WO1994002451A1 - Halo alkynyl urea derivatives, a method for their production and fongicidal compositions containing them - Google Patents
Halo alkynyl urea derivatives, a method for their production and fongicidal compositions containing them Download PDFInfo
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- WO1994002451A1 WO1994002451A1 PCT/US1993/007024 US9307024W WO9402451A1 WO 1994002451 A1 WO1994002451 A1 WO 1994002451A1 US 9307024 W US9307024 W US 9307024W WO 9402451 A1 WO9402451 A1 WO 9402451A1
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- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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- This invention is directed to novel fungicidal agents. More particularly, this invention is directed to urea derivatives, the preparation thereof, and their use as fungicidal and algaecidal agents.
- U.S. Patent No. 1,841,768 teaches the preparation of chloro and bromo substituted ethine carbinols. They are disclosed as pharmaceutically valuable and for therapeutic use.
- U.S. Patent No. 2,989,568 also relates to the preparation of chloro and bromo-substituted acetylenic alcohols. The compounds are described as useful as corrosion inhibitors and inhibitors for plating baths.
- U.S. Patent No. 2,791,603 is directed to carbamates (urethanes) of tertiary acetylenic carbinols useful as anti-convulsants.
- U.S. Patent No. 3,436,402 teaches certain halogenated carbamates of diaryl substituted alkynes.
- R., R, and R,. are independently H or an unsubstituted or substituted alkyl, aryl, arylalkyl, alkenyl, alkylaryl or cycloalkyl group having from one to not more than 20 carbon atoms, R is H or a substituted or unsubstituted alkyl group having from one to not more than 20 carbons and having from one to three linkages (valences) corresponding to m, and X is I or Br.
- This invention provides halo alkynyl urea derivatives of the formula:
- R, R., R b , -R ⁇ ., X, m and n are as defined above.
- the various groups R quarant R b and R c may be the same or different, but R,. is H or alkyl when either R a or R b or both are aryl.
- R,. is H or alkyl when either R a or R b or both are aryl.
- none of R, R,, R b , and R,. have
- This invention is directed to halo alkynyl urea derivatives according to
- This invention is also directed to the preparation of the compounds of the formula I by reacting an amine of the formula:
- R,, R b or R examples include hydrogen and linear or branched alkyl groups of from 1 to 6 carbon atoms represented by any of methyl, ethyl, propyl,
- cycloalkyl radicals with from 4 to 8 carbon atoms, including cyclopentyl, cyclohexyl and cycloheptyl groups, and arylalkyl and alkylaryl groups of 6 to 10 carbon atoms such as phenyl, tolyl, naphthyl, and benzyl.
- Such moieties also can be substituted with radicals that do not adversely affect the process for making the halo alkynyl urea of the above formula or its use as a fungicide or algaecide.
- Preferred substituents include hydroxyl, cyano or nitro groups or halogen atoms.
- Compounds of formula I in which both R, and R b are either hydrogen or methyl, as well as those compounds in which one or both of R, and R b is hydrogen or one is methyl are preferred.
- linear or branched alkyl groups of from 1 to 20 carbon atoms represented by R include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups as well as the branched isomers of the alkyls having from 5 to 12 carbon atoms. It is preferred if R represents a group having 8 or fewer carbons.
- R is a cycloalkyl of from 4 to 8 carbon atoms it may, for example, be a cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl group.
- R represents a lower alkyl of from 1
- R represents, for example, propyl, butyl, or cyclohexyl group.
- R may also represent linear or branched alkenyl groups or cycloalkenyl groups, such as propenyl, butenyl, pentenyl and hexenyl groups and the respective isomers of the alkenyls mentioned having 4-8, preferably, 5 or 6 carbon atoms, including cycloalkenyls.
- the moieties represented by R also can be substituted with radicals that do not adversely affect the process for making the halo alkynyl urea of the above formula or its use as a fungicide or algaecide.
- Preferred substituents include hydroxyl, cyano or nitro groups or halogen atoms.
- the isocyanates of Formula III may include any R group that will form a compound according to Formula I upon reaction with an amine of Formula II.
- Such isocyanates include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, and cyclohexylisocyanate.
- the alkynyl ureas of this invention may also be synthesized by the reaction of amines of Formula II with alkyl di-isocyanates or alkyl tri-isocyanates c ormula in to produce an alkyl group substituted with two or three alkynyl ure, Oieties.
- Such polyisocyanates are well known in the polyurethane art, and include hexamethylene-l ,6-diisocyanate, tetramethylene-l,4-diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'- dicyclohexylmethyl diisocyanate, and the like.
- the preferred halo alkynyl ureas of this invention are iodo alkynyl ureas.
- the iodo alkynyl ureas of Formula I may be synthesized by reacting primary or secondary amines of Formula II with equimolar amounts of the isocyanates of Formula HI and iodinating the resultant alkynyl urea according to standard procedures. It will be apparent to the skilled worker that bromo alkynyl ureas of Formula I may be prepared similarly.
- alkynyl urea is carried out at temperatures from about 0° to 100°C, preferably from about 20° to 70°C, usually in an inert solvent.
- suitable solvents include ethylene chloride, dimethyl formamide, toluene, chlorobenzene, methylene chloride, and tetrahydrofuran and the like.
- the reaction can be accelerated with catalysts such as, for example, dibutyltin carboxylates of fatty acids.
- Catalysts that may be used also include tertiary bases such as triethylamine.
- urea is the procedure for halogenation of alkynes taught in Singer, U.S. Patent 3,923,870 incorporated herein by reference. Surprisingly, the procedure of this invention can be used to produce an unsubstituted halo alkynyl urea from an alkynyl amine.
- An alkynyl amine according to formula II is reacted with hydrocyanic acid to form alkynyl urea which can then be halogenated in a second step.
- the halogenation reaction selectively substitutes the alkynyl carbon in preference to the urea nitrogen.
- the compounds according to the invention are suitable, for example, for the preservation of technical products, such as paints, glues, dispersions, or cold lubricants, or for the antimicrobial treatment of joint caulking compounds, such as silicon caulks. They are also suitable for the elimination of mold, for example, mold on wet walls, ceilings, or floors, for the preservation of wood, and for the antimicrobial treatment of plastics, such as polyolefm or polyvinyl chloride (PNC) foils. Furthermore, the compounds according to the invention can be used as disinfectants or as preservatives for cosmetics.
- the antimicrobial compositions described herein are particularly effective as fungicidal compositions.
- one or more compounds according to the invention can be incorporated by a known method into liquid, paste, or solid preparations that are in the form of solutions, suspensions, or emulsions.
- the compounds of the invention should be present in a fungicidally or algaecidally effective amount and preferably will be present in amounts of from about 0.01 to 5% by weight based upon the weight of the total antimicrobial preparation, although other concentrations are possible depending upon the specific application. Concentrates for the make-up of such ready-for-use preparations may conveniently contain the compounds of the invention in amounts of up to 50% by weight, based upon the weight of the total concentrate.
- the remainder of the antimicrobial composition will contain conventional formulation ingredients, such as, for example, water, organic solvents such as, for example ethanol, isopropanol, acetone, toluene and ethyl acetate, surfactants and binders.
- conventional formulation ingredients such as, for example, water, organic solvents such as, for example ethanol, isopropanol, acetone, toluene and ethyl acetate, surfactants and binders.
- the compounds according to the invention should comprise from about 0.001 to 5% by weight, preferably from about 0.01 to 3% by weight, based upon the weight of the total preparation. In most instances an antimicrobial composition such as that described above will be admixed with the desired substance. However, it is within the scope of the invention that one or more compounds of Formula I could be added directly.
- the fungicidal activity of the iodopropargylalkyl urea derivatives were determined by standard microbiological test methods, as well as international norms (MIC, ASTM, DIN). As an example of a very effective alkyl derivative the butyl compound was evaluated.
- Ch ⁇ etomi m globositm 50 ppm x spergill s niger 250 ppm
- the fungicidal efficacy was determined according to the ASTM Standard
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Abstract
Novel fungicidal compounds are urea derivatives of iodo alkynyls, having formula (I), in which R is H or an alkyl group having one to not more than 20 carbon atoms, Ra to Rc are H or a substituted or unsubstituted alkyl, aryl, aralkyl or cycloalkyl group having from one to not more than 20 carbons and Rc is H or alkyl when Ra or Rb is aryl, n and m are a whole number integers between 1 and 3, and X is I or Br. These compounds have shown great fungicidal activity, particularly when used in surface coating compositions, such as paint formulations, and for the protection of wood and wood type material.
Description
HALO ALKYNYL UREA DERIVATIVES, A METHOD FOR
THEIR PRODUCTION AND FUNGICIDAL COMPOSITIONS
CONTAINING THEM
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
This invention is directed to novel fungicidal agents. More particularly, this invention is directed to urea derivatives, the preparation thereof, and their use as fungicidal and algaecidal agents. REVIEW OF RELATED ART
One of the most effective and efficient classes of fungicides now known is generally considered to be the organically substituted mercury compounds. They have been particularly valuable because they control attack by a wide spectrum of micro-organisms, may be used at low concentration, and have
considerable permanence when this characteristic is desirable (as in surface coatings). However, the reputation of these compounds has deteriorated recently because of toxic and environmental hazards, and they are being eliminated or phased out as commercial fungicides.
Other fungicides which have been developed and which have been placed on the market from time to time as mercurial substitutes are listed below, but none of these has proved to be entirely satisfactory. a. Captan - not stable to hydrolysis, particularly in alkaline systems; b. trans, di-n-propyl-l,2-ethene - not stable in aqueous systems; c. 4-methyl sulfonyl tetrachloropyridine - not stable in alkaline
systems; d. 2-(4 Thiazolyl)-benzimidazole - expensive and relatively ineffective against Alternaria sp. (a prevalent organism in the south); e. p-chloro (or methyl) phenyl diiodomethyl sulfone - causes yellowing, ineffective in oil-based systems and relatively susceptible to degradation due to weathering; f. octylisothiazolone - expensive, relatively susceptible to degradation due to weathering, and requires zinc oxide as a synergist.
Certain halogenated acetylenic alcohols and derivatives therefrom have been described for various uses.
U.S. Patent No. 1,841,768 teaches the preparation of chloro and bromo substituted ethine carbinols. They are disclosed as pharmaceutically valuable and for therapeutic use. U.S. Patent No. 2,989,568 also relates to the
preparation of chloro and bromo-substituted acetylenic alcohols. The compounds are described as useful as corrosion inhibitors and inhibitors for plating baths. U.S. Patent No. 2,791,603 is directed to carbamates (urethanes) of tertiary acetylenic carbinols useful as anti-convulsants. U.S. Patent No. 3,436,402 teaches certain halogenated carbamates of diaryl substituted alkynes.
In U.S. Patent 3,923,870, Singer disclosed iodopropargyl carbamate and
taught the use of this compound as a fungicide. Others confirmed the use of halopropargyl carbamate and its derivatives as fungicides (Versfelt, et al. (1984), GB 2,140,299; Morell (1987), J. Wood Fiber Sci. 19:388-391; Leathers, et al. (1989), U.S. Pat. 4,806,263; Gertjejansen, et al. (1989), For. Prod. J.. 39:15-19; Kusaba, et al. (1989), U.S. Pat. 4,841,088; and Rayudu (1990), EP 0 365 121). Bacteriocidal activity has also been reported for propargyl ethers by Makhsumov, et al. (1968, Izv. Akad. Nauk. SSSR. Ser. Khim.. No. 11, 2591-2593). N-(3-iodopropargyl) carbazole was disclosed by Shklover, et al. (1990, Mol. Cryst. Liq. Crvst.. Vol. 180B, pp. 417-423), but no utility was suggested for the compound.
Despite the number of alternatives to organo-mercurial fungicides, there remains a need for novel compounds with fungicidal activity.
SUMMARY OF THE INVENTION
It is the object of the invention to provide novel fungicidal and algaecidal
agents.
It is also an object of the invention to provide halo alkynyl ureas of the formula:
I
[XC ~≡ C-[C]n-N-CO-NH]mR
I I
Rb Rc
where m and n are whole number integers between 1 and 3 and may be the same or different, R., R,, and R,. are independently H or an unsubstituted or substituted alkyl, aryl, arylalkyl, alkenyl, alkylaryl or cycloalkyl group having from one to not more than 20 carbon atoms, R is H or a substituted or unsubstituted alkyl group having from one to not more than 20 carbons and having from one to three linkages (valences) corresponding to m, and X is I or Br.
This invention provides halo alkynyl urea derivatives of the formula:
R.
I
[XC ≡ C-[C]n-N-CO-NH]mR Formula I
where R, R., Rb, -R<., X, m and n are as defined above. The various groups R„ Rb and Rc may be the same or different, but R,. is H or alkyl when
either Ra or Rb or both are aryl. Preferably, none of R, R,, Rb, and R,. have
more than 8 carbons.
These compounds have shown fungicidal activity, particularly when used in surface coating compositions, such as paint formulations, and for the
protection of wood and wood type material.
DETAILED DESCRIPTION OF THE INVENTION
This invention is directed to halo alkynyl urea derivatives according to
formula I. This invention is also directed to the preparation of the compounds of the formula I by reacting an amine of the formula:
R.
I
HC ≡ C-CC -NHRc Formula II
I Rb
with an equimolar amount of a suitable isocyanate of the formula:
R[NCO]m Formula III
where m, R and R, to -R, are defined as above and, in a second step, halogenating the product to form the compounds of the general formula of the invention:
R.
I
[XC≡C-[C]n-N-CO-NH]mR
Examples of R,, Rb or R,. include hydrogen and linear or branched alkyl groups of from 1 to 6 carbon atoms represented by any of methyl, ethyl, propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and hexyl groups and branched isomers thereof, or alkenyl groups of from 2 to 8 carbon atoms represented by vinyl, allyl, propenyl, butenyl, pentenyl and hexenyl groups and the respective isomers of the alkenyls mentioned having 4-8, preferably, 5 or 6 carbon atoms, including cycloalkenyls. Examples of R„ Rb or R«. also include cycloalkyl radicals with from 4 to 8 carbon atoms, including cyclopentyl, cyclohexyl and cycloheptyl groups, and arylalkyl and alkylaryl groups of 6 to 10 carbon atoms such as phenyl, tolyl, naphthyl, and benzyl. Such moieties also can be substituted with radicals that do not adversely affect the process for making the halo alkynyl urea of the above formula or its use as a fungicide or algaecide. Preferred substituents include hydroxyl, cyano or nitro groups or halogen atoms. Compounds of formula I in which both R, and Rb are either hydrogen or methyl, as well as those compounds in which one or both of R, and Rb is hydrogen or one is methyl are preferred.
Examples of linear or branched alkyl groups of from 1 to 20 carbon atoms represented by R, include methyl, ethyl, propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups as well as the branched isomers of the alkyls having from 5 to 12 carbon atoms. It is preferred if R represents a group having 8 or fewer carbons. If R is a cycloalkyl of from 4 to 8 carbon atoms it may, for example, be a cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl group. Compounds in which R represents a lower alkyl of from 1
to 6 carbon atoms are more preferred. Especially preferred compounds are those which R represents, for example, propyl, butyl, or cyclohexyl group. R may also represent linear or branched alkenyl groups or cycloalkenyl groups, such as propenyl, butenyl, pentenyl and hexenyl groups and the respective isomers of the alkenyls mentioned having 4-8, preferably, 5 or 6 carbon atoms, including cycloalkenyls. The moieties represented by R also can be substituted with radicals that do not adversely affect the process for making the halo alkynyl urea of the above formula or its use as a fungicide or algaecide. Preferred substituents include hydroxyl, cyano or nitro groups or halogen atoms.
The isocyanates of Formula III may include any R group that will form a compound according to Formula I upon reaction with an amine of Formula II. Such isocyanates include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, and cyclohexylisocyanate. The alkynyl ureas of this invention may also be synthesized by the reaction of amines of Formula II with alkyl di-isocyanates or
alkyl tri-isocyanates c ormula in to produce an alkyl group substituted with two or three alkynyl ure, Oieties. Such polyisocyanates are well known in the polyurethane art, and include hexamethylene-l ,6-diisocyanate, tetramethylene-l,4-diisocyanate, cyclohexane 1,4-diisocyanate, 4,4'- dicyclohexylmethyl diisocyanate, and the like.
Based on antifungal efficacy, the preferred halo alkynyl ureas of this invention are iodo alkynyl ureas. The iodo alkynyl ureas of Formula I may be synthesized by reacting primary or secondary amines of Formula II with equimolar amounts of the isocyanates of Formula HI and iodinating the resultant alkynyl urea according to standard procedures. It will be apparent to the skilled worker that bromo alkynyl ureas of Formula I may be prepared similarly.
The synthesis of alkynyl urea is carried out at temperatures from about 0° to 100°C, preferably from about 20° to 70°C, usually in an inert solvent. Suitable solvents include ethylene chloride, dimethyl formamide, toluene, chlorobenzene, methylene chloride, and tetrahydrofuran and the like. The reaction can be accelerated with catalysts such as, for example, dibutyltin carboxylates of fatty acids. Catalysts that may be used also include tertiary bases such as triethylamine. A preferred method of halogenating the alkynyl
urea is the procedure for halogenation of alkynes taught in Singer, U.S. Patent 3,923,870 incorporated herein by reference.
Surprisingly, the procedure of this invention can be used to produce an unsubstituted halo alkynyl urea from an alkynyl amine. An alkynyl amine according to formula II is reacted with hydrocyanic acid to form alkynyl urea which can then be halogenated in a second step. The halogenation reaction selectively substitutes the alkynyl carbon in preference to the urea nitrogen.
Due to their microbiostatic and microbiocidal effect, the compounds according to the invention are suitable, for example, for the preservation of technical products, such as paints, glues, dispersions, or cold lubricants, or for the antimicrobial treatment of joint caulking compounds, such as silicon caulks. They are also suitable for the elimination of mold, for example, mold on wet walls, ceilings, or floors, for the preservation of wood, and for the antimicrobial treatment of plastics, such as polyolefm or polyvinyl chloride (PNC) foils. Furthermore, the compounds according to the invention can be used as disinfectants or as preservatives for cosmetics. The antimicrobial compositions described herein are particularly effective as fungicidal compositions.
For use in antimicrobial compositions, one or more compounds according to the invention can be incorporated by a known method into liquid, paste, or solid preparations that are in the form of solutions, suspensions, or emulsions. In preparations ready for use, the compounds of the invention should be present in a fungicidally or algaecidally effective amount and preferably will be present in amounts of from about 0.01 to 5% by weight based upon the weight of the
total antimicrobial preparation, although other concentrations are possible depending upon the specific application. Concentrates for the make-up of such ready-for-use preparations may conveniently contain the compounds of the invention in amounts of up to 50% by weight, based upon the weight of the total concentrate. The remainder of the antimicrobial composition will contain conventional formulation ingredients, such as, for example, water, organic solvents such as, for example ethanol, isopropanol, acetone, toluene and ethyl acetate, surfactants and binders.
When the antimicrobial or fungicidal compositions are admixed with a desired substance to preserve the substance, the compounds according to the invention should comprise from about 0.001 to 5% by weight, preferably from about 0.01 to 3% by weight, based upon the weight of the total preparation. In most instances an antimicrobial composition such as that described above will be admixed with the desired substance. However, it is within the scope of the invention that one or more compounds of Formula I could be added directly.
The examples below are intended to illustrate the invention and should not be construed as limiting the invention thereto. Example 1; 3-Iodo-2-Propynyl-n-bιιtyI-Urea
0.1 mol. (5.5g) of propargylamine was placed in a reaction flask and dissolved in 20g of tetrahydrofuran (THF), then 0.1 mol. (9.9g) of n-butyl isocyanate was added dropwise. The exothermic reaction was controlled by
cooling so that the temperature did not exceed 50'C. After a reaction time of 10 minutes, the urea precipitated out. For an additional 30 minutes, the reaction mixture was kept at 50'C, then the solvent was evaporated under vacuum, and the slight yellow propargyl butyl urea was used without further purification (15. lg = yield 98%).
In a second step the propargyl butyl urea was iodinated in the presence of solvents (for example, hydrocarbons, aromatics, ethers, esters, alcohols) according to literature procedures. (See, e.g., Singer, U.S. Patent 3,923,870, incorporated herein by reference.)
Then the residual solvent was removed by vacuum drying procedure, and
24.3g (87.9% yield of the theory) were obtained as a creme yellow powdery substance which was recrystallized into a white crystallinic substance (melting point 131 to 133°C). The substance has a moderate overall solubility, with good solubilities in alcohols and slight solubility in hydrocarbons. It is practically insoluble in water.
Molecular Formula: CgH13IN2O
Molecular Weight: 280.11
Analysis % C H I
calculated 34.27 4.64 45.30 found 34.52 4.68 44.01
IR (film: cm^ IC ≡C: 2175; (HC≡C: 2115) MS:
254 I2 (recombination)
Example 2; 3-Iodo-2-Propynyl Propyl Urea
The procedure described in Example 1 was followed. The reaction was set up using 5.5g (0.1 mol) of propargylamine, which was placed in a reaction flask and dissolved in 20g of THF, then 8.5g (0.1 mol) of propyl isocyanate was added dropwise. After holding for further 30 minutes at 50°C, the solvent was evaporated, and the resulting cremish yellow solid powder (yield: 13.6g = 97.1 %) was used for the iodination without further purification. The iodinated product (yield: 22.3g = 86%) was a white crystalline powder which melted at 138-139°C.
Molecular Formula: C7HnIN2O Molecular Weight: 266.09
Analysis % H
calculated 31.45 4.12 47.51 found 31.63 4.20 46.85
The fungicidal activity of the iodopropargylalkyl urea derivatives were determined by standard microbiological test methods, as well as international norms (MIC, ASTM, DIN). As an example of a very effective alkyl derivative the butyl compound was evaluated.
Efficacy of 3-iodo-2-propynyl-butyl urea:
A modified MIC petri dish method according to Schultz et al., 1990
Phytochem.. 29: 1501-1507 (incorporated herein by reference) revealed the following approximate values of concentration for 100% inhibition of growth:
Aureobasidium pullulans 100 ppm
Chαetomi m globositm ( 50 ppm x spergill s niger 250 ppm
The fungicidal efficacy was determined according to the ASTM Standard
Method D1413 -76 (Reapproved 1986) (incorporated herein by reference) as well as DIN Standard Method EN 113 (published February 1986, and incorporated herein by reference), and it is reported as the concentration of fungicide required to protect (pcf-pounds of fungicide impregnated per cubic foot or Kg/m3-kilograms of fungicide impregnated per cubic meter).
Gloeophyllum trαbeum 0.018-0.020 pcf
Coriol s versicolor 0.020-0.022 pcf
Coniophorα puteαnα 0.053-0.055 pcf
Poriα placenta ) 0.042 pcf Serpula lacrymans 0.6-0.9 kg/m3
The preceding examples are provided by way of illustration and are not
intended to limit the scope of this invention. The teaching of the present disclosure will no doubt suggest numerous variations to those skilled in the art, and these variations are within the contemplation of the present invention, which is limited only by the appended claims.
Claims
1. A compound of the formula
R.
I
[XC as C-[C]n-N-CO-NH]mR
2. The compound according to claim 1 in which R is substituted alkyl, branched alkyl or cycloalkyl and the substituents are selected from the group consisting of hydroxyl, halogen, cyano and nitro.
3. The compound according to claim 1 in which at least one of R, Ra, Rb, and R,. is substituted with at least one substituent selected from the group consisting of hydroxyl, halogen, cyano and nitro.
4. The compound according to claim 1 in which none of R, Ra, Rb, and Rc have more than 8 carbons.
5. The compound according to claim 1 in which X is I.
6. The compound according to the formula of claim 1 in which n is 1.
7. The compound according to claim 6 where R is selected from the group consisting of ethyl and propyl.
8. The compound according to claim 1 which is 3-Iodo-2-propynyl-butyl urea.
9. The compound according to claim 1 which is 3-Iodo-2-propynyl-tert-butyl urea.
10. The compound according to claim 1 which is 3-Iodo-2-propynyl-hexyl urea.
11. The compound according to claim 1 which is 3-Iodo-2-propynyl-methyl urea.
12. The compound according to claim 1 which is 3-Iodo-2-propynyl-isopropyl urea.
13. The compound according to claim 1 which is 3-Iodo-2-propynyl-isobutyl urea.
14. The compound according to the formula of claim 1 in which n is 2.
15. The compound according to claim 1 wherein R is H.
16. A method of making the compound of claim 15 comprising the steps of: a. reacting hydrocyanic acid with an amine of the formula
R.
I
HC≡C-[C]n-NHRc
wherein Rt to R,. are independently H or a substituted or unsubstituted alkyl, aryl, alkaryl or cycloalkyl group having 1-20 carbons and n is a whole number integer between 1 and 3; b. reacting the product of step (a) with a halogen molecule selected from the group consisting of I2 and Br2.
17. A fungicidal composition comprising a compound of claim 1 and a diluent.
18. The composition according to claim 17 in which X is I.
19. The composition according to claim 17 in which n is 1.
20. The composition according to claim 19 where R is selected from the group consisting of ethyl and propyl.
21. The fungicidal composition according to claim 17 comprising 3-Iodo-2-propynyl-butyl urea and a diluent.
22. The fungicidal composition according to claim 17 comprising 3-Iodo-2-propynyl-tert-butyl urea and a diluent.
23. The fungicidal composition according to claim 17 comprising
3-Iodo-2-propynyl-hexyl-urea and a diluent.
24. The fungicidal composition according to claim 17 comprising 3-Iodo-2-propynyl-methyl-urea and a diluent.
25. The fungicidal composition according to claim 17 comprising
3-Iodo-2-propynyl-isopropyl urea and a diluent.
26. The fungicidal composition according to claim 17 comprising 3-Iodo-2-propynyl-isobutyl urea and a diluent.
27. The composition according to claim 17 in which n is 2.
28. The composition according to claim 17 wherein R is H.
29. The composition according to claim 17 in which R is substituted alkyl, branched alkyl or cycloalkyl and the substituents are selected from the group consisting of hydroxyl, halogen, cyano and nitro.
30. The composition according to claim 17 in which at least one of R, R,, Rb, and R,. is substituted with at least one substituent selected from the group consisting of hydroxyl, halogen, cyano and nitro.
31. The composition according to claim 17 in which none of R, R,, Rb, and Rc have more than 8 carbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU47865/93A AU4786593A (en) | 1992-07-24 | 1993-07-26 | Halo alkynyl urea derivatives, a method for their production and fongicidal compositions containing them |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91804192A | 1992-07-24 | 1992-07-24 | |
| US918,041 | 1992-07-24 | ||
| US9540393A | 1993-07-23 | 1993-07-23 | |
| US095,403 | 1993-07-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1994002451A1 true WO1994002451A1 (en) | 1994-02-03 |
Family
ID=26790180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1993/007024 WO1994002451A1 (en) | 1992-07-24 | 1993-07-26 | Halo alkynyl urea derivatives, a method for their production and fongicidal compositions containing them |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU4786593A (en) |
| WO (1) | WO1994002451A1 (en) |
Citations (5)
| 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 |
| GB2138292A (en) * | 1983-04-18 | 1984-10-24 | Troy Chemical Corp | Haloalkynes and their use as fungicides |
| GB2140299A (en) * | 1983-04-18 | 1984-11-28 | Troy Chemical Corp | Use of haloalkynyl carbamates in treating micro-organisms |
| US4841088A (en) * | 1986-08-26 | 1989-06-20 | Sumitomo Chemical Company, Limited | Iodopropargyl carbamate derivative, a method for its production and fungicidal compositions containing it as an active ingredient |
| EP0365121A1 (en) * | 1988-08-24 | 1990-04-25 | Buckman Laboratories International, Inc. | Ester of carbamic acid useful as a microbicide and preservative |
-
1993
- 1993-07-26 WO PCT/US1993/007024 patent/WO1994002451A1/en active Application Filing
- 1993-07-26 AU AU47865/93A patent/AU4786593A/en not_active Abandoned
Patent Citations (5)
| 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 |
| GB2138292A (en) * | 1983-04-18 | 1984-10-24 | Troy Chemical Corp | Haloalkynes and their use as fungicides |
| GB2140299A (en) * | 1983-04-18 | 1984-11-28 | Troy Chemical Corp | Use of haloalkynyl carbamates in treating micro-organisms |
| US4841088A (en) * | 1986-08-26 | 1989-06-20 | Sumitomo Chemical Company, Limited | Iodopropargyl carbamate derivative, a method for its production and fungicidal compositions containing it as an active ingredient |
| EP0365121A1 (en) * | 1988-08-24 | 1990-04-25 | Buckman Laboratories International, Inc. | Ester of carbamic acid useful as a microbicide and preservative |
Also Published As
| Publication number | Publication date |
|---|---|
| AU4786593A (en) | 1994-02-14 |
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