A study of St. von Kostaneckis synthesis of alpha naphthoflavone
by Wendell Iver Wall
A THESIS Submitted in partial fulfillment of the requirements for the Degree of Master of Science in
Chemistry
Montana State University
© Copyright by Wendell Iver Wall (1933)
Abstract:
1. Alpha-naphtholflavone was not successfully prepared by the writer in studying Kostanecki’s
synthesis.
2. The various steps along the synthesis were studied with special emphasis on products of
2-benzalacetonaphthol preparation. More work on the final steps is necessary.
3. Several possible tautomers of intermediate products were isolated.
4. One definite example of a possible molecular rearrangement is cited.
5. A method for obtaining more uniform results and better yields was found for the 3-aceto-1-naphthol
preparation.
6. It was shown that color did not correlate with the various melting points in the case of
2-aceto-1-naphthol as pointed out by Witt and Braun.
7. In future runs of 2-benzalacetonaphthol it seems more desirable to use less than the calculated
amount of sodium hydroxide and heat reaction longer.
8. This study opened up many new, interesting and unsolved problems for future investigation. A STUDY OF S T . YON ICOSTANEGKIt S SYNTHESIS'
OF ALPHA NAPHTHOFLAYONE.
BY
WENDELL I , WALL.
A THESIS
S u b m itte d i n p a r t i a l f u l f i l l m e n t o f t h e
r e q u ir e m e n ts , f o r t h e D e g re e o f
M a s te r o f S c i e n c e i n C h e m is try
A p p ro v e d ;
C hairm an o f G r a d u a te C om m ittee
Bozem an, M o n tan a
J u n e i 1933
''-'iiV l ’ i - v ' t 1A -I A
U/ I 5 "s
TABLE OF G CMiENTS
Page
I a t r o d u c t i o n . 4 - - ^ - - ^ - - ^ - - - - - ----- --S -A c e to -l-E a p h th o l -
3
-
*«*
5
- - - ----------- --- - -
9
R uns o f S ^ A o e to - I - N a p h th o l (T a b le I , )
-----— --- -------8
P u r i f i c a t i o n R uns on S - A c e to - I - N a p h th o l ( T a b le 11»)
S - B e n z a l a c e t o - I - N a p h t h o l - - - ----------- --- ---------'•--------- --- - - - -—
Runs: o f S - B e n z a la c e t o - I - N a p h t h o l ( T a b le 1 1 1 » )
A c e ty l-S -B e h z a la c e to -I-N a p h th o l
-
-
-
- - - - - - - - I ?
- - — -----—
----------- - - - - - - - - - - -
S p e c i a l R uns o f Gompounds C and. E
- - ------------------ - - •—
B r o m in a tI o n a n d A l c o h o li c P o ta s s iu m
-1 1
----------- --- - - --------- - - 1 5
R uns o f A c e t y l - S - B e n z a l a c e t o - I - N a p h t h o l ( T a b le I V ; )
A lp h a -N a p h th o f la v o n e - -
- - -
- - 19
-
- - - SO
- ---------- - - S I
H y d ro x id e T re a tm e n t ( T a b le V. )
- - - S3
Sum mary — — — — — — — — — — — — — — — — —— — — — — — — — — — —— —— — 34
44553
A STUDY OE S T & VON KOSTiNlCKI*S SYNTHESIS
OE ALPHA NiPHTHOELAVONEi
INTRODUCTION J
The p u r p o s e o f t h i s i n v e s t i g a t i o n *
ta in e d i t s
w h ic h i s s t a t e d i n t h e t i t l e ,
s tim u lu s ., o r i g i n a l l y , fro m t h e econom ic f a c t o r , dem and.
oh
A lp h a -
n a p h th o f l a v q n e was p e r h a p s f i r s t p r e p a r e d b y K o s ta n e c k i i n h i s s t u d i e s o f
th e f la v o r s g ro u p s?
I t h a s , l i k e o t h e r n u m ero u s e x a m p le s o f l a b o r a t o r y c u r ­
i o s i t i e s , d e v e lo p e d th r o u g h o c c a s i o n a l i s o l a t e d an d s p o r a d i c r e s e a r c h e s t o
b e a d e s i r a b l e l a b o r a t o r y an d c o m m e rc ia l r e a g e n t ^ ’ ® I n r e c e n t y e a r s t h e r e
h a v e b e e n a t t e m p t s t o p r e p a r e a lp h a - n a p h t h o f la v o n e by t h e E a stm a n Kodak Com­
p a n y i n o r d e r t o m e e t t r a d e dem ands, b u t , a s f a r a s i s know n, a l l e n d e a v o r s
7
have been u n s u c c e s s f u l.
A lp h a - n a p h th o f la v o n e h a s b e e n shown to b e . u s e f u l a s a n i n d i c a t o r i n
I
w a t e r p u r i f i c a t i o n c o n t r o l w h ere c h l o r i n e i s u s e d a s a s t e r i l i z i n g a g e n t .
A r e l a t i o n s h i p e x i s t s b e tw e e n t h e o x i d i z i n g a b i l i t y o f a g iv e n sam ple o f w a te r ,
a n d t h e n e c e s s a r y am ount o f c h l o r i n e f o r d e s t r u c t i o n o f t h e b a c t e r i a p r e s e n t .
By t i t r a t i n g c h l o r i n a t e d w a te r w ith a lp h a - n a p h t h o f la v o n e a s a n i n d i c a t o r ,
th e
p o i n t w h ere a n e x c e s s o f c h l o r i n e i s p r e s e n t can e a s i l y b e d e t e c t e d , and t h u s
a s u f f i c i e n c y m a in ta in e d ,
N a p h th o f la v o n e h a s a l s o b e e n shown t o be m ore s e n ­
s i t i v e to th e p re s e n c e o f io d in e
( 1 ; 1 , 0 0 0 ,0 0 0 ) t h a n s t a r Ch^
The- m eth o d i n v e s t i g a t e d i n t h i s r e s e a r c h w as t h a t o f K o s t a n e c k i * s .
T h is m e th o d w as a l s o b r i e f l y t r i e d f o r c o m m e rc ia l p r o d u c t i o n b y Dr^ 0 . E .'
S h e p p a rd w h ile w i t h t h e E a stm a n Kodak Company, a n d i t r e s u l t e d i n a f a i l u r e .
The l i t e r a t u r e c i t e s a l s o o t h e r s who h a v e t r i e d t h e m e th o d .and. h a v e b e e n u n ­
s u c c e s s f u l in th e c a s e o f b e ta -n a p h th o fla v o n e ,
H ow ever, t h e m ethod h a s b e e n
d u p l i c a t e d b y P f e i f f e r a n d Grim m er s u c c e s s f u l l y ^
OtIxer m e th o d s o f s y n t h e s ­
i z i n g a l p h a - n a p h t h o f la v o n e a r e a l s o fo u n d i n t h e l i t e r a t u r e but. w e re n o t
Q
in v e s tig a te d b y th e w r i te r ?
K b s ta n e c k i r S- m e th o d , a lt h o u g h som ew hat cum­
b e rs o m e , seem ed m ore o r th o d o x a n d l o g i c a l t h a n t h o s e o f o t h e r i n v e s t i g a t o r s .
I t was t h e a im o f t h e w r i t e r t o w o rk o u t s t e p b y s t e p t h e s y n t h e s i s
a n d t o i s o l a t e t h e d e s i r e d e n d p r o d u c t s i n p u r e f o n ru
L a b o ra to x y c o n d i t i o n s
w ere v a r ie d i n e v e ry c a s e , su c h a s te m p e ra tu re , tim e , p ro c e d u re an d co n cen ­
t r a t i o n o f re a g e n ts !
The s u c c e s s o f e a c h s t e p was. b a s e d u p o n c o r r e l a t i o n i n
e v e ry c a se w ith th e in te rm e d ia te p ro d u c ts o b ta in e d by E o a ta n e c k ij th e u ltim ­
a t e a im b e in g , g o o d y i e l d s *
c o r r e c t m e ltin g p o in t, c o lo r an d c r y s t a l l i n e fo rm .
I n p r a c t i c a l l y a l l th e s te p s th e r e a c t i o n s a p p e are d t o b e v e iy l a b i l e and
even s l i g h t v a r i a ti o n s o f c o n d itio n s a f f e c te d c o n s id e r a b ly t h e p ro d u c ts ob­
ta in e d ;
E o r t h i s r e a s o n m any p r o d u c t s o f s i d e r e a c t i o n s w e re i s o l a t e d i n
th e p u re s t a t e .
I n m any c a s e s o h e w as l e d t o b e li e v e ; t h a t t a u t o m e r s w e re o b ­
ta in e d in s te a d o f th e p ro d u c ts sought f o r ;
w o u ld h a v e b e e n t o
.A lthough t h e i d e a l c o n d i t i o n
d e f i n i t e l y e s t a b l i s h t h e i d e n t i t y o f t h e v a r i o u s compounds*
t h e v a s t am ount o f tim e a n d w ork r e q u i r e d to do t h i s f o r c e d the- w r i t e r t o
abandon t h i s s i t u a t i o n ;
I n some c a s e s * how ever* u l t i m a t e a n a l y s i s , o f t h e
com pounds w ere a t t e m p t e d b u t d e f i n i t e i d e n t i t y was n o t e s t a b l i s h e d ;
The
phenom ena o f 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 o f o n e compound w a s v e r y e v i d e n t
i n one c a s e ;
A m ore d e t a i l e d d i s c u s s i o n o f t h e r e s u l t s o f t h i s w ork w i l l be
g i v e n in . t h e e x p e r i m e n t a l p a r t o f t h i s p a p e r ;
A m o d i f i c a t i o n o f t h e m eth o d
o f p r e p a r i n g 2 - a e e t o - l n a p h th o l* w h e re b y one c a n g e t b e t t e r y i e l d s a n d a m o re
p u r e p r o d u c t was w o rk ed o u t ;
A m o re d e t a i l e d d e s c r i p t i o n o f t h i s w i l l a l s o
b e g iv e n i n th e e x p e rim e n ta l p a r t o f t h i s p a p e r;
The p r e s e n c e o f ta u to m e r s
i* 5 .£
in . th.e c a s e o f 2 a c e t o - l - n a p h t h o l h a s b e e n p o s t u l a t e d b y W i t t a n d B ra u n 9 i n
t h e i r s tu d y o f t h e a c e t o n a p h t h o l s s
T h is, sam e g r o u p in g w as p r e s e n t th ro u g h -^
o u t t h e r e m a in d e r o f t h e i n t e r m e d i a t e p r o d u c t s so o n e w o u ld n a t u r a l l y p o s tu ^
l a t e t h a t ta u to m e rs e x is te d i n th e o th e r in te r m e d ia te s ;
8-A0ET0-1-HAPHTH0L.
M e th o d ;
.
T he m e th o d u s e d i n p r e p a r i n g 2 - a c e t o - l - n a p h t h o l was t h a t
- .g
o u t l i n e d b y W i t t a n d - B r a u n iv T he p r o c e d u r e i s b r i e f l y a s f o l l o w s ;
D is s o lv e
60 go o f a l p h a - n a p h t h o l i n 3 0 c e ; o f a c e t i c a c i d a n d 45 g , o f a c e t i c a n h y ­
d r id e ; to t h i s m ix tu re ad d 30 g , o f z in c c h lb r i d e .
H e a t t h e m i x t u r e f o r 30
.
m i n u t e s o n a h o i l b a t h a t a t e m p e r a t u r e Of 1 4 0 oC« i n a 500 cc» r o u n d b o tto m
fla s k *
c o n n e c te d w ith a r e f l e x C o n d e n s e r;
T hen p o u r i n t o t h e m i x t u r e a b o u t
300 c c i o r m o re o f h o t w a t e r a n d s t i r u n t i l a r e d o i l y l a y e r s e p a r a t e s o u t
a t t h e b o tto m o f t h e f l a s k ; ' i f t h e r e d l a y e r d o e s n o t s e p a r a t e a t t h e bottom *
n o t enough hO t w a t e r h a s b e e n added*
w ill,
S e p a ra te th e r e d o i l y la y e r o f f an d i t .
th ro u g h slo w c o o lin g * c o n g e a l i n t o a c r y s t a l l i n e p a s t e ;
I t i s th e n
l e a c h e d w i t h s e v e r a l p o r t i o n s o f a l c o h o l u n t i l t h e r e d c o l o r i n g m a t t e r is ;
re m o v e d .
The r e m a in in g l i g h t g r e y c r y s t a l s a r e r e c r y s t a l l i z e d fro m a lc o h o l*
t h e r e b y p r o d u c in g a d e t o n a p h t h o l i n a p p l e g r e e n c r y s t a l s ; m e l t i n g a t I O l-IO S 0Gi
D i s c u s s i o n O f E x p e r im e n ta l. Work. On 2 - A c e t o - l - H a p h t h o l :
The f i r s t d i f ­
f i c u l t y e n c o u n te r e d i n t h i s s t e p w a s t h e i n c o n s i s t e n c y o f t h e y i e l d s ;
I t w as
fo u n d t h a t i f one h e a t e d t h e p r e p a r a t i o n to o l o n g , t o o much o f t h e r e d o i l y
6
i m p u r i t i e s w e re p r o d u c e d .
I f o n e h e a te d t h e m i x t u r e a b o v e t h e b o i l i n g , p o i n t
o f a c e t i c a n h y d r i d e (1 4 0 ° C ») , t h e r e w as a. t e n d e n c y to p ro d u c e t h e d l - a c e t o
n a p h th o l and l a r g e q u a n t i t i e s o f th e r e d o i l y l i q u i d im p u r ity .
(S e e f a b l e I )
I t w as f o u n d t h a t on a d d in g a n e x c e s s , o f a c e t i c a n h y d r id e a n d h e a t i n g i t f o r
a b o u t a n h o u r a t 140°C«> o n e c o u ld p r o d u c e a lm o s t e n t i r e l y t h e 2 , 4 d i a e e t o
,n a p h t h o l m e l t i n g a t 140° C .
The c o n d i t i o n s o f t h e p r o c e d u r e w e re w o rk ed b u t
s o t h a t t h e w r i t e r fo u n d h e CouLd o b t a i n good y i e l d s o f a c e t o n a p h t h o l c o n ­
s i s t e n t l y a n d t h a t t h e ‘p r o d u c t w as much l i g h t e r i n c o l o r , a n d b e t t e r a p p e a r i n g
o n e t h a n t h o s e o b t a i n e d b y t h e o r i g i n a l m e th o d ,
fh e c o lo r o f t h e c r y s t a l s
a f t e r r e c r y s t a l l i z a t i o n v a r i e d fro m l i g h t y e llo w t o a p p l e g r e e n and t h e m e l t ­
i n g p o i n t v a r i e d fro m 97 t o 1 0 1 ; t h e l i g h t e r c o l o r e d p r o d u c t u s u a l l y e x h i b i t ­
i n g t h e lo w e r m e l t i n g p o i n t i
G -'atterm ann, i n w o rk in g w ith a c e t o n a p h th o s , c la im ­
e d t h a t t h e o r t h o a C e to n a p h th o l was a p p l e g r e e n i n c o l o r a n d m e l te d a t 1 0 1 &
105."" He a l s o p o s t u l a t e d t h a t t h e l i g h t y e llo w c o l o r e d Compound; o f m e l t i n g
p o i n t O f 9 8 -9 9 0C. was t h e p a r a is o m e r .
T h is ' w a s; h o w e v e r; d i s p u t e d by, W i t t
a n d B ra u n , who. f o u n d t h a t o n f u r t h e r r e c r y s t a l l i z a t i o n a n d p u r i f i c a t i o n f ro m
a l c o h o l o f t h e o r t h o Compound, one o b t a i n e d t h e lo w e r m e l t i n g p o i n t d e r i v a t i v e
o f t h e l i g h t e r c o lo r *
T h a t t h e - m e l t i n g p o i n t d ro p p e d i n s t e a d o f r i s i n g w i t h
i n c r e a s e i n p u r i t y w a s e x p l a i n e d by t h e . f a c t t h a t t h e r e w e re tw o ta u t o m e r s o f
2 - a e e t o - l - h a p h t h o l ; o n e fo rm b e i n g a lm o s t c o l o r l e s s a n d h a v in g a low m e l t i n g
p o i n t ; a n d t h e o t h e r , t h e g r e e n c o lo r e d fo rm ; w ith a m e l t i n g p o i n t o f 1 0 1 IO S0C .
V a r io u s g r a d a t i o n s o f c o l o r a n d m e l t i n g p o i n t s b e tw e e n t h e s e two ex­
tr e m e s w e re s o l i d s o l u t i o n m i x t u r e s o f t h e two fo rm s*
W i t t a n d B ra u n c la i m to
h a v e p r e p a r e d a p a r a compound w i t h a m e l t i n g p o i n t o f 1 9 8 ° C.
A f t e r m a k in g s e v e r a l a t t e m p t s t o p r e p a r e 2 - B e n z a l - a e e t o - 1 - n a p h t h o l ;
w h ic h r e s u l t e d I n o b t a i n i n g c o n s i s t e n t l y g o o d y i e l d s o f a y e llo w p r o d u c t ; n o t
7 ■»
h a v in g t h e p r o p e r t i e s o f t h e b e n z a l d e r i v a t i v e , i t w as th o u g h t- d e s i r a b l e t o
i n v e s t i g a t e th e 2 -a c e to -1 -n a p h th o I »
QZhe p r o b a b i l i t y t h a t t h e y e llo w compound,
o b t a i n e d b y t h e w r i t e r was t h e ta u to m e r o f t h e E -B e n z a l a e e t o n a p h t h o l , seem ed
lik e ly .
The a p p r o a c h m ade b y t h e w r i t e r w as t o t a k e d i f f e r e n t s h a d e s o f
o r t h o - a c e t o n a p h t h o l a n d b o i l i n a l c o h o l w ith d e c o l o r i z i n g c a r b o n , f i l t e r an d
" r e c r y s t a l l i z e s e v e r a l tim e s .
T h e re w as f o u n d t o be no d e f i n i t e c o r r e l a t i o n
b e tw e e n c o l o r a n d m e l t i n g p o i n t ;
Of t h e n i n e d i f f e r e n t s h a d e s a n d c o l o r f r a c ­
t i o n s p r o d u c e d , i t was e s t a b l i s h e d t h a t a p a l e s tr a w y e llo w compound h a d t h e
h i g h e s t m e l t i n g p o i n t o f 9 8 - 1 0 0 ° C ., . w h i l e t h e l o w e s t h a d a p a l e g r e e n c o l o r ,
m e l t i n g a t 9 6 . 5 t. 98°G .
p a le y e llo w .
The c o l o r s i n m o st c a s e s w e re p a l e g r e e n t o y e llo w a n d
T h e r e w as a g e n e r a l o v e r l a p p in g o f m e l ti n g p o i n t s a n d c o l o r .
The d e c o l o r i z i n g c a rb o n rem o v e d c o n s i d e r a b l e g r e e n c o l o r fro m t h e a c e t o n o p h t h o l s
in a l l cases.
The r e s u l t s a r e t a b u l a t e d i n T a b le I I .
I t is e s ta b lis h e d ,
t h e r e 6=-
f o r e , t h a t th e g re e n c o lo r, i s a n im p u rity o f th e a e e to n a p h th o l an d t h a t th e
p u r e p r o d u c t i s p a l e y e ll o w , m e l t i n g a t 97-=99°G. - H ow ever, th e w r i t e r , i n w ork­
in g w ith th e a lc o h o lic e x tr a c t i o n s o f th e r e d o i l y im p u r itie s o f 3 - a c e t o - l n a p h t h o l , b e l i e v e s t h a t t h e g r e e n c o l o r i s c l o s e l y a s s o c i a t e d w ith t h e r e d o i l
i m p u r i t i e s . a n d t h a t a ta u to m e r o f th e y e llo w i s a p u r p l e c o l o r e d compound.
T h is p o s s i b i l i t y w i l l be d is c u s s e d l a t e r i n t h i s p a r t o f th e p a p e r.
I n t h e new m eth o d t o b e o u t l i n e d f o r t h e s a t i s f a c t o r y p r e p a r a t i o n o f
2 - a c e to - l- n a p h th o l; a l l m o d if ic a tio n s o f th e g e n e ra l p ro c e d u re have b e e n fo u n d
b y e x p e r im e n t t o m a t e r i a l l y a i d i n o b t a i n i n g g o o d y i e l d s a n d u n if o r m p r o d u c t s ;
TABLE I .
RUKtS OF' 2-ACET0-1-IMPHTH0L.
Eo o
Gram s o f
a -n a p h th o l
used .
B er cent
... . . y i e l d -
I;
Si
s.
■4o
Si
6»
7.
Si
9.
36
60
60
30
30
30
60
60
. SO
5
63
3
88
33
13
IQ i
Ili
SO
315
19
60
IS i
IS i
Mi
350
190
400
70
50
73
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300
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30
130
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9 4 -9 5
9 5 -9 8
9 8 -9 9
9 6 -1 0 0
98—101
9 8 -1 0 0
9 8 -1 0 0
9 9 -1 0 0
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9 8 -1 0 0 * * /
9 8 -1 0 0 * *
9 8 -1 0 0 * *
9 8 -9 9 ,5 * *
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Apple: g r e e n
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* T ills p r o d u c t w as t h e 2 , 4 - D ia c e to - 1 - n a p lr b I i o l .
~
** T he r e a c t i o n m i x t u r e w as m e c h a n i c a l l y s t i r r e d w h i l e a d d in g t h e
a c e t i c a n h y d rid e i
M 15 g ram s i n e x c e s s o f a c e t i c a n h y d r i d e w as u s e d ;
TABLE I I
PURIFICATION RUNS ON 2-ACET0-1-NAPHTH0L„
N o .*
T im es r e c r y s t a l l i z e d
fro m d e c o l o r i z i n g
c a rb o n . .
I. '
2.
3*
4;
5;
6;
7.
8;
9.
I
2
2
I
2
I
I
I
I
C o lo r o f
p ro d u ct
.
P a le g reen
P a l e y e llo w
L ig h t a p p le g re e n
P a l e g r e e n y e llo w
Y e llo w
Same as, (5 )
ft
ItIt
Y
It
Y
IY
(4)
It ’
M e ltin g :, p o i n t
9 6 » 5 -9 8
9 6 » 7 -9 8 o2
9 7 ;8 - 9 9
9 7 ; 5 - 9 9 ;8
9 8 ;0 -1 0 0
9 7 .5 - 9 8
9 8 .0 - 9 9
9 7 ;5 - 9 9
9 7 .5 - 9 8
M o d if ie d M ethod f o r P r e p a r a t i o n .o f 3-A ce t o -I- N a p R th o 1 1
The sam e p r o ­
p o r t i o n o f i n g r e d i e n t s i s u s e d a s i n th e: o r i g i n a l p r o c e d u r e ^ e x c e p t t h a t o n e t h i r d m ore a c e tic .- a c i d i s d e s i r a b l e i
D is s o lv e th e a lp h a -n a p h th o l an d th e
f r e s h l y f u s e d a n d p u l v e r i z e d Z n C lg i n t h e a c e t i c a c i d b y h e a tin g , on a. w a te r
b a th e
A l l o f t h e Z nG lg w i l l n o t d i s s o l v e ;
T hen p l a c e t h e m ix t u r e o n a
m e c h a n ic a l s t i r r e r a llo w in g , t h e a c e t i c a n h y d r id e t o d r o p i n s lo w ly fro m a
s e p a ra to ry fu n n e l;
T he a c e t i c a n h y d r id e s h o u ld be a d d e d r a p i d l y e n o u g h so
t h a t t h e h e a t o f t h e r e a c t i o n m a i n t a i n s t h e te m p e r a t u r e o f t h e s o l u t i o n i n t h e
f l a s k fro m 7 0 -8 5 ° 0 »
S tirrin g
s h o u ld b e c o n ti n u e d f o r o n e - h a l f h o u r a f t e r a l l
th e a c e tic , a n h y d rid e h a s been ad d e d & C onnect th e f l a s k to a r e f l e x c o n d e n se r
a n d h e a t on a w a t e r h a t h f o r 1 0 -1 5 h o u rs *
T r a n s f e r t o a n o i l b a t h and h e a t
fro m I t o S h o u r s a t I g S 0 C=., a f t e r w h ic h t h e t e m p e r a t u r e i s g r a d u a l l y r a i s e d
t o I S S - I i O 0Co ( u n c o r r e c t e d ) f o r about, f i v e t o 10 m i n u t e s i
Remove t h e o i l
b a t h a n d c o n d e n s e r fro m f l a s k a n d a l l o w t o c o o l s l i g h t l y ;
Tb t h e s o l u t i o n
r- ^ • "••••• Li;.-.--,.•
10 =
a d d D o i l i n g w a te r w i t h s t i r r i n g
a t t h e b o tto m o f t h e f l a s k .
o r s h a k in g u n t i l a r e d o i l y l a y e r s e p a r a te s ,
The: r e d o i l i s s e p a r a t e d fro m t h e w a te r w ith" a
s e p a r a t o r y f u n n e l and p l a c e d i n a b e a k e r t o c o o l .
a c ry s ta llin e p a s te .
The s u b s t a n c e c o n g e a ls t o
The p a s t e o r c r y s t a l s a r e b ro k e n up a n d p l a c e d i n t o
a b o u t 1 5 0 c c i o f c o ld a l c o h o l , s t i r r e d a n d f i l t e r e d ;
T h e .c r y s t a l s a r e t h e n
w a sh e d w i t h s e v e r a l s m a ll, p o r t i o n s o f c o ld a l c o h o l & A f t e r m o st o f t h e red : im p u r i t i e s h a v e b e e n w a sh e d o f f t h e p r o d u c t i s ' r e c r y s t a l l i z e d fro m a l c o h o l .
Y e l­
lo w i s h g r e e n n e e d l e - l i k e c r y s t a l s o f 2 - a c e t o - l - n a p h t h o l a r e o b t a i n e d , m e ltin g ;
a t 9 8 -1 0 0 °C ;
The y i e l d i s 50 t o 60 g ram s, .w h ic h i s a p p r o x i m a t e ly 70 p e r c e n t
o f th e t h e o r e ti c a l y ie ld ;
A lc o h o l E x t r a c t i o n s o f E e d I m p u r i t i e s Form ed fro m A c e to M a p h th o l P r e p ­
a ra tio n s ;
A f te r c o n s id e r a b le q u a n ti ti e s o f th e a lc o h o l e x tr a c tio n s o f th e
2 - a c e t o - l - n a p h t h o l p r e p a r a t i o n h a d b e e n c o l l e c t e d , i t w as t h o u g h t d e s i r a b l e :
t o d i s t i l l o f f t h e a l c o h o l a n d a c e t i c e s t e r fo rm e d .
A f te r d i s t i l l a t i o n and
a w a t e r b a t h , t h e r e re m a in e d a t h i c k o i l y l i q u i d w hich w o u ld - n o t s o l i d i f y on
c o o lin g .
The m a ss was p l a c e d i n w a t e r m ade s l i g h t l y a c i d w i t h a c e t i c a c i d and
b o ile d f o r s e v e ra l h o u rs.
The w a t e r w as d e c a n t e d o f f o f t h e b l a c k m a ss a t t h e
b o tto m a n d m o re w a te r was a d d e d a n d b o i l e d .
The w a t e r w a s h in g s w e re c o o le d
t o a b o u t 1 0 °G . a n d a f l a k y c r y s t a l l i n e m ass- p r e c i p i t a t e d out&
w e re p a l e r o s e c o l o r e d p l a t e s ;
The c r y s t a l s
T h e re w e re c o n s i d e r a b l e q u a n t i t i e s o f t h e
m a t e r i a l o b t a i n e d b u t no w o rk was done i n a n a tt e m p t t o
id e n tify it*
T h ro u g h ­
o u t t h i s p a p e r t h e p a l e r o s e c o lo r e d compound w i l l b e r e f e r r e d t o a s (A) *
b l a c k m ass; n o t s o l u b l e i n t h e h o t w a te r , s o l i d i f i e d on c o o l i n g ;
b o t t l e d a n d a llo w e d t o s t a n d s e v e r a l m o n th s ;
The m a s s w a s
I t was t h e n n o t i c e d to have, p a l e
g r e e n n e e d l e - l i k e c r y s t a l s s u b lim e d a ro u n d t h e b l a c k m a s s ;
u n d o u b te d ly 2 - a c e t o - l - n a p h t h o l .
The
The c r y s t a l s w e re
The s u b s ta n c e was t h e n d i s s o l v e d i n h o t a l c o -
11 *
h o i a n d i t w e n t i n t o s o l u t i o n g i v i n g a b e a u t i f u l d a r k r e d d i s h p u r p l e c o lo r =
Gn c o o l i n g b l a c k c r y s t a l s w e re o b ta in e d =
E b i s b l a c k c o l o r e d compound, s h a l l
b e r e f e r r e d to h e r e a f t e r i n t h i s p a p e r a s
(B ).
The c r y s t a l s w e re h o m o g en io u s
i n a p p e a r a n c e a n d g a v e a m e l t i n g p o i n t o f IO O -IO l0G,
Oh d i l u t i n g
I iq i n o r , m ore, o f a d a r k p u r p l e c r y s t a l l i n e m a t e r i a l p r e c i p i t a t e d =
p o i n t was 1 0 0 ,5 - 1 0 0o8°G«
t h e m o th e r
The m e l t i n g
From g e n e r a l, a p p e a r a n c e a n d m e l t i n g p o i n t s t h e y a r e
p r o b a b l y t h e sam e com pound.
Compound B w as a llo w e d t o s t a n d f o r a c o u p le o f
m o n th s u n c o v e r e d , on a t r a y i n a l o c k e r ;
On e x a m in in g t h e s u b s ta n c e a g a i n
n u m ero u s n e e d l e c r y s t a l s : o f a, p a l e g r e e n c o l o r w e re p r e s e n t m ix e d w ith t h e
b la c k ;
I t i s .e s t i m a t e d t h a t a t l e a s t t w e n t y - f i v e p e r c e n t o f t h e m i x t u r e was
p a le g ree n c r y s t a l s ;
T h i s w o u ld i n d i c a t e p o s s i b l y t h e m a t e r i a l i s a m i x t u r e
o f t h e tw o t a u t o m e r s o f 2 - a c e t o - l - n a p h t h o l ;
2 -a c e to -l-n a p h th o l a re id e n tic a l;
The m e l ti n g p o i n t o f B-a n d t h e
T h a t t h e s u b s t a n c e s w e re t a u t o m e r i c fo rm s
o f e a c h o t h e r was n o t d e f i n i t e l y e s t a b l i s h e d a n d m ore r e s e a r c h , a lo n g t h i s , l i n e
i s n e c e ssa ry ;
B-BSSZAL-hCBTO—1—NAEHTHOL .
M e th o d ;
I n 100 gram s; o f a l c o h o l d i s s o l v e 10 gram s o f 2 - a c e t o - l - n a p h t h o l ,
To th e m ix t u r e a d d 6 g ram s o f b e n z a l d e h y d e a n d s t i r m e c h a n i c a l l y ;
A fte r a l l
.
t h e i n g r e d i e n t s a r e d i s s o l v e d a d d v e r y s lo w ly 20 g ram s o f a. 50 p e r cent; NaOH
s o lu tio n .
T he. s o l u t i o n g r a d u a l l y t u r n s a l i g h t o r a n g e t o r e d c o l o r ;
I n a,
f l a s k c o n n e c te d w ith a r e f l u x c o n d e n s e r t h e m a t e r i a l i s h e a t e d f o r I h o u r on
a w a te r b a t h ;
Too l o n g h e a t i n g a c c o r d in g t o IC o sta n e c k i w as u n d e s i r a b l e ;
A fte r
t h e e n d o f t h e r e a c t i o n , t h e c l e a r r e d l i q u i d i s p o u r e d i n a b o u t 4 0 0 -6 0 0 e e , . .
o f c o l d w a te r w h ic h i s b e in g m e c h a n i c a l l y s t i r r e d ;
i s fo im e d w h ic h i s f i l t e r e d o f f ;
A- d a r k r e d gummy p r e c i p i t a t e
To t h e f i l t r a t e a d d 'c a u t i o u s l y a c e t i c o r
—
12
« •
h y d r o c h l o r i c a c id u n t i l t h e s o lu t i o n : i s . s t i l l a l k a l i n e b u t j u s t a b o u t n e u t r a l .
T h is c a n b e d e te r m in e d b y t h e c o l o r o f t h e f i l t r a t e w h ic h i s a l i g h t o r a n g e
i n c o m p a ris o n t o t h e a c i d o r n e u t r a l c o n d i t i o n w h ic h i s d e c i d e d l y y e llo w w i t h
t h e r a p i d f o r m a ti o n o f a p r e c i p i t a t e s
th e re i s
In th e s l i g h t l y a lk a lin e c o n d itio n
so m e tim e s a f o r m a t i o n o f a n o r a n g e p r e c i p i t a t e s
g r e a tly f a c i l i t a t e s c o a g u la tio n o f th e p r e c ip ita te s
te r e d and d is s o lv e d i n h o t a lc o h o ls
M e ch a n ica l, s t i r r i n g
The p r e c i p i t a t e i s f i l ­
By c a r e f u l f r a c t i o n a l c r y s t a l l i z a t i o n *
c o o l i n g g r a d u a l l y a n d d i l u t i n g w i t h w a te r* d a r k o r a n g e c r y s t a l s w e re o b t a i n e d
w h ic h g i v e a m e l t i n g p o i n t on r e c r y s t a l l i z a t i o n o f 1 2 6 s 5 0~127°C„
a r e v e r y s m a lls
A l i g h t - o r a n g e f r a c t i o n i s a l s o o b t a i n e d w h ic h on r e c r y s t a l ­
l i z a t i o n fro m a l c o h o l comes o u t i n p l a t e s w h ic h m e l t a t 7 6 ° - 7 8 0C»
s ta llin e
The y i e l d s
Brown c r y ­
i m p u r i t i e s w e re a l s o s e p a r a t e d fro m t h i s , f r a c t i o n a t i o n ;
The s l i g h t l y a l k a l i n e f i l t r a t e fro m w h ic h th e o r a n g e p r e c i p i t a t e h a d
been f i l t e r e d i s a c i d i f i e d w ith a c e t i c o r h y d r o c h lo r ic a c id s
T h e re i s fo rm e d
l a r g e q u a n t i t i e s o f a y e llo w p r e c i p i t a t e w h ic h i s l e t s t a n d f o r a few m in u te s
a n d g iv e n a n o c c a s i o n a l s h a k i n g .
to p , and i s f i l t e r e d o f f .
a c e tic a c id .
The p r e c i p i t a t e f l o c c u l a t e s ,
r i s i n g to th e
The p r e c i p i t a t e i s r e c r y s t a l l i z e d fro m a l c o h o l o r
The c r y s t a l s b e in g b r i g h t y e llo w p l a t e s m e l t a t 9 5 ;5 0- 9 6 06',
Some
o f t h i s y e llo w m a t e r i a l i s a l s o o b t a i n e d i n t h e f i n a l d i l u t i o n o f t h e a l c o h o l
f i l t r a t e s in th e p u r i f i c a t i o n o f th e above o ra n g e p r e c i p i t a t e .
The o r a n g e c r y s t a l s w i t h a m e l t i n g p o i n t o f. 1 2 6 ;5 0-1 2 7 ° C , s h a l l be known
i n t h i s p a p e r a s compound (Q ), t h e l i g h t o r a n g e c r y s t a l s w ith a m e l t i n g p o i n t
o f 760-7 S °G , a s com pound (D) a n d t h e y e llo w c r y s t a l s m e l t i n g a t 9 5 ,5 0-9 6 ° Q , a s
compound ( E ) .
K o s ta n e c k i s t a t e s t h a t 2 - b e n z a l a c e t o - l - n a p h t h o l c r y s t a l l i z e s i n
o r a n g e c o l o r e d l e a v e s a n d h a s a m e l ti n g p o i n t o f 1 2 5 -1 2 60C ,
T h is m e th o d i s
o r i g i n a l t o t h e a u t h o r e x c e p t t h e r e a c t i o n q u a n t i t i e s w hich a r e K o s t a n e c k i s S ,
- IS -
• D i s o u s s i o a o f E z p e r iB im t on. S - B e a z a le c e to - l^ H a p h tlio I s
I n a tt e m p t in g :
t o p r e p a r e 3 - b e n z a l a c e t o n a p h t h o l , m uch d i f f i c u l t y - w as p r e s e n t e d when t h e y ie ld - s
o f t h e 2 - b e n z o l a c e t o n a p h t h o l (G) w e re n e g l i g i b l e a n d l a r g e y i e l d s o f a n u n id e n ­
t i f i e d y e llo w compound (E) w e r e o b t a i n e d ;
S e v e r a l a tt e m p t s w e r e m ade a n d a
v a r i e t y o f c o n d i t i o n s e x p e rim e n te d w i t h (T a b le I I I ) j b u t o n l y i n a few i n s t a n ­
c e s w e re a n y y i e l d s o f K o s t a n e e k i f S b e n z a l com pound i s o l a t e d ;
I n a lm o s t e v e r y
a t t e m p t , on t h e f i r s t , d i l u t i o n o f t h e p r e p a r a t i o n w ith c o ld w a t e r , one o b t a i n e d
a r e d s t i c k y m ass w h ic h was s o l u b l e i n a h c o h o l a n d a c e t i c a c i d .
A tte m p ts t o
r e c r y s t a l l i z e t h e m a t e r i a l fro m e i t h e r a l c o h o l o r a c e t i c a c i d an d f r a c t i o n a l
f e c r y s t a l l i z a t i o n b y d i l u t i o n o f t h e s o l v e n t w i t h w a te r y i e l d e d s m a l l a m o u n ts
o f a brow n po w d er w h ic h m e l te d a t, 123—1 38°G;
T h is may b e sem e 2—b e n z a l a c e t o -
n a p h th o l> b u t t h e y i e l d s w e re so s m a l l; a n d t h e p r o d u c t so d i f f i c u l t t o p u r i f y
t h a t a t t e m p t s t o o b t a i n t h e com pound fro m t h i s s o u r c e w e re a b a n d o n e d ;
I t is
v e r y d i f f i c u l t t o i n t e r p r e t t h e r e s u l t s o f t h e v a r i o u s r u n s b e c a u s e o f t h e m any
u n d e te r m i n a b le f a c t o r s a f f e c t i n g t h e r e a c t i o n s ;
Many tim e s t h e r e s u l t s c o u l d
n o t b e d u p lic a te d in sub seq u en t t r i a l s ;
T im e o f R e a c t i o n :
t i o n w as s t u d i e d ;
The e f f e c t o f v a r y i n g t h e tim e o f h e a t i n g t h e r e a c ­
I n r u n ( I ) o f T a b le I I I t h e m ix t u r e was r e f l u x e d f o r th r e e -
h o u r s a n d a llo w e d t o
s ta n d u n t i l c o o l ;
T h i s was t h e o n l y tim e t h a t a n y a p p r e c ­
i a b l e am o u n ts o f 3 - b e n z a l a e e to n a p h t h o I w as o b ta in e d *
l e s s th a n t h e s t i p u l a t e d am ount o f EaOH u s e d ;
in g t h e r e a c ti o n ;
T h e re w a s c o n s i d e r a b l y
T h i s inay h a v e b e e n a f a c t o r a i d ­
I n a l a t e r r u n (3 ) th e r e a c t i o n w as r e f l u x e d f o r 6 to 8 h o u r s .
H one o f compound O w as i s o l a t e d on p u r i f i c a t i o n ;
T h e re was a s m a ll y i e l d o f t h e
gummy r e d b e a z a ld e h y d e polym er* a n d a. good y i e l d Of com pound E®
14 *»
Two r u n s w e re m ade t o d ie t e rm in e t h e e f f e c t o f' n o t h e a t i n g t h e r e a c t i o n
t h e s p e c i f i e d h o u r*
I n r u n (3 ) t h e tim e w as o n e - h a l f h o u r*
y i e l d o f G b u t t h e r e w as a c o n s i d e r a b l e y i e l d o f D a n d Th
tim e w as f i f t y m in u te s *
T h e r e w a s .n o
I n r u n (4 ) t h e
T h e re was no b e n z a ld e h y d e p o ly m e r fo rm e d *
Good y i e l d s
o f compound E a n d some D w e re o b ta in e d *
Gonee n t r a t i o n :
i n a t t e m p t w as m ade to d e te r m in e t h e e f f e c t o f d e c r e a s ­
i n g t h e c o n c e n t r a t i o n o f so d iu m h y d r o x id e *
The e f f e c t o f r u n ( I ) is. m e n tio n e d
in d is c u s s io n o f th e r e a c ti o n tim e .
(4 ) s l i g h t l y o v e r t h r e e ^ f i f t h s o f
t h e am ount o f NaOH w as u s e d ;
b e n z a ld e h y d e p o ly m e r ;
In ru n
T h e re w as a f o r m a t i o n o f l e s s o f t h e gummy r e d
An e x c e l l e n t y i e l d o f E was o b t a i n e d ;
sam e c o n c e n t r a t i o n a s (4 ) was u s e d ;
No p o ly m e r was fo rm e d ;
I n r u n (5 ) the.
D ilu tio n o f th e
r e a c t i o n m i x t u r e w i t h w a t e r o b t a i n e d a n o r a n g e p r e c i p i t a t e w h ic h g a v e some o f
com pound C on f r a c t i o n a l r e c r y s t a l l i z a t i o n
In ru n
a
A g o o d y i e l d o f E w as o b t a i n e d ;
(6 ) s l i g h t l y o v e r t h r e e - f o u r t h s o f NaOH was u s e d ;
T h e r e was som e r e d d i s h
o r a n g e p r e c i p i t a t e fo rm e d on d i l u t i o n w h ich y i e l d e d a s m a l l q u a n t i t y o f C and.
D;
N o t a s good a y i e l d o f E w as o b t a i n e d ;
q u i r e d a l k a l i w as a d d e d ;
I n ru n (?) a b o u t h a l f o f th e r e ­
Gn a c i d i f y i n g r e a c t i o n m i x t u r e a n d d i l u t i o n ^ a n o r a n g e
p r e c i p i t a t e fo rm e d w h ic h o n r e c r y s t a l l i z a t i o n g a v e com pound.D;
A ru n (8) was made i n w hich th e o n e - h a l f q u a n t ity o f a l k a l i was a d d e d .
t o th e r e a c t i o n m ix tu r e w h ich h a d b e e n p r e v io u s l y warmed;
d a rk brown p r e c i p i t a t e w ith no compound E fo rm ed ;
The p r o d u c t w as a
The warming o f th e a l k a l i
p ro d u c e d v e r y u n d e s ir a b l e r e s u l t s ;
I t was o b s e r v e d t h a t i n t h e p r e c i p i t a t i o n o f com pound E fro m t h e r e a c ­
t i o n m ix t u r e , t h a t s o m e tim e s t h e p r e c i p i t a t e w ould t u r n a y e l l o w i s h brown, on
s ta n d in g b e fo r e i t c o u ld b e f i l t e r e d .
I f t h e compound i s f i r s t r e c r y s t a l l i z e d
fro m g l a c i a l a c e t i c a c i d a n d t h e n fro m a l c o h o l , a v e r y .p u re p r o d u c t i s o b t a i n e d ,.
“ 15
TABLE. H I ,
RUTS OF. S-BENZALACETO-l-JTAPHTHOL«,
N-Oi
U
So
4i
5.
6;
So
9o
IO i
Ho
IS 0
ISo
14i
15 o
16 d
Grams o f
a c e to n a p h th o l
u se d ,
Grams o f
50gg BfaOH
u sed
100
SO
55
100
100
SO
10
10
50
100
10
18
15
40
SO
SO
. 150
55
300
ISO
130
55
IS
10
100
400
100
ISO
140
SG
40
SO
R e a c tio n
h e a tin g
tim e
(h o u rs ) •
3
6^8
0 :5
OiS
I.
I
■ I
I
OiS
I
I
I
S i5
I
I
I
Y ie ld o f gram s i n .
C-D)
(E) , CO)
tra d e
4
S
is
I
—
8
■8
b la c k gummy ia ass
6 ■ 52
73
5
S
y
2
7
8
5
SS
tra c e
tra c e
14» 5
S
4
IS
. <£»
-
I n T r e s tig a tio n . o f Oomgmid E ;
90
35
SO
68
95
10
18
■■ -
B ecause o f th e c o n tin u a l f i n e y i e l d s o f .
t h e y e llo w compound u n d e r a lm o s t a l l e x p e r i m e n t a l c o n d i t i o n s t h e w r i t e r t h o u g h t
i t a d v i s a b l e t o f u r t h e r i n v e s t i g a t e t h e com pound«
f u r i c a c i d s o l u t i o n w i t h a r e d d i s h y e llo w c o l o r ,
The com pound w e n t i n t o s u ita p ro p e rty s im ila r to th a t o f
S -b e n z a la c e to n a p h th o l,
P e r h a p s t h e m o st s t r i k i n g phenom ena i n r e g a r d t o t h e compound was i t s
u n d e r g o in g a c h a n g e o f m e l t i n g p o i n t o n s t a n d i n g ,
A q u a n t i t y o f t h e s u b s ta n c e
h a d b e e n p r e p a r e d a n d p u r i f i e d f o r t h e p u r p o s e o f m a k in g a n u l t i m a t e a n a l y s i s e
The com pound on s u c c e s s i v e .r e c r y s t a l l i z a t i o n s fro m a l c o h o l e x h i b i t e d a c o n s t a n t
m e l t i n g p o i n t o f 95o5~96°G»
The q u a n t i t y t h a t wad n o t u s e d w as b o t t l e d a n d
s e t a s i d e o v e r t h e summer m o n th s ,
When, w o rk was re s u m e d t h e f o l l o w i n g f a l l ,
t h e Compound w as a g a i n r e e r y s t a l l i z e d a n d fo u n d t o h a v e a m e l t i n g p M f if
.U M - i - V r Liii-AMA
- 16
1 3 5 o 5 -1 2 7 6*
T h i s show s e v id e n c e O f some p o s s i b l e m o l e c u l a r r e a r r a n g e m e n t*
I n an a tt e m p t t o h a v e some m o re o f t h e compound u n d e rg o t h e same c h a n g e ;
s e v e r a l s a m p le s o f d i f f e r e n t p r e p a r a t i o n s w ith m e ltin g : p o i n t s o f 95-96°C w e re
p l a c e d i n sam ple . b o t t l e s and. e x p o s e d t o d a y l i g h t b y p l a c i n g i n an u n s h a d e d
sp o t out of d o o rs;
A f t e r s e v e r a l m o n th s , a m e l t i n g p o i n t w as a g a i n t a k e n ; and
i t w as fo u n d n o t t o h a v e c h a n g e d i n e i t h e r o f t h e sa m p le s*
I t was th o u g h t t h a t
p o s s i b l y warm t e m p e r a t u r e s m ig h t e f f e c t the- c h a n g e , so t h e s a m p le s w e re p l a c e d
i n a warm ro o m n e a r a w a t e r b o i l e r *
s a m p le s w e re s t i l l u n c h a n g e d ;
A f t e r a m o n th t h e m e ltin g ; p o i n t s o f t h e
A: s a m p le o f t h e compound w as p l a c e d i n a l c o h o l
a n d r e f ! u s e d f o r s e v e r a l d a y s w i t h s t i l l n o c h an g e o f m e l t i n g p o i n t ;
A ll e f­
f o r t s t o d u p l i c a t e t h e c h a n g e i n m e l t i n g p o i n t w ere u n s u c c e s s f u l *
&he w r i t e r b e l i e v e s , h o w e v e r, t h a t t h e compound d i d u n d e rg o s u c h a
change;
P r o o f c o u ld n o t b e e s t a b l i s h e d , b e c a u s e o f n o t b e i n g a b l e t o a t t a i n
o r d e te r m i n e c o n d i t i o n s f a v o r a b l e f o r t h e c h a n g e ;
I f t h e compound d i d u n d e r ­
g o t h a t c h a n g e ; i t m u s t d e f i n i t e l y b e a t a u to m e r o f compound CE, b e c a u s e t h e
m e l t i n g p o i n t a f t e r t h e c h a n g e i s i d e n t i c a l w i t h t h a t o f compound C0
S e v e r a l c o m b u s tio n s o f t h e compound w e r e made*
A n a l y s is
H o; •
I
f»Ho
#c .
■- #0%
8
7 .3 0 4
5 .1 1 4
5 ;5 9
7 ; 13
5 .9 7
5 .4 1
5*63.
5 .6 3
7 5 ; 64
7 6 .1 9
7 7 ; 10
7 6 ; 35
4 8 ;1 5 )
87; 6 )
4 3 .2 3 }
)
A ve;
5 ; 63
7 6 ;7 7
S
3
4
5
6
7
C a l c u l a t e d f o r m u la ;
A A sig n ed f o r m u l a :
gI S 8H
1 7 ;6
6V
3 - b e n z a la c e to n a p h th o l:
g I S hH
1 7 .0 5
1 8 ; 69
1 7 .3 1
1 6 .5 1
KOH
s o lu tio n
becam e
e x h a u s te d
cV
^ 17 F u r t h e r w ork o n t h i s compound i s n e c e s s a r y to- d e f i n i t e l y e s t a b l i s h i t s
id e n tity .
The w r i t e r w as u n a b le t o p o s t u l a t e a n y s t r u c t u r e o f t h e compound
f r o m t h e c a l c u l a t e d e m p e r ic a l f o r m u la a n d t h e c o n d i t i o n o f its formation®
ACETYL<^BMZALS;GET0“ 1 “3MPHTH0L
M e th o d :
P l a c e 1 0 g ra m s o f S ^ b e n z a l a e e t o n a p h t h o l i n a f l a s k c o n t a i n ­
i n g 40 t o 5 0 g ra m s o f a c e t y l c h l o r i d e *
C onnect to a r e f i n e co n d en ser and ad d
5 gram s o f f r e s h l y f u s e d so d iu m a c e t a t e *
h o u rs.
R e f lu x o n a w a t e r b a t h fro m 4 t o 6
A f t e r r e a c t i o n h a s t a k e n p l a c e , c o o l t h e s o l u t i o n down- b e lo w room tem ­
p e r a t u r e . and. a d d w a t e r d r o p b y d r o p t h r o u g h t h e c o n d e n s e r t u b e u n t i l a l l t h e
e x c e s s a c e t y l c h l o r i d e i s d e s tr o y e d *
c e ss, sh ak e and f i l t e r .
Then a d d 5 0 t o 100 cc* o f w a t e r i n e x ­
R e c r y s t a l l i z e fro m d i l u t e a l c o h o l i
The a c e t y l d e r i v a ­
t i v e a c c o r d in g t o K o s ta n e c k i c r y s t a l l i z e s i n y e llo w p l a t e s f ro m d i l u t e , a l c o h o l ,
h a v in g a m e l t i n g p o i n t o f 95-96°G *
T h is i s t h e a u t h o r ’ s own m ethod*
D i s c u s s i o n o f E x p e rim e n t o n A c e t y l - S - B e n z a l a c e t o - I - M a p h t h o l :
Much d e ­
t a i l e d w ork o n t h i s s t e p o f t h e s y n t h e s i s c o u ld n o t b e d o n e ^ due t o t h e l a c k
o f 2 - b e n z a l a c e t o n a p h t h o l w i t h w h ic h t o w ork*
a c e ty la tio n p ro d u c ts p u r i f i e d .
In - o n l y a fe w c a s e s w e re t h e
T he r e a s o n f o r t h i s w as; f i r s t *
t h a t ' t h e m ix - '
t t i r e s o f com pounds p r e p a r e d w e re v e r y d i f f i c u l t t o i s o l a t e ev e n b y f r a c t i o n a l
r e c r y s t a l l i z a t i o n a n d se co n d * t h a t t h e s t a r t i n g " m a t e r i a l u s u a l l y u s e d w as com­
pound E .
An a t t e m p t t o g e t n a p h t h o f l o v a n e f r o m t h i s compound w as made w i t h o u t
a n y a t t e n t i o n g iv e n t o t h e i n t e r m e d i a t e p r o d u c ts *
“• 18 “
In. tEie: e a s e w h e re t h e compound C w as u s e d t h e i n t e m e d i a t e s w e re i s o l a ­
t e d i n e ach c a s e a n d a l s o i n two r u n s w i t h compound E .
The r u n s o f t h e s e com­
p o u n d s fro m t h e 2 - b e n z a l a c e t o n a p h t h o l t h r o u g h t o t h e f i n a l p r o d u c t w i l l b e
t r e a t e d s e p a r a t e l y i n t h i s ' p a p e r*
I n . r u n ( I ) o f T a b le IV the. a c e t y l compound fo rm e d o n r e c r y s t a l l i z a t i o n
g a v e y e ll o w c o l o r e d p l a t e s m e ltin g : a t 9S-QS0C*
The compound h a d a s l i g h t l y
■ d is a g r e e a b le o d o r a n d t h e c r y s t a l l i n e s t r u c t u r e was s l i g h t l y d i f f e r e n t fro m
t h e compound E w h ic h w as a c e t y l a t e d .
h a d b e e n a c h e m ic a l c h a n g e .
T h is w as t h e o n l y i n d i c a t i o n I h a t t h e r e
The- o n l y r e a s o n f o r d o u b t w as t h a t t h e o r i g i n a l
compound a n d t h e p r o d u c t b o th h a v e th e : same m e l t i n g p o i n t*
T h ere i s a p o s s i­
b i l i t y t h a t a c e t y l a t i o n d id n o t t a k e p l a c e ;
S e v e r a l a c e t y l a t i o n s w e re r u n o f com pound E , b u t. c o m p le te p u r i f i c a t i o n
o f t h e p r o d u c t s w as n o t a f f e c t e d b e f o r e b r o m in a tin g t h e compound i n t h e n e x t
s te p *
On h e a t i n g a c e t y l a t i o n r e a c t i o n f o e 1 0 t o 14 h o u r s , a* m i x t u r e o f l i g h t
>.y e ll o w c r y s t a l s w i t h l a r g e q u a n t i t i e s o f d i s t i n c t l a r g e s q u a r e p l a t e s o f a
d a r k e r y e llo w compound, w as. o b ta in e d *
M e ltin g p o i n t o f t h e p r o d u c t r a n g e d fro m
90 t o 96°C ( im p u r e ) ;
I n f u n (2 ) o f compound C o f p r o d u c t fro m r u n ( 5 ) , T a b le I I I , a y e llo w
c r y s t a l l i n e s u b s ta n c e w as o b t a i n e d w h ich m e l t s a t 1 2 5 -1 2 6 °0 *
I n a c e t y l a t i o n o f b o th , com pounds C a n d E t h e p r o d u c t s o f b o th r u n s
show ed no a p p r e c i a b l e c h a n g e i n m e ltin g : p o i n t s fro m t h a t o f t h e o r i g i n a l com­
pounds;
The g e n e r a l a p p e a r a n c e o f th e - p r o d u c t s d i d show some c h a n g e a s t o •
c o lo r and c r y s t a l l i n e
s tru c tu re .
W h e th e r a c e t y l a t i o n d e f i n i t e l y h a d t a k e n
p la c e o r n o t i s s t i l l a m a tte r to b e s e t t l e d .
- 19 TABLE' H =
i
HUNS OE ACETYL-2“ BEMZAIAGET0“ l “NAPHHi0L»
No*
I*
2*
s;
4.
5.
Grams o f maL
t e r i a l used
(C)
(D)
(E)
10
4
23
68
.68
Qi
23
7;
8;
15
20-
9;
G -I
E -I
'■
10
18
34
R e a c tio n
h e a tin g
tim e
(h o u rs)
•. G h a r a c t e r i s t l o s o f P r o d u c ts
Y i e ld
■ g ra m s
12
0 ,5
6
15
4
12
12
10
8
I
15
n o t d e f ’it
»
It
tl
It:
ir
tt
It
10
8
8
V
tt
2 8
40
. C r y a ta ls - G o lo r Y e llo w p l a t e s
w
n e e d le s
V
p la te s
M ix tu r e
tt- ■
’?
it
D a rk y e llo w
p la te s
M ix tu r e
D eep y e llo w
Y e llo w p l a t e s
■
M. -P.
.9 5 -9 6
1 2 5 -1 2 6
9 7 -9 9
9 0 - 9 1 .5
9 5 -9 6
7 8 -8 5
.1 0 8 -1 1 0
1 2 5 .5 - 1 2 7
9 5 -9 6
AGETYL-g-BENZALAGETO-l^NAPHTHOLDIBBOIVEDE
M e th o d :
To 10 gram s1 o f a c e t y l - 2 " b e n z a l a c e t o n a p h t h o l d i s s o l v e d i n 300
g ram s o f c a rb o n d i s u l f i d e i s a d d e d a n e q u im o le c u l a r p r o p o r t i o n o f b ro m in e (3 p e r
c e n t s o lu tio n in c a rb o n d is u lf id e )
v e r y s lo w ly w i t h m e c h a n ic a l s t i r r i n g : .
h y d ro g e n b ro m id e s h o u ld b e e v o lv e d :
No
A f t e r a llo w in g c o n s i d e r a b l e tim e f o r the:
r e a c t i o n t o t a k e p la c e * t h e c a r b o n d i s u l f i d e i s d i s t i l l e d o f f o n a w a te r b a t h
u n t i l a b o u t 50 c e . o f r e a c t i o n m i x t u r e in. c a r b o n d i s u l f i d e r e m a in i n t h e f l a s k *
T h is i s t h e n w ash ed i n t o a b e a k e r a n d t h e c a rb o n d i s u l f i d e i s a llo w e d to
o ra te o ff;
evap­
T h e p ro d u c t* a c c o r d i n g t o K o s ta n e c k i,. on r e c r y s t a l l i z a t i o n fro m b e n ­
z i n e i s w h i t e n e e d l e s m e l t i n g a t 1 8 6 -1 8 7 °G .
T h is m eth o d i n c o r p o r a t e s a. few
v a r i a t i o n s , o f K o s t a n e c k i ' s m e th o d w h ic h i s n o t c l e a r l y o u t l i n e d i n l i t e r a t u r e ^
I
a n d i s t h e m e th o d u s e d b y t h e a u t h o r .
A 20
"GHSGHCeHs
+
CS,
B rg
D is c u s s io n - o f E x p e r im e a t a l Work on A c e ty l" 2 - - E e n z a la c e to - l- N a p I ith o I d i~
b r o m id e ;
I n a t t e m p t s t o b n o m in a te im p u re m i x t u r e s o f t h e a c e t y l a t i o n p r o d u c t
o f com pound E , much h y d ro g e n b ro m id e was g i v e n o f f i
C o p lin g o f t h e r e a c t i o n
i n i c e w a t e r b a t h a n d g r e a t d i l u t i o n s o f t h e r e a c t i o n p r o d u c t s i n c a rb o n d i s u l ~
f i d e d id n o t a id th e s i t u a t i o n to a n y g r e a t d e g re e .
s o l u b l e i n b e n z e n e and c a rb o n d i s u l f i d e *
The p r o d u c t s w e re v e r y
On r e c r y s t a l l i z a t i o n , s e v e r a l t i m e s
fro m a l c o h o l , a p a l e y e llo w s u b s t a n c e m e l t i n g fro m 125-127°C » was o b t a i n e d .
No
w h i t e c o l o r e d c r y s t a l s w e re o b t a i n e d i n t h i s s t e p t o a g r e e w ith t h e d i b ro m id e
o f K o s t a n e c k i ’ s ; ' P u r i f i c a t i o n o f t h e p r o d u c t s o f a l l t h e b r o m in a tio n r u n s be® ■
f o r e a t t e m p t i n g t h e f i n a l s t e p o f t h e s y n t h e s i s w as o m i t t e d ; • T a b le V show s
r u n s o f b r o m i n a ti o n e x p e rim e n ts *
A1PH&®NAPHTH0FLAV0NE
M e th o d ;
S u sp e n d 10 gram s: o f t h e d i b ro m id e o f a c e t y l - 2 - b e n z a l a c e t o n a p h t h o l
i n 100 c c . o f a lc o h o l *
S t i r m e c h a n i c a l l y a n d a d d i n p r o p o r t i o n t h r e e m o le s o f
p o ta s s iu m h y d r o x id e i n a 50 p e r c e n t w a t e r s o l u t i o n .
s o l u t i o n w i t h a r e d d i s h y e llo w c o lo r *
The d ib r o m id e g o e s i n t o
A f t e r r e a c t i o n h a s t a k e n p l a c e , w h ic h
m ay b e f a c i l i t a t e d b y w arm ing s l i g h t l y o n a w a te r b a t h , w a t e r i s a d d e d t o th e ;
s o lu t i o n and th e a lp h a -n a p h th o fla v o n e p r e c i p i t a t e s o u t.
c r y s t a l l i z e d fro m a l c o h o l .
A c c o rd in g t o K o s t a n e c k i , b e a u t i f u l p a l e y e llo w
l e a f l e t s s h o u ld b e o b t a i n e d m e l t i n g a t 1 5 4 -1 5 5 0C,.
o r i g i n a l w ith th e a u th o r .
I t i s f i l t e r e d a n d re®
The m e th o d , a s o u t l i n e d , i s
-
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A tte m p t te» p r e p a r e :
. OC-CHi
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D is c u ss io n :, of:. E x p e rliiL e a ta l Work on A l p h a - H a p h th o l ll a y o ii e :
H i t a n d m iss,
m e th o d s w e re t r i e d i n a lm o s t e v e r y c a s e i n a n a t t e m p t t o o b t a i n t h e n a p h th o f la v o n e »
T he p r o d u c t s o f t h e b r o m i n a ti o n w e re t r e a t e d w ith a l c o h o l i c p o t a s ­
siu m h y d r o x id e a n d s t i r r e d u n t i l s o l u t i o n t o o k p l a c e s
s o l u t i o n w as o b t a i n e d a t a l l tim e s , i n t h e a lc o h o l *
A r e d d is h , y e llo w c o lo r e d
I t was t h o u g h t d e s i r a b l e t o
r e f l u x t h e r e a c t i o n f o r m i x t u r e a fe w m in u te s , b e f o r e d i l u t i n g w i t h w a t e r t o o b ­
t a i n th e p ro d u c t.
A c i d i f y i n g t h e f i l t r a t e a l s o b r i n g s down m o re o f t h e p r o d u c t
i f any ex c ess a lk a li i s u sed .
A s id e fro m t h e tw o r u n s on com pound C a n d E , o n l y one o t h e r r u n g a v e
a n y th i n g t h a t was o f i n t e r e s t ;
' A p a l e y e ll o w s u b s ta n c e was fo rm e d a f t e r s t r o n g
h e a tin g , w i t h t h e a l c o h o l i c p o t a s s i u m h y d r o x id e , w h ic h o n r e c r y s t a l l i z a t i o n fro m
a l c o h o l , h a v e a m e l t i n g p o i n t o f 1S 5-126°C '.
h a d t h e same p r o p e r t i e s ^
i n g w i t h a l k a l i w ere m ad e;
a tiv e te s t a f te r .
The d ib ro m id e o f t h e tw o r u n s a l s o
Q u a l i t a t i v e t e s t s f o r b ro m in e b e f o r e a n d a f t e r t r e a t *
The compound g a v e a p o s i t i v e t e s t b e f o r e a n d a n e g ­
The m e l t i n g p o i n t s b e f o r e a n d a f t e r w e re t h e sam e;
The
m e l t i n g p o i n t s w ere 1 3 7 -iIS S 0G;
No a lp h a - n a p h t h o f l a v o n e was o b t a i n e d .
SPECIAL RUNS OP COMPOUNDS C AND E
.
S p e c i a l r u n s o f com pounds C a n d E o b t a i n e d i n t h e 2 - b e n z a l a c e t o n a p h t h d l
p r e p a r a t i o n w e re m ade t h r o u g h t h e f i n a l s t e p s ;
The i n t e r m e d i a t e p r o d u c t s w e re
- 22
p u r i f i e d , b y r e c r y s t a l l i z a t i o n i n e a c h s t e p f o r t h e s a k e o t c o m p a rin g t h e two
ru n s;
A re su m e o f t h e r u n s i s g iv e n b e lo w ;
Run S - I :
(P ro d u c t o f ru n ( I ) ,
T a b le .I I I 0 )
I ; A c e ty la tio n .
D ark y e llo w p l a t e s fro m a l c o h o l ; M0P . 93—S6°G », ( E b s t a n e c k i s f M;P» 95—96 C*)
2 . B ro m in at i o n ; • HBr g iv e n o f f ^
Y e llo w n e e d l e s fro m a l c o h o l i M .P . 1 2 5 -1 2 7 0C«, ( K o s ta n e c k is t M .P . 1 8 6 -1 8 7 G. )
P o s i t i v e b ro m in e t e s t ;
3» A l c o h o l i c KOH.
B o i l e d w i t h a l c o h o l a n d d e c o l o r i z i n g c a r b o n . P a l e g r e e n c r y s t a l s , M .P ; 1 2 7 . 5 1 2 8 % . , ( K o s t a n e c k i s t M .P . 1 5 4 -1 5 6 °G . } . d i s s o l v e d i n c o n c e n t r a t e d s u l f u r i c ,
a c i d w i t h a n o r a n g e y e llo w c o l o r ;
I s . s o l u b l e i n h o t a l c o h o l , a c e t o n e , benzene.;.
N e g a t iv e q u a l i t a t i v e t e s t f o r b ro m in e ;
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a n d l a c k o f t im e t o m ake f u r t h e r a n a l y s e s , t h e a u t h o r th o u g h t i t u n d e s i r a b l e t o
a t t e m p t t o a s s i g n a f o r m u la t o t h e p r o d u c t . .
R un H - I i
(P ro d u c t o f r u n ( I ) ,
T a b le I I I . )
I ; A c e ty la te d ;
B r i g h t y e llo w l e a v e s ; H .P ; 1 2 5 ;5 - 1 2 6 % ;, ( 'K o s ta n e c k is f M .P . 9 5 - 9 6 % .)
2 . B r c m i n a ti o n . HO HBr g i v e n . o f f .
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( K o s t a n e c k i s f M .P; 1 8 6 - 1 8 7 % .) P o s i t i v e b ro m in e t e s t .
3 . A l c o h o li c KOH..
R e flu x : f o r o n e - h a l f h o u r .
O ran g e c r y s t a l s f ro m b e n z e n e , u s i n g d e c o l o r i z i n g c a r ­
b o n . M .P . 1 7 3 - 1 7 5 % ., ( K o S ta n e c k is t M ;P . 1 5 4 - 1 5 6 % .) ; W ent i n t o s u l f u r i c a c i d
w ith a deep re d c o lo r .
S o lu b le i n h o t a c e t o n e a n d b e n z e n e . A l p h a - n a p h th o f la v o n e
g iv e s a g re e n f lu o re s c e n c e in c o n c e n tra te d s u l f u r i c a c id ;
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A lp h a - n a p h t ii o lf l a v o n e was n o t ' s u c c e s s f u l l y p r e p a r e d "b y t k e w r i t e r
i n s tu d y in g E o s ta n e c k it s s y n th e s i s .
S9
The v a r i o u s s t e p s a lo n g t h e s y n t h e s i s w e re s t u d i e d w i t h s p e c i a l
e m p h a s is on p r o d u c t s o f 2 - b e n z a l a c e t o n a p h t h o l p r e p a r a t i o n .
M ore w ork on t h e
f i n a l s te p s i s n e c e ssa ry ;
: Sa
S e v e r a l p o s s i b l e t a u to m e r s o f i n t e r m e d i a t e p r o d u c t s w e re i s o l a t e d .
4;
One d e f i n i t e exam ple o f a p o s s i b l e m o l e c u l a r r e a r r a n g e m e n t i s c i t e d ;
5.
£ m eth o d f o r o b t a i n i n g m ore u n if o r m r e s u l t s a n d b e t t e r y i e l d s w as
fo u n d f o r t h e 2 - a c e t o - l - n a p h t h o l p r e p a r a t i o n ;
6.
I t was shown t h a t c o l o r d i d n o t c o r r e l a t e w ith t h e v a r i o u s m e l t i n g
p o i n t s i n t h e c a s e o f 2 - a c e t o - l - n a p h t h o l a s p o i n t e d o u t b y W itt a n d B ra u n ;
7.
I n f u t u r e ru n s o f 2 -b e n z a la c e to n a p h th o l i t
seem s m o re d e s i r a b l e t o
u s e l e s s t h a n th e c a l c u l a t e d am ount o f so d iu m h y d r o x id e a n d h e a t r e a c t i o n
lo n g e r;
8.
T h is s t u d y o p e n e d u p m any new, i n t e r e s t i n g a n d u n s o lv e d p ro b le m s
f o r fu tu re in v e s tig a tio n ;
ACEHGWIiSDGMEKffi
The a u t h o r h e r e w is h e s t o e x p r e s s h i s s i n c e r e a p p r e c i a t i o n a n d t h a n k s
t o B r . 0 . E» S h e p p a rd f o r h i s p e r s o n a l g u id a n c e a n d i n s p i r a t i o n d u r i n g t h i s
re se a rc h ;
n e s s to
je c t.
He a l s o w is h e s t o th a n k t h e E a s tm a n Kodak Company f o r t h e i r w i l l i n g ­
c o o p e r a te a n d s u p p ly i n f o r m a t i o n a n d d a t a o f t h e i r r e s e a r c h on t h e s u b ­
He a l s o w is h e s t o t h a n k Sam i W afa K a j a n i f o r a i d i n m a k in g a n a l y s e s .
-
25
-
■LITERATURE CITATIONS
1«.
B a r g e r and. S t a r l i n g , J . 6 . S . 1 0 7 , 412 ( 1 9 1 5 ).
Se
G a tte n n a n n , B e r . ESi, 5534 ( 1 8 9 2 ) .
5.
Me. H ahn, I*. S c h u ta a n d S . P a u l i d e s ; Z . Hyg. I n f e e ti o n s k r a n ld x .,
1 0 8 , 4 5 9 -7 5 ( 1 9 2 8 ) .
4.
K o s ta n e c k ij B e r . 5 1 , 7 0 5 -1 0 ( 1 8 9 8 ) .
5.
P f e i f f e r a n d G rim m er, B e r . SOi 925>
Si
R u h e m a n n ,' B e r . 4 7 , 120 ( 1 9 1 4 ) .
7.
0 . E . S . a n d C . Mi S . No; - 2694» B e p t . o f O rg . Ohem. E . K. Co.
8.
T am bor, P l a t t n e r a n d - -Zach, H e lv . C him . A e ta -9j 463 ( 1 9 2 6 ).
9.
W i t t a n d B ra u n , B e r . 4 7 , 3 2 1 9 -2 7 (1914)
( 1 9 1 7 ).
b u n d kv
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