DE1618955C3 - Fungicides and insecticides - Google Patents

Description

HO

CH = CR ₁ R ₂

tert.-QHg

in which R _{1 is} a hydrogen atom, a cyano, carbomethoxy, carbethoxy or acetyl group and R _{2 is} a cyano, nitro, carboxyl or acetyl group or a group of the general formula COOR ₃ , in which R _{3 is} an alkyl radical with 1 to 4 carbon atoms.

2. Use of the 2,6-di-tert-butylphenol compounds according to Claim 1 as fungicides and Insecticides.

The invention relates to fungicidal and insecticidal agents, characterized by a content of one 2,6-di-tert-butylphenol compound of the general formula I

tert-QH,

HO

CH = CR ₁ R ₂

terL-QHg

in which R _{1 is} a hydrogen atom, a cyano, carbomethoxy, carbethoxy or acetyl group and R _{2 is} a cyano, nitro, carboxyl or acetyl group or a group of the general formula COOR ₃ , in which R _{3 is} an alkyl radical with 1 to 4 carbon atoms, and the use of these compounds as fungicides and insecticides.

Rice is one of the most important agricultural products and the damage to the rice plants by insect pests is of great importance. Some insect pests can use those currently available Insecticides cannot be controlled effectively. Furthermore, those currently available are good working Insecticides are highly toxic to humans and mammals and have adverse effects on rice plants. As common fungicides for agriculture, compounds have been used that contain elements which are extremely toxic to humans and mammals, such as the organomercury type fungicides.

The invention is based on the surprising finding that the 2,6-di-tert-butylphenol compounds of the general formula I not only have an excellent fungicidal and insecticidal effect, but in addition, they do not cause any damage to plants and are harmless to humans and mammals are.

Some of the 2,6-di-tert-butylphenol compounds of the general formula I are known. As far as she is known, they have been used as polymerization inhibitors, antioxidants and stabilizers.

These compounds are stable and can protect useful plants from phytopathogenic fungi over long periods of time without any adverse influence on the plants. The compounds have both a preventive and a curative effect on rice brandy (Piricularia oryzae). This effect is independent of the time and type of application. However, the compounds show a particularly excellent preventive effect when mixed with antibiotics such as blasticidin S or kasugamycin, which has a strong healing effect, or with 0,0-diethyl-S-benzylthiophosphate or O-ethyl-S- benzyl phenyl thiophosphonate, which also has powerful healing properties, is used. In this case, rice blight can be prevented and fought even better.
When the compounds of the general formula I are used at the same time as 0,0-dimethyl-0- (3-methyl-4-nitrophenyl) thiophosphate, fungicidal and insecticidal effects can be achieved without chemical conversion of the active ingredients.

Furthermore, the compounds of general formula I can be used in a mixture with conventional fungicides, such as copper compounds, organomercury compounds, organoarsenic compounds and organosulfur compounds, or with conventional antibiotics such as blasticidin S, kasugamycin, streptomycin, chloramphenicol and cellocidin. In addition, the compounds of general formula I can be used for the simultaneous prevention and control of two or more types of insect pests in a mixture with insecticides of the carbamate type and insecticides such as hexachlorobenzene, Ο, Ο-diethyl-Op-nitrophenylthiophosphate, S - [1,2 - to - (ethoxycarbonyl) ethyl] - 0,0 - dimethyldithiophosphate, S - methylcarbamoylmethyl-0,0-dimethyIdithiophosphat or O - ethyl - O - ρ - nitrophenyl - phenylthiophosphonate can be used. In all cases the effectiveness of the individual compounds is not reduced. Rather, a synergistic effect is achieved through the combination of the components.
The insecticidal action of the compounds of general formula I is evident not only against leaf mites, which attack fruit trees, forest trees and vegetable plants, scale insects and corn worms, which occur in grain stores, and beetles, as well as mosquitoes and flies, but also against other insects belonging to the order Lapidoptera , Hemiptera and Coleoptera include, and versus nematodes.

Specific compounds of general formula I are listed below:

tert-C + Ht,

tert-QH,

(2) HO

CH = CHCN

tert-QHc,

(3) HO

COOCH,

tert.-QHg tert.-QHc,

(4) HO

COOC ₂ H ₅

COOC ₂ H ₅

(5) HO- / ^ CH = CH-COOQH ₅

tert.-QHg

tert.-QHg tert-QHg (6) ^H ° -O ~ \
tert-C ₄ Hg tert-C ₄ Hg (7) Ηθ- ^ 3> - tert-C ₄ Hg tert-C ₄ Hg (8th) I.
tert.-QHg (9) tert-C ₄ Hg
HO-O- tert-C ₄ Hg tert-C4Hg (10) Ho ^ y tert-C ₄ Hg (H) tert-C4Hg
_Η0 -ζ \ -CH = CHCOOH -CH = CHNO ₂ -CH = CHCOOQH ₉ - COCH ₃
-CH = c / COOQH ₅ COCH ₃ -CH = c / COCH ₃ COOCH ₃
-CH = c / COOCH ₃

tert-QHc,

The compounds of general formula I can be according to customary methods by reacting 3,5-di-tert-butyl-4-hydroxybenzaldehyde with compounds of the general formula

CH.

in which R ₁ and R _{2 have} the above meanings, produce.

When used as fungicides, the compounds of general formula I can alone without Addition of other ingredients can be used. For easier application, however, they are combined with the usual Carriers, diluents and auxiliaries

z. B. to dusts, wettable powders, emulsifiable Prepared concentrates or granules. These agents can also contain other fungicides, Contain insecticides, herbicides and similar agricultural chemicals or fertilizers.

For the production of insecticidal agents such as emulsifiable concentrates, wettable powders, The compounds of general formula I are used with conventional carriers, Diluents and auxiliaries processed by customary methods. These funds can also common insecticides based on organic phosphoric acid esters, chlorinated hydrocarbons, Pyrethrum ingredients and synthetic pyrethrum analogs, acaricides, nematocides, fungicides, Contain herbicides or fertilizers.

Examples 1 to 8 explain the production of fungicidal agents, Examples 9 to 13 the production of insecticidal agents.

B e i s ρ i e 1 1

65 parts of the compound (2), 5 parts of a wetting agent of the type of a polyoxyethylene alkylphenol ether and 30 parts of kaolin are mixed. A wettable powder with an active ingredient content is obtained of 65%. For use, the powder is diluted with water and then sprayed.

Example 2

50 parts of the compound (10), 5 parts of a wetting agent of the alkylbenzenesulfonate type and 45 parts Diatomaceous earth is thoroughly ground and mixed together. A wettable powder is obtained with an active ingredient content of 50%. For use, the powder is diluted with water and then sprayed.

Example 3

3 parts of compound (8) and 97 parts of clay are thoroughly powdered and mixed together. A dust with an active ingredient content of 3% is obtained.

Example 4

2 parts of compound (2), 2 parts of O, O-diethyl-S-benzylthiophosphate and 96 parts of talc are thoroughly pulverized and mixed together. A dust is obtained.

Example 5

2 parts of the compound (3), 0.2 part of blasticidin S and 97.8 parts of talc are thoroughly pulverized and mixed together. A dust is obtained.

Example 6

2 parts of the compound (6), 2 parts of Ο, Ο-dimethyl-0- (3-methyl-4-nitrophenyl) thiophosphate and 96 parts of talc are thoroughly pulverized and mixed together. A dust is obtained.

Example 7

2 parts of the compound (4), 2 parts of 3,4-dimethylphenyl-N-methylcarbamate and 96 parts of clay are thoroughly pulverized and mixed together. A dust is obtained.

Example8

2 parts of the compound (1), 2 parts of O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate, 0.2 part of Blasticidin S, 0.4 part of iron methyl arsonate and 95.4 parts of clay were thoroughly pulverized and mixed together. A dust is obtained.

Example 9

65 parts of compound (2), 5 parts of a wetting agent of the Polyoxyäthylenalkylphenoläthertyp and 30 parts of kaolin are mixed thoroughly. A 65% wettable powder is obtained. For use the powder is diluted with water and sprayed.

Example 10

File 5 of compound (6) and 95 parts of talc will. thoroughly pulverized and mixed. A 5% dust is obtained.

Example 11

4 parts of the compound (3), 2 parts of sodium lignosulfonate and 94 parts of a clay with a grain size of 0.074 mm are mixed with one another in this order. After kneading with a a small amount of water, the mixture is granulated and dried. A granulate preparation is obtained with 4% active ingredient.

Example 12

5 parts of the compound (11), 65 parts of methyl iso-

butyl ketone and 20 parts of an emulsifier

mixed together in this order. Man

receives a homogeneous, emulsifiable concentrate. To the

ίο In use, the concentrate is diluted with water

and sprayed. _. . , ._. Example 13

2 parts of the compound (7) and 3 parts of the compound (8) are dissolved in 50 parts of acetone. the

The solution is thoroughly mixed with a mixture of 35 parts of talc with a grain size of 0.074 mm, 40 parts of clay and 20 parts of finely divided silica mixed. The acetone is then evaporated off. A 5% dust is obtained.

Typical test results with regard to the fungicidal effectiveness of the compounds of the general Formula I are given below.

Experimental example 1

Rice plants grown to the three-leaf stage in flower pots about 7.5 cm in diameter are with the compounds to be examined in the specified concentration in an amount of 7 ml sprayed per pot. One day after spraying

the rice plants are treated with a spore fluid from Piricularia oryzae Car. inoculates. Subsequently the fungicidal effectiveness of the compounds is determined. The results are shown in Table I. In the table, "preventive value" means

a numerical value that is calculated using the following equation:

Prevention value = number of stains in untreated area

minus the number of stains in the treated area

Number of stains in untreated area

100,

No phytotoxic effects were observed with any of the compounds.

Table I. Concentrate " Afflicted In front connection tration leaves diffractive worth (ppm) - (%) (%) ■ 100 0.0 100.0 (1) 100 0.0 100.0 (2) 100 0.0 100.0 (3) 100 5.4 92.7 (4) 100 8.7 86.3 (5) 100 8.1 84.1 (6) 100 • 2.5 96.4 (V) 100 7.6 89.2 (8th) 100 7.4 ■ 89.0 (9) 100 8.5 85.7 (10) 30th 10.3 83.5 Phenyl mercury acetate 100 15.9 ■ 79.8 3,5-di-tert-butyl 4-hydroxybenz- aldoxime 100.0 0.0 No treatment

Experimental example 2

Tests for effectiveness against rice brandy

Prevention attempt. ..

Rice plantings of 1 m ² each are made. If the rice plants are three to four leaved

Once reached stage, the compounds to be investigated are used as dusts on the rice plants dusted in an amount of 3 kg per 10 ares. A day after that, the rice plants are coated with a spore fluid from Piricularia oryzae Car. inoculates. On-

finally, the number of spots formed is counted to the preventive value according to the equation to be calculated as in experimental example 1. The results are summarized in Table II:

60

Healing effect

^{Rice plantings of 1 m 2} each are produced in the same way. When the rice plants have reached the three- to four-leaf stage, they are treated with a spore fluid from Piricularia oryzae Car. inoculates. One day later, those to be examined will be. Compounds as a dusting agent dusted on the rice plants in an amount of 3 kg per 10 ares. Then the number of educated

Stains were counted to calculate the healing value according to the equation as in Experimental Example 1. The results are also shown in Table II. O, O-dimethyl-O- (3-methyl-4-nitrophenyl) thiophosphate is hereinafter referred to as Compound A (Vbd. A).

Table II

Dust

Active ingredient

focus

tration

Preventive value

Healing value

Vbd. (7)
Vbd. (3)
Vbd. (1)
0,0 diethyl S-benzyl thiophosphate
Blasticidin S.
Vbd. (7)
and

O, O-diethyl-S-benzyl thiophosphate
Vbd. (3) and
Blasticidin S.
Vbd. (1),
Blasticidin S,
Vbd. A

2.0 2.0 2.0 2.0

0.2 2.0 "

2.0.

2.0V

0.2 /

2.0

0.2

2.0

91.3 94.2 95.6 82.7

59.6 99.6

86.5 88.4 87.1 88.0

93.3 99.4

Experimental example 4

Trial of the effectiveness against the green rice yassids

The population density of green rice jasids in a flooded rice field with Ϊ Ar per section is determined according to the recording procedure. Then the compounds to be examined in the form of dust on the rice field in an amount of 3 kg / 100 a. A day then the number of surviving Reisjassids in each section is determined. The results are in Table IV compiled.

15 Table IV

20th

\ 100.0 100.0 - 30 100.0 99.8 35 0.0 0.0

Iron methyl arsonate 0.4 Without treatment -

Experimental example 3

Investigation into the effectiveness against the two-bladed rice borer

On a flooded rice field of 0.5Ar each 3 kg / 10 ares of dust are dusted 10 days after the point in time when the growth of two-winged Rice burs is strongest. After 50 days, 50 rice plants per section are examined. the Results are shown in Table III.

Table III

Dust

Vbd. A

Vbd. (6) and

Vbd. A

Vbd. (1)

Vbd. A

Blasticidin S and iron methyl arsonate

No treatment - 61.5

Active ingredient ratio concentrate the afflicted tration stem 2.0 9.5 2.0 Ί
2.0 y 9.1 2.0 " 2.0
0.2 9.0 0.4

Dust ■ Active ingredient Index of the living * * concentrate Reisjassids after tration Pollinate (%) before the 1.5. Pollinate 3,4-dimethyl 2.0 105 phenyl-N-methyl- 1 1 ■ ' carbamate Vbd. (4) and 2.0 Ί
2.0 y 3,4-dimethyl phenyl-N-methyl- 100 carbamate - Without treatment 100

Experimental example 5 '

Investigation of the effectiveness against rice brandy

.. On rice plants standing in the water with are infected, the compounds to be examined are in the form of dusts in a Amount of 3 kg / 10 ares dusted on. Then the. Disease relationship is the. Intended for rice plants. The results are shown in Table V. . . ". ' ...

Table V '. - · ■ · '· .- ..

Dust 50 Iron methyl arsonate Active ingredient.
Ifnn7f> n Disease Ratio (%) after VbA (I), tration before the Pollinate 55 iron methyl arsonate, (%) Pollinate 15.4 Vbd. A and 0.4 12.5 Blasticidin S. 2.0 15.0 Without treatment 0.4 13 1 2.0 ^1J l ' 0.2 64.2 - 13.1

Experimental example 6

Field tests regarding the effectiveness against rice blight

The compounds to be investigated are tested in the form of dusts with 1% active ingredient ^{content in two rice fields each 15 m 2 in} size, and the results are obtained.

509537/413

Waseasahi variety rice plants are transplanted from the greenhouse to the rice field on June 4th and pulled until the end of the experiment. The dusts are in an amount of 3 kg / 10 ar dusted on June 25th and July 1st. The number of infected leaves is counted on July 5th. In table VI the results are compiled.

Table VI

connection

concentration

Affected leaves

(1) 1.0 0.0

(2) 1.0 1.2

(3) 1.0 0.9

(4) 1.0 3.8

(5) 1.0 6.7

(6) 1.0 7.8

(7) 1.0 2.2

(8) 1.0 9.6

(9) 1.0 8.4

(10) 1.0 9.5

(11) 1.0 3.2 3,5-di-tert-butyl-4-hydroxy-1.0 45.6 benzaldoxime

Phenyl mercury acetate 0.3 10.1

No treatment - 93.4

Experimental example 7

On blotchy kidney bean plants that grow to a size in flower pots about 7.5 cm in diameter At the stage of two leaves, large numbers of spider mites (Tetranychus uriticae Koch). Then the plants with the compounds to be examined are in the specified concentration sprayed in an amount of 7 ml per pot. After 48 hours, the number will be of the spider mites killed. The results are summarized in Table VII. S-methylcarbamoylmethyl-O, O-dimethyldithiophosphate is referred to as connection B (Vbd. B).

put in 1 liter beakers. 50 house mosquito larvae are placed in each of the beakers. The mortality is determined after 24 hours. The results are summarized in Table VIII.

Table VIII IO Vbd. (1)
as a wettable powder Active ingredient mortality connection ¹⁵ Vbd. (3)
as granules Konzcii "
tration Vbd. (5)
as a wettable powder (ppm) (%) 20 Vbd. A
as a wettable powder 0.02 82.3 0.2 100.0 0.2 98.4 0.2 100.0

Experimental example 9

Eggplant plants in the 5- to 6-leaved stage come with a large number of two-spotted Spider mites (Tetranychus telarius Linne) staggered on the back of the leaves. The ones to be examined Compounds are applied at the specified concentration in an amount of 1501 per 10Ar to the Plants are sprayed, and the number of spider mites is determined at time intervals. The results are compiled in Table IX.

Table VII Active ingredient mortality connection concentrate tration (ppm) (%) 0.02 100 Vbd. (L) as a wettable powder 0.02 79 Vbd. (2) as a wettable powder 0.02 80 Vbd. (11) as an emulsifiable concentrate 0.02 85 Vbd. B ^W as an emulsifiable concentrate

Table IX Effective
ctnff Pay your • spider mites *) 7 days 12 days connection MUIi-
focus next 2 1 40 t ration (ppm) 3 days 5 days 0.02 1241 0 21 35 Vbd. (9) 45 as wettable powder 0.02 965 50 231 93 Vbd. (2) as wettable powder 0.02 1131 120 99 42 50 Vbd. (11) as wettable powder 0.02 1320 35 Vbd. B 1220 638 55 as an emulsifier cash the Blii ittering of concentrate 1003 1201 Without treatment *) Number of survivors Spider mites 60 ten plants in the five-leaved stage.

Experimental example 8

Liquids of the compounds to be examined with the specified concentrations (ppm) are Experimental example 10

In flower pots about 12.5 cm in diameter became annual radishes in the 6- to 7b! ättriaen stage spiked with a large number of spider mites (Tetramychus uriticae Koch). Be on the leaves

11th

the compounds to be investigated as dusts in the specified concentrations in an amount of 8 kg / 10 ares dusted. The mortality is determined after 72 hours. The results are in Table X compiled.

Table X

Dust

Vbd. (6)

according to example 10
Vbd. (7) and (8)
according to example 13

Active ingredient concentrations
tration

mortality

5
5

100
100

Experimental example 11

The compounds to be investigated as well as 0,0 - dimethyl - S - (1,2 - diethoxycarbonylethyl) - di-

thiophosphate (compound C) are processed into dusts according to Example 10 and in a Amount of 800 g / are dusted on kidney bean plants with a large number of spider mites (Tetranychus uriticae Koch) are infested. The Ver-

searches are carried out on three test plantings each with an area of 100 m ² , and the results are averaged.

The insecticidal effect is determined on the basis of the number of spider mites on 50 leaves for 10 days

later collected in the untreated and treated plantings. In Table XI are the Results compiled. The suppression value is calculated according to the following equation:

Suppression value =

(Number of spider mites in the untreated area) (Number of spider mites

in the treated area)

(Number of spider mites in the untreated area)

Table XI

Dust

Substance under-account depressurization worth

Vbd. (1)

Vbd. (2)

Vbd. (3)

Vbd. (4)

Vbd. (7)

Vbd. (8)

Vbd. (10)

Vbd. (11)

Vbd. C

No treatment

100.0

100.0

100.0

83.4

88.4

91.2

83.4

90.0

60.5

Experimental example

The effectiveness of the compounds listed in Table XII against rice blight was determined according to the Experimental example 1 investigated. The results are shown in Table XII.

Table XII concentration Affected leaves Former'iniGiwcrl connection (ppm) (% l 100 0.0 100.0 (I) 100 0.0 100.0 12) 100 0.0 100.0 (3) 100 6.5 »15.8 (5) 100 IN 9.S.6 17) 100 5Y 96.2 (9)

13th

continuation

connection

Concentration (rpm)

Affected leaves

Preventive value

Cl

HO

CH = GH - NO ₂ *)

Cl

HO

CH ₃ **)

CH = C

Cl

'NO ₂

100

100

No treatment- ■■ .- .. ■

*) Connection X of the known JA-PA 26 960/64.
**) Compound XI of the published JA _r PA 26960/64.

40.2

43.4

100.0

35.2

30.9

0.0

Claims (1)

Patent claims: 1. Fungicidal and insecticidal agents, characterized by a content of one 2,6-di-tert-butylphenol compound of the general formula tert.-QHg