Chemosphere, Vol.25, No.3, pp 271-276, 1992 0045-6535/92 $5.00 + 0.

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Printed in Great Britain Pergamon Press Ltd.

SYNTHESIS AND STRUCTURE VERIFICATION OF TWO PREVIOUSLY

UNCHARACTERIZED PENTACHLOROBIPRENYLS: PCB 108 A N D PCB 127

Erkki Mannila

Department of Chemistry, University of Jyv~skyl~,

P.O.B. 35, SF-40351, Jyv~skyl~, Finland

( R e c e i v e d i n G e r m a n y l 5 May1992;accepted3June1992)
ABSTRACT

The synthesis and structure verification of two previously uncharacterized

polychlorinated biphenyl (PCB) congeners mono-ortho-substituted 2,3,3',4,5'-
pentachlorobiphenyl (PCB 108) and non-ortho-substituted 3,3',4,5,5'-pentachlo-
robiphenyl (PCB 127) is described. The synthesis was done by the method of
aromatic a r y l a t i o n in the presence of isopentyl nitrite. The p u r i f i c a t i o n and
separation of the compounds was done by flash-chromatography on AI~O 3- and
charcoal columns. The structures were verified by IH NMR, 13C NMR, IR and mass
spectroscopy.

KEYWORDS: PCB, coplanar pentachlorobiphenyl, IH NMR, 13C NMR, IR, mass spectros-
copy

INTRODUCTION

The w o r l d w i d e industrial use of PCBs has caused environmental problems because

of their chemical p e r s i s t e n c e and lipophilic nature which c o n t r i b u t e s to their
bioaccumulation in higher trophic levels in the food chain including man
(Kannan et al. 1988). The low acute toxicity of n o n - o r t h o - s u b s t i t u t e d coplanar
PCB congeners (tetra-, penta- and hexachloro-) and their relatively high
amounts found in the environment is causing a great risk to humans and wildlife
(Safe, 1984, Tanabe et al., 1987). Mullin et al. (1984) have s y n t h e s i z e d all
209 PCB congeners. However few of them were not in pure form and some of them
was lacking NMR data. PCB 108 and PCB 127 were now s y n t h e s i z e d in pure forms
for toxicological studies and as the model compounds for the analysis of
environmental samples (Kopponen et al., 1992, M~ntyl~ et al., 1990).

271
272

EXPERIMENTAL

2,3,3',4,5'- and 3 , 3 ' , 4 , 5 , 5 ' - p e n t a c h l o r o b i p h e n y l were s y n t h e s i z e d by aromatic

arylation m e t h o d (Cadogan 1962, M u l l i n et al., 1984, V e t t e r et al. 1991,). 1,0g
(6mmol) 3,5-dichloroaniline and 10,0g (55mmol) 1,2,3-trichlorobenzene were
mixed and w a r m e d up until 1 , 2 , 3 - t r i c h l o r o b e n z e n e melted and d i s s o l v e d also 3,5-
dichloroaniline. Isopentyl nitrite was then added d r o p w i s e into the m i x t u r e and
the temperature was slowly raised up to 130C. The addition of isopentyl
nitrite was c o n t i n u e d until all 3 , 5 - d i c h l o r o a n i l i n e had reacted. The r e a c t i o n
was f o l l o w e d by gas chromatography. In the end of the r e a c t i o n the ratio of two
isomers formed was 5:1 2 , 3 , 3 ' , 4 , 5 ' - p e n t a c h l o r o b i p h e n y l b e i n g the m a i n product.
The excess of 1,2,3-trichlorobenzene was removed by d i s t i l l a t i o n at reduced
pressure. The products were purified by eluting them through a basic AI203
column with n - h e x a n e and the isomers were separated by a c h a r c o a l column. The
mixture was eluted into the charcoal column first with n - h e x a n e / C H 2 C l 2 (2%) and
the elution was c o n t i n u e d until all 2 , 3 , 3 ' 4 , 5 ' - p e n t a c h l o r o b i p h e n y l was eluted.
The c h a r c o a l c o l u m n t r a p p e d 3 , 3 ' , 4 , 5 , 5 ' - p e n t a c h l o r o b i p h e n y l w h i c h was r e l e a s e d
in pure form by r e v e r s e d elution with toluene. The u n c o r r e c t e d m e l t i n g points
were 121-122C for 2 , 3 , 3 ' , 4 , 5 ' - and 153-154C for 3 , 3 ' , 4 , 5 , 5 ' - p e n t a c h l o r o b i p h e n -
yl. The s t r u c t u r e s are p r e s e n t e d in Figure i. IH NMR spectra were m e a s u r e d in
deuteroacetone and 13C NMR spectra in CDCI 3. TMS was used as an internal
standard. ~H and Z3C NMR spectral data is given in Table 1 and 2. Mass- and
infrared s p e c t r a are shown in Figure 2 and 3.

INSTRUMENTS

IH and 13C NMR s p e c t r a w e r e recorded on JEOL GSX-270 FT NMR s p e c t r o m e t e r at 270

and 67,9 MHz respectively, IR spectra on P e r k i n - E l m e r 283 I n f r a r e d s p e c t r o p h o -
tometer and mass spectra on Varian MAT-212 Mass s p e c t r o m e t e r (at 70 eV) connec-
ted to V a r i a n M o d e l 3700 gas c h r o m a t o g r a p h (SE 54/25 m).

DISCUSSION

The s y n t h e s i s was carried out using the Cadogan c o u p l i n g p r o c e d u r e (Cadogan,

1962). In the a n a l y t i c a l field on c h l o r o a r o m a t i c c o m p o u n d s in the e n v i r o n m e n t
the c h a r c o a l c o l u m n s y s t e m has been developed to f r a c t i o n a t e d i f f e r e n t type of
compounds d e p e n d i n g on the p l a n a r i t y of the structures. (Jensen et al. 1974).
In this w o r k the c h a r c o a l column was used in the s y n t h e t i c scale to separate
q u a n t i t a t i v e l y PCB 108 and PCB 127 in pure form by the r e v e r s e d e l u t i o n with
toluene. The s t r u c t u r e v e r i f i c a t i o n was based on the s p e c t r o s c o p i c data. IH NMR
spectra were of first order and consistent with the s t r u c t u r e s PCB 108 and PCB
 273

C[ Ci C[ cI cI

cI CI CI
2,3,3 ', 4,5 ' -pentachloro- 3,3 ' ,4 , 5 , 5 ' - p e n t a c h l o r o -
b i p h e n y l , P C B 108 b i p h e n y l , P C B 127

Figure i. T h e structures of P C B 108 a n d P C B 127.

Table I. IH c h e m i c a l shifts from TMS in a c e t o n e d6and coupling constants

of P C B 108 a n d P C B 127.

Compound Chemical shift, ppm Coupling constant, Hz

PCB 108 H(2') 7.449 J(H2',H4')=J(H4',H6') 1.93

4(4') 7.550 J(H5,H6) 8.33
H(5) 7.659
H(6) 7.430
H(6') 7.449

PCB 127 H-2 7.932 J(H2',H4')=J(H4',H6 ') 1.83

H-2' 7.755
H-4' 7.528
H-6 7.932
H-6' 7.755

Table 2. O b s e r v e d and calculated t3C c h e m i a l shifts of P C B 108 and

PCB 127 in C D C L 3 (ppm f r o m TMS).

PCB 108 PCB 127

Cl-substitution 2,3,3',4,5' 3,3',4,5,5'

carbon obs. calc. obs. calc.

C1 139.15 137.64 139.13 139.54
C2 133.53 132.18 127.82 127.40
C3 135.04 133.69 135.64 132.78
C4 135.04 133.60 132.38 130.79
C5 129.10 128.59 135.64 132.78
C6 129.06 127.77 127.82 127.40
Cl' 141.97 140.65 141.31 140.16
C2' 128.49 127.01 126.17 126.57
C3' 135.66 135.08 136.53 135.32
C4' 129.55 129.01 129.26 128.78
C5' 135.66 135.08 136.53 135.32
C6' 128.49 127.01 126.17 126.57
 [AeOLl L ~ I fl3d pu~ 801 flO~ ~o e l ~ P e ~ s S S ~ R "~ a~nD33
I
~,!1-~-'~-- :,, ,4 . . , ~ ,
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el,
B~ 7Fzt
_al
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7LC
 275

127. Signals w e r e well r e s o l v e d and p r o t o n - p r o t o n c o u p l i n g c o n s t a n t s w e r e

normal as listed in Table 1 (Yanagisawa et al., 1986a, M u l l i n et al., 1984).
In t3C NMR s p e c t r a the signals of the u n s u b s t i t u t e d carbons w e r e obvious but
the other signals could not be readily assigned. For further i n t e r p r e t a t i o n
the c a l c u l a t i o n of the chemical shifts of the carbons from the values of
biphenyl a d d i n g the single substituent effects and two s u b s t i t u e n t interac-
tion effects in 2,3-, 3,4- and 3 , 5 - s u b s t i t u t i o n cases was done and shown in
Table 2 (Yanagisawa et al., 1986b, K n u u t i n e n J. et al., 1980, L ~ t j ~ n e n et
al., 1978). M a s s spectra were almost identical (Figure 2). M p e a k m/z=324
was very d o m i n a t e in both spectra which indicates the c h e m i c a l and structu-
ral p e r s i s t e n c e also of these PCB isomers. In the s p e c t r u m of PCB 127 there
was an a d d i t i o n a l peak m/z=57 (5%) compared to the s p e c t r u m of PCB 108. In
IR spectra m o r e d i f f e r e n c e s could be seen between the isomers (Figure 3).
The s t r u c t u r e of PCB 127 is more symmetrical than the s t r u c t u r e of PCB 108
which e x p l a i n s the larger number of bands in the s p e c t r u m of PCB 108.

ACKNOWLEDGEMENTS

I wish to e x p r e s s special thanks to Dr. Erkki K o l e h m a i n e n and Mr. R e i j o

K a u p p i n e n for r e c o r d i n g the NMR spectra and Mrs. M i r j a L a h t i p e r ~ for recor-
ding the mass spectra.

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