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

Abstract

Chloride 2-

Description

The invention relates to new biologically active chemical compounds, specifically to 2- (5 alkylthio) ethyl ammonium ester and ammonium chloride esters of the general formula 1 OCHjCHz-S-CH-1CHjJ -CHj SG where R is H, CH: j; C-0-10, exhibiting the properties of plant growth regulators, fungicides and nematocytes. Known 2-chloroethyltrimethylammonium chloride (TUR), which is an analogue of the proposed compounds T, of the formula G (SO3 to -sng-cng-n c1, where R is halogen, which is a plant growth regulator ij. The lack of this compound is its toxicity to warm-blooded animals. Analogues on the structure of the proposed substances are also p-acetaminophenol 2-bromoethyl ester of the formula IT O-CHoGHoBr and 2-bromoethyl bromide ether pammonium phenol of the formula 1Y O-CH CH BrJBr The substance of the formula I11 is known to control growth, fungicide and nematode LL / CI J W y nJtUjilti to k y h 1. ri .., ii, iUJ XI ti.iit-bii ", cide properties, and the substances of formula IV have growth-regulating and nematocidal properties. By a combination of indicators, these analogs are inferior in structure to the proposed substances (see Table 2, 3, examples 6, 7). The development of new biologically active substances exhibiting complex growth regulatory, fungicidal and nematocine activity with reduced toxicity for warm-blooded animals. This goal is achieved by the properties of the new 2-chloride (5-c1-LCHI) thio) ethyl esters of p-ammoniumphenol of general formula 1, which are obtained in a known manner by reacting alkyl mercaptides with haloalkyuxy ethers of p-ammonium phenol in the presence of a base, followed by hydrochlorination 4j. The new 2- (5-alkylthio) chlorinated ethyl esters of p-ammonium phenol are white crystalline substances readily soluble in polar organic solvents and water. The structure and individuality of the obtained 2- (5-alkylthio) ethyl esters of p-ammoniumphenol are proved by elemental analysis data (Table 1), and IR and CMR spectra, Example 1. 2- (5-ethylthio) ethyl ester of p- ammo: iphenol OCHgCH - S-CH CHjlcf to a sodium ethylate alcohol solution prepared from 1.84 g (0.08 g-atom) of metallic sodium and 120 ml of absolute ethanol are added at 20s to 11.9 g (0.04 mol a) p-ammonium phenol 2-bromo ethyl ester and 2.5 g (0.04 mol) of ethyl mercaptan and the reaction mixture is boiled for 2 hours. After cooling the mixture to rooms The precipitate of sodium bromide is separated in temperature and the filtrate is evaporated. 100 ml of benzene was added to the residue and the resulting solution was washed with water (3 times with 100 ml portions). After drying over anhydrous sodium carbonate at dry () - (+ 20) C, dry hydrogen chloride is passed into the benzene solution until it is absorbed. The crystals are separated, recrystallized from alcohol, washed with ether, and dried with air. The output of 5.8 g (62%). M.p. 148 - 149 ° С. Found,%: with 51,41; H 6.68; From 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 - Y are prepared in the same way. EXAMPLE 2. 2- (3-sec-butylthio) chloride p-ammonium phenol ethyl ester HjN- -OCH CHj-S-CH-CHjCHj C1 11.9 g (0.04 mol) p-ammonium enol-3 methyl bromide, 6 g ( 0.04 mol) sec-butylmercap3 .95 tann 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 ethanol, and the reaction mixture is boiled 1 , 5 h. Cool the mixture to room temperature, separate the sodium bromide precipitate, filtrate The residue is dissolved in 100 ml of benzene and the solution is washed with water (3 times with 100 ml portions), the benzene solution is passed through anhydrous sodium carbonate and dried, and the crystals are dried until the absorption is stopped. The crystals are 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. c, ng OS Calculated,%: C 55.04; H 7.71; C 13.53; N 5.35; S 12.24. EXAMPLE 3 Chloride 2- (5-H-butylthio) ethyl, p-ammonium pyrophenol ester —oHgCH2-3-cNg- (cNg) g-cNz j cG To an alcoholic solution of sodium ethoxide, prepared from 0.92 g (0.04 g atom) of metallic sodium and 60 ml of absolute ethanol are added at 20 ° C with 5.94 g (0.02 mol). p-ammonium phenol 2-bromo ethyl ether and 1.8 g (0.02 mol) p-butyl mercaptan and the mixture is boiled for 2 hours. Cool the reaction mixture to room temperature, separate the sodium bromide precipitate, after evaporation of the filter in vacuo the residue it is dissolved in 80 ml of benzene and washed with rasboron (3 times 80 ml portions). I dry the benzene solution over sodium carbonate (anhydrous) and dry hydrogen chloride until absorption ceases. Crystals are separated, recrystallized from propyl Bogo alcohol, washed with ether and dried in air. Yield 4.0 g (77%) m.p. 180-182 ° C. Found,%: C 54.76; H 7.70; SG 13.83; N 5.33; S 11.98. C ,, Calculated,%: C 55.04; H 7.71; C1 13.53; N 5.35; S 12.24. EXAMPLE 4 Chloride of 2- (3-H-amylthio) Ethyl ester of p-ammoniumphenol: CH2 5-cIg (ch2) 5-СН, СГ 11.9 g (0.04 mol) of methyl bromide 2-Bromoethyl p-ammoniumphenol and 4.16 g (0.04 mol) of p-amylmercaptan 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 ethanol. The reaction mixture is boiled for 1 h, cooled to room temperature, the precipitate is separated from sodium bromide 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 with 100 ml portions). The benzene solution is dried over anhydrous sodium carbonate and dry hydrogen chloride is passed through until absorption is stopped. The crystals are separated, recrystallized from propyl alcohol, washed with ether and dried in air. Yield 6 g (55%). M.p. 187189 ° 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 and Meper 5. 2-(5-docecylthio) ethyl ester of p-ammonium phenol OCH2CH2 $ -CHg (CH2) u-CH5 I C1 to an alcoholic solution of sodium thiote prepared from 184 g (0.08 g -atomic sodium metal and 120 ml of absolute ethanol, at 11 ° C added 11.9 g (0, .04 mol) of 2-bromo ethyl ester of p-ammonium phenol and 8.09 g (0.04 mol) of dodecylmercaptan and the mixture is boiled for 1 h. 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, washed with benzene solution water (3 times in 100 ml portions). Dry the solution over anhydrous sodium carbonate and dry the dry chlorine chloride until absorption is stopped. 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. PRI me R 6. Regulation of the growth of the roots, stems and leaves of plants. Experience - laboratory. Objects of study are salad, oats. Growth regulating activity is studied on seedlings of plants grown in Petri dishes on agar medium according to a known method (5j. In Petri dishes on hardened agar containing a certain concentration, seeds are laid out. Seed germination occurs in a thermostat (three days; temperature (+22) (+24) ° C.) The 4-day seedling cups are then placed in an illuminated cabinet for growing plants, after which the length of the roots, stems and leaves of the seedlings is measured. In the control variant, frozen agar-agar is used. to water. TUR: 2-chloroethyltrimethylammonium chloride (an analogue of iT) is taken as a reference, as well as an anaG 1 log 2-bromoethyl ester of p-acetaminophenol and an analog e: bromide 2-bromo ethyl ester of p-ammoniumphenol. As a result of the experiment, install ( see Table 2) that the compounds according to the nature of the effects on lettuce and oats are related to plant growth regulators. Inhibit the activity of the proposed compounds is higher than analogues 2 and 3. It is also higher compared to the TUR drug. The selectivity of the new compounds is observed. At a decrease in concentration (0.001%), the properties of the inhibitor are higher than that of the dicotyledonous plants (lettuce). On single-lot (oats), new compounds in a concentration of 0.001-0,0001% show a stimulating effect. The most pronounced inhibitors at a concentration of 0.01% are compounds 111 and Y, and stimulants of seed germination and growth of monocotyledonous (final.00001%) compound I-Y. PRI me R 7. Fungicidal activity of compounds. Experience - laboratory. Object of study: pure cultures of phytopathogenic fungi - Alternaria radicina M.D. et E; Aspergillus niger V.Tiegh BKM F 412; Fusarium oxysporum SchlechtBKM F-1182; Helminthosporium sativum P.K. et BHUUA; Venturia inaequalis (Cooke) Wint. The fungicidal properties are determined by the method of inhibition of the growth of the mycelium of fungi on agarized potato glucose medium. A sample of the substance dissolved in water is added to the molten agar, mixed and poured into Petri pieces. After hardening, 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 plates. The following standards are used as standards: chemically pure phenol, p-acetaminophenol 2-bromoethyl ester (analog 2j), sodium sulfate (PCPH), technical sodium pentachlorophenol (PCPHa), tetramethylthiuram disulfide (TMTD, 80% wettable powder), and 2-chloro ethyl trimethyl ammonium mheephylmethyroxide. 60% active ingredient). The repetition is fourfold. The results obtained (see Table 3) show that the new compounds have a pronounced fungicidal action, exceeding the activity of the analogue of TUR and phenol and approaching the activity of the PCP standards Na and TMTD. Aspergillus, gelmintosporium and venturi are more sensitive to the effects of new compounds. The most active compounds are 1-W. PRI me R 8. Fumigant properties of new compounds. Experience - laboratories. Object of study: disputes Asp. niger A lawn planted with spores of the fungus is placed over the substance applied in the center of the lid of the petri dish. For 3 days, the growth and development of the fungus is observed at +26 C. It has been established that the new compounds do not contain volatile substances and do not affect the growth and development of the fungus, unlike the standards of PCP Na (forms the top 795 area of the fungus growth above the substance), phenol and thiobenol (inhibit the growth of fungus in the cup). PRI me R 9. Nematocidal activity of new compounds. The nematocidal activity of the substances studied on the Meloido gyne incognita gall nematode in vegetation experiments carried out under conditions of heat. Substance activity is studied at a consumption rate of 1000 kg / ha and determined 45 days after setting the experiment on the number of galls formed per unit length of the plant root expressed as a percentage relative to the control. The results of the experiments are presented in table. 3. The data obtained indicate the presence of a high nematocidal action of the proposed compounds, which in their activity are somewhat superior to the standard — nonmagon and analogs of fzl M. Example 10. Toxicological studies. The sharpness of the toxicity of the new 2- (5-alkylthio) ethyl esters of p-ammonium phenol is determined on white molons weighing 19-21 g at intraperitone. 2- (5-alkylthio) ethyl esters of p-ammonium

 OSNGSNGZH-SN-SHSNG) SNS with GH introduction. The LD5 value (, (average lethal dose), expressed in mg / kg of live weight) serves as an indicator of toxicity. The results of statistical experiments are processed according to the method of Litchfield and Wilcoxon in the modification of Rota Sj. As a result of the conducted studies, it was established that the LDDD dannpps of drugs is at the level. analogues 2 and, in comparison with the reference drug TUR (preparative form, 60% of the active principle), they are less toxic (LD otURA is 180 mg / kg) (see tab. 3). Thus, it is experimentally established that the proposed substances have t properties of plant growth regulators and at the same time fungicidal and nematocidal properties. Depending on the concentrations, they can both inhibit and stimulate the growth of individual parts of plants, thus creating a prerequisite for increasing their productivity and improving product quality. superior to the closest analogue of the TUR drug. The proposed substances are less toxic to warm-blooded animals than the TUR drug. Table t

The continuation of the table.1.

(in Test results on growth-regulating activity of new compounds% to control plants) (duration of the experiment is 7 days) Table 2

eleven

Length of plant parts

Compounds

Concentrate Salad

compounds I,

stem

the root is 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. ten

29 48 98 92 102

0.5

0.1

0.01

0.001

12

959391

Continued table. 2 0.Vaciness

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 Fungicide,

X - t

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

Claims (1)

Chlorides of 2- (5-alkylthio) ethyl esters of η-ammonium phenol of the general formula [nzya-o-osngSKg-z-sn-shyig ^ sn,] sg to where K is H, CH 5; η -0-10. exhibiting the properties of plant growth regulators, fungicides and nematocides. 8TS p „959391 959391