DE1768130C3 - Isocyanodiphenyl (thio) ethers and processes for their preparation and their use for combating acarids - Google Patents

Description

25th

(Π)

30th

in which Alk, X, R and n have the abovementioned meaning, is reacted in a manner known per se in the presence of bases with dehydrating agents.

3. Use of the isocyanodiphenyl (thio) ethers according to Claim 1 for combating acarids.

40

The present invention relates to the subject matter characterized in the claims.

It has already become known that aromatic isonitriles have acaricidal properties (cf. German Palentschrift 12 09 798). Of these prior art isonitriles, the following are particular strong acaricidal effect: 4-isocyanophenyl-dodecyl ether, 2-isocyano-4,6-dichloro-diphenyl ether and 2-isocyano-diphenyl thioether.

It has now been found that the new isocyanate diphenyl ethers of the general formula

Alc

(D

55

60

in which Alk stands for alkyl with 1 to 4 carbon atoms, X stands for sulfur or oxygen, R door halogen, Alkyl with 1 to 4 C atoms or alkoxy with 1 to C atoms and / 1 means 0, 1 or 2, strong have acaricidal properties.

It has also been found that the isocyanate diphenyl ethers of the general formula (I) are obtained by whom one the formamides of the general formula

NH-CHO

in which Alk, X and R have the abovementioned meaning have implemented in a manner known per se in Gegenwan of bases with dehydrating agents

Surprisingly, the isocyanate diphenyl ethers according to the invention show a considerably higher acaricidal effect Effect than the aromatic isonitriles known from the prior art, which are chemically closest Are active ingredients of the same type of action. The substances according to the invention are thus an asset of technology.

If you use 4-formylamino-4'-tert-butyl-diphenylthioether as starting materials, the The course of the reaction can be represented by the following equation.

(CH ₃ J ₃ C

NH-CHO
(III)

The isocyano-diphenyl ethers according to the invention are clearly characterized by the general formula (1). In this formula, R preferably represents chlorine, bromine or fluorine, methyl, ethyl, methoxy and ethoxy, Alk preferably represents butyl, in particular tert-butyl, and for methyl.

The formamides according to formula (II) required as starting materials are only partially known. However, the new can be prepared in a simple manner by the known processes from the corresponding known amines. The amines are z. B. boiled in formic acid for 1 to 10 hours; after concentration, the partially crystalline formamides are obtained directly. However, the amines in an inert solvent such as methylene chloride, 1 to 10 hours at 0 to 8O ⁰ C with a mixture of acetic anhydride and formic acid to be treated. The formamides obtained in this way are washed with dilute aqueous soda solution and dried.

In the preparation of the isocyano diphenyl ethers, solvents can be used, such as hydrocarbons, e.g. B. benzene and gasoline, chlorinated hydrocarbons, e.g. B. methylene chloride, ether, e.g. B. dioxane and esters, e.g. B. ethyl acetate

Phosgene is primarily used as the dehydrating agent, but other acyl chlorides such as phosphorus oxychloride, benzene sulfonyl chloride and cyanuric chloride can also be used. Pyridine, triethylamine or potassium tert-butoxide are expediently used as bases. The Reaktionslenipcraturen be between -20 and +100 ⁰ C, preferably between 0 'and ¹¹ 5O C.

The isocyanate-diphenyl ethers are obtained in a particularly simple manner if the corresponding Formamides presented together with triethylamine in methylene chloride and phosgene in this mixture initiates.

Working up is carried out in the usual way, for. B. one introduces ammonia into the reaction mixture, separates from the precipitated ammonium chloride and 'concentrates the solution. «■

The active ingredients according to the invention have strong acaricidal properties with low wannabes toxicity and phytotoxicity. The effects set in quickly and last a long time. The active ingredients can therefore be used with good success for combating mites (acarina). , ₅

Among the mites, the spider mites (Tetranychidae), like the common spider mite, are particularly important (Tetranychus urticae), the fruit tree spider mite (Panonychus ulm); Gall mites, like the currant graze !! - miIbe (Eriophyes ribis) and the Tarsonernids, such as Tarsonemus pallidus; as well as ticks.

The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are made in a known manner, z. B. by mixing the active ingredients with extenders, i.e. liquid solvents and / or solids Carriers, optionally with the use of surface-active agents, that is to say emulsifiers and or dispersants. In the case of the use of water as an extender, z. B. also orga " nisehe solvents used as co-solvents will. The main liquid solvents that can be used are: aromatics, such as xylene and benzene, chlorinated aromatics such as chlorobenzenes, paraffins such as petroleum fractions, alcohols such as methanol and Butanol, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; as solid carriers: natural rock flour, such as kaolins, Clays, talc and chalk, and synthetic rock powder, such as finely divided silica and Silicates; as emulsifiers: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates and aryl sulfonates; as a dispersant: e.g. lignin, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations as a mixture with other known ones Active ingredients are present.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.

The active ingredients can be used as such in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granulates be applied. It is used in the usual way, for. B. by spraying, squirting, casting, Dusting, scattering.

The active ingredient concentration can be larger in the ready-to-use active ingredient preparations Areas fluctuate. In the case of the usual preparations, it is generally between 0.0001 and 10 percent by weight, preferably between 0.0005 and 5 percent by weight. In special formulations, the z. B. after the ULV-Verfaren (ultra low volume) are applied, the drug concentrations are between 40 and 95 percent by weight. In addition, the compounds according to the invention also show certain fungicidal properties.

Example A.

Tctranychus test

Solvent ... 3 weight files

Dimethylformamide

Emulsifier 1 part by weight

Alkylaryl polyglycol ethers

For the production of an appropriate preparation of active ingredients 1 part by weight of active ingredient is mixed with the specified amount of solvent containing the specified amount of emulsifier and diluted the concentrate with water to the desired concentration.

With the preparation of the active compound are bean plants (Phaseolus vulgaris) which are approximately one height from 10-30 cm, sprayed dripping wet. These bean plants are strong with all developmental ladia attacked by the common spider mite (Tetranychus urticae).

After the times given, the effectiveness of the active compound preparation is determined by the counts dead animals. The degree of destruction obtained in this way is given in%. 100% means all spider mites were killed, 0% means that no spider mites have been killed.

Active ingredients, active ingredient concentrations, evaluation times and results are based on the following Table shows:

(Plant-damaging mites) Tetranychus urticae

Active ingredients

Active ingredient

concentration in%

! ration after 48 Sld.
in %

C ₁₂ H ₂₅ -O
(known)

NC

0.2 100

0.02 100

0.002 0

5 continuation

Active ingredients

Active ingredient killing

concentration in %

! ration after 4P hours in%

(known) (CHj) ₃ C (CH ₃ )., C (CH ₃ J ₃ C

(CH ₃ J ₃ C

OCH ₃

NC

OCH ₃

(CH ₃ J ₃ -C- / VS

I ₃ J ₃ C

C!

NC 0.2
0.02

0.2
0.02

0.2
0.002

100 0

80 0

0.2
0.02
0.002 100
100
95 0.2
0.02
0.002 100
100
100 0.2
0.02
0.002 100
100
95 0.2
0.02
0.002 100
100
100

100 100 100

100

100

90

0.2 100 0.02 100 0.002 80

0.1 HK) 0.02 100 0.004 100

example 1

OCH ₃

190 g of S-methoxy- ^ formylamine ^ '- tert-butyl-diphenyl ether are dissolved in 1 methylene chloride and treated with 165 g of triethylamine. At 0 to 10 ⁰ C. 75 g of phosgene initiates and stirred for 2 hours at 2O ⁰ C to react further. The reaction solution is then saturated with ammonia and the separated ammonium chloride is filtered off. The residue remaining after the solution has been concentrated is redissolved in ethanol.

Yield: 100 g of 3-methoxy-4-isocyano-4'-lert.-butyl-diphenyl ether. Mp. 85 to 86 ° C.

Manufacture of formamides

3.8 mol of formic acid (98%) and 1.3 mol of acetic anhydride are mixed and after half a Hours of a solution of 1 mole of amine in 1 to 1.5 1 of methylene chloride was added dropwise. It is left for 2 to 4 hours react further, add 1 l of water and wash the methylene chloride phase with dilute soda solution. The organic phase is dried and concentrated completely. The mostly crystalline residue is if necessary redissolved and dried. The yields are 90 to 96% of theory.

(CH ₃ J ₃ C-

Example 2

NC

If 5980 g of 2-formylamino-4-methyl-4'-lert-butyl-diphenylthioether are used with 6500 g of triethylamine and 3000 g of phosgene as in Example 2, 4200 g of 2-isocyano-4-methyl-4'-tert-buty! -diphenylthioether are obtained, Mp. 98 to 99 ° C.

Example 5

(CH ₃ J ₃ C

If 1100 g of 2,5-dimethyl-4-formylamino-4'-tert-butyl-diphenylthioether are reacted with 1150 g of triethylamine and 430 g of phosgene as in Example 2, 850 g of 2,5-dimethyl-4-isocyano- 4'-tert-butyl diphenylthioether. Mp. 40 to 41 ⁰ C.

Example 6

35 If 530 g of 2-formylamino-4-methyte-4'-methyl-diphenylthioether are reacted with 525 g of triethylamine and 220 g of phosgene as in Example 2, 490 g of 2-isocyano-4-methyl-4'-methyl- diphenylthioether. Mp. 59 to 61 ⁰ C.

Example 7

1400 g of 4-formylamino-4'-tert-butyl-diphenylthioether are dissolved in 5 l of methylene chloride and mixed with 1300 g of triethylamine. At 0 to 10 ° C., 700 g phosgene initiates and allowed for 3 hours at 20 ⁰ C to react further. The reaction solution is then saturated with ammonia and the separated ammonium chloride is filtered off. The residue remaining after the solution has been concentrated is washed with isopropanol.

Yield: 1000 g of 4-isocyano-4'-tert-butyl-diphenylthioether. Mp. 66 to 67 ° C.

Example 3

If 1215 g of 4-formylamino-4'-methyl-diphenyl-thioether are added to 1020 g of triethylamine and 500 g Phosgene analogously to Example 2 to give 1040 g of 4-isocyano-4'-methyl-diphenylthioether. Fp. 74 to 76 ° C.

Example 8

(CH ₃ J

₃ J ₃

If 220 g of 2-CMor-4-formylamino-4 '- tert-butyldiphenylthioether are reacted with 160 g of triethylamine and 75 g of phosgene as in Example 2, 130 g of 2-chloro-4-isocyano-4' are obtained tert-butyl diphenylthioether.

Mp. 98 to 99 ° C.

If 185 g of 2-formylamino-4-chloro-4-tert-butyl-diphenylthioether are reacted with 135 g of triethylamine and 70 g of phosgene as in Example 2, 90 g of 2-isocyano-4-chloro-4'-tert are obtained .-Butyl-diphenylthioether. Mp. 79 to 8I ⁰ C.

Example 9

OCH,

Example 4

(CH ₃ J ₃ C

(CH ₃ J ₃ C

NC

NC

If 31.5 g of S-methoxy- ^ formylamino ^ '- terL-butyl-diphenylthioether with 25.6 g of triethylamine and

709 611/69

(a)

O ₂ N

A mixture of 3.20 kg 2.4-dichloronitrobenzene, 2.50 kg of p-tert-butylphenol and 1 kg of dimethyl sulfoxide is heated to 78 ⁰ C. Then they are mixed with 1.20 kg of potassium hydroxide (powder) in approx. 50 g portions, the temperature not exceeding 83 ° C

11.8 g of phosgene analogous to Example 2 to obtain 24 g of S-methoxy ^ -isocyano ^ '- tert-butyl-diphenylthioether. The product is oily viscous and contains an intense isocyanate band in the infrared spectrum 2120 cm- '.

Example 10

(CHj) ₃ C

15 1 kg 2-formylamino-5-chloro-4'-terl.-butyl-diphe-

Nyl ethers are heated to 55 ° C together with 1.03 kg of ethylamine in 8 liters of benzene. One leads into the Mixture 0.43 kg of phosgene, then cools it down to 5 ° C, saturates the solution with gaseous ω Ammonia and washes them several times with 5 liters of water each time.

The organic phase is separated off and concentrated, and the residue is ^{stirred with 1.5 kg of methanol at 0 °} C., filtered off with suction and dried.

The yield is 0.69 kg (73% of theory) of 2-isocyano-5-chloro-4'-tert-butyl diphenyl ether.

Mp = 99-101 ° C.

The formyl compound required as a starting material is z. B. available as follows:

may. The reaction mixture is allowed to react for 3 hours at 80 ° C. and is then poured into 25 l of water with vigorous stirring. The solid crude product is vigorously stirred once with 13 kg of methanol and then with 6 kg of methanol, filtered off with suction and dried ^{at 40 ° C.} Yield: 3.0 kg (60% of theory). Mp. = 89 to 90.5 ° C.

(CH ₃ J ₃ C

NH,

1 kg of 2-nitro-5-chloro-4'-tert-butyl-diphenyl ether is dissolved in 3 liters of methanol at 20 to 30 ° C and 40 atm Hydrogen pressure hydrogenated with Raney nickel. After the catalyst has been removed, the solution is concentrated and the solid residue was recrystallized from ethanol. Yield: 0.8 kg (90% of theory).

Mp = 52 to 53 ° C.

(CHj) ₃ C

NH-CHO

To a solution of 1 kg of 2-amino-5-chloro-4'-tert-butyl diphenyl ether in 3 l of methanol, a mixture of 0.43 kg of acetic anhydride is added at 20 to 25 ° C. with stirring and 0.370 kg of formic acid were added dropwise. The mixture is left to react for 1 hour and is cooled then to 0 ° C.

The crystalline reaction product is filtered off with suction, washed with water and dried. Yield: 0.92 kg (82% of theory).

Mp = 140 to 143 ° C

55 "*" "

Claims (2)

Patent claims: I. Isocyano-diphenyl (thio) ether of the general formula Alc (D in which Alk stands for alkyl with 1 to 4 carbon atoms, X stands for sulfur or oxygen, R stands for door, ₅ halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and η 0, I or 2 means. 2. Process for the preparation of the isocyanodiphenyl (thio) ethers according to claim 1, characterized in that characterized in that one formamides of the general formula