CA1259626A - Carbamates of iodo substituted alkynes and fungicidal preparations thereof - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

The invention comprises novel compounds from the group of 1-iodo substituted alkynes and their use as algacides. Compositions containing urethanes of 1-iodo substituted alkynes and methods for employing them as algacides 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 growth of algae and algae-like microorganisms. The carbamates according to the invention have the following formula [I-C?C-(CH2)n-O-?-NH]mR

in which R is selected from the group of aryl, aralkyl, and substituted aryl groups where the aryl group is substituted by lower alkyl or halo groups, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are both 1 when R is aryl.

Description

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BACKGROUND OF THE INVENTION
U.S. Patent 3~923~870 describes the synthesis of urethanes of l-halogen substituted alkynes and their fungicidal activity and use in compositions and various matrices as fungicides.
U~S~ Patent 4~276~211 describes the use of urethanes of l-halogen substituted alkynes and combinations of these compounds with epoxides to provide color stabilized fungicides for use in coatingsO
Certain carbamates have been employed as insect-icides and herbicides. The insecticide SevinTM (carbamyl or naphthyl methyl carbamate) is known to be algacidal in the range between 1 and 100 ppm ~g./ml.). However, even when tested at 100 ppm, it only reduced the population of an axenic culture of Chlorella pyrenoidosa by 30% (Christie, 1969, "Pesticide Microbiology").
"ZectranTM," a mexacarbate formulation has been claimed to prevent photosynthesis in blue green algae (bacteria). However, in "normal" spray applications it did not pose a threat to aquatic algae (Snyder and Sharidan, 197~)~
This formulation, ZectranTM, was not intended to be used as an algacide and is, therefore, not particularly useful for that purpose.
Phenylcarbamates, fre~uently employed as herbicides, have demonstrated activity against blue green algae (bacteria).
Propham, Chloropropham and Barban (tradenames) caused a 50 reduction in the growth of blue green algae in the range between 0.3 and 70 ppm (data from Hill and Wright, 1978)o Barban did not inhibit all of the algae species tested. Like Sevin and Zectran, the phenyl carbamates are not structurally urethanes of l-halogen substituted alkynes.

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It has also been known in the past to use mercury compound~
which have limited effectiveness and toxicity shortcomings.
Copper compounds have activity and can be used but have the disadvantage for many applications that they are colored.
Tribut~1 tin oxide has been used but it is relatively expensive for these purposes and shows unsatisfactory s~abi-lity for exterior exposure.
Although some various compounds have been employed for limited use in lakesl ponds and areas of stagnant water~ there has not been a wide recognition of the need for 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. However, these materials are presently unacce~table by the Environmental Protection Agency and are possible environmentally hazardous when so used.

SUMMARY OF THE INVENTION
An object of the invention is the production of novel, selected urethanes of halogenated substituted alkynes. These 25 1 novel compounds are generally substituted by aralkyl and sustituted aryl groups.
Another object of the invention is to employ enerally the urethanes if l-halogen substituted alkynes as alg~acides for i destruction and control of algae and algae-like microorganisms including but not limited thereto certain protozoa which may be classified with algae.

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Another object is to describe compositions includinq but not limited thereto, coating compositions, protective compositions, decorative compositions and the like bu~ not limited thereto for the control of algae.
A further object is the description of methods using such various compositions which control algae in paints, coatings, caulkings, linings, sealants, sprays, lacquers, finishin~
compositions, polishes, wood, mortar, concrete, cement,fillers, molding compounds, waxes, resins, polymers, fibers and the like~

DETAILED DESCRIPTIO~ OF THE I~7ENTION
This invention involves the use of urethanes of 1-halogen I substituted alkynes to control and prevent~the growth of algae l and to kill already existing algal growths. These com~ounds 15 ¦ have been found to have outstanding alqacidal activity are derivatives of l-iodo-substituted alkynes having the generic formula:
[ I-C=C-(CH2)n~-~-N-]mR
,~,.
where R is selected from substituted and unsubstituted alkyl, aryl and alkyl aryl groups having from one to not more than 20 carbon atoms and having from one to three linkages corxesponding to m, and m and n are whole number inte~ers between 1 and 3, l and may be the same cr different.
These compounds have been shown to have many advantages as algacides for controlling and destroying many different species of algae and algae-like microorganisms, They are very stable even when incorporated into aqueous and non-aqueous compositions.
and are deactivated and/or destroyed only by prolonged exposures to high temperatures.

~259~ 6 They possess only low toxicity towards anim~ls, birds and other wildlife and domestic animals and toward man.
Consequently, their use in the algacidal compositions require only the usual good practice and procedures in handling and such precautions as are well established and in use for handling commercial and household biocides.
Laboratory tests have indicated that the ure~hane compounds of the invention can be combined with other biocides as desired to both broaden and enhance their activity and extend the areas of their usefulness. .
The compositions in which they are used may contain a relative wide variety of componen-ts such as are well known in the art.
The compounds useful in the invention may be used when generally employed as algacides in concentrations from 0.01 percent up to 12.0 percent by weight, in some cases depending on their stabilities in the compositions employed including whether they are aqueous or non-aqueous. In some instances, the compounds may be employed as premixed dispersions, They may also be prepared as solutions or dispersions and therea~ter added to the final protective compositions. For examples, 3-iodo-2-propynyl-N-butyl carbamate (Polyphase) 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 algae specie(s), or similar species which are to be controlled or destroyed~ For instance, in some cases, it may be necessary to employ up to approximatelv 40 perce~ It by weight of the compounds to control and~or destroy certain algae and algae-like microorganisms and, for instance und~r certain conditions of well-established growth.
1.

,.:1 ~59 For their use as algacldes, the urethanes of l~halogen substituted alkynes, dissolved or solubilized in water and for a variety of organic solvents, can be incor~orated into a wide variety of compositions which require protection and freedom from algal growth, including wood and mortar, and most paints, coatings, caulkings, fillers and the like. ~hen emploved as algacides, urethanes of l-halogen substituted alkynes are active as algacides and for control against algal species found growing in marine, fresh water, terrestrial and aerial situations. They are also active against species found in water cooling towers, clogging irrigation canals and growing on mortar and wood and find use as especiallv valuable agents when used for these objectives.

The compositions may be for example, all types of water-based latex paints including acrylic ~nd pva latex Paints and chlorinated rubber-vinyl paints, oil alkyl paints, oil based stains, pigmented paints and protective and decorative compositions, rubber and/or asphalt containing roof coatings, inorganic and polymeric caulkings, molding materials, sealants, ; 20 silicone compositions, liquid compositions, both aqueous and non-aqueous adapted for painting, dipping or spraying as well as other types of protective compositions for the many widely used applications of such materials.
It has also been found that these algicidal compounds are particularly valuable for applications in clogging problems in irrigation ditches, canals, conduits and the like where the Batrachospermun (red algae) are particularly troublesome.

1~ i ~ ~ ~59~2~ .
It is also possible to use these algacidal compounds for control of the so-called "red tide" problem which is generally caused by one or more algal species from the class Dinophxceae.
The compounds ma~ also be used to prevent odors by controlling, limiting, and/or destroying the algae population in water, such as in irrigation systems, water towers, recirculating sewage water systems and similar water holding and transporting systems.
: In particular, and of this group, the urethane compound 3-iodo-2-propynyl-N-butyl carbamate 5known as Polyphase, a tradename o Troy Chemical Corporation) has been found highly effeotive and useful as an algacide.
In another featl.lre of the invention, the group of novel urethanes of l-iodohydroxy alkynes having the formula [I-C~C-(C~2)n-0-~-NH]mR in which R is selected from the group of aralkyl and substituted aryl groups, and m and n are whole number integers between 1 and 3 and may be the same or diferent have been found highly effective as algacides.
The algal groups which can be treated effecti~ely by ~he ZO. compounds and compositions of this invention include algae in the Divisions Chlorophyta (green algae), Chr~so~hyta (yellow-green algae), Cyano~hyta tblue-green algae or bacteria), Euglenophyta (euglenoides), Phaeophyta (brown algae), and Rhodophyta (red algae); the algae against which the compounds

2~ and compositions are effective are in no way limlted to these groups r to the species er~raced thereby.

-~ 9~ 6 The algae used for testing the compounds and compositionsfor algae contxol and algacidal activity were obtained from Ward's Natural Science Establishment of Rochester, N.Y.
The individual algae which were tested are shown and described more completely in the Examples, as shown by the data, the compound5 were highly effective in controlli~g the qrow~h of algae tested.
Examples which are set forth below are intended for illustrative purposes only. The data of the tables and the test results are presented to exemplify the use of the compounds and various coating compositions containing them but are not intended to limit the invention specifically thereto or to limit the compounds and compositions in their algacidal activity or to any particular algal classes or species or to the specific amounts .
or concentrations of the algacides employed to control the algal species tested. It is well known in the art that it is usually easier to control or prevent growth than it is to kill an already growing algal population. It is also known to be easier to control a small rather than a large population of algal organisms. The Examples are especially intended to show the algacidal properties of the compounds and compositions containing them and particularly to show illustra~ive data on the effectiveness of the compositions for such species as are protected by thick capsules as well as those which grow and multiply rapidly as thick colonies, such as Scytonema species which have thick capsules and Nostoc species which grow as thick colon s.

-11 ~2~9~26 Exa~p:e 1 Preparation of p-chlorophenyl urethane of hydroxy-icdo~propyne cl--~NH-~-o-cH2-c-c-I

0.2 Moles of hydroxyiodopropyne (IC=C-CH2OH~ as a 70%
solution in ether, dried with anhydrous sodium sulfate, is mixed with 0.2 moles of ~-chlorophenyl isocyanate and a few drops of dibutyl tin dilaurate ~s added as catalyst~ An exothermic reaction occurs~ The mixture is refluxed until reaction is complete, A yield of 21g of pale cream precipitate with an approximate m.p. of 95a- 100C is filtered from the clear filtrate and partial evaporation yields 22 grams,of additional precipitate with a m.p. of 93- 95 .
~ Iodine= 36,8; theoretical = 37.8~.

Example 2 Preparation of 3-methylphenylurethane of hydroxy-iodo-propyne NH-~-O~CH2-C--C-I

The reaction for preparation of the product of Example 1, is followed, except that m-tolyl isocyanate is used instead of p-chlorophenyl isocyanate. The product is isolated from the reaction mixture after standing in the freezer overnight after an initial filtration to remove a small amount of sediment.
The yield is 37 gramS of pale cream crystals with a melting point of 93~C.
% Iodine = 39.97; theoretical - 40.2~.

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~;~5 Example 3 Preparation of mixed diurethanes of hydroxy-iodopropyne and toluene diisocyanate lI-C_~-C~2-0-~-NH-]2- [80% 2,4- and 20~ 2,6-tolyl]

S Hydroxyiodopropyne and a commercial preparation of mixed isomers of toluene diisocyanate known as Mondur TD-30 (Trademark3 a product produced by Mobay Chemical Co., and consisting of 80% 2, 4- and 20% 2, 6- isomers are reacted together in the molar ratio of 2.15 m HIP thydroxyiodopropyne) to 1 mole dis~cyanate. 6~g of a 72% solution of HIP in e~her is mixed with 200g methylene chloride, 1/3 cc dibutyl tin dilaurate, and 19.2g Mondur TD-30 is added slowly over a period of 50 minutes. When all reactant has been added, the mixture is heated to reflux and methylene chloride is added as required, about'250g in all to keep the precipitate that forms dispersed~
The reaction mixture is held at reflux 2 1/2 hours and allowed to stand overnight.. The following morning, it is filtered to obtain 51g of a cream colored powder melting at 174~- 177~C. .
xamp~e 4 Preparation of diurethane of hydroxy-iodopropyne and 4,4'-methylene diphenyl isocyanate.

I-C-C-CH2-0-~-NH- ~ CH2 ~ -NH-~-O~H2-C-C-I~
~rhe reaction for preparing the pro of Example 3 is followed except that the isocyanate used is 4,4i methylene diphenyl isocyanate, obtained as Mondur M tTrademark) from Mobay Chemical~ The yield reaction of 39g HIP and 25g Mondur M
was 55.5g of a cream colored powder having a m.p~ of 165 - 168~C
and an iodine content of 40% (theoretical = 41.4~).

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Example 5 Preparation of diurethane of hydroxy-iodopropyne and toluene . 2,4- diisocyanate -......... ~I-C-C-C-CH2-0-~-NH-~2- [2,4-tolyl]

This product was made according to the procedure of .
Example 3, but using toluene 2,4 diisocyanate (~ondur TDS~
Trademark, Mobay Chemical~.. The yield ~s 52g cream colored powder with an approximate mO p. of 181 - 184 C and an iodine content of 47~ (theoretical = 47.2%1.
Example 6 Preparation of benzyl urethane of hydroxy-iodopropyne CH2-NH-~-o-cH2-c-c I

14.6 g HIP is dissolved in 20 cc ether and 0.1 cc dibutyl tin dilaurate is added. To this is added during 1~2 hour, : 16.7g benzyl isocyanate. An exotherm brings the temperature up to 3~C and preoipitation occurs~ Mixing is continued for : an additional 1/2 hour and the reaction mixture filtered and washed with ether t~ yield 20.5g cream colored powder with a 20 ~ m.p. of 107 - llO~Co This product is reslurried with ether and refiltration yields 17.5g of very pale cream crysta~s;
m.p, = 112~- 113`' . % Iodine = 39.4; theoretical = 40.36.

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Example 7 Various well-known nutrient solutions, such as Bri~stol's solution, Erdschreiber solution, soil-water medium and other liquid media were combined with appropriate quantities of an aqueous solution containing 100~3./ml, of 1-iodo-2-propynyl ~-butyl carbamate (Polyphase, a trademark of Troy Chemi~al Corp.~ in screw capped tu~es. The tubes were inoculated with an active culture of Carteria sp., Chlamydomonas sp., Eudorina sp., Haematococcus sp., Pandorina sp., Volvox sp., or other algal species which would grow well on the medium.
Controls were prepared by co~bining the media wi~h H20 and inoculated with an algal species. For example, the following mixtures were prepared and inoculated wlkh Prorocentrum and challenged with Polyphase.

Preparation of Test Solutions.

* Erdscheibers H2O Polyphase** Inoculum Concentration Solution (ml.) (ml.) (l-iodo-2-(ml.) Pol~phase propynyl-N-(~3./ml~) butyl-carbamate) Solution (ml ) . . __ 7.00 0.00 o.oo 3.00 0.00 6.50 o.oo 0.50 3.00 5.00 6.00 0.00 1.00 3.00 10.0 5.50 0.00 1.50 3.00 15.0 5.00 0.00 2.00 3.00 20.0 4.50 0.00 2.50 3.00 25.0 4.00 0.00 3.00 3.00 30.0

3.50 0.00 3.50 3.00 35.0 3.00 0.00 4.00 3.no 40.0 ~.50 0.00 4.50 3.00 45.0 2.00 0.00 5.00 3.~0 50~0 _ 2.00 5.00 0.00 3.0~ 0.00 * Standard marine salt used by algalogists as a growth medium.

~* 100 ~. Polyphase per ml.

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The tubes inoculated with Prorocentrum were ~ncubated under cool white fluorescent light (40W~ at about 20for 2 days and examined microsoopically. Viahle (motile~ cells were observed both in control tubes without Polyphase and in the tubes containing 5 ~'g. o Polyphase per ml. ~la~le cells were not observed in the tubes containing concentrations of ~0 ~g./ml~
and higher Polyphase.
When species of green algae were employed as the inoculum, chlorosis ~the bleaching or disappearance of the green color~
could often be employed to detect the toxic level of PolYphase to the algae, Either micxoscopic examination, chlorosis or both were employed to study these species. These techniques were employed with all unicellular and~or microscopic algal species tested, the test results being shown in Table 2 below.
Example 8 Solutions were prepared as described in Example 7, except that the final volume in each instance without the inoculum was ten milliliters. The inoculum consisted of filaments of algal species, such as Spiro~yra and Scytonema, cut piec~s 20 ¦ of large marine a}gae, such as Ulva, and marble size colonies of species, such as Nostoc. The small amount of water adhering to the filaments, pieces and colonies was ignored, Chlorosis was employed to detect khe algacidal activity of Polyphase.
Both fresh-water and marine species were tested as described in Examples 7 and 8 summarized in Table 2. It was shown that Pol~phase demonstrated excellent algacidal activity against both groups of organisms. Marine algae are separated in Table 3. Polyphase and analogs of Polyphase could have applications in the treatment of marine al~al b1oomsr such as "red tides."

Since Polyphase is soluble in water ~o the extent of about _ 175 ppm. (~g./ml.) and analogs of varying solubilities in water ~;~59~

are available, it was concluded that saturated solutions in water would contain sufficient biocide to control the hardiest algae.

Toxicity of 3-iodo-propynyl-n-butyl carbamate ~Pol~phase~
Towards_Alqae in Aqueous Media Toxic Level of Or~anism PolyE~ase-~ ml.3 Division Chlorophyta ~Green Algae) S - 40 Class Chloroph~cea.e Order Volvocales 10 - 20 1. Carteria sp. 10 2. Chlamydomonas rhinhardtii 15 3. Eudorina sp. 20

4. Haematoccus sp. 10

5. Pandorina sp. 20

6. Plat~monas sp. 10

7. Volvox sp. 2a Order Ulotrichales

8. Ulothrix sp. 40 Order Ulvales

9. Ul~la sp. 30 Order Oedogoniales lQ. Oedogonium sp. 15 Order Cladophorales ~ 11. Cladophora sp. 25 12. Pithophora sp. 25 : Order Chlorococcales . 5 - 23 13. Ankistrodesm~s sp. 10 ¦~ To~ic Level of Organism ~L~S~;2f:; ~ol~phase ~ /ml . ) 14. Chlorella pyreniodosa 2Q
15. Hydrodi~yon sp. 5 16, Protosiphon sp. lQ
17. Scenedesmus spp 5 Order Zygnematales 15 - 3Q
18. Closterium sp. 30 19. ~ougeotia sp~ 20 20, Spiro~yra sp. 15 Class Charoph~ceae Order Charales 21. Nitella sp.
Division ChrysoPhyta (Yellow Green Algae) 15 - 35 Class Xanthoph~ceae Order Heterotrichales 22. Botrydiopsis sp. 30 23. Tribonema sp. 15 Oxder Heterosiphonales 24. Botrydium sp. 20 25. Vaucheria sp. 10 Class Chrysophyceae Order Chrysomonadales 26. Synnra sp. 15 Class ~acillariophyceae Order Pennales 27. Navicula sp. 35 Division Euglenophyta Order Eugleniales 28. Astasia sp. 15 .
29. Euglena gracilis l~reen form) 35 30. Phacus sp. 15 31. Trachelomonas sp. 5 Division Pyrrophyta (Desmokontes and Dinoflagellates) Class _e mokontae 3. Order Desmonadales 32. Prorocentrum sp~ 10 1~

I Toxia Level of Organism ~59~6 Poly~ha-se (~1,/ml~?
Class Dinophyceae Order Perdini~les 33. Peridinium sp. 15 Division Rho~ophyta (Red Algae) Subclass Bangiodeae 34. Porphyridium sp. 15 Subclass Florideae 35. Batrachospermun sp. 35 Uncertain Systematic Position 36. Khodochorton sp. 30 ~ncertain Systematic Position Class Cryptophyceae Order Cryptomonodales 37. Chilomonas sp. 25 Division Cyanophyta (Cyanobacteria) Class Myxophyceae (Myxobacteria~
: lBlue Green Algae (Bacteria)] 15 - 75 Order Chroococcales 40 - 60 38. Anacystis sp. 60 39. Gloeocapsa sp. 40 40~ Merismopedia sp. 55 ~ .
~rder Oscillatoriales l5 - 75 41. Anabaena sp. 35 42. Cyli~drospermum sp. 15 43. Gloeotrichia sp. ~ --- 40 44. Lyngbya sp. 65 45. Nostoc sp. 55 O
46. Oscillatoria sp. 60 47. Phormidium sp. 75 48. Scytonema sp. 60 49. Spirulina sp. 25 50~ Tolypothrix sp. 40 ' 59~2~-` .

Toxic Level of Organism Polyphase (~./ml.) Division Chlorophyta (Green Algae) Order Volvocales l. Platymonas sp. 20 Order Ulvales . 2. Ulva sp. 30 Division Chr~sophyta (Yellow Green Algae~
: Order Chrysomonadales 3. Synura sp. 15.
Division P~rrophyta Order Desmonadales 4. Prorocentrum sp. 10 Division Rhodophyta Order Bangiales lS 5. Posphridium sp. 15 . Uncertain Systematic Position .
6. Rhodochorton sp. 30 Division Cyanobacteria 7. Spirulina 25 Division Phaeophyta (Brown Algae) 8. Fuscus 65 S~6-Example 5 Schleicher and Schnell Analytical Paper (#740-E, ~"
Diam. - 12 mm~ discs were dipped ~nto 1% - 40% solutions of the compound(s) tested which were dissolved in acetone. A 'T' pin pushed through the center of each disc was employed to hold it during dipping and subsequent drying, The treated discs were air-dr~ed by holding them on the ~T' pins pushed into corkboard.
Protease agar plates were prep~red and seeded with a "lawn"

of hlorella pyrenoidosa from an axenic culture. Treated air dried discs, containing Polyphase or its analogs as identified in Table 4 were placed in the center of each plate. The petri dishes were incubated under a cool whi~e fluorescent light (40W) at am~ient temp. (about 20U) until algal growth was obtained (about 6 days). The size of the zone of inhibition was measured from the edge of the disc to the edge of the algal growth (in mm.). The data obtained in reported in Table 5 below.
It was observed that the urethanes of l-iodo substituted alkynes, the compounds of the invention, demonstrated high toxicity towards Chlorella pyrenoidosa. Thus it ~as been shown that these compounds including Polyphase exhibit toxicity towards a large range of algal species in every major division from a wide range of habitats and occupying a wide range of niches in the known classes of algae.

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Che~ical Structures of Compounds Tested Includin~ P~ly~hase Compound ** Polyphase I-c-c-cH2 - o - c-NH-cH2cH2cH2cH3 I-C~C-CH2-0-C-NH-Butyl(n) B .
I-c-c-cH2-cH2-o-c-NH--cx3 ,~ C O -NH-C-O-CH2-C_C-I

I-C~C-CH2-0 t~-NH-CH2CH3 E O

\ -NH-C-O-CH2-C-C-I `

I-C-C-CH2-0-~-NH-Hexyl(n) I-C~-C-C'.2- 0 ~ `.i;i-Oc ~H Cl ~ -NH-c-o-cH

*I ~ -NH-C-O-CH2-C-C-I

5~3~ `; .

[I ~C-CH2-0-C-NH-]2-[80% 2,4- and 20~ 2,6-tolYl~

I-CSC-FH2-0-C-NH- <~3-CH~-NH-C-o-CEr2-C$-]

*L O
[I-C-C-CH2-0-C-NH-]2 [2,4-tolyl~

*M ~ CH2-NH-C-O-CH2-C_C-I

* These compounds are new compositions of matter and are : claimed herein as such.
** Tradename - Troy Chemical Corporation 59~ i TAsLE 5 Sensitivity of Chlorella pyrenoidosa to Com~ounds Tested Includina PQ1YPhaSe .. . __ Sample tCompound) Solvent Concentration Inhibitory Zone (mm.) Polyphase Acetone 1.0 10 Polyphase " 2.0 11 Polyphase " 5.0 12 Polyphase " 40.0 13 A " 1.0 10 B " 1.0 14 C " 1.0 ` 9 D " 1.0 14 E " 0.5 10 F " 1.0 8 G " 1.0 7 *H " 1,0 13 " 1.0 9 *I " 1.0 20 *J " 1.0 6 .
*K " 1.0 5 *L " 1.0 5 *M " 1.0 42 - ~-1~36 Example 10 Formulations of latex paint~ oil alkyd paint, and oil based st~In (details of formulations shown herein after in Ta~les 7, 8 and 9) were prepared from commercially available materials. Polyphase was added at levels of 2,4 and 6 lbs.flOO gallons. Filter paper sheets were coated or treated with the formulations and control containing no Pol~hase,dried an d discs 12 mm~ in diameter cut from the sheets. These discs were placed on plates containing proteose agar which had been seeded with a lawn of Chlorella pyrenoidosa and incubated as described in Example 9. Zones of inhibition were measured as described in Example 9. The test results are recorded in Table 6.
It was observed that a small zone of inhibition was obtained on controls which did not contain Polyphase. This anomaly is caused by the solvents and biocides which are normally added to paints and other coatings to protect them from bacterial growth. However, after applica~ion as coatings, these toxic agents are removed by weathering leaving the coatings unprotected. Larger zones of inhibition were observed in Polyphase protected coatings. These results clearly demonstrate the added and prolonged protection of Polyphase use.

5~ 6 T~BLE 6 Algal Protect-Ion of Coatings ContaXnin~ Poly~hase S~mple Polyphase Zone of No-. (l~s.!100. gal.)Inhibition (mm.) Alkyds (oil alkyd paint) la. (.control). ~ 4 1~. 2 6 lc. 4 10 ld. 6 13 Stains (oil based stain) 2a. (control~ O 6 2b. 2 8 2c. 4 10 2d. 6 13 Latices (alkyd latex paintl 3a~ (.control~ O 0 3b. 6 4 TA~LE 7 Qil ~lkyd Paint (l-a, b, c & dl Composltion Dry Wt.
(.non-volatile) Material lbs. ~ls. Clbs~) . , ~
Heat-bodied linseed oil 225 28.0 225 Alkali-refined linseed oll 75 10.0 75 Beo~osol, P296-60 CTrademark, Reichhold Chem.) 75 10.0 45 Mineral Spirits 195 30.0 : --Cobalt drier 6% 2.5 0.3 --Calcium drier 6% 5 a . 6 --Anti-skinning agent 2 0.2 Non-chalking titanium dioxide 300 8.8 300 Talc 3Q0 12.6 300 Suspending agent 5 _ 0.3 5 1184.510Ø8 950 l-a No Polyphase ----- ---l-b 2 lbs/100 gal. ~ - 0.8 lbs. active PP/950 lbs. dry wt~
l-c 4 I- _______ 1.6 lbs. "
l-d 6 " ------- 2.4 lbs. "

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Oil Based Stain (2~ a,b,c, & d) White Alk~d Oil Stain Mat~r~al lbs. Gal. Dry W~.~lbs.
Titanium dioxide 50 1.46 50 Suspension agent 3 0.3 3 Bec.kosol P296-60 ~Trademark Reichhold Chem.2 141 18.2 84.6 Raw linseed oil8510.95 85 Mineral spirits45168.85 Cobalt drier 6~1.10.12 ~alcium drier 6% 2.8 0.35 Anti-skimming agent 1 0;13 734.9106.36 222.6 2,a No Polyphase -------2,b 2 lbs. PP/100 gal. ---- 0.8 lbs. PP/223 lbs, dry 2,c 4 " ---- 1.6 lbs. PP/224 2,d 6 " . ---- 2.4 lbs. PP/225 5~ 6` -``

Acrylic Latex Paint (3 - a and bl Composition Material lbs.yals. Dry wt./lbs.
Water 354 42.5 Cellosize QP-15~00 (Trade~ark Union Carbide2 3.750,3 3,8 Tamol 731 CTrademark Rohm ~
Haas) lO.Q1,1 2~5 Lecithin 2.00Q.2 2~0.
Ethylene glycol 15~01.6 Carbitol (Trademark Union Carbide) 10.~1~2 Defoamer~999 _ .
-(Tradename, Troy Chemical Corp.) 2.001.3 Titanium dioxide 275 8.1 275 Talc 85.Q3.6 85 ~ica 50~02.1 50 Rhoplex, AC35 (Trademark, Rohm &
Haas) 364 40.3 167 _ 1170.75lQ2.3 585 3,a No Polyphase 3,b 6#PP*/10.0 gal. ---~ - 2.4 lbs. PP~585 # dr~

*Poly~hase ~;259~.

Example ll Polyphase was added at levels between 0~1 and 1,0%
~approximately equal to between 1 and 10 lbs~ n gallonsl to a roof coating material~ The roof coating material called Traycote (trademark) (the composition of w~ich is shown in Table 10, with and without Polyphase) was caated onto standard 1" x 3" glass microscope slides, allowed to dry for 2 days, and leached with distilled water for 3 days. The coatinqs were cut from the slides using a razor blade and plated onto proteose agar covered with a lawn of Chlorella pyrenoidosa cells. The plates were incubated under cool white fluorescent light (40W) for 2 days and examined. A green "lawn" of algal cells was observed growing to the edge of the control coating without Polyphase. The observation included growth under the surface of the control coating (as viewed in reflec~ed light); however, no growth whatever was observed under coa~ing samples cont~ining greater than or equal to 0.4% Polyphase. In addition, zones of inhibition between 0.5 and 4.0 mm. wide were observed around the protected coatings.

9G~

Com~Fosition of Roof Coatin~Material Traycote (Tradem~rk - Traycote, Inc~ of Col~m~iap 5,C,~ is a protectiye ro~fing coating ha~ing the following c~mposition (.lbs./l~0 gallons);
Mater~al Lbs./10~ gal.
Ethylene ~lycol 23,3 Natrasol 25QHR (Trademark, Hercules ~nc.) 4.0 Water 197.8 Nopco NXZ (Trademark, Diamond Shamrock) 93.2 Tamol 250 (Trademark, Rohm ~ Haas~ 4-7 Calcium Carbonate 93.2 Titanium dioxide 65.3 Talc 279.5 Acrylic Latex Resin442.6 Aqueous ~mmonia (26 Baume~ 1.9 *Troysan 174 (Trademark -Troy Chemical Corp.)2.5 * Troysan 174 is a volatile bactericide employed for "in-can"
preservation.

;~

~5~

Exam~le 12 A commerci~lly ay~ hle rubber~zed asphalt roof coating materi~l haYing t~e composition shown in Table 1~ was combined with Troysan ~rrademark of Troy Chemical Corp.~ Polyphase AF-l foxmulation. The ~ctive Polyphase con~ent of this formulation is 40 percen~ and the remaining ine~t ingredients are solvents.
The mxxture contained ~.0, Q,5, 1.0, 1.5 ~nd 2~0 percent Polyphase AF-l and 0~0, 0.2, 0.4, 0.6 and 0,8 percent active Polyphase by weight.
These samples were applied to glass slides with a wooden tongue depressor and dried or three days. They were removed from the slides with a razor blade and placed, smooth surface down, on the surface of proteose agar plates seeded with Chlorella pyrenoidosa. The samples were incubated for 7 days under 40W white fluorescent light at ambient temperature (about 22~).
Chlorella pyrenoidosa grew up to and under ~he surface of the control sample not containing Polyphase. Its growth was inhibited and it ~ailed to grow under the surface of samples containing Polyphase at all concentration levels. Zones of inhibition were observed at G.6 and 0.8 percent active Polyphase.

Composition of Rubberized Asphalt Roo~ Coatinq Material Asphalt 50.
Attagel(Tradename Engelhaxdt Industries) (thickenerl 15 ~raton rubber (Trademark - Shell Oil) ~5 Lecithin and surfactants ~l Aromatic process oil ~ 5 High flash naphtha 24-25 -59~ `
Example 13 Solutions of Polyphase in ethanol were prepared at levels of 0.0, O.lr 0,-2, 0.4, 0.6, 0,8 and 1.0 grams per 100 ml.
The solutions were transferred to an "Omit" air dispenser a~d sprayed onto the surface of proteose agar in petri dishes.
The proteose agar had previously been inoculated with Chlorella pyrenoidosa which would grow producing a "lawn" of cells upon the surface. The petri dishes were incubated under 40W cool white fluorescent light for one week at ambient temperature ~about 22~).
Chlorella pyrenoidosa grew covering the surface of the agar sprayed with ethanol which did not contain Polyphase.
Some spotty growth occurred at 0.1 and 0.2 grams/100 ml. levels of Polyphase. No growth at all was observed on plates sprayed with 0.4g per 100 ml. and higher levels of Polyphase.

Claims (33)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Urethanes of 1-iodohydroxy alkynes having the formula [I-C?C-(CH2)n-O-?-NH]mR

in which R is selected from the group of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo groups, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are not both 1.

2. Urethanes having the formula of Claim 1 in which m is 1.

3. Urethanes having the formula of Claim 1 in which m is 2.

4. Urethanes having the formula of Claim 1 in which m is 3.

5. Urethanes having the formula of Claim 1 in which n is 1.

6. Urethanes having the formula of Claim 1 in which n is 2.

7. Urethanes having the formula of Claim 1 in which n is 3.

8. The compound,

9. The compound,

10. The compound, [I-C?C-CH2-O-?-NH-]2 - [80% 2,4 - and 20% 2,6 - tolyl]

11. The compound,

12. The compound, [I-C?C-CH2-O-?-NH-]2 - [2,4-tolyl]

13. The compound,

14. Protective compositions, adapted for controlling growth of algae and algae-like microorganisms which contain effective concentrations of urethanes of 1-iodohydroxy alkynes having the formula [I-C?C-(CH2)n-O-?-NH]mR

in which R is selected from the group of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are both 1 when R is aryl.

15. Decorative compositions, adapted for controll-ing growth of algae and algae-like microorganisms which contain effective concentrations of urethanes of 1-iodo-hydroxy alkynes having the formula [I-C?C-(CH2)n-O-?-NH]mR
in which R is selected from the group of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between l and 3 and may be the same or different, provided that m and n are both 1 when R is aryl.

16. Coating compositions, adapted for controlling growth of algae and algae-like microorganisms which contain effective concentrations of urethanes of 1-iodohydroxy alkynes having the formula [I-C?C-(CH2)n-O-?-NH]mR

in which R is selected from the group of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between 1 and 3 and may be the same or different provided that m and n are both 1 when R is aryl.

17. The method for controlling the growth of algae and algae-like microorganisms which comprises incorporating into protective compositions effective amounts of at least one compound selected from the group consisting of urethanes of 1-iodo substituted alkynes, having the formula [I-C?C-(CH2)n-O-?-NH]mR

in which R is selected from the group consisting of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are both 1 when R is aryl.

18. The method of Claim 17 in which m is 1 in the formula of the urethane compound.

19. The method of Claim 17 in which m is 2 in the formula of the urethane compound.

20. The method of Claim 17 in which m is 3 in the formula of the urethane compound.

21. The method of Claim 17 in which n is 1 in the formula of the urethane compound.

22. The method of Claim 17 in which n is 2 in the formula of the urethane compound.

23. The method of Claim 17 in which n is 3 in the formula of the urethane compound.

24. The method for controlling the growth of algae and algae-like microorganisms which comprises incorporating into protective compositions effective amounts of at least one compound selected from the group consisting of 1-iadohydroxy alkynes having the formula [I-C?C-(CH2)no--?-NH]mR

in which R is selected from the group of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are both 1 when R is aryl, and 3-iodo-2-propynyl-N-butyl carbamate.

25. The method of Claim 24 in which m is 1 in the formula of the urethane compound.

26. The method of Claim 24 in which m is 2 in the formula of the urethane compound.

27. The method of Claim 24 in which m is 3 in the formula of the urethane compound.

28. The method of Claim 24 in which n is 1 in the formula of the urethane compound.

29. The method of Claim 24 in which n is 2 in the formula of the urethane compound.

30. The method of Claim 24 in which n is 3 in the formula of the urethane compound.

31. The method of Claim 24 in which the urethane compound is 3-iodo-2-propynyl-N-butyl carbamate.

32. The method for controlling the growth of algae and algae-like microorganisms which comprises contacting said microorganisms with effective amounts of at least one compound selected from the group consisting of urethanes of 1-iodo substituted alkynes, having the formula [I-C?C-(CH2)n-o-?-NH]mR

in which R is selected from the group consisting of aryl, aralkyl and substituted aryl groups having not more than 20 carbon atoms where the substituted aryl group is substituted by lower alkyl or halo, and m and n are whole number integers between 1 and 3 and may be the same or different, provided that m and n are both 1 when R is aryl, and 3-iodo-2-propynyl-N-butyl carbamate.

33. The method of Claim 32 in which the urethane compound is 3-iodo-2-propynyl-N-butyl carbamate.