SU959391A1 - 2-(s-alkylthio)-ethyl ester chlorides of ammonium phenol having growth regulating effect for plants,fungicides and hematocides - Google Patents

Abstract

Chlorides 2-

Description

The invention relates to new biologically active chemical compounds, specifically to 2-(5-alkylthio) ethyl chlorides of ammonium ether of the general formula 1 OCHjCHz-S-CH-lCHjJ -CHj CH where R is H, CH:j; μ is 0-10, exhibiting the properties of plant growth regulators, fungicides and nematicides. 2-Chloroethyltrimethylammonium chloride (TUR) is known, which is an analogue of the proposed compounds T, formula G (3O3 k -CHG-CHG-NH 2 , where R is a halogen, which is a plant growth regulator ij . The disadvantage of this compound is its toxicity to warm-blooded animals. Analogues in structure of the proposed substances are also 2-bromoethyl ether of p-acetaminophenol of the formula IT O-CHOGHoBr and bromide 2-bromide ether of p-ammonium phenol of the formula 1Y O-CH CH BrJBr The substance of the formula I11 is known to have growth-regulating, fungicidal and nematode-cidal properties, and the substance of the formula 1Y is known to have growth-regulating and nematicidal properties. Based on the totality of indicators, the indicated analogs are inferior in structure to the proposed substances (see Tables 2, 3, Examples 6, 7). The aim of the invention is to find new biologically active substances exhibiting complex growth-regulating, fungicidal and nematicidal activity with reduced toxicity for warm-blooded animals. This aim is achieved by the properties of new 2-(5-alkylthio) ethyl chlorides of p-ammonium phenol of general formula 1, obtained by a known method by reacting alkyl mercaptides with halogenated ethers of p-ammonium phenol in the presence of a base, followed by hydrochlorination 4j . The new 2-(5-alkylthio) ethyl chlorides of p-ammonium phenol are white crystalline substances, readily soluble in polar organic solvents and water. Structure and individuality The obtained 2-(5-alkylthio) ethyl chlorides of p-ammonium phenol are proven by the data of elemental analysis (Table 1) and IR and CMR spectra. Example 1. 2-(5-ethylthio) ethyl chloride of p-ammonium phenol OCHgCH - S-CH CHjlcf is added to an alcoholic solution of sodium ethylate prepared from 1.84 g (0.08 g-atom) of metallic sodium and 120 ml of absolute ethyl alcohol at 20 s, 11.9 g (0.04 mol) of 2-bromoethyl bromide of p-ammonium phenol and 2.5 g (0.04 mol) of ethyl mercaptan are added and the reaction mixture is boiled for 2 hours. After cooling the mixture to room temperature, the sodium bromide precipitate is separated and the filtrate is evaporated. To 100 ml of benzene are added to the residue and the resulting solution is washed with water (3 times in portions of 100 ml). After drying over anhydrous sodium carbonate at () - (+20) C, dry hydrogen chloride is passed into the benzene solution until its absorption ceases. The crystals are separated, recrystallized from alcohol, washed with ether and dried in air. Yield 5.8 g (62%). mp 148 - 149 ° C. Found, %: C 51.41; H 6.68; C 15.46; N 5.83; S 13.42. C,(jH|jC1N05 Calculated, %: C 51.37; H 6.91; C1 15.16; N 5.99; S 13.71. Compounds 11-U are obtained similarly. Example 2. Chloride 2-(3-sec-butylthio)ethyl ester of p-ammonium phenol HjN- -OCH CHj-S-CH-CHjCHj Cl 11.9 g (0.04 mol) of 2-bromoethyl bromide of p-ammonium enolase, 6 g (0.04 mol) of sec-butyl mercaptan are added to an alcoholic solution of sodium ethylate prepared from 1.84 g (0.08 g-atom) of metallic sodium and 120 ml of absolute ethyl alcohol, and the reaction mixture is boiled for 1.5 h. The mixture is cooled to room temperature, the sodium bromide precipitate is separated, the filtrate is evaporated in vacuum. The residue is dissolved in 100 ml of benzene and the solution is washed with water (3 times in portions of 100 ml). After drying over anhydrous sodium carbonate, dry hydrogen chloride is passed into the benzene solution until absorption ceases. The crystals are separated, recrystallized from benzene, washed with hexane and dried in air. Yield 7.2 g (69%). mp 178 - 180 ° C. Found, %: C 54.90; H 7.54; Ct 13.56; N 5.18; S 11.98. s, h OS Calculated, %: C 55.04; H 7.71; C 13.53; N 5.35; S 12.24. Example 3. Hydrogen chloride 2-(5-N-butylthio)ethyl ether of p-ammonium phenol -ocCH2CH2-3-CH2-(CH2)2-CH3 j CH3 To an alcoholic solution of sodium ethylate prepared from 0.92 g (0.04 g-atom) of metallic sodium and 60 ml of absolute ethyl alcohol are added at 20 C 5.94 g (0.02 mol) of 2-bromoethyl bromide of p-ammonium phenol and 1.8 g (0.02 mol) of p-butyl mercaptan and the mixture is boiled for 2 hours. The reaction mixture is cooled to room temperature, the sodium bromide precipitate is separated, after evaporation from the filter in a vacuum, the residue is dissolved in 80 ml of benzene and washed with a solution of water (3 times in portions of 80 ml) Dry the benzene solution over anhydrous sodium carbonate and pass dry hydrogen chloride through until absorption ceases. Separate the crystals, recrystallize from propyl alcohol, wash with ether and dry in air. Yield 4.0 g (77%). M.p. 180-182°C. Found, %: C 54.76; H 7.70; CH 13.83; N 5.33; S 11.98. C1, Calculated, %: C 55.04; H 7.71; Cl 13.53; N 5.35; S 12.24. Example 4. 2-(3-H-amylthio)ethyl chloride of p-ammonium phenol:CH2 5-CI2-(CH2)5-CH, CH2 11.9 g (0.04 mol) of 2-bromoethyl bromide of p-ammonium phenol and 4.16 g (0.04 mol) of p-amyl mercaptan are added at 20 C to an alcoholic solution of sodium ethylate prepared from 1.84 g (0.08 g-atom) of metallic sodium and 120 ml of absolute ethyl alcohol. The reaction mixture is boiled for 1 hour, cooled to room temperature, the sodium bromide precipitate is separated and the filtrate is evaporated in vacuo. The residue is dissolved in 100 ml of benzene and the solution is washed with water (3 times in portions of 100 ml). The benzene solution is dried over anhydrous sodium carbonate and dry hydrogen chloride is passed through until absorption ceases. The crystals are recrystallized from propyl alcohol, washed with ether and dried in air. Yield 6 g (55%). mp 187-189°C. Found, %: C 56.88; H 8.15; C 13.06; N 5.24; S 11.32. Calculated, %: C 56.59; H 8.05; Cf. 12.85; N 5.07; S 11.62. P D i m e r 5. Chloride 2-(5-docetylthio)ethyl ester of p-ammonium phenol OCH2CH2 S-CH2-(CH2)n-CH5 I Cl to an alcoholic solution of sodium ethylate prepared from 184 g (0.08 g-atom) of metallic sodium and 120 ml absolute ethyl alcohol, 11.9 g (0.04 mol) of 2-bromoethyl bromide of p-ammonium phenol and 8.09 g (0.04 mol) of dodecyl mercaptan are added at 20 C and the mixture is boiled for 1 hour. The reaction mixture is cooled to room temperature, the sodium bromide precipitate is separated, after evaporation of the filtrate, the residue is dissolved in 100 ml of benzene, the benzene solution is washed with water (3 times in portions of 100 ml). The solution is dried over anhydrous sodium carbonate and dry hydrogen chloride is passed through until absorption ceases. The crystals are separated, recrystallized from benzene, washed with ether and dried in air. Yield 7.0 g (47%). M.p. 202-204°C. Found, %: C 63.92; H 9.43; Ct 9.76; N 4.02; S 8.29, C gHjjpfNOS Calculated, %: C 64.21; H 9.47; Ct 9.47; N 3.74; S 8.57. Example 6. Regulation of growth of roots, stems and leaves of plants. Experiment - laboratory. Objects of study - lettuce, oats. Growth-regulating activity is studied on plant sprouts grown in Petri dishes on an agar medium using a known method (5j. Seeds are laid out on solidified agar containing a substance of a certain concentration in Petri dishes. Seed germination occurs in a thermostat (three days; temperature (+22) (+24)°C). Then the dishes with sprouts are placed on 4 The shoots are placed in a fume hood with lighting to continue growing the plants, after which the length of the roots, stems and leaves of the seedlings is measured. In the control variant, solidified agar-agar containing only water is used. The preparation TUr: 2-chloroethyltrimethylammonium chloride (analogue of iT) is taken as a standard, and the analogue 2-bromide ether of p-acetaminophenol and the analogue 2-bromide ethyl ether of p-ammoniumphenol are also tested. As a result of the experiment, it is established (see Table 2) that the proposed compounds, by the nature of their action on the growth of lettuce and oats, are classified as plant growth regulators. The inhibitory activity of the proposed compounds is higher than that of analogues 2 and 3. It is also higher compared to the preparation TUr. The selectivity of the action of the new compounds is observed. With a decrease in concentration (0.001%) the inhibitor properties are more pronounced in relation to dicotyledonous plants (lettuce). On monocotyledonous plants (oats) new compounds in concentration of 0.001-0.0001% exhibit stimulating action. The most pronounced inhibitors in concentration of 0.01% are compounds I11 and Y, and stimulators of seed germination and growth of monocotyledons (conc. 0.0001%) are compounds I-Y. Example 7. Fungicidal activity of compounds. Experiment - laboratory. Object of study: pure cultures of phytopathogenic fungi - Alternaria radicina M.D. et E; Aspergillus niger V.Tiegh BKM F 412; Fusarium oxysporum Schlecht BKM F-1182; Helminthosporium sativum P.K. et BHUUA; Venturia inaequalis (Cooke) Wint. Fungicidal properties are determined by the method of inhibiting the growth of fungal mycelium on an agarized potato-glucose medium. A sample of the substance dissolved in water is added to melted agar, mixed and poured into Petri dishes. After solidification, the agar is inoculated with pieces of mycelium. After 70 hours of exposure at 26 C, the diameter of the colonies is measured and the growth energy of the fungi is determined as a percentage of the control. An adequate amount of solvent - water - is added to the control dishes. The following are used as standards: chemically pure phenol, 2-bromoethyl ether of p-acetaminophenol (analog 2j), technical pentachlorophenol sodium (PCP Na), tetramethylthiuram disulfide (TMTD, 80% wettable powder) and 2-chloroethyltrimethylammonium chloride (TUR, preparative form, 60% by active substance). The repetition is fourfold. The results obtained (see Table 3) show that the new compounds have a pronounced fungicidal effect, exceeding the activity of the analog 3, TUR and phenol and approaching the activity of the standards PCP Na and TMTD. Aspergillus, helminthosporium and venturi are more sensitive to the action of the new compounds. Compounds 1-III are the most active. Example 8. Fumigant properties of the new compounds. Experiment - laboratories. Object of study: spores of Asp. niger. A lawn seeded with fungal spores is placed over a substance applied to the center of a Petri dish lid. The growth and development of the fungus is observed for 3 days at +26 C. It was found that the new compounds are non-volatile substances and do not affect the growth and development of the fungus, unlike the standards PCP Na (forms an inhibition zone for fungal growth over the substance), phenol and thiobeneol (inhibit fungal growth in the dish). Example 9. Nematicidal activity of new compounds. The nematicidal activity of the substances is studied on the root-knot nematode Meloidogyne incognita in pot experiments, which are carried out under warm conditions. The activity of the substances is studied at a consumption rate of 1000 kg/ha and is determined 45 days after the experiment by the number of galls formed per unit length of the plant root and is expressed as a percentage in relation to the control. The results of the experiments are presented in Table 3. The data obtained indicate the presence of a high nematicidal effect in the proposed compounds, which in activity are somewhat superior to the standard - nemagon and analogues of fzl M. Example 10. Toxicological studies. The acute toxicity of new 2-(5-alkylthio) ethyl chlorides of p-ammonium phenol is determined on white mice weighing 19-21 g with intraperitoneal injection. 2-(5-alkylthio) ethyl chlorides of p-ammonium phenol

osNgSNg-z-sn-ssNg) snz sG nom in the introduction. The LD5(, (median lethal dose) value, expressed in mg/kg of live weight, serves as an indicator of toxicity. The results of statistical experiments are processed using the Litchfield and Wilcoxon method modified by Roth Sj. As a result of the studies, it was established that the LD5(,, data for the preparations is at the level of analogues 2 and , and in comparison with the reference preparation TUR (preparative form, 60% of the active ingredient), they are less toxic (LD5(,, data for TUR is 180 mg/kg) (see Table 3). Thus, it is experimentally established that the proposed substances have the properties of plant growth regulators and, at the same time, fungicidal and nematicidal properties. Depending on the concentration, they can both inhibit and stimulate the growth of individual parts of plants, thereby creating the prerequisites for increasing their productivity and improving the quality of products. By their activity The compounds proposed are superior to the closest analogue, the drug TUR. The proposed substances are less toxic to warm-blooded animals than the drug TUR. Table t

Continuation of table 1.

(in Results of tests on growth-regulating activity of new compounds % of control plants) (duration of the experiment 7 days) Table 2

11

Length of plant parts

Connections

ConcentrateSalad

connections I radio,

stem

root 1110.01 4 . O 0.001 64 77 0.0001 93 103 0.001 0.001 0.0001 Analog 2 0.0001 Analog 0.0001 . 1 .0

29 48 98 92 102

0.5

0,1

0.01

0,001

12

959391

Continuation of table 2 . 0. Germination

Salad

Oats

Oats

sheet

root 36 113 120

22 38 80 77 86

11 35 97 85 93

72

98

95

98

101

102

102

98

101

96 46 102 104 Fungicidal,

X - t

Table 3 nematicidal activity and toxicity for warm-blooded animals of new compounds

Claims (1)

Chlorinated 2-(5-alkylthio)ethyl esters of η-ammonium phenol of the general formula [NZYA-O-osngSKg-z-sn-ssjg^sn,] sG k where K - H, CH 5; η -0-10. exhibiting properties of plant growth regulators, fungicides and nematicides. 8C p„ 959391 959391