Environmental Letters
ISSN: 0013-9300 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/lesa17
Chlorination in Dilute Aqueous Systems; 2,4,6Trichlorophenol James G. Smith , Siow-Fong Lee & Aharon Netzer To cite this article: James G. Smith , Siow-Fong Lee & Aharon Netzer (1975) Chlorination in Dilute Aqueous Systems; 2,4,6-Trichlorophenol, Environmental Letters, 10:1, 47-52, DOI: 10.1080/00139307509435807 To link to this article: http://dx.doi.org/10.1080/00139307509435807
Published online: 02 Sep 2009.
Submit your article to this journal
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Citing articles: 3 View citing articles
Full Terms & Conditions of access and use can be found at http://www.tandfonline.com/action/journalInformation?journalCode=2esa20 Download by: [University of Florida]
Date: 05 November 2015, At: 14:40
ENVIRONNENTAL LETTERS, 10(1), 47-52 (1975)
CHLORINATION IN DILUTE AQUEOUS SYSTBIS; 2,4,6-TRICHLOROPHENOL
Downloaded by [University of Florida] at 14:40 05 November 2015
KEY KORDS: James G
Water t r e a t m e n t , p o l y c h l o r i n a t e d compounds
. Smith*,
Siow-Fong Lee*, and Aharon N e t z e r t
*Department o f Chemistry U n i v e r s i t y o f Waterloo Waterloo , O n t a r i o tl\rater. and Wastewater Treatment Subdivision Canada C en t r e f o r I n l a n d Waters Burlington, Ontario ABSTRACT C h l o r i n a t i o n o f wastewaters can cau se e x t e n s i v e tra nsform a t i o n s o f o r g a n i c contaminants.
I n t h e case of phenol, t h e r e -
a c t i o n p a t h is o n l y p a r t i a l l y understood.
In an e f f o r t t o e l u -
c i d a t e t h i s r e a c t i o n , 2 , 4 , 6 - t r i c h l o r o p h e n o l i n d i l u t e aqueous s o l u t i o n was t r e a t e d with ex ces s hypochlorous a c i d a t pH 3.5-6. The major p r o du ct s here 2 , 6 - d i ch l o r o q u i n o ne and 2 , 4 , 4 , 6 - t e t r a -
~hloro-2,5-cyclohexadienone. Ad d i t i o n al p o l y c h l o r i n a t e d s p e c i e s are formed i n minor amounts by t h e a d d i t i o n o f c h l o r i n e a n d / o r hypochlorous a c i d t o t h e ar o mat i c r i n g . INTRODUCTION The r e a c t i v i t y o f aqueous c h l o r i n e s o l u t i o n s makes c h l o r i n a t i o n an e f f e c t i v e means o f c o n t r o l l i n g b a c t e r i a l growth i n
47 Copyright 0 1975 b y hlarcel Dekker, Inc. All Rights Reserved. Neither this work nor any p a t may he reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher.
SMITH, LEE, AND NETZER
48
municipal water supplies and wastewaters
’.
Ilomver, this reactivity
can result in chlorination and/or oxidation of organic contaminants rhich leads to unpleasant tastes and odours in the treated water. Phenol is a particularly troublesome’ impurity since very small quantities of 2,6-dichlorophenol can give a characteristic off-taste
Downloaded by [University of Florida] at 14:40 05 November 2015
to water.
Such taste-odour problems are frequently corrected by
overchlorination Iihich drives the reaction to the 2,4,6-trichloro-
’.
phenol stage and even furtherzb’
The nature of the final pro-
ducts is unknom. Our interest in the chlorination of organic compounds in dilute aqueous solution prompted an examination of 2,4,6-trichlorophenol.
In this communication rie describe the identification of
some of these reaction products. EXPERINENTAL All reactions involved 2.5g of 2,4,6-trichlorophenol (mp 67-69’) and 1250 ml of 0.5% w/v hypochlorous acid freshly prepared by diluting 5% w/v sodium hypochlorite (Baker reagent) with doubly distilled deionized water and acidifying to an initial pH of 6.0 (or 3.5) with hydrochloric acid. Dissolution was rapid after mixing the reagents d
and the solution was stirred for 20-24 hr. to allow the reaction to go to completion.
Normally, the reaction flask has wrapped with
aluminium foil to exclude light. Reaction products Kere isolated by extracting the solution with three 500 ml. portions of benzene.
The extracts \;ere washed with
water, dried (NgSOb) and evaporated. The residue was placed on 140 g of silica gel (blerck, .063-.200 mm) in a column wrapped with aluminium foil and elution effected with carbon tetrachloride graded to
49
CHLORINATION OF AQUEOUS 2,4,6-TRICHLOROPHENOL
benzene with 15 m l f r a c t i o n s b e i n g c o l l e c t e d .
The f r a c t i o n s were
examined by t h i n l a y e r chromatography and combined a c c o r d i n g l y . The i n d i v i d u a l i s o l a t e d components here c h a r a c t e r i z e d by t h e i r i n f r a - r e d , nmr and mass s p e c t r a .
The f o l l o w i n g T a b l e summarizes
Downloaded by [University of Florida] at 14:40 05 November 2015
t h e r e s u l t s o b t a i n e d with t h e e q u a t i o n showing t h e c o u r s e o f t h e reaction. TABLE I
2
1 w t . crudea p r o d u c t , g.
1Jt. o f f column, mgm.
4
3
Wt. o f compounds, mgm. 1 2 3 4
A'
6.0
0.902
475
0
106
0
13
B
6.0
1.14
62 8
209
111
66
0
C
6.0
1.37
646
406
125 n o t determined
D
3.5
1.82
1080
514
123
(a)
I s o l a t e d by benzene e x t r a c t i o n
(b)
T o t a l weight o f f r a c t i o n s from column
(c)
Not p r o t e c t e l from l i g h t .
50
0
DISCUSSION The p r i n c i p a l p r o d u c t s cjf t h e r e a c t i o n are 2 , 4 , 4 , 6 - t e t r a c h l o r o 2 , 5 - ~ y c l o h e x a d i e n o n e , 1, and 2,6-dichloro-p-benzoquinone, 2 .
Their
i d e n t i f i c a t i o n was based on t h e i r s p e c t r a and was confirmed by m i x t u r e m e l t i n g p o i n t with a u t h e n t i c
sample^^'^.
E a r l i e r r e p o r t s 6 have d e s -
c r i b e d t h e i s o l a t i o n of 2 i n r e a c t i o n s performed a t pH 2-3.
The
formation o f 1 h a s been r e p o r t e d b ef o r e but n o t i n aqueous s o l u t i o n . I n a c e t i c a c i d , c h l o r i n a t i o n produces 1 and through f u r t h e r r e a c t i o n 5 ' 7 o t h e r p o l y c h l o r i n a t e d p r o d u c t s resembling 3 and 4 . The p o s s i b i l i t y o f t h e i n t e r c o n v e r s i o n o f 1 and 2 was i n v e s t i -
Downloaded by [University of Florida] at 14:40 05 November 2015
g a t e d by t r e a t i n g each o f t h e s e compounds with hypochlorous a c i d . K h i l e some r e a c t i o n s l o wl y o ccu r r ed , no i n t e r c o n v e r s i o n o f 1 and 2 was n o t e d .
I n s t e a d , an u n i d e n t i f i e d m a t e r i a l c h a r a c t e r i z e d by a
c a r b o n y l frequency a t 1800 cm-' has formed. A number of minor p r o d u c t s were a l s o formed.
Two o f t h e s e
have t e n t a t i v e l y been as s i g n ed s t r u c t u r e s 3 and 4 on t h e b a s i s o f the spectral data.
Compound 3, an o i l , s h o re d a b s o r p t i o n due t o an
OH group a t 3550 cm-' and a carbonyl group a t 1767 cm-'.
The l a t t e r ,
frequency c h a r a c t e r i z e s a car b o n y l f l a n k e d by f o u r c h l o r i n e s 7 .
The
absence o f a b s o r p t i o n i n t h e 1500-1600 cm-' r e g i o n s u p p o r t s t h e a b sence o f unsaturation.
No p a r e n t i o n \;as d e t e c t e d i n t h e mass s p e c t r a
b u t t h e f r a g m e n t a t i o n p a t t e r n co u l d be r a t i o n a l i z e d by assuming l o s s o f C 1 + HC1 from t h e p a r e n t t o g i v e (CsH303C14)'.
Subsequent f r a g -
mentation by t h e loss o f v a r i o u s combinations o f C1, H C l , H 2 0 , CO t h e n account f o r t h e remaining prominent fragments. Compound 4 was a y el l o w s o l i d and i t s i n f r a - r e d spectrum showed
a carbonyl frequency a t 1702 cm-' and a C=C frequency a t 1580 cm-', c h a r a c t e r i s t i c 7 o f t h e co n j u g at ed arrangement shohn.
The nmr s p e c -
trum showed o n l y t h e v i n y l p r o t o n resonance a t 7.47 6 hhile t h e mass spectrum s h o m d a p p r o p r i a t e i s o t o p e c l u s t e r s a t C6HOC15 @ I + , p a r e n t i o n ) and PI+-Cl,
N+-2C1, b l + - C O C l , bl+-C0-2Cl, M+-C0-3C1.
I t i s noteworthy t h a t t h e m a t e r i a l balance i n t h e s e experiments
i s low with approximately 50% of t h e o r g a n i c material remaining i n
CHLORINATION OF AQUEOUS 2,4,6-TRICHLOR0PHEh1OL
51
t h e aqueous l a y e r ' o r perhaps being l o s t by v o l a t i l i z a t i o n .
Recovery
o f t h e o r g a n i c p r o d u c t s from t h e chromatographic column was a l s o low. I n p a r t , t h i s l o s s appears due t o p h o t o l y t i c a l l y induced decomposition o f t h e c h l o r i n a t e d p r o d u c t s s i n c e a marked i n c r e a s e i n recovery was
Downloaded by [University of Florida] at 14:40 05 November 2015
o b t a i n e d by p r o t e c t i n g t h e r e a c t i o n and t h e chromatography from l i g h t . I t h a s been r e p o r t e d 6 t h a t 2 , 6 - d i c h l o r o -p -benzoquinone i s p h o t o l y t i -
c a l l y decomposed t o "humic l i k e material" a t pH 7.0 i n aqueous s o l ution. I t i s e v i d e n t t h a t hypochlorous a c i d produces non-phenolic
p r o d u c t s by o x i d a t i o n ( e . g . 2) and by t h e a d d i t i o n o f c h l o r i n e and/ o r hypochlorous a c i d t o t h e a r o m a t i c r i n g '
The
(e.g. 1, 3 and 4 ) .
t o x i c o l o g i c a l p r o p e r t i e s o f t h e s e p o l y c h l o r i n a t e d s p e c i e s are unknohn but t h e y are decomposed by bases and r e d u c i n g agents" t i m e s with t h e formation o f new c h l o r o p h e n o l s .
some-
I n view o f t h e chem-
i c a l s e n s i t i v i t y o f t h e s e compounds, t h e chemical s e p a r a t i o n s o f
c h l o r i n a t i o n r e a c t i o n p r o d u c t s s h o u l d be employed with c a u t i o n .
REFERENCES 1.
2.
G.C. Ii'hite, Handbook of C h l o r i n a t i o n , pp. 278-465, van Nostrand Reinhold Co., 1972.
(a) M.B.
E t t i n g e r and C.C.
Ruchhoft, J. h e r . IVater Iforks ASSOC.,
433.561 (1951); (b) R.H. B u r t t s c h e l l , A.A. Rosen, F N . Pliddleton, and P1.B.
Ettinger,
x, z, 205
(1959)
3.
( a ) H.R. Eisenhauer, J . Water P o l l . Control Fed., 3 , 1116 (1964); (b) G.F. Lee and J . C . M o r r i s , J. A i r IVater P o l l . , 5 419 (1962).
4.
Beilstein,
5.
L,
633 (1929)
P. Svec, A.M. Sorensen, andbI. Zbirovsky, Org. Prep. Proc. I n t . , 209 (1973)
-5,
Downloaded by [University of Florida] at 14:40 05 November 2015
SMITH, LEE, AND NETZER
52
28,
6.
J . E l i a s e k and A . J u n g d r t , C o l l . Czech. Chem. Corn., (1963).
7.
( a ) L. V o l l b r a c h t , 1V.G.B. Huysmans, 1V.J. hlijs, and H . J . Hageman, T e t r a h e d r o n , 2,6265 (1968); ( b ) E. M o r i t a and E.1.W. D i e t r i c h , Can. J. Chem., 47, 1943 (1969) and r e f e r e n c e s c i t e d t h e r e i n .
8.
The aqueous l a y e r showed a t o t a l o r g a n i c carbon of 360 mgm p e r l i t e r . These compounds are p r e s e n t l y under i n v e s t i g a t i o n .
9.
Such a d d i t i o n r e a c t i o n s o c c u r w i t h s u r p r i s i n g e a s e . For a r e c e n t d i s c u s s i o n s e e P.B.D. de l a Mare, Acc. Chem. Research, ?, 361 (1974).
10. R. F o r t , Ann. Chim. ( P a r i s ) ,
4,
s e r i e s 13, 203 (1959) Received March 25, 1975 Accepted A p r i l 1, 1975
2163
ISSN: 0013-9300 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/lesa17
Chlorination in Dilute Aqueous Systems; 2,4,6Trichlorophenol James G. Smith , Siow-Fong Lee & Aharon Netzer To cite this article: James G. Smith , Siow-Fong Lee & Aharon Netzer (1975) Chlorination in Dilute Aqueous Systems; 2,4,6-Trichlorophenol, Environmental Letters, 10:1, 47-52, DOI: 10.1080/00139307509435807 To link to this article: http://dx.doi.org/10.1080/00139307509435807
Published online: 02 Sep 2009.
Submit your article to this journal
Article views: 2
View related articles
Citing articles: 3 View citing articles
Full Terms & Conditions of access and use can be found at http://www.tandfonline.com/action/journalInformation?journalCode=2esa20 Download by: [University of Florida]
Date: 05 November 2015, At: 14:40
ENVIRONNENTAL LETTERS, 10(1), 47-52 (1975)
CHLORINATION IN DILUTE AQUEOUS SYSTBIS; 2,4,6-TRICHLOROPHENOL
Downloaded by [University of Florida] at 14:40 05 November 2015
KEY KORDS: James G
Water t r e a t m e n t , p o l y c h l o r i n a t e d compounds
. Smith*,
Siow-Fong Lee*, and Aharon N e t z e r t
*Department o f Chemistry U n i v e r s i t y o f Waterloo Waterloo , O n t a r i o tl\rater. and Wastewater Treatment Subdivision Canada C en t r e f o r I n l a n d Waters Burlington, Ontario ABSTRACT C h l o r i n a t i o n o f wastewaters can cau se e x t e n s i v e tra nsform a t i o n s o f o r g a n i c contaminants.
I n t h e case of phenol, t h e r e -
a c t i o n p a t h is o n l y p a r t i a l l y understood.
In an e f f o r t t o e l u -
c i d a t e t h i s r e a c t i o n , 2 , 4 , 6 - t r i c h l o r o p h e n o l i n d i l u t e aqueous s o l u t i o n was t r e a t e d with ex ces s hypochlorous a c i d a t pH 3.5-6. The major p r o du ct s here 2 , 6 - d i ch l o r o q u i n o ne and 2 , 4 , 4 , 6 - t e t r a -
~hloro-2,5-cyclohexadienone. Ad d i t i o n al p o l y c h l o r i n a t e d s p e c i e s are formed i n minor amounts by t h e a d d i t i o n o f c h l o r i n e a n d / o r hypochlorous a c i d t o t h e ar o mat i c r i n g . INTRODUCTION The r e a c t i v i t y o f aqueous c h l o r i n e s o l u t i o n s makes c h l o r i n a t i o n an e f f e c t i v e means o f c o n t r o l l i n g b a c t e r i a l growth i n
47 Copyright 0 1975 b y hlarcel Dekker, Inc. All Rights Reserved. Neither this work nor any p a t may he reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher.
SMITH, LEE, AND NETZER
48
municipal water supplies and wastewaters
’.
Ilomver, this reactivity
can result in chlorination and/or oxidation of organic contaminants rhich leads to unpleasant tastes and odours in the treated water. Phenol is a particularly troublesome’ impurity since very small quantities of 2,6-dichlorophenol can give a characteristic off-taste
Downloaded by [University of Florida] at 14:40 05 November 2015
to water.
Such taste-odour problems are frequently corrected by
overchlorination Iihich drives the reaction to the 2,4,6-trichloro-
’.
phenol stage and even furtherzb’
The nature of the final pro-
ducts is unknom. Our interest in the chlorination of organic compounds in dilute aqueous solution prompted an examination of 2,4,6-trichlorophenol.
In this communication rie describe the identification of
some of these reaction products. EXPERINENTAL All reactions involved 2.5g of 2,4,6-trichlorophenol (mp 67-69’) and 1250 ml of 0.5% w/v hypochlorous acid freshly prepared by diluting 5% w/v sodium hypochlorite (Baker reagent) with doubly distilled deionized water and acidifying to an initial pH of 6.0 (or 3.5) with hydrochloric acid. Dissolution was rapid after mixing the reagents d
and the solution was stirred for 20-24 hr. to allow the reaction to go to completion.
Normally, the reaction flask has wrapped with
aluminium foil to exclude light. Reaction products Kere isolated by extracting the solution with three 500 ml. portions of benzene.
The extracts \;ere washed with
water, dried (NgSOb) and evaporated. The residue was placed on 140 g of silica gel (blerck, .063-.200 mm) in a column wrapped with aluminium foil and elution effected with carbon tetrachloride graded to
49
CHLORINATION OF AQUEOUS 2,4,6-TRICHLOROPHENOL
benzene with 15 m l f r a c t i o n s b e i n g c o l l e c t e d .
The f r a c t i o n s were
examined by t h i n l a y e r chromatography and combined a c c o r d i n g l y . The i n d i v i d u a l i s o l a t e d components here c h a r a c t e r i z e d by t h e i r i n f r a - r e d , nmr and mass s p e c t r a .
The f o l l o w i n g T a b l e summarizes
Downloaded by [University of Florida] at 14:40 05 November 2015
t h e r e s u l t s o b t a i n e d with t h e e q u a t i o n showing t h e c o u r s e o f t h e reaction. TABLE I
2
1 w t . crudea p r o d u c t , g.
1Jt. o f f column, mgm.
4
3
Wt. o f compounds, mgm. 1 2 3 4
A'
6.0
0.902
475
0
106
0
13
B
6.0
1.14
62 8
209
111
66
0
C
6.0
1.37
646
406
125 n o t determined
D
3.5
1.82
1080
514
123
(a)
I s o l a t e d by benzene e x t r a c t i o n
(b)
T o t a l weight o f f r a c t i o n s from column
(c)
Not p r o t e c t e l from l i g h t .
50
0
DISCUSSION The p r i n c i p a l p r o d u c t s cjf t h e r e a c t i o n are 2 , 4 , 4 , 6 - t e t r a c h l o r o 2 , 5 - ~ y c l o h e x a d i e n o n e , 1, and 2,6-dichloro-p-benzoquinone, 2 .
Their
i d e n t i f i c a t i o n was based on t h e i r s p e c t r a and was confirmed by m i x t u r e m e l t i n g p o i n t with a u t h e n t i c
sample^^'^.
E a r l i e r r e p o r t s 6 have d e s -
c r i b e d t h e i s o l a t i o n of 2 i n r e a c t i o n s performed a t pH 2-3.
The
formation o f 1 h a s been r e p o r t e d b ef o r e but n o t i n aqueous s o l u t i o n . I n a c e t i c a c i d , c h l o r i n a t i o n produces 1 and through f u r t h e r r e a c t i o n 5 ' 7 o t h e r p o l y c h l o r i n a t e d p r o d u c t s resembling 3 and 4 . The p o s s i b i l i t y o f t h e i n t e r c o n v e r s i o n o f 1 and 2 was i n v e s t i -
Downloaded by [University of Florida] at 14:40 05 November 2015
g a t e d by t r e a t i n g each o f t h e s e compounds with hypochlorous a c i d . K h i l e some r e a c t i o n s l o wl y o ccu r r ed , no i n t e r c o n v e r s i o n o f 1 and 2 was n o t e d .
I n s t e a d , an u n i d e n t i f i e d m a t e r i a l c h a r a c t e r i z e d by a
c a r b o n y l frequency a t 1800 cm-' has formed. A number of minor p r o d u c t s were a l s o formed.
Two o f t h e s e
have t e n t a t i v e l y been as s i g n ed s t r u c t u r e s 3 and 4 on t h e b a s i s o f the spectral data.
Compound 3, an o i l , s h o re d a b s o r p t i o n due t o an
OH group a t 3550 cm-' and a carbonyl group a t 1767 cm-'.
The l a t t e r ,
frequency c h a r a c t e r i z e s a car b o n y l f l a n k e d by f o u r c h l o r i n e s 7 .
The
absence o f a b s o r p t i o n i n t h e 1500-1600 cm-' r e g i o n s u p p o r t s t h e a b sence o f unsaturation.
No p a r e n t i o n \;as d e t e c t e d i n t h e mass s p e c t r a
b u t t h e f r a g m e n t a t i o n p a t t e r n co u l d be r a t i o n a l i z e d by assuming l o s s o f C 1 + HC1 from t h e p a r e n t t o g i v e (CsH303C14)'.
Subsequent f r a g -
mentation by t h e loss o f v a r i o u s combinations o f C1, H C l , H 2 0 , CO t h e n account f o r t h e remaining prominent fragments. Compound 4 was a y el l o w s o l i d and i t s i n f r a - r e d spectrum showed
a carbonyl frequency a t 1702 cm-' and a C=C frequency a t 1580 cm-', c h a r a c t e r i s t i c 7 o f t h e co n j u g at ed arrangement shohn.
The nmr s p e c -
trum showed o n l y t h e v i n y l p r o t o n resonance a t 7.47 6 hhile t h e mass spectrum s h o m d a p p r o p r i a t e i s o t o p e c l u s t e r s a t C6HOC15 @ I + , p a r e n t i o n ) and PI+-Cl,
N+-2C1, b l + - C O C l , bl+-C0-2Cl, M+-C0-3C1.
I t i s noteworthy t h a t t h e m a t e r i a l balance i n t h e s e experiments
i s low with approximately 50% of t h e o r g a n i c material remaining i n
CHLORINATION OF AQUEOUS 2,4,6-TRICHLOR0PHEh1OL
51
t h e aqueous l a y e r ' o r perhaps being l o s t by v o l a t i l i z a t i o n .
Recovery
o f t h e o r g a n i c p r o d u c t s from t h e chromatographic column was a l s o low. I n p a r t , t h i s l o s s appears due t o p h o t o l y t i c a l l y induced decomposition o f t h e c h l o r i n a t e d p r o d u c t s s i n c e a marked i n c r e a s e i n recovery was
Downloaded by [University of Florida] at 14:40 05 November 2015
o b t a i n e d by p r o t e c t i n g t h e r e a c t i o n and t h e chromatography from l i g h t . I t h a s been r e p o r t e d 6 t h a t 2 , 6 - d i c h l o r o -p -benzoquinone i s p h o t o l y t i -
c a l l y decomposed t o "humic l i k e material" a t pH 7.0 i n aqueous s o l ution. I t i s e v i d e n t t h a t hypochlorous a c i d produces non-phenolic
p r o d u c t s by o x i d a t i o n ( e . g . 2) and by t h e a d d i t i o n o f c h l o r i n e and/ o r hypochlorous a c i d t o t h e a r o m a t i c r i n g '
The
(e.g. 1, 3 and 4 ) .
t o x i c o l o g i c a l p r o p e r t i e s o f t h e s e p o l y c h l o r i n a t e d s p e c i e s are unknohn but t h e y are decomposed by bases and r e d u c i n g agents" t i m e s with t h e formation o f new c h l o r o p h e n o l s .
some-
I n view o f t h e chem-
i c a l s e n s i t i v i t y o f t h e s e compounds, t h e chemical s e p a r a t i o n s o f
c h l o r i n a t i o n r e a c t i o n p r o d u c t s s h o u l d be employed with c a u t i o n .
REFERENCES 1.
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G.C. Ii'hite, Handbook of C h l o r i n a t i o n , pp. 278-465, van Nostrand Reinhold Co., 1972.
(a) M.B.
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( a ) H.R. Eisenhauer, J . Water P o l l . Control Fed., 3 , 1116 (1964); (b) G.F. Lee and J . C . M o r r i s , J. A i r IVater P o l l . , 5 419 (1962).
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P. Svec, A.M. Sorensen, andbI. Zbirovsky, Org. Prep. Proc. I n t . , 209 (1973)
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J . E l i a s e k and A . J u n g d r t , C o l l . Czech. Chem. Corn., (1963).
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( a ) L. V o l l b r a c h t , 1V.G.B. Huysmans, 1V.J. hlijs, and H . J . Hageman, T e t r a h e d r o n , 2,6265 (1968); ( b ) E. M o r i t a and E.1.W. D i e t r i c h , Can. J. Chem., 47, 1943 (1969) and r e f e r e n c e s c i t e d t h e r e i n .
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The aqueous l a y e r showed a t o t a l o r g a n i c carbon of 360 mgm p e r l i t e r . These compounds are p r e s e n t l y under i n v e s t i g a t i o n .
9.
Such a d d i t i o n r e a c t i o n s o c c u r w i t h s u r p r i s i n g e a s e . For a r e c e n t d i s c u s s i o n s e e P.B.D. de l a Mare, Acc. Chem. Research, ?, 361 (1974).
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s e r i e s 13, 203 (1959) Received March 25, 1975 Accepted A p r i l 1, 1975
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