CA1258227A - Repellents and toxicants for aquatic invertebrate animals from urethanes of 1-halogen substituted alkynes and compositions containing same and uses thereof - Google Patents
Repellents and toxicants for aquatic invertebrate animals from urethanes of 1-halogen substituted alkynes and compositions containing same and uses thereofInfo
- Publication number
- CA1258227A CA1258227A CA000451898A CA451898A CA1258227A CA 1258227 A CA1258227 A CA 1258227A CA 000451898 A CA000451898 A CA 000451898A CA 451898 A CA451898 A CA 451898A CA 1258227 A CA1258227 A CA 1258227A
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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.
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.
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.
, ,~,~
, `
:
~ 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 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 :
~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.
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 ' 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.
~,, . , .. ` ~ I
' 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 ,~ ._ 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.
,, 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.
Turbatrix medium (Ward's Natural ~cience ~stablishment) was combined with an aqueous 3-iodo~2-propynyl-n-butyl carbamate .
'
_ _ _ 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.
, ,~,~
, `
:
~ 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 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 :
~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.
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 ' 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.
~,, . , .. ` ~ I
' 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 ,~ ._ 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.
,, 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.
Turbatrix medium (Ward's Natural ~cience ~stablishment) was combined with an aqueous 3-iodo~2-propynyl-n-butyl carbamate .
'
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
~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 _ .
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.~.
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 !~
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: !
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.~.
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 !~
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 :
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 .' ~ 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.
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 :~
~ -16-.' 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 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 `.
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.
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.
, ~, 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.
~', The sensitivity of the Tunicote StYella partita to the carbamate was determined as described in Example 1. Styella `.,, .,,.
`
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 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 , ~.~ ~
~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.
.
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 .' ~ 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.
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 :~
~ -16-.' 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 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 `.
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.
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.
, ~, 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.
~', The sensitivity of the Tunicote StYella partita to the carbamate was determined as described in Example 1. Styella `.,, .,,.
`
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 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 , ~.~ ~
~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.
.
Claims (33)
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 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:
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.
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.
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 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 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 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 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.
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.
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 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.
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.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48578683A | 1983-04-18 | 1983-04-18 | |
| US485,786 | 1983-04-18 | ||
| US59115484A | 1984-03-19 | 1984-03-19 | |
| US591,154 | 1984-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258227A true CA1258227A (en) | 1989-08-08 |
Family
ID=27048478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451898A Expired CA1258227A (en) | 1983-04-18 | 1984-04-12 | Repellents and toxicants for aquatic invertebrate animals from urethanes of 1-halogen substituted alkynes and compositions containing same and uses thereof |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU577780B2 (en) |
| CA (1) | CA1258227A (en) |
| NL (1) | NL8401242A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2533331B2 (en) * | 1986-08-26 | 1996-09-11 | 住友化学工業株式会社 | Carbmate derivatives and agricultural and horticultural fungicides containing them |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923870A (en) * | 1973-07-11 | 1975-12-02 | Troy Chemical Corp | Urethanes of 1-halogen substituted alkynes |
| US4276211A (en) * | 1980-03-10 | 1981-06-30 | Troy Chemical Corporation | Stabilization composition for coating composition |
| CA1259626A (en) * | 1983-04-18 | 1989-09-19 | William Singer | Carbamates of iodo substituted alkynes and fungicidal preparations thereof |
-
1984
- 1984-04-12 CA CA000451898A patent/CA1258227A/en not_active Expired
- 1984-04-17 AU AU27019/84A patent/AU577780B2/en not_active Ceased
- 1984-04-17 NL NL8401242A patent/NL8401242A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NL8401242A (en) | 1984-11-16 |
| AU577780B2 (en) | 1988-10-06 |
| AU2701984A (en) | 1984-10-25 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |