Environmenlul Toxicology and Chemislry, Vol. 8 , pp. 1159-1 163, 1989 0730-7268/89 $3.00 + .

00
Printed in the USA. Pergamon Press plc

Short Communication
AQUEOUS CHLORINATION OF RESORCINOL
VICTORL. HEASLEY,MICHAELD. BURNS,NATHANA. KEMALYAN,
TAWNYA C. MCKEE, HINAKOSCHROETER, BRADR. TEEGARDEN
and SCWT E. WHITNEY
Department of Chemistry, Point Loma Nazarene College, San Diego, California 92106
ROBERTL. WERSHAW*
U.S. Geological Survey, Arvada, Colorado 80002

(Received 3 January 1989; Accepted 1 May 1989)

Abstract -An investigation of the aqueous chlorination (NaOCl) of resorcinol is reported. The
following intermediates were detected in moderate to high yield at different pH values and varying
percentages of chlorination: 2-chloro-, 4-chloro-, 2,4-dichloro-, 4,6-dichloro- and 2,4,6-trichloro-
resorcinol. Only trace amounts of the intermediates were detected when the chlorination was con-
ducted in the presence of phosphate buffer. This result has significant implications since resorcinol
in phosphate buffer has been used as a model compound in several recent studies on the formation
of chlorinated hydrocarbons during chlorination of drinking water. Relative rates of chlorination
were determined for resorcinol and several of the chlorinated resorcinols. Resorcinol was found
to chlorinate only three times faster than 2,4,6-trichlororesorcinol. The structure 2,4,6-trichloro-
resorcinol was established as a monohydrate even after sublimation. A tetrachloro or pentachloro
intermediate was not detected, suggesting that the ring-opening step of such an intermediate must
be rapid.

Keywords- Resorcinol Chlorination Chloroform Phosphate buffer

Humic substances

INTRODUCTION chloroform production, we decided to make a thor-

It is widely assumed that chloroform, CHCl,,
in drinking water results primarily from the reac-
tion of chlorine, C1+ (C1+ represents HOCl and/
or OCl-), with the 1,3-dihydroxybenzene compo-
nents of humic materials. This assumption is based
on studies of the aqueous chlorination of various
model 1,3-dihydroxybenzenes, particularly resor-
cinol(1) (note: boldface numbers refer to different
chemical species, as shown in the chemical equa-
tions; see Fig. l). These model-compound studies
were done in the presence of a high-phosphate
buffer concentration (0.2 M) to maintain the pH at
a desired level, ormally 7 [1-31.
During oudvestigation on the mechanisms of
the aqueodchlorination of 1 in the presence of
phosphate buffer, we became suspicious that phos-
phate was participating in the reaction and altering
the structure of the products. Because of the im-
portance of the chlorination of 1in the studies of
*To whom correspondence may be addressed.
Any use of trade names in this report is for descrip-
tive purposes only and does not constitute endorsement
by the U S . Geological Survey.
1159
ough investigation of the early stages of the aque-
ous chlorination of 1 in the presence and absence
of buffer. By early stages, we refer to all intermedi-
ates formed prior to the opening of the aromatic
ring. As far as we could determine from the liter-
ature, only superficial, qualitative examinations
have been made of the chlorination of 1 in the pres-
ence of phosphate [2,3] and no data are available
in the absence of phosphate.
EXPERIMENTAL
Chlorination procedure
Sufficient 1 was dissolved in water in a round-
bottomed flask, equipped with a magnetic stirrer,
to give a solution of approximately 5 x lop2 M.
Sodium hypochlorite, NaOC1, solution (5%) was
added dropwise to the desired percent reaction. The
pH was monitored continually with a pH meter
and maintained at k0.5 pH units from the indi-
cated values by adding small increments of dilute
HCl after each addition of NaOCl. Acid was
needed because the pH gradually rose as the reac-
tion proceeded, Prior to analysis, the pH was ad-
justed to 2.
1160 V. L. HEASLEY
& 1
OH &I
2
OH
OH OH
CI CI
3 4
&ICI OH c%l CI OH
5 6
Fig. I . Chemical structures of resorcinol and its chlori-
nated derivatives.
In the reactions involving buffer, a ratio of
HPOz-/H,POi- = 0.76 (2 M) maintained the pH
at 7.
Compounds involved in the study
Resorcinol (l),4-chlororesorcinol(3) and 4,6-
dichlororesorcinol(4) were obtained in high purity
from Aldrich Chemical Company. 2-Chlororesor-
cinol(2) was prepared according to the synthesis
developed by Schamp [4]. 2,4-Dichlororesorcinol
(5) was synthesized by limited chlorination of 2 and
identified by its mass spectrum. All of the inter-
mediates were identified in the reaction mixture by
gas chromatography combined with mass spec-
trometry (GC-MS analysis).
Special attention was given to establishing the
structure of 2,4,6-trichlororesorcinol(6). We have
confirmed that sublimed 6, the highest purity we
could attain, exists as the monohydrate. This struc-
ture is strongly supported by elemental analysis and
' H nuclear magnetic resonance (NMR) studies,
and suggested by GC analysis. The calculated ele-
mental analysis for C6H302C13.Hz0is C, 31.10;
H, 2.15; C1, 46.00, and the measured analysis of
our product is C, 31.43; H, 2.03; C1, 46.42. The
NMR of 6 in acetone D6 (Aldrich Gold Label)
showed aromatic-H at 7.80 ppm and 0 - H at 5.42
ppm in a ratio of 1 to 4. The NMR in CDCl,, in
which 6 is slightly soluble, was less clear. The
aromatic-H (7.65 ppm) and 0 - H (6.20 ppm) were
in a ratio of 1:1.5. The GC data suggest that 6
ET AL.
probably eluted through the capillary column as a
hydrate. The retention times, as presented later in
this report, for all of the chlororesorcinols except
6 were reasonably close together with a range of
2.25 min. Yet, the retention time for 6 was approx-
imately 3.5 min beyond the end of the range. This
suggests that there is a different aspect to this struc-
ture. The mass spectrum of 6 did not indicate the
hydrate. The structure of 6 was further confirmed
by conversion with diazomethane to the dimethyl
ether, 1,3-dimethoxy-2,4,6-trichlorobenzene. The
structure of the ether was confirmed by GC-MS.
Both the monohydrate and nonhydrate struc-
tures have been reported for 6. Cavelti [5] reports
the hydrate structure. His synthesis, which we used
to make 6, involves chlorination of 1 with sulfuryl
chloride followed by recrystallization from water.
Elemental analysis of this product, following ex-
tensive drying under vacuum, implied extra water
in addition to the one water in the hydrate. Stelt,
Suurmond and Nauta [6] indicated that the non-
hydrate can be obtained by reduction of 2,2,4,4,5,
6,6-heptachlorocyclohexadione- 1,3 followed by
recrystallization from water. We repeated this pro-
cedure and obtained a product that appeared to be
identical in all respects to the product from sulfuryl
chloride.
Sublimed 6 exists as short, white needles with a
melting point of 67.5 to 69°C. Cavelti [5] reports
that "anhydrous" 6 melts at 72" and the monohy-
drate at 83°C. Stelt et al. [6] report a melting point
of 82 to 835°C for their product. We never ob-
tained a product melting above 69°C. Apparently
our monohydrate corresponds to Cavelti's "anhy-
drous" product.
Analysis procedures
GC analyses were performed on a Hewlett-Pack-
ard 5890 gas chromatograph and a Hewlett-Pack-
ard 3390 integrating recorder with a 25-m capillary
column coated with methyl silicone, under temper-
ature programming conditions of 120 to 180°C at
10"C/min. Under these conditions, the retention
times (min) were: 1 (6.59), 2 (5.74), 3 (7.08), 4
(7.25), 5 (7.69), 6 (1 1.37) and p-chlorophenol, the
internal standard (5.31). NMR spectra were ob-
tained on a Varian T-60A spectrometer. A Hewlett-
Packard 5970 mass spectrometer, interfaced to the
gas chromatograph, was used to obtain the mass
spectra.
Relative rate determination
Approximately equimolar mixtures (2 x lo-, M
in each) of the various compound pairs were chlo-
 Aqueous chlorination of resorcinol 1161

rinated from 10 to 20% completion under normal trace amounts of the intermediates that were too
reaction conditions (pH 7) and were analyzed for small to measure quantitatively by GC analysis
remaining starting materials. The amount of inter- were formed.
fering product, which was formed from 1, was The ratios of the rates of chlorination in the ab-
found to be insignificant when compared to the sence of buffer of 1 and some of the chlororesor-
starting compound. Relative rates were calculated cinols were determined. These ratios are: k,/k3,
from the following equation: kl/k4 and k,/k3 equal to 1.0 k 0.5; kl/ks equal to
2.9 k 0.2.
An intense, transient purple color was formed
when NaOCl was added to 1. This color has been
reported previously by Christman and others [7].
We observed that a more intense color forms when
NaOCl is added to 2,4,6-trichlororesorcinol( 6 ) .
We assume, therefore, that the color is the result of
where A ; and A , represent the original moles of a charge-transfer complex between 6 and C1+. Our
the two compounds; A ; and Af represent the final data indicate that 1 is essentially gone at 400%
moles of the two compounds; and V , and V, repre- chlorination, and only a trace of the intermediates
sent the original and final volumes. remain at 500%. A tetrachloro or pentachloro in-
termediate was not detected by GC analysis.
RESULTS
DISCUSSION
Chlorination of 1 with aqueous sodium hypo-
chlorite (NaOC1) at different pH levels in the The fact that only trace amounts of the inter-
absence of phosphate buffer produced varying mediates were detected from chlorination in the
amounts of the following chlororesorcinols: 2- presence of phosphate buffer in this study and in
chlororesorcinol (2), 4-chlororesorcinol (3), 4,6- that of Christman and others [7] has important im-
dichlororesorcinol (4), 2,4-dichlororesorcinol (5) plications for the previous studies of Norwood and
and 2,4,6-trichlororesorcinol (6). The pH levels others [2] and Boyce and Horning [3], because
were maintained by addition of small increments of these studies were particularly concerned with iden-
dilute acid. The percentages of the products are tification of ring-opened products. We suspect that
shown in Table 1. These quantitative data were ob- the structures and relative amounts of these ring-
tained from chlorination of -5 x lop2 M solutions opened products may have been affected by phos-
of 1. Qualitative gas chromatographic (GC) anal- phate. Our assumption is that the intermediates,
ysis showed that percentages of products were probably at the earliest stage (steps leading to 2 or
similar for chlorination of lop3 M and lop4 M so- 3), were diverted by phosphate. The diversion step
lutions of l . Chlorination in the presence of phos- likely involved attack by phosphate ion on a cation
phate buffer gave drastically different results. Only precursor, resulting in a phosphate ester that would
be too polar to pass through the GC column. Al-
though we did not attempt to isolate the phosphate
esters, we do have some evidence that they were
Table 1. Chlororesorcinols from the chlorination of 1 formed, Isolation of a chlorination product by
in the absence of buffer ether extraction, followed by elemental analysis of
the crude product, showed a high ash content in the
Material
"70 balance case of reactions run in phosphate buffer. We at-
pH reaction 2 3 4 5 6 ("70)" tribute the ash to a phosphate ester, such as
(RO),P02Na.
2 100 14.3 31.6 8.1 22.0 24.0 103 The data in Table 1 indicate that chlorination in
2 10 12.3 42.4 7.8 21.4 16.1 94
0 100 9.5 26.8 7.7 22.5 33.5 90 the absence of phosphate buffer produces the chlo-
0 10 11.3 30.2 8.7 26.9 22.9 94 roresorcinols anticipated from electrophilic substi-
7 100 4.4 18.0 8.2 15.1 54.3 58 tution in moderate to high yield, depending on the
7 50 5.5 19.6 8.1 18.6 48.2 76 percent completion. Material balances lower than
7 10 6.0 20.2 8.4 23.0 42.4 86 100% probably involve conversion of 6 to ring-
2 10 5.8 21.6 9.0 23.9 39.7 87
opened products. The percentages of the mono-
"Material balance of the products based on the NaOCl chlororesorcinols (2 and 4) are higher at high pH
added. levels, apparently because the rate of conversion to
1162 V. L. HEASLEY
ET
6 and ring-opened products is slower at high pH
than at low pH, as indicated by the lower amount
of 6 and the higher material balance at the higher
pH values.
The data in Table 1 also indicate that at pH 7 a
steady-state level of the intermediates is closely ap-
proached at 10% reaction and has been reached at
50% reaction, since little change occurs at 100%.
Based on the following considerations, we con-
clude that the 4- (or 6-) position is about 1.5 times
more reactive than the 2-position (the position be-
tween the hydroxy groups): (a) the relative rate data
show that 2 and 3 react (chlorinate) at the same
rate; (b) the ratio of 2:3 remains essentially con-
stant at 0.3 across the pH range, suggesting that 3
c'o('
OH
"@iH CI
CI
6
Fig. 2.
Fig. 3.
AL.
is formed approximately three times faster than 2;
but (c) there are two equivalent 4- (6-) positions for
the single 2-position, which reduces the relative re-
activity per position to 1.5. These data are inter-
esting; they indicate that the sterically hindered
2-position is more reactive than might be antici-
pated from electrophilic substitution in other meta
substituted aromatic systems, but it is not the exclu-
sive position of attack as has been suggested by
Rook [8]. In this regard it should be noted that
Boyce and Horning [3] have indicated attack at
either the 2- or 4-positions in their reaction scheme.
The relative rates indicate that substitution of
two chlorines in the aromatic ring does not decrease
the rate of C1+ attack over that of 1 itself. The rel-
QH 0
H
-
 Aqueous chlorination of resorcinol
ative rate data for 1 and 6 are surprising. These
data indicate that even with three chlorine atoms 6
is still approximately one-third as reactive as 1. Per-
haps 6 exists partially in the enol form that ac-
counts for its high reactivity (see Fig. 2). The enol
content would have to be low, though, since the
NMR spectrum in D,O-acetone showed only a
single type of proton.
A concerted effort was made to detect the inter-
mediate that follows 6 on the reaction pathway,
presumably the tetrachloro intermediate (7),but
without success. From our experiences with GC, we
feel certain that 7 would have been detected had it
been present. Therefore, we conclude that it is rap-
idly converted to the pentachloro intermediate @),
and that 8 immediately undergoes ring-opening to
produce CHC13and other products, as suggested
in the equations shown in Figure 3.
Acknowledgements-The authors thank the Research As-
sociates of Point Loma Nazarene College for partial sup-
port of the research.
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1163
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