THE PHOTODECOMPOSITION OF BROMACIL

KENNETH W. MOILANEN and DONALD G. CROSBY

Department o f Environmental Toxicology
University o f California
Davis, California 95616

The action of sunlight on dilute (1-10 ppm) aqueous solutions of the herbicide
bromacil (5-bromo-3-sec-butyl-6-methyluracil) resulted in the formation of only
one detectable photoproduct, 5-bromo-6-methyluracit, in very low yield. The
almost quantitative recovery of starting material, even after prolonged periods of
irradiation, indicated that bromacil was very stable toward sunlight. The N-
dealkylated photoproduct proved to be much less stable toward sunlight wave-
lengths, forming principally 6-methyluracil. No 5-bromouracil was detected.

Bromacil, 5-bromo-3-sec-butyl-6-methyluracil (I), is a herbicide used in amounts up

to 24 lb per acre to control a wide range of grasses and broad-leaf weeds and generally is
considered to be rather persistent (Hull 1970). However, Kearney et al. (1969) reported
that a 1 ppm aqueous solution of bromacil was completely decomposed in 10 min when
exposed to ultraviolet (UV) light at 254 nm, although a 10 ppm solution was much
more resistant to phototysis. Thin solid films of bromacil also were reported to be
degraded rapidly by the same UV light (Jordan et al. 1965), but in neither instance were
any products identified. The purpose of the present investigation was to reexamine the
light stability under more natural conditions and to identify products of the sunlight
photodecomposition of aqueous solutions of bromacil with special attention to possible
formation of 5-bromouracil, which has been reported to be a carcinogen (McGahen and
Hoffman, 1963a, 1963b, 1966).

Materials and m e t h o d s

5-bromo-3-sec-butyl-6-methyluracil (I). This was an analytical standard [E.I. duPont

de Nemours and Company, mp 158-159°C (Lit. 158-159°C) (Hull, 1970)].

5-bromo-6-methyluracil (III). 6-Methyluracil (3.8 g, 0.03 mote) was suspended in 30%

aqueous hydrogen peroxide (6.3 ml, 0.08 mole) at 0°C, and 9 ml (0.08 mole) of 48%
aqueous hydrobromic acid was added dropwise to the stirred suspension while the tem-
perature was held below 35°C. After being stored overnight, the precipitated solid was
isolated by filtration, washed with cold water, dried, and recrystallized from water to give
III (4.7 g, 73%) which decomposed at 237°C [Lit. 240-242°C (dec), (Elderfietd and
Prasad 1960)].

Anal Calcd. for CsHsBrN202 : C 29.30, H 2.46, N 13.67. Found: C 29.26, H 2.39,
N 13.59.

Archives of Environmental Contamination

and Toxicology, Vol. 2, No. l, 1974
© 1974 by Springer-Verlag New York Inc.
4 K.W. Moitanen and D. G. Crosby

Infrared (IR) spectrum: 3356 (Nit), 3247 (NH), 1730 (CO), and 1669 (CO) cm-1.
Nuclear magnetic resonance (NMR) spectrum: 2.05 8 (CH3) and 7.36 8 (NH). Ultraviolet
(UV) spectrum: ~tma x 197 and 274 nm.

5-bromo-l,3,6-trimethyluracil (IV). Ten ml of isobutyl alcohol was used to dissolve

5-bromo-6-methyluracil (100 mg), which was then treated with 100 ml of ethereal
diazomethane and allowed to stand overnight. The alcohol and ether were removed on a
rotary evaporator, and the residue was recrystallized from ethanol to give 61 mg of IV,
mp 141-142°C [Lit. 141-142°C (Namirski and Wojciechowski 1967)].

IR spectrum: 1728 (CO) and 1661 (CO) cm-1. l~lass spectrum: m/e 232 (parent),
175 (base, CsH6BrNO ).

Photolysis. Laboratory irradiation of aqueous solutions of bromacil and its photo-

products was performed in a preparative-scale photoreactor (Crosby and Tang 1969),
which closely simulated the effects of sunlight. Amounts of photoproducts sufficient for
isolation and identification were prepared in this equipment, starting with 200-ppm
solutions of I in deionized water. Irradiations in outdoor summer sunlight were conducted
with one liter volumes of solutions through which filtered air was bubbled to ensure
aerobic conditions and agitation. Volume was kept constant by frequent additions of
deionized water.

The stability of I toward sunlight wavelengths was determined by irradiating a 10-ppm

aqueous solution for 6 days in the photoreactor while air was bubbled through it.
Repetition with the lamp turned off provided the dark control. Both solutions were
analyzed by gas-liquid chromatography (GLC) and thin-layer chromatography (TLC). The
same procedure was used to examine the stability of III, and the products were analyzed
by combined gas chromatography-mass spectrometry (GC-MS).

After four (summer) months of irradiation, both the indoor and outdoor photolysates
were extracted with five 250-ml portions of redistilled benzene, and the combined
extracts were evaporated to about 1 ml under vacuum and examined by GLC and TLC.
The aqueous phase was reduced to dryness on a rotary evaporator, and the residue
dissolved in 10 ml of methanol and methylated with excess ethereal diazomethane. The
resulting ether solution was evaporated to about 1 ml under a stream of nitrogen and
analyzed by GLC and TLC.

Chromatography. An F&M Model 720 chromatograph equipped with a thermal con-

ductivity detector and a 2 ft × 1/8 in. (id) stainless steel column containing 2% SE-30
silicone gum on 60/80 mesh, acid-washed, DMCS-treated Chromosorb G (Perco Supplies,
San Gabriel, Calif.) was used for GLC. The initial column temperature was 100°C; final
column temperature 250°C; program rate 10°C/min; injection port temperature 250°C;
detector temperature 300°C; helium carrier gas flow rate 40 ml/min.

Combined gas chromatography-mass spectrometry (GC-MS) was accomplished with a

Finnegan Model 3000 Peak Identifier equipped with a 4 ft × 2 mm (id) glass column
 The Photodecomposition of Bromacil 5

containing 5% OV-17 on 60/80 mesh, acid-washed, DMCS-treated Chromosorb G. The

initial column temperature was 70°C; final column temperature 230°C; program rate
10°C/min; injection port temperature 220°C; separator temperature 250°C; helium
carrier gas flow rate 15 ml/min.

TLC was carried out on Brinkmann Silica Gel F-254 (0.5 mm thickness) containing 1%
zinc orthosilicate:manganese phosphor, with water-saturated n-butanol as developing
solvent, and spots were detected by fluorescence quenching.

Photoproduets. Unchanged bromacil was eluted at 183°C and identified by comparison

of its elution temperature and IR spectrum with those of the starting material. The single,
methylated photolysis product of the aqueous fraction was collected in a glass capillary
tube as it eluted at 165°C, purified by rechromatography, and identified by comparison
of its elution temperature and IR spectrum with those of an authentic specimen.

The Rf values for bromacit and 5-bromo-6-methyluracil were 0.74 and 0.68, respec-
tively. No other substances were detected within a detection limit of 1 gg.

Results and discussion

Although bromacil absorbs UV light up into the sunlight region (Xmax277 nm),
benzene extracts of photolysis mixtures contained only unreacted bromacil. The aqueous
phase contained only a single photoproduct, 5-bromo-6-methyluracil (III), formed in
very low yields and isolated as the more volatile 1,3-dimethyl derivative (IV) (Fig. 1). The
same results were obtained when a 1-ppm solution was irradiated for 2 weeks. Decom-
position of the herbicide was slow; 96% still remained unchanged after irradiation of a
10-ppm solution in the photoreactor for 6 days, and the yield of III was only 200 #g
(2.2%). The rapid breakdown reported by Kearney etal. (t969)and Jordan et al. (1965)
could be due to their use of the energetic 254 nm mercury arc light which does not
simulate natural conditions.

These results indicate that bromacil is rather stable toward sunlight and undergoes
only N-dealkylation, even upon prolonged irradiation. A number of other N-alkylamides
are much more readily dealkylated in light, including monuron (Crosby and Tang 1969),
metabromuron (Rosen and Strusz 1968), and diphenamid (Rosen 1967). Bromacil's
stability to photooxidation is unexpected in view of the normally reactive secondary-
alkyt group and the reported photolytic dealkylation of the analogous thymine derivative,
1,3,5-trimethyturacil, in aqueous solution (Atcantara and Wang 1965). The facile addition
of water to the 5,6~ouble bond of 1,3-dimethyl-5-fluorouracil followed by dehydro-
halogenation (Fikus et al. 1964; Fikus et al. 1965; Lozeron et al. 1964), and the formation
of 5-bromouracil dimers (Smith 1963, 1964) in irradiated aqueous media make the
limited reactivity of bromacil even more surprising; differences in the energy of irradiation
again may be responsible. Since N-dealkylation was the only type of reaction observed in
our experiments, an unstable intermediate carbinolimide such as II would be expected
and has been isolated as a product of the metabolism of bromacil by plants (Gardiner et al.
6 K.W. Moilanen and D. G. Crosby

H CH 3
I I
CH2N2 w
Et20
Br H MeOH Br N~-CH3

H Light/,, ~ ' ~ O
I
N /
/ ~ , N2U
O2' (111)
% (IV)

Br'/ ~ ~CH-CH 3
- .
1 - .

~,)
H~Cy~N-.
|°".~oll
I
H~c..N~\, I

B r @ N"Cl__CH3 H
g I
CH2CH 3
o
_ (ll) _ (v)

Fig. 1. Photodecomposition of bromacil in water.

1969a) and animals (Gardmer et al. 1969b). If present during photolysis, it was below
the limit of TLC detection.

Dealkylation appears to be the rate-limiting step in the photolysis of I. Irradiation of a

lO-ppm aqueous solution of the photoproduct II! for 6 days followed by methylation
and analysis by GC-MS indicated an 85% conversion to four volatile substances (Table I).
The major product, 6-methyluracil (V), represented a 37% yield. A substance eluting at
very high temperature (230°C) provided a mass spectrum identical to that of III, suggest-
ing dissociation of dimer (Smith 1963, 1964). Consequently, III can be expected to

Table I. Photolysis of 5-bromo-6-methyluracil

Elution Peak area Parent

Peak no. temperature, ° C mm 2 m/e Assignmenta

1 73 159 84 VIII
2 111 1050 154 V
3 175 429 172 VII
4 192 423 232 III
5 230 763 232 DimerofIII

aMethylated derivatives.
 The Photodecomposition of Bromacil 7

appear at only very low levels during photolysis of I, and the related 5-bromouracit which
has been reported to be carcinogenic (McGahen and Hoffman 1963a, 1963b, 1966) was
never observed.

Neither of the other two photoproducts contained bromine, and their mass spectra
were consistent with the structures shown below.

0
HO1 4 ~ 1 ~ N/ H

N~N~ H
H OH

(vl) (viii)

The addition of a molecule of water to the 5,6-double bond of V would result in the
formation of 5-hydroxy-6-methyl-5,6-dihydrouracil (VI) as reflected in an m/e of 172
for its methylated derivative (VI1). Subsequent photooxidation could provide
2-hydroxyimidazole (Vlll) m/e 84, which would not be expected to undergo methylation
with diazomethane.

Conclusions
The slow breakdown of bromacil in sunlight indicates that photodecomposition
probably makes only a minor contribution to the environmental disappearance of this
herbicide. However, photolysis might become important in the presence of natural
photosensitizers (Ross and Crosby 1973), which could accelerate N-dealkylation to III in
water with subsequent rapid degradation.

Acknowledgments
This study was supported in part by USDA Regional Research Project W-45. Technical
assistance was provided by Michael Hardesty, Alson Lee, and George F. Mallett.

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Manuscript received June 7, 1973; accepted August 15, 1973