DE1939418C - Fertilize 0.5 (2 methyl pyridyl) phosphorus compound - Google Patents

Description

RC, -C ₃ -alkyl or alkoxy, phenyl or di-

methylamino,
R 'Ci-C ₃ -alkyl and
X is oxygen or sulfur.

2. Pesticides, characterized by a content of a compound according to Claim 1.

The invention relates to 0,5- (2-methyl-pyridyl) -phosphorus compounds the general formula

R X

whereby

R'O

RC ₁ -C ₃ -alkyl or alkoxy, phenyl or dimethylamine-,

R 'C, -C ₃ -alkyl and
X is oxygen or sulfur.

All of these compounds as defined above have excellent pest control properties.

The known pyridyl phosphorus compounds contain two methyl radicals in the pyridyl radical, which in sit o-position to the nitrogen atom, while others have no substituents in the pyridyl radical.

It has now surprisingly been found that the new compounds are much more effective insecticidal Have properties than the previously known compounds.

The preparation of the compounds according to the invention takes place by reacting a phosphoric acid chloride with 2-methyl-5-hydroxypyridine or a its alkali salts in the presence of an inert organic solvent according to the following reaction equation:

R X

\ ll

P-Cl + NaO

/
RO

+ NaCl

The reaction is carried out between 20 and 100 ⁿ , whereupon the reaction product is obtained after washing and drying or distillation in a high vacuum.

The 2-methyl-5-hydroxypyridine in turn can

by converting formaldehyde and furfuryl

amine in acidic medium according to Niels Clauson K a a s

and Max Meister, Acta Chemica Scandinavica 21, No. 4, p. 1104 (1967).

example 1

Production of O, 5- (2-methyl-pyridyl) -O, O-diethyl phosphate

O
PO- ^

C ₂ H ₅ O

A solution of 5.173 g (0.03 mol) of diethyl chlorophosphate in 80 ml of acetone is added dropwise to a suspension of 3.93 g (0.03 mol) of the sodium salt of 2-methyl-5-hydroxypyridine in 70 ml of acetone.

This mixture is kept at room temperature for 30 minutes and then on for 2 hours Heated to 30 to 40 "C, after which it is again held at room temperature for 1 hour. After cooling down

and filtering off the sodium chloride formed, the acetone is evaporated off. The residue is extracted with chloroform, then washed and dried. After removal of the chloroform in vacuo, 5.05 g of the product are obtained by distillation with a yield of 68.6%; n'S = 1.470; Boiling point: 108 to 110 ^° C. at 0.05 torr.

Analysis for C ₁₀ H ₁₆ NO ₄ P. 245 MG.

Calculated ... C 48.97, H 6.53, N 5.71, P 12.65%: found .... C 48.87, H 6.67, N 5.89, P 12.84% .

Example 2
0.5- (2-methyl-pyridyl) -O, O-diethyl thiophosphate

C ₂ H ₅ O

PO ^ ₁

A solution of 3.77 g = (0.02 mol) diethyl chlorothiophosphate in 70 ml of acetone is added dropwise to a suspension of 2.62 g (0.02 mol) of the sodium salt of 2-methyl-5-hydroxypyridine in 80 ml of acetone. This reaction mixture is kept at 50 to 55 ° C. for IV4 hours and the acetone is then drawn off. After being taken up in chloroform, the product is washed and dried, whereupon 4.05 g of the product are obtained by distillation with a yield of 77.6%; η g = 1.5080; Boiling point: 110 ° C at 0.08 torr.

Analysis for C ₁₀ H ₁₁₁ NO ₃ PS. 261 MG.

Calculated ... C 45.97, H 6.13, N 5.36, P 11.87%: found .... C 46.14, H 6.27, N 5.20, P 12.08%.

Example 3

0.5- (2-methyl-pyridyl) -O, O-di-n-propyl phosphate HC ₃ H ₁ O O

Ml ^

p — o-

η C ₃ H ₇ O

Example 4 0.5- (2-methyl-pyridyl) -O, O-di-isopropyl phosphate

ISO-C ₃ H ₇ OO

P-O-

4.01 g (0.02 mol) of di-n-propyl chlorophosphate, dissolved in 70 ml of acetone, are again added dropwise to 2.62 g (0.02 mol) of the sodium salt of 2-methyl-5-hydroxypyridine in 80 ml of acetone . The mixture is refluxed for 2 hours. After cooling and removal of the sodium chloride formed, the acetone is distilled off. After being taken up in chloroform, the product is washed and dried, whereupon the solvent is distilled off in vacuo. 4.8 g of the crude product are obtained with a yield of 87.9%; ir = 1.4670.

Analysis for C ₁₂ H ₂₀ NO ₄ P. 273 MG.

Calculated ... C 52.74. H 7.32. N 5.12. P 11.35%: found .... C 52.45. H 7.63. N 4.97. P 11.41%. ISO-C ₃ H ₇ O

CH,

A solution of 4.01 g (0.02 mol) di-isopropyl chlorophosphate in 70 ml of acetone is added to a solution of 2.62 g (0.02 mol) of the sodium salt of 2-methyl-5-hydroxypyridine dropped into 80 ml of acetone.

The rest of the procedure is as in Example 3, 4.8 g of the crude product being obtained in a yield of 87.9%; n [ = 1.4615.

Analysis for C ₁₂ H ₂₀ NOjP. 273 MG. Calculated ... C 52.74, H 7.32. N 5.12, P! 1.35%; found .... C 51.39, H 7.67, N 4.92, P i 1.49%.

The following products have been manufactured in the same way:

at
game R. 5 C ₁₁ H ₅ 6th C ₂ H ₅ 7th CH ₃ 8th (CH.,) ₂ N 9 iso-CjH-O IO CH ₃

C ₂ H ₅

C ₂ H ₅

CH ₃

C ₂ H ₅

ISO-C ₃ H, O

CH ₃

1.5825

1.4885

O j 1.4985

1.4875

1.4975

1.5465

Sdpkt Torr

100 C 0.035 98 C «. 065 108 CÜl 110 to 112 ° C / 0.05 yield

90

70

39.8

77

70, o

83

analysis

C%

ber.57.33
found 57.29

ber. 52.40
found 52.24

ber.47.76
geC 47.63

ber.49.17
found 49.10

ber.49.82
found 49.73

ber.44.23
found 44.43

Test report

The insecticidal properties of these compounds resulted from numerous comparative tests, the compounds according to the invention were compared with structurally similar products, who are known. The following comparison compounds were involved:

calc. 5.46
found 5.35

ber.6.98
found 7.05
ber. 5.97
gei. 6.25

ber. 6 96
found 7.17

ber.6.92
found 6.75

ber.5.53
found 5.62

D. (C ₄ H ₉ O) ₂ - P - O

example 1

H %

N '

ber.

ber.

ber. gel ".

ber.

ber.

ber.

4.77 4.82

6.11 5.93

6.96 6.82

11.47 11.65

4.84 4.66

6.45 6.31

CH ₃ N CH ₃

about gef.

ber.

ber.

ber.

found

ber.

ber

10.58! 0.74

13.53 13.49

15.42 15.22

12.70 12.84

10.72 10.93

14.28 14.31

B. (JSO-C ₃ H ₇ O) ₂ -P- O

C. (C ₂ H ₅ O) ₂ -PO

Test with Musca domestica (house fly)

10 adult flies aged 4 to 5 days are placed in a Petri dish with a lattice lid. These Petri dishes are treated immediately by spraying them with 5 ml of an acetone solution of the relevant active substance to be tested.

The evaluation is carried out by counting the dead

and live flies 1 hour after treatment.

Under these conditions the products yielded

according to Examples 1. 2, 6, 7 and 10 a total

Mortality of the flies at a dose of 50 mg / l,

while the well-known products A and B cans in

of the order of 500 and 100 mg / 1 required,

to achieve a corresponding effect.

i 939

Example 2
Test with Ephestia kuhniella

Tablets made from unleavened bread are impregnated with three drops of an acetone solution of the test material Product. After evaporation of the solvent, 10 eggs of Ephestia kuhniella are on the bottom the tablet, which is covered with a glass pane to prevent it from escaping. To A mortality test is carried out 7 days.

The table below shows the minimum concentration indicated what is required to ensure complete mortality of the parasite in question to achieve. These values clearly show the superiority of the products according to the invention compared to the known comparable products.

Product of example Minimum dose
for 100% mortality possible 1 0.5 3 10 5 5 6th 5 7th 0.5 A (known) 50 B (known) 100 C (known) 50 D (known) HX)

Example 3
Test with Tetranychus urticae (mite)

One cuts out of bean leaves which one Colonization of Tetranychus urticae in all stages. Slices of 2 cm in diameter made from the one treated by spraying with an acetone solution of the product to be tested, with various Concentrations are applied. Check with a binocular magnifying glass 2 days after the treatment the percentage of mortality achieved.

40 order of 80% to achieve, and a 50 times larger dose of products A and B for a complete mortality of the test animals.

In the same experiment, well-known insecticides such as O, O-diethyl-S- (4-oxo-1,2,3-benzotriazine-3 (4 H (-ylmethyl) -phosphorodithioate or S- (1,2-di- (ethoxycarbonyO-ethyO-dimethylphosphorihiolothionate) or Ö.O-dimethyl-O- (2.4.5-trichlorophenyl) phosphorothioate), in doses on the order of grams liter to be applied to a full To achieve mortality of the test animals.

Of course, the products according to the invention were also loved these laboratory tests used in numerous outdoor experiments using normal conditions of use. These tests revealed remarkable effectiveness of these compounds in various Directions, this extending to numerous species of insects and acarids, such as

Polychrosis botrana or Clysia ambiguella.

C cirpocüpsü pornoneüa.

Laspeyresia sp ..

Psylliodes chrysocephala.

Bhniulus guttulatus or Archiboreiulus

pallidus.

C Muarinia tritici.
C'urculionidae.
Musca domestica.

Calandra granaria or Calanuia oryzac
Ceratitis capitata.
Meligcthes aeneus.
Dacus olea.
Psila rosae or Hylcmia antigua or

Hylemia brassicae.
Noctuidae.

Pegomyia betae or Pegomyia hysociami.
Sparganothis pilleriana.
Pyrausta nubilalis.
Elateridae.

Melolontha melolontha or Popilia sp ..
Par.onychus sp. or Eotetranychus sp. or

Tetranychus sp. or Bryobia sp. or

Vasates sp. or Eriophyes sp.

In this example, the product after Bei-45 also yielded

game 7 particularly interesting results since the complete Mortality is already achieved at a dose of 0.5 mg 1. The products of Examples 1, 5, 6 and 10 also produce a good effect against acariums with doses between 5 and 10 mg 1.

Example 4
Test with Blatella germanica

Five full-grown specimens of ss Blatella germanica are placed in a Petri dish with a gilter lid. These Petri dishes are treated immediately by spraying them with 5 ml of an acetone solution of the active ingredient, which one wants to test under different concentrations. 48 hours 6c after this treatment, the mortality achieved is checked.

Elei this experiment gave the products after Examples 1, 2, 3, 5, 6 and 7 complete mortality for doses from 0.05 g / l.

Under the same conditions, however, an approximately five-fold larger dose of the known products C and D is required to prevent mortality in the large Prodenia sp ..
Heliothis sp ..
Peetinophora gossypiella.
Dysdercus sp ..
Earias sp ..
Diparopsis sp.

The table shows the corresponding designations listed in different languages, with no corresponding ones for the latter insects Trivial notations are given.

The multiple potency of these compounds allow their use against very different ones Harmful cultures in the field of land and • local economy. in viticulture as well as in the home Field or in the field of public health, with the choice of one or the other of the The compounds listed above depend on the type of pest to be controlled and the certain properties of the product, such as toxicity. Activity spectrum, etc.

In the practical conditions of use, the doses to be used can be used within wide limits

vary depending on the type of insect being controlled and the effectiveness of the product.

When carried out in the wild, ixMimmimited compounds of those described above Kind, especially those according to Examples 1 and 2, result in complete destruction of the insects Doses of 5 to 10 g of active ingredient per hectolitre, while on the other hand, with certain others, less effective products or, in the case of pests that are difficult to destroy, the doses to be used up to 100 or 200 g could go until a complete annihilation of the pest in question was reached would.

The compounds according to the invention are only very rarely used in practice in pure form Shape, with the exception of applications very minor

Quantities (U.L.V.). Most often these will be connections mixed with various additives and carriers or diluents, which are liquid and / or can be solid in order to obtain suitable forms of application for the various purposes. Depending on the situation, these application forms can be in the form of granules, as dusts, as pasting agents, as emulsifiable concentrates, solutions, etc., always depending on the physicochemical Properties of the products concerned and the intended use.

The production of such preparations is known and is dealt with in particular in the factories "Chemistra of the pesticides" by D. E. H. F rear. 3rd edition, pp. 409-433, or "Fungicides" by E. Torgcson. Vol. 1, Capital 6, pp. 153 to 193.

Claims (1)

Patent claims: 1. 0.5- (2-methyl-pyridyl) -phosphorus compounds of the general formula R X R'O whereby