sta ted .

The G rig n a rd r e a g e n t was p re p a re d from 1 . j j gm. m ol. of a l k y l h a l i d e + 10>?, and 1*33

* atom of msignesium.

The magnesium was %)laped in a one l i t r e , two necked f l a s k and co vered w ith 350 c . c . of sodium d r i e d e t h e r .

The

whole was s t i r r e d m e c iia n ic a lly , u s in g a s t i r r e r f i t t e d w ith a m ercury s e a l .

A few c c s . of the a l k y l iia lid e was added

to the e t h e r , and th e whole warmed on a w a te r b a th .

/hen

tlie r e a c t i o n iiad s t a r t e d , a f u r t h e r j^O c . c . of sodium d r i e d e t h e r was added, and the a l k y l h a l i d e run in so tiui.t the e t h e r b o i l e d g e n t l y .

a f u r t h e r 100 c . c . of e t h e r was

added when a p p ro x im a te ly th re e q u a r t e r s of the a l k y l iia lid e had been run i n .

On th e com pletion of the a d d i t i o n , the

G rig n a rd re a g e n t was b o i l e d f o r h a l f an h o u r.

I t was th e n

c o o le d and syphoned i n t o a two l i t r e , two necked f l a s k , a t the same time f i l t e r i n g throU£^h a pad of g l a s s wool, to remove any u n r e a c te d lir'^neBium. The amide to be added was k e p t in a d e s s i c a t o r , u nder vacuum f o r 48 h o u rs b e fo re u s e .

The tube from which the

oroide was added to the G rig n a rd r e a g e n t , was f i t t e d w ith a < u ic k f it j o i n t a t one end ( t o f i t i n t o the second neck of the f l a s k ) and a p lu n g e r a t the o t h e r .

The amide

c o u ld th e n he added a l i t t l e a t a time@

The g a s t h a t was

ev o lv ed was c o l l e c t e d from the top of the c o n d e n se rs, in f l a s k s immersed in a l c o h o l / C 02 tra p s *

Two t r a p s were u se d ,

the f i r s t h e in g k e p t a t - 10®G. and th e second a t - 72®C. The f i r s t tra p p e d th e e t h e r , n o t condensed by the two con­ d e n s e r s , and the second, the gaseous hydrocarbo ns t h a t were evolved*

The amide was added to the c o ld G rig n a rd s o l u t i o n ,

b u t th e v ig o ro u s r e a c t i o n soon b roug ht the e t h e r to i t s b o i l i n g p o in t*

The a d d i t i o n of the amide in a l l c a s e s took

between t h i r t y and f o r t y f i v e m in u te s .

The s o l u t i o n was

th e n b o i l e d f o r t h r e e h o u rs , the g a s e s b eing c o l l e c t e d th ro u g h o u t th e r e a c t i o n .

S t i r r i n g was c o n tin u e d a l l th e

tim e , a s th e e t h e r in s o l u b le o r g a n o -m e ta llic compound c o l l e c t e d on th e bottom of the f l a s k and caused much bumping. A f t e r t h r e e h o u rs b o i l i n g , th e c o n te n ts of the f l a s k were c o o le d , and decomposed by p o u rin g oi^o i c e .

In some

c a s e s , an a tte m p t was made to decompose the e t h e r s o lu b le and i n s o l u b le l a y e r s s e p a r a t e l y , b u t t h i s was found to be d iffic u lt. The e t h e r l a y e r was d ec an ted i n t o a s e p a r a t i n g f u n n e l, and th e i n s o l u b le magnesium compounds d i s s o l v e d by adding c o n c e n t r a t e d h y d r o c h lo r ic a c id d i l u t e d w ith an e q u a l volume of w a te r .

The w a te r l a y e r was e x t r a c t e d s i x tim e s w ith

e t h e r , and the combined e t h e r l a y e r s d r i e d over anhydrous p o ta ss iu m c a r b o n a t e .

The e t h e r was d i s t i l l e d o f f , from a

vs

w a te r b a t h , th ro u g h a nin e in c h column packed w ith Fenske h e lic e s.

The r e s id u e was th en f r a c t i o n a t e d th ro u g h a

tw elve in c h column, packed w ith Fenske h e l i c e s , and f i t t e d w ith a h e a ti n g j a c k e t .

The f r a c t i o n s were c o l l e c t e d in

weighed t e s t tu b e s , and t h e i r w eig h ts found im m e d ia tely . The r e f r a c t i v e i n d i c e s of the f r a c t i o n s were ta k e n on an Abbe r e f r a c t o m e t e r , and th o se bu lked which had the same, o r a p p ro x im a te ly the same, v a l u e s . The y i e l d of k e to n e from the e x p e rim e n ts was c a l c u l a t e d in e a c h c a s e .

The y i e l d of n i t r i l e was d i f f i c u l t to s t a t e

a c c u r a t e l y , a s t h e r e was no c l e a r s e p a r a t i o n between the n i t r i l e and the e t h e r f r a c t i o n s .

In a d d i t i o n , in th o se

r e a c t i o n s where a h ig h p e rc e n ta g e of ketone was prod uced , th e n i t r i l e was u s u a l l y p r e s e n t in a condensed s t a t e in th e h ig h b o i l i n g r e s i d u e .

When u sin g t e r t - butylmagnesium

brom ide, th e d i - t e r t i a r y b u ty l formed u s u a l l y d i s t i l l e d o ver in th e same te m p e ra tu re range a s the n i t r i l e , th u s making the c a l c u l a t i o n of n i t r i l e im p o s s ib le . The f l a s k s c o n t a in in g the condensed g a s e s were removed from th e a lc o h o l/C 0 2 t r a p s , and the c o n t e n t s allo w ed to e v a p o ra te i n t o a g r a d u a te d a s p i r a t o r b o t t l e , f i l l e d w ith b rin e .

The volume was m easured, and th e g as th e n p a ss e d

th ro u g h two c o n c e n tr a te d s u lp h u r ic a c id t r a p s , and the u n ­ a b so rb e d g as c o l l e c t e d ov er b r in e in a n o th e r g ra d u a te d a s p ira to r.

The c o n c e n t r a t e d a c i d removed any u n s a t u r a t e d

g a s in the volume c o l l e c t e d «

Sim nary o f Re s u i t s %

-

of k e t o n e s p r o d u c e d f r o m t h e r e a c t i o n s

RMgBr where

i\m id e s : -

R Is:-

A ce tam ide

Propionam ide

B u t y r a m id e

Isobutyram ide

Pinalam ide

n-Propyl

n eg lig ib le

61^

66%

67%

25%

45 ^

58%

n eg lig ib le

Isopropyl

II

n-B utyl

6^

65^

70%

67%

26%

Iso h u ty l

-

34^

36%

-

-

N egligible

29^

30%

y?%

n eg lig ib le

sec-b u ty l te rt-b u ty l

.

II

n eg lig ib le

N eg lig ib le

neg lig ib le

II

%

y?

s howing t h e e f f e c t of t h e c oncenA^^j^ion of the G r i g n a r d s o l u t i o n on t h e % y i e l d of k e t o n e /

G r i g n a r d RlÆgBr where R i s : -

Amide

n-B utyl

n-Propyl D il*

Cone.

But^^ramide

66^

66^

Isobutyram ide

67^

70^

Pinalam ide

25^

i>l%

D il,

Cone.

26^

66^

Summary o_f r e s u i t s showing r e l a t ij)n s h i p b e t w e e n t he ^

t

h

e

h e a t i n g t im e. t h e

voliune o f g a s e v o l v e d and fo y i e l d o^_ j^gtone 1 . B u t y r a m i d e a n d ^ - p r o p y l m a g n e s i m r i ‘b romide S t r e n g t h of

H e a t i n g fim e

RMgBr s o l u t i o n

Volume of g a s

Y i e l d of

eo llected

K etone

D ilute

3 hours

14,925 c . c .

66^

It

15 m i n u t e s

1 0 g900 c . c .

63^

H

11 h o u r s

15,420 c . c .

64%

3 hours

1 6 )3 0 0 c . c .

66^

C oneentrated

2 . P i n a l a m i d e on n~ propylm agnesiim i b r omid^ S t r e n g t h of

H e a t i n g Time

RMgBr s o l u t i o n

Volume o f g a s

Y i e l d of

co llected

K etone

D ilute

3 hours

12*050 c . c .

25%

H

5 hours

1 2 ,1 0 0 c . c .

y?%

It

10 h o u r s

15,600 c . c .

41^

3 hours

15,300 c . c .

67^

C oncentrated P inalam ide S t r e n g t h of

on n - h u t y l m a ^ n e sium brom ide H e a t i n g Time

RMgBr s o l u t i o n D ilu te C oncentrated

Volume of g a s

Y ie ld of

co llected

K e to n e

3 hours

11,225 c . c .

26^

3 hours

12,000 c . c .

66%

4 . A c e t a mide an d n - p r o p y jm a g n e s iu ip bro m id e s t r e n g t h of

H e a t i n g Time

RMgBr s o l u t i o n D ilute C oncentrated

Volume o f g a s

Y i e l d of

co llected

K etone

3 hours

10,200 c . c .

n eg lig ib le

3 hours

1 5 ,4 0 0 c . c .

It

Volumes o f g a s c o l l e c t e d showing: tha^

con c e n t r a t e d s u lp h u r ic acjLd

RMgBr where

A m ides:-

R is: -

A ce tam id e

Propionam ide

Butyram ide

Isobutyram ide

T o tal

T otal

T o tal

T o tal

U n sat,

Uns a t .

U nsat.

P inalam ide

U nsat•

T o tal

U n sat•

n-Propyl

1 0 ,2 0 0

1,660

14,250

2,500

14,925

2,500

15,300

2,300

12,050

2,000

Isopropyl

1 2 ,4 0 0

2,250

13,500

2,500

15,000

2 ,4 0 0

15,130

2,600

12,050

1,750

11,250

1,600

11,250

1,500

10,750

1,200

1 1.225

1,225

-

2,200

n -B utyl Iso b u ty l

9,550 -

-

1 4 ,2 0 0

sec-b u ty l

9,150

9,750

te rt-b u ty l

8,950

1 1 ,7 0 0

14,750

-

10,500 1,500

1 1 ,5 0 0

-

1

2.350

8,600

1,700

11,525

11,750

1,900

9,500

( A l l v o lu m e s q u o t e d a r e f o r t h e u se o f * r d of a m o l e c u l e of a m i d e ,

,J ^ e n

o n ly

3^_G_ji8Gdp t h e n e c e s s a r y c o r r e c t i o n ]ms b e e n a p p l i e d tj3 make t h e v o lu m e s c o m p a r a h l e ) .

The g a s ^p lu m e s r e c o r d e d above have a p o s s i b l e e r r o r Z ^

They c a n n o t be t a k e n a s a b s o l u t e v a l u e s , b u t have been u s e d c o m p a r a t i v e l y .

%

G_«1 c P ro p io K a jn id e an d n -p ro p y Im a p n e^ iu m b rom id e

Q.UAlTTmES

Magnesium

32*4 gm.

n - p r o p y l bromide

l 8 o gm.

Propionam ide

2 4 «3 gm*

W eight o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) ^6 gm. 12

20

F ractio n

Bp

Weight

1

34.50

10 gm.:

E th er

-

2

34.50-35°

10 gm.

E th er

-

3

350-66°

1 gm.

E th er

-

4

660-69.5°

2 gm.

1 .4 2 4 2

1 .4 2 1 2

5

69.50-121°

3 gm.

1 .4 0 0 9

1.3977

6

121°-122°

3 gm.

1 .4 0 3 9

1 .4 0 0 7

7

122°-122.5°

3 gm.

1 .4 0 4 0

1 .4 0 0 8 1.4008

8

122.50

5 gm.

1 .4 0 4 0

9

122.50

2 . 5gm.

1 .4 0 4 0

1.4008

10

122.50

2 . 5gm.

1 .4 0 4 1

1.4009

11

122.50

2 gm.

1 .4 0 4 1

1 .4 0 0 9

12 ■

122.5°

2 . 5gm.

1 .4 0 4 1

1 .4 0 0 9

8 gm.

1.4532

1.4500

R esidue

1

Y i e l d of k e t o n e = 2 0 • ? gm. ( 6 l ^ of t h e t h e o r e t i c a l ) Volume of g a s c o l l e c t e d = 1 4 *2^0 c . c * Volume o f u n s a t u r a t e d g a s = 2*500 c . c . P r e p a r e d s e m i c a r b a z o n e f r o m , P R . 9 * M.P. I l l . 5 °

;

?/

G .2. P r o p i

onajaide and is o p r o p y lm ^ y e s iu g i bromide

W eight o f p ro d u c t ( w it h e t h e r w a sh in g s) = 74 gm.

19

20

PR.

Bp.

We ig h t

1

340

1 1 .5 gm.

E th e r

-

10 gm.

E th e r

-

9*5 gm.

E th e r

-

2

340-34.50

3

3 4.5^-35^

“d

4

35^

8 .5 gm.

E th e r

-

5

35®

8 gm.

E th e r

-

Mainl^r e t h e r

-

6

350-400

4 .5 gm.

7

400-1100

3 gm*

- 1.3873

1.3869

8

1100-1120

2 gm.

1.3970

1.3966

9

1120-1130

3*5 gm.

1.3979

1.3975

10

1130-1140

4 gm.

1.3980

1.3976

1 gm.

1.3990

1.3986 j

6*5 gm.

1.4578

1.4574

1140

11 R e si­ due

Y ie ld of k eto n e = 1 0 .5

{ 32 % of th e t h e o r e t i c a l )

gm.

Volume of g a s c o l l e c t e d

=

13#^00 c .c *

V olum e

=

2,500 c . c .

of

unsatu rated

gas

)

P r o p io n amide and n -b u t y Imagine sium bromide w e ig h t o f p ro d u ct ( w ith e t h e r w a sh in g s) = 6 9 # 5 gm. FR.

Bp

1

3 4 .5 0

2

3 4 .5 0 - 3 5 0

3

3 5 0 -1 0 0 °

4

w e ig h t

1 8 .5

20 %

11 gm .

E th e r

-

10 gm.

E th e r

-

4 gm .

1 .4 0 3 4

1 .4 0 2 8

io o °-i3 5 °

7 . 5 gm .

1 .4 0 5 8

1 .4 0 5 2

5

135“ -146°

2 . 5 gm .

1 .4 0 6 1

1 .4 0 5 5

6

1400-148°

3 . 5 gm .

1 .4 0 8 8

1 .4 0 8 2

7

148°

7 gm .

1 .4 0 9 0

1 .4 0 8 4

8

1 4 7 0 -1 4 8 0

1 .4 0 9 0

1 .4 0 8 4

9

148°

6 gm .

1 .4 0 9 0

1 .4 0 8 4

10

148°

3 gm .

1 .4 0 9 1

1 .4 0 8 5

11

1 4 8 0 -1 5 0 0

1 gm .

1 .4 1 1 3

1 .4 1 0 7

6 gm .

1 .4 5 7 2

1 .4 5 6 6

R esid u e

Y ie ld

o f k e t o n e = 25

V olum e o f g a s c o l l e c t e d

5.5

gm .

( 6 ^% o f t h e

th e o re tic a l)

= 1 1 ,2 5 0 c . c .

V olum e o f u n s a t u r a t e d g a s = 1 ,6 0 0 c . c . P re p a re d

s e m i c a r b a z o n e f r o m P R #9 *

9 8 . 5 ®- 9 9 °

Re s t a r t e d next day.

j

93

Propionam ide and isobutylpLagpesium bromide w e ig h t o f p ro d u c t ( w it h e t h e r w a sh in g s ) = 6 2 gm* PR.

Bp

1

34.75°

2

We i g h t

22

20

%

1 0 . 5 gm.

E ther

3 4 . 7 5 ° - 35°

11 gm.

E th er

3

35°-3 6 °

9 . 5 gm,

E th er

4

360-940

4 gm.

5

940-107°

2 gm.

1.3973

1.3977

6

1 0 7 0 -1 3 1 0

3 gm.

1 .3 9 8 3

1.3987

7

1310-134°

2 gm.

1 .4 0 2 1

1.4025

8

1340-1350

3 gm.

1 .4 0 2 9

1.4033

9

1350-136°

5 gm.

1 .4 0 2 9

1.4033

3 gm.

1 .4 0 3 9

1 .4 0 4 3

0 . 5 gm,

1 .4 0 5 3

1 .4 0 5 7

4 . 5 gm.

1 .4 5 7 0

1.4574

10 11 Residue

1360 1360-1380

M ainly e t h e r

Y i e l d o f k e t o n e = 13 gm. ( 3 4 ^ of t h e t h e o r e t i c a l ) Volume o f g a s c o l l e c t e d = 1 4 ,2 0 0 c . c .

9^

Prop i onaiii de^ and s e c -butylma^ne s ium broraide W eight of p ro d u ct ( w ith e t h e r w a sh in g s ) = 4 3 . 5 gm. 16

20

7 gm.

E th er

-

34.5°

7 gm.

E th er

-

3

34.5°-940

7 gm.

M ainly e t h e r

4

94°-102°

1 . 5 gm.

1 .4 0 0 4

1.3988

5

102°-133°

1 . 5 gm.

1 .4 0 1 1

1.3995

6

1 3 3 0 .1 3 5 0

2 . 5 gm.

1.4079

1.4063

7

135°-136°

6 gm.

1.4081

1.4065

PR.

Bp

Weight

1

34.9°

2

-

8

136°

1 . 5 gm.

1.4081

1.4065

9

136°

1 gm.

1.4081

1.4065

6 . 5 gm.

1.4490

1.4474

R esidue

•

Y i e l d of k e t o n e = 11 gm. ( 2 9 % of t h e t h e o r e t i c a l ) The r e s i d u e c o n t a i n e d some s o l i d .

T h i s was f i l t e r e d

o f f , b u t t h e r e was i n s u f f i c i e n t f o r r e c r y s t a l l i z i n g . M . P . i 8 5 ° - 1 8 8 ®G.

T h i s was p r o b a b l y a f o r m of t h e c o n ­

densed n i t r i l e .

The r e s i d u e was d i s t i l l e d d i r e c t l y *

b u t h a d no c o n s t a n t b o i l i n g p o i n t : 20 PR. 1 2

Bp 160°

“d 1 .4 1 2 0

160°-220° 1.4496

Volume o f g a s c o l l e c t e d = 9 *7^0 c . c

>

9C

G_# $ P ropionaiaide and tert" b u ty lm a p n e siu m 'bromide Weight o f p ro d u ct ( w it h e t h e r w a sh in g s ) = 34 gm. 20 PR. 1

Bp.

we i g h t

34. 5“

7 gm.

E th er

6 gm.

E ther

2

3 4 .5 0.350

3

350-760

9 . 5 gm.

4

760-800

3 . 5 gm.

5

800-86“

1 gm.

6

860-950

1 gm.

7

95“ -101“

1 gm.

R esi­ due

n

D

M ainly e t h e r

0 . 5 gm.

F r a c t i o n s 4 -7 i n c l u s i v e , and the r e s i d u e , c o n t a in e d th e w hite c r y s t a l l i n e hydrocarbon d i - t e r t - b u t y l . CH. C H ,—

/

I

C

I

CH3

CH.

I

C

ICH3

CH,

^

Y ie ld of k etone - n e g l i g i b l e . Volume of g a s c o l l e c t e d = 1 1 , 7^0 c . c *

%

G ^. B u t y r a m id e and n^propylmai^ne sium b ro m id e OTAITTITIBS Magnesium

3 2 . 4 gm.

n - p r o p y l b ro m id e

180 gm.

B u t y ra m id e

29 gm.

E th er

350

C.C .,

350

C .C .,

100

c . c .

W e ight o f p r o d u c t ( a f t e r e t h e r rem oved) = 68 gm. PR.

Bp.

W eight

4°

1

350.360

9 gm.

E ther

-

2

360

10 gm.

E th er

-

3

360-490

8 gm.

4

490.740

2 . 5 gm.

1.4093

1.4071

5

740 -9 6 .5 ®

2 . 5 gm.

1.3981

1.3959

6

9 6 . 5 ® - i o 5 ® 1 . 5 gm.

1 .3 8 9 1

1.3869

7

305° - 1 4 0 ®

3 gm.

1.3992

1 .3 9 7 0

2 gm.

1 .4 0 9 0

1.4068

142®

2 . 5 gm.

1.4092

1 .4 0 7 0

10

142°

3 . 5 gm.

1.4093

1.4071

11

142°

3 gm.

1.4093

1.4071

12

142®- 14a 5 °

4 gm.

1.4093

1.4071

13

142. 5®

5 gm.

1.4093

1.4071

14

142. 5°

5 gm.

1.4 0 9 4

1.4072 >

6 gm.

1.4549

1.4527

8 9

R esidue

1 4 0 ®-1 4 2 ®

M ainly e t h e r -

►

9y

Y ie ld o f k e to n e = 25 gm.

{66%

o f the t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d = 1 4 ,9 2 5 c . c . Volume o f uns a t u r a t e d g a s = 2$500 c . c *

?(T

G_#8 • B u t y r a m i d e an d n - p r o p y lm a g n e s iu m brom id e H e a t i n g tim e - 11 h o u r s w e i g h t of p r o d u c t ( a f t e r e t h e r removed) = 70 gm* 21

20

Bp*

Weight

1

35°

12 gm.

E ther

-

2

350

10 gm.

E th er

eth er

-

3

350-100°

4

1000-141°

4 . 5 gm.

1 .3 9 4 2

1.3946

5

1410-142°

2 gm.

1.4065

1 .4 0 6 9

6

142®

3

1 .4 0 6 6

1.4070

7

142°

6

1.4066

1.4070

8

1420- 142. 5°

6 . 5 gm.

1 .4 0 6 7

1.4071

9

1 4 2 . 5°-143°

5 gm.

1 .4 0 6 7

1 .4 0 7 1

2 gm.

1 .4 0 6 8

1.4072

6 gm.

1 .4 5 2 1

1.4525

10 R esid u e

143®

10 gm.

Y i e l d of k e t o n e = 24*5 gm$

M ain ly

gm.

( 64-% o f t h e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d = 15*420 c*c«

J

B u t y r a m i d e a n d n - p r o p y l m a p n e s i i i y b ro m id e Q.UABTITIES Magnesium

2 4 «3 gm,

n - p r o p y l b ro m id e

135 gm.

B u t y r a m id e

21*75 gm.

H e a t i n g 15 m i n s . o n l y

W eig ht o f p r o d u c t ( a f t e r e t h e r rem ove d) = 69 gm*

24

20

1 1 . 5 gm.

E th e r

-

10 gm.

E th er

-

11 gm.

E ther

-

HR.

Bp.

We i g h t

1

340

2

340-34.5®

3 4

3 4 .5 0 -1 0 0 °

9 gm.

1.3811

1.3827

5

1000- 140°

4 gm.

1.3941

1.3957

6

140°-143°

1 gm.

1.4030

1.4046

7

1430

2 gm.

1.4052

1.4068

]

8

1 4 3 ° -144°

4 gm.

1.4052

1.4068

1

9

144°

4 .5 gm.

1.4054

1.4070

10

144°

4 .5 gm.

1.4054

1.4070

11

144°

3 gm.

1.4055

1,4071 /

1 gm.

1.4069

1.4085

2 .5 gm.

1.4610

1.4626

12 R esidue

144°-1470

Y i e l d o f k e t o n e = 18 gm.

( 6 3 ^ of t h e t h e o r e t i c a l )

Volume of g a s c o l l e c t e d = 8 ,2 0 0 c . c .

R esidue T h is was d i s t i l l e d and c o l l e c t e d in 3 f r a c t i o n s *

The

b o i l i n g p o in t was n o t c o n s t a n t * 20 PR*

Bp* 150®

1.4107

2

15 0 0 -1 7 0 0

1.4151

a l l contained

3

17 0 0 - 2 7 0 0

1.4573

n itro g en .

1

—

The s e m i c a r b a z o n e f ro m f r a c t i o n 7 b a d M.P* 1 3 4 - 1 3 4 *^^.

»0


(66^ of th e t h e o r e t i c a l )

Volume of g a s c o l l e c t e d = l 6 »3^0 c . c .

\

/2

B u ty ra m id e on n - p r o p y lm a ^ n e sium b rom id e An a t t e m p t was m ade, i n t h i s e x p e r i m e n t , t o s t o p th e r e a c t i o n a n d decom pose i m m e d i a t e l y .

The p r o d u c t s may

g i v e an i n d i c a t i o n o f t h e i n t e r m e d i a t e com pound. QUAI^ITIES n - p r o p y l b ro m id e

4-9 . 5 gm.

Mag ne s ium

8 .1 gm.

B u ty ra m id e

29 gm.

E th e r

100 c . c . ,

100 c . c .

The G r i g n a r d r e a g e n t was p r e p a r e d , f i l t e r e d f u n n e l an d r u n o n to t h e b u t y r a m i d e .

i n t o a d r o p p in g

The m i x t u r e was d e ­

com posed i n t h e u s u a l w ay. W eig ht of p r o d u c t ( w i t h e t h e r w a s h in g s ) = 2? gm. (2 gm. b u ty r a m i d e was l e f t w i t h p r o d u c t a f t e r t h e e t h e r h a d been d i s t i l l e d

o ff).

The l i q u i d was d i s t i l l e d d i r e c t l y i n t o t h r e e f r a c t i o n s 1.

3 4 ®-9 0 °

M a in ly e t h e r

2.

9 0 ° - 1 2 0 ‘>

1 .3 9 0 7

3.

120° - 146=

1 .4 0 1 8

12 gm. 20

(»!) )

R e s id u e

6 gm. 4 gm. 3 g m .(s o lid )

The m e l t i n g p o i n t o f t h e r e s i d u e t o s 1 1 4 = -1 1 $= s o l i d r e s i d u e was b u t y r a m i d e . Volume o f g a s c o l l e c t e d = 5 .7 5 0 c . c .

i . e . th e

i ù3

G jl2 .

Butyraiaide and isop rop ylm agn e sium bromid e W eight o f p ro d u ct ( w it h e t h e r w a sh in g s) = 65 gm# 20

PR.

B p.

We i g h t

19 "D

“d

1

340

1 1 . 5 gm.

E th e r

-

2

340

E th e r

-

E th e r

-

9 gm.

3

3 4 0 - 3 4 .5 °

4

3 4 . 5 ®-132®

8 gm.

M a in ly e t h e r

5

1320-134®

2 gm.

1 .4 0 4 5

1 .4 0 4 1

6

1 3 4 0 - 1 3 4 .5 0

3*5 gm.

1 .4 0 4 9

1 .4 0 4 5

7

1 3 4 .5 °

4 . 5 gm.

1 .4 0 4 9

1 .4 0 4 5

8

1 3 4 .5 °

5 . 5 gm.

1 .4 0 4 9

1 .4 0 4 5

9

1 3 4 .5 °

1 . 5 gm.

1 .4 0 5 3

1 .4 0 4 9 >

6 gm.

1 .4 7 7 9

1 .4 7 7 5

Re s i d u e

1 0 . 5 gm.

Y i e l d o f k e t o n e =% I 7 gm#

-

( 4 5^ o f th e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d = 15*000 c#c# Volume of u n s a t u r a t e d g a s = 2 ,4 0 0 c#c*

)

Butyram ide and n -b u ty lin a g n esiu in brom ide W eight

of

product

(a fte r

eth er

rem oved)

= 7 1 * 5 gm#

18 FR*

Bp.

1

3 4 . 5 0 .3 5 0

We i g h t

20

“D

9 gm.

B th e r

-

8* 5 gm.

E th er

-

2

35“

3

350-70®

7 gm.

4

7 0 0 -1 1 6 0

6 gm.

1 .4 0 9 1

1 .4 0 8 3

5

1 1 6 0 -1 6 0 0

2 gm.

1 .4 0 7 0

1 .4 0 6 2

6

1 6 0 0 -1 6 3 0

2 .5 gm .

1 .4 1 3 8

1 .4 1 3 0

7

1 6 3 0 -1 6 4 0

6 gm.

1 .4 1 4 9

1 .4 1 4 1

M ain ly

eth er

-

0^

8

1640

6 gm.

1 .4 1 5 0

1 .4 1 4 2

9

1640

5«5 gm.

1 .4 1 5 0

1 .4 1 4 2

10

1640

7 .5 gm .

1 .4 1 5 0

1 .4 1 4 2

11

1 6 4 0 - 1 6 4 .5 0

5 gm.

1 .4 1 5 2

1 .4 1 4 4 J

6 gm.

1 .4 5 4 0

1 .4 5 3 2

R esid u e

Y ield

of

k eto n e

V olum e

of gas

V olum e

of

=

(70 % o f

30 g m *

c o llected

unsatu rated

= 11*2^0

gas

= 1*^00

th e

c*c. c .c .

th e o re tic a l)

to r

G .1 4 , B u ty ramide and. is o b u t y Imagne sium brom ide W eight o f p ro d u ct ( w ith e t h e r w a sh in g s) = 6 1 ,5 20

PR.

Bp.

We i g h t

1

3 4 .5 °

10 gm.

E th e r

1 0 , 5 gm.

E th e r

2

3 4 .5 0 - 3 5 0

3

35° - i o 3 - 5°

4

1 0 3 .5 0 - 1 5 1 0

3 .5 gm.

1 .3 9 8 5

5

1 5 1 0 .1 5 4 .5 0

2 . 5 gm.

1 .4 0 8 9

6

1 5 4 .5 °-155°

4 . 5 gm.

1 .4 0 9 4

7

155°

4 . 5 gm.

1 .4 0 9 5

8

1 5 5 ‘>

4 gm.

1 .4 1 0 1

9

1 55 0 -1 5 6 0

1 gm.

1 .4 1 0 4

8 gm.

1 .4 5 5 5

R e s id u e

8 gm.

M a in ly e t h e r

Y i e l d o f k e t o n e = 15*5 gm, (3 6 ^ of t h e t h e o r e t i c a l ) Volume o f g a s c o l l e c t e d = 1 4 , 7^0 c . c .

>

/o 6

Butyram id^ and s e c "butylmapne sium brom ide W eight o f p ro d u ct { w ith e t h e r w a sh in g s) = ? ! gm# 18 PR.

Bp.

34 . 5°

8 gm.

E th er

-

2

34. 5°

9 gm.

B th e r

-

3

34. 5°

9 .5 gm . E t h e r

-

4

3 4 . 50 -9 1 0

6 . 5 g m . 1 .3 7 7 8

1 .3 7 7 0

5

9 1 0 .9 5 0

6 . 5 g m . 1 .3 9 8 1

1 .3 9 7 3

6

9 5 0 -1 4 3 0

2 . 5 g m . 1 .3 9 6 2

1 .3 9 5 4

7

1 4 3 0 -1 5 4 0

1 gm.

1 .4 0 8 1

1 .4 0 7 3

8

1 5 4 0 -1 5 5 0

3 . 5 g m . 1 .4 1 3 1

1 .4 1 2 3

9

1 5 5 0 - 1 5 5 .5 0

6 . 5 g m . 1 .4 1 3 1

1 .4 1 2 3

155. 5®

3 gm.

1 .4 1 3 1

1 .4 1 2 3

12 gm.

1 .4 6 0 4

1 .4 5 9 6

Re s i d u e

V olum e The

“d

20

1

10

Y ield

We i g h t

of

k eto n e

of gas

resid u e PR. 1

= I

c o lle c te d

w as

= 1 0 ,$ 0 0

d is tille d

. Bp. ----- >

{^0 % o f

3 gm.

155®

th e c#c#

d ire c tly :-

4 '

1 .4 1 5 1

1 .4 1 3 5

2

1 5 5 0 -1 6 5 0

1 .4 1 5 4

1 .4 1 3 8

3

1650- 200°

1 .4 1 8 1

1 .4 1 6 5

4

200° - 280°

1 .4 6 1 4

1 .4 5 9 8

th e o re tic a l)

N

J

B utyram ide _and ,te r t-'b u ty j^ a g n e sium b r A f t e r h e a t i n g f o r 3 h o u r s , a n d c o o l i n g , th e e t h e r l a y e r an d i n s o l u b l e co m p lex s e p a r a t e d , l e a v i n g a s l i g h t l y c l o u d y e th e r la y e r.

The d e c o m p o s i t i o n o f t h e two l a y e r s s e p a r a t e l y

was a t t e m p t e d , w i t h t h e r e s u l t s t a b u l a t e d below *

I t was

d i f f i c u l t t o g e t a c o m p le te s e p a r a t i o n * W eig ht o f p r o d u c t fro m e t h e r s o l u b l e l a y e r ( w ith e t h e r w ash in g s)

=

26 gm*

FR.

Bp*

w eig h t

1

3 4 . 5 0 .3 5 0

10 g m .

2

3 5 0 -7 0 0

2 .5 gm .

3

9 0 0 -9 5 0

4 .5 gm .

1 S odium f u s i o n

4

9 5 0 -1 1 6 0

4 .5 gm .

j s h o w e d ’n i t r o g e n

R esid u e

1 gm.

p re se n t.

From f r a c t i o n 3 , th e p r o d u c t was d i s t i l l e d d i r e c t l y a n d n o t t h r o u g h a c o lu m n . F r a c t i o n s . 3 an d 4 w ere a m i x t u r e o f b u t y r o n i t r i l e a n d th e s o lid h ydrocarbon, d i - t e r t i a r y - b u t y l *

lOlQ

W eig ht o f e t h e r i n s o l u b l e p r o d u c t = 35 gm* ( w ith e t h e r w ash in g s) 1 5 .5

m .

Bp.

We i g h t

1

3 5 *5 ''

10 gm.

E th e r

20 "D

2

3 5 0 5 0 .1 1 3 0

7*5 gm.

1 .3 6 7 1

1 .3 6 5 3

3

1 1 3 0 -1 1 7 0

4 gm.

1 .3 8 6 2

1 .3 8 4 4

4

117®

4 . 5 gm.

1 .3 8 6 2

1 .3 8 4 4

5

117®

4 gm.

1 .3 8 6 2

1 .3 8 4 4

1 gm.

1 ,4 1 5 8

1 .4 1 6 0

R e s id u e

Volume of g a s c o l l e c t e d

= 11*500 c # c .

Volume o f u n s a t u r a t e d g a s = 2 ,3 5 0 c . c . An a t t e m p t was made to f i l t e r o f f t h e s o l i d h y d r o c a r b o n , b u t i t was f o u n d t o be e x t r e m e l y v o l a t i l e .

/Of

G .17o Butyram id e and t e rt-am yIm agne sinm brom ide Q.UATOITIiilS

T e r t -am y l b ro m id e

(1 mol« + 10^ )

l 6 6 gm,

B u ty ra m id e

(0 , 2$ m o l,)

2 1 , 7 $ gm. 2 4 .3 gm.

M agnesium

"When t h e am ide was a d d e d t o th e G r i g n a r d r e a g e n t , t h e r e a c t i o n w a s, a s u s u a l , v i g o r o u s , ' A f t e r f u r t h e r h e a t i n g t h e e t h e r l a y e r became c l e a r .

T h i s phenom enon h a s b e e n

n o t e d b e f o r e , when w o rk in g w i t h t e r t - b u t y I m a g n e s i u m b ro m id e W eigh t o f p r o d u c t

*

63 gm.

PR.

Bp.

We i g h t

4 ^

1

3 1 . 5 ° - 3 3 . 7 5 '’

11 gm.

E th e r

2

33. 75° - 34. 5"

1 1 ,5 gm* E t h e r

3

3 4 . 5 » - 9 6 . 5

11 gm.

M a in ly e t h e r

4

9 6 .5 ° -1 0 0 °

9 . 5 gm.

1 .3 9 7 6

5

100°-1140

5 . 5 gm.

1 .3 9 8 5

6

1 1 4 ° - 1 1 $=

6 gm.

1 .3 9 0 1

7

1 15°

2 gm.

1 .3 8 9 2

8

------ ^165®

1 gm.

1 .4 2 1 2

9

1650

2 gm.

1 .4 3 0 9

F r a c t i o n s 8 an d 9 w ere c o l l e c t e d b y d i r e c t d i s t i l l a t i o n 1 , $ gm, b u ty r a m i d e w ere f i l t e r e d tilla tio n

(M .P. 1 1 $ ° - 1 1 ^ . ^ % ) .

o ff b efo re th is d is -

/oy

Uo s o l i d d i - t e r t -am y l was n o t e d i n t h i s c a s e , a s th e q u a n t i t y o f h i g h b o i l i n g r e s i d u e was t o o s m a l l f o r d i s t i l l a t i o n t h r o u g h a colum n*

no

0 .1 8 . Isob u tyra m id e ajidjfl-:] Q.UAFPITIB3

M agnesium

3 2 .4 gm.

n - p r o p y l b ro m id e

l8o gm.

Iso b u ty ra m id e

29 gm.

E th e r

350 c . c . ,

350 c . c . , 100 c.c©

W eig h t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) = 65 gm. FR. 1

Bp. 340

2

3 4 0 - 3 4 .5 0

3

3 4 .5 0 - 1 0 5 »

4

W eig ht

1 7 .7 5

20 “d

1 3 . 5 gm. E t h e r

-

1 1 . 5 gm. E t h e r

mm

5 gm.

1 .3 8 9 0

1 .3 8 8 1

1 0 5 “ -1 3 3 °

1 . 5 gm.

1 .3 9 8 0

1 .3 9 7 1

5

1 3 3 0 -1 3 4 »

6 . 5 gm.

1 .4 0 5 4

1 .4 0 4 5

6

1 3 4 » - 1 3 4 , 5»

6 . 5 gm.

1 .4 0 5 4

1 .4 0 4 5

7

1 3 4 .5 “

6 gm.

1 .4 0 5 4

1 .4 0 4 5

8

1 3 4 .5 “

6 . 5 gm.

1 .4 0 5 4

1 ,4 0 4 5

9

1 3 4 .5 0 - 1 3 6 °

1 . 5 gm.

1 .4 0 6 1

1 .4 0 5 2

1 . 5 gm.

1 .4 2 7 1

1 .4 2 6 2

R e s id u e

Y i e l d o f k e t o n e = 2 5 .5 gm. ( 6 ? ^ of t h e t h e o r e t i c a l ) Volume o f g a s c o l l e c t e d « 15*300 c . c . Volume o f u n s a t u r a t e d g a s = 2 ,3 0 0 c . c .

(t l

G ^1 9 .

I s o b u ty r amide and n -p rop ylm agn esiu m brom ide QUAiirm a s M agnesium

32#4 gm«

n - p r o p y l b ro m id e Iso b u ty ra m id e

180 gm. V 29 gm.

E th e r

2^0 c . c . , 120

c .c .

W eig h t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) » 7 4 .5 gm. Bp,

¥e i g h t

1

3 4 . 5° - 35°

12 gm.

E th e r

2

35°

10 gm.

E th e r

3

35°

10 gm.

E th e r

-

4

35° . 4 7 . 5°

3

E th e r

-

5

4 7 .5 ° -1 0 2 .5 °

3 gm.

1 .3 9 4 9

1 .3 9 5 9

6

1 0 2 .5 ° - 1 3 2 °

1 . 5 gm. 1 .3 9 7 1

1 .3 9 8 1

7

1 3 2 0 -1 3 4 °

1 .4 0 2 8

1 .4 0 3 8

8

1 3 4 ° -!3 4 .5 °

5«5 gm. 1 .4 0 2 9

1 .4 0 3 9

9

1 3 4 .5 °

5 . 5 gm. 1 .4 0 3 0

1 .4 0 4 0

4 gm.

1 .4 0 3 0

1 .4 0 4 0

4 gm.

1 .4 0 3 1

1 .4 0 4 1

3 . 5 gm. 1 .4 0 3 2

1 .4 0 4 1

1 , 5 gm. 1 .4 3 6 5

1 .4 3 7 5

FR .

10

1 3 4 . 5° - 135°

11

135°

12

135°

R esid u e

4 gm.

-

Y i e l d o f k e t o n e = 2 6 .5 gm. ( 7 0 % o f t h e t h e o r e t i c a l ) Volume o f g a s c o l l e c t e d Volume o f u n s a t u r a t e d g a s

*

15*500 c . c .

=»

3*750 c . c .

i f 2.

G .2 0 . Iso b u tyra m i d e and i s opr opy Imagne si\im brom ide W eight o f p ro d u ct ( w ith e t h e r w a sh in g s ) » 75*5 gm. 20 "D

1 8 .7 5

m .

Bpo

We i g h t

1

340

12 gm.

E th e r

-

2

340

1 2 .5 gm. E t h e r

-

3

3 4 0 - 3 4 .5 0

13 gm.

E th e r

4

3 4 .5 0 -6 0 °

10 gm.

M a in ly e t h e r -

5

6 0°-120°

3 gm.

1 .3 9 3 6

1 .3 9 3 1

6

1 20°-122°

1 gm.

1 .3 9 9 1

1 .3 9 8 6

7

1 2 2 ° -1 2 3 .5 °

4 gm.

1 .4 0 0 9

1 .4 0 0 4

5«5 gm. 1 .4 0 1 0

1 .4 0 0 5

8

1 2 3 .5 0 - 1 2 4 °

9

124°

10

124°

11

124°

6 gm.

1 .4 0 1 0

1 .4 0 0 5

4 . 5 gm. 1 ,4 0 1 2

1 .4 0 0 7

R e s id u e

2 gm.

1 .4 0 1 5

1 .4 0 1 0

2 gm.

1 .4 3 9 9

1 .4 3 9 4

Y i e l d o f k e t o n e = 22 gm,

( 5^% o f t h e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d

=

Volume o f un s a t u r a t e d g a s

»

o

#

2 ,6 0 0 c . c .

ff3

Iso 'b u ty ra ^ id e and n -b u ty l ^ g^nesiiu% brom ide W eight o f p ro d u ct ( w ith e t h e r w a sh in g s ) » 8 2 gm* PR.

Bp*

20 “D

1 7 .5

We i g h t

1

3 4 .0 .3 4 .5 0

1 2 «5 gm. E t h e r

-

2

3 4 .5 °

12 gm.

E th e r

-

3

3 4 .5 0 . 9 5 0

8 , 5 gm.

1 .3 6 5 8

1 .3 6 4 8

4

95o -io i«

5 gm*

1 .4 2 1 0

1 .4 2 0 0

5

1 0 1°-107°

3 gm.

1 .4 1 1 7

1 .4 1 0 7

6

1070-155°

4 . 5 gm.

1 .4 0 3 0

1 .4 0 2 0

7

1 5 5 0 -1 5 6 .5 ®

2 gm.

1 .4 1 2 0

1 .4 1 1 0

8

1 5 6 . 5 ® -i$ 7 °

5»5 gm.

1 .4 1 2 2

1 .4 1 1 2

9

1 5 7 ° - 1 5 7 . 5°

5 . 5 gm.

1 .4 1 2 4

1 .4 1 1 4 f

6 gm.

1 .4 1 2 4

1 .4 1 1 4

10

1 5 7 0 -1 5 8 0

11

1580

6 gm.

1 .4 1 2 4

1 .4 1 1 4

12

1580

3 , 5 gm.

1 .4 1 2 4

1 .4 1 1 4 ,

2 . 5 gm.

1 .4 3 0 5

1 .4 2 9 5

R e s id u e

Y i e l d o f k e t o n e # - 2 8 .5 gm.

{67% o f t h e

th e o re tic a l)

Volume o f g a s c o l l e c t e d

=

1 0 ,7 5 0 c . c *

Volume o f u n s a t u r a t e d g a s

*

1 ,2 0 0 c . c *

P r e p a r e d s e m ic a r b a z o n e fro m F R .I O .

M .P. 1 1 0 ®C.

//4

G .2 2 . Iso b u t y r amide an d se c -b u ty lm a g n es iim bromid e W eight o f p ro d u ct ( w ith e t h e r w a sh in g s) = yo gm. 22 FR.

Bp.

W eig ht

1

35»

1 2 . 5 gm. E t h e r

2

35°

1 2 . 5 gm. E t h e r

20 “d -

3

3 5 0 - 8 0 .5 0

8 . 5 gm.

M a in ly e t h e r

4

8 0 ,5 0 - 9 4 0

4 . 5 gm.

1 .3 9 2 8

1 .3 9 3 6

5

9 4 o_g6 °

3 . 5 gm.

1 .3 9 5 0

1 .3 9 5 8

6

9 6 0 -1 4 5 0

2 gm.

1 .4 0 0 4

1 .4 0 1 2

7

1 4 5 0 -1 4 8 0

2 gm .

1 .4 0 7 2

1 .4 0 8 0

8

1480

6 . 5 gm.

1 ,4 0 8 9

1 .4 0 9 7

9

1480

5 gm.

1 .4 0 9 3

1 .4 1 0 1

10

1 4 8 0 -1 5 0 0

2 . 5 gm.

1 ,4 0 9 4

1 .4 1 0 2

11

1 5 0 0 -1 5 4 0

1 gm.

1 .4 0 9 8

1 .4 1 0 6

Sodium

3 . 5 gm.

1 .4 5 2 9

1 .4 5 3 7

fu sio n

R e s id u e

showed n i t r o g e n p r e s e n t . Y i e l d o f k e t o n e = l 6 gm.

( 37^ o f t h e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d

=

8 ,6 0 0 c . c .

Volume o f u n s a t u r a t e d g a s

»

1*700 c . c .

I s o b u t y r a m i d e a n d t e r t - b u t y Im a g n e siu m b r omide H e r e , a n a t t e m p t was made t o decom pose t h e two l a y e r s se p a ra te ly , n itrile

so t h a t th e d i - t e r t - b u t y l a n d t h e i s o b u t y r o -

c o u l d be d i s t i l l e d

se p a ra te ly .

A g a in , t h e r e s u l t s

b e lo w show t h a t t h e a t t e m p t was n o t e n t i r e l y

su c c e ssfu l.

E th e r so lu b le W eigh t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) PR.

B p. •

We i g h t

16 °D

1

3 4 .5 °

8 . 5 gm.

E th e r

2

3 4 .^ °

6 gm.

E th e r

«

27*5

20 “d

The r e m a i n d e r vras d i s t i l l e d d i r e c t l y . 1

—> 95°

7 gm.

1 .3 8 9 3

1 .3 8 7 7

2

950-102°

3 gm«

1 .3 8 2 1

1 .3 8 0 5

3

102° - 104°

2 gm.

W hite s o l i d

E th e r in so lu b le W eight o f p r o d u c t ( w i t h e t h e r w a s h in g s ) = 25*5 20

16 FR.

Bp.

We i g h t

“d

"D

1 1 . 5 gm.

E th e r

-

5 gm.

E th e r

1

3 4 .5 0 -3 5 °

2

3 5 ° .3 9 °

3

3 9 0 -1 0 0 °

3 . 5 gm.

1 .3 8 9 7

1 .3 8 8 1

4

1000-104°

2 gm.

1 .3 7 8 1

1 .3 7 6 5

Volume o f g a s c o l l e c t e d

*

1 1 , 75^ c . c .

Volume o f u n s a t u r a t e d g a s =

1 ,9 0 0 c . c .

G .2 4 . P ln a la m id e and n-p rop yIm agnesiu m brom ide W eight o f p ro d u ct ( w ith e t h e r w a sh in g s) » 5 6 gm.

1

20 "D

1 1 .7 5

B p.

we I g h t

3 4 .5 °

12 gm.

E th e r

-

2

3 4 . 5° - 5 5 . 5°

12 gm.

E th e r

3

5 5 .5 0 .9 1 0

0 , 5 gm.

1 .3 8 8 9

1 .3 8 5 6

4

9 1 0 -1 0 4 0

2 . 5 gm.

1 .3 8 7 0

1 .3 8 3 7

5

1 0 4 0 -1 0 5 0

3 gm.

1 .3 8 3 3

1 .3 8 0 0

Went s o l i d

-

6

1050

3 gm.

7

1050

4 gm.

rt

tt

-

8

1 0 5 0 -1 4 2 0

2 gm.

1 .3 9 8 0

1 .3 9 4 7

9

1 4 2 0 -1 4 4 0

1 . 5 gm.

1 .4 1 4 0

1 .4 1 0 7

2 gm.

1 .4 1 4 1

1 .4 1 0 8

3 gm.

1 .4 1 4 1

1 .4 1 0 8

10 11

1440 1 4 4 0 -1 4 5 0

12

1450

2 gm.

1 .4 1 4 2

1 .4 1 0 9

13

1450

2 gm.

1 .4 1 4 3

1 .4 1 1 0

1 gm.

1 .4 4 6 2

1 .4 4 2 9

R e s id u e

Y i e l d o f k e t o n e = lOoÇ gm. Volume o f g a s c o l l e c t e d Volume o f u n s a t u r a t e d g a s

{ 25% of th e

= «

th e o re tic a l)

1 2 , 0^0 c*c* 2 ,0 0 0 c , c »

in

P i n a l a m i d e an d n - p ro p y Im a g n e s iu rn bro m id e g u m ? IT D38 n - p r o p y l "bromide

135 gm. (1 m o l. + 10^ )

M agnesium

2 4 . 3 gm. (1 ato m )

P in a la m id e

2 ^ . 2 $ gm. (0*25 m o l . )

E th e r

2^0 c .c # * 100 c . c #

W eight o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) = $6 gm# 2 2 .5

20

PR.

Bp.

We i g h t

1

3 4 ,3 “

10 gm.

2

35°

1 1 . 5 gm. E t h e r

3

3 5 0 -4 0 0

4 , 5 gm.

E th e r

4

40 0-1 0 20

2 . 5 gm.

1 .3 8 0 9

1 .3 8 1 9

5

1 0 2 0 -1 4 0 0

3 gm«

1 .3 8 7 9

1 .3 8 8 9

6

1 4 0 0 -1 4 4 0

1 . 5 gm.

1 .4 0 8 2

1 .4 0 9 2

7

1 4 4 0 -1 4 5 0

6 gm.

1 .4 0 8 5

1 .4 0 9 5

8

1 4 4 0 -1 4 5 0

7*5 gm.

1*4091

1 .4 1 0 1

E th e r

-

9

1450

5 gm.

1 .4 0 9 2

1 .4 1 0 2

10

1450

1 . 5 gm.

1 .4 0 9 2

1 ,4 1 0 2

n e g li­ g ib le

1 .4 2 3 1

1 .4 2 4 1

R e s id u e

Y i e l d o f k e t o n e « 21*5 gm# (6 7 ^ o f t h e t h e o r e t i c a l ) Volume of g a s c o l l e c t e d « ll^ÇOO c . c #

ut

G #26 # P in a la m id e and n -p rop yIm agnesium brom ide QUAUTITIBS n - p r o p y l b ro m id e

I 3 5 gm. (1 m o l. + 10%)

H e a tin s

M agnesium

2 4 . ] gm. ( l ato m )

tim e =

P in a la m id e

25*25 gm. ( 0 .2 5 m o l* )

5 hours

S th e r

250 C . O . ,

250 c . c . ,

100

c.c

W eig h t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) = 66 gm. 2 4 .5

'

20

PR.

Bp.

we i g h t

1

3 4 .8 0

9 gm.

E th e r

-

2

3 4 .8 0

9 gm.

E th e r

-

3

3 4 .8 0

10 gm.

E th e r

4

3 4 .8 0 - 3 5 0

11 gm.

E th e r

5

35° - 9 5 . 5°

2 . 5 gm.

1 .3 8 0 3

1 .3 8 2 1

6

95 . 5° - i 03o

2 gm.

1 .3 7 8 6

1 .3 8 0 4

7

1 0 3 0 -1 4 2 0

3 gm.

1.383!)

1 .3 8 5 3

8

1 4 2 0 - 1 4 6 .5 0

1 gm.

1 .4 0 6 4

1 .4 0 8 2

9

1 4 6 .5 0 - 1 4 7 °

3 . 5 gm.

1 .4 0 9 7

1 .4 1 1 5

1470

3 . 5 gm.

1 .4 1 0 1

1 .4 1 1 9

1470

4 gm.

1 .4 1 0 1

1 .4 1 1 9

1 gm.

1 .4 1 4 0

1 .4 1 5 8

2 gm.

1 .4 3 7 0

1 .4 3 8 8

10 11 12 R e s id u e

'

1 4 7 0 -1 5 2 0

Y i e l d o f k e t o n e = 12 gm. Volume o f g a s c o l l e c t e d

)

j

(37% of t h e t h e o r e t i c a l ) = 9»050 c . c .

(The p r o d u c t fro m a r e a c t i o n t h a t h a s b e e n h e a t e d f o r

lo n g e r, in d e x ).

shows a w i d e r r a n g e i n t h e v a l u e s f o r t h e r e f r a c t i v e

no

P i n a l a m i d e a n d n--p ro p y Imagne a ium b ro m id e Q.ÜAHTITIBS n - p r o p y l b ro m id e

135 gm.

M agnesium

24«3 gm.

P in a la m id e

25»25 gm.

E th e r

250

H e a tin g

C .C .,

(tim e = 250

C.C»,

100 c . c )

10 h o u r s

W eig h t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) = 8 7 . 5 gm. 20 FR.

1

We i g h t

Bp 34. 5®

12 gm.

2

34. 5° - 35° ■

3

35“

10 gm.

4

35“

13 gm.

5

3 5 0 -4 2 °

1 1 . 5 gm.

6

420 - 100°

3 gm.

7

1 0 0 0 -1 0 7 0

1 . 5 gm.

8

1 0 7 0 -1 4 3 0

1 . 5 gm.

9

1 4 3 0 -1 4 5 0

1 gm.

10

1 4 5 0 - 1 4 5 .5 0

2«5 gm.

11

1 4 5 .5 0 - 1 4 6 °

3 . 5 gm.

12

1460- 148°

3 gm.

13

1 4 8 0 -1 5 0 °

3 gm.

Sodium f u s i o n showed

14

1 5 0 0 -1 5 3 0

3 gm.

n itro g e n p re s e n t.

R esid u e

Y ie ld of k eto n e

1 1 . 5 gm.

3 gm. ( a p p r o x . ) « I 3 giû. ( 41 ^ o f t h e t h e o r e t i c a l )

fXl

( A g a in , l o n g e r 'b o i l i n g , g i v e s a p r o d u c t w i t h a much g re a te r re fra c tiv e

in d e x r a n g e , a n d some h i g h b o i l i n g

n i t r o g e n - c o n t a i n i n g c o m p o u n d s). Volume o f g a s c o l l e c t e d = 1 1 ,7 0 0 c . c *

/a i

G .2 8 . P in a la m id e and n -p ro p y lm a g n esiu m brom ide Q.UAUTITIB3 n - p r o p y l b ro m id e

$4 gm*

M agnesium

9 «7 gm@

P in a la m id e

10#1 gm«(i^tb. m ol*)

E th e r

1^0 c * c .,

90 c . c *

The G r i g n a r d r e a g e n t was made in t h e u s u a l way*

The

p i n a l a m i d e was a d d e d t o t h e f i l t e r e d s o l u t i o n , a n d th e w hole decom posed on i c e , A fte r d i s t i l l i n g

im m e d ia te ly .

o f f th e e t h e r , 40 ^ o f t h e o r i g i n a l

am ide was o b t a i n e d fro m t h e e t h e r l a y e r * was o b t a i n e d ,

so i t

Eo o t h e r p r o d u c t

i s assu m ed t h a t t h e r e s t o f th e am ide

i s in th e w a te r l a y e r . Volume o f g a s c o l l e c t e d

=

2 ,0 0 0 c . c *

A f t e r p a s s i n g t h r o u g h c o n c e n t r a t e d s u l p h u r i c a c i d , 1 ,9 5 0 c . c * was c o l l e c t e d .

P in a la m id e and 1sopropylm agnesium bromide Q jjA m m iE s

Is o p ro p y l bromide

135

(1 niol. + 10 %)

Magnesium

24*3 gm. (1 atom)

P in alam id e

25*25 gme (0 .2 5 mol*)

E th er

250 c . c * , 250 C .C ., 100 c .c *

w eight of p ro d u c t ( w ith e t h e r w ashin gs) = 36 gm* PR.

Bp.

1

34 .5 °

w eig h t

20

16 .7 5

“d

1 0 .5 gm. E t h e r

-

E th e r

-

1 3«5 gm.

1.3798

1.3785

1000- 104®

2 gm.

1.3792

1.3779

5

1040-104.50

3 gm.

1.3792

1.3779

6

104.50

. 5*5 gm.

1.3792

1.3779

7

104.50

1 gm.

1.3796

1.3783

2

34 . 5° - 3 5 . 5°

3

35 . 5®-iooo

4

7 gm.

Y ie ld of k eto n e - n e g l i g i b l e * Volume of g a s c o l l e c t e d

*

12,500 c . c .

Volume of u n s a t u r a t e d g a s

*

1 , 7^0 c .c *

/24

G ejO , P i n a l a m i d e an d n -'b u ty lm a ^ n e sixim brom ide qUAlTTITIBS n - W t y l b ro m id e

i Ç l gm. (1 m o l. + 10%)

M agnesium

2 4 .3 gm. (1 ato m )

P in a la m id e

2 5 .2 5 gm. ( 0 .2 5 m o l . )

S th e r

250

C .C .,

250

c . c . ,

W eight o f p r o d u c t ( w i t h e t h e r w a s h in g s ) » 73 gm. 20

PR.

Bp.

We i g h t

1

34.75®

12 gm.

E th e r

2

3 4 .7 5 °

12 gm.

E th e r

12 gm.

E th e r

3

3 4 .7 5 ° -3 5 °

4

3 5 0 -1 0 0 °

5

1000- 102°

6

6 gm.

1 .3 8 5 1

4 . 5 gm.

1 .3 9 8 2

1 0 2 ° -1 0 3 ,5 °

3 gm.

1 .3 9 0 9

7

1 0 3 .5 0 -1 0 6 °

1 gm.

1 . 3880

8

1 0 6 0 -1 6 4 °

4 gm.

1 .3 9 3 8

9

1 6 4 0 - 1 6 7 .5 0

1 . 5 gm.

1 .4 1 4 0

10

1 6 7 .5 0 - 1 6 8 0

3 . 5 gm.

1 .4 1 6 2

11

1 6 8 0 -1 6 9 0

4 gm.

1 .4 1 7 2

12

1 6 9 0 -1 7 4 °

2 gm.

1 .4 2 0 9

2 . 5 gm.

1 .4 4 2 0

R esid u e

’

,

W eight o f k e t o n e = 9 gm. {26% of th e t h e o r e t i c a l ) Volume of g a s c o l l e c t e d Volume of g a s u n s a t u r a t e d

= 8 ,4 2 5 c . c . = 925

100

c *c

G .1 1 . P i n a l a m id e a n d n-T jutylm agne sium bro m id e qUÆNTITIBS n - b u t y l b ro m id e

1^1 gm. (1 m o l. + 1 0 ^ )

M agnésium

2 4 .3 gm.

P in a la m id e

25*25 gm.

( 0 .2 5 m o l . )

B tb e r

250 c . c . ,

100 c . c .

(1 a to m )

W eig h t o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) = 8 3 . 5 gm. 23

Bpo

1

3 4 .5 °

9 gm.

E th e r

-

2

3 4 .5 0

10 gm.

E th e r

-

3

3 4 .5 0 - 3 5 0

11 gm.

E th e r

-

4

3 5 0 -4 00

8 gm.

E th e r

-

5

4 0 0 -1 0 0 0

9 gm.

1 .4 0 6 4

1 .4 0 7 6

6

1 0 0 0 -1 0 5 0

7 gm.

1 .4 0 1 9

1 .4 0 3 1

7

1 0 5 0 -1 6 0 0

2 gm.

1 ,4 0 5 0

1 .4 0 6 2

8

1 6 0 0 -1 6 5 0

1 , 5 gm.

1 .4 1 3 4

1 .4 1 4 6

9

1 6 5 0 -1 6 7 0

2 . 5 gm.

1 .4 1 3 6

1 .4 1 4 8

10

1 6 7 0 -1 6 8 0

6 gm.

1 .4 1 4 2

1 .4 1 5 4

11

1680

5 gm.

1 .4 1 4 2

1 .4 1 5 4

12

1680

6 . 5 gm.

1 .4 1 4 2

1 .4 1 5 4

13

1 6 8 0 - 1 6 8 .5 0

2 gm.

1 .4 1 5 2

1 .4 1 6 4

1 gm.

1 .4 3 5 1

1 .4 3 6 3

R e s id u e

W eig ht

20 "D

FRo

Y i e l d o f k e t o n e « 23*5 gm.

( 6 6 ^ o f th e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d = 8 ,9 5 0 c . c .

/*2

P in a la m id e and se c -b u ty lm a g n e siu m bromide Q.UA1TTITIES s e c - b u t y l b r o m id e

151 gm* (1 mol a + 1 0 ^ )

Magnesium

2 4 . 3 gm.

P inalam ide

25*25 gm.

E th er

2 50 c • c * p 2 50 c « c . ^ 100 c*c*

W eight of p r o d u c t ( w i t h e t h e r w a s h i n g s ) » ^6 gm. 20

22.5

PR.

Bp.

W eight

1

3 4 .5 - ’

11 gm.

2

34.5®

1 0 , 5 gm • E t h e r

3

34.5°

9 gm.

“

d

E ther

E th er

-

4

3 4 .50.940

1 . 5 gm. 1 . 3 8 6 8

1.3878

5

940.950

2 gm.

1.3913

1.3 9 2 3

6

9 50.95.50

3 gm.

1.3911

1.3921

7

9 5 .5 ° - 9 6 ®

2 . 5 gm. 1 .3 9 0 0

1.3910

8

96°-100°

2 . 5 gm. 1 .3 8 7 0

1.3880

9

1000- 104°

1.3902

1.3812

-

3 gm.

10

1040-104,50

2 . 5 gm. 1 . 3 7 7 3

1.3783

11

104.50

2 . 5 gm. 1 . 3 7 7 1

1.3781

12

104,50-1100

1 gm.

1.3 8 0 4

1.3794

Y ield of ketone n e g l i g i b l e . Volume of g a s c o l l e c t e d

=

8,6 5 0 c . c .

Volume of u n s a t u r a t e d g a s = 1 ,6 5 0 c . c .

1:^7

P i n a l a m i d e a n d t e r t - b u t y l m a g n e s i u i a brom ide The e t h e r l a y e r was a g a i n c o l o u r l e s s , h u t s l i g h t l y c l o u d y . T h i s h a s been n o t i c e d r e p e a t e d l y t h r o u g h o u t t h e s e e x p e r i m e n t s when u s i n g t e r t - b u t y l G r i g n a r d r e a g e n t s . W eight o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) PR.

Bp.

W e ig h t

1

340

8 gm.

2

3 4 0 .3 5 0

=

42 gm.

7 . 5 gm.

D istilled d ire c tly 3

34.50-100°

4 gm.

4

100°-105°

6 gm.

5 6 7 A little

105° 1050-106° 106°

6 gm.

A ll a m ixture of s o l i d

5 gm.

hydrocarbon sm elling stro n g ly

3 gm.

of t r i m e t h y l a c e t o n i t r i l e

o f f r a c t i o n 6 g a v e a n im m e d ia te t e s t f o r

u n s a t u r a t i o n , w h ic h i s n o t g i v e n by t r i m e t h y l a c e t o n i t r i l e . Volume o f g a s c o l l e c t e d

=

9*500 c . c *

u r

G .3 4 . K - d i e t 3i y l a c e t a m i d e a n d n - p r o p y l m a g n e sium "bromicle Q.UAOTIT IBS n - p r o p y l brom ide

180 gm.

Magnesium

3 2 . 4 gm. (1-^rd a t o m )

E -diethylacetam ide

3 8 . 3 gm. ( i r d m o l . )

E th er

350

C .C .,

( l ^ r d m ol. )

350

c . c . *

100

c . c .

On a d d i n g t h e S’- d i e t h y l a c e t a m l d e to th e G r i g n a r d r e a g e n t , a very vig o ro u s r e a c t i o n o c c u rre d .

A w hite p r e c i p i t a t e

was f o r m e d immedisitel^r. Weight o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) FR.

Bp. . 5c»35o

We i g h t

2 0.5 «D

9 . 5 gm.

E th er

» 44*5 gm. 20 "D

1

34

2

350-58°

8 , 5 gm.

M a in ly ether

3

5 80-870

1 gm.

1.3904

1.3906

4

870-92.50

1 . 5 gm.

1.3897

1.3899

5

9 2.50-950

3 gm.

1.3897

1 .3 8 9 9

6

980-106°

1 gm.

1 .3 9 4 9

1.3951

7

1060-1350

2 gm.

1 .4 0 2 4

1.4026

8

1350-160°

3 gm.

1 .4 2 2 0

1 .4 2 2 2

9

1600-1630

2 ,5

1.4321

1.4323

10

1630-1750

3 gm.

1 .4 3 3 9

1 .4341

11

1750-2230

4 gm.

1.4459

1.4461

12

2 2 3 0 -2 4 3 0

3 gm.

1.4688

1.4690

gm.

From f r a c t i o n 6 , t h e p r o d u c t was d i s t i l l e d d i r e c t l y and

f2 i

n o t t h r o u g h a column « Volume of g a s c o l l e c t e d

=

1 2 ,2 5 0 c . c .

F r a c t i o n s 5 s.nd 11 were t e s t e d f o r n i t r o g e n b y sodium f u s i o n * F r a c t i o n 5 c o n t a i n e d no n i t r o g e n * F r a c t i o n 11 c o n t a i n e d n i t r o g e n *

J io

H -d ie tliy lp r o p io n a jn id e and n -p rop ylin agn esiu iii brom ide Q.UAmiTIES n - p r o p y l bro m id e

135 gm.

Magnesium

2 4 . 3 gm.

D i e t h y l p r o p i onamide

3 2 . 2 5 gm.

E th er

250

C .C .,

250

C .C .,

W e ight o f p r o d u c t ( w i t h e t h e r w a s h i n g s )

»

20 Bp

We i g h t

1

3 4.5°

10 gm.

E th er

2

3 4.5°

10 gm.

E th er

3

3 4 , 5 0 - 6 0 ° 11 gm.

FR.

M ainly e t h e r

4

600-1150

4 gm.

1.4003

5

1 1 5 0 -1 2 0 0

1 gm.

1.3997

6

1200-1210

3*5 gm.

1 .4 0 1 9

7

1 2 10-1230

2 , 5 gm.

1 .4 0 1 8 (

8

1230

1 gm.

1 .4 0 2 9 3

9

—> 1260

1 gm.

1,4085

10

1 2 6 0 -1 3 6 0

1 . 5 gm.

1.4109

11

13 6 0 - 1 5 5 0

2 gm.

1.4133

12

1 5 5 0 -1 6 5 0

1 . 5 gm.

1 .4 2 4 1

13

1 6 50-1800

3 . 5 gm.

1,4321

14

1800-1810

3 . 5 gm.

1.4349

15

1 8 1 0 -1 8 4 0

3 gm.

1.4348

16

1 8 40-1850

2 gm.

1.4333

100

c . c .

6 3 «5 gm.

From f r a c t i o n 9 » t h e p r o d u c t was d i s t i l l e d d i r e c t l y an d n o t t h r o u g h a column* As t h e p r o d u c t was d i s t i l l e d

it

d ecom posed, g i v i n g o f f

fumes s m e l l i n g s t r o n g l y o f d i e t h y l a m i n e , Y ield of ketone =

7 gm- ( 2 8 ^ of t h e t h e o r e t i c a l )

Volume o f g a s c o l l e c t e d = 7*000 c *c #

Ace t amide a n d n - p r o p y Imagine slum brom ide »n

,,

^

j r ^

—

m

,i i >»r>

#,

— i—

y— m, ^

-mu

^

- w —•

Q .U AITTrriE S

n - p r o p y l b ro m id e

l8o gm#

Magnesium

3 2 .4 gm«

A ce ta m id e

19*7

E th er

3?0 c . c # ,

35^ c . c . ,

100 c . c .

P r o d u c t was t h e y e l l o w c o n d e n s e d n i t r i l e . M .P. 179° ~ l 8 4 ° . The p r o d u c t was d i f f i c u l t t o i s o l a t e a s i t was v e r y s o l u b l e i n w a t e r , and a l m o s t i n s o l u b l e i n e t h e r . h ig h b o ilin g liq u id

20

(nj)

Volume o f g a s c o l l e c t e d

A few c . c . of

1 . 4 7 4 8 ) was a l s o p r o d u c e d # *

1 0 ,2 0 0 c #c #

G -az. A oetairiid e

and

is o p ro p y lm a g n e siu m

b ro m id e

The p r o d u c t was a g a i n t h e y e l l o w c o n d e n s e d n i t r i l e . S u fficien t

(2 g m , ) was o b t a i n e d f r o m t h e e t h e r s o l u t i o n

t o have a n a l y s e d .

I t c r y s t a l l i z e d from b o i l i n g benzene

s o lu tio n in yellow n e e d le s . A nalysis

R equired

c

5 8 . 5^

H

7 >3%

F

3 4 .1^

Found 59.3^ 6.2$2 33^

(T his a n a ly s is i s not p e r f e c t .

A s m a l l amount o f

u n r e a c t e d a c e t a m i d e may hav e b e e n p r e s e n t i n t h e s a m p l e ) Volume o f g a s c o l l e c t e d

*

1 2 ,4 0 0 c . c .

G, ^ 8 . Ac e t ami de a n d

t y l p ia^ ne s i um ~br omi de

On -g-rd m o l e c u l e o f a m i d e , Volume o f g a s c o l l e c t e d

9 » 550 c . c ,

A l a r g e amount o f t h e s o l i d n i t r i l e

was a g a i n p r o d u c e d , h u t

a s th e l i q u i d p r o d u c t sm elt of k e to n e ,

t h e w hole e x p e r i m e n t

was r e p e a t e d on l a r g e r q u a n t i t i e s * QUAITTITIEiS n - B u t y l b r o m id e

361*4 gm.

Magnesium

58*4 gm*

A c e ta m id e ( 0 .8 m o l* )

47*2 gm.

W e ight o f p r o d u c t ( w i t h e t h e r w a s h i n g s ) » ^ 8 gm* The p r o d u c t was f r a c t i o n a t e d , a n d a p p r o x i m a t e l y 1 c , c * f r a c t i o n s w ere t a k e n a t a tim e : 12 FR.

,

Bp

20 “d

1

34 0 .3 8 0

“d E th er

2

380-100°

1 .4 2 5 3

1 .4 2 2 1

3

1000-102°

1.4232

1 .4 2 0 0

4

1020-103.50

1 .4 2 0 3

1.4171

5

103.50-104.50

1 .4 1 4 8

1 .4 1 1 6

6

104.50-106°

1.4160

1 .4 1 2 8

7.

10 6 0 - 1 0 9 0

1.4183

1.4151

8

1090-111.50

1 .4 1 2 0

1 .4 0 8 8

.

12 FRc

20

Bp lll-5o-112