REPELLENTS AND TOXICANTS FOR AQUATIC INVERTEBRATE ANIMALS FROM URETHANES OF 1-HALOGEN SUBSTITUTED ALKYNES AND COMPOSITIONS CONTAINING SAME AND USES THEREOF

REPULSIFS ET TOXIQUES POUR INVERTEBRES AQUATIQUES, OBTENUS A PARTIR D'URETHANES DE DERIVES DE SUBSTITUTION D'ALCYNES HALOGENES EN 1; COMPOSITIONS RENFERMANT CES PRODUITS ET LEURUTILISATION

English Abstract

ABSTRACT
The invention comprises use of compounds selected from the
group of 1-iodo substituted alkynes as repellents and toxicants
of aquatic invertebrate animals. Compositions containing ure-
thanes of 1-iodo substituted alkynes and methods for employing
them as such repellents and toxicants are also disclosed and
claimed. The invention more specifically includes the use of
3-iodo-2-propynyl-n-butyl carbamate and compositions containing
it for control of undesirable and harmful aquatic invertebrate
animals. The repellent activity of these carbamates induces an
avoidance response in the aquatic invertebrate animals. In
addition, non-motile animal aquatic pests, particularly those
involved in biofouling, are killed by the toxicants of the 1-iodo
substituted alkyne group of compounds.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed, are defined as follows:
1. Compositions, adapted for repelling,
controlling and destroying aquatic invertebrate animals
which contain effective concentrations of urethanes of 1-
halogen substituted alkynes having the formula
<IMG>
in which R is selected from the group consisting of
substituted or unsubstituted alkyl, aralkyl, alkaryl,
alkenyl, cycloalkyl, and cycloalkenyl groups having one to
not more than 20 carbon atoms and having one to three
linkages corresponding to m and n, and m and n are whole
number integers between 1 and 3 and may be the same or
different, and a carrier therefor.
2. Compositions adapted for repelling,
controlling, and destroying the growth of aquatic in-
vertebrate undesirable animals which contain effective
concentrations of urethanes of 1-iodo substituted alkynes
having the formula:
<IMG>
in which R is selected from the group consisting of sub-
stituted or unsubstituted alkyl, aryl, aralkyl, alkaryl,
alkenyl, cycloalkyl, and cycloalkenyl groups having one
to not more than 20 carbon atoms and having one to three
linkages corresponding to m and n, and m and n are whole
number integers between 1 and 3 and may be the same or
different, and a carrier therefor.
-21-

3. The composition of Claim 2 in which the
urethane of 1-iodo substituted alkyne is 3-iodo-2-
propynyl-n-butyl carbamate.
4. Compositions, adapted for repelling,
controlling, and destroying aquatic invertebrate animals
which contain effective concentrations of urethanes of 1-
halogen substituted alkynes having the formula
<IMG>
in which R is selected from the group of cycloalkyl,
alkyl, aralkyl and substituted aryl groups, and m and n
are whole number integers between 1 and 3 and may be the
same or different, and a carrier therefor.
5. Compositions, adapted for repelling,
controlling, and destroying aquatic invertebrate animals
which contain effective concentrations of urethanes of 1-
iodo substituted alkynes having the formula
<IMG>
in which R is selected from the group consisting of sub-
stituted or unsubstituted alkyl, aryl, aralkyl, alkaryl,
alkenyl, cycloalkyl, and cycloalkenyl groups having one
to not more than 20 carbon atoms and having one to three
linkages corresponding to m and n, and m and n are whole
number integers between 1 and 3 and may be the same or
different, and a carrier therefor.
6. Coating compositions, adapted for con-
trolling and destroying aquatic invertebrate pests
which contain effective concentrations of urethanes of 1-
iodo substituted alkynes having the formula
-22-

<IMG>
in which R is selected from the group consisting of sub-
stituted or unsubstituted alkyl, aryl, aralkyl, alkaryl,
alkenyl, cycloalkyl, and cycloalkenyl groups having one
to not more than 20 carbon atoms and having one to
three linkages corresponding to m and n, and m and n are
whole number integers between 1 and 3 and may be the same
or different, and a carrier therefor.
7. The compositions of Claim 6 in which m is
3 in the formula of the urethane compound.
8. The compositions of Claim 6 in which n is
1 in the formula of the urethane compound.
9. The compositions of Claim 6 in which n is
2 in the formula of the urethane compound.
10. The compositions of Claim 6 in which n is
3 in the formula of the urethane compound.
11. The compositions of Claim 6 in which the
urethane of 1-iodo substituted alkyne is 3-iodo-2-
propynyl-n-butyl carbamate.
12. The method for repelling, controlling, and
destroying aquatic invertebrate animals which comprises
contacting said animals with compositions containing at
least one compound selected from the group consisting of
urethanes of 1-iodo substituted alkynes, having the
formula
<IMG>
in which R is selected from the group consisting of sub-
stituted or unsubstituted alkyl, aryl, aralkyl, alkaryl,
alkenyl, cycloalkyl, and cycloalkenyl groups having one
-23-

to not more than 20 carbon atoms and having one to three
linkages corresponding to m and n, and m and n are whole
number integers between 1 and 3 and may be the same or
different, and a carrier therefor.
13. The method of Claim 12 in which m is 1 in
the formula of the urethane compound.
14. The method of Claim 12 in which m is 2 in
the formula of the urethane compound.
15. The method of Claim 12 in which m is 3 in
the formula of the urethane compound.
16. The method of Claim 12 in which n is 1 in
the formula of the urethane compound.
17. The method of Claim 12 in which n is 2 in
the formula of the urethane compound.
18. The method of Claim 12 in which the
urethane of l-iodo substituted alkyne is 3-iodo-2-
propynyl-n-butyl carbamate.
19. The method of Claim 12 in which the aquatic
animals are those which cause or contribute to marine bio-
fouling.
20. The method of Claim 12 in which the aquatic
animals are those which cause or contribute to the des-
truction of wood or wood products in aquatic systems.
21. The method of Claim 12 in which the said
urethanes are repellents and toxicants for undesireable
aquatic invertebrate animals.
22. The method of Claim 12 in which the said
urethanes are repellents for motile aquatic invertebrate
animals thereby avoiding the toxic activities of said
animals.
-24-

23. The method for repelling or destroying
aquatic invertebrate life forms with compositions
containing at least one compound selected from the group
consisting of urethanes of l-iodo substituted alkynes,
having the formula
<IMG>
in which R is selected from the group consisting of
substituted or unsubstituted alkyl, aryl, aralkyl,
alkaryl, alkenyl, cycloalkyl, and cycloalkenyl groups
having one to not more than 20 carbon atoms and having one
to three linkages corresponding to m and n, and m and n
are whole number integers between 1 and 3 and may be the
same or different, and a carrier therefor.
24. The method of Claim 23 in which m is 1 in
the formula of the urethane compound.
25. The method of Claim 23 in which m is 2 in
the formula of the urethane compound.
-25-

26. The method of Claim 23 in which the life forms are
protozoa.
27. The method of Claim 23 in which the life forms are
aquatic mollusks.
28. The method of Claim 23 in which the life forms are
aquatic worms.
29. The method of Claim 23 in which the life forms are
aquatic snails.
30. The method of Claim 23 in which the life forms are
mosquito larvae.
31. The method of Claim 23 in which the life forms are
tunicates.
32. The method of Claim 23 in which the life forms are
barnacles.
33. The method of Claim 23 in which the life forms are
coelenterates.
-26-

Description

5~3~27
FIELD OF THE INVENTION
_ _ _
The invention generally comprises the use
and methods of use of urethanes of l-iodo substituted
alkynes (carbamates) as repellents and toxicants for
the control of aquatic invertebrate animals. Com-
positions containing these compounds are also a p~art
of the invention.
BACKGROUND OF THE INVENTION
. _
U.S. Patent 3,923,870 describes the s~nthe-
sis of urethanes of l-halogen substit~ted alkynes and
their fungicidal actlvity and use in compo~itions and
various matrices as fungicides.
U.S. Patent 4,276,211 describes the ~se ~f
urethanes of l-halogen substituted alkynes and cOm-
binations of these compounds with epoxides to pr-ovide
color stabilized fungicides for use in coatings.
Certain carbamates have been employed as
insec~icides and herbicides. The insecticlde Seven
(carbamyl or naphthyl methyl carbamate3 is known ta be
algacidal in the range between 1 and 100 ppm (100
yg./ml.). However, even when tested at 10~0 ppm, it
only reduced the population of an axenic culture of
Chlorella pyrenoidosa by 30% (Christie, 196~9, 'iPesti-
cide Microbiology").
ZECTRAN (trade mark), a mexacarbate form-l-
lation, has been claimed to prevent photosynthesis in
blue green alg~ae (bacteria). However, in "normall'
spray applications it did not pose a threat to a~atic
algae (Snyder and Sharidan,1974). This formulation,
; :
: .
. .. .
. ' '' .
.

1~58~7
zectran, was not intended to be use~d as an algacide
and is, therefore, not particularly usèful for that
purpose.
Phenylcarbamates, freq~entLy employ~ as
herbicides, have demonstrated activi~y a~ains~ bl~e
green algae (bacteria). PROPHAM, CHLOROPROP~AM and
BARBAN (trade marks) caused a 50% red~ctio~n in th~è
growth of blue green algae in the range bet~een 0,3
and 70 ppm (data from Hill and Wrigh~t, 1978). ~a~ban
did not inhibit all of the algal species tested, Li~e
Seven and Zectran, the phenyl carbamates a-~e n~
structurally speaking, urethanes of l-halo~n su~-
stituted alkynes.
Compounds and compositions o;ft~n~e~-pl~yed
against aquatic pests include vario~s comp~o~nds~ of
copper, tin and zinc, creosote, haloge~na-~ed ph~ ls
.
and others. Inexpensive copper, tin a~d zi;nc o~x~des~
are employed because of low cost rather~than hi~ ~
activity. More expensive organometallic co~pourlds àrè
employed because of high activity against partia~LaP
; ~ organisms or groups of organisms. Each ~ th~e ~no~
toxicants has its own unique and specifi~ biocidal
spectrum of activity and most have disadvantages
including environmental problems.
It has also been known in the past to ~se
:~
mercury compounds as marine and aquatic toxica~nts.
~ They have limited efectiveness and toxicity short-
.~ ,
comings.
Tributyl tin oxide has been used but it is
~ 30 relatively expensive for these purposes and shaws
; unsatisfactory stability for exterior exposure.
,
-4-
,~,~
,
`
:

~ 582~:7
Although some various compounds have been employed for
limited use in lakes, ponds and areas of stagnant water, there
; has not been a wide recognition of the need Eor algacides in
coatings until recently. It has been found possible to "load"
certain compositions with such materials as zinc oxide but this
causes problems in pigmented paints and coatings, has low
algacidal activity and gives stability problems with coatings.
For the special application of use in water towers such as
cooling and holding towers, such materials as chlorine and sodium
hypochlorite have been used especially as al~acides. However,
these materials are considered to be unacceptable by the
Environmental Protection Agency and are potentially
environmentally hazardous when so used.
SUMMARY OF THE INVENTION
An object of the invention is to employ generally the ure-
thanes of l-halogen substituted alkynes as repellents and
toxicants for destruction and control of aquatic invertebrate
animals including but not limited thereto aquatic protozoa,
hydrozoa, bryozoa, planaria, barnacles, shipworms, snails,
mussels, mosquito larvae, and tunicates.
Another objective is to describe compositions including but
not limited thereto, coating compositions, protective composi-
tions, and other compositions and the like but not limited thereto
for the control of aquatic invêrtebrate animals.
A further object is the disclosure and description of methods
using such various compositions to control aquatic invertebrate
animals in and~or on in conjunction with paints, ~oatings,
caulkings, linings, sealant~, sprays, lacquers, finishing composi-
tions, polishes, wood, mortar, concrete, cement, fillers, molding
~ compounds, waxes, resins, polymers, fibers and the like.
; -5-
- .
.

1'~58227
D13TAILl~l) nESCRIPTION OF T~IE INVENTION
This invention involves the use of urethanes of l-halogen
substituted alkynes to repel, control, and prevent the growth of
aquatic invertebrate animals and to kill already existing animals
of this type. These compounds have been found to have repellent
and toxicant activities are derivatives of l~iodo-substituted
; alkynes having the generic formula:
O
[ ~ ( 2)n ]m
where R is selected from the group consisting of substituted or
unsubstituted alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl,
and cycloalkenyl groups having from one to not more than 20
carbon atoms and having from one to three linkages corresponding
to m and n, and m and n are whole numher inte~ers between 1 and
3, and may be the same or different.
These compounds have been shown to have many advanta~es as
algacides for controlling and destroying many different species
of the aquatic invertebrates. They are very stable even when
incorporated into aqueous and non-aqueous compositions including
seawater, and are deactivated and/or destroyed only by prolonged
~xposures to high temperatures. In addition, they have been
shown to be relatively harmless to useful motile vertebrate
animals .
Also, they possess only low toxicity towards animals, birds
and other wildlife and domestic animals and toward man. Conse-
quently, their use in the compositions described and claimed
herein require only the usual good practice and procedures in
handling and such precautions as are well established and in use
for handling commercial, household, and marine biocides and
toxicants.

~2S8227
These urethane compounds can be combined with other biocides
as desired to both broaden and enhance their activity and extend
the areas of their usefulness for the aquatic invertebrates.
The compositions in which they are used may contain a rela-
tive wide variety of components such as are well known in the
art. In many instances, they will be used in seawater.
The cornpounds useful in the invention may be used when
generally employed as repellen-ts and toxicants in concentrations
from about 0.001 percent up to about 12.0 percent by weight, in
some cases depending on their stabilities in the compositions and
media employed including whether they are aqueous or non-aqueous.
In some instances, the compounds may be employed as premixed
dispersions. ~hey may also be prepared as solutions or disper-
sions and thereafter added to the aqueous medium in which they
are employed. For examples, 3-iodo-2-propynyl-n-butyl carbamate
is found to be soluble in water at a level of about 150-200 parts
per million.
In all instances it is necessary to employ an effective
amount (concentration) of the urethanes to accomplish control
and/or destruction of the particular species which is to be
repelled, controlled or destroyed. For instance, in some cases,
it may be necessary to emp]oy up to approximately 15 percent by
weight of t~e compounds to destroy certain undesirable marine
animals but a lesser concentration will function effectively as a
repellent.
For the uses descri~ed h~rein, the ure-thanes of l-halogen
substituted ~lkynes, dissolved or solubili~ed in water, can he
incorporated into or coated onto a wide variety of compositions
which require protection and freedom from marine animals, in-
cluding wood and mortar, and many paints, coakings, caulkings,
fillers and the like. Urethanes of l-halogen substituted alkynes

1258~:7
are active for control against aquatic syecies ~ound in marine,
fxesh water, terrestrial and aerial situations. They are also
ac-tive against certain species found in water cooling towers,
irrigation canals and in growth on mortar and wood and find use
as especially valuable agents when used for these ob~ectives.
The compositions may be for example, all types of water-based
latex paints including acrylic and PVA latex paints and chlorinated
rubber-vinyl paints, oil alkyd paints, oil hased stains, pigmented
paints and protective and other types of compositions, rubber
and/or asphalt containing coatings, inorganic and polymeric
caulkings, molding materials, sealants, silicone compositions,
liquid compositions, hoth aqueous and non-aqueous adapted for
painting, dipping and/or spraying as well as other types o~
compositions for the many widely used applications of such
materials.
It has also heen found that these repellent and toxicant
compounds are particularly valuahle for applications in clogging
problems in irrigation ditches, canals, conduits, as well as
around doc~s and marinas and on water craft and the like where
the marine animals may be particularly troublesome and difficult
to control.
Urethanes of l-halogen substituted alkynes have a unique
spectrum of activity against aquatic pest~ involved in biofouling.
They are active against wood boring aquatic invertebrates and
repellent towards other aquatic invertehrates. Aquatic inverte-
brates demonstrating the avoidance response can be desirable
species whlch escape to safety. They can also be undesirable
specie which settle on unprotected substrates such as wood,
resins, fibrous materials, hair, wool, paper and paper substi-
tutes.

~ 32~7
In particular, and of this group, the ure-thane compound
3-iodo-2-propynyl-n-butyl carbamate ~known as Polyphase, a trade-
name of ~roy Chemical Corporation) has been found highly effec-
tive and useful both as a repellent and as a toxicant.
In another feature of the invention, the group of novel
urethanes of 1- odohydroxy alkynes having the Eormula
[I-C_C-(C~2)n-0-C-N~I]mR in which R is selected from the group con-
sisting of aralkyl anfl substituted aryl groups~ and m and n arewhole number integers between 1 and 3 and may be the same or
different have been found highly effective.
The individual species which were tested are shown and
described more completely in the Examples, as shown by the data,
the compounds were highly effectlve in repelling and destroying
the species tested.
Examples which are set forth below are intended for illus-
txative purposes only. The data of the tables and the test
results are presented to exemplify the use of the compounds as
repellents and toxicants for aquatic invertebrate animals but are
not intended to limit the invention specifically thereto or to
limit the compounds and compositions in their activity against
the aquatic invertebrate animals or to any particular classes or
species or to the speciic amounts or concentrations of the
carbamates employed to control the species tested. It is well
known in the art tha-t it is usually easier to repel the animals
than it is to kill an already existing and growing population.
It is also known to be easier -to control a small rather than a
large population of marine animals. Time is also an important
factor.

8;~27
EXAMPLE 1
Agnotobiotic cultures of pro-tozoa were obtained from Wardls
Natural Science Estahlishment, Rochester, New Yo~k. In carrying
out the experiments described below, cultures were transferred to
fresh media, incubated for a suitable length of time at ambient
temperature, and examined microscopically for growth to estahlish
effectiveness of the compounds and/or compositions.
Known volumes of Eresh culture having adequate growth were
employed as inocula. Depending upon the species being studied,
tubes receiviny the inocula contained liquid media and/or sterile
water (controls). Known volumes of aqueous solutions containing
3-iodo-2~propynyl-n-butyl carbamate were added and the concentra-
tion of the carbamate calculated from the total volum~.
The test cultures were incubated for a suitabla controlled
length of time and then examined microscopically. ~ctive protozoa
were observed in controls and at failing levels of ~he compound(s)
being tested. The absence of protozoa inaicated that that level
had effectively killed the protozoa.
The protozoa employed in these tests are usually found in
many kinds oE aquatic ecosystems. A number of the major and most
commonly occurring taxonomic groups of protozoa were represented
in the tests. The results were:
~ 3-iodo-2-propynyl
; n-butyl carbamate
(ppm)
Protozoan Alive Killed
~ctinospherium 9 16
Blepharisma 14 16
Chilomonas 15 25
Paramecium 9 16
Tetrahymena 9 16
:
-10-

~5~7
In addition, these carhamate compounds may exhihit varying
degrees of toxicity as well as repellancy characteristics toward
motile aquatic life in general. The fact -that they also exhibit
characteristics of repellancy limits and modifies their toxic
effects and since, usually, large volumes of water are involved,
this serves as an effective diluent.
EXAMPLE 2
Axenic cultures of protozoa were obtained from either Ward's
Natural Science Establishment or the American Type Culture
Collection. Cultures were transferred to fresh meclia, incubated
for suitable well established lengths of time and temperatures
and examined microscopically for growth.
Known volumes of fresh cultures shown as having adequate
growth by examination were employed as inocula. Dependinq upon
the species, tubes receiving the inocula contained known volumes
of sterile agar ~slants) and overlays, sterile liquid media
and/or sterile water (controls). Known volumes of aqueous
3-iodo-2-propynyl-n-butyl-carbamate solutions were added and the
carbamate concentration cal~ulated from the total liquid volume.
The volume of agar was disregarded in the calculation. Therefore,
the values obtained as calculated represent ~he highest level of
exposure during the test.
The test cultures were incubated for a suitable length of
time at a suitable temperature and examined microscopically.
Active protozoa were observed in controls and at failing levels
~levels with low or inadequate activity). The absence of protozoc
indicated that that level had effec-tively killed the protozoa.
Protoæoa as described above are pathogenic in invertebrate
and/or vertebrate animals. In one instance (Tsypanosoma cyclops)
the pathogen came from monkeys and was a potential human pathogen
(Class III). The results of these -tests were:

125~227
3-iodo-2-propynyl
n-butyl carbamate
(ppm)
Protozoan Alive Killed
Crithidia faciulata 17 29
Herpotomonas muscarum 17 23
Herpetomonas samuelpessoai 29 38
Leishmania adleri 40 46
; Leishmania algamae 60 65
Leishmania hertigii 65 70
Leishmania tarentolae 55 60
Tritrichomona augusta 10 15
; Trypanosoma cyclops 30 40
Trypanosoma ranarum 29 44
EXAMPLE 3
'
Specimens of the scyphozoan urelia aurita were obtained
from the Marine Biological Laboratory at Woods Hole, Mass. These
specimens were maintained in well aerated aquaria provided with
under-the-gravel filters, limestone gravel botto~s and pieces of
wood to provide surfaces for attachment. The suhstituted iodo
alkyne, (3-iodo-2-propynyl-N-butyl carbamate) solutions were
prepared in artiEicial seawater and tests carried out in 1.5 1.
aquaria. These aquaria were similar to holding tanks, except
that seawater was not filtered and aeration was provided through
air stomas.
Animals were held in the^solutions over a week end period
(2-2~ days) and examined. Animals killed by the solutions did
` not demonstrate an avoidance response to touch and rapidly decom-
; posed. Living animals demonstrated an avoidance response and
moved about when returned to the holding tanks. The lowest level
which was toxic and killed Aurelia aurita was 10 ppm (20 ~g/ml)
of 3~iodo-2~propynyl-n-butyl carbamate.
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1:~58;~27
The following compounds are also found to be ~qually or
somewhat less toxic towards Aurelia aurita:
4-iodo-3-bukynyl methyl carhamate
3-iodo-2-propynyl cyclohexyl carbamate
3-io~o--2-propynyl-n-octyl carbamate
3-iodo-2-propynyl phenyl carbamate
3-iodo-2-propynyl-4-chlorophenyl carbamate
di (3-iodo-2-propynyl) 4, 41-diphenyl methane carbamate
3-iodo-2-propynyl benzyl carbamate
EXAMPLE 4
,~ ._
Hydroids belonging to the genera Obelia and Tubularia were
tested as described in Example 1, except that the hydroids were
attached to marine algae which were placed in the tes-t aquaria.
Obelia and Tubularia were killed by 1 ppm (1 ~g/ml.~ of the
carbamate which was the lowest level tested. Suitable controls
without use of the carbamate contained living hydroids at the end
of the experiments.
,,
EXAMPLE 5
Two species of bryozoa were obtained and tested as described
in Example 1. The first species came from the Marine Biological
Laboratory and was killed by 5 ppm (5 ~g/ml.) of 3~iodo-2 propynyl-
n-butyl carbamate. The second species was obtained from Cape
I Fear Biolo~ical Supply Co., Southport, North Carolina and was
killed by 25 ppm (25 llg/ml.) of 3-iodo-2-propynyl-n-butyl
carhamate.
EXAMPLE 6
Turbatrix medium (Ward's Natural ~cience ~stablishment) was
combined with an aqueous 3-iodo~2-propynyl-n-butyl carbamate
-13-
.
'

2~7
~solution (100 ppm) in screw cap test tubes in various ratios.
~The resulting levels were 10, 20, 30, 40 and 50 ppm of the car-
bamate. Controls were prepared by combining the medium with
distilled water. The tubes were each inoculated with one drop of
active Turbatrix aceti culture (Ward's) and incubated for 7 days.
Active animals were found in all controls and at 10 ppm.
The nematodes were killed at 20 ppm and higher and no animals
were observed microscopically in the solutions at the killing
concentration level.
The following compounds are also found to be equally or
somewhat less to~ic towards Turbatrix aceti: ¦
4-iodo-3-butynyl methyl carbamate
3-iodo-2-propynyl cyclohexyl carbamate
3-iodo-2-propynyl-n-octyl carbamate
3-iodo-2-propynyl phenyl carbamate
3-iodo-2-propynyl-4-chlorophenyl carbamate
di (3-iodo-2-propynyl) 4, 41-diphenyl methane carbamate
3-iodo-2-propynyl benzyl carbamate
EXAMPLE 7
_ .
A wood boring isopod-Sthaeroma quadridemtum - species was
ohtained from Cape Fear Biological Supply Co. and tested for its
sensitivity to 3-iodo-2-propynyl-n-butyl carbamate. Solutions
having a volume of 10.0 ml. were prepared in test tubes and the
animals transferred to the tubes. The lowest level of carbamate
which killed Sthaeroma quadridentum was 30.0 ppm (30 ~g/ml.~.
EXAMPLE 8
Three cultures of different planaria representing different
genera and species were obtained from Ward's Natural Science
Establishment. Animals were picked up on the end of a spatula
-14-
!~

1 ~L~.5~227
i and transferred to test tubes containing aqueous 3-iodo-2-propynyl-
N-butyl carbamate solutions. Five (5) animals were employed in
each test at 0 (distilled water control), 10, 18, 25 and 31 ppm
of carbamate. All of the animals belonging to the three genera
survived in the distilled water control. All were killed in less
than two hours at 10 ppm and higher.
The following compounds are also found to be equally or
somewhat less toxic towards Planaria: !
4-iodo-3-butynyl methyl carbamate
3-iodo-2-propynyl cyclohexyl carbamate
3-iodo-2-propynyl-n-octyl carbamate
3-iodo-2-propynyl phenyl carbamate
3-iodo-~-propynyl-4-chlorophenyl carbamate
di (3-iodo-2-propynyl) 4, 4 -diphenyl methane carbamate
3-iodo-2-propynyl benzyl carbamate
:
EXAMPLE 9
Barnacles belonging to the genera Balanus, Chathamalus and
Polycites were obtained from the Marine Biological Laboratory,
Cape Fear Biological Supply Co. and Gem Cultures, Fort Brag,
California. These animals were tested as described in Example 1.
The results of these experiments are shown in the following
Table:
Minimum Toxic
Common Name Organism Level tPPm)
l Acorn ~arnacles Balanus amphitrittii1.0
; Beburneus 0.8
Chathamalus frigilus5.0
Goose-necked Barnaclès Polycites polymerus 50.0
.'
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~ 27
RXAMPL~ 10
Two planks (h inches wide x 4 inches thick) containin~
living shipworms (Toredo bankie) were obtained f~om Cape Fear
Biological Supply Co. They were cut into one foot lengths and
held in two pails containing either artificial ~eawater or a
saturated solution of 3-iodo-2-propynyl-n-butyl carbamate in
seawater (total volume 80 liters each). After 5 days exposure,
the planks were split open with a hammer and chisel. The control
without the carbamate contained living shipworms (5 worms de-
tected), whereas all of the shipworms (7 worms) were killed by
the saturated carbamate solution.
EXAMPLE 11
A total of 100 Limnoria were removed from cultures and
placed in each 500 ml. beaker. The beakers contained 0 (control
without acetone), 0 (control with acetone), 1, 5, 10, 25 and
50 ppm 3-iodo-2-propynyl-n-butyl carbamate in filtered Auxbury
Bay seawater. The bealcers were monitored after 24, 48 and 96
hours and the number of dead Limnoria counted at the end o each
observation. The numbers were examined statistically and the
LC50 calculated to be 18.6 ppm with 95% confidence limits of
16.86 to 20.59 ppm. The data were:
3-iodo-2-propynyl-
n-butyl carbamate Number Dead (hrs.)
2448 96Total Dead
0,0 2,2~ 0,0 0,1 2,3
1 1 0 1 2
3 0 0 3
2 6 2 10
13 22 75
100 - - 100
:~
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1~582~
EXAMPh~ 12
Three species oE snails were obtained from Ward's Natural
Science Establishment. Two belonged to the gene~ra ~
(Ward's No. 87 W4121l and Planorbis (Wardls No. 87 W4161) and one
species was unidentified (Ward's No. 87 W4101). Three snails of
each species were employed in each test in aqueous 3-iodo-2-
propynyl-n-butyl carbamate solutions. The levels tested were 0
(distilled water control), 5, 10, 15, 20 and 25 ppm of the
carbamate. Snails were held in the test solutions for 24 hours.
All of the ~nails survived at 0 and 5 ppm o carbamate. All of
the snails were killed at 10 ppm and higher of the carbamate.
The following compounds were found -t:o have about the same
order of toxicity towards Ward's No. 87 W4101:
4-iodo-3-butynyl methyl carbamate
3-iodo-2-propynyl cyclohexyl carbamate
3-iodo-2-propynyl-n-octyl carbamate
3-iodo-2-propynyl phenyl carbamate
3-iodo-2-propynyl-4-chlorophenyl carbamate
di (3-iodo-2-propynyl) 41, 41-diphenyl methane carbamat
3-iodo-2-propynyl benzyl carbamate
EXAMPLE 13
The interiors of two five gallon pails were divided ver-
tically in half with a pen. Pail No. 1 had one-half painted with
an unprotected oil alkyd paint. Pail No. 2 had one~half painted
with the same unprotected oil alkyd paint and the other half with
this paint containing the equivalent of 6 Ibs. o 3-iodo-2-
propynl-n-butyl carbamate per one hundred gallons of paint.
The paint was dried for four days; the pails filled two-
thirds full with water and ten (10) Planorbis snails distributed
at random in each pail. rrhe snails had been obtained Erom Ward's
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`.

lZ5~3~2~ ~
~atural Science Establishment, Rochester, New York. The snails
were held in the pails overnight and their distribution
determined.
Snails were randomly distrihuted on painted and unpainted
surfaces in the control pail without carbamate. In the pail
painted with the carbamate con-taining paint, the snails demon-
stra-ted an avoidance response and were repelled from the car-
hamate containing paint. They were found only on the unpainted
surfaces in this pail. This example clearly shows that these
carbamate materials are repellents for snails and useful as such
in coatings and resins compositions.
EXAMPLE 14
Fresh water mussels (genus ~nio) were obtained from Ward's
Natural Science Establishment. The experimental procedure is
described in Example 1, except that sand was employed as the
bottom material and fresh water rather than seawater. The
mussels demonstrated an avoidance response and by tightly closin~
their shells were able to survive exposure to a 100 ppm of
carbamate for 24 hrs.
, ~,
EXAMPLE 15
Mosquito larvae were added to aqueous solutior.s of 3-iodo 2-
propynyl-N-butyl carbamate having a total volume of 100 ml. The
larvae were killed by a concentration of 8 ppm ~2 g/ml.) in less
than 24 hrs. Mosquito larvae survived in controls and at lower
levels.
~',
EXAMPLE 16
The sensitivity of the Tunicote StYella partita to the
carbamate was determined as described in Example 1. Styella
`.,,
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.,,.
`

partita was obtained from Cape Fear Biological Supply Co. The
lowest level which killed the animals was 25 ppm. The tunicates
are usually classified with the Urochordata, which are considered
to be lower vertebrate pests rather than invertebrates.
~ExaMpLE 17
Analogs of the 3~iodo-2-propynyl-n-butyl carbamate were
tested against acorn barnacles belonging to the species Balanus
eburneus which is commonly called the ivory barnacle. The pro-
cedure employed is described in Example 1 and the results are
shown in the following table:
Laboratory Prep Chemical Minimum
No. Structure ~ethal Con. (ppm)
~ NH-C-O-C~2-C=C-I
LL-lll-E I-C--C-CH2-0-C-NH ~ 16.0
CH3
LL-lll-F I_C_C-CH2-0-C-NH-CH2-CH3 5.0
The Examples described above include the very wide range of
aquatic pests which are known to be involved in either biofoulin~
and/or the destruction of wood in the marine environment. The
organisms killed were generally sessile pests. Some motile
invertebrates which may be considered to be desirable are re-
pelled by urethanes of the l-halogen substituted al~ynes.
However, as a consequence of these avoidance responses, unde-
sirable organisms are also repelled and thus surfaces protected
from their undesirable and destructive activities.
This patent is in no way limited to the invertebrate animals
described in the examples above. The range of activity de~on-
strate that many other invertebrates can be controlled by the use
of urethanes of l-halogen substituted alkynes.
It is also contemplated that this invention includes the
control of lower vertebrate pests which are often sessile and
11
, ~.~ ~

~2~ 7
involved in biofoullng. For instance, Example 10 contains the
results of actual experiments in which the activity of urethanes
of l-halogen substituted alkynes against this group was clearly
demonstrated.
The repellent-toxicant solutions employed in these experi-
ments were prepared by one of two methods. The fir~-t method was
carried out by dissolving 0.100 grams of the compound in
distilled water in a 1000 ml volumetric flask and bringing the
mixture to volume with water. This solution contained 100 ppm of
the compound which was subsequently diluted. The second method
was done by dissolving 1.00 grams of the compound in acetone in a
100 ml volumetric Elask, giving a solution containing 10,000 ppm
of the compound. Dilutions were made using either fresh or
seawater as required and indicated. Suitable controls containing
the same levels of acetone were employed when the second method
was used to prepare the test solutions.
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