DE2407403A1 - PESTICIDES AGENTS - Google Patents

Description

SUMITOMO CHEMICAL COMPANY, LIMITED
Osaka, Japan

"Pesticide Agents"

Priority: February 16, 1973, Japan, No. 19 618/1973

5-benzyl-3-furylmethylchrysanthemate, hereinafter referred to as "resmethrin" is due to its low toxicity to warm blooded animals and its high insecticidal effect on insect pests in households and agriculture is a very valuable insecticide. Resmethrin is mainly used in households as an insecticide in the form of spray preparations and oil sprays. It but is also found to a large extent in agriculture, in particular for the protection of vegetable and tobacco plantations and in Nurseries use. The disadvantage of using res-, methrin is its urine-like odor, which is presumably caused by decomposition or degradation products. "This odor nuisance precludes §a # r use.

The invention "is based on the object of creating a pesticidal agent based on resmethrin, which after application does not cause odor nuisance This task is carried out by

. 409835/1039

a pesticide yellow, which is characterized by a Content of S-benzyl-jJ-furylmethylchrysanthemat of the formula I.

.CH,

CH ₀ OC - CH CH - CH = CCT ° '

^0M 3 .3

as well as 2,2 ^f -methylene-bis- (6-tert-butyl-4-ethylphenol), hereinafter referred to as compound P, of the formula II

OH OH

^{n W} "* (H)

in an amount of 1 to 100 percent by weight, based on the Compound of the formula I, and optionally a UV absorber.

Compound P is known as an antioxidant that is added to transport containers for food to prevent it from rotting. to inhibit.

A large number of antioxidants have been studied, but they have not been suitable for the purposes of the invention. at other antioxidants such as 2,6-di-tert-butyl-4-methyl-. phenol (hereinafter referred to as compound A), 4,4'-thio-bis- (6-tert-butyl-3-methylphenol) (hereinafter referred to as Compound B), phenyl-β-naphthylamine (hereinafter referred to as Compound C 2,2,4-trimethyl-1,2-dihydroxyquinoline condensate (hereinafter referred to as compound D), mercaptobenzimidazole (hereinafter referred to as compound E), tris (nonylphenyl) -

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phosphite (hereinafter referred to as compound F) and dilaurylthio-di-propionate (hereinafter referred to as Compound G) was found to have a much lower odor-inhibiting effect than that of the Connection P detected. In particular, the compounds E, F and G show no effects at all.

Further investigations showed that with the combined use of resmethrin, the compound P and customary UV absorbers such as p-tert.-butylphenylsaucylate (hereinafter referred to as compound I. referred to), 2-hydroxy-4-methoxybenzophenone (hereinafter referred to as Compound J), 2-hydroxy-4-oxybenzylbenzophenone (hereinafter referred to as Compound K), 2-hydroxy-4-octoxybenzophenone (hereinafter referred to as Compound L), 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole (hereinafter referred to as' compound M) and 2-carboxyeth'yl-3> 3'-diphenylacrylonitrile (hereinafter referred to as Compound N) achieved even better effects v / can ground. If the resmethrin is only given a UV- ·. Absorber, so practically no odor-inhibiting effect is achieved.

The compounds added to the resmethrin can be used in an amount of 1 to 100 percent by weight, based on the resmethrin will; Additions in the range from 5 to 10 percent by weight are preferred.

Using compound A, a well-known antioxidant, together with the resmethrin and a UV absorber, the odor-inhibiting effect is significantly less than when it is used the connection P.

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The pesticidal agent of the invention contains resmethrin and the corresponding other additives in an amount of preferably

1 to 90 percent by weight based on the total weight of the pesticidal agent. The pesticidal agent according to the invention can can also be mixed with other insecticides, as well as with a synergist such as piperonyl butoxide.

The examples illustrate the invention. Parts and percentages relate to weight, unless stated otherwise.

example 1

2 g of resmethrin were each dissolved with 0.1 g of the compounds P, A, B, E and F in acetone and diluted to a volume of 100 ml. In each case 1 ml of the solutions prepared in this way (each with 20 mg resraethrin) was evenly distributed on a filter paper (11 cm in diameter) and exposed to artificial light of 5600 to 5800 lux with a wavelength range similar to sunlight for the period of time given in Table I. After the irradiation, the odor of each filter paper sample was organoleptically evaluated.
The results are summarized in Table I.

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Table I.

•
additions A. Strength of the odor after irradiation 3 hours of irradiation Connection P B. 1 hour of irradiation Control
rehearse E. 1 2 ρ 1 2 no additives 1 4th 2 4th 2 5 3

The numbers listed under the strength of the odor mean:

1 - no urine-like odor

2 - slight urine-like odor.

3 - urine-like odor.

4 - strong urine-like odor

5 - very strong urine-like odor.

From Table I it can be seen that the compound P used with resmethrin in its odor-inhibiting effect (suppression the undesirable urine-like odor) is far superior to the other additives.

Example 2

The compounds P, A and the UV absorber J were added to resmethrin in the proportions listed in Table II. The mixtures were converted into a 2 percent resmethrin solution in acetone solved.

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- 6 - "1

Each solution was applied to filter paper according to Example 1 and exposed to artificial light. The results of the organoleptic tests are summarized in Table II.

Table II

to - is sentences concentration
of additives in
acetone
(%) Typical smell
after irradiation 3 hours.
Irradiate
lung ■ Invention
dungge
would mean with
tel '- P 0 _; 2 1 H.
Irradiate
lung 2 Control
rehearse P + J 0 _? 2 + O _T O2 1 1 P + J .0.02 + O ₇ 2 1 1 J 0.2 1 3 A + J 0.2 + 0 _r 02 2 3 no additives O 1 5 • 5

The rating numbers have the same meaning as in Table I.

From Table II it can be seen that the odor-inhibiting effect with the combination of the compounds P and J is greater than with the compound P alone, or the combination of the compounds A and J.

Example 3

Off ^; The additives indicated in Table III were prepared according to Example 2 test solutions. 1 ml each of this solution (with 20 mg resmethrin) was applied to filter paper with a diameter of 11 cm. After the solvent had evaporated, the samples were left for 1 day in a room without exposure to sunlight, and the odor developed was determined organoleptically.

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~ ⁷ ~

telt. The results are summarized in Table III.

Table III

additions P. concentration
of additives in
acetone
■ (#) Typical smell of - -
leaving it standing . Days
10 '. ¹ 5 20th Inventions
appropriate
middle
r P + J V. 5 ■ 2 2 1 Control sample J 0.1 + 0 ₇ 1 1 1 2 1 no additives 0 _; 2 1 4th 3 1 0 . 3 5 3 1 4th

The rating scale has the same meaning as in Table I.

From Table III it can be seen that the combination of compounds P and J with resmethrin an "essential" even after a long time show stronger odor-inhibiting effect compared with resmethrin alone, also the combination with the compounds P and J shows a particularly good effectiveness.

Example 4

1.0 g resmethrin, 0.1 g compound P and 5.0 g piperonyl butoxide were dissolved in odorless kerosene and brought to a total weight of 20 g. A spray can was made with this solution filled. Then 80 g of a * 1: 1 mixture of monofluorotrichloromethane (Freon 11) and difluorodichloromethane were put into the spray can (Freon 12) bottled. Spray (a) was obtained.

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1.0 g of resmethrin, 0.05 g of compound P, 0.05 g of compound J and 5.0 g of piperonyl butoxide were dissolved in odorless kerosene and then in the ^T. 'Described above. ^T he treated. The spray (b) was obtained.

1.0 g resmethrin and 5.0 g piperonyl butoxide were in odorless Dissolved kerosene and then treated further as described above. The spray (c), which was used as a control preparation, was obtained served.

1.0 g of resmethrin, 0.1 g each of the compounds A, B and C and 5.0 g of piperonyl butoxide was dissolved in odorless kerosene, and then treated in the above-described 7, ^T else. The sprays (d), (e) and (f) are obtained as a control preparation.

Twelve pieces of filter paper with a diameter of 20 cm were attached to the front of a room and the spray can mixtures (a), (b), (c), (d), (e) and (f) each in an amount of 10 g sprayed onto two pieces of paper at a horizontal distance of 30 cm from the paper. The filter paper remained at the ^T hang .iand. After 1 week, the odor was evaluated. After evaluation, the same sprays were sprayed onto the same filter papers in the same amount. Table IV summarizes the results of organoleptic tests which were obtained after spraying four times over a period of 4 weeks.

L · J

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-Q-

Table IV

, (a) Time interval 2 boil 3 "'/ ocher * I. 4 cook Spray center] (b) 1 week - 3 " 3 . 4th Inventiveness
moderate means (c) 4th 1 2 1 Control ■ (d) 2 20th 20th 20th rehearse (e) 20th 14th 18th 20th U). 16 20th 20th 20th 20th 20th 20th 20th 20th

Annotation:

The numbers listed in the table correspond to the number of test persons who detected a urine-like odor, 10 people each take a pair of samples of the filter paper sprayed with the same spray agent with regard to the odor ' rated.

When using the pesticidal agents according to the invention, the number of people who have a urine-like appearance with these agents is Observed odor, significantly less than in the control experiments. In this experiment, the intensity of the odor was not measured as in Examples 1, 2 and 3, but rather instead, the presence or absence of the odor. The reason is that the type of smell does not differ with the intensity changes. This is why this method is very practical. Because the odor did not disappear despite the repetition for 4 weeks The practical value of this method is not very high.

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Example 5

25 g of resmethrin, 1 g of compound P and 1 g of compound I. were dissolved in xylene to a total weight of 75 g. This solution was mixed with 25 g of the emulsifier Sorpol 2020. An emulsifiable concentrate (g) was obtained. Using the compound K in place of the compound I, an emulsifiable concentrate (h) was prepared in the same manner.

25 g of resmethrin and 1 g of compound P were dissolved in xylene and then treated in the same way. The emulsifiable one was obtained Concentrate (i).

25 g of resmethrin and 1 g each of compounds A, D and E were dissolved in xylene and in the same way in the emulsifiable concentrates (j), (k) and (l) transferred as control samples served. The concentrates obtained in this way were diluted 100 times with water and 10 ml each of the diluted emulsions in 'a spray gun filled. The emulsions obtained were each placed under a pressure of 1.41 atm on the wall of a room Applied filter paper of 20 cm diameter sprayed at a horizontal distance of 30 cm from the paper. After that it was the filter paper was left hanging for 1 week and the odor was organoleptically evaluated by 75 test persons, with 5 test persons each had to evaluate 1 pair of two mixtures. the Experimental results are summarized in Table V. The graph shows the relative position of each sample according to the strength of the urine-like odor. The experiments were carried out according to the Thurstone-Mosteller method, described in

K. Ichikawa, Sensory Test (A Course of duality Control), L " ^-1

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Γ. Π

August 1966, .page 44 Ms 53, Union of Japanese Scientist and Engineers' Inc.

Table V

spray (S) (G) (H) (i) (G) OO (D relative
position inventive
appropriate-
middle OO 2 1 O 0 0 -1.58 Control
rehearse (i) 3 X _n . 2 O 0 0 -1.20 ω 4th 3 0 O 0 -1.02
I. OO 5- 5 \ 3 2 1.20 (D ■ 5 5 5. 2 X _n 2 1.11 5 5 5 3 3 X _n 1.28

-1.0

1.0

weaker

Strength of the urine-like odor

stronger

Annotation;

The numbers in the table indicate the number of test persons who had the urine-like odor in the case of the one given in the column Perceived means more strongly than with the means given in the series.

Both the results summarized in the table and the graph show that the spray compositions (g) f 00 and (i) 'of the invention with respect to the urine-like odor clearly differ after spraying from the emulsions (j), (k) and (l) used as control samples.

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Example 6

25 g tetramethrin (3,4,5,6-tetrahydrophthalimidomethylchrysanthemate) v / are processed according to Example 5 to an emulsifiable concentrate (m) as a control sample. The emulsions (g), (h), (j) and (m) were each on filter paper according to Example 5 sprayed on. After 1 tfoche the organoleptic became Test carried out with 60 test persons, with 10 persons each had to examine a pair of 2 samples. The test results are summarized in Table VI. The graphic The illustration shows the relative position of each sample according to the strength of the urine-like odor (measured according to Thurstone-Mosteller).

Table VI

spray (G) (G) (H) (d) (m) relative
position Inventive
appropriate
middle (H) \ ^ LfN 0 6th 0 Control
rehearse (d) LfN \\ 0 6th 0 (m) 10 10 \ ^ 10 1.80 4th 4th 0 -O ₇ 73

(ü)

1.0

thinner ''. stronger

Strength of the urine-like odor

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From Table VI and the graph, it can be seen that the odor of sprays (g) and (h) of the invention clearly differs from that of the control sample (J). The strength of the odor of the sprays (g) 'and (h) comes from the odor very close to the spray agent (m), which contains tetramethrin as the main component, that does not develop a urine-like odor. This means that the urine-like odor of the spray (g) and (h) degraded to such an extent that it is difficult to determine. This is from a practical point of view very important.

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Claims (3)

Patent claims Pesticide, marked by a content of 5-benzyl-3-furylmethylchrysanthemate of the formula H Η ".CH ₇ -CH ₀ OC-C. C-CH = CC ^J as well as at 2.2 ^! -Methylene-bis- (6-tert-butyl-4-ethylphenol) of the formula II OH OH in an amount of 1 to 100 percent by weight, based on the Compound of the formula I, and optionally a UV absorber. 2. Pesticidal agent according to claim 1, characterized by a content of 5 to 10 percent by weight of the compound Formula II and the UV absorber, based on the compound of formula I. 3. Pesticidal agent according to claim ^ and 2, characterized in that that the UV absorber is a p-tert-butylphenyl salicylate " 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-oxybenzylbenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- (2'-kydroxy-4'-octoxyphenyl) benzotriazole or 2-carboxyethyl-3,3'-diphenylacrylonitrile is. 409835/1039