DE1249001B - Molluscicide means - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

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AOIn

1249001
S 82612IV a / 451 November 28, 1962 August 31, 1967

The invention relates to agents for combating molluscs in particular of the genera Oncomelania, Australorbis, Bulinus or Lymnea, the active ingredient being a triphenylmethylamino compound of the general formula

(C ₆ Hs) ₃ C-NR ₂

or their addition salt with an acid and which are characterized in that in this Formula —NR2 the groups molluscicidal agents

- NO

- • α

means.

The snails of the genera Oncomelania, Australorbis and Bulinus are intermediate hosts of Schistosomes and the snails of the genus Lymnea intermediate hosts of the liver fluke. The fight this snail is said to reduce the frequency of occurrence of schistosomiasis and fascioliasis reduce.

The active ingredients are produced by mixing trityl chloride with morpholine or pyrrolidine or Furfurylamine reacts in the presence of a hydrogen chloride acceptor.

The reaction is preferably carried out in the presence of an inert solvent. Suitable solvents are e.g. B. aromatic hydrocarbons such as benzene, acetonitrile and ketones, ζ. Β. Acetone or methyl ethyl ketone. The amine used for the reaction in a suitable excess or a tertiary amine, in particular triethylamine, can be used as the hydrogen chloride acceptor. Inorganic bases are not suitable for use as hydrogen chloride acceptors in this reaction because the water formed by the reaction with the hydrogen chloride decomposes the trityl chloride. The reaction is preferably carried out at an elevated temperature, in particular at temperatures between 50 and 150 ^° C.

The reaction mixture can be worked up by suitable methods. For example can the amine hydrochloride formed is separated off by filtration and the mother liquor crystallizes out Concentrate the desired product, separate it and clean it if necessary, z. B. by dissolving from a suitable solvent. Alternatively, you can use the reaction mixture Pour in water, being the hydrochloride applicant:

"SHELL" Research Limited, London

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dr. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Named as inventor:

Clive Beresford Challis Boyce, Herne, Kent; Panayiotis Nicolaou Manis,
Sittingbourne, Kent (UK)

Claimed priority:
Great Britain 30 November 1961

(41548),

dated September 26, 1962

(41 548)

of the amine dissolves and the desired product separates out as a precipitate, which is purified if necessary can be.

The preparation of the active ingredients is not the subject of the present invention.

N-Tritylmorpholine melts at 174 to 176 ⁰ C after crystallization from ethanol. After re-solidifying, it melts at 185 to 186 ⁰ C.

Analysis for C ₂₃ H ₂₃ NO:
Found ... C 83.7, H 7.0, N 4.2%; calculated ... C 83.9, H 7.0, N 4.2%.

N-Tritylpyrrolidine melts at 131 to 132.5 ° C after dissolving from ethanol.

Analysis for C ₂₃ H ₂₃ N:
Found ... C 88.4, H 7.3, N 4.4%; calculated ... C 88.2, H 7.3, N 4.5%.

The hydrochloride, melting point 146 to 147 ^° C., was obtained by passing dry hydrogen chloride through an ethereal solution of the base.

Analysis for C ₂₃ H ₂₃ N · HCl:
Found ... Cl 9.9%;
calculated ... Cl 10.1%.

709 639/52 (1

3 4

N-Tritylfurfurylamine melts at 101 ° C after a water-immiscible organic

twice dissolving from ethanol. Contain liquid and an emulsifier. the

Analysis for C24H21NO ^m · * water immiscible organic liquid

Found ... C 85.2, H 6 5 N 4 2% • ^ T, ^Z '. ^B -J- "hydrocarbon, such as toluene,

calculated C849 H62 N4'l »L ' ^{5 xylene> a mineral oil} > ^like kerosene, or an im

Derecnnet ... c 84, V, H 6.2, M 4.1 / 0. Horticultural used petroleum spray oil or

In addition to against Australorbis glabratus, a chlorinated hydrocarbon such. B. a chlorinated

N-tritylmorpholine in the lowest tested benzene, carbon tetrachloride or trichlorethylene,

Concentration of 0.125 ppm against Bulinus Trune. As emulsifiers are z. B. the above

catus, B. Angolensis and Tropicorbis centrimetralis 10 can be used.

and in a concentration of 0.06 ppm against the preparations according to the invention Limnea natalensis and L. auricularia as toxic. also be wettable powders that contain the active ingredient in N-Tritylmorpholine has the additional advantage of finely divided form and a dispersing agent, a lower toxicity for acid animals, since the acute ones such as lignosulfonates or polyacrylates, or a oral toxicity (LD50) for rats about 1500 mg per 15 dispersants and a wetting agent, e.g. B. Sodium Kilograms Body weight was. lauryl sulfate, sodium N-methyl-N-oleyl laurate, Na-

N-Tritylmorpholine is found in neutral or weak trium salts of petroleum sulfonates, sodium dioctyl

Especially effective in alkaline waters is sulfosuccinate, sulfonated esters of fatty alcohols

but slowly hydrolyzed in acidic waters, or sodium salts of alkylbenzenesulfonates,

whereby it loses its molluscicidal effectiveness. 20 hold. A finely divided,

In contrast, N-Tritylfurfurylamine exhibits in acidic solid, absorbent carriers such as absorbent ones

Waters a significantly larger hydrolysis clay or synthetic silica, incorporated

persistence on. Be an aqueous dispersion with. Optionally, stabilizers can be used for

the pH value 6.1 and a content of 1 ppm the active ingredient, such as ethanolamine, quaternary am-

N-tritylfurfurylamine was still active after% hours, 25 monium compounds, urea, hexamethylene

to I00 ^(l / o fatal. tetramine, phenols, naphthols or chelating

The molluscicidal preparations according to the invention, e.g. B. Alkali salts of ethylenediaminetetra-

In addition to the active ingredient, genes contain a solid acetic acid to be incorporated. Preferably brings

or liquid carrier and / or a surface-man the preparation in a jet mill on one

active agent. 30 particle diameters of at most 5 μ, preferably

Aqueous dispersions in which the active ingredient is partially from at most 1 to 2 μ.

diameter of 5 μ or, less, preferred preparations according to the invention with active ingredient wise of less than 1 μ, and especially colloidal and carriers can also take the form of granules, Has dimensions, exhibit particularly high granules, tablets, blocks or thin plates molluscicidal effectiveness. To produce should have 35. These can be absorbed by impregnation Dispersions are made according to a particularly render carrier such. B. from porous bricks, clay-suitable processes a concentrated solution of granules or fibers, such as paper or fabric, the active ingredient and a dispersing agent are prepared with a solution of the active ingredient, in a water-miscible solvent or a mixture of the active ingredient can be used into the water to be treated, e.g. B. in the water 40 and a finely divided, absorbent carrier a river, pond, irrigation canal or the like, granulate or granulate according to known methods, poured. The water-miscible solvent can also be the active ingredient in a melted For example, a water-soluble aliphatic ketone can dissolve thermoplastic resin as a carrier and the such as acetone or methyl ethyl ketone, then granulate or granulate a water-soluble mixture, Licher alcohol, such as methyl, ethyl or isopropyl 45 Alternatively, you can use the active ingredient in the solution alcohol, dimethylformamidoderl-ethoxy-ethanol- (2) of a resin in an organic solvent be. The dispersant makes expediently dissolve, evaporate the solvent and the back-5 Granulate up to 20 percent by weight, preferably 5 to 10, of the product. These preparations can be used against weight percent of the solution. When pouring the water or used against earth mollusks. Solution in water gives an opalescent 50 Preferably, the dispersion according to the invention, the preparations of the active ingredient in colloidal form mixed with mollusc baits, such as contains bran, carbohydrates, proteins, hydrolyzed and highly toxic to water snails is. The dispersant used may be non-proteins, e.g. B. peptones or amino acids, verionic be e.g. B. a Polyalkylenoxydkondensa- applies. The amount of the active ingredient is here tion product of alkylphenols, such as the condensate 55 expediently 0.25 to 1 percent by weight, on the sation product of 1 mole of octylphenol with 8 to bait related.

10 moles of ethylene oxide, or it can be ionic, such as preparations according to the invention without bait

the sodium salts of secondary alkyl esters are preferably used in the form of dispersions

sulfuric acids with 10 to 20 carbon atoms ions with a content of 0.25 to 1.0 weight

In the alkyl group, the sodium salts of sulfo 60 share active ingredient per 1 million parts of water. A

naten of alkylaryl polyethers or the salts are a fundamental advantage of the ingredients according to the invention

(especially the calcium salts) of alkylarylsulfo- preparations with bait is that the content

such as calcium dodecylbenzenesulfonate. Also of active ingredient to the volume of the body of water in which

Mixtures of non-toxic and ionic can be applied, unrelated.

Dispersants can be used. 65 The table below shows the results

Furthermore, the preparations according to the invention can be given by tests which are

genes to be emulsifiable concentrates with water, the appropriate compounds and the one from the German

a solution or dispersion of the compound in Auslegeschrift 1 110 941 known isobutyltriphenyl

methylamine were run to be effective to consider as a molluscicide. In these tests, five adult snails (Australorbis glabratus) Exposed to an aqueous dispersion of the toxin for 24 hours. The snails were then Rinsed in fresh water and kept in fresh water for 24 hours. At the end of this The time the death was determined. The experiments were repeated four times.

The aqueous dispersions used in the tests were prepared as follows:

The compound in question (10 mg) was dissolved in 1 ml of acetone, which is 8 mg of the nonionic, water-soluble one known under the trade name Triton X-100 Alkyl aryl polyether alcohol as an emulsifier contained, and the resulting solution diluted to 500 ml with tap water. The thus obtained aqueous dispersion contained 20 parts per million (ppm) of the compound and 16 ppm of Triton X-100 and 1600 ppm acetone. This was made with water

ίο diluted, being dispersions with lower concentrations of the connection.

° / o destruction of Australorbis glabratus

NR ₂ = - N

NR ₂ = -NH CH ₂

NR ₂ = - N

NR ₂ = - N

HCl

Comparison connection:
NR ₂ = NH CH ₂ CH (CHs) ₂
») Ph - phenyl.

100

100

100

100

100

Concentration in ppm
0.5 0.25 0.12 0.06

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

100

0.03

80

30th

50

40

40

0.015

30th

So N-Tritylmorpholine is in larger dilutions effective against Australorbis glabratus as isobutyltriphenylmethylamine. N -tritylfurfurylamine, N-tritylpyrrolidine and isobutyltriphenylmethylamine are about equally effective, but have N-tritylfurfurylamine and N-tritylpyrrolidine as well as N-tritylmorpholine have the advantage of a lower Toxicity door fish.

In a medium containing N-tritylmorpholine, N-tritylpyrrolidine or N-tritylfurfurylamine, bilharzia-transmitting snails could be killed within 24 hours, while fish • (Lebistus Vecticulatum) remained in the same medium. As a relationship between toxicity for snails and fish toxicity was more than for N-tritylmorpholine and N-tritylpyrrolidine 100 found, but a ratio was found for the known compound isobutyltriphenylmethylamine of only 4. For N-tritylfurfurylamine it was found that the ratio was in any case more than 10 amounts to.

N-Tritylmorpholine is also more effective than isobutyltriphenylmethylamine. It works in one Concentration of 1 ppm in 15 minutes 90% lethal, while isobutyltriphenylmethylamine only has the same effect in 30 to 40 minutes. Further, N-tritylmorpholine is more than 100 times less water soluble (<0.04ppm) than isobutyltriphenylmethylamine (4 ppm). This extremely low water solubility of N-Tritylmorpholine is for the Use in baits of particular importance, as these baits last more than 4 weeks of their effectiveness keep.

Claims (1)

Claim: Means for combating molluscs, in particular the Genera Oncomclania, Australorbis, Bulinus or Lymnea, which as an active ingredient is a triphenylmethylamino compound of the general formula (C, iH ₅ ) iC - NR, or their addition salt with an acid, characterized in that in this formula - NR ₂ the groups - N - N or - NHCH ₂ means. Considered publications:
German interpretative document No. 1 110 941. 709 639/920 ». 67 © Bundesdruckerei Berlin