DE2908651A1 - 1,5-BIS (ALPHA, ALPHA, ALPHA, -TRIFLUOR-P-TOLYL) -1,4-PENTADIEN-3-ON- (1,4,5,6-TETRAHYDRO-2-PYRIMIDYL) -HYDRAZONE AND THE USE THEREOF AS AN INSECTICIDE - Google Patents

Description

27.296

AMERICAN CYANAMID COMPANY Wayne, New Jersey, U.S.A.

1,5-bis (a, a, a-trifluoro-p-tolyl) -1,4-pentadien-3-one (1,4,5,6-tetrahydro-2-pyrimidyl) hydrazone and its use as

insecticide

Additional patent application to P 27 39 098.3

909838/0713

1 , 5-bis (g _y g _# a4: r if luor-p-tolyl? -1,4-pentadien-3-on-

tetrahydro-2-pyrimidyl) hydrazone and its use as

insecticide

Additional patent application for P 27 39 098.3)

The invention relates to 1,5-bis (α, α, α-trifluoro-p-tolyl) -1,4-pentadien-3-one- {1,4,5,6-tetrahydro-2-pyrimidyl) hydrazone and its use as an insecticide. In particular, the invention relates to a development of the subject matter of the German Patent application P 27 39 098.3.

The parent application describes a relatively broad class of pentadienone hydrazones of the following general formula:

.NO,

NIl-C

^N R

I 6

HC = CH-C - CH = CH

where R ₁ and R _{2 are} each hydrogen, halogen, CF ₃ , Cj-C.-alkyl, Cj-C4-alkoxy or Cj-C-alkylthio and where R-. Denotes hydrogen or methyl, with the proviso that in the case of R ₃ = Methal, R ^ and R ₃ also denote methyl; and where R ₄ and R _{5 are} each hydrogen or C 1 -C alkyl or together are an alkylene group having 2 to 6 carbon atoms, an alkylene group having 2 to 4 carbon atoms, a dimethylalkylene group having 2 to 4 carbon atoms, which can be substituted by one or two methyl groups or a phenyl group or a 1,2-cyclohexylene group and where R _{g is} hydrogen or Cj-C ^ -alkyl or salts of these compounds.

909838/0713

While the specific compound of the present invention falls within the general formula above, it is in not specifically mentioned in the main application. It has now been found that this particular compound is excellent insecticidal effects unfolded.

In the following, the invention is explained in more detail with the aid of exemplary embodiments.

example 1 Production of 1,5-bis (α, α, α-trifluoro-p-tolyl) -1,4-pentadiene-

3-one (1,4,5,6-tetrahydro-2-pyrimidinyl) hydrazone

^H / \

^(F 3 ^C \ / ^CH = CH-) ₂ C = 0 + ΗΙ · Η ₂ Ν-ίί— ' .-

^(F 3 ^C \ N-CH = CIH) ₂ C = IHI- ^. ·

27.7 g (0.075 mol) of the dienone and 18.0 g (0.075 mol) of the hydrazine are reacted in refluxing isopropanol for 3 to 4 hours. The isopropanol is then drawn off, leaving a pale yellow solid. This is carefully washed with ether. The yellow solid is stirred with 200 ml of ether and with 50 ml of saturated sodium bicarbonate. After 15 minutes, the ether layer is dried and concentrated, leaving a light yellow solid with a weight of 25.0 g (72% of theory). A small sample is recrystallized from toluene / hexane. A bright yellow solid with a melting point of 196 to 197 ^° C. is obtained.

909838/0713

Analysis calculated for N ₄ FgC ^ ₃ EU ₀ :

CH N

calculated found

59 , 24 4th , 29 12th , 02 58 / 55 4th , 53 12th , 00

Example 2 Poison bait test at Blatella Germanica Linnaeus Test procedure

The experiments are carried out in cages measuring 20.32 cm in diameter and 6.35 cm high. The round side wall is made of stainless steel and carries a glass pane with 20.32 cm Diameter as the bottom. The cages are covered with copper wire netting (C16 meshes / 2.5 cm). It will be 100 mg, 25 mg or 6.25 mg of the technical grade compound are added to each 5 g of peanut butter and this mixture is poured into a plastic bowl with an inner height of 8 mm and an inner diameter filled by 30 mm. The final concentration consists of 2, O or »0.5 and 0.125%, respectively. The mixtures are each 2 min touched. 1 bowl with the treated bait and a bowl with 5 g of untreated laboratory food are placed in each cage as luahlnahrung as well as 100 ml water with wick. Then there 20 adults of the species Blatella are placed in each cage

Germanica Linnaeus. The cages are kept at about 27 ^° C. and 35% relative humidity and the mortality is determined by counting. The data are in Table I.

compiled.

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- -S "Table I.

Percent mortality

structure

Blatella Germanica

Linnaeus

11 day mortality 2.0% 0.5% 0.125

100

100

100

Example 3 Poison bait test in Solenopsis invicta Buren Test procedure

The tests are carried out in 30 ml disposable plastic medicine trays with an upper inner diameter of 40 mm, a lower inner diameter of 32 mm and a height of 38 mm. A hole is made in the bottom of each bowl drilled with 6 mm diameter. A layer of plaster of paris and building cement (ratio 9: 1) is poured onto the floor. The plaster mix covers the hole and serves as a wick. It attracts water when the bowl is filled with water Foam cushion with a thickness of about 6 mm is provided. The bowls are placed in a trough and with a covered another inverted trough to prevent rapid evaporation of the water from the foam cushion. humidity is necessary in order to keep the humidity in the bowls high enough and a drainage of the Avoid ants. Cement is added to create a hard mix through which the ants cannot escape tunnels can build.

About 24 hours before the start of the test, 20 worker ants from colonies collected in the field are placed in each test chamber.

90 9.83 8 / 0.7 13

29.Q-8651

This holding time is allowed before the actual treatment the ants to recover from the intervention and to orientate themselves in the containers.

The test substance is placed directly in the feed, e.g. B. soybean oil, dissolved. The toxic solution is offered to the ants in cotton swabs saturated with your material, which are placed in small caps in the test chamber. Preliminary tests are carried out at concentrations of 1.0, 0.1 and 0.01% "

The ants ingest the poisoned bait for 24 hours. The poison bait is then removed and the ants remain in the cage without food for a further 24 hours. Then you give Put new cups in the chamber with a cotton ball soaked in soybean oil and leave this food during the rest of the test duration. At intervals of 1, 2, 3, 6, 8, 10 and 14 days from the start of administration of the poisonous food, the number of ants lying on the ground and mortality is determined by counting. Everyone Test is carried out in three replicas. The room temperature is held at 75-2 F. The data are summarized in the following table.

Table II

Percent mortality

structure

Solenopsis invicta

Boers
14 day mortality

1.0%

0.1%

αο / Λ

1OO

909838/0713 ORIGINAL INSPECTED

Example 4

The insecticidal effectiveness of the compound according to the invention is proven by the following experiments, using amounts of 10 to 1000 ppm for various insects. Details of the test means and the procedures for evaluating the tests are given below:

Test agent

(A) 100 mg of the test material is weighed out and placed in a funnel which fits onto a 113 g narrow neck bottle is set. The test material is then rinsed into the bottle with 35 ml of acetone. Then again this Poured in amount of water and again this amount of acetone. In this way, a solution of 1000 ppm is obtained Test compound in 65% acetone. If the material is not soluble, it is crushed with a glass rod and applied in the form of a suspension.

(B) This stock solution (A) is used to prepare 3OO ppm solutions or suspensions. To do this will be 30 ml of the stock solution (A) are pipetted into a bottle with 70 ml of 50% acetone, to form a Concentration of 300 ppm. Further dilutions with 50% acetone are made.

(C) Tests with 10 ppm acetone solution: 1 ml of the stock solution (A) is pipetted into 99 ml of acetone, a concentration of 10 ppm being obtained. Further dilutions are made with 50% acetone if desired.

Initial tests

HeIiothis virescens Fabricus

A cotton plant with two real leaves spread out

909838/0713

is immersed in 3OO ppm solution for 3 s with stirring.

2 2

A cheesecloth with the dimensions of 1.27 cm to 1 _f 91 cm and having about 50 to 100 eggs of the indicated insect species, which have h a Older from 0 to 24, is dipped in the test solution and placed on a leaf of the cotton plant. This arrangement is then placed under a hood to dry. Then the leaf with the treated eggs is removed from the plant and placed in a 226 g Dixie cup with a wet 5 cm dental wick, which is then covered with a lid. The other leaf is placed in a similar cup with a wick and a piece of the same cloth with 50-100 newly hatched larvae is added before covering this cup with a lid. The whole is left for three days at 80 ° F and 50 % relative humidity. Then the number of killed freshly hatched larvae is determined, as well as the number of larvae hatched from the eggs. It is also determined whether there is an inhibition of feed intake or whether disturbances of other kinds impair normal development.

Secondary tests Heliothis virescens Fabricus, third skin stage

Three cotton plants with just spread out cotyledon leaves are immersed in a 1000 ppm solution and placed under a hood to dry. After drying, each cotyledon is cut in half and 10 each are placed in a 28 g plastic medicine cup containing a 1.25 cm dental wick saturated with water. A specimen of the test insect in the second skin stage (larva) is then placed in each cup. The cups are covered and held at 80 ^° F and 50% relative humidity for 3 days. After that, the mortality is determined by counting. If more than 75% of the larvae are killed, further tests are carried out.

909838/0713

Triehoplusia ni Hübner, third molting stage

A real leaf of a cotton plant is put into the test solution immersed and moved there for 3 s and then removed and dried under an evacuable hood. After drying the sheet is moistened with a 9.0 cm Petri dish Filter paper given on the floor. Then 10 larvae of the third molting stage are added, whereupon the Petri dish with covered with a lid. After 3 days at 80 F and 50-10% relative humidity, mortality is determined by counting. In the event of a mortality greater than 75%, further tests are carried out.

Spodoptera eridania Cramer

Sieva Lima bean plants are cut back to a stage with two primary leaves spread out (7.5 to 10 cm) and immersed in the test solution for 3 seconds with agitation and then placed under a hood to dry. After the leaves are dry, they are cut off and each cut leaf is placed in a 10 cm Petri dish which contains a piece of damp filter paper and 10 larvae of Spodoptera eridania Cramer in the third molting stage, each about 9.5 mm in length, are added . The Petri dishes are covered and left to stand in a room for 2 days at a temperature of 80 ^° C. and at 50% relative humidity. Mortality is determined by counting after 2 days.

Seven days after treating the plants, leaves are again cut out and the test procedure repeated. The mortality in this test demonstrates the residual activity of the compounds.

The data obtained are summarized in the following table.

909838/0713

Table III

link Heliothis virescens
Fabricus 300
TpM 100
TpM 10
TpM Larvae 300
TpM 100
TpM 10
TpM H.viresc.
3.How
tion s- 100
TpM Tricho-
plusia
ni 100
IpM Spodoptera
eridania 100
TpM 10 7
TPM TPM 1,5-bis (α, α, α-tri- Eggs 0 100 100 0 stage 100 1000
TpM 100 1000
TpM 100 70 100 fluor-p-toly1) -1.4 - 1000
TpM 100 100 pentadiene-3-one- (1,4,5, 6 - 100 tetrahydro-2-pyrimidir yi) - hydrazone

tr *

CD (X)

Claims (4)

PATENT CLAIMS / iy compound of the formula V ^ NH-NC (CH- \ -N 2. 1,5-bis (α / α, α-trifluoro-p-tolyl) -1,4-pentadien-3-one (1,4,5,6-tetrahydro-2-pyrididinyl) hydrazone. 3. A method of combating insects, characterized in that the insects, their habitat, their Brings breeding sites or their food into contact with an insecticidally effective amount of a compound of the following formula \ N -N «C (CH» CH 4. The method according to claim 3, characterized in that 1,5-bis (α, α, α-trifluoro-p-tolyl) -1,4-pentadien-3-one- (1,4,5,6- tetrahydro-2-pyrimidinyl) hydryzone begins. 909838/0713