SU681044A1 - Esters or amides of 3-methyl-3-(4'methylpentene-3'-yl)-phenylpropen-2-ic acid as insecticides with juvenile activity - Google Patents

Description

This invention relates to new cinnamic acid derivatives, namely, esters or amides of 3-methyl-3- (4-methylpentene-3-yl) -phenylpropen-2-oic acid of formula I where R is OR, NHR, NR R is CHs , CjHs, CH (CHj) a, possessing selective juvenile susceptibility (III) on Aedes aegypti mosquitoes. Known substances with ASA, as a rule, have a wide spectrum of action on different groups of insects, although the degree of activity may vary. An example of such a substance is a mixture of Low, which is approximately the same; activity on mosquitoes, bedbugs and turtles 1. Its main component is known as an insecticide with SA; the mixture. Low serves as a convenient reference in bloc tests 2. Some derivatives of the substituted cinnamic acid of the formulating formula RO-CH-COOR are also known, where R is H, alkyl, R is 3s-substituted or unsubstituted phenyl and cyclohexyl, used as insecticides, violating the metamorphosis of insects of various species 3. However, these compounds, as well as derivatives of substituted cinnamic acid of the general formula f-.SI, -R. / - (CH2) rt-CCH-CC) OR, 3) 4, are too broad in range and cannot be used. be against a certain type of insect. The purpose of the invention is the preparation of esters or amides of substituted 3-methyl-3-phenylpropen-2-oic acid of general formula (I) as insecticides to selective GOAs. The obtained derivatives of formula (I) differ from Aedes aegypti with a selective effect against mosquitoes. selectively valid compounds with SA. Compounds of formula (I), where R -, OCjHg is obtained from p-acetyl-d-phenylsilic acid ethyl ester (I) by reaction with ethylene glycol, the resulting ethylene ketal is reacted with methylmagnesium iodide, followed by hydrolysis and dehydration to ketone (IV ). The resulting ketone is subjected to mutual interaction (MjOHb JC% 0) s, fCU where the esters of the total (I) f where R is OCHj, OCH {CH5) 2 is obtained by re-refining the ethyl ether of the formula with alcoholic alcohols. The general formulas (I), where R NCCjHg), are obtained by amidating acid chloride (), where K OCjHg, Constants of the synthesized compounds of general formula (I) are given in Table. 1. Biological tests of the synthesized compounds carried out on mosquitoes and on two types of bugs showed that, although the derivatives of this group did not exceed the standard {Blend-Low), they have a high specificity of action for commers. So, the most active among them is compound I, where K OSZ N. In addition, the compounds are in form (I), where R g, and (I), where H NiCjHsJjf have a toxic effect on carp larvae. On the bedbugs of Rhodnius proEixus and the harmful turtle EXirygaster integriceps these substances are practically inactive. The results of biological tests of the synthesized compounds are given in table. 2. The following are examples of the preparation of the properties and the procedure for conducting the SA for the compounds obtained (Example 1. A mixture of 33.0 g of this p-acetyl-y-phenylbutyric acid (II) levoid ether, 46 ml of ethylene glycol, 250 MP of benzene and 0.2 g of p-toluene sulfonic acid are heated with a Dean-Stark nozzle for 60 hours.After this, the reaction mixture is cooled, washed with soda-solution, water, dried with sodium sulfate. Dissolve and distill off the residue. 26 g (66%) of ethylene ketal of ethyl ester p acetylphenylsyl acid (III) are obtained with t, bale 175-178 C / VIS with with dimethylphosphonucleus c1-sll methyl ether (Wittig-Horner reaction) followed by isolation of the desired product (I), where R is in free form or as ethers of the general formula {I), where OCH (CH3) 2, or as acid, or in the form of amide. Reaction scheme: DCHjIVi a SlgjOjJ: / 2 mm, n | ° 1, 5058, Thin-layer chromatography (those) on SiEufoE plates in the system acetone: heg / tan - 2: 5 (Rf 0.54), Retention time 2015 (G / KZS, Tsvet-Z device; 3 m column, 3 mm diameter, 5% on chromatone (60-80 mesh). Those 4 column temperatures, carrier gas speed 80 jvui / MHH; in the following examples, the column temperature and carrier gas velocity are specified in each specific case). IR spectrum (UR-20 device): 1060, 1610, 1735 cm1 Found:%: 68.74; H 8.05. C 16 22P4 Calculated,%: C 69.04; H, 7.96; To a griner reagent, prepared from 7.35 g of MD, 18.8 ml of methyl iodide in 100 ml of dry ether, a solution of 32 g (III) and 40 gp of ether is added during 30 minutes. Stir for 1 h at 20 ° C and 3 h at boiling. The mixture is extracted with ether, the ether extracts are sieved with water, sodium acetate with sodium sulfate, and the ether is distilled off. The residue 30g is dissolved in 60 ml of acetone, 10 MI7 of 10% HC is added and the mixture is stirred for 4 hours at room temperature. The acetone is distilled off, the residue is diluted with you and extracted with ether. The ether extracts are washed with water, dried with sodium sulfate, then the ether is distilled off, the residue 24 g is dissolved in 60 ml of xylene, 0.25 g of crystalline iodine is added and heated for 4 hours with a Dyne-CfapKa nozzle - Cooled, washed with sodium oisulfite solution , water and dry the sodium sulfate. The solvent is distilled off, and the residue is fractionated and 14.7 g (60%) of n - (4-megylpentene-3-. -Yl) -acetophenone (IV) are obtained, v. Kip. 14815GS / 1 f / iM, n2 ° 1.5359, R, 0.49 (TLCSlEufot conditions are similar to III. Retention time 614 (conditions are similar (111). IR spectrum 5847,1610,1685 cm. Found: С 82 , 87; H 8.93.

Calculated,%: C 83.12; H 6.96.

2, 4-ЛД1НИТрофенилгидразон, т. Pl „1.50-1С (from alcohol).

Found,%: 62.96; H 5.66; 14.93.

C oHjjN.O.

Calculated,%: C, 62.81; H 5.79; 14.65,

Under a dry nitrogen atmosphere, a suspension of sodium hydride in tetrahydrofuran (THF), prepared from 1.07 g of a 50% suspension of sodium hydride in mineral oil and 1-0 ml of THF, was added at 5 ° C to 4.37 g of dimethylphosphonoacetic acid ethyl ester and mixed at room temperature for 3 h. Then re-cooled to and add 4.5 g of ketone (IV) in 5 ml of THF. Stir for 1 h at 5 ° C, 1 h at, 3 h at boiling and leave on

N OCH

THF is distilled off, the residue is diluted with water and extracted with ether. The ether extracts are washed with water, 21st, again with water and dried with sodium sulfate. The ether is distilled off, the residue is distilled, and 3-methyl-3- (4-methylpentene 3-yl) -phenylpropen-2-oic acid ethidate is obtained. The retention time was 10 22 (cis--), 1325 (trans-), the column temperature was 210 ° C, S2 90 ml / min.

IR spectrum: 847, 1610, 1635, 1715 CM-Pm and m e. P 2. To a solution of sodium methylate, obtained from 0.1 g of sodium and 30 ml of methyl alcohol, add 10 g of ether (I) and boiling T 5 h. Cool, poured into water, acidified with hydrochloric acid, extracted with ether. Essential extracts of proNuJBaK) T with water and dried with sodium sulfate. After distilling off the solvent, the residue is fractionated and 3-methyl-3- (4-methylpentene 3 yl) -phenylpropen-2-oic acid methyl ester is obtained. The conditions of GLC are similar to ether (II). A retention time of 1015 (trans), 8 30 Ccis).

IR spectrum: 847, 1610, 1715 cm

Compound (I), where R is OCH (CH 3) 2, is obtained similarly using sodium isopropoxide. The retention time is 1418 (trans), 1145 (for cis conditions of GLC, see ester (II).

IR: 847, 1610., 1635, 1715 CM-J

Example C: To a solution of 2.0 g of ether (I) in 30 ml of CjHsOH and 8 ml of% O, add 3 ml of 50% NaOH and leave for 20 hours at room temperature. The alcohol is distilled off in vacuo, the residue is diluted with water and extracted with ether. The aqueous layer at 0 ° C is acidified with 10% NrZO, extracted with ether, the ether extracts are washed with water and dried. 7 With sodium sulfate. The ether is distilled off, the residue is recrystallized from hexane and 3-methyl-3- (4-methylpentene-3-yl) -phenylpropen-2-acid acid is obtained.

IR Spectrum 847, 1610, 1635, 1690, 2800-3300 cm /

Example 4. To a solution of 1.0 g of the acid of example 3 in 20 ml of dry chloroform, O, 7 ml of triethylamine were added, cooled to 0 ° C, and 0.5 ml of chloro ether in 2 ml of chloroform was added. Stir at 30 minutes, then at 20 ° C for 2 hours. Cool, add 0.6 ml of diethylamine in 2 ml of chloroform, stir at 0 ° C for 30 minutes and 3 hours at. The reaction mass is washed with water, dilute sulfuric acid, again with water,

5 Chloroform is distilled off, the residue is diluted with ether, rotted with soda solution, water, dried with sodium sulfate, ether is distilled off, the residue (1.0 g) is purified by preparative TLC to obtain N-diethylamide-3-methyl-3- ( 4-methylpentene-3 -yl) -phenylpropen-2-oic acid.

IR spectrum: 847, 1610, 1630, 1650 cm-. .

The retention time is 2350 (column temperature 220C, N2 100 ml / min).

Compound (I), where R -, is obtained in a manner similar to that using ethylamine.

IR spectrum: 847, 1230, 1550, 1610,

0 1630, 1655, 3300

The retention time is 2045 (column temperature, N2 100 ml / min). Example 5. When tested on Aedes aegypti mosquitoes, fourth-stage larvae 1-2 days prior to pupation were placed for 24 hours in solutions of various concentrations. The substances are added to water in 0.1 ml of acetone, at least 100 larvae are used for each concentration (25 each). When tested on larvae of the third stage, the exposure was prolonged (from the moment of processing to pupation). The effect is determined by the number of dead insects, and SC-50 by regression lines on probitlographic paper.

When tested on Rhodnius Q proEixus bugs, the compounds were applied topically in 1 µl of acetone on the tergites. The abdomen of the nymphs a day after feeding with blood, after an imaginal molt on a 19-point scale, the degree of residualness of the imaginary larval traits was assessed, and then the dose causing the average effect was established graphically (i.e. 10 points).

When tested on a harmful Eurygaster integriceps bug, solutions of 0 substances were applied to larvae of the fifth stage. The degree of juvenile effect was assessed after molting on a 5-point scale. A Low mixture was used as a reference.

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Claims (4)

with the invention The esters or amides of 3-methyl-3- (4 tilpenten-3-yl) -phenylpropen-2 acids by a formula wherein juvenile actuality. Sources of information, attention during examination 1. Krimer M, 3., Shamshurin A. A. Chemistry of the juvenile hormone and its analogues, Chisinau, 1972, p. ; 2. The patent of France No. 2121260, C, C 07 C 121/00, opouzlik. 1972. 3. Authors certificate of the USSR 282811, cl. A 01 N 119/30, f. 4.A. Franke und an. Synthetische. TuveniEhormone III, p-Substituirte 4 phenyEbuten-l-carbonsaure 5, pheny penten-l-carbonsanre derivative, HeEv. chim, acta, 1975, 58. 1, c. 283, 293.