A nalytictg C h i m l c a A c t a 535

Elsevier Publishing Company, A t n s t e r d a t n

Printed in The Netherlands

THE COLORIMETRIC DETERMINATION OF TERTIARY ALCOHOLS

WITH AN ALDEHYDE-ACID REAGENT

~I. It. F . A S H ~ V O R T H AND 1. VJE~-NN

Institute f o r Organic Chemistry, .4,~ctlytical Section, University of the Sactr. Saarbriiche~'- (Gero2any)
(l/eceived October 1 3 t h . 1969)

T h e m o s t w i d e l y u s e d c o l o r i n l e t r i c p r o c e d u r e for d e t e r m i n i n g alcohols is t h a t
b a s e d o n t h e so-called KOMAROWSKY r e a c t i o n t. T h e r e a g e n t is a n a r o m a t i c a l d e h y d e
in t h e p r e s e n c e of acid. Its chief a p p l i c a t i o n h a s b e e n t o t h e d e t e r m i n a t i o n of h i g h e r
a l c o h o l s ("fusel oil", m a d e u p m a i n l y of i s o b u t a n o l a n d i s o p e n t a n o l ) in s p i r i t s a n d
a l c o h o l i c b e v e r a g e s 2-1't. W o r k h a s b e e n p u b l i s h e d on t h e d e t e r m i n a t i o n also of
s u g a r a l c o h o l s t5 a n d p o l y a l c o h o l s x~-ln a n d of s o m e o t h e r c o m p o u n d classes s u c h as
o l e f i n e s a n d r e l a t e d c o m p o u n d s (e.g. s o r b i c lu a n d l a e v u l i n i c 0-° a c i d s a n d t e r p e n e s el. o~).
T h e r e has, h o w e v e r , b e e n s u . r p r i s i n g l y l i t t l e r e f e r e n c e to d e t e c t i o n or d e t e r m i n a t i o n
of t e r t i a r y alcohols. DAL NOG2~.R~ AND Mvrcrn~.LL ~n a n d ROS~XNTItAL:,3R''8 q u o t e d
t e r t i a r y b u t a n o l as y i e l d i n g c o l o u r w i t h a t y p i c a l a l d e h y d e - a c i d r e a g e n t . O n l y
KOLESNIKOV '-''1 a p p e a r s to h a v e d e v e l o p e d a q u a n t i t a t i v e m e t h o d , n a m e l y for t e r t i a r y
( a n d s e c o n d a r y ) a l c o h o l s in p l a n t m a t e r i a l . In t h e p r e s e n t w o r k , a n a t t e m p t is m a d e
t o fill u p t h i s g a p .
P a r a m e t e r s d e m a n d i n g s t u d y are: n a t u r e a n d c o n c e n t r a t i o n of a l d e h y d e ,
a c i d a n d a l c o h o l ; s o l v e n t o r d i l u e n t ; t h e o r d e r of m i x i n g of t h e s e c o m p o n e n t s ; a n d
r e a c t i o n t e m p e r a t u r e a n d t i m e . A w i d e r a n g e of a c i d s a n d e s p e c i a l l y of a l d e h y d e s
h a s b e e n e m p l o y e d in p r e v i o u s w o r k . A c i d s i n c l u d e t h e c o m m o n m i n e r a l acids,
s u l p h u r i c , h y d r o c h l o r i c , p h o s p h o r i c a n d p e r c h l o r i c as well as a c e t i c a n d p - t o l u e n e -
s u l p h o n i c acids. B e n z a l d e h y d e o r a s u b s t i t u t e d ( - O H , - O R , - N R z , also -NOo,
-CI, - S O 3 H ) b e n z a l d e h y d e h a s n e a r l y a l w a y s b e e n t h e a l d e h y d e c o m p o n e n t ;
c i n n a m a l d e h y d e a n d f u r f u r M d e h y d e ( t h a t u s e d o r i g i n a l l y b y KOMh.ROWSI<Y) a p p e a r
o n l y o c c a s i o n a l l y . T h e p r i n c i p a l s o l v e n t s u s e d are w a t e r , e t h a n o l a n d a c e t i c acid.
P r e l i m i n a r y s t u d i e s l e d us to c h o o s e as t h e m o s t s u i t a b l e c o m p o n e n t s of t h e
r e a c t i o n m i x t u r e : s u l p h u r i c acid, p - d i m e t h y l a m i n o - or p - h y d r o x y b e n z a l d e h y d e , a n d
w a t e r o r acetic acid.

3"~r~X
, I,~ It I M "~.N T A L

Reagents
S u l p l m r i c acid (96%) a n d glacial a c e t i c a c i d ( a n a l y t i c a l g r a d e , Merck) w e r e
used.
p - D i m e t h y l a m i n o - a n d p - h y d r o x y b e n z a l d e h y d e s ( r e a g e n t g r a d e Merck) w e r e
purified further by crystallisation from water; the purity was checked by thin-layer
chromatography.
Variou s reagent-grade alcohols were purified by distillation or recrystallisation ;

Algal. Chim. Acta, 4 9 ( 1 9 7 o ) 5 3 5 - 5 4 0

536 ' M. R. F. ASHWORTH, I. V E N N

the purities were checked by gas chromatography. Tert-butanol was dried with
s o d i u m s u l p h a t e , frozen o u t a n d f i n a l l y d i s t i l l e d .

Solutions
T h e a l d e h y d e s w e r e d i s s o l v e d c a u t i o u s l y in t h e s u l p h u r i c a c i d at o°; t h i s
r e a g e n t c o u l d be s t o r e d in a n a m b e r b o t t l e for s e v e r a l w e e k s w i t h o u t sensible d e t e r i -
oration.
S o l u t i o n s of a l c o h o l s w e r e p r e p a r e d in w a t e r o r glacial a c e t i c adid.

Apparatus
U n i c a m S P 8 o o , w i t h I-era c u v e t t e s .

Procedure
M i x t u r e s of t h e ~ l d e h y d e r e a g e n t in s u l p h u r i c a c i d a n d t h e a l c o h o l s o l u t i o n
in w a t e r o r a c e t i c a c i d w e r e h e a t e d in g l a s s s t o p p e r e d t u b e s f o r v a r i o u s t i m e s a t
t e m p e r a t u r e s r a n g i n g f r o m 5o to ioo% A f t e r r a p i d c o o l i n g in ice w a t e r , t h e c o n t e n t s
of t h e t u b e s w e r e t r a n s f e r r e d t o c u v e t t e s . A b s o r b a n c e s w e r e m e a s u r e d a g a i n s t b l a n k
s o l u t i o n s w i t h o u t a l c o h o l w h i c h h a d b e e n s i m i l a r l y t r e a t e d , or s p e c t r a w e r e r e c o r d e d .

I1E S U L T S

Di,nethylamino benzaldehyde
S o l u t i o n s c o n t a i n i n g 2 or 3 rag of t h i s a l d e h y d e p e r 3 m l of 9 6 % s u l p h u r i c
acid w e r e u s e d ; 2.96 m l of t h i s w e r e m i x e d w i t h o . o 4 nil of a l c o h o l s o l u t i o n . C o l o u r
d e v e l o p m e n t w i t h tert-butanol a t t a i n e d a m a x i m u m a f t e r a b o u t 5 m i n , a f t e r w h i c h
the colour intensity slowly declined. This reaction time was chosen for quantitative
w o r k a n d a b s o r b a n c e s w e r e m e a s u r e d a t 498 n m , t h e s p e c t r a l m a x i m u m .
E s s e n t i a l l y s t r a i g h t lines r e l a t i n g t h e a b s o r b a n c e a n d t h e a m o u n t of tert-
b u t a n o l w e r e f o u n d . A n a b s o r b a n c e of u n i t y w a s o b t a i n e d w i t h a b o u t 8/~g of a l c o h o l
for t h e m o r e c o n c e n t r a t e d a l d e h y d e r e a g e n t , a n d w i t h a b o u t 6 / x g of a l c o h o l for t h e
more dilute reagent.
T h i s p r o c e d u r e s u f f e r e d f r o m c o m p a r a t i v e l y h i g h s e n s i t i v i t y to c h a n g e s in
.the c o n c e n t r a t i o n of w a t e r in t h e m i x t u r e , i n c r e a s e of w h i c h s u p p r e s s e d c o l o u r
formation. Moreover, it was difficult to mix the small sample efficiently into the
v i s c o u s c o n c e n t r a t e d acid. T h e p r o c e d u r e w a s s u b s e q u e n t l y a b a n d o n e d in f a v o u r of
that described immediately below.

p-Hydroxybenzaldehyde
M i x t u r e s of tert-butanol w i t h p - h y d r o x y b e n z a l d e h y d e in 9 o - 9 5 % s u l p h u r i c
acid g a v e s o l u t i o n s o n h e a t i n g w h i c h p o s s e s s a n a b s o r p t i o n m a x i m u m a t 437 rim.
T h i s m a x i m u m is also s u p p r e s s e d b y i n c r e a s e in t h e w a t e r c o n c e n t r a t i o n , g i v i n g w a y
to a n o t h e r m a x i m u m a t 575 n m ( v i o l e t s o l u t i o n ) . F i g u r e x s h o w s t h e i n f l u e n c e of
w a t e r c o n t e n t o n t h e a b s o r b a n c e a t 575 n m . T h e h i g h e s t a b s o r b a n c e v a l u e , w h e t h e r
after I 5 o r 3o r a i n at 5 o°, c o r r e s p o n d s r o u g h l y t o t h e m e d i u m 9 6 % s u l p h u r i c a c i d -
w a t e r (2 + x ) . T h i s m i x t u r e is still r a t h e r v i s c o u s a n d e v o l v e s c o n s i d e r a b l e h e a t o n
m i x i n g w i t h w a t e r . F o r q u a n t i t a t i v e w o r k , s u l p h u r i c a c i d - w a t e r (x + i) w a s t h e r e f o r e
e m p l o y e d , so t h a t t h e s e t w o d i s a d v a n t a g e s w e r e m i t i g a t e d , y e t n o t a t t h e e x p e n s e
of a s e r i o u s s l u m p in a b s o r b a n c e f r o m t h e h i g h e s t v a l u e .

.A,~al. C l d m . A n t s , 4 9 ( 1 9 7 o ) 5 3 5 - 5 4 °
COLORIMETRIC DETER~IINATION OF T E R T I A R Y ALCOHOLS 537

A b s o r b a n c e v a l u e s w e r e t h e n o b t a i n e d f o r d i f f e r e n t a m o u n t s o f tert-butanol
b y m e a n s o f t h e s a m e p r o c e d u r e a s t h a t d e s c r i b e d for d i m e t h y l a m i n o b e n z a l d e h y d e .
T h e a l d e h y d e r e a g e n t c o n t a i n e d 5 m g o f a l d e h y d e p e r m l of 9 6 % s u l p h u r i c a c i d -
w a t e r ( I + i ) ; 2 . 9 6 m l o f t h i s a n d o . o 4 m l o f a l c o h o l s a m p l e w e r e h e a t e d for IO m i n
a t I o o ° a n d a b s o r b a n c e s w e r e m e a s u r e d a t 575 n m a g a i n s t b l a n k s t r e a t e d in t h e s a m e
w a y . A s a t i s f a c t o r y l i n e a r r e l a t i o n w a s f o u n d , w i t h d a t a r e p r o d u c i b l e t o w i t h i n X~/o.
T h i s p r o c e d u r e w a s t e s t e d o n s o m e o t h e r t e r t i a r y a l c o h o l s ; t h e r e s u l t s are

%0.
0
x
0

x x
x
8c 0

0
J~
o.5-
l/I
t-i
<[

ComDosition oi mixtures
9 6 e l . sulDhuri¢ o c l d - w o t e r
Fig. I. Influenceof watcr content on ztbsorbanco at 575 nm. 2 /tgof tevt-butanol and 0.5 mg of
p-layclroxybenzaldehydo in ].5 ml o f s o l u t i o n . Reaction t i m e a t 50°: (Q)) z5 rain, ( X ) 30 rain.

lot
Tr "r'rr
JR"

¢-
¢2

¢n
,~ 0 . 5 -

- '~:Tr'r

16 - ~ 2 x ~o "3
C o n c e n t r a t i o n o f a l c o h o l ( m o l e / I)
F i g . z. C a l i b r a t i o n c u r v e s for t e r t i a r y a l c o h o l s , z5 m g o f a l d e h y d e i n 3 m l of 9 6 % sulphuric
acid-water (z + i). A l c o h o l s : (I) M e a C - O H , (II) I%{czC(tBu)-OH, (III) MozC(Et)-OH, (IV)
M e C ( I ~ t ) a - O H , (V) E t , C - O H , (Vl) ~ - P r a C - O H , ( V I I ) • - B u . C - 0 H .

A~al. Chim. A a a , 49 (197o) 5 3 5 - 5 4 °

538 M. R. F: ASHWORTFI, I. VENN
i

TABLE I
COLORIMETRIC DETERMINATION OF TERTIARY ALCOHOLS WITH p-H YD ROXYBEN EALDBH YDI~/
SULPI[ URIC ACID ~

Tertiary Wavelength of Molar absorptivity Smallest determinable

alcohol m a x i m u m (rim) (cm~/mmole) amounts (l~g)
Me:,C-OH 575 ,t.8 " IO 4 o.I-o.2
MeyC(tBu)-OI-I 569 t.9- Io 't o.5-t .o
Me~C(Et)-OH 556 6 . 4 • I o '~ 2 . o - 5 .o
M eC(Et)z-OI-[ 558 5 . o - i o :3 2 . 0 - 5 .o
]'YtaC-OH 552 3.7 " to~ 5.o-~o
n-I'raGOI-1 556 7.6 " r o '~ 20
,n-]3u:jC-OH 556 2. t • I o z 5°

" 5 mg of aldehyde p0r nil of 96¢~'o sulphuric ;tcid-watcr (t-I-t).

g i v e n in F i g . 2 a n d T a b l e I. T h e 2 o o - f o l d d i m i n u t i o n in s e n s i t i v i t y f r o m t e r t - b u t a n o l
t o t r i - n - b u t y l c a r b i n o l is s t r i k i n g .
No c o l o u r w a s y i e l d e d u n d e r t h e s e c o n d i t i o n s b y v a r i o u s p r i m a r y a l c o h o l s
f r o m C~ u p t o C1 s. S e c o n d a r y a l c o h o l s y i e l d c o l o u r b u t less s e n s i t i v e l y . F o r e x a m p l e ,
i o - i o o t i m e s as m u c h i s o p r o p a n o l as t e r t - b u t a n o l is r e q u i r e d t o g i v e t h e s a m e
absorbance.
Water has a similar influence on results with some other hydroxy- and
a l k o x y a l d e h y d e s , s u c h as t t n i s a t d e h y d e , v a n i l l i n a n d e t h y l v a n i l l i n , m - H y d r o x y -
b e n z a l d e h y d e r e s e m b l e s p - d i m e t h y l a m i n o b e n z a l d e h y d e m o r e in t h a t w a t e r s u p p r e s s e s
colour formation without yielding another maximum; o-hydroxybenzaldehyde,
salicylaldehyde, evidently yields too intense a colour without alcohol.

DISCUSSION

D u I < ~ 5 d e s c r i b e d t h e i s o l a t i o n of d i b e n z a l a c e t o n e f r o m m i x t u r e s of i s o p r o p a n o l
a n d b e n z a l d e h y d e in 9 M s u l p h u r i c a c i d o r 12 M h y d r o c h l o r i c a c i d a f t e r h a v i n g
h e a t e d u n d e r r e f l u x f o r 4 h. I n t h e p r e s e n t w o r k , t h e s a m e p r o d u c t w a s o b t a i n e d
f r o m t h i s m i x t u r e ( s u l p h u r i c a c i d a l s o ca. 9 M ) a f t e r it h a d s t o o d f o r s o m e IO d a y s .
It could be isolated from the red precipitate formed and also from the filtrate from.
t h i s p r e c i p i t a t e . T h e f i l t r a t e a l s o c o n t a i n e d m o n o b e n z a l ~ c e t o n e . S o l u t i o n s of di-
b e n z a l a c e t o n e in c o n c e n t r a t e d s u l p h u r i c acid s h o w e d t h e s a m e s p e c t r u m w i t h
m a x i m u m a b s o r b a n c e at 46o n m , as the i s o p r o p a n o l / b e n z a l d e h y d e / s u l p h u r i c acid
mixtures.
T h e p r o t o n i s a t i o n y i e l d i n g a l i g h t - a b s o r b i n g s p e c i e s m a y be f o r m u l a t e d :
• [+ 4.

(CoHn--CH =CH--)yC =O -> ( C o H n - - C H = C H - - ) o . C - - O t t

+
(Coil 5 - - C H = CH--)-.C =OH
D i b e n z a l a c e t o n e c o u l d be r e d u c e d w i t h s o d i u m b o r o h y d r i d e t o d i s t y r y l c a r b i n o l ,
(C oH 5INCH = C H - - ) e C H O H . T h i s c a r b i n o l d i s s o l v e d in 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
t o y i e l d a s o l u t i o n w i t h a n a b s o r b a n c e m a x i m u m a t 56o n m . W i t h i n s o m e m i n u t e s ,
however, this maximum disappeared and was replaced by that at 460 nm, found for

A~al. Gldm. Acta, 49 (x97o) 535-54o

COLORIMETRIC DETERMINATION OF TERTIARY ALCOHOLS 539

s o l u t i o n s of b e n z M a c e t o n e in t h e acid. T h e c a r b i n o l was p r e s u m a b l y f o r m e d i n a n
initial r e a c t i o n b e t w e e n i s o p r o p a n o l a n d b e n z a l d e h y d e a n d w a s s u b s e q u e n t l y o x i d i s e d
t o t h e k e t o n e . T h e s p e c i e s a b s o r b i n g a t 5 6 0 n m m a y be a e a r b o n i u m i o n of w h i c h o n e
r e s o n a n c e f o r m is (CGHs---:CH = C H - - ) 2 C H . I t is e v i d e n t l y so r a p i d l y c o n v e r t e d i n t o
t h a t a b s o r b i n g a t 460 n m t h a t it d o e s n o t s h o w in t h e a b s o r b a n c e s p e c t r u m of t h e
isopropanol/benzaldehyde/sulphuric acid mixture. However, the corresponding
a b s o r b a n c e m a x i m u m of s o l u t i o n s in s u l p h u r i c a c i d of p , p ' - d i m e t h o x y d i s t y r y l c a r b i n o l
c o u l d be r e c o g n i s e d in t h e a b s o r b a n c e s p e c t r u m of m i x t u r e s of i s o p r o p a n o l w i t h
a n i s a l d e h y d e in s u l p h u r i c a c i d s h o r t l y a f t e r m i x i n g . It, too, d i s a p p e a r e d s w i f t l y ,
g i v i n g w a y t o t h e s a m e m a x i m u m as t h a t y i e l d e d b y p , p ' - d i m e t h o x y d i b e n z a l a c e t o n e
in s u l p h u r i c acid. T h i s s u p p o r t s t h e h y p o t h e s i s t h a t c a r b i n o l is f o r m e d b e f o r e o x -
i d a t i o n , as o p p o s e d to DUKE'S p r o p o s a l of o x i d a t i o n of a l c o h o l t o k e t o n e , f o l l o w e d b y
formation of unsaturated ketone through reaction with the aromatic aldehyde.
So far, it h a s n o t b e e n p o s s i b l e t o i d e n t i f y a n y i n d i v i d u a l c o m p o u n d s r e s u l t i n g
f r o m r e a c t i o n of tert-butanol w i t h a n a r o m a t i c a l d e h y d e in a c i d s o l u t i o n . T h e i n f r a r e d
a b s o r b a n c e s p e c t r u m of t h e solid c o l o u r e d p r o d u c t f o r m e d in t h e m i x t u r e of tert-
butanol, p-hydroxybenzaldehyde a n d s u l p h u r i c a c i d (or h y d r o c h l o r i c a c i d o r
a l u m i n i u m chloride) i n d i c a t e d t h a t C - - O l i n k s h a d d i s a p p e a r e d a n d t h a t C = C
links h a d b e e n f o r m e d . O n e p o s s i b i l i t y is t h a t t r i s t y r y l c a r b i n o l is y i e l d e d , a n a l o g o u s l y
to t h e f o r m a t i o n of d i s t y r y l c a r b i n o l f r o m i s o p r o p a n o l :
3 A r C H O + ( C H . ~ ) a C - - O H -+ ( A r - - C H = C H - - ) a C - - O H
T h i s m a y t h e n give t h e t r i s t y r y l c a r b o n i u m i o n as c o l o u r e d species. I n f u r t h e r a n a l o g y
to t h e s c h e m e s u g g e s t e d a b o v e , o x i d a t i o n c o u l d t a k e p l a c e :
(+) (+)
Ar--CH = CH---C (--CH = CH--Ar) o ,-o A r - - C H - - C H = C (--CH = CH~Ar).,.
oxidation
(+)
Ar--C--CH = C(--CH = CH--Ar)2 +-~ A r - - C - - C H =C(--CH =CH--Ar)2
II I
I+~OH OH
A t t e m p t s are b e i n g m a d e t o p r e p a r e a n d s t u d y t r i s t y r y l c a r b i n o l ( p r e p a r a t i o n
t h r o u g h r e a c t i o n of d i b e n z a l a c e t o n e w i t h s t y r y l m a g n e s i u m halide). P r e l i m i n a r y
i n d i c a t i o n s a r e t h a t t h e t r i s t y r y l c a r b i n o l d o e s in f a c t y i e l d t h e s a m e s p e c t r u m in
s u l p h u r i c a c i d as t h a t o b t a i n e d f r o m m i x t u r e s of tert-butanol, b e n z a l d e h y d e a n d
s u l p h u r i c acid. I t is h o p e d t o r e p o r t l a t e r , w i t h m o r e e x p e r i m e n t a l detail, all t h o s e
r e s u l t s c o n c e r n e d w i t h e l u c i d a t i o n of t h e n a t u r e of t h e c o l o u r e d species.

O n e of u s (I.V.) w i s h e s t o t h a n k t h e F o n d s d e r C h e m i s c h e n I n d u s t r i e , Dtissel-
dorf, for a s c h o l a r s h i p , d u r i n g t h e t e n u r e of w h i c h m u c h of t h i s w o r k w a s c a r r i e d o u t .

SUMMARY

A c o l o r i m e t r i c d e t e r m i n a t i o n of s e v e r a l t e r t i a r y a l c o h o l s w i t h a r e a g e n t
c o n s i s t i n g of a n a r o m a t i c a l d e h y d e a n d s u l p h u r i c a c i d is d e s c r i b e d . T h e n a t u r e of
t h e c o l o u r e d r e a c t i o n p r o d u c t ( s ) is b r i e f l y d i s c u s s e d .

A n a l . C h i m . . d c t a , 4 9 ( 1 9 7 o) 5 3 5 - 5 4 °
54 0 M.R.F. A S I ~ W O R T H , I. V E N N

Rf.:SUM~-

O n ddcrit u n d o s a g e c o l o r i m ~ t r i q u e de p l u s i e u r s ~Icools terti~ires & l ' a i d e d ' u n

r6~ctif c o n s t i t u ~ 4 ' u n a l d e h y d e a r o m a t i q u e en milieu acide sulfurique. O n d i s c u t e
b r i ~ v e m e n t le m ~ c a n i s m e d e la r ~ a c t i o n .
i
ZUS~kMM~NFASSUNG

E s w u r d e eine k o l o r i m e t r i s c h e B e s t i m m u n g einiger tertiiiren A l k o h o l e b e -

schrieben. Sie b e r u h t auf der R e ~ k t i o n m i t e i n e m a r o m a t i s c h e n A l d e h y d in s c h w e f e l -
s a u r e m Milieu. Der C h e m i s m u s der F a r b r e a k t i o n w u r d e k u r z diskutiert.

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