DE1795453C2 - 0,0-dimethyl- or 0,0-diethylthiol or -thionothiolphosphoric acid (2-oxobenzthiazolino) methyl ester and process for their preparation - Google Patents

Description

OR

wherein R is methyl or ethyl radicals.

2. Method of making the thiol b / w. Thionothiol organophosphate according to claim 1. marked in characterized / eichnei, one duii in a known manner, N-Haloger.methylbenzthiazolone- (2) of the formula

■ CC)

■ .- ■ - ■ N '

CH, halogen

with alkali or ammonium salts of O.C) -Dialkyllhiol- or -thioiiothiolphosphorsäuren of the general formula

RO O (S)

I;

P SH

RO

where R means methyl or ethyl radicals.

40 N-methylol compounds, which have a good kontaktin'-ckii / ide effect especially against aphids, spider mites, mosquito larvae and grain beetles, are described.

It has now been found that the previously unknown Thiol or i hionoihioiphosphorsäureesier of the constitution (I) given above if mäVin is known per se N-halomethylben7lhiazolone- (2) the formula

The invention concerns new OO-Dimetlnl- b / w. C) .O- Diälhvl-thiol- b / w. -thionothiolphosphoric acid- \ 2 - oxobwizthiazolino) - melhylesler of the general J-ormel

O (S)

N-

CW, SP

I /

OR

II)

OR

taorin R means methyl or ethylresle, as well as a Process for their manufacture.

From the published documents of the Austrian Patent 2,13905 are already O.O-Dialkylthiol- or -thionolhiolphosphorsäurecster of N-Methylolbcn / oxazolonen known. The aforementioned Compounds are characterized by an insecticidal and acaricidal effect as well as a fungicidal Effectiveness with good plant tolerance.

Furthermore, in German Patent 64064 thionophosphoric acid esters are heteroeyclic

C - = O

CH ₁ -HaIOgCn

with alkali or ammonium salts of O.O-Dialkvllhiol-'bzw. -thionothiolphosphoric acids of the ailiiemeincn formula

RO C) (S)

P-SH

IiIi;

RO

converts, where in the last-mentioned formula the symbols R have the meaning given above.

The implementation is appropriate for room or slightly elevated temperature, e.g. B. in the range from 20 to 60 C. and in the presence of an inert solvent performed. For the mentioned / wake up leeiunet is an aqueous-alcoholic medium or a purely organic solvent. z. B. a ketone such as acetone or methyl ethyl ketone.

In general, the two reaction components are used in an approximately equimolar cm ratio, however, it may be advantageous. the ihiol- or thionothiolphosphoric acid salt in Apply excess.

The N-halomethylbenzthia / olone- (2) required as starting materials for the manufacturing process are also easily accessible on an industrial scale: they can be obtained in a known manner from the corresponding N-methylol compounds by reaction with thionyl chloride or concentrated hydrochloric acid.

The thiol or thionothiol phosphoric acid esters according to the invention are partly well-crystallized, hardly water-soluble compounds. Partly the products are also viscous oils. not even under greatly reduced pressure can be disintegrated without decomposition.

The more in accordance with the invention! Draw connections through a very good contact insclicidal. partly also systemic effectiveness with relatively low Warm-blooded toxicity.

Compared to the documents published in the Austrian patent 2 13 90i and the German patent 10 64064 known compounds of analogous constitution and the same Wirktingsrichlung possess the products when used against a large number of insect pests surprising, technically valuable figures. This clear superiority of the proper Thiophosphoric acid ester can be obtained from the results summarized in the table below from comparative experiments. The insecticidal and acaricidal effectiveness of the products against

relevant insect pests were determined as follows:

A. Mosquito larvae test

Test animals: Yellow love mosquitoes (Aedes aegypti) solvent. . . 99 parts by weight of acetone

Emulsifier 1 part by weight of ben / yl

hydmxydipheny! polyglycol ether

To produce an appropriate preparation, 2 parts by weight of the active ingredient in question are dissolved in 1000 parts by volume of solvent which contains the amulpaior in the amount specified above. The concentrate obtained in this way is diluted with water to a lower concentration. ' ⁵

The aqueous active compound preparations are poured into glasses and about 25 mosquitos are then placed in each glass.

After 24 hours, the degree of destruction is determined in percent. Here,! 00 "means that all larvae have been killed and 0. that no larvae at all have been killed.

B. Aphid test (contact effect)

Solvent. . . 3 parts by weight acetone

Emulsifier 1 part by weight of Alkaline

polyglycol ether

For making a suitable preparation 1 part by weight of the active ingredient in question is mixed with the specified amount of solvent. which contains the said amount of I-emulsifier, and

Verdehsversuch c

dilutes the concentrate obtained in this way with water to the desired concentration.

With this active ingredient preparation, coal lances (Brassiea oleracea). which are strongly infested by the Pfip; irhbl, -) U!; MK (My? üs persicae) up sprayed to dripping wet.

After 24 hours, the degree of destruction is determined in percent. 100 "·». Means that all and (.). dal.) no aphids were killed.

C. Spider mite test

Solvent. . . 3 parts by weight of acetone

1 mulgator 1 part by weight! Alkylaryl

polyglycol ether

To produce an appropriate preparation, 1 part by weight of the active ingredient in question is mixed with the specified amount of solvent that contains the specified amount of L-emulsifier, and diluted the concentrate thus obtained with water to the desired concentration.

With this active ingredient preparation, bean plants (Phaseolus vulgarisl. Which are approximately one height from 10 to 30 cm, sprayed to runoff. The plants are strong with all developmental tendencies infested by the bean spider mite (Tetranychus lelariusl

After 4N hours, the effectiveness of the preparation determined by counting the dead animals and the degree of destruction thus obtained in percent a η! shine. UM) ",, means that all and Π. That none Spider mites were killed.

ML! I K (MlSlIlUlIUnI

C ( c- ο

"■■ ·. ^S NS OCH ₁

! Ilen, S P

(KW,
according to the invention)

VV.iinihluli ·! - lo \ i / il; M llll. . U.ilU

pci ο-, ι

Insecticides and .ik.in / ide effectiveness

KKK) mosquito larvae

Effective vh.i konzL'nir.itMii in "u in "n KX) 0.01 100 0. (K) I KK) 0. (K) Ol

l CO
NS OCH,

CW, SP

OCH,

■ KKK)

(known from the laid out documents of the Austrian patent 2 13 905. Example i)

[ ¹ J c ■■ ο

^Λ Ν S OCIL

ι II · - ■

CIL S P

Miickenlarvae 0.01 100 0. (K) I KK) 0. (KK) I. 0

Aphids 0.01 100 (UH) I 50 Spider mites 0.01 K) O 0. (K) I 90

(according to the invention)

OC

continuation

Verlimduiii! (KuiiMiuuiom)

[XT.

c and .iLiM / idi: Wirkviinkeil

We! Si.iffki, n / ciiii, i! I,

Ah!

f ^V ° c = o

^! NS OC ₁ H,

II /

CH ₂ SP

OC ₂ H ₅

(known from the documents laid out
of the Austrian patent 2 13 905.
Example 4)

i C = S
NS OC, H _s

j I

CH ₁ -OP

Aphids 0.01 100 0.001 0 Spider mites 0.0! ¹ H \ 0.001 (I. Mosquito larvae 0.01 Kl (I 0.00! 0

Mosquito larvae 0.001 100 0.0 (K) I. !) Aphids 0.01 KK) 0.001 0

«Known from DAS 10 64064. Example 5)

Example I.
. SS

[C ■■ - () i:

N- Ii OCH,

CH, S P

OCH,

50 g (0.2 mol) of N-bromomethylbenzothiazolone- (2) (1- "p. 119 C) and 42 g (0.24 mol) of o'.O-dimeihylthionothiolphosphoric acid Ammonium in 200 ecm acetone and stir the solution at room temperature, the temperature of the mixture slowly increasing to 33 to 35 C rises. When the reaction has subsided. the reaction mixture is still half an hour stirred, then mixed with water and the separated Oil added to benzene. After the Henzol solution with water and sodium bicarbonate solution been washed isl. the former is dried over sodium sulfate and the solvent is distilled The distillation residue is then cooled to 0 C and mixed with a little isopropyl alcohol rubbed in, whereby the oil solidifies in crystalline form. After I Imkristallisicren from an ether Pctrolalliermixture the O.O-dimethyl-thionolhiolphosphoric acid is obtained - (2 - oxobenzthiazolino) - methyl ester in loim colorless, coarse crystals with a melting point of 49 C. The yield heträgl 45 g corresponding to ^ 0.2 ".. der Theory.

Analvse for a molecular weight of 321.4:

Calculated
found .

N 4.36. P 9.64%:
N 4.31. P 9.65%.

The mean toxicity of the compound is an the rat per os over 1000 mg per kilogram Ί icr.

By S ; ι ι e I 2

S S

c-o,;

ClT SP

OCMl.

OCMK

73 (0.3 mol) N-bromomethylbenzthiazolone- (2l (melting point 119 C) are in an aqueous solution of of 150 g ((). 3.3 mol) O.O-diethylthionothiolphosphoric acid Sodium, to which 20 ecm of acetone have been added, suspended. The temperature of the rises The reaction mixture slowly increases to 34 C, and the N-bromomethylbenzothiazolone- (2) disappears. Man stir the mixture overnight, then add water and take the precipitated oil in benzene on. The reaction mixture is then worked up as described in the previous example. Man rcontains the Ο, Ο-diethyl-thionothiolphosphoric acid-2-oxobenzthiazolino) methyl ester in the lorm of a helluclben Oil. The yield is SO i>, accordingly 76.2% of theory.

Analysis for a molecular weight of 349.4:

Calculated ... N 4.01. S 27.53. PK.S7%:
found .... N 3.9N. S 27.X9. P 8.53%.

Average toxicity (DU,) of the compound 5 (K) mg per kilogram of rat after oral administration.

Claims (1)

Patent claims: I. Ο, Ο - dimethyl b / w. Ο, Ο - diethyl thiol or -ihionothioiphosphoric acid - (2 - oxobenzthia / olino) - methyiester of the general formula Sx OlS) C = O j N ■ 'I OR ! II / CH ₂ SP