Product
Chemistry
Science
Chapter
for
Halohydantoins
September
7,
2004
U.
S.
Environmental
Protection
Agency
Office
of
Pesticide
Programs
Antimicrobials
Division
Nov.
21,
2002
MEMORANDUM
SUBJECT:
Data
Evaluation
Record
(
DER)
for
the
product
formulations
Containing:
Dantobrom,
Dantochlor
and
Glychlor.

TO:
Ben
Chambliss,
Acting
Team
Leader,
Team
32
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C)

FROM:
A.
Najm
Shamim,
Ph.
D.,
Chemist
Regulatory
Management
Branch
Antimicrobials
Division
(
7510C).

THRU:
Connie
Welch,
Chief
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C).
Page
3
of
9
PRODUCT
CHEMISTRY
DATA
EVALUATION
RECORD
For
Product
Formulation:
(
1)
Dantobrom
(
2)
Dantochlor
(
3)
Glychlor
Active
Ingredients:
(
1)
Dantobrom
1­
Bromo­
3­
chloro­
5,5­
dimethylhydantoin
1,3­
dichloro­
5,5­
dimethylhydantoin
1,3­
dichloro­
5­
ethyl­
5­
methylhydantoin
(
2)
Dantochlor
1,3­
dichloro­
5,5­
dimethylhydantoin
1,3­
dichloro­
5­
ethyl­
5­
methylhydantoin
(
3)
Glychlor
1,3­
dichloro­
5,5­
dimethylhydantoin
BACKGROUND
Registrants
have
submitted,
in
support
of
reregistration,
six
studies
on
the
product
chemistry
of
dihalodialkydantoins.
Studies
were
specifically
submitted
for
the
following
products:
Dantobrom,
Dantochlor,
and
Glychlor.
Each
product
contains
1,3­
dichloro­
5,5­
dimethylhydantoin
as
an
active
ingredient.
However,
Dantobrom
also
contains
the
active
ingredients
1­
Bromo­
3­
chloro­
5,5­
dimethylhydantoin
and
1,3­
dichloro­
5­
ethyl­
5­
methylhydantoin
and
Dantochlor
also
contains
the
active
ingredient
1,3­
dichloro­
5­
ethyl­
5­
methylhydantoin.
These
studies
were
reviewed
for
following
the
Group
A:
Series
830­
Product
Identity,
Composition
and
Analysis
Test
Guidelines
and
the
Group
B:
Series
830­
Physical
and
Chemical
Properties
Guidelines.
The
six
studies
reviewed
include:
(
1)
Dantochlor,
Phase
III
Reregistration
Requirements,
Analysis
and
Certification
of
Product
Ingredients
(
MRID
41953­
01C);
(
2)
Preliminary
Analysis
of
Glychlor
(
6836­
109)
and
Dantochlor
(
6836­
114)
(
MRID
433159­
02);
(
3)
Glychlor,
Phase
III
Reregistration
Requirements,
Analysis
and
Certification
of
Product
Ingredients
(
MRID
419528­
01C);
(
4)
Dantobrom,
Reregistration
Phase
II
Requirements,
Analysis
and
Certification
of
Product
Ingredients
(
MRID
419527­
01C);
(
5)
Preliminary
Analysis
of
1­
Bromo­
3­
Chloro­
5,5­
Dimethylhydantoin
(
BCDMH)
(
MRID
424785­
01);
and
(
6)
an
unititled
product
chemistry
data
requirement
chapter
for
DantobromTM
S
(
MRID
350117­
010).
Page
4
of
9
FINDINGS
A.
Product
Identity,
Composition
and
Analysis
1.
Product
Identity
and
Composition
(
Guideline
#
830­
1550)
1.
Product
Names:
Dantobrom,
Dantochlor,
and
Glychlor
3.
Common
Names,
Chemical
Names,
Empirical
Formulas,
and
CAS
Numbers:

1,3­
dichloro­
5,5­
dimethylhydantoin
(
DCDMH)
=
Dichlorodimethylhydantoin
2,4­
Imidazolindinedione
C
5
H
6
Cl
2
N
2
O
2
CAS
Number
118­
52­
5
1­
Bromo­
3­
chloro­
5,5­
dimethylhydantoin
(
BCDMH)
=
Bromochlorodimethylhydantoin
2,4­
Imidazolindinedione
C
5
H
6
BrClN
2
O
2
CAS
Number
16079­
88­
2
1,3­
dichloro­
5­
ethyl­
5­
methylhydantoin
(
DCEMH)
=
Dichloroethylmethylhydantoin
2,4­
Imidazolindinedione
C
6
H
8
Cl
2
N
2
O
2
CAS
Number
89415­
87­
2
2.
Description
of
Material
Used
to
Produce
the
Product
(
Guideline
#
830­
1600)

The
starting
materials
used
to
produce
Dantobrom
 
S
and
the
specifications
and
methods
of
analysis
are
listed
in
Table
1
of
the
product
chemistry
data
requirement
document
submitted
by
the
Registrant
for
Dantobrom.
The
starting
materials
include
trisodium
salt
of
ethylenediamine
tetraacetic
acid,
aqueous
ammonia,
carbon
dioxide,
acetone,
methyl
ethyl
ketone,
hydrogen
cyanide,
sodium
bromide,
chlorine,
and
caustic
soda
3.
Description
of
Production
and
Formulation
Process
(
Guideline
#
830­
1650)

The
bromochloro­
5,5­
dialkyhydantoins
are
produced
by
the
chlorination
of
a
mixture
of
5,5­
dimethylhydantoin
(
DMH)
and
5­
ethyl­
5­
methylhydantoin
(
MEH)
in
the
presence
of
sodium
bromide.
The
mixed
hydantoins
are
produced
by
the
Bucherer­
Bergs
reaction.
The
mixture
of
5,5­
dialkylhyddantoins
is
then
halogenated.
Page
5
of
9
Preparation
of
Mixed
Hydantoins
A
stainless
steel
autoclave
is
charged
with
water,
a
trace
of
sodium
salt
of
ethylenediaminetetracetic
acid
to
chelate
soluble
iron,
and
a
20%
excess
of
29.7%
aqueous
ammonia
based
on
stoichiometry.
Carbon
dioxide
is
added
at
elevated
pressures
until
the
formation
of
ammonium
bicarbonate
is
complete
(
the
pressure
stabilizes
at
3.06
atm.
or
2325
mm
Hg).
A
molar
equivalent
of
ketones,
consisting
of
0.8
moles
acetone
and
0.2
moles
of
methyl
ethyl
ketone,
and
hydrogen
cyanide
are
reacted
at
elevated
temperatures
and
pressure
(
71
to
80
o
C,
3.06
atm.
or
2326
mm
Hg;
finished
at
4.42
atm.
or
3359
mm
Hg)
until
cyclization
is
complete.
The
aqueous
mass
is
steamed
at
atmospheric
pressure
until
its
ammonia
content
is
less
than
500
ppm,
and
water
is
added
to
restore
it
to
its
original
volume.

Preparation
of
Dantobrom
Chlorine
and
dilute
hydroxide
are
added,
in
about
10%
molar
excess,
to
the
diluted
reaction
mass
of
the
mixed
hydantoins
and
sodium
bromide
at
less
than
25

C
in
the
pH
range
of
7.2
to
7.6.
The
product
precipitates
as
it
forms.
On
reaction
completion,
the
product
is
filtered,
washed
with
water,
and
dried
at
71
to
79
o
C.

Preparation
of
Dantobrom
S
Dry
product
is
fed
from
interim
storage
to
a
hopper
which
continuously
feeds
a
two­
roll
briquetting
machine.
The
product
briquettes
are
screened
to
remove
fines
which
are
then
recycled
to
the
hopper.

4.
Discussion
of
Formation
of
Impurities
(
Guideline
#
830­
1670).

The
impurities
formed
during
the
production
of
Dantobrom
 
S
include
sodium
chloride
and
water
(
gaseous
form).
Sodium
chloride
is
the
by­
product
of
the
reaction
between
aqueous
sodium
hydroxide
and
chlorine.
It
is
removed
by
washing
the
halogenated
hydantoin
mixture
and
is
measured
by
Analytical
Method
developed
by
registrants
(
R­
136).
Water
is
given
off
during
desiccation
of
the
product
and
is
measured
by
Registrants'
Analytical
Method
R­
125A.

5.
Preliminary
Analysis
(
Guideline
#
830­
1700)

A
preliminary
analysis
study
was
provided
for
Glychlor
and
Dantochlor
(
MRID
433159­
02)
and
for
1­
Bromo­
3­
chloro­
5,5­
dimethylhydantoin
(
MRID
424785­
01).
The
preliminary
analysis
study
for
Glychlor
and
Dantochlor
included
analytical
results
on
the
appearance
and
the
percent
of
DMH
radical,
MEH
radical,
active
chlorine,
chloroform
insolubles,
and
volatiles
in
five
batches
of
the
two
test
substances.
The
analytical
results
are
presented
in
Table
1.
Page
6
of
9
Table
1:
Appearance
and
Ingredient
Concentrations
of
Dantochlor
and
Glychlor
Test
Substance
Appearance
Percent
DMHradical
Percent
MEHradical
Percent
Active
Chlorine
Percent
Chloroform
Insolubles
Percent
Volatiles
Percent
Closure1
Dantochlor
Fine,
White,
Free
Flowing,
Crystalline,
Solid,
FFVFM2
50.8
to
54.3
11.1
to
14.4
34.4
to
36.6
0.1
to
0.6
0.09
to
0.7
101
to
102
Glychlor
Fine,
White,
Free
Flowing,
Crystalline,
Solid,
FFVFM2
63.5
to
64.0
<
0.1(
below
the
detection
limit)
36.3
to
37.9
0.04
to
0.6
0.02
to
0.08
101
to
102
1.
Closure
is
the
rounded
sum
of
the
unrounded
average
ingredient
concentrations.
2.
FFVFM
=
Free
from
visible
foreign
matter.

The
preliminary
analysis
study
for
1­
Bromo­
3­
chloro­
5,5­
dimethylhydantoin
provided
the
amount
of
bromide,
chloride,
and
ionic
chloride
present
in
samples
from
five
different
lots.
Ionic
chloride
is
an
impurity
in
BCDMH.
The
mean
concentration
values
for
each
of
the
tested
lots
are
presented
in
Table
2.

Table
2:
Mean
Concentration
Values
of
Bromide,
Chloride,
and
Ionic
Chloride
in
BCDMH
Lot
Number
Percent
Bromide
Percent
Total
Chloride
Percent
Ionic
Chloride
Net
Percent
Chloride
Mean
percent
Assay
062492­
1
32.05
15.96
0.78
15.18
99.41
61092­
1
32.17
15.59
0.86
14.73
98.38
60892­
1
31.71
15.73
0.81
14.92
98.08
62692­
3
32.17
16.05
0.85
15.20
99.70
62592­
2
30.74
15.39
0.95
14.45
95.04
In
addition,
Preliminary
analysis
results
for
Glychlor,
Dantochlor,
and
Dantobrom
were
also
provided
in
MRID
419528­
01C,
419530­
01C,
and
419527­
01C,
respectively.

6.
Certified
Limits
(
Guideline
#
830­
1750).

The
certified
limits
for
Glychlor,
Dantochlor,
and
Dantobrom
were
provided
by
the
registrants
(
MRID
419528­
01C,
419530­
01C,
and
419527­
01C,
respectively).

The
registrants
provided
the
analytical
methods
for
enforcement
limits
are
for
Glychlor
(
MRID
419528­
01C,
for
Dantochlor
(
MRID
419530­
01C),
and
for
Dantobrom
(
MRID
in
419527­
01C).

7.
Submittal
of
Samples
(
Guideline
#
830­
1900)
Not
provided.
Page
7
of
9
B.
Physical
and
Chemical
Properties
Physical
and
chemical
properties
for
Dantobrom
 
S
were
provided
(
MRID
350117­
010)

1.
Color
(
Guideline
#
830­
6302).
Off­
white.

2.
Physical
State
(
Guideline
#
830­
6303)
The
test
substance
is
a
powder.

3.
Odor
(
Guideline
#
830­
6304).
A
slight
chlorine
odor.

4.
Stability
to
Sunlight,
Normal
and
Elevated
Temperatures,
Metals/
Metal
Ions
(
Guideline
#
830­
6313)
Dantobrom
is
stable
in
the
dry
state.
It
decomposes
exothermally
at
180

C.
It
is
attacked
by
strong
alkalies,
acids,
and
moisture.
It
also
will
react
with
readily
oxidizable
materials.

5.
Oxidation/
Reduction:
Chemical
Incompatibility
(
Guideline
#
830­
6314)
Dantobrom
is
an
oxidizer
and
it
will
react
with
materials
which
are
readily
oxidized
such
as
cellulosics,
lubricating
oils,
and
reducing
agents.
In
that
it
yields
oxygen
readily
to
stimulate
the
combustion
of
organic
matter,
Dantobrom
is
classified
as
an
oxidizer
according
to
49
CFR
173.151.

6.
Flammability/
Flame
Extension
(
Guideline
#
830­
6315)
Not
Applicable
7.
Explodibility
(
Guideline
#
830­
6316).
Not
Applicable.

8.
Storage
Stability
(
Guideline
#
830­
6317).
DantoBromTM
was
stored
for
18
months
period
at
room
temperature
in
a
virgin
polyethylene
bag
in
a
fiber
drum.
Total
halogen
as
bromine
was
71.5%
at
the
start
and
at
71%
at
the
end
of
the
experiment.

9.
Miscibility
(
Guideline
#
830­
6319).
Not
Applicable
10.
Corrosion
Characteristics
(
Guideline
#
830­
6320)
Dantobrom
does
not
attack
low
density
polyethylene.
It
is
not
corrosive
to
metals
in
the
complete
absence
of
water.
In
the
presence
of
traces
of
moisture
it
will
attack
galvanized
iron,
stainless
steel,
copper,
and
bronze.

11.
Dielectric
Breakdown
Voltage
(
Guideline
#
830­
6321).
Not
Applicable.

12.
pH
of
Water
Solutions
or
Suspensions
(
Guideline
#
830­
7000)
(
1%
slurry
at
25

C),
the
pH
was
determined
to
be
3.6.
Page
8
of
9
13.
UV/
VIS
Absorption
(
Guideline
#
830­
7000)
Not
Applicable.

14.
Viscosity
(
Guideline
#
830­
71000).
Not
Applicable
15.
Melting
Point/
Melting
Range
(
Guideline
#
830­
7200)
The
melting
range
of
Dantobrom
is
between
120
and
148

C.

16.
Boiling
Point/
Boiling
Range
(
Guideline
#
830­
7220).
Not
Applicable
17.
Density/
Relative
Density/
Bulk
Density
(
Guideline
#
830­
7300)
When
packed,
the
bulk
density
of
Dantobrom
is
60
lbs/
ft
3
).

18.
Dissociation
Constant
in
Water
(
Guideline
#
830­
7370)
Not
Applicable.

19.
Particle
Size,
Fiber
Length,
and
Diameter
Distribution
(
Guideline
#
830­
7520)
Not
Applicable.

20.
KOW
(
n­
Octanol/
H2O)
(
Guideline
#
830­
7550,
7560,
and
7570)
Registrants
did
not
provide
the
data.

21.
Water
Solubility:
(
Guideline
#
830­
7840,
7860).
The
solubility
of
Dantobrom
in
water
at
25

C
is
0.54
grams/
100
grams.
Dissolution
process
is
accompanied
by
hydrolysis.

22.
Vapor
Pressure
(
Guideline
#
830­
7950).
Not
Applicable.

Conclusions
and
Recommendations:

The
product
Chemistry
data
has
been
reviewed
and
is
acceptable.
However,
registrants
are
required
to
submit
the
K
OW
and
solubilities
of
the
test
substance
in
non­
aqueous
solvents.
Page
9
of
9
BIBLIOGRAPHY
Kastra,
H.
P.
(
1991)
"
Dantobrom,
Reregistration
Phase
II
Requirements,
Analysis
and
Certification
of
Product
Ingredients".
MRID#
419527­
01C.

Severs,
L.
W.
(
1992)
"
Preliminary
Analysis
of
1­
Bromo­
3­
Chloro­
5,5­
Dimethylhydantoin
(
BCDMH)".
MRID#
424785­
01.

Sloan,
R.
J.
(
1994)
"
Preliminary
Analysis
of
Glychlor
(
6836­
109)
and
Dantochlor
(
6836­
114)".
MRID#
433159­
02.

Katstra,
H.
P.
(
1991)
"
Glychlor,
Phase
II
Reregistration
Requirements,
Analysis
and
Certification
of
Product
Ingredients".
MRID#
419528­
01C.

Kastra,
H.
P.
(
1991)
"
Dantochlor,
Reregistration
Phase
II
Requirements,
Analysis
and
Certification
of
Product
Ingredients".
MRID#
419530­
01C.

Unknown
Author.
(
Unknown)
"
Product
chemistry
data
requirements".
MRID#
350117­
010.
