IL28633A - Insecticidal and fungicidal compositions containing benzylidene-malonic acid derivatives - Google Patents

Description

nnVin niVaan ximesn o»jrin m sij? malum INSECTICIDAL AND FUNGICIDAL COMPOSITIONS CONTAINING BENZYLIDENE-i50L¾RIC ACID DERIVATIVES and^ This invention relates to a novel fungicidal'insecticidal composition. More particularly, the invention pertains to a fungicidal insecticidal composition containing a certain phenol derivative as an active ingredient.

Rice crop is one of the most important agricultural products, and the damage of the rice crop due to injurious insects is a question of great significance. However, some of such injurious insects cannot be effectively killed by application of agricultural chemicals available at present. Moreover, the chemicals available at present suffer from such drawbacks that they are high in toxicity to men and cattle to bring about a great danger in the handling thereof, and give detrimental effect to crops. A s the conventional agricultural fungicides, there have been used compounds containing elements which are extremely toxic to the human body, like the organo -mercury type fungicides. This is a serious problem not only for those engaging in agriculture but also for the general consumers. In view of such actual situation as mentioned above, there has been desired the advent of fungicides which contain no toxic elements, have strong fungicidal activities and are less in toxicity to men and cattle as well as in detrimental effects on crops.

The present invention provides excellent fungicides capable of satisfying the above desire. The present inventors made repeated studies, aiming to obtain fungicides which are not only excellent in fungicidal effect but also are usable without any fear. As the result, the inventors have attained the present invention. The inventors have further found that the above -mentioned fungicides display also the actions of insecticides ca able of safel and advanta eousl reventin insects.

It is therefore the object of the present invention to provide compositions having actions to kill agricultural fungi in combination with actions to kill agricultural and sanitary injurious insects which are harmless to men and cattle and are usable without any fear.

The above-mentioned object can be achieved, in accordance with the present invention, by fungicidal insecticidal compositions characterized by containing as active ingredient at least one compound represented by the general formula wherein is a hydrogen atom, a cyano group or a group represented by -COOR3 or -COR4; and R2 is a cyano group, a nitro group or a group represented by -COORg or -COR^, where Rg is a hydrogen atom or a lower alkyl group; and ^ is a lower alkyl group.

The compounds represented by the above general formula are stable and can protect crops from pathogenic fungi for a long period of time without giving any detrimental effect to the crops. Thus, the excellent fungicidal and insecticidal effects and the stability of the pres ent compounds are useful and valuable characteristics as agricultural fungicides and agricultural and sanitary insecticides. It is the present inventors that have first found such characteristics.

As to the fungicidal activity, which is the first character -istic, the present compounds have both preventive and curative effects on rice blight, in particular. Even when applied independently, therefore the resent com ounds make it ossible to sufficientl achieve the However, the present compounds are particularly excellent in preventive effect and therefore when, utilizing said characteristic, the present compounds are used in admixture with such antibiotic as Blastocidin S or Kasugamycin, which is strong in curative effect, or with Ο, Ο-diethyl- S-benzylphosphorothioate or O -ethyl -S-benzyl-phenylphosp onothioate, which is strong in curative effect as well, at least the additive effect of prevention and cure is attained, and rice blight can be prevented and exterminated more accurately than in the case where each chemical is used independently. In order to promote the enhancement in prevention and extermination of injurious insects and to attain the simultaneous prevention and extermination of rice blight and rice sheath blight or the simultaneous fungicidal and insecticidal effect on rice blight and rice stem borers, there is sometimes used a mixed formulation comprising an organo -arsenic compound, which is effective towards rice sheath blight, and an organo -mercury compound, which is effective towards rice blight, or a mixed formulation comprising an organo -mercury compound or antibiotic and an organo -phosphorus insecticide. In the case of these mixed formulations, however, chemical reactions take place between the active ingredients to form less effective components, and therefore there are frequently observed the cases where the effects of such mixed formulations are inferior to those of the individual constituents , In the case of the present compounds, no such drawbacks are brought about even when they are mixed, in order to be used for the above purpose, with 0, 0-dimethyl-0-(3 -methyl-4-nitrophenyl)phos- phorothioate ("Sumithion", registered trade name produced by Sumitomo a a not with any of such fungicides as copper compounds, organo -mercury compounds, organo -arsenic compounds and organo- sulfur compounds, or with any of such antibiotics as Blastocidin S, Kasugamycin, Streptomycin, chloramphenicol and cellocidin. In addition thereto, the present compounds can be used, for the purpose of simultaneous prevention and extermination of 2 or more kinds of injurious insects, in admixture with any of carbamate -type insecticides and such insecticides as BHC, para-thion, Malathon, Sumithion, EPN, (registered trade name for an insecticide produced by Geigy Co. ) and Dimethoate. The present com-pounds can further be used in admixture with any of the aforesaid fungicides. In any cases, however, the preventive and exterminative effects of the individual chemicals are not reduced. It would therefore be naturally thought of for those skilled in the art that by the combinations of chemicals, synergistic effects due to mixing may be expected.

The second characteristic, i. e. the insecticidal activity, of the present compounds is such that compositions containing the present compounds as active ingredients are not only markedly effective on leaf mites, which attack fruit trees, forests and vegetables; scales, billbugs which damage stored cereals; and beetles and such sanitary injurious insects as mosquitoes and flies, but also show insecticidal activity on insects belonging to Lapidoptera, Hemiptera and Coleoptera and on nematodes. This shows the fact that the present compounds can advantageously prevent and exterminate agricultural and sanitary injurious insects.

Useful compounds for the object of the present invention are as shown below, but the compounds of the present invention are, of tert-C^g COOCH 3 COOCH The compounds of the present invention can be easily prepared by treating 3 , 5 -di -tert-butyl-4 -hydroxybenzaldehyde with compounds represented by the general formula / Rl CH2 < R2 wherein and are as defined before, followed by dehydration and condensation.

In actual application as fungicides, the present compounds may be used in a pure form without incorporation of other components. However, in order to make easier the use of the present compounds as agricultural fungicides, they may be formulated into any forms ordinarily adopted for agricultural and horticultural fungicides, such as for example, dusts, wettable powders, emulsifiable concentrates and granular preparations.

In formulating the present compounds into the above forms, not only agricultural spreaders may be incorporated to enhance and secure the effects of the present compounds but also other fungicides, insecticides, herbicides and the like agricultural chemicals or fertiliz¬ ers may be used in admixture, as has already been mentioned.

Insecticidal compositions containing the present compounds according to procedures thoroughly known to those skilled in the art, without necessitating any particular conditions, and may be put into use adopting any desired forms and carriers. In formulating the present compounds into the above forms, agricultural excipients and extenders may be incorporated to enhance and ensure the effects of the present compounds. Further, the present compounds can be readily mixed with other active ingredients such as, for example, organo -phosphorus insecticides (Sumithion, Malathon, EPN, Dimethoate, etc. ), chlorine-type insecticides (EHC, DDT, Endorin, etc. ), pyrethroide -type insecticides (pyrethrin, allethrin, Neo-Pynamin (a registered trade mark of Sumitomo Chem. Co. , Ltd. ), etc. ), miticides, nematocides, fungicides, herbicides, fertilizers and the like, whereby multi-purpose compositions can be prepared without causing any detrimental effects due to mixing and without reducing the effects of individual constituent chemicals. Moreover, due to the mixing, the effects of the present compounds can be ensured and enhanced.

The preparation of the present compositions as fungicides will be illustrated further in detail below with reference to examples. It is, however, needless to say that the kinds and mixing proportions of compounds and additives are not limited to only those shown in the examples but are variable to a wide scope. The names of the compounds employed are represented by the numbers of the compounds exemplified previously.

Example 1 65 parts of the compound (2), 5 parts of a wetting vehicle (polyoxyethylene alkylphenol ether type) and 30 parts of kaolin are mixed to ether to obtain a wettable owder havin a main in redient content of sprayed.

Example 2 50 parts of the compound ( 10), 5 parts of a wetting vehicle (alkylbenzenesulfonate type) and 45 parts of diatomaceous earth are thoroughly crushed and mixed together to obtain a wettable powder having a main ingredient content of 50% . In application, the powder is diluted with water and is then sprayed.

Example 3 3 parts of the compound (8) and 97 parts of clay are thoroughly pulverized and mixed together to obtain a dust having a main ingredient content of 3%. In application, the dust is dusted as such. Example 4 2 parts of the compound (7), 2 parts of O, O-diethyl-S-benzylphosphorothioate and 96 parts of talc are thoroughly pulverized and mixed together to obtain a mixed dust. In application, the mixed dust is dusted as such.

Example 5 2 parts of the compound (3), 0. 2 part of Elastocidin S and 97. 8 parts of talc are thoroughly pulverized and mixed together to obtain a mixed dust. In application, the mixed dust is dusted as such. Example 6 2 parts of the compound (6),, 2 parts of Sumithion and 96 parts of talc are thoroughly pulverized and mixed together to obtain a mixed dust. In application, the mixed dust is dusted as such.

Example 7 2 parts of the compound (4), 2 parts of 3, 4 -dimethylphenyl- is dusted as such.

Example 8 2 parts of the compound (1), 2 parts of Sumiotin, 0. 2 part of Elastocidin S, 0. 4 part of iron methylarsonate and 95. 4 parts of clay are thoroughly pulverized and mixed together to obtain a mixed dust. In application, the mixed dust is dusted as such.

Typical test results concerning the effects of the present fungicides will be shown below.

Test Example 1 Flower pot test: To rice plants cultivated to a 3 -leaved stage in flower pots of about 3 inches in diameter, individual chemicals at a given concentration were sprayed in a proportion of 7 ml per pot. One day after the spray, the rice plants were inoculated with a cultured liquid of spores of Piricularia Oryzae Car. Thereafter, the fungicidal effects of the test chemicals were examined to obtain the results as shown in Table 1. In the table, the preventive value represents a numerical value calculated according to the equation; Number of spots in non -treated area Preventive _ - Number of spots in treated area χ i no value Number of spots in no -treated area No phytotoxicity was observed in every chemical. 9 Table 1 ConcenAffected Preventive Compound tration leaves value (p. p. m. ) <%) (%) ( 1) 100 0. 0 100. 0 (2) 100 0. 0 100. 0 (3) 100 0. 0 100. 0 (4) 100 5. 4 92. 7 (5) 100 8. 7 86. 3 ( 6) 100 8. 1 84. 1 (7) 100 2. 5 96. 4 (8) 100 7. 6 89. 2 (9) 100 7. 4 89. 0 (10) 100 8. 5 85. 7 Phenylmercuric 10. 3 83. 5 acetate 3 , 5-Di-tert-butyl-4- 100 15. 9 79. 8 hydroxybenzaldoxime Non -treatment 100. 0 0. 0 Test Example 2 Effectiveness tests on rice blight: Preventive test: A rice nursery of 1 m per section was prepared. When the rice plants had reached a 3 -4 leaved stage, individual test dusts were dusted onto the rice plants in a proportion of 3 kg per 10 ares. One day after, the rice plants were inoculated with a liquid of spores of Piri-cularia Oryzae Car. Thereafter, the number of spots generated was counted to calculate preventive values according to the same equation as in Test Example 1. The results were as shown in Table 2.

When the rice plants had reached a 3 -4 leaved stage, the rice plants were inoculated with a liquid of spores of Piricularia Oryzae Car. One day after, individual test dusts were sprayed onto the rice plants in a proportion of 3 kg per 10 ares. Thereafter, the number of spots generated was counted to calculate curative values according to the same equation as in the case of the preventive values. The results were as shown in Table 2.

Table 2 Concentration Preventive Curative Chemical of active value value ingredient (%) Compound (7) dust 2. 0 91. 3 86. 5 Compound (3) dust 2. 0 94. 2 88. 4 Compound (1) dust 2. 0 95. 6 87. 1 0, 0-Diethyl-S-benzyl- 2. 0 82. 7 88. 0 phosphorothioate dust Blastocidin S dust 0. 2 59. 6 93. 3 99. 6 99. 4 Mixed ) Compound (3) 2. 0 100. 0 100. 0 dust \ Blastocidin S 0. 2 {Compound (1) 2. 0 Blastocidin S 0. 2 Sumithion 2. 0 100. 0 99. 8 Iron methyl - 0. 4 arsonate Non -treatment 0. 0 0. 0 Test Example 3 Effectiveness test on two-brooded rice borers: To an aquatic rice field of 0. 5 are per sectional area, borers had been most vigorous . After 50 days, 50 rice plants per tion were investigated. The results were as shown in Table 3.

Table 3 Sumithion dust 2. 0 9. 5 Mixed ) Compound (8) 2. 0 9. 1 dust S Sumithion 2. 0 Compound ( 1) 2. 0 Sumithion 2. 0 9. 5 Blastocidin S 0. 2 Iron methylarsonate 0. 4 Non -treatment 61. 5 Test Example 4 Effectiveness test on green rice leaf hoppers : The habitat density of green rice leaf hoppers in an aquatic rice field of 1 are per sectional area was measured according to dip up method. Thereafter, individual test dusts were dusted to the rice field in a proportion of 3 kg per 10 ares. One day after, the number of survival leaf hoppers in each section was measured to obtain the results as shown in Table 4.

Table 4 Concentration Index of living leaf hoppers Chemical of active ingredient Before dusting After dusting (%) 3 , 4 -Dimethylphenyl-N - 2. 0 105 1 , 5 methylcarbamate dust Compound (4) 2. 0 Mixed 3 , 4-Dimethylphenyl-dust 106 1. 1 2. 0 N -methylcarbamate Test Example 5 Effectiveness test on rice sheath blight: To aquatic rice plants in a paddy field where rice sheath blight had broken out, individual test dusts were dusted by means of a manual duster in a proportion of 3 kg per 10 ares. Thereafter, the disease ratio of rice plants was examined. The results were as shown in Table 5.

Table 5 Concentration Disease ratio (%) Chemical of active ingredient Before dusting After dusting <%) Iron methylarsonate dust 0. 4 12. 5 15. 4 /Compound (1) 2. 0 Mixed ) Iron methylarsonate 0. 4 13. 1 15. 0 dust ] Sumithion 2. 0 VBlastocidin S 0. 2 Non-treatment - 13. 1 64. 2 Next, the preparation of the present compositions as insec¬ ticides will be illustrated below with reference to examples. It is, however, needless to say that the additives and mixtures in the examples are variable to a wide scope. The figures in the parentheses show the numbers representing the compounds exemplified previously.

Example 9 50 parts of the compound (1), 5 parts of Tokuseal Gu-N (registered trade name for a product of Tokuyama Soda K. K. ), 40 parts of Radiolite L 40, and 5 parts of Sorpol 5029 (registered trade name for an emulsifier produced by Toho Kagaku K. K. ) are thoroughly mixed together to obtain a wettable powder having a main ingredient content of 50%. In application, the wettable powder is diluted with water and is Example 10 65 parts of the compound (2), 5 parts of a wetting vehicle (polyoxyethylene-alkylphenol ether type) and 30 parts of kaolin are thoroughly mixed together to obtain a 65% wettable powder. In applica-tion, the powder is diluted with water and is sprayed.

Example 11 parts of the compound (6) and 95 parts of talc is thoroughly mixed and pulverized together to obtain a 5% dust. In application, the dust is dusted as such.

Example 12 4 parts of the compound (3), 2 parts of sodium lignin sulfonate and 94 parts of 200 mesh clay are mixed together in this order. After kneading with a small amount of water, the mixture is granulated by means of a granulator and is dried to obtain a 4% granular prepara -tion. In application, the granular preparation is sprinkled as such. Example 13 parts of the compound (11), 65 parts of methylisobutyl-ketone and 20 parts of Sorpol 2020 (registered trade name for an emulsifier produced by Toho Kagaku K. K. ) are mixed together in this order to obtain a homogeneous emulsifiable concentrate. In application, the concentrate is diluted with water and is sprayed.

Example 14 2 parts of the compound (7) and 3 parts of the compound (8) are dissolved in 50 parts of acetone. The solution is thoroughly mixed, while stirring, with a mixed powder comprising 35 parts of 200 mesh talc, 40 parts of clay and 20 parts of white carbon. Subsequently, acetone is removed by vaporization to obtain a 5% dust. In application, the Typical test examples concerning the effects of the present insecticides will be shown below.

Test Example 1 On mottled kidney bean plants cultivated to a 2 -leaved stage in flower pots of about 3 inches in diameter, a large number of Tetra-nychus uriticae Koch were parasitized. To the plants, test chemicals at a given concentration were individually sprayed in a proportion of 7 ml per pot. After 48 hours, the number of killed insects was counted to obtain the results as shown in the following table: Concentration . ...

Chemical (diluted to) Mortality Wettable powder of Example / 9 200, 000 times 100% Wettable powder of Example 110 200, 000 " 79% Emulsifiable concentrate of Example ·¾3 200, 000 " 80% Dimethoate emulsifiable 200, 000 " 85% concentrate Test Example 2 Liquids of test chemicals at given concentrations (p. p. m. ) were individually charged in 1 liter beakers. Into the beakers were put each 50 northern house mosquito larvae, which had been continuously reared in the laboratory of the inventors. After 24 hours, the mortality of the mosquito larvae was observed to obtain the results as shown in the following table: Concentration Mortality Chemical (p. p. m. ) (%) Wettable powder of Example 9 0. 02 82. 3 Granular preparation of Example £ \% 0. 2 100. 0 Test Example 3 In a field , egg apple plants were grown to a 5-6-leaved stage, and a large number of Tetranychus telarius Linne were parasitized on the back of the leaves. Thereafter, test chemicals at a given concentration was sprayed in a proportion of 150 liters per 10 ares, and the habitat density of the Tetranychus telarius Linne was measured with the lapse of days. The results were as shown in the following table: Habitat density * Aft ,er A C fJter A „ ft,er A , fter 3 days 5 days 7 days 1 „2 d ,ays „ Wettable powder of Example L 9 1241 0 2 1 " " Example 1 0 965 50 21 35 " " Example / 13 1131 120 231 93 Dimethoate 1320 35 99 42 on -treatment 1003 1201 1220 638 * Habitat density: The number of survival mites observed on the leaves of 10 plants individually having 5 leaves.

Test Example 4 In flower pots of about 5 inches in diameter, seasonless raddishes parasitized with a large number of Tetramychus uriticae Koch were grown to a 6 to 7-leaved stage. To the leaves, test dusts at a given concentration were dusted in a proportion of 8 kg per 10 ares by means of a bell jar duster. After 72 hours, the mortality of mites were observed to obtain the results as shown in the following table: Chemical Mortality (%) Dust (5%) of Example 1 100 Test Example 6 Test on Alternaria leaf spot of apple : Wet table powders of each compound were diluted with water to obtain 500 p.p.m. concentration of test compositions* Each of the test compositions was applied to the farm according to the following conditions: Variety of the trees : India ( apple) , young tree of five years old.

Scale : Three replicates with 5 trees in a plot* Application: Each solution of the test compositions was sprayed with a sprayer in an amount of 10 1/plot , a total application six-times, i.e., I S May, 28 May, 7 June, i& June, 1 July and 9 July of 966· Examination : The number of diseased spots on 10 upper perfectly developed leaves ©n 10 new tree- tops of each tre was counted* The results are shown in Table 6 below* Table 6 ···· Deran (Commercially used : * fungicide) • • • J 28.6 * 71 ·- Non-treatment : 95.6 I 68*5 : Notes: « j The present compounds.

;The compounds having structures similar to the ··· present compounds.

;The compounds of the Israel. Patent Application No. 275 6. ••99 ; Deran is a commercially available fungicide which contains 75 of 2f3-dinitro-1 , -dithioanthraq iinone as an active ingredient.

Claims (12)

HAVING HOW particularly described and ascertained the nature of our said invention and in what manner the same is to be ' performed, we declare that what we claim is : LXJQXRH

1 . A fungicidal composition containing as a main ingredient at least one compound represented by the general formula wherein Rj is a hydrogen atom, a cyano group or a group represented by -COOR3 or -COR^; and R2 is a cyano group, a nitro group or a group represented by -COORg or COR^, where Rg is a hydrogen atom or a lower alkyl group; and R4 is a lower alkyl group. and/

2. A fungicidaldnsecticidal composition containing as a main ingredient a compound represented by the general formula

3. fungicidal insecticidal composition containing as an active ingredient a compound represented by the general formula

4. A fungicidaliTnsecticidal composition containing as an active ingredient a compound represented by the general formula

5. A fungicidal L 'innsseeccttiicciicdal composition containing as an active ingredient a compound represented by the general formula

6. fungici al 'insectici al composit on containing as an active ingredient a compound represented by the general formula aridJ .

7. A fungicidal'insecticidal composition containing as an active ingredient a compound represented by the general formula H = CHCOOH

8. ungicidal insecticidal composition containing as an active ingredient a compound represented by the general formula

9. A fungicidaldnsecticidal composition containing as an active ingredient a compound represented by the general formula CHCOOC4H9 - (n)

10. A fungicidal nsecticidal composition containing as an active ingredient a compound represented by the general formula audi

11. A fungicidal /insecticidal composition containing as an active ingredient a compound represented by the general formula

12. A fungicidal nsecticidal composition containing as an active ingredient a compound represented by the general formula Dated this Twelfth day of September 1967.