Water Research Vol. 10, pp. 985 to 990. Pergamon Press 1976. Printed in Great Britain.

MODEL STUDIES IN AQUEOUS CHLORINATION:

THE CHLORINATION OF PHENOLS IN
DILUTE AQUEOUS SOLUTIONS
JAMES G. SMITH, SIOW-FONGLEE and AHARONNETZER*
Guelph-Waterloo Centre for Graduate Work in Chemistry, Waterloo Campus,
Department of Chemistry, University of Waterloo, Waterloo, Ontario, and
*Water and Wastewater Treatment Subdivision, Canada Centre for Inland Waters,
Burlington, Ontario, Canada

(Received 3 0 April 1976)

Abstraet---A study of the chlorination of four phenols in dilute aqueous solution at initial pH's of
6.0 and 3.5 is described. Extensive chlorination is observed under these mild reaction conditions. Identi-
fication of the products indicates that the reactions occurring involve chlorination to more highly
chlorinated phenols, oxidation to chlorinated p-benzoquinones, chlorine addition to the aromatic ring
to form chlorinated 2,5-cyclohexadienones,and addition of 2 moles of chlorine or one each of chlorine
and hypochlorous acid to give chlorinated cyclohexenones and chlorinated hydroxycyclohexenones.

INTRODUCTION by solvent extraction, the mixtures separated by

column chromatography and the products identified
The weU-known reactivity of aqueous solutions of by their spectral properties.
chlorine (White, 1972) to micro-organisms has led to Details of the procedure, spectral properties and
its extensive use as a disinfectant of municipal water interpretation of the data are given in the experimen-
supplies and waste waters. This reactivity suggests tal section. The infra-red spectra were particularly
that organic pollutants present in these aqueous solu- helpful in view of the earlier work by Denivelle (1956,
tions may themselves react to produce chlorine-con- 1957, 1958, 1959), Fort (1959), Vollbracht et al., (1968)
taining products.
and Morita (1969) with chlorinated cyclohexenones.
With the exception of halohydrin formation from In these earlier studies the carbonyl frequencies were
alkenes and the haloform reaction of methyl ketones, correlated with the number of flanking chlorines and
relatively little is known of the chemical behaviour • with the presence or absence of conjugated double
of organic compounds towards aqueous solutions of bonds. Additional correlations of the absorption fre-
chlorine. Insofar as environmental problems are con- quencies of the double bonds were also made.
cerned, the best studied case concerns the reactions Table 1 summarizes the overall quantitative results
of phenol which, when present as a contaminant of obtained in the isolation and separation procedures.
water supplies, lead to unpleasant taste and odours It will be noted that a loss of material is observed
in the chlorine-treated end product. It has been at two stages---in the initial isolation of the reaction
shown by Ettinger (1951), Burttschell et al., (1959), product (benzene ext'd) and during the column chro-
Eisenhauer (1964) and Lee and Morris (1962) that matography (9/o off-column). In both these instances
chlorine treatment leads to mono- and di-chloro- the degree of loss increases at the higher pH and with
phenols and that the taste and odour problem is the lower degree of chlorination of the starting
solved by over-chlorination which forces the reaction phenol. It should be stressed at this point that all
to proceed at least to the 2,4,6-trichlorophenol stage. practical precautions were taken to protect the reac-
It has also been demonstrated by Eisenhauer (1964)
tion products from the photolytic decomposition
and Lee and Morris (1962) that this over-chlorination reported in our preliminary communication (Smith
leads to unknown non-phenolic products. The et al., 1975).
research described in this paper was undertaken to The loss observed in recovery from the aqueous
elucidate further this last stage in the chlorination
reaction solution in the case of 2,4,6-trichlorophenol
process.
is due to the formation of water-soluble products. The
RESULTS A N D D I S C U S S I O N
extracted aqueous solution showed high total organic
carbon and additional products can be isolated by
To this end the reaction of excess hypochlorous concentration of the aqueous solution followed by
acid with dilute aqueous solutions of 2,4,6-trichloro- extraction with ethyl acetate. These products have yet
phenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol to be examined in detail. The additional loss of mater-
and p-nitrophenol at initial pH's of 6.0 and 3.5 has ial which occurred during the column chromatogra-
been examined. The reaction products were isolated phy on silica gel is presumably due to irreversible
985
986 JAMES G. SMITH, S1ow-FONG LEE and AHARON NETZER

Table 1. Material balance in the chlorination of selected phenols

benzene Off-column Identified

phenol* pH ext'd, g. (°,~)t (%)~

Trichloro 6 1.14~l.37 47- 55 62 -82

3.5 1.82 59 66
Nitro 6 1.50 68 69
3.5 2.20 88 79
Tetrachloro 6 1.71 99 72
3.5 2.18 73 76
Pentachloro 6 2.47 84 8l
3.5 2.49 87 68

* 2.5 g of phenol were used in each experiment.

t" weight % of material placed on the column.
:~weight % of material isolated from the column.

reactions with the chromatography substrate since in-
tense dark colors developed on the column.
Of the material recovered by chromatography,
60-80% by weight was either identified or separated
into pure components and these characterized spectro-
scopically. The conclusions from these studies are sum-
marized in Fig. 1, equations 1 4 , with the percentage
figures under the formulae being weight percentages
of the total material obtained after chromatography.
From these four equations it can be seen that there
are several characteristic features to the reactions. As
anticipated, aromatic substitution to a more highly
chlorinated phenol occurs although the apparent dis-
placement of the nitro group by chlorine is unex-
pected (equation 2). Oxidation of the phenol to a
chlorinated benzoquinone (i.e. 1, 12) is a second fea-
ture of these reactions. While such oxidations are
usually effected under more rigorous reaction condi-

OH 0 0 0

Ct 2 Ct 2
. + + ........ (I)

Ct 2 HO Ct 2 OH

Ct 0
pH6,0 18% 33*/= H%
pH 3 5 I 1% 48% 5%

OH 0 OH OH 0 0

. . . . . . . . (2)

Ct , H OH + Ct z H
I
NO 2 0 NO 2 el NO 2
I 2 3 4 5

pH6,0 20% I% 0,3% 39*/=

pH 3,5 26% -- 52%

OH OH 0 0 0 0

Cl~'~Clz unknown "'" (3)

+ ~,.
z l JCt
lI + rap. 125"
CL

Ct C( Ct Ct Ct2
6 7 8 9 I0 II

pH6.0 5% 3% 51% 24% 9%

pH35 ~ 37% 55% 8% II % 10%

=*plus 4% chloronil 12

OH 0 0 0 0 0

Cl Ct CI + CI CI + + CI2 Ct2 + .* .... (4)

~Cl Ct Cl CI Ct CI2

Ct CI 0 Ct Cl 2
6 12 7 9 I0

~6.0 30% 3*/= co'/. 27%

pH3.5 28% 6*/= 15% 18%

Fig. 1. Reactions of phenols with hypochlorous acid.

 Model studies in aqueous chlorinatiot~
OH
c t ~ c t Cl + Cl
m,
Paro
at'tack
CI
Ortho [
at'tack Cl +
OH
Cl~cl2 -H ÷ i, C t ~
Ct
Fig. 2. Mechanism of the addition of chlorine.
tions, chlorobenzoquinone formation under mild
reaction conditions has been reported by Eliasek
(1963) and recently by Murphy et al., (1975). These
last workers also noted that the reaction led to prod-
ucts in which aromatic hydrogens were absent. The
third feature of the reaction is the addition of one
mole of chlorine (or hypochlorous acid) to the phenol
forming chlorinated 2,5-cyclohexadienones (i.e. 7 and
equation 1) and the addition of two moles of chlorine
or hypochlorous acid to form chlorinated cyclohex-
enones (i.e. 9, 10) and/or chlorinated hydroxycyclo-
hexenones (i.e. 4, 5, 8). Addition of chlorine to aro-
matic rings has been known for many years although
the structure of many of the products has been clari-
fied only relatively recently by the efforts of Deniville
and Fort. Stroh (1962) has reviewed much of this ear-
lier work. Generally, the addition occurs when the
reactive ortho and para positions are substituted, and
mild reaction conditions are employed with non-
aqueous solvents such as acetic acid. In a recent
article, de la Mare (1974) has reviewed the mechanism
of this reaction and suggests that electrophilic attack
at a substituted position (i.e., ipso attack) followed
by loss of a proton from the hydroxyl group, rather
than from the ring, occurs. The process is illustrated
in Fig. 2 with 2,4,6-trichlorophenol. The products
from this reaction are 2,5-cyclohexadienones (from
para attack), which are isolable, and 2,4-cyclohexa-
dienones. Additional reaction presumably occurs with
the latter compound to provide cyclohexenones such
as those shown in equations (2), (3) and (4). Interest-
ingly enough, such addition reactions are not con-
fined to phenols but have been reported for polycyclic
aromatic hydrocarbons and phenolic ethers as well
as other aromatic compounds, and such reactions are
reviewed by Stroh (1962) and de la Mare (1974). A
recent example of the addition of chlorine to anisole
is reported by Watson and Heeschen (1974).
Two other compounds were isolated in minor
amounts, octachlorocyclobexadiene 13 (from tetra-
987
OH 0
Cl
-H + i,
0 0
cl2 ClY " HCt2~"~Ct~-
CL Ct
Y=CL or OH
and pentachloro-phenols) and octachlorodibenzo-
dioxin 14 (from pentachlorophenol). It is conceivable
that these may be due to impurities in the starting
phenols (the former would arise from hexachloro-
benzene as an impurity). However, the formation of
hexachlorobenzene and octachloro dibenzodioxin by
pyrolysis of pentachlorophenol has been reported by
Kulka (1961) and Sandermann et al. (1957). The possi-
bility that these products are formed from the starting
phenols cannot be excluded at this stage.
Cl Ct
CI Ct2 CI- T -u "/~"x- Cl
/
Cl Cl
13 14
This research has demonstrated that extensive
chlorination of phenols in dilute aqueous solution can
occur to give highly chlorinated non-phenolic prod-
ucts. It remains to be seen whether such reactions
occur when the concentrations of phenols and chlor-
ine are reduced to the 1-10 ppm level; this is the next
objective in our present program.
One note of caution is suggested by the present
study. Some of the compounds isolated are known
to be thermally sensitive (Fort, 1959), to be sensitive
to base (Fort, 1959), and to be photolytically reactive
(Eliasek, 1963). Isolation and analytical procedures
which involve separation by base extraction or analy-
sis involving high temperatures (e.g. gas chromatogra-
phy) may lead to transformations of the components
actually present in the original aqueous sample. The
sensitivity of the observed products to base also sug-
gests that chlorination of the phenols at pH's greater
than 7 may lead to results quite different from those
reported here. Indeed, reports by Moye and Sternhell
(1966), Strunz et al., (1969) and Burgstahler et al.,
(1966) suggest that ring contraction can occur to give
988 JAMES G. SMITH, SIOW-FONG LEE and AHARON NETZER

chlorinated non-aromatic derivatives containing five- plates were unstable--within a day additional absorp-
membered rings. In any event, it is evident that exper- tion bands developed in the nmr and i.r. spectra and
iments of the type described here should be repeated extra spots were seen by analytical tlc.
at pH's of 8.0. A repetition of this experiment gave 155 nag of 2,6-
dichloro-p-benzoquinone, !, 20 mg of p-nitrophenol,
EXPERIMENTAL 4mg of 2,3,4,6-tetrachlorophenol, 3, and 350mg of
the unstable "Fraction 3". In this instance, the indivi-
All reactions involved 2.5 g of the starting phenol dual 10 ml fractions were combined so as to give par-
which had been recrystallized to a constant melting tial resolution of two major components. The first
point and 1250 ml of 0.5% w/v hypochlorous acid of these showed in the i.r. spectrum (neat) an OH
freshly prepared by diluting 5% w/v sodium hypoch- group at 3500, a carbonyl at 1740 and strong bands
lorite (Baker reagent) with doubly distilled deionized at 1680, 1580, 1340, 940, 900, 870, 840, 750crn -1. The
water and acidifying to an initial pH of 6.0 (or 3.5) nmr spectrum showed a vinyl proton at 6 7.28 (J =
with hydrochloric acid. Dissolution was rapid after 2 Hz) and a second proton at 6 5.15 (J = 2 Hz) as
mixing the reagents and the solution was stirred for well as a strong OH resonance. Note that the nitro
2(~24 hr at allow the reaction to go to completion. group appears absent. Structure 5 is suggested for this
The reaction flask was wrapped with aluminium foil material.
to exclude light. The second component showed in the i.r. spectrum
Reaction products were isolated by extracting the (neat) an OH band at 3530, a carbonyl at 1775, a
solution with three 500 ml portions of benzene. The nitro group at 1550 and 1342, as welt as strong bands
extracts were washed with water, dried (MgSOa) and at 1582, 1070 and 715cm -1. The nmr spectrum
evaporated. The residue was placed on 140 g of silica showed a vinyl proton at 7.67 (J = 2Hz) and a
gel (Merck, 0.063-0.200mm) in a column wrapped second proton at 5.55 (J = 2 Hz) as well as a strong
with aluminium foil and elution effected with the sol- OH resonance. Structure 4 seems reasonable for this
vents described below, with 10 or 15ml fractions component. The mass spectrum supported this assign-
being collected. The fractions were examined by thin ment. No parent ion was visible but a four-chlorine
layer chromatography and combined accordingly. isotope cluster at M + --NO2, and three-chlorine iso-
The individual isolated components were character- tope clusters M ÷ ~ C I - - C O , M--HC3--NO2,
ised by their infra-red, nmr and mass spectra. M - - H C I - - N O 2 - - C O were all present.
Infra-red spectra were recorded on a Beckmann IR
10 spectrophotometer, nmr spectra on a Varian T-60 p-NITROPHENOL (pH 3.5)
instrument and mass spectra on an AEI MS-30
The previous run was repeated with the initial pH
double beam double focusing mass spectrometer with
adjusted to 3.5. From the reaction products there
perfluorokerosene in the reference beam. Analyses
were isolated 509 mg of 2,6-dichloro-p-benzoquinone,
were performed by Galbraith Laboratories, Knox-
1, and 15 mg of p-nitro-phenol.
ville, Tenn.
In addition, fractions 3 and 4 (total 1.0 g) was the
For brevity, in the following experimental section,
mixture of compounds 4 and 5. This material was
those compounds identified by mixture melting point
rechromatographed using benzene graded to ben-
and by comparison of their spectral data with those
zene-I 5% ethyl acetate but only a partial separation
of authentic samples are listed without detail. New
was effected.
compounds are described with supportive spectral
data.
2,3,4,6-TETRACHLOROPHENOL (pH 6)
2,4,6-Trichlorophenol. The results obtained in these
experiments have been reported elsewhere (Smith, The benzene-extracted products were chromato-
1975) and are summarized in Fig. 1, equation (1) for graphed using benzene graded to benzene-15% ethyl
comparison. acetate and the following materials were isolated.
Fractions 1 and 2 (839mg) were rechromato-
p-Nitrophenol (pH 6) graphed using less polar solvents (vide infra).
The following compounds were isolated; 206 nag of Fractions 5-8 (525mg) were recrystallized from
2,6-dichloro-p-benzoquinone, 1; 3 mg of 2,3,4,6-tetra- CHC13: Pet. ether (30~:~0°) to give 314mg of pale
chlorophenol 3; 88mg of unreacted p-nitrophenol; yellow crystals, mp 118-119°; nmr (CDC13) 3.4 (d,
and 10 mg of 2,6-dichloro-4-nitrophenol, 2. J = 4 Hz, 1, exchanges with D20), 4.93 (d, J = 4 Hz,
One of the major products, "fraction 3" (400 rag) 1, collapses to singlet on addition of D20); i.r. (neat)
was an oil whose i.r. spectrum showed a strong OH 3540 (OH), 1773 ( ~ ) , 1621, 1385, 1170, 1072, 1000,
band at 3520, two earbonyl bands at 1775 and 1740, 870, 730, 668, 640 cm-1. Structure 8 was assigned to
C-NOz at 1550 and 1340 as well as additional strong this compound. The mass spectrum showed a parent
bands at 1480, 1070, 910 and 870cm 1. The fraction ion with a six-chlorine isotope cluster at m/e 316 and
is a mixture and separation was attempted by pre- fragment ions at M--C1, M--CO---OH, M ~ -
parative tlc using benzene-15% acetic acid as a deve- HC1, M--C1--HC~---CO, M--{CI2CO ) supported this
loping solvent. The products recovered from the tic assignment. Anal. calc'd for C6H202C16: C, 22.78; H,
 Model studies in aqueous chlorination 989

0.63; CI, 66.45%. Found: C, 22.27; H, 0.53; C1, ethyl acetate. The following compounds were iso-
65.78%. lated; 5.5mg of octachloro-1, 4-cyclohexadiene, 13;
Fractions 16-21 (155 mg) were recrystaUized from 569 mg of the isomeric "octachlorophenol" mixture 9
CHC13: 30-60? pet ether to give 70rag of white and 10; 69 mg of chloranil, 12; 411 mg of hexachloro-
needles, mp 123.5-125 °, 11; nmr (CDC13) 6 4.90 2,5-cyclohexadienone, 7; and 629mg of recovered
(broad, 1, exchanges with D20), 6.50 (s, 1); i.r. pentachlorophenol.
(CHC13) 3540 (OH), 3130, 1800 (C------Overy strong),
Pentachlorophenol (pH 3.5)
1620, 1250, 1160, 950, 850, 820cm -t. The mass spec-
trum showed a three C1 isotope cluster at m/e 198. The preceding experiment was repeated and chro-
Anal: Found: C1, 56.55%. As yet, this compound has matography gave the following products; 395 mg of
an unknown structure. the isomeric mixture of 9 and 10; 606 mg of recovered
Fractions 1 and 2 were rechromatographed using pentachlorophenol; 329mg of hexachloro-,5-cyclo-
hexane as an eluting solvent. hexadienone, 7; and 137 mg of chloranil, 2.
Fraction A (414mg) contained the majority of the Some of the individual 10 ml fractions which con-
material. This oil showed no resonance peaks in the sisted principally of the isomeric mixture 9 and 10
nmr and must therefore be perchlorinated. The i.r. (an oil) were observed to contain crystals. These frac-
(neat) showed a carbonyl absorption at 1778 (with tions were combined, treated with hexane and filtered.
shoulder at 1740) 1568, 1113, 1068, 953, 861,840, 802, The filtrate was recombined with the remainder of
785, 657, 620cm-1. This is probably a mixture of 9 and 10. The solid, 5.5 mg, mp 303-305 °, proved to
the isomeric "octachlorophenols" 9 and 10 which be octachlorodibenzodioxin, 14 (reported mp 330-
have carbonyl absorptions (Denivelle, 1958, 1959) of 332°). Identification was based on the mass spectrum
1778 and 1745 and ~ absorptions of 1592 and which was identical to that of 14 (Boos, Buu-Hoi
1580crn-1, respectively. It has not been possible to et al., 1972) and showed a prominent eight chlorine
separate these isomers as yet. parent ion at m/e 456.
Rechromatography did provide 10 mg of a white
solid mp 83-88 ° whose nmr had no resonance and Acknowledgement--The authors are grateful to Environ-
whose i.r. (CHCI3) was very simple, 1620, 1590, 1140, ment Canada for the support of this research.
940cm -~. The mass spectrum of this compound
showed an eight-chlorine isotope cluster at m/e 352
and fragment ions at M---C1, M--2CI, M--3C1, REFERENCES
M----4C1 and several other lower mass fragments of
Boos W. (1975) Research Laboratories, Uniroyal Ltd.,
the CxCly type (x and y are integers smaller than 6). Guelph, Ontario, kindly supplied a reference mass spec-
Structure 13, octachloro-l,4-cyclohexadiene is pro- trum.
posed for this compound. Burgstahler A. W., Lewis T. B. & Abdel-Rahman M. O.
Fraction B (50mg) was recrystaUized from n-hex- (1966) Products from the base-catalyzed chlorination of
phenol. A new synthesis of (+)--caldariomycin, J. Org.
ane to give 25mg, mp 106-107 °. The nmr showed Chem. 31, 3516-3522.
no resonances and the i.r. (CHC13) 1697, 1581, 1270, Burttschell R. H., Rosen A. A., Middleton F. M. & Ettinger
l l l 0 c m -1. The compound is undoubtedly octa- M. B. (1959) Chlorine derivatives of phenol causing taste
chloro-2,5-cyclohexadienone, 7, reported mp 106- and odour J. Am. Wat. Ass. 51, 205-214.
Buu-Hoi N. P. & Saint-Ruf G. (1972) The Fragmentation
107°; the i.r. is identical with that reported (Denivelle,
of dibenzo-p-dioxin and its derivatives under electron
1956) for this compound; Anal: calc'd for C6OC16, impact, J. Heterocyclic Chem. 9, 691-693.
70.47% C1; Found 70.47% C1. de la Mare P. B. D. (1974) Pathways in electrophilic aro-
Fraction C (80 mg) was recrystallized from chloro-matic substitutions. Cyclohexadienes and related com-
form and 30-60 ° pet ether to give 54 mg of 2,3,4,5,6- pounds as intermediates in halogenation. Acc. Chem.
Res. 7, 361-368.
pentachlorophenol, 6. Denivelle L. & Fort R. (1956) Sur la chloruration de mono-
phenols polysubstitu6s. Pentachloroph6nol: preparation
2,3,4,6-Tetrachlorophenol (pH 3.5) de "hexachloroph~nol". Bull. Soc. Chim. France 1834-
The benzene-extracted products were separated by 1839.
using n-hexane graded to benzene and then to ethyl Denivelle L. & Fort R. (1957) Sur la chloruration de mono-
phenols polysubstitu6s. I. Pentachloroph6nol pr6p-
acetate. The following compounds were isolated; aration de l'hexachloro-l,2,4,4,5,6-cyclohexadi6ne-l,5-
181 mg of the isomeric "octachlorophenols" (9 and one-3. Bull Soc. Chim. France 724-728.
10); 88mg of hexachloro-2,5-cyclohexadienone, 7; Denivelle L. & Fort R. (1958) Sur la chloruration de mono-
586 mg of pentachlorophenol, 6; 62 mg of chloranil, ph6nols polysubstitu6s. Pentachloroph6nol: Preparation
de l'octochloro-2,2,3,4,5,5,6,6-cyclo-hex~ne-3-one-1 ou
12; 130 mg of 2,2,3,4,6,6-hexachloro-5-hydroxy-3-cyc- "octochloroph~nol-5. Bull. Soc. Chim. France 459-464.
lohexenone, 8; and 162mg of the unknown com- Denivelle L. & Fort R. (1959) Sur la chloruration de mono-
pound 11. ph6nols polysubstitu6s. Pentachloroph6nol: preparation
de l'octochloro-2,3,4,4,5,5,6,6-cyclo-hex6ne-2-one-1 ou
Pentachlorophenol (pH 6.0) "octochloroph6nol-7". Bull. Soc. Chim. France 392-401.
Eisenhauer H. R. (1964) Oxidation of phenolic wastes---II.
Chromatography was effected with 30-60 ° petro- Oxidiltion with chlorine. J. Water Poll. Control Fed. 36,
leum ether graded to benzene than to benzene-30% 1124-1128.
990 JAMESG. SMITH, SIow-FONG LEE and AHARONNETZER
Eliasek J. • Jungivert A. (1963) The mechanism of phenol
chlorination in aqueous solutions. Collection Czech.
Chem. Commun. 28, 2163-2170.
Ettinger M. B. & Ruchhoft C. C. (1951) Effect of stepwise
chlorination on taste- and odor-producing intensity of
some phenolic compounds. J. Am. War. Wks. Ass. 43,
561--567.
Fort R. (1959) Les pseudo-esters ph6noliques de l'acide
hypochloreux: les derives de la chloro-4-cyclohexa-
di6ne-l,5-one-3. Ann. Chim., Paris 4, 203-247.
Kulka M. (1961) Octahalogenodibenzo-p-dioxins. Can. J.
Chem. 39, 1973~1976.
Lee G. F. & Morris J. C. (1962) Kinetics of chlorination
of phenol-chlorophenolic tastes and odours. Int. J. Air.
Wat. Poll. 6, 419-43l.
Morita E. & Dietrich M. W. (1969) Polychloro-alicyclic
ketones--I. Polychloro-2-methylcyclohexenones, polych-
Ioro-3-methylcyclohexenones, and related polychloro-
cyclohexadienones. Can. J. Chem. 47, 1943-1950.
Moyc C. J. & Sternhell S. (1966) The degradation of
aromatic rings; the action of hypochlorite on phenols.
Aust. J. Chem. 19, 2107-2118.
Murphy K. L., Zaloum R. & Fulford D. (1975) Effect of
chlorination practice on soluble organics Water Res. 9,
389 396.
Sandermann W., Stockmann H. & Casten R. (1957) On
the pyrolysis of pentachlorophenol. Chem. Bet. 90, 690-
692.
Smith J. G, Lee S-F. & Netzer A. (1975) Chlorination in
dilute aqueous systems: 2A,6-trichlorophenol. Environ.
Letts. 10, 47-52.
Stroh R. (1962) The early literature of this reaction is
reviewed in Methoden der Oryanischen Chemie (Houben-
Weyl) Vol 5, Part 3, pg. 679-695, (Ed. E. Muller),
Thieme, Stuttgart.
Strunz G. M., Court A. S. & Komlossy J. (1969) Synthetic
analogues of crystosporeopsin: the action of hypochlor-
ite on m-cresol. Tetrahedron Letts. 3613--3614.
VoUbracht V., Huysmans W. G. B., Mijo W. J. & Hagemen
H. J. (1968)Chlorination of phenol and aryl substituted
phenols in acetic acid. Formation of unsaturated chlori-
nated cyclohexanone derivatives. Tetrahedron 24, 6265-
6275.
Watson W. D. & Heeschen J. P. (1974) Formation of
1,3,4,5,6-pentachloro-4-methoxycyclohexene from the
chlorine chlorination of 4-chloroanisole. Tetrahedron
Letts 695-698.
White G. C. (1972) Handbook of Chlorination. pp. 278-526.
van Nostrand Reinhold, Amsterdam.