PL189472B1 - N-phenyldiureas with a diethylenethioether group and method of obtaining them - Google Patents

Abstract

1. N-phenyl-dicarbamides with diethylene-thioether groups, with general formula 1, where R refers to an atom of chlorine, bromine, a methyl or methoxyl group. 2. The method of producing N-phenyl-dicarbamides with diethylene-thioether groups, with general formula 1, where: R refers to an atom of chlorine, bromine, a methyl or methoxyl group. It is characterised in that bis(2-isocyanateethyl) sulphide is subjected to reaction with aromatic amines with the general formula 2, where R has the meaning defined above. The reaction is carried out in the medium of an inert organic solvent at room temperature in the atmosphere of an inert gas.

Description

The subject of the invention is novel N-phenyldiureas with a diethylene thioether group showing insecticidal activity and a method of their preparation.

There are known N-phenyldiureas with symmetrical dialkylene ether and alkylene diethies, containing two substituted ureido groups in the molecule, linked to aromatic rings, and an ether bridge or, respectively, two ether bridges linked to alkylene groups. The preparation of these compounds involves the reaction of aliphatic diisocyanates with a symmetrical dialkylene ether or alkylene diethyl moiety with aromatic amines.

The invention relates to N-phenyldiureas with a diethylene thioether group of the general formula I, wherein R is chlorine, bromine, methyl or methoxy. These compounds contain in the molecule a thioether bridge linked to ethylene groups and two substituted ureido groups, each of them bonded to one aromatic ring.

The method of producing N-phenyldiureas with diethylene thioether according to the invention consists in reacting a bis (2-isocyanatoethyl) sulfide with aromatic amines of the general formula 2, in which R is chlorine, bromine, methyl or methoxy in an inert medium organic solvent, at room temperature, under an inert gas atmosphere. The organic solvent is diethyl ether and the inert gas is nitrogen. The resulting reaction mixtures are then left for several hours while stirring.

The bis (2-isocyanatoethyl sulfide) used for the synthesis is obtained by nitrosating the bis (2-isocyanatoethyl) sulfide to give bis (2-azido-carbonyl ethyl) sulfide, which is then subjected to a Curtius rearrangement in an inert organic solvent.

A significant advantage of the method according to the invention is simple technology and low cost of raw materials. The products obtained are easy to separate from the reaction mixture and are characterized by a high degree of purity.

The compounds according to the invention show insecticidal activity in tests carried out on a five-day-old imago of female housefly (Musca domestica).

The method according to the invention, without limiting its scope of protection, is presented in the following example.

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IR spectra were recorded on a spectrophotometer FT IR 2000, and ¹H and ^l3 C NMR on a Varian Gemini 200.

Example. To a solution of 0.0145 mol of an aromatic amine: 4-chloroaniline, 4-bromoaniline, 4-methylaniline (p-toluidine) or 4-methoxyaniline (p-anisidine) in 30 ml of anhydrous diethyl ether is added under an atmosphere of dry nitrogen while 1 g (0.0058 mol) of bis (2-isocyanatoethyl sulfide) was stirred. The reaction mixtures are then left for several hours at room temperature, under nitrogen atmosphere, while stirring. The obtained precipitates are filtered off, washed several times with small amounts of cold diethyl ether and then crystallized from a mixture of methanol and dimethylformamide. Proceeding in this way a: sulfide, bis [2- (4-chlorophenyl) ureidoetylowy] (I) of melting point 258,5-260 ° C and a molecular formula C18H20Cl ₂ N4O ₂ S (427.36 MC).

Analysis: IR (KBr, cm '): 3335, 1563 (NH), 2968, 2929 (CH alif.), 1631 (C = O), 643 (CSC); * H NMR (TMS, DMSO-D6, δ ppm): 2.62 (t, 4H, CH2-S-CH2), 3.26 (q, 4H, 2CH'-N), 6.32 (t, 2H , 2CH2-NH), 7.23 7.40 (AA'BB ', 8H arom), 8.72 (s, 2H, 2C-NH arom); ¹³ C NMR (TMS, DMSO-D6, δ ppm): 31.22 (CH ₂ -S), 39.13 (CH ₂ -N), 119.22, 128.50 (CH arom), 124.55 (C-Cl arom), 139.52 (arom CN), 155.03 (C = O), bis [2- (4-bromophenyl) ureidoethyl sulfide] (II) mp 268-269 ° C and molecular formula C2 ₀ H20Br2N4O2S (MC 516.26).

Analysis: IR (KBr, cm ¹ ): 3338, 1562 (NH), 2968, 2929 (CH alif.), 1633 (C = O), 666 (CSC); ^! H NMR (TMS, DMSO-D6, δ ppm): 2.62 (t, 4H, CH2-S-CH2), 3.26 (q, 4H, 2CH2-N), 6.32 (t, 2H, 2CH2 -NH), 7.35 (m, 8H arom), 8.72 (s, 2H, 2C-NH arom); "C NMR (TMS, DMSO-d6, δ ppm): 31.23 (CH2-S), 39.16 (CH ₂ N), 112.41 (Br-C arom.), 119.68, 131, 39 (CH arom), 139.95 (CN arom), 155.00 (C = O), bis [2- (4-methylphenyl) ureidoethyl sulfide] (III), m.p. 242-243 ° C and formula total C20H26N4O2S (MC 386.52).

Analysis: IR (KBr, cm ¹ ): 3339, 1567 (NH), 2969, 2930 (CH alif.), 1635 (C = O), 644 (CSC); 1 H NMR (TMS, DMSO-D6, δ ppm): 2.19 (s, 6H, 2CH3), 2.61 (t, 4H, CH2-S-CH2), 3.25 (q, 4H, 2CH2- N), 6.22 (t, 2H, 2CH'-NH), 7.00, 7.25 (AA'BB ', 8H arom), 8.43 (s, 2H, 2C-NH arom); C ^H NMR (TMS, DMSO-d6, δ ppm): 20.23 (CH3), 31.38 (CH ₂ -S), 39.16 (CH2-N),

117.92, 129.06 (CH arom), 129.86 (C-CH3 arom), 137.95 (arom CN), 155.27 (C = O), sulfide bis [2- (4-methoxyphenyl) ureidoethyl (IV) with a melting point of 224.5-226 ° C and the summarized formula C20H26N4O4S (MC 418.52).

Analysis: IR (KBr, cm ⁴ ): 3340, 1563 (NH), 2957, 2936 (CH alif.), 1631 (C = O), 662 (CSC); * H NMR (TMS, DMSO-D6, δ ppm): 2.60 (t, 4H, CH2-S-CH2), 3.24 (q, 4H, 2CH2-N), 3.67 (s, 6H, 2OCH3), 6.17 (t, 2H, 2CH2-NH), 6.78, 7.26 (AA'BB ', 8H arom), 8.34 (s, 2H, 2C-NH arom); C NMR (TMS, DMSO-D6, δ ppm); 31.40 (CH ₂ -S), 39.10 (CH ₂ -N), 55.12 (CH3-O),

113.93, 119.59 7C-H arom (, 133.61 (C-N arom (, 154.09 (C-OCH3 arom), 155.43 (C = O).

Preliminary test for the insecticidal activity of N-phenyldiureas I-IV.

The assessment of the insecticidal activity of the new N-phenyldiureas I-IV was performed in laboratory conditions, using a five-day-old imago of female housefly (Musca domestica) as a bioindicator. Each of the tested compounds was used in dimethylformamide solution in the following concentrations: 0.1%, 0.01% and 0.001%.

On the surface of Petri dishes with a diameter of 10 cm, 1 ml of the prepared solutions was applied with a pipette in a spiral motion to each lower and upper dish. For the control, dimethylformamide alone was used. The control insects were subjected to the same treatments as the insects with the tested preparations. After evaporation of the solvent, 10 pieces of a five-day-old female housefly imago were placed in each of the lower plates. The insects were anesthetized with carbon dioxide. Then the plates were covered and kept in an air-conditioned room at 25 ° C.

The evaluation of the insecticidal activity of the tested compounds was carried out after 24 hours, and then after 29 hours from the start of the experiment, assessing the percentage of insect mortality after these periods. Insects treated with individual preparations were compared each time with insects from the control object. The experiment was performed in triplicate for each of the given concentrations. The results obtained, the mean of three replicates, are presented in the table.

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In the preliminary test, the insecticidal activity was demonstrated by N-phenyldiureas III and IV, which did not contain a halogen atom in the aromatic rings. Compounds I and II showed no insecticidal properties in this test.

Table

N-Phenyldiurea Insect mortality,% after 24 hours after 29 hours AND - - II - - III 45-50 70 IV 60 85-90

Detailed test for the insecticidal activity of N-phenyldiurea IV.

N-Phenyldiurea IV, which showed good insecticidal activity in the pretest, was then subjected to a detailed test to further evaluate its insecticidal efficacy.

For the detailed test, compound IV was prepared as a series of solutions in dimethylformamide with geometrically decreasing concentrations (gamma using a multiplier of γ = 0.7).

Nine solutions of N-phenyldiurea IV in dimethylformamide were prepared with the following concentrations: 3 xy, 2.1 x γ, 1.47 x γ, 1.029 x γ, 0.720 x γ, 0.504 x γ, 0.352 x γ, 0.246 x γ, 0.172 x γ.

The detailed test was performed in the same way as the entrance test. After 24 hours, N-phenyldiurea IV showed 60-65% insect mortality, and after 29 hours, 90-95% effectiveness.

Thus, in the detailed test performed, N-phenyldiurea IV showed very good insecticidal activity.

MODEL 1

PATTERN 2

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Claims (3)

Patent claims 1. N-Phenyldiureas with a diethylene thioether group of general formula I, in which R is chlorine, bromine, methyl or methoxy. Process for the preparation of N-phenyldiureas with a diethylene thioether group of general formula I, in which R is chlorine, bromine, methyl or methoxy, characterized in that bis (2-isocyanatoethyl) sulfide is reacted with aromatic amines of general formula 2 wherein R is as defined above, in an inert organic solvent, at room temperature, under an inert gas atmosphere. 3. The method according to p. The process of claim 2, wherein the organic solvent is diethyl ether and the inert gas is nitrogen.