DE1668838C2 - O-methyl- and O-ethyl-O- (2,5-dichloro-4-bromophenyl) -phenylthiophosphonate and their use as active ingredients in insecticides - Google Patents

Description

Example 2

Production of O-ethyl-O- (2,5-dichloro-4-bromophenyrj-phenyIthiophosphonat

The invention relates to the new compounds A solution of 3.4 g of potassium hydride in 10 ml

O-methyl-O- (2,5-dichloro-4-bromophenyI) -phenylthio-water was added to a solution of 12.2 g of 2,5-diphosphonate and O-ethyl-O- (2,5-dichloro-4 -bromophe- chloro- i-bromobenzene in 100 ml of acetone in a 3-necked nyl) phenylthiophosphonate and their use flask with a mechanical stirrer and a as active ingredient in insecticides, if necessary together with a reflux condenser, was added. Mimit inert substances. The mixture was stirred and heated to reflux.

Although numerous insecticides are already on the market, add to the stirred, refluxing mixture are, which are used to monitor harmful effects, a solution of 13.2 g of O-ethyl-phenylthio-insects, especially in the field of land phosphorus chloride in 50 ml of acetone, was added. To economy, let use successfully, there is a completion of the addition, the mixture was 15 minutes Constant need for further selective insecticides, stirred for a long time, heated under reflux and then cooled, which are only effective against specific insect species.

but are harmless to other insect species. The reaction mixture was used to remove the

Selective insecticides are great for using acetone heated on a steam bath. the Monitoring of one or more special harmful residue was extracted with diethyl ether, the Some species of insect in an area where numerous extracts have been found with cold aqueous sodium. Various species of insects are found. droxyd and washed with ice water and then

The object of the invention was to provide new, selectively dried inseconds over calcium chloride. The extract has been used to tackle anticidal compounds. _Filtered off from the calcium chloride crystals and under

It has now been found that this task is increased by reduced pressure to the diethyl ether to remove the new compounds mentioned at the beginning. After filtering through a glass, the O-ethyl-O- (2,5-dichloro-4-bromocidene, optionally together with inert substances, phenyl) -phenylthiophosphonate was used in the form of a liquid, which was obtained as an active ingredient in selective insect frit can be. with a refractive index of 1.6203 at 26 ° C,

The compounds according to the invention can produce which solidified on standing.

by adding 2,5-dichloro-4-bromophenyl When used as an active ingredient for a selective

the vernyl halide according to the invention is reacted with the corresponding O-alkylphenylthiophosphorus insecticide. The last-mentioned compound, in general, of an insecticidal preparation, can for its part result from the corresponding phenylthionation in a form which has a toxic effect on the insects phosphonic acid dichloride by treatment with the 45 amount, if necessary together with inert equivalent alkyl alcohol. bindings, incorporated. With the help of such insecticides

In the preparation of the compounds according to the invention, it is possible to use the active compound gen is explained in the following examples: at the location of the pest infestation in any desired

Amount to apply. In the case of insecticidal preparations In the case of 1 1 50 lines, it can be solids, for example Manufacture of O-methyl-O- (2,5-dichloro- ^dusts ' ^{grains or} wettable powders, or around

4-bromophenyl) phenylthiophosphonate liquids, for example solutions, aerosols or

emulsifiable concentrates.

7.5 g (0.0025 mol) of 2,5-dichloro-4-bromophenol were insecticidal dusts z. B. are produced,

the dissolved in 25 ml of acetone and in a 3-neck 55 by putting the active compound together with Round bottom flask fitted with a mechanical stirrer, a solid inert support material, e.g. B. Talk, Sound an internal thermometer and reflux condenser or certain types of silica or pyroses was introduced. In the flask was put a phyllite, ground and mixed. Granular preparations Solution of ί g (0.025 mol) of sodium hydroxide in can be prepared by making granular Given 5 ml of water. The contents were stirred 60 carriers, such as. B. attapulgites or vermiculites, and then slowly a solution of 5.2 g which usually has a particle size of 0.3 to (0.025 mol) of O-methylphenylthiophosphonyl chloride in 1.5 mm, with the normally in one 25 ml of acetone was added. The reaction mixture was dissolved active compound in appropriate solvent stirred, refluxed for 15 minutes and impregnated. Wettable powders that can be immersed in water and / then cooled. 65 or oil up to any desired concentration of

The reaction mixture obtained was fil- active compound can be dispersed triert, the filtrate could be prepared to remove the acetone by distilling concentrated dusts in a vacuum. The residue was incorporated with a wetting agent.

3 4

In some cases the insect breathes according to the invention can be applied. In some active compounds in common organic solutions, those on the soil or planting agents, such as. B. kerosene or xylene, sufficient surface-applied compounds of the soluble, so that they can be absorbed directly in the form of these solutions plants, and the insects can be used. Often it is also purposeful - 5 thereby poisoned in a systemic way,
moderate, solutions of the insecticides according to the invention. The above uses of insecticides are based on compounds under elevated pressures to aerosols on the fact that almost all of insects are dispersed. However, preferred liquid insecticidal preparations that cause direct or indirect preparations are the emulsifiable concentrates that are the result of their foraging. In fact, the active compound of the present invention and the large number of harmful insects may widely contain a solvent as well as an emulsifying agent as inert based on the nature of their food carrier material. Classify such emulsifiable intake. For example, there are chewing concentrates that can be mixed with water and / or oil up to any insect, such as the Mexican bean beetle, the desired concentration of active compound, southern army worms, cabbage worms, grasshoppers, which can be used as sprays on the site of the insect - 15 Colorado potato beetles , Pest caterpillars, and the infested are diluted. In those in these con- Larva of the great gypsy moth. There are also centrates most frequently used emulsifiers, the stinging-sucking insects, such as. B. the non-ionic or mixtures of pea louse, house fly, grain bug, Singnichtionischen with anionic surface-active cicadas and plant bugs.
Means. * _ao Another group of insects includes those

A typical insecticidal preparation used by those who feed on the inside of the plant. To do this, turn the compounds of the invention than hear the drill, such as. B. the caterpillar of the European active substance is obtained is found in the following European corn borer and the larva of the owl moth; worms Example explained in which all quantities on or grain beetles, such as. B. the codling moth, the are based on weight. 35 cotton caps! 'Iäfer, the plum cutter, the melon worm and the apple maggot; Leaf miners, like

B e i s ρ i e 1 3 z. B. the apple leaf miner and the beet leaf miner

Producing a dust ^flowing S ^{e; and} bile insects such as wheat nodule and phylloxera.

Active connection according to example 1 ... 10 3 ° insects which are below the surface of the earth

Gripping powdered talc 90 are called underground insects.

this includes pests such as apple wool, the

The above components are found in a mechanical Japanese beetle and the larva of the grain rootworm,

Mix niche grinder mixers and grind up to the point to be used for monitoring the insects

a homogeneous, free flowing dust of the desired amount of active compound according to the invention

Particle size is obtained. This dust is dependent on numerous factors, such as: B. the respective

direct application at the location of the insect infestation against a special insect, the intensity of the infestation, the

suitable. Weather, the nature of the environment and the nature of the

The compounds according to the invention can be used in preparation. For example, the application can be used as insecticides in a known manner. 40 only 28 or 56 g of the active compound per acre. One method of killing insects, to be adequate to lightly colonizing one, is to apply an insecticidal mass to the site of the insect infestation to its diet, which is an inert carrier to bring conditions under control, while and as an active ingredient a compound according to 0.45 kg or more of the active compound per acre of the invention in an amount toxic to the insects may be required to cope with a severe infestation. The concentration of the insects according to the invention under conditions favorable for their development in the insecticidal preparations varies.
strongly depending on the type of preparation and the intended purpose, but contain the insecticides particularly valuable since they are generally about 0.05 to about 5 ° selective with regard to their insecticidal preparations. The compounds are 95% by weight of the active compounds according to the invention, for example particularly effective against insects of the compound. In a preferred embodiment, order Lepidoptera, to which the Southern Army Worm of the invention belongs, the insecticidal preparations contain while other insects are non-toxic to about 5 to about 75 percent by weight of the active, even to such compounds. The masses can also add another 55 insects that have the same type of food ingestion additives, such as B. stabilizers, distributing agents have.

Deactivators, adhesives, adhesives, fertilizers, the usefulness of the inventive

Activators and / or synergetic agents contain. bonds as insecticides can be caused by various

The compounds according to the invention can be demonstrated in test experiments. Be at a number you many ways to monitor insect comparable ^e ° tests, the test compounds were prepared, applies. Insecticides which are to be used as gastric poisons or by dissolving the compounds in acetone and the protective substances can be applied to acetone solution dispersed in distilled water, the surface on which the insects feed or feed on the 0.2 percent by volume of a dispersant move. Insecticides containing as type of alkylaryl polyether alcohols.
Contact poisons or exterminating agents can be used 65 In an attempt to control harmful insects, treatment of the surface on which the insect crawls, lima bean leaves on the top and bottom or as Incense treatment of the air, in the page with the above preparation in the below

sprayed concentrations and ten larvae of the southern army worm (in its late third Appearance) for a feeding time of 48 hours offered. At the end of this period, mortality was observed. Some of the received Results are given in the following table I:

Table I. Test chemical

Product of

Example 1 - J

Product of ί

Example 2 \

Concentration, actual 7 “GenaIt

the chemical

in the sprayed

liquid

0.01
0.001

0.01
0.0075
0.005
0.0025

mortality

100 90

100

100

1.00

90 percent destruction of the
"Southern Army Warms"

5 concentration
(ppm ( control
(V.) Connection to Bei
game 1,
¹⁰ comparative subsidy K 10
20th 100
50

Percentage destruction of the
"Southern Army Worm"

To demonstrate the superior effectiveness of the compounds according to the invention as an active ingredient Partly in insecticidal preparations, the experiments described below were carried out in which the selective effectiveness of the inventive Product according to Example 1 with the insecticidal effectiveness of recognized good commercial products compared to different insect pests. The following were specified Get results:

• Connection according to example 1

2,2-bis (p-chlorophenyl) -1,1,1-trifluoroethane

percentage concentration

0.10
0.05
0.01

0.10
0.05
0.01

To

24 hour

the

100 100 100

35

Table II

Percentage destruction of larvae of the "southern army worm"

Test connection

Connection after
example 1

Comparative substance F

Application amount (0.454 kg / Tomorrow)

1/2
1/2

Days after treatment

0; 3 [7

100 100

100 39

87 19

Percentage destruction of larvae Test connection To whom
amount of manure
(0.454 kg / 0 of 8th 15th 29 "Southern Army Worm" Tomorrow) connection Days after the
treatment after Bei 100 1 100 100 90 game 1 1/2 Comparative 100 72 50 , 7 subslance II .. 1/2 100 Comparative 97 0 0 7th substan /. 1 ... 1/2 0 90 0 0 0 Control; .... 0 57 0

Table III
Percentage destruction of »Cutworm«

40 concentration
0.454 kg /
tomorrow To
48 hours
the 45 Connection according to 1
game 1 y 0.25
0.5
1 85
100
100 50 Comparison substance F J 0.25
0.5
1 30th
35
90 Comparative substance GJ
55 I. 0.25
0.5
1 0
20th
.55 Comparison substance AJ
60 2,3-dihydro-2,2-dimethyl-
benzofuranyl-7-N-me-f
ethyl carbamate J.
6,7,8,9,10,10-hexafluoro 0.25
0.5
1
0.25
0.5
1.0 0
5
25th
0
5
25th 6,9-methano-2,4,3-ben- ί
zodioxalhicpien J. 0.25
0.5
1.0 15th
10
25th

Table IV

Percentage destruction of German cockroaches (concentration 10 mg / 0.09 m ^a )

Old fr des 1 day after The rest the Be (Weeks) plot 1 100 2 100 4th 100 Connection to Bei 8th 100 game 1 12th 100 16 100 20th 80 24 100 1 100 2 100 4th 90 Comparative substance E 8th
12th 10
0 16 0 20th 10 24 20th

Table V

Try green corn

5
connection Dosie
tion
(0.454 kg) percent
ear
worm sentence of be
Ears
Drilling
wu rm fell
"Army
worm" 10
connection
after Bei
game 1 1.5 0 7.5 3.5 Comparison sub
punch A 1.5 0 30th 21 Comparison sub
punch B 1.5 1.5 23 - 19 ' ao comparison sub
punch C 0.5 4.0 5.5 22nd Comparison sub
punch D 6.0 8.5 46 51 35 sample - 16.0 49 56

Table V!

Comparison substances

l-naphthylmethyl carbamate

2-chloro-l- (2,4 ₁ 5-trichlorophenyl) -vinyldimethylphosphonat

Dimethyl phosphate ester of 3-hydroxy-n-methyl-cis-crotonamide

a bacterial organism

Ο, Ο-dimethyldithiophosphate of diethyl mercaptosuccinate

Ο, Ο-diethyl O-nitrophenyl phosphorothioate

S-methyl n - [(methylcarbamyl) oxy] thioacetimidate

S-iDimethoxyphosphinyloxyi-NsN-dimethyl-cis-crotonamide

0,0 diethyl 0- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate

0,0-Dimethyl-0-2,5-dichloro-4-bromophenyl thiophosphate

209681/266

Claims (3)

Diethyl ether extracted and the extract was then patent claims: ■ with 100 ml of a 5 "/ own aqueous sodium hydroxide solution and then twice with water 1. O-MethyI-O- (2,5-dichloro-4-bromophenyI) - wash. The ether extract was made from magnesium phenyl thiophosphonate. 5 sulfate dried, filtered and the filtrate under mixed 2.O- ethyl - O - (2,5 - dichloro - 4 - bromophenyl) - heated under reduced pressure to remove the diethyl phenylthiophosphonate ether. This gave O-methyl- 3. Use of the compound according to An O- (2,5-dichloro-4-bromophenyl) phenylthiophosphonate spoke 1 and 2 as an active ingredient in insecticides, gel as a pale yellow liquid residue with a Bre possibly together with inert substances. io ching index of 1.6385 at 22 ° C, that when standing became solid.