IL44299A

IL44299A - 2-substituted-4,5,5-trihalo-isothiazolidin-3-ones

Info

Publication number: IL44299A
Application number: IL44299A
Authority: IL
Original assignee: Rohm & Haas
Priority date: 1973-02-28
Filing date: 1974-02-27
Publication date: 1977-04-29
Also published as: DE2408911A1; IL44299A0; CH563108A5; BE811722A; NL7402682A; JPS49117628A; FR2219165A1; FR2219165B1; GB1449030A

Description

t η a 42092 This invention concerns certain novel isothiazolid their biocidal compositions containing and their utilization in the control of The novel of the invention have the formula wherein R is cycloalkyl of up to 6 carbon phenyl or phenyl tuted by halogen or 2 R is halogen 3 R is preferably chlorine or and X preferably chlorine or the two X substituents being the same or Also included within the invention are salts of compounds of Formula I and metal salt complexes with compounds of Formula salt complexes of analogous compounds bein described in Patent Specification 1 Representative R substituents include cyclohexyl benzyl phenyl 3 and 2 3 Representative R and R substituents include The alkyl substituents represented by can have either or spatial Typical compounds of the invention 5 In a preferred embodiment of the is an unsubstituted alkyl group up to 10 carbon 2 X is and R is methyl chlorine and R is All of the of the can be prepared by of a one of the wherein R2 and are as defined The preparation and properties of the from which of the invention are made are described in Israeli Patent The can bo out over a broad ure preferably about most preferably about 25 to such ethyl butyl dimethyl the like are An excess of the halogenating agent e if The product of the reaction can be isolated by convenient such as or the Among the suitable halogenating agents for making the compounds of the invention are sulfuryl sulfuryl iodine iodine and the Chlorine and bromine are the preferred halogenating Those of the invention in 2 which R is a methyl group can also be prepared by the cyclization of a of the formula wherein R 1 is as defined The cyclization is generally carried out by simultaneous addition of a halogenating such as and the amide to a such as ethyl butyl dimethylformamide or the The cyclization about can be isolated the reaction by any suitable The following examples are set forth to illustrate this invention but are not intended to limit it in any Table I sets forth typical of the invention prepared as described along with their elemental analyses and melting points or boiling Specific illustrative preparations of the compounds of Examples and are described after Table All temperatures are in degrees Centigrade and percentages by weight unless otherwise TABLE I Elemen E X Cl Cl OS 6 5 3 2 2 Cl Cl CH3 3 CI Cl Cl Cl Cl Cl Cl D Cl Cl Cl 39 8 Cl Cl Cl 9 CI Cl 0 Cl Cl Cl TABLE I Eleme c 11 clo Cl Cl Cl 12 CI Cl OS Cl Cl Cl 5 CH2C6H5 Cl Cl 6 ci Cl Cl Cl Cl 6 5 17 Cl Cl Cl 31 utyramide in equal portions at minute and of The temperature is maintained between and during the The mixture is allowed to warm to room temperatur and filtered to remove suspended The filtrate is washed with dilute aqueous sodium bicarbonate until The solution is dried over anhydrous magnesium sulfate and evaporated leaving a The oil is distille The is shown by thin layer chromatography to contain two Approximately 3 g of this materi is chromatographed on a silica dry column developed with methylene The column is divided in three equal Extraction with ether of the portion nearest the solvent followed by evaporation of the gives g of colorless which solidifies to a white solid Method B To a solution of g of in 20 ml of acetate at room temperature is added over 10 g of White solid precipitates while the temperature rises to a high of about and slowly The solid redissolves by the end of chlorine The solution is degassed and evaporated under reduced pressure leaving of yellow oil which solidifies on Crystallization of the solid heptane gives g of 2 E 7 Preparation of To a solution of g of crude in 100 of ethyl acetate is added over 15 minutes 3 g of During chlorine addition the temperature rises to about After cooling to room temperature the solution is evaporated to g of dark amber A TLC of this oil shows that it contains at least six The oil is chromatographed on silica with the leading third of the is extracted with The extract is concentrated and dried to give 31 g of yellow Recrystallization from ether gives g of yellow tan Example 8 Preparation hydrochloride in 100 of ethyl acetate is added 100 of To this mixture is added over g of The temperature rises but is maintained below by The solid dissolves after about 5 When the chlorine addition the mixture is to causing separation of g of The filtrate concentrated under reduced pressure to remove ethyl acetate and Dilution of the concentrate with water causes separation of an oil which solidifies on The is on a silica dry column developed with The half of the column is extracted with centration of the extract gives g of Method B To a suspension of g of pure and dry hydrochloride in 200 of ethyl acetate is added over 1 71 g of The reaction temperature rises to 55 in hour and the solid is dissolved after about The solution is degassed and evaporated under reduced pressure to give a cream color The mush is shown by TLC to contain two major Crystallization of the mush from methanol gives g of Evaporation of the filtrate gives of material which is chromatographed on a dry column with The fraction close to the solvent front is extracted and gives g of crude tion from methanol gives g of white crystalline of 5 To a solution of g of in 100 of ethyl acetate is over g of The temperature rises to ig of about during which solid first separates and then es The solution is concentrated reduced pressure to give g of A TLC shows major oil is then chromatographed on a silica dry with Extraction of the leading half of the column ether followed by evaporation gives g of crude Distillation provides g of pure Preparation of The procedure of Example 12 is followed using g of in 100 of ethyl acetate and g of chlorine added in The reaction temperature rises to about 68 Evaporation of the reaction solution gives an orange The oil chromotographed on silica dry column with The leading half of the column is extracted with ether and evaporated to yield g of crude Distillation gives g of pure mm The novel isothiasolidinones of the invention are active wh ch are particularly useful for the control of For the isothiazolidinones are especially effective as bactericidal and slimicidal Furthermore these novel compounds have generally demonstrated expectedly fast against undesirable microorganisms Antibacterial and fungicidal activity evaluated by the Serial Dilution Test Titer wherein a series of broths containing varying dilutions of a test compound and an organism are halved starting with a dilution of The values which are summarized in Table represent the maximum dilution in parts per million by weight at which the compound under evaluation renders complete control of the aureus Escheri hia coli and Pseudomo as aeruginosa were the bacterial organisms employed in this and the fungi employed Aspergillus and us stoloni er TABLE II 7 125 125 125 8 125 63 125 9 125 63 63 10 63 125 63 11 125 125 63 12 125 125 13 125 125 125 15 16 125 125 18 The isothiazolidinones of t e are also effective as plant bactericides plant Among the phytopathogenic bacteria and fungi are controlled by compounds of the invention are bean powdery mildew rice blast late blight cereal rust recon downy and bacterial leaf spot When used as plant bactericides or the isothiazolidinones are generally applied at a rate of about to about 25 pounds per preferably to about pounds per The rate of application is usually dependent on the isothiazolidinone the phytopathogenic organism to be the method and type of and other similar control of a living organism is achieved in accordance this invention by contacting the organism with an isothiazolidinone of the invention in an amount which is effective to control the Any of the techniques knovm in the art can be employed to disseminate the isothiazolidinones in a manner so as to achieve the contact with the organism to be The compounds of this invention can be readily utilized slimicides and fungicides in any locus and particularly in aqueous such example swimming paper pulp aqueous polymer based and the In these compounds and compositions containing them can function as for soap sanitizing such as in laundry soaps and preservatives for metal such as cutting preservatives for fiber spin finish and the The isothiaaoiidinones of the invention are also useful as laundry sanitizing in which fast is particularly about tc 10 by weight and preferably about about by of the isothiazolidinone is added to a soap or detergent to make a sanitizing laundry Isothiazolidinones can also be added to the laundry wash generally at a concentration of about to about 1000 parts per million by In a locus subject to contamination by microorganisms can be protected in accordance with this invention by incorporating into the locus an isothiazolidinone of the invention in an amount which is effective to control the The term is meant to include attack by microorganisms which leads to a chemical or physical breakdown or disintegration of the locus as well as proliferation of the microorganisms the locus without an accompanying deleterious The exact amount of isothiazolidinone of vary with the medium being the microorganisms being the particular isothiazolidinones or compositions containing the isothiazolidinones being the degree of control and other in a liquid medium suitable control is obtained when the isothiazolidinones are incorporated in the range of to parts per The term as employed in the claims this application is construed as the effect o adversely affects the existence growth of any living organism or This effect may complete killing arresting in reduction in number or any combination of these The isothiazolidinones of the invention are also useful as paint preservatives and paint Microbial activity in and emulsions is inhibited when the isothiazolidinones are incorporated into the The isothiazolidinones are mildewcides for paint films when in paint The isothiazolidinones of this invention are especially useful as agricultural bactericides and they are particularly valuable when in bactericidal and fungicidal Such compositions normally an agronomical ble carrier and an isothiazolidinone of the invention or mixture of such isothiazolidinones as the active Where necessary or surfactants or other additives may be incorporated to give uniformly formulated By acceptable is meant any substance which can be utilized to or diffuse chemical incorporated therein without impairing the effectiveness of the toxic agent and which does permanent damage to the or agronomic For use as the compounds of this invention are usually taken up in an agronomically acceptable carrier or formulated so as to render them isothiazolidinones of the Invention can be formulated as wettable emulsion granular aerosols or flowable emulsifiable In such the isothiazolidinones are extended with a liquid or solid carrier when suitable surfactants are Compounds of this invention can be dissolved in a such as and Such solutions are easily extended with The isothiazolidinones of the invention can be taken up on or mixed with a finely particled solid as for inorganic and Organic carriers can also be Dust concentrates ar commonly made wherein isothiazolidinones of the invention are present in the range of 20 to by For ultimate these concentrates are normally extended with additional solid from about 1 to by Wettable powder formulations are made by incorporating the compounds of this invention in an finely divided solid along with a surfactant which may be one or dispersing or spreading agents or blend of The isothiazolidinones of the invention are usually present in the range of 10 to by weight and the surfactants in from to by emulsifying and wetting agents include polyoxyethylated derivatives of alkylphenols fatty fatty and alkylarenesulfonates and dialkyl Spreading and oleic acid phthalic Dispersing agents include such materials as the salt of the copolymer of aleic anhydride and an olefin such as d iisobutylene ligninsulfonate sodium One convenient method for preparing a solid formulation is to impregnate the toxicant onto the solid carrier by means of a volatile such as In this manner such as plant synergists and various can also be formulations can be prepared by the isothiazolidinones of this invention in an agronomically acceptable organic solvent and adding a emulsifying Suitable solvents are usually and may be found in the chlorinated alcohol and amide classes of organic Mixtures of solvents are commonly The surfactants useful as emulsifying agents may constitute about to by weight of the emulsifiable concentrate and may be cationic or in Anionic surfactants include alcohol sulfates or arene sulfonates and sulfosuccinates surfactants include fatty acid alkylamine salts and fatty acid alkyl quaternary ammonium emulsifying agents include alkylene oxide adducts of alkylphenols fatty alcohols mercaptans and fatty The concentration of the active ingredients vary from 10 to preferably in the range of 25 to For use as phytopathogenic the compounds of the invention should be applied in an effective amount sufficient to exert the desired biocidal activity by techniques well known in the this will involve the application of the isothiazolidinones of the invention to the locus to be protected in an effective when incorporated in an agronomical acceptable in certain situations it may be desirable and advantageous to apply the onto the locus to protected without the benefit of any substantial amount of This is a particularly effective method when the physical nature of the isothiazolidinone is such as permit what is as that when the compounds are in form or substantially soluble in higher boiling The application rate of vary depending upon the purpose for such the being the frequency of dissemination and the For use as agricultural bactericides and dilute sprays can applied at concentrations of to 20 pounds of the active isothiazoLidinone ingredient per 100 gallons of They are usually applied at to 10 per 100 gallons and preferably to 5 pounds 100 In more concentrated the active ingredient is increased by a factor of 2 to With dilute applications are usually made to the plants until is whereas with more concentrated or sprays the materials are applied as of this invention may be sed the agents or may be oyed in other te insecticide or coinparable insufficientOCRQuality

Claims

1. 44299/2 M- WHAT WE CLAIM IS or a salt or a metal salt complex of the compound of formula I wherein R1 is (C^C^) alkyl , phenyl (C^C^alkyl , cycloalkyl of up to 6 carbon atoms, phenyl or phenyl substituted by halogen or (C^-C^ ) alkyl ; 2 R is halogen or (C-^-C^ alkyl ; 3 . ' R . is halogen; and X is halogen, the two X substituents being the same or different.

2. A compound according to Claim 1 , wherein 1 · 3 R is ci~C2o alkyl' each X substituent and R is chlorine 2 . and R is methyl or chlorine.

3. A compound according to Claim 1 being any one of the compounds whose preparation is described in foregoing Examples 1-17.

4. A biocidal composition which' comprises a carrier and a compound according to any of Claims

5. A method of controlling microorganisms which comprises contacting the microorganisms with an effective amount of a compound according to any of Claims 1-3. 44299/2

6. A method according to Claim 5 wherein the microorganisms are bacteria or fungi.

7. A method according to Claim 5 wherein the microorganisms are phytopathogenic bacteria or fungi.

8. A method for protecting a locus subject to contamination by microorganisms which comprises incorporating into the locus a compound according to any of Claims 1-3 in an amount which is effective to control the microorganisms.

9. A method according to Claim 8 wherein the locus is an aqueous medium.

10. A laundering composition which comprises a soap or a synthetic detergent and a compound according to any of Claims 1-3.

11. Paper pulp, aqueous polymer dispersions, water-based paints, fabrics, leather, cosmetics, sanitizing agents, metal working compositions, fuels and fiber spin finishes and containing, as a biocide, a compound according to any of Claims 1-3.