CA1113857A - 1-acryloyl-3-(substituted)phenyl ureas - Google Patents
1-acryloyl-3-(substituted)phenyl ureasInfo
- Publication number
- CA1113857A CA1113857A CA319,369A CA319369A CA1113857A CA 1113857 A CA1113857 A CA 1113857A CA 319369 A CA319369 A CA 319369A CA 1113857 A CA1113857 A CA 1113857A
- Authority
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- Canada
- Prior art keywords
- compound
- acryloyl
- lbs
- methyl
- fungicide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Biochemistry (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Textile Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
1-ACRYLOYL-3-(SUBSTITUTED)PHENYL UREAS
Abstract of the Disclosure 1-Acryloyl-3-(substituted)phenyl ureas have been found to be highly effective as fungicides when incorporated into or applied to agricultural media, plastics, paints or the like.
Abstract of the Disclosure 1-Acryloyl-3-(substituted)phenyl ureas have been found to be highly effective as fungicides when incorporated into or applied to agricultural media, plastics, paints or the like.
Description
1~13~ 7 Detailed DescriPtlon of the Invention Useful agricultural crops, plant life in general, paints, painted surfaces and plastics often are attacked by various types of common fungi. Particularly, fruit and vegetable bearing plants frequently host fungi which may damage the fruit or vegetable to the point where it cannot be marketed and, therefore, drastic reduction in harvest income can result. Also, plastics and painted surfaces used or stored in moist atmospheres are often attacked by fungi which produces unsightly surfaces.
It has now been found that crops of the above nature, plastics, paints and the like can be protected by applying to such substrates a compound of the formula .
, O
I. X ~ -NH-C-NH-CO-CH~CH2 wherein X represent~ H, Cl, CN, OR, COOR, SR, NO2 or R wherein R is linear or branched saturated loweralkyl. These acryloyl ureas are effective at concentrations of 10-5000 ppm and these concentrations are not damaging to the plants or crops them-selves, and they do not discolor paints to which they are added or plastics in which they are incorporated.
The compounds of the above formula can be applied directly to paints or plactic iormulations or they can be '~
.
. ~
, .. . .
applied to agronomical substrates as solutions or dusts.
Sprays are preferably prepared from a water-dispersible or from an emulsifyable liquid concentrate. Such concentrates can be made by dissolving the active ingredient in dimethyl-S sulfoxide, tetrahydrofuran, chloroform, tetrahydrofurfuryl alcohol, or acetone, a mixture thereof or a mixture o either of these solvents with small amounts of water, lower alkanols, dimethylformamide, dimethylacetamiàe or the like.
.
Concentrates should contain between 25 and 50~ by weight lu of the acryloyl ureas.
Sprayable dusts can be prepared from tbe above ureas using customary dusting powders, e.g., finely divided bentonite, chalk, clay, calcium carbonate, silica, kaoline, ; talc, fuller's earth, etc. and containing agriculturally acceptable wetting agents, detergents, etc. Solid composi-; tions of this nature can also be prepared in the form o wettable powders which easily disperse in water for spraying.
SolLd formulations p~eferably contain between 25 and 75~ by weight of the shown urea.
It has now been found that crops of the above nature, plastics, paints and the like can be protected by applying to such substrates a compound of the formula .
, O
I. X ~ -NH-C-NH-CO-CH~CH2 wherein X represent~ H, Cl, CN, OR, COOR, SR, NO2 or R wherein R is linear or branched saturated loweralkyl. These acryloyl ureas are effective at concentrations of 10-5000 ppm and these concentrations are not damaging to the plants or crops them-selves, and they do not discolor paints to which they are added or plastics in which they are incorporated.
The compounds of the above formula can be applied directly to paints or plactic iormulations or they can be '~
.
. ~
, .. . .
applied to agronomical substrates as solutions or dusts.
Sprays are preferably prepared from a water-dispersible or from an emulsifyable liquid concentrate. Such concentrates can be made by dissolving the active ingredient in dimethyl-S sulfoxide, tetrahydrofuran, chloroform, tetrahydrofurfuryl alcohol, or acetone, a mixture thereof or a mixture o either of these solvents with small amounts of water, lower alkanols, dimethylformamide, dimethylacetamiàe or the like.
.
Concentrates should contain between 25 and 50~ by weight lu of the acryloyl ureas.
Sprayable dusts can be prepared from tbe above ureas using customary dusting powders, e.g., finely divided bentonite, chalk, clay, calcium carbonate, silica, kaoline, ; talc, fuller's earth, etc. and containing agriculturally acceptable wetting agents, detergents, etc. Solid composi-; tions of this nature can also be prepared in the form o wettable powders which easily disperse in water for spraying.
SolLd formulations p~eferably contain between 25 and 75~ by weight of the shown urea.
2~ In order to illustrate the process ~or using the present invention, reference is made to the following examples which are not to be understood as limiting the invention in any form. The acryloyl phenyl ureas are prepared in accord-ance with known methods such as those described in Belgian Patent 715,~39 or by Gabel et al. in J. Orq. Chem., 23, 644-6 (1~58).
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. . . .
Examples 1 - 3 The antifungal properties of the above compounds were established in accordance with the following examples ~- of standard tests:
-5 A) PhYtophtora infestans (Late Tomato Blight).
Bonny Test tomato plants geown to 5-leaf stage in a green-house on Swiss Farm potting soil in 7-ounce styrofoam pots with weekly 20-20-20 fertilizer application at 20-28 C. day - and 15-20 C. night temperature are treated with a solution or suspension of the fungicide. Both leaf surfaces are sprayed to run-off with a DeVilbiss atomizer at 10 psi. The - formulations are prepared by dissolving the fungicide in an acetone-Tween~ 20 mixture and diluting the solution with water to a fungicide concentration of 1000 ppm.
Two days after the plant treatment, a swarmspore .~, suspension (10,000/ml) is sprayed on the lower leaf surface with the above atomizer to a point just be~ore cun-of ~he plants are then maintalned at 100~ humldity and 17 C.
for 24 hours and subsequently kept under the above greenhouse conditions until symptoms appear. The fungicidal activity is judged by the percent of necrosis of the third, fourth and fifth leaves.
! 8) Pyricularia orYze. Rice plants are grown to same stage and under the same conditions as the tomato plants in (A) except that they are thinned to 3 plants per pot. The solution or suspension of (AJ is applied in the same fashion.
Two days after the plant preparation, the plants .:
are inoculated as in (A) but with a spore suspension contain-ing 50,000 spores/ml., and maintained as in (A). The fungi-
. . . .
Examples 1 - 3 The antifungal properties of the above compounds were established in accordance with the following examples ~- of standard tests:
-5 A) PhYtophtora infestans (Late Tomato Blight).
Bonny Test tomato plants geown to 5-leaf stage in a green-house on Swiss Farm potting soil in 7-ounce styrofoam pots with weekly 20-20-20 fertilizer application at 20-28 C. day - and 15-20 C. night temperature are treated with a solution or suspension of the fungicide. Both leaf surfaces are sprayed to run-off with a DeVilbiss atomizer at 10 psi. The - formulations are prepared by dissolving the fungicide in an acetone-Tween~ 20 mixture and diluting the solution with water to a fungicide concentration of 1000 ppm.
Two days after the plant treatment, a swarmspore .~, suspension (10,000/ml) is sprayed on the lower leaf surface with the above atomizer to a point just be~ore cun-of ~he plants are then maintalned at 100~ humldity and 17 C.
for 24 hours and subsequently kept under the above greenhouse conditions until symptoms appear. The fungicidal activity is judged by the percent of necrosis of the third, fourth and fifth leaves.
! 8) Pyricularia orYze. Rice plants are grown to same stage and under the same conditions as the tomato plants in (A) except that they are thinned to 3 plants per pot. The solution or suspension of (AJ is applied in the same fashion.
Two days after the plant preparation, the plants .:
are inoculated as in (A) but with a spore suspension contain-ing 50,000 spores/ml., and maintained as in (A). The fungi-
-4-.
cidal activity is measured as the index of number of lesions per fourth leaf/leaf area.
C) Puccinia r_condita f. sp. tritici (Leaf rust).
The pre-treatment is carried out on Yorkster wheat exactly ` 5 as in (B) except for using the plants in the l-leaf stage.
Inoculation follows the above method except that the uredospore suspension contains 20,000 spores/ml. and the plants are maintained as above and judged as in (B) on the basal leaf.
The results, expressed as % of protection are shown below.
Exam~leppmest A Test B Test C
~= 3-C1100 100 99 92 X- 4-Me 100 100 99 87 . 10 30 78 71 ., 1 o __ __ X~ 4-C1100 100 99 83 97 a7 Standard* 100 97 100 100 *For tests (A) and (C), the test results are com-pared with industry standard, manganous ethylenebis (dithio-carbamate) known as Maneb~ or Dithane~M-22. Results of (B) are compared with O-ethyl-S,S-diphenyl phosphorodithioate, known as Hinosan~, the current standard of the industry. In all tests, the initial 1,000 ppm fungicide solution or sus-pension is further diluted to determine the activity at 100 and 10 ppm.
~ .
~ -5-.
~$~
As will be noted, the current compounds compare favorably with the results obtained from current industry standards.
,~
ExamPle 4 In an ln vitro test, some of the compounds of formula I are tested in an agar plate minimum inhibitory concentration (MIC) screen from a solution in dimethyl-formamide against a challenge mixture of Rhizoctonia sP
No. 657 and 659. The results show that Compound I where 0 X i9 chlorine in the 3- or 4- position or X is a 4-methyl group has a MIC of 10 ppm.
Example 5 - In an ln vitro MIC test, the amount of the test compound of formula I needed to prevent fungi growth is established. In this test, agar containing the test compound at a specified concentration i~ inoculated with 1 ml. of a broth containing 10,000 units each of A. ni2er and P. fun,i-culosum. The agar plates inoculated in this fashion are incubated at 30 C. for 2 weeks and growth of the microorgan-isms is visually inspected to establish the MIC. The follow-ing table shows the results of the ureas of formula I, show-ing the X-substituents.
i .
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Urea I MIC
X = H 100 X = 2-C1 100 X = 3-C1 10 X - 2-Me 100 X = 3-Me 10 X = 4-Me 100 X - 2-OEt 1000 X = 4-OEt 10 `- X ~ 2-OMe1000 X = 4-OMe 100 . X = 4-COOEt10 ExamPle 6 In a test similar to that described in Example 5, l-phenyl-3-acryloyl urea is tested against certain specific fungi. The compound shows a MIC of 10 against Chaatomium globossum, MYrothecium verrucaria, A versicolor, Fusarium oxys~orium and an MIC of 100 against P. citrinum, Alterneria and Rhizopus nigricans.
The corresponding l-p-tolyl-3-acryloyl urea and the 1-~4-chlorophenyl)-2-acryloyl urea both show MIC of 10 against Chaetomium globussum; the latter compound shows the same activ-ity against Rhizo~us nigricans while the former shows a MIC
. ~ .
of 100 against all the above fungi.
Example_7 A cotton fabric sample is soaked in acetone contain-ing l-phenyl-3-acryloyl urea in such a fashion that after , ; ., , drying, the fabric contains 0.5~ by weight of the test compound. The fabric is placed in nutrient agar and in-o cubated for 24 hours at 37 C. After inoculating the agar with mixed spores, A. ni2~ . flavus, C. ~lobusum and P. funiculosum and storing at 28 C. for 14 days, no growth of any of the organisms is observed.
Example 8 Wooden tongue depressors are dipped into a modi-fied acrylic paint composition made according to the follow-ing method.
Water 215.9 lbs.
Anionic surfactant 10.5 lbs.
Non-ionic surfactant 2.5 lbs.
Dispersing agent 1.5 lbs.
Hydroxyethylcellulose 2.3 lbs.
Ethylene glycol 25 lbs.
De~oamer 3 lbs.
Titanium dioxide 237.5 lbs.
Magnesium silicate 237.5 lbs.
Fungicide of structure I 4 lbs./100 gals.
The above ingredients are dispersed for 20 minutes ; and then blended with a mixture of Acrylic emulsion 390.8 lbs.
Long oil alkyd 30.8 lbs.
j 25 Cobalt drier 0.2 lbs.
Zirconium drier 0.6 lbs.
Defoamer 1.0 lbs.
, Tributylphosphate 9.2 lbs.
Ammonia 1.~ lbs.
.
.~ ' .
. .
After the paint is dried, the painted surface is inoculated with a mixture of A. Pullulans, P. funiculosum and A. niqer, containing 10,000 spores/ml of each. The samples are then placed in a mold box for a period of : o 4 weeks at 30 C and 90~ relative humidity. The following . table shows results of the paint samples with the current fungicide, a control (no fungicide) and a sample containing the same amount of Amical~ 50 (~-tolyl diiodomethylsulfone containing 25% inert materials), a commercially accepted fungicide. The ratings are: 0 for no growth on sample, 1 for 0-25% growth, 2 for 25-50% growth, 3 for 50-75% growth and 4 for 75-100% growth of spores over the painted surface.
ComPound Rating - X5H o Xs3-C1 2 X~4-Cl 0 X~4-Me 0 Control (no fungicide) 4 Amical~ 50 0 ExamPle 9 A further test is carried out on tomato plants grown in accordance with Examples 1-3, Test A, using a suspension ~; of 10,000 spores/ml of Alternaria solani (early blight) and .. o ~r 25 the plants are then kept at 21 C. and 100% humidity for 24 hours and maintained and observed as in Test A: With the compound of formula I (X 5 4-Me) at 1000 ppm, a 0.7%
necrosis results, while with industry standara Maneb , the same concentration results in 1.7%. No injury to the plant is observed in either case.
_ g _ ~3~3~`7 Although the above examples primarily demonstrate the fungicidal effects of the compounds of structure I
wherein X is loweralkyl, loweralkoxy or chlorine in any of the ring positions of the phenyl moiety, it is noted that when X is cyano, nitro or a mercapto group, similar protection of agricultural crops or an industrial substrate is obtained. Particularly, the following compounds produce similar results as shown in Examples 1-3: 1-(4-cyanophenyl)-, 1-(4-methylthiophenyl)-, 1-(2- or 4-nitrophenyl)- and 1-(4-ethoxycarbonylphenyl)-3-acryloyl ureas and the corresponding thioureas. The latter also produce results analogous to those shown in Example 4.
As will be seen from the results of the above accelerated fungicical tests, fabrics, paints, painted surfaces and crops are well protected against the most common fungL and in many instances, the current compounds are far superior in their protective quality than the currently used standards in the respective lndustries with the further and most impoctant advantage that the above compounds are environmentally acceptable.
When crops are to be protected with the above compound, the described wettable powder or emulsifiable concentrate is best applied in an aqueous spray containing ~! 0.0001-0.1% by weight of the fungicide, preferably between 0.001 and 0.05%. These compositions may also contain be-~; tween 0.1 and 5% by weight of a wetting agent, such as an alkyl sulfate, an alkylaryl sulfonate, a sulfosuccinate, a polyethylene glycol ether, or the like. Dusting powders made with the current fungicides and finely divided, inert ., diluents preferably also contain the fungicide in the above concentration.
For use in paint or other coatings, the above compounds can be added in amounts of 0.01 to 1.0% by S weight, preferably between 0.3 and 0.6~. When used in s.,:
textiles, including cellulosics, wool, synthetics, a stock solution for treating the fabric is best prepared in such a fashion that when the continuously moving woven or non-woven fabric travels through the bath containing the above compound, it picks up between 0.05 and 1.0% by weight of said compound, calculated on a dried weight. The necessary level of fungicide can thus be added to any of the various solutions that are ordinarily used in the finishing treat-ment of textiles.
For use as a fungicide in a polymeric material suitable for extruding, molding or foaming, the compound of structure I is best added to the polymeric powder or to one of the monomer mixes from which the polymer i9 formed.
In these instances, the funglcide i9 preferably used in such a concentration that the final structure contains between 0.1 and 1.0~ by weight thereof.
.
.,, .. ..
, ,',",!
. .
' ' .
,
cidal activity is measured as the index of number of lesions per fourth leaf/leaf area.
C) Puccinia r_condita f. sp. tritici (Leaf rust).
The pre-treatment is carried out on Yorkster wheat exactly ` 5 as in (B) except for using the plants in the l-leaf stage.
Inoculation follows the above method except that the uredospore suspension contains 20,000 spores/ml. and the plants are maintained as above and judged as in (B) on the basal leaf.
The results, expressed as % of protection are shown below.
Exam~leppmest A Test B Test C
~= 3-C1100 100 99 92 X- 4-Me 100 100 99 87 . 10 30 78 71 ., 1 o __ __ X~ 4-C1100 100 99 83 97 a7 Standard* 100 97 100 100 *For tests (A) and (C), the test results are com-pared with industry standard, manganous ethylenebis (dithio-carbamate) known as Maneb~ or Dithane~M-22. Results of (B) are compared with O-ethyl-S,S-diphenyl phosphorodithioate, known as Hinosan~, the current standard of the industry. In all tests, the initial 1,000 ppm fungicide solution or sus-pension is further diluted to determine the activity at 100 and 10 ppm.
~ .
~ -5-.
~$~
As will be noted, the current compounds compare favorably with the results obtained from current industry standards.
,~
ExamPle 4 In an ln vitro test, some of the compounds of formula I are tested in an agar plate minimum inhibitory concentration (MIC) screen from a solution in dimethyl-formamide against a challenge mixture of Rhizoctonia sP
No. 657 and 659. The results show that Compound I where 0 X i9 chlorine in the 3- or 4- position or X is a 4-methyl group has a MIC of 10 ppm.
Example 5 - In an ln vitro MIC test, the amount of the test compound of formula I needed to prevent fungi growth is established. In this test, agar containing the test compound at a specified concentration i~ inoculated with 1 ml. of a broth containing 10,000 units each of A. ni2er and P. fun,i-culosum. The agar plates inoculated in this fashion are incubated at 30 C. for 2 weeks and growth of the microorgan-isms is visually inspected to establish the MIC. The follow-ing table shows the results of the ureas of formula I, show-ing the X-substituents.
i .
, .. .
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.. ,., .. ~ , - . : ~
:: , ~3~ ~
Urea I MIC
X = H 100 X = 2-C1 100 X = 3-C1 10 X - 2-Me 100 X = 3-Me 10 X = 4-Me 100 X - 2-OEt 1000 X = 4-OEt 10 `- X ~ 2-OMe1000 X = 4-OMe 100 . X = 4-COOEt10 ExamPle 6 In a test similar to that described in Example 5, l-phenyl-3-acryloyl urea is tested against certain specific fungi. The compound shows a MIC of 10 against Chaatomium globossum, MYrothecium verrucaria, A versicolor, Fusarium oxys~orium and an MIC of 100 against P. citrinum, Alterneria and Rhizopus nigricans.
The corresponding l-p-tolyl-3-acryloyl urea and the 1-~4-chlorophenyl)-2-acryloyl urea both show MIC of 10 against Chaetomium globussum; the latter compound shows the same activ-ity against Rhizo~us nigricans while the former shows a MIC
. ~ .
of 100 against all the above fungi.
Example_7 A cotton fabric sample is soaked in acetone contain-ing l-phenyl-3-acryloyl urea in such a fashion that after , ; ., , drying, the fabric contains 0.5~ by weight of the test compound. The fabric is placed in nutrient agar and in-o cubated for 24 hours at 37 C. After inoculating the agar with mixed spores, A. ni2~ . flavus, C. ~lobusum and P. funiculosum and storing at 28 C. for 14 days, no growth of any of the organisms is observed.
Example 8 Wooden tongue depressors are dipped into a modi-fied acrylic paint composition made according to the follow-ing method.
Water 215.9 lbs.
Anionic surfactant 10.5 lbs.
Non-ionic surfactant 2.5 lbs.
Dispersing agent 1.5 lbs.
Hydroxyethylcellulose 2.3 lbs.
Ethylene glycol 25 lbs.
De~oamer 3 lbs.
Titanium dioxide 237.5 lbs.
Magnesium silicate 237.5 lbs.
Fungicide of structure I 4 lbs./100 gals.
The above ingredients are dispersed for 20 minutes ; and then blended with a mixture of Acrylic emulsion 390.8 lbs.
Long oil alkyd 30.8 lbs.
j 25 Cobalt drier 0.2 lbs.
Zirconium drier 0.6 lbs.
Defoamer 1.0 lbs.
, Tributylphosphate 9.2 lbs.
Ammonia 1.~ lbs.
.
.~ ' .
. .
After the paint is dried, the painted surface is inoculated with a mixture of A. Pullulans, P. funiculosum and A. niqer, containing 10,000 spores/ml of each. The samples are then placed in a mold box for a period of : o 4 weeks at 30 C and 90~ relative humidity. The following . table shows results of the paint samples with the current fungicide, a control (no fungicide) and a sample containing the same amount of Amical~ 50 (~-tolyl diiodomethylsulfone containing 25% inert materials), a commercially accepted fungicide. The ratings are: 0 for no growth on sample, 1 for 0-25% growth, 2 for 25-50% growth, 3 for 50-75% growth and 4 for 75-100% growth of spores over the painted surface.
ComPound Rating - X5H o Xs3-C1 2 X~4-Cl 0 X~4-Me 0 Control (no fungicide) 4 Amical~ 50 0 ExamPle 9 A further test is carried out on tomato plants grown in accordance with Examples 1-3, Test A, using a suspension ~; of 10,000 spores/ml of Alternaria solani (early blight) and .. o ~r 25 the plants are then kept at 21 C. and 100% humidity for 24 hours and maintained and observed as in Test A: With the compound of formula I (X 5 4-Me) at 1000 ppm, a 0.7%
necrosis results, while with industry standara Maneb , the same concentration results in 1.7%. No injury to the plant is observed in either case.
_ g _ ~3~3~`7 Although the above examples primarily demonstrate the fungicidal effects of the compounds of structure I
wherein X is loweralkyl, loweralkoxy or chlorine in any of the ring positions of the phenyl moiety, it is noted that when X is cyano, nitro or a mercapto group, similar protection of agricultural crops or an industrial substrate is obtained. Particularly, the following compounds produce similar results as shown in Examples 1-3: 1-(4-cyanophenyl)-, 1-(4-methylthiophenyl)-, 1-(2- or 4-nitrophenyl)- and 1-(4-ethoxycarbonylphenyl)-3-acryloyl ureas and the corresponding thioureas. The latter also produce results analogous to those shown in Example 4.
As will be seen from the results of the above accelerated fungicical tests, fabrics, paints, painted surfaces and crops are well protected against the most common fungL and in many instances, the current compounds are far superior in their protective quality than the currently used standards in the respective lndustries with the further and most impoctant advantage that the above compounds are environmentally acceptable.
When crops are to be protected with the above compound, the described wettable powder or emulsifiable concentrate is best applied in an aqueous spray containing ~! 0.0001-0.1% by weight of the fungicide, preferably between 0.001 and 0.05%. These compositions may also contain be-~; tween 0.1 and 5% by weight of a wetting agent, such as an alkyl sulfate, an alkylaryl sulfonate, a sulfosuccinate, a polyethylene glycol ether, or the like. Dusting powders made with the current fungicides and finely divided, inert ., diluents preferably also contain the fungicide in the above concentration.
For use in paint or other coatings, the above compounds can be added in amounts of 0.01 to 1.0% by S weight, preferably between 0.3 and 0.6~. When used in s.,:
textiles, including cellulosics, wool, synthetics, a stock solution for treating the fabric is best prepared in such a fashion that when the continuously moving woven or non-woven fabric travels through the bath containing the above compound, it picks up between 0.05 and 1.0% by weight of said compound, calculated on a dried weight. The necessary level of fungicide can thus be added to any of the various solutions that are ordinarily used in the finishing treat-ment of textiles.
For use as a fungicide in a polymeric material suitable for extruding, molding or foaming, the compound of structure I is best added to the polymeric powder or to one of the monomer mixes from which the polymer i9 formed.
In these instances, the funglcide i9 preferably used in such a concentration that the final structure contains between 0.1 and 1.0~ by weight thereof.
.
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. .
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,
Claims (10)
OR PRIVILEGE IS CLAIMED, ARE DEFINED AS FOLLOWS:
1. The process of protecting paints, painted surfaces, textiles, useful plants or crops against attack by common fungi consisting essentially in applying to such substrates an antifungally effective amount of a compound of the formula wherein X is H, Cl, CN, OR, COOR, SR, NO2 or R with R being loweralkyl.
2. The process of Claim 1 wherein said amount is between 10 and 5000 ppm.
3. The process of Claim 1 wherein X is Cl.
4. The process of Claim 1 wherein X is H.
5. The process of Claim 1 whecein X is methyl.
6. The process of Claim 5 wherein said methyl is in m-position.
7. The process of Claim 5 wherein said methyl is in p-position.
8. An agricultural antifungal composition contain-ing, as the active ingredient, a compound in accordance with Claim 1 and an agronomically acceptable diluent.
9. The composition of Claim 8 in the form of a water-emulsifyable concentrate.
10. The composition of Claim 8 wherein said concen-trate uses acetone as the liquid phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87525378A | 1978-02-06 | 1978-02-06 | |
| US875,253 | 1978-02-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1113857A true CA1113857A (en) | 1981-12-08 |
Family
ID=25365465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA319,369A Expired CA1113857A (en) | 1978-02-06 | 1979-01-09 | 1-acryloyl-3-(substituted)phenyl ureas |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS54110324A (en) |
| AU (1) | AU521539B2 (en) |
| CA (1) | CA1113857A (en) |
| DE (1) | DE2904309A1 (en) |
| FR (1) | FR2415962A1 (en) |
| GB (1) | GB2015342B (en) |
| PH (1) | PH16330A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2929863A1 (en) * | 1979-07-24 | 1981-02-19 | Bayer Ag | NEW N-ARYL-N'-ACRYLOYLUREID, A METHOD FOR THE PRODUCTION AND THEIR USE |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE888316C (en) * | 1943-12-25 | 1953-08-31 | Cassella Farbwerke Mainkur Ag | Process for the production of arylacrylureas and polymers derived therefrom |
| GB1221116A (en) * | 1967-05-15 | 1971-02-03 | Armour Grocery Products Compan | Antiseptic detergent compositions comprising n-acyl-n'-(halogenated) aryl ureas |
| DE2059872A1 (en) * | 1970-12-05 | 1972-06-15 | Merck Patent Gmbh | Thioureas, process for their production and their use for pest control |
| DE2512171A1 (en) * | 1975-03-20 | 1976-10-14 | Bayer Ag | 2,3-DIHALOGEN-ALKANOYL-UREA, METHOD FOR THEIR MANUFACTURE AND THEIR USE AS FUNGICIDES |
-
1979
- 1979-01-09 CA CA319,369A patent/CA1113857A/en not_active Expired
- 1979-01-10 AU AU43244/79A patent/AU521539B2/en not_active Ceased
- 1979-01-18 JP JP347479A patent/JPS54110324A/en active Pending
- 1979-01-18 PH PH22078A patent/PH16330A/en unknown
- 1979-01-31 FR FR7902540A patent/FR2415962A1/en active Granted
- 1979-02-05 DE DE19792904309 patent/DE2904309A1/en active Granted
- 1979-02-05 GB GB7903963A patent/GB2015342B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU4324479A (en) | 1979-08-16 |
| GB2015342B (en) | 1982-05-19 |
| PH16330A (en) | 1983-09-05 |
| DE2904309A1 (en) | 1979-09-06 |
| DE2904309C2 (en) | 1989-04-27 |
| FR2415962A1 (en) | 1979-08-31 |
| FR2415962B1 (en) | 1984-02-17 |
| GB2015342A (en) | 1979-09-12 |
| JPS54110324A (en) | 1979-08-29 |
| AU521539B2 (en) | 1982-04-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |