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Beiträge zur ökologischen Chemie CX
Chemosphere No. i, pp 45 - 48, 197~.
Pergamon Press.
Printed in Great Britain.
B E I T R A G E ZUR 0 K O L O G I S C H E N C H E M I E CX 1
THE OF J.P.
CHROMATOGRAPHIC TECHNICAL
Lay,
D. Kotzias,
(Reeeived in G e z ~ m y 27 ] o v ~ b e r
BEHAVIOUR
"CHLORALKYLENE-9" W.
Klein,
and F. Korte
I~75; reeelved in FK :~or imblle&tion i ~ecelaber i~75)
Institut f~r 5kologische C h e m i e der Gesellsehaft f~r Strahlenund Umweltforschung m b H M~nchen 5205 St. Augustin l und Institut ffir C h e m i e der Technischen Universit~t M ~ n c h e n 805 F reising- Weihenstephan West
Germany
T he t e c h n i c a l p r o d u c t " C h l o r a l k y l e n e - 9 " i n v e s t i g a t e d is a m i x t u r e of m o n o - , d i - and t r i i s o p r o p y l a t e d as w e l l as u n s u b s t i t u t e d 2, 4' - d i c h l o r o b i p h e n y l , s y n t h e s i z e d with 0 . 9 p a r t s i s o p r o p y l c h l o r i d e u s i n g the F r i e d e l - C r a f t s
alkylation method.
Due to s i m i l a r t e c h n o l o g i c a l p r o p e r t i e s of C h l o r a l k y l e n e - 9 as c o m p a r e d to t r i - and t e t r a c h l o r o b i p h e n y l s , t h i s p r o d u c t is in the e v a l u a t i o n as a s u b s t i t u t e f o r the r e s p e c t i v e t e c h n i c a l P C B ' s. We a r e s t u d y i n g the b e h a v i o u r of t h i s p r o d u c t u n d e r e n v i r o n m e n t a l c o n d i t i o n s i n c l u d i n g its fate 2,3 in v a r i o u s e c o s y s t e m s . T h e c h r o m a t o g r a p h i c data, g i v e n h e r e ,
should have p r a c t i c a l v a l u e in the a n a l y s i s of C h l o r -
alkylene-9 following its possible technical use.
M A T E R I A L S AND M E T H O D S C h l o r a l k y l e n e - 9 was k i n d l y s u p p l i e d by P r o d e l e c , C o u r b e v o i e / F r a n c e .
Tb_ C_h_~_°~.~t°_g_~.~_P_hZ Only with two d i m e n s i o n a l T L C c e r t a i n s e p a r a t i o n s can be a c h i e v e d . Th e o p t i m u m s o l v e n t s y s t e m s f o r T L C w e r e found to he n - h e x a n e / e t h y l a c e t a t e m i x t u r e s . All t e s t e d s o l v e n t s w e r e a n a l y t i c a l g r a d e (Merck). T L C p l a t e s (20 x 20 era, s i l i c a gel 60, F254, l a y e r t h i c k n e s s 0, 5 m m , Merck) were used.
CIX. C o m m u n i c a t i o n : K. H u s t e r t , H. P a r l a r , and F . K o r t e , C h e m o s p h e r e , in p r e s s .
45
46
No. I
The best separation i s s h o w n in F i g .
result obtained for technical Chloralkylene-9
w i t h two d i m e n s i o n a l T L C
1. T h e f i r s t d i m e n s i o n d e v e l o p m e n t w a s m a d e w i t h n - h e x a n e / e t h y l
10:1, t h e s e c o n d w a s m a d e u s i n g o n l y n - h e x a n e .
acetate
The separated products were marked
with the
a i d of a f l u o r e s c e n t l a m p . _Ga _sc _hro m a t_o_gra_phy Apparatus
conditions : Gaschromatograph, 2 m glass column;
Model Fractovap
2300 f r o m C a r l o E r b a
1 % O V 1 on W - A W - D M C S 8 0 / 1 0 0
Detector
63Ni E C D
Temperature
D e t e c t o r 250 ° C, I n j e c t o r 220 ° C, C o l u m n 175 ° C
Carrier
N 2 (20 m l / m i n . )
gas
mesh
D e t e c t o r r i n s i n g gas : N 2 (40 m l / r n i n . ) P a p e r s p e e d of recorder The separation
5 mm/min. of the c o m p o n e n t s by G L C i s s h o w n in F i g . 2.
GC - MS Mass spectra were recorded
w i t h a L K B 9000 s p e c t r o m e t e r
( i o n i s a t i o n e n e r g y 70 eV), e q u i p p e d
w i t h an a d d i t i o n a l E C D . Column
: 2 m g l a s s w i t h 1% OV 1 on W - A W - D M C S 8 0 / 1 0 0 m e s h
Temperature
: 150 ° C + 3 ° C / m i n u t e
Carrier
: H e l i u m 40 m l / m i n .
gas
T h e T a b l e g i v e s a s u r v e y of t h e m o s t i m p o r t a n t m o l e c u l e a n d f r a g m e n t lene-components
a f t e r G C - M S s e p a r a t i o n and i d e n t i f i c a t i o n .
p o n d to t h o s e of t h e g a s c h r o m a t o g r a m
in F i g .
i o n s of t h e C h l o r a l k y -
T h e i n d i c e s of the p e a k s c o r r e s -
2.
RESULTS AND DISCUSSION B y m e a n s of two d i m e n s i o n a l mixture haviour,
could be separated.
TLC,
a t o t a l of 7 c o m p o n e n t s of t h e t e c h n i c a l C h l o r a l k y l e n e - 9
However,
on t h e b a s i s of t h e i r v e r y s i m i l a r
it w a s i m p o s s i b l e to s e p a r a t e t h e m o n o - ,
p a n y i n g t h e 2, 4' - d i c h l o r o b i p h e n y l
chromatographic
d i - and t r i i s o p r o p y l a t e d
(major component ~
be-
compounds accom-
60%).
Of t h e f i v e m o r e p o l a r p r o d u c t s o n l y one c o u l d b e i d e n t i f i e d b y G C - M S , n a m e l y a m o n o i s o p r o p y l - 2, 4' - d i c h l o r o b i p h e n y l . The different chromatographic in F i g . position.
b e h a v i o u r of the i d e n t i f i e d m o n o i s o p r o p y l a t e d
isomers,
as shown
1, m a y r e s u l t f r o m H - b o n d i n g of t h e c h l o r i n e and i s o p r o p y l s u b s t i t u e n t in n e i g h b o u r i n g
No. i
47
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No. i
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F i g . 1 S e p a r a t i o n of c o m p o n e n t s of the t e c h n i c a l C h l o r a l k y l e n e - 9 u s i n g two d imensional TLC, solvents: n-hexane/ e t h y l a c e t a t e 10:1 and n - h e x a n e .
Fig. 2 GLC of the technical Chloralkylene-9. (Sample volume 1 pl ~ 6 ng, 2 m column with I% OV I) Intensities of peaks 8 and 9 were eightfold magnified.
A b e t t e r s e p a r a t i o n of the i n d i v i d u a l c o m p o n e n t s of C h l o r a l k y l e n e - 9 was a c h i e v e d u s i n g a 2 m GLC c o l u m n . The GL c h r o m a t o g r a p h i c r e s u l t s s h o w e d an o p p o s i t e e l u t i o n p a t t e r n of the s e p a r a t e d s u b s t a n c e s in c o n t r a s t to T L C . T h e s e s u b s t a n c e s w e r e i d e n t i f i e d by G C - M S a n a l y s i s . The m a s s s p e c t r o m e t r i c f r a g m e n t a t i o n s of t h e s e s u b s t a n c e s gave c h a r a c t e r i s t i c m e t a s t a b l e ions f o r the i s o p r o p y l a t e d c o m p o u n d s e x c e p t f o r the one m o n o i s o p r o p y l a t e d 2, 4' - C 1 2 - b i p h e n y l i s o m e r of the polar TLC fraction. ACKNOWLEDGEMENT T h i s w o r k was a s s i s t e d by P r o d e l e c , C o u r b e v o i e / F r a n c e ,
and is c o m p l e m e n t a r y to the
p r o g r a m on " P C B s in the E n v i r o n m e n t " s u p p o r t e d by the F e d e r a l M i n i s t r y f o r S c i e n c e and
Technology. REFERENCES 1. H u s t e r t , K . ,
H. P a r l a r ,
and F . K o r t e , C h e m o s p h e r e , in p r e s s .
2. B e g u m , S., J . P . L a y , W. K l e i n und F . K o r t e , Beitr/~ge z u r 6 k o l o g i s c h e n C h e m i c CIII, C h e m o s p h e r e 4, pp 241-246, 3. K o t z i a s , D. and W. K l e i n , u n p u b l i s h e d .
1975.
Pergamon Press.
Printed in Great Britain.
B E I T R A G E ZUR 0 K O L O G I S C H E N C H E M I E CX 1
THE OF J.P.
CHROMATOGRAPHIC TECHNICAL
Lay,
D. Kotzias,
(Reeeived in G e z ~ m y 27 ] o v ~ b e r
BEHAVIOUR
"CHLORALKYLENE-9" W.
Klein,
and F. Korte
I~75; reeelved in FK :~or imblle&tion i ~ecelaber i~75)
Institut f~r 5kologische C h e m i e der Gesellsehaft f~r Strahlenund Umweltforschung m b H M~nchen 5205 St. Augustin l und Institut ffir C h e m i e der Technischen Universit~t M ~ n c h e n 805 F reising- Weihenstephan West
Germany
T he t e c h n i c a l p r o d u c t " C h l o r a l k y l e n e - 9 " i n v e s t i g a t e d is a m i x t u r e of m o n o - , d i - and t r i i s o p r o p y l a t e d as w e l l as u n s u b s t i t u t e d 2, 4' - d i c h l o r o b i p h e n y l , s y n t h e s i z e d with 0 . 9 p a r t s i s o p r o p y l c h l o r i d e u s i n g the F r i e d e l - C r a f t s
alkylation method.
Due to s i m i l a r t e c h n o l o g i c a l p r o p e r t i e s of C h l o r a l k y l e n e - 9 as c o m p a r e d to t r i - and t e t r a c h l o r o b i p h e n y l s , t h i s p r o d u c t is in the e v a l u a t i o n as a s u b s t i t u t e f o r the r e s p e c t i v e t e c h n i c a l P C B ' s. We a r e s t u d y i n g the b e h a v i o u r of t h i s p r o d u c t u n d e r e n v i r o n m e n t a l c o n d i t i o n s i n c l u d i n g its fate 2,3 in v a r i o u s e c o s y s t e m s . T h e c h r o m a t o g r a p h i c data, g i v e n h e r e ,
should have p r a c t i c a l v a l u e in the a n a l y s i s of C h l o r -
alkylene-9 following its possible technical use.
M A T E R I A L S AND M E T H O D S C h l o r a l k y l e n e - 9 was k i n d l y s u p p l i e d by P r o d e l e c , C o u r b e v o i e / F r a n c e .
Tb_ C_h_~_°~.~t°_g_~.~_P_hZ Only with two d i m e n s i o n a l T L C c e r t a i n s e p a r a t i o n s can be a c h i e v e d . Th e o p t i m u m s o l v e n t s y s t e m s f o r T L C w e r e found to he n - h e x a n e / e t h y l a c e t a t e m i x t u r e s . All t e s t e d s o l v e n t s w e r e a n a l y t i c a l g r a d e (Merck). T L C p l a t e s (20 x 20 era, s i l i c a gel 60, F254, l a y e r t h i c k n e s s 0, 5 m m , Merck) were used.
CIX. C o m m u n i c a t i o n : K. H u s t e r t , H. P a r l a r , and F . K o r t e , C h e m o s p h e r e , in p r e s s .
45
46
No. I
The best separation i s s h o w n in F i g .
result obtained for technical Chloralkylene-9
w i t h two d i m e n s i o n a l T L C
1. T h e f i r s t d i m e n s i o n d e v e l o p m e n t w a s m a d e w i t h n - h e x a n e / e t h y l
10:1, t h e s e c o n d w a s m a d e u s i n g o n l y n - h e x a n e .
acetate
The separated products were marked
with the
a i d of a f l u o r e s c e n t l a m p . _Ga _sc _hro m a t_o_gra_phy Apparatus
conditions : Gaschromatograph, 2 m glass column;
Model Fractovap
2300 f r o m C a r l o E r b a
1 % O V 1 on W - A W - D M C S 8 0 / 1 0 0
Detector
63Ni E C D
Temperature
D e t e c t o r 250 ° C, I n j e c t o r 220 ° C, C o l u m n 175 ° C
Carrier
N 2 (20 m l / m i n . )
gas
mesh
D e t e c t o r r i n s i n g gas : N 2 (40 m l / r n i n . ) P a p e r s p e e d of recorder The separation
5 mm/min. of the c o m p o n e n t s by G L C i s s h o w n in F i g . 2.
GC - MS Mass spectra were recorded
w i t h a L K B 9000 s p e c t r o m e t e r
( i o n i s a t i o n e n e r g y 70 eV), e q u i p p e d
w i t h an a d d i t i o n a l E C D . Column
: 2 m g l a s s w i t h 1% OV 1 on W - A W - D M C S 8 0 / 1 0 0 m e s h
Temperature
: 150 ° C + 3 ° C / m i n u t e
Carrier
: H e l i u m 40 m l / m i n .
gas
T h e T a b l e g i v e s a s u r v e y of t h e m o s t i m p o r t a n t m o l e c u l e a n d f r a g m e n t lene-components
a f t e r G C - M S s e p a r a t i o n and i d e n t i f i c a t i o n .
p o n d to t h o s e of t h e g a s c h r o m a t o g r a m
in F i g .
i o n s of t h e C h l o r a l k y -
T h e i n d i c e s of the p e a k s c o r r e s -
2.
RESULTS AND DISCUSSION B y m e a n s of two d i m e n s i o n a l mixture haviour,
could be separated.
TLC,
a t o t a l of 7 c o m p o n e n t s of t h e t e c h n i c a l C h l o r a l k y l e n e - 9
However,
on t h e b a s i s of t h e i r v e r y s i m i l a r
it w a s i m p o s s i b l e to s e p a r a t e t h e m o n o - ,
p a n y i n g t h e 2, 4' - d i c h l o r o b i p h e n y l
chromatographic
d i - and t r i i s o p r o p y l a t e d
(major component ~
be-
compounds accom-
60%).
Of t h e f i v e m o r e p o l a r p r o d u c t s o n l y one c o u l d b e i d e n t i f i e d b y G C - M S , n a m e l y a m o n o i s o p r o p y l - 2, 4' - d i c h l o r o b i p h e n y l . The different chromatographic in F i g . position.
b e h a v i o u r of the i d e n t i f i e d m o n o i s o p r o p y l a t e d
isomers,
as shown
1, m a y r e s u l t f r o m H - b o n d i n g of t h e c h l o r i n e and i s o p r o p y l s u b s t i t u e n t in n e i g h b o u r i n g
No. i
47
0 0
0
C
L~
l~
co
•
oo !~ 0
~
co
0
i
0 0
0
t~
o
u~ ,-.-4
0
0 0
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0
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0 ,....t t~
-d 0
u~
0 0
0 0 ff,l
c,l
0 0
0 0
0
0
II
%
48
} m~,
No. i
¸
L ~!
i)lh
~*~1~1
[l,[N,,pl,,pvl
D,
('1, lhphenvls
',h,,,~,t~,~p, opvl - ('i) -l;[phe,w]
,,';/"'"~) t
~
}
2.4
I /2-1¢iphenyl
\
4¸
.;i,
*
.
'b/ 4
i
0::' @) 0
F i g . 1 S e p a r a t i o n of c o m p o n e n t s of the t e c h n i c a l C h l o r a l k y l e n e - 9 u s i n g two d imensional TLC, solvents: n-hexane/ e t h y l a c e t a t e 10:1 and n - h e x a n e .
Fig. 2 GLC of the technical Chloralkylene-9. (Sample volume 1 pl ~ 6 ng, 2 m column with I% OV I) Intensities of peaks 8 and 9 were eightfold magnified.
A b e t t e r s e p a r a t i o n of the i n d i v i d u a l c o m p o n e n t s of C h l o r a l k y l e n e - 9 was a c h i e v e d u s i n g a 2 m GLC c o l u m n . The GL c h r o m a t o g r a p h i c r e s u l t s s h o w e d an o p p o s i t e e l u t i o n p a t t e r n of the s e p a r a t e d s u b s t a n c e s in c o n t r a s t to T L C . T h e s e s u b s t a n c e s w e r e i d e n t i f i e d by G C - M S a n a l y s i s . The m a s s s p e c t r o m e t r i c f r a g m e n t a t i o n s of t h e s e s u b s t a n c e s gave c h a r a c t e r i s t i c m e t a s t a b l e ions f o r the i s o p r o p y l a t e d c o m p o u n d s e x c e p t f o r the one m o n o i s o p r o p y l a t e d 2, 4' - C 1 2 - b i p h e n y l i s o m e r of the polar TLC fraction. ACKNOWLEDGEMENT T h i s w o r k was a s s i s t e d by P r o d e l e c , C o u r b e v o i e / F r a n c e ,
and is c o m p l e m e n t a r y to the
p r o g r a m on " P C B s in the E n v i r o n m e n t " s u p p o r t e d by the F e d e r a l M i n i s t r y f o r S c i e n c e and
Technology. REFERENCES 1. H u s t e r t , K . ,
H. P a r l a r ,
and F . K o r t e , C h e m o s p h e r e , in p r e s s .
2. B e g u m , S., J . P . L a y , W. K l e i n und F . K o r t e , Beitr/~ge z u r 6 k o l o g i s c h e n C h e m i c CIII, C h e m o s p h e r e 4, pp 241-246, 3. K o t z i a s , D. and W. K l e i n , u n p u b l i s h e d .
1975.