DE1642240B - Phosphoramidates and pesticides containing them - Google Patents

Description

ίο implements and then the latter with a Amine of the general formula

where X is an oxygen or sulfur atom, Y is bromine or iodine, R _{1 is} methyl or ethyl and R _{2 is} hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl or sec-butyl.

2. Pesticides, which as the active component a phosphoramidate of the general formula

H ₂ NR ₂

contain, in which X is an oxygen or sulfur atom, Y is bromine or iodine, R _{1 is} methyl or ethyl and R _{2 is} hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl or sec-butyl, together with suitable ones Carriers and / or aggregates.

- ρ

ρ
\

The invention relates to phosphoramidates of the general formula

^C1 X OR ₁

where X is an oxygen or sulfur atom, Y is bromine or iodine, R _{1 is} methyl or ethyl, R _{2 is} hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl or sec-butyl, as well as pesticides which are used as active component contain a phosphoramidate of this formula together with suitable carriers and / or additives.

The phosphoramidates of the formula I can be prepared in a simple manner by a Phosphoric acid or thiophosphoric acid phenol ester dihalide of the general formula

(H)

first with an alcohol of the general formula R ₁ OH (III)

to react

The implementation of a phosphoric acid or thiophosphoric acid phenol ester dihalide of the formula II with an alcohol of the formula HI can be carried out in the presence or absence of a solvent. As Lö solvents can be used, for example: halogenated hydrocarbons, such as carbon tetrachloride, Dichloroethane, dichloroethylene, etc. In order to achieve the most complete implementation possible, it is desirable to use the alcohol of the formula II in excess (125 to 150% of theory) to be applied. The implementation of the monochloride obtained of the formula IV with the amine of the formula V is preferably carried out with cooling in order to avoid side reactions. It is desirable that a reaction temperature of 30 to 50 ° C is not exceeded.

As has been found, the new phosphoramidates of the formula I have good insecticidal and fungicidal properties Properties. They can therefore be used to control pests that occur in agriculture, but also in the home.

stop occurring, be used. For example, they can be used on the emerging vegetation to avoid infestation with insects without damaging the plants.
The new active ingredients of the formula I can be used alone or together with suitable additives customary in formulation technology. There are thus numerous application forms for the new active ingredients, which will be discussed in more detail below.

The sprayable solutions for direct use contain z. B. mineral oil fractions of high to medium, in particular above 100 ⁰ C Hegendem boiling range, such as diesel oil or kerosene, also coal tar oil or oils of vegetable or animal origin, and hydrocarbons, such as alkylated naphthalenes, tetrahydronaphthalenes, xylenes, cyclohexanols, and optionally also ketones, chlorinated Hydrocarbons such as tetrachloroethane, trichlorethylene or tri- and tetrachlorobenzenes.

For use in aqueous application forms, emulsion concentrates, pastes or wettable Wettable powder with the addition of water. As an emulsifier or dispersant non-ionic products come into consideration, e.g. B. Condensation products of aliphatic alcohols, Amines or carboxylic acids with a long-chain hydrocarbon radical of about 10 to 30 carbon atoms with ethylene oxide, such as the condensation product of octadecyl alcohol and 25 to 30 mol Ethylene oxide or that of soy fatty acid and 30 moles of ethylene oxide or that of technical Oleylamine and 15 months! Ethylene oxide or that

Dodecyl mercaptan and 12 moles of ethylene oxide p7 can also be used as condensation products of ethylene oxide with hydroaromatic polycyclic carboxylic acids or amines. Among the anion-active emulsifiers that can be used are: the sodium salt of nodecyl alcohol sulfuric acid ester, the sodium salt λ r dodecylbenzenesulfonic acid, the potassium or Tn-sanolamine salt of oleic acid or abietic acid from mixtures of these acids, or the sodium " ak of a petroleum sulfonic acid. Quaternary ammonium and phosphonium compounds, such as e.g. B. Cety'vridiniumchlorid or Dioxyäthylbenzyldodecylammoniumchlorid into consideration '

The new funds come in the form of dust emission plans or spreading agents for use, they can be used as solid carriers talc, kaolin, bentonite, sand, calcium carbonate, calcium phosphate, but also coal, Contain cork flour and wood flour and other materials from their origin. The different PreoTraie 'can in the usual way an addition of Sen which the distribution, the adhesive strength or improve the muscle contraction, contain; as Such substances should be mentioned: fatty acids, resins, glues Casein "or, for example, alginates. The use of the preparations in granulated form is also very useful, Such preparations are never used in crop protection and hygiene according to the usual spray, Casting. Dusting and smoking processes.

In the following examples, parts mean parts by weight percentages mean percentages by weight Temperatures are given in degrees Celsius.

example 1

400 ε 2 of 5-dichloro-4-iodophenol were added over a period of one hour to a well-stirred solution of phosphorus oxychloride in pyridine. The whole thing was left to stand for 24 hours with stirring at room temperature. The precipitated pyridine hydrochloride was then filtered off with suction and the excess of phosphorus oxychloride was distilled off (remaining residues of POCl ₃ were removed in vacuo) The residue was distilled in a short column under the lowest possible vacuum 350 g O - (- 2,5 - dichloro - 4 - iodo - phenyl) - phosphoric acid dichloride, sp. 136 to 138 °, at 0.2 mm Hg,

B. 40 g of methanol was dissolved in 300 ml of carbon tetrachloride. This solution was added dropwise to a solution of 406 g of the dichloride obtained according to A. in 21 carbon tetrachloride. Through external cooling it was ensured that the temperature of 25 ° was not exceeded. After 45 minutes it was nitrogen was blown through the reaction product in order to drive off hydrochloric acid formed.

A solution of 84 g of methylamine in 800 g of ice-cold solution was added dropwise to the product thus obtained Ether, whereby vigorous external cooling ensured that the temperature of 25 "" was not exceeded. The amidation product was washed with water to remove methylamine hydrochloride to remove and then dried the organic solution. Then the solvent evaporated and the remaining oily product - consisting of 2,5-dichloro-4-iodophenyl-methylphosphoric acid-N-methylamide - put in the refrigerator for crystallization. Melting point from hexane 110 ° (compound no. 1).

The following phosphoramidates were also prepared in a similar manner:

Connection no. R ₁ 2 CH ₃ 3 CH ₃ 4th CH ₃ 5 CH ₃ 6th CH ₃ 7th CH ₃ 8th C ₂ H ₅ Example 2

C ₂ H ₅ C ₃ H ₇ (n) C ₃ H ₇ (iso) C ₄ H ₉ (n) C ₄ H ₉ (sec.) CH ₃ melting point

ö \ n'o ' 1.6215

86 to 88 ° (hexane) 50 to 5 Γ (hexane) 100 to 101 ° (hexane) oil n? 1.5733

66 to 68 ° (cyclohexane-hexane)

87 to 90 ° (hexane)

A. 289 g of 2,5-dichloro-4-iodophenol were refluxed together with 0.95 g of anhydrous magnesium chloride and 960 g of phosphorus trichloride until the evolution of hydrogen chloride ceased. The excess phosphorus trichloride was distilled off at normal pressure. Was then added at room temperature to 32 g of sulfur and the mixture was heated for 30 minutes at 150 to 170 ⁰ C. Subsequently, the temperature was raised slowly to 260 °. After cooling, the liquid part was poured off the resin and distilled in a high vacuum. This gave 245 g of O- (2,5-dichloro-4-iodophenyl) thiodichlorophosphate, sp. 163 to 17G ^Q / O, 2 mm Hg.

55 B. 211 g of the dichlorides obtained according to A were presented in 250 ml of methylene chloride. 32 g of methanol were added dropwise at 20 °. Then one held the Solution for 16 hours at the boil. After evaporation of the solvent and the volatile

60 portions in vacuo were obtained as a residue 194 j O - methyl - O (2,5 - dichloro - 4 - iodo - phenyl) - thiochlor phosphate as a yellow oil.

C. 41.8 g of the monochloride obtained according to B were placed in 150 ml of methylene chloride. Man IaG

65 to this in 30 minutes at room temperature a 10% ethereal solution containing 6.2 g of methylamine, zi drops. The mixture was stirred for one hour at. The methylamine hydrochloride was rinsed with water:

washed, then the methylene chloride solution was washed with saturated sodium bicarbonate solution and dried over sodium sulfate evaporation of the solvent in vacuo gave the O-methyl-O- (2,5Hdichlor-4-iodophenylHbiophosphoric acid-N-methylareaid, which, recrystallized from cyclohexane, melts at 81 to 83 ° (compound no. 9).

The following
phoramidate produced:

R ₁ -OS ^C1

MI p - o

R ₂ -HN

Connection no. R. R ₂ Melting point 3 10 CH ₃ C ₂ H ₅ 60 to 61 ° (methanol) 11th CH ₃ C ₃ H ₇ (n) 56 to 57 ° (cyclohexane) 12th CH ₃ C ₃ H ₇ (iso) 83 to 84 ° (methanol) 13th CH ₃ C ₄ H ₉ (n) 49 to 50 ° (cyclohexane) example

A. 374 g of 4-bromo-2,5-dichlorophenol were at 20 Slowly introduced to 28 ° in a mixture of 765 ml of phosphorus oxychloride and 122 g of pyridine. the The mixture was stirred overnight and then suction filtered. The excess of phosphorus oxychloride was distilled off (last in vacuo) and the remaining residue was distilled in a high vacuum. Man received 303 g of 4-bromo-2,5-dichlorophenyl-phosphoric acid dichloride with a boiling point of 128 to 135 ° / 0, 15 mm Hg.

B. 35.9 g of the dichloride obtained according to A were dissolved in 200 ml of carbon tetrachloride and at 20 to 25 ° in 15 minutes with 4 g of methanol, dissolved in 30 ml of carbon tetrachloride, added. The solution was stirred for 30 minutes at 25 ° and then nitrogen was blown through the solution to remove the hydrogen chloride to remove. A solution of 8.4 g of methylamine was added dropwise to the product thus obtained

3 ° in ether so that the temperature of 30 ° was not exceeded. The amidation product was washed with water to remove methylamine hydrochloride. After the organic solution had been dried over sodium sulfate, the solvents were distilled off in vacuo. The residue obtained was O-methyl-O- (4-bromo-2,5-dichlorophenyl) -phosphoric acid-N-methylamide, which, recrystallized from hexane, melts at 76 ° to 77 ° (compound no. 14). The following phosphoramidates were prepared in an analogous manner:

R ₁ OO ^C1

P - O

R ₂ HN

y ν

Cl

Br

Connection no. R, R ₂ Melting point 15th CH ₃ C ₂ H ₅ 73 to 74 ° (hexane) 16 CH ₃ C ₃ H ₇ (n) 55 ° (hexane) 17th CH ₃ C ₃ H ₇ (iso) 97 to 98 ° (hexane) 18th CH ₃ C ₄ H ₉ (n) n? 1.5498 19th CH ₃ C ₄ H ₉ (iso) 64 to 65 ° (petroleum ether)

Example 4

A. In a manner analogous to that described in Example 2A, 242 g of 4-bromo-2,5-dichlorophenol were obtained and 960 g phosphorus trichloride and 32 g sulfur 203 g 4-bromo-2,5-dichlorophenylthiodichlorophosphate from boiling point 142 to 14870.2 mm Hg.

B. In a manner analogous to that described in Example 2 B, 187 g of 4-bromo-2,5-dichlorophenylthio-dichlorophosphate were obtained and 32 g of methanol, 180 g of O-methyl-O - (4 - bromo - 2,5 - dichlorophenyl) - thiochlorophosphate as a yellow oil.

C. 22 g of the monochloride obtained according to B were placed in 90 ml of methylene chloride. To this end, 7 g of isopropylamine were added dropwise over 30 minutes at room temperature. The mixture was stirred for a further hour at 25 °, and the isopropylamine hydrochloride was washed out with water. The organic layer was then washed out with saturated sodium bicarbonate solution and dried over sodium sulfate. After evaporation of the solvent in vacuo, the residue obtained was O-methyl-O- (4-bromo-2,5-dichlorophenyl) -thiophosphoric isopropylamide, which ^{melts recrystallized from hexane at 66 to 67 ° C.} (compound no. 20).

The following phosphoramidates were prepared in an analogous manner:

55

R ₁ - OS

R, HN

Cl

- O - <ζ \ - Br
Cl

Connection no. R, R ₂ Melting point 21
22nd
23 CH ₃
CH ₃
CH ₃ CH ₃
C ₂ H ₅
C ₃ H ₇ (n) 82 ° (petroleum ether)
54 to 56 ° (petroleum ether)
u? 1.5808

Example p Dust

Equal parts of an active ingredient according to the invention and precipitated silica were finely ground. Through Mixing with kaolin or talc can consist of dusting agents with preferably 1 to 6% active ingredient content getting produced.

Wettable powder

For example, to prepare a wettable powder, the following components were mixed and finely marry:

Parts of active ingredient according to the present invention, parts of highly adsorptive silica, Parts of Bolus alba (kaolin), 3.5 parts of reaction product from p-tert-octyl

phenol and ethylene oxide, 1.5 parts of l-benzyl-2-stearyl-benzimidazole-6,3'-disulfonic acid sodium.

Emulsion concentrate

a) Easily soluble active ingredients were also formulated as an emulsion concentrate according to the following rule:

Parts active ingredient, Parts xylene,

Parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate

were mixed. When diluting with water to the desired concentration, a sprayable emulsion was created, b) 60 parts of a prepared according to Example 1

S phosphoramidates were mixed with 10 parts of Aerosol OT (dioctyl ester of sodium sulfonosuccinic acid) and 30 parts of kerosene mixed. This concentrate was dispersed in water to make one further dilutable spray.

ίο c) 200 g of N-isopropyl-O-methyl-O- ^ S-dichloro- ^ iodophenyl phosphoramidate were with a mixture of 108 g of a nonionic dispersant and 12 g of an ionic dispersant mixed and that Whole in a mixture of 348 g xylene and 348 g

■ 5 dissolved cyclohexanone. This gave 1016 g, respectively. 1000 ml of a 20% emulsion concentrate that can be diluted with water to form stable emulsions can be.

20th

Granules

7.5 g of one of the active ingredients of the formula I were dissolved in 100 ml of acetone and the acetone solution thus obtained was added to 92 g of granulated attapulgite. The whole was mixed well and the solvent removed in a rotary evaporator. One received a granulate with 7.5% active ingredient content.

Example 6

In a contact test with 5% dust, various compounds according to the invention were used gen achieves the following results:

Active ingredient

O
Il O - P - OCH ₃

NHC ₂ H ₅

O OCH ₃

II / ο —ρ

NHC ₃ H ₇ -GsO)

NHCjHrfiso)

Limit concentration in mg of active ingredient

per m ² for lOOV.igc destruction

in 24 hours

cockroach americ. ² ] russ. ³ ) Exposit
Flour beetle *) larva on time
Bacon beetle ⁵ ) larva Rhod House- German
Sche ') ! 2 50 Imago 100 Imago 25th nius ⁶ ) grill ⁷ ) 52 25th 50 - 100 25th SO 12th 12th 12th 50 100 - 100 25th 25th 2S 25th 25th 25th 100 100 : 200 50 25th 25th - - 50 200 - 200 25th 25th 200 6th - - 25th 50 6th

Fur käfcr larvc ⁸

209 53

continuation

ίο

Active ingredient

Limit concentration in mg of active ingredient

per m ² for 100% destruction

in 24 hours

americ. ] Horse. ³ ) Exposure time larva Bacon beetle ⁵ ) larva Rhod House 50 50 Flour beetle ⁴ ) 50 Imago 25th nius ⁶ ) grill ⁷ ) 25th 100 Imago - 25th 50 25th 25th cockroach
j ",. - 50 200 12th German
cal ¹ ) 50 25th 25th

Fur beetle larva ⁸ )

S OCH ₃

II / ο —ρ

NHCH ₂

S OCH ₃

II /

ο —ρ \

NHCH ₃

Legend:

1. Phyllodromia germanica.

2. Periplaneta americana.

3. Blatta orientalis.

4. Tenebrio molitor.

5. Dermestes frischii.

6. Rhodenius prolixus.

7. Acheta domestica.

8. Attagenus pellio.

Example 7

The effects against ectoparasites and vectors of some of the different compounds were made determined as follows.

A. Rhipicephalus bursa (ticks)

Five hungry adult ticks were counted in a glass tube and placed in 2 ml of an aqueous one for 1 minute Dispersion from a dilution series with 100, 10, 1 and 0.1 ppm test substance immersed. The tube was then closed with a standardized cotton ball and turned upside down so that the Active ingredient emulsion could be absorbed by the cotton wool. The evaluation took place after 2 weeks. Two repetitions were run for each attempt.

B. Dermanyssus gallinae (chicken mites)

: The test was carried out in the same way as method A, but with 20 mites. The evaluation took place after 72 hours.

C. Lucilia sericata (Blow fly)

In small glass vessels 30 newly hatched larvae with 2 g of minced horse meat were fed loading with an aqueous dispersion of the test substance 35

acted. The determination of the limit concentration of active ingredient was carried out in 3 test series on different Days, carried out with new generations of flies and new dilution series. It turned out the limit values for 100% destruction after 24 hours.

D. Aedes aegypti (larvae)

In 10 ml of different concentrations one emulsifies The formulation of an active ingredient were larvae (Li stage) of the yellow fever mosquito during Held for 24 hours. The limit concentration (100% mortality) was determined with a dilution series that starts with 1 ppm.

E. Australorbis glabratus (snails)

Groups of 5 snails with a shark through

knives of 15 mm were for 24 hours at 2C

up to 22 ° in aqueous solutions from a dilution

series with 25, 12, 6, 4, 3, 2 and 1 ppm test substance;

The snails were then immersed for 48 hours

The dam put in clear water and fed

became the limit concentration (100% mortality

definitely

The table shows the limit concentration for 100% destruction.

; Connection no. Snails
A. glabratus Ticks
R. bursa Blow flies
I ~ sericata Mosquitoes
A. aegypti (larvae) Chicken mites
D. gallinae 4th 3 10 2 0.01 10 5 3 10 1 0.05 10 15th 3 · 10 0.8 0.1 100 9 3 10 1 0.025 1 11th 3 10 ' 1 0.012 1 12th 3 10 1 0.012 1 13th 3 10 3 0.006 1 10 3 * 10 1.5 0.002 1

Example 8

The test for the nematocidal effect was carried out in the following way: 5-1 bottles became two Thirds filled with well washed quartz sand. Then 1 ml of the solution to be examined was added. The contents of the bottle were vigorously stirred for thorough mixing. In each bottle were about 100 nematodes (Panagrellus redivivus) given, the whole thing shaken after putting on the cap and then left for 48 hours. The mortality of the nematodes was now determined. Any concentration was performed in four repetitions. Compounds No. 1, 5, 6, 7, 14, 18 and 19 showed a strong killing effect on plant parasites even at the greatest dilution (2.5 ppm) Nematodes.

Example 9 A comparative acaricide test was carried out on the following compounds:

Cl

Cl

O OCH ₃

ο —ρ ⁷

CH ₃

CH, German patent application P 1642240.5

II

IV

the same

the same

the same

the same

the same

German patent specification 1 174104

2579

13th

Test execution

Primary leaves of French beans, occupied with all stages of development by Tetranychus urticae

were, were sprayed with a spray mixture which contained 0.08% of one of the active ingredients I to VII. After 2 and 7 days, the percentage death of the animals was determined with the binocular microscope.

Eggs 2 days 7 days Killing in 2 days % Adults 2 days 7 days Connection no. - 100 Larvae 90 100 100 - 90 100 7 days 100 100 I. - 100 90 100 100 100 II - 90 100 100 100 90 III - 100 100 100 100 100 IV - 100 100 100 100 100 V - - 60 100 - 60 VI 100 VII 60

The comparative experiment shows that compound VII from German patent specification 1,174,104 is a clear one shows less activity against Tetranychus urticae larvae and adults than the compounds according to the invention I to VI and that it is completely ineffective against Tetranychus urticae eggs.

2579

Claims (1)

Patent claims: 1. Compounds of the general formula
Cl to a diester of the general formula Cl (IV)