SU1590040A3 - Method of producing derivatives of esters of carbamic acid - Google Patents

Abstract

The invention relates to the preparation of derivatives of carbamic acid esters, in particular the compounds of the common C 6H 5-OC 6H 4-para-O- (CH 2) 2-N [C (O) OR 1] -S-NX-C ( O) OR 2 where R 1 -C 1 -C 4-alkyl

R 2 - C 8 - C 12-alkyl

X is C 1 -C 4 -alkyl or C 6H 5-OC 6H 4-para-O- (CH 2) 2- with R 2 -C 1 -C 4 -alkyl exhibiting pesticidal activity that can be used in agriculture. The goal is to create new more active substances of the specified class. The synthesis is carried out by reacting the compound f-ly C 6H 5 -O-C 6H 4-para-O- (CH 2) 2-NH-C (O) -OR 1 with the compound f-ly S (Y) 2, where R 1 is indicated above

Y is halogen or one is halogen, and the other is NX-C (O) -OR 2

when X is C 1 -C 4 -alkyl and R 2-C 8 -C 12-alkyl. The new compounds are less toxic and more active than 2- (4-phenoxy-phenoxy) ethylcarbamic acid ethyl ester. 4 tab.

Description

The invention relates to a method for producing new derivatives of complex

of carbamic acid of general formula

VOCHjCHzN

. Where R - Alksht C, -04; RJ - alkyl X - alkyl Cj-C, or a group of the formula

ICH2CH2 which exhibit pesticidal activity.

The purpose of the invention is to develop a method for obtaining new complex derivatives, COOR,

,

(I)

X-N-COOH.

carbamic acid esters, which, as compared to limestone analogues, exhibit a higher pesticidal activity in structure.

The invention is illustrated by the following examples.

Example 1. N, N -sulphenylbis 2- (4- (phenoxy-phenoxy) -ethyl) Jcarbamic acid ethyl ester (active principle 1).

 3.1 g (0.01 mol) of 2- (4-phenoxy-phenoxy) ethylcarbamic acid ester, 20 ml of anhydrous methylene chloride, 0.90 ml (0.011 mol) of anhydrous pyridine and 0 , 36 g (0.003 mol) of 4- (dimethylamino) -pyridine is loaded with 0.35 ml (0.0055 mol) of sulfur dichloride, and the mixture is stirred at room temperature for 18 hours.

Then, 30 ml of chloroform is added to the reaction mixture, followed by successive washing with 20 ml of 5% hydrochloric acid, saturated NaHCOj and water, dried with magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue obtained is purified by column chromatography. Obtain 0.77 g (27.3%) in liquid light yellow. Oil 4

I Found,%: S 5,07; N 4.43; C, 64.54; H 5.73.

Calculated,%: S 5.19j N 4.33; C, 64.01; H 5.54.

JR spectrum: 1711 ().

Example 2. Ethyl ether

To a solution of 15.0 g (0.05 mol) of 2- (4-phenoxy-phenoxy) -α-ethyl-urea acid ethyl ester in dry pyridine is rolled over 10 minutes to 20.2 g (0.0575 mol) octyl ether N-chloropitol and o-N-methyl-acid carbamide with stirring and cooling with ice water, after which the mixture was stirred for 15 hours at room temperature. Pyridine was distilled off in vacuo.

ten

Water and ether are added to the residue, the mixture is acidified with 5% HC1 and the two phases are mixed well. The aqueous phase is extracted twice more with ether, the combined aqueous phases are washed with a 5% solution of NaHCO3 and water and then dried over MgSO4. The solvent is then removed under reduced pressure.

The product is purified by column chromatography using silica gel. Yield 31.3%.

Found,%: S 6.18; N 5.40; 25 C, 62.53; H 7.38.

Vyisleno,%: S 6.02; N 5.49; C, 62.61; H 7.49.

IR spectrum, cm-: () 17114.

N- (n-docenylnioxyN, N -sulfinyl-bis 2- (4-phenoxy-phenoxy) -ethyl) 7-carbamic acid ethyl ester (dey-JQ carbonyl) - (n-butylamino) -sulphenyl-2- (4- phenoxy-phenoxy) -ethyl} carbamoic acid (active principle 12), yield 30.2%.

S 5.20; N

beginning 7).

Chilled with ice water, a solution of 2.0 g (0.0066 mol) of 2- (4-phenoxy-phenoxy) -ethylcarbamic acid ethyl ester. 6 ml of anhydrous tetrahydrofuran. and 1.1 ml (0.008 mol) of triethylamine are mixed with 0.24 ml (0.0084 mol) of thionyl chloride and the mixture is stirred at room temperature for 18 hours. Then 10 ml of benzene and 10 ml of San are added to the mixture, the resulting solution is washed with 10 ml of 5% hydrochloric acid, with a saturated solution of NaHCOj and with water, and the solvent is removed by distillation with 1T.

The resulting compound after chromatographic purification yields 0.68 g (61%) as a liquid viscous oil.

Found,%: S 4.94; N 4.32; C, 62.95; H 5.59.

Calculated,%: S 5.02; N 4.28; C, 63.08; H 5.48.

UR spectrum: 1717 (); 1298. ().

Example 3. Preparation of ethyl 35

Found,%: C, 66.20; H 8.50. Calculated,%:

4.54; N 4.34;

40

45

50

S 5.30; C, 66.02; H 8.69.

JB spectrum: 1715 ().

Example 4. Laboratory experiments on a white-skin garden pieris brasicae. .

The insecticidal action of the active substances was tested on 24-hour caterpillars of the garden squirrel at the post-development stage, developed in laboratory conditions. Doses of the tested active substances 0.0001-0.1 μg in the form of 2 μl of an acetone solution were applied to the back of the tracks. Each dose was tested on 25–50 tracks. Processed} 51e caterpillars (12-15 in each batch) are stored in 0.5-liter plexiglas glasses, closed with a cloth, at 25 ° C and 18-hour illumination with daylight. As feed

N-C (n-octyloxycarbonyl) ether — cabbage leaves were given to the caterpillars.

- (Methylamino)} - Sulfenyl J-2 (4-phenoxy-phenoxy) -ethyl-carbamine hydroxyl.

The effect of the active substances was assessed after the skin was dropped or pupated. The percentage of non-active was determined.

0040.4

To a solution of 15.0 g (0.05 mol) of ethyl ester of 2- (4-phenoxy-phenoxy) -ethyl-carbamide acid in dry pyridine is rolled over 10 minutes to 20.2 g (0.0575 mol) of octyl ether N - chloropitol and o-N-methyl-acid carbide with stirring and cooling with ice water, after which the mixture is stirred for 15 hours at room temperature. Pyridine is distilled off in vacuo.

ten

Water and ether are added to the residue, the mixture is acidified with 5% HC1 and the two phases are well mixed. The aqueous phase is extracted twice more with ether, the combined aqueous phases are washed with a 5% solution of NaHCO3 and water and then dried over MgSO4. The solvent is then removed under reduced pressure.

The product is purified by column chromatography using silica gel. Yield 31.3%.

Found,%: S 6.18; N 5.40; C, 62.53; H 7.38.

Vyisleno,%: S 6.02; N 5.49; C, 62.61; H 7.49.

IR spectrum, cm-: () 17114.

Ethyl ester N- (n-dochenyloxy S 5.20; N

five

Found,%: C, 66.20; H 8.50. Calculated,%:

4.54; N 4.34;

0

five

0

S 5.30; C, 66.02; H 8.69.

JB spectrum: 1715 ().

Example 4. Laboratory experiments on a whitehouse garden pieris brasicae. .

The insecticidal action of the active substances was tested on 24-hour caterpillars of the garden squirrel in the last stage of development, bred under laboratory conditions. Doses of the tested active substances 0.0001-0.1 μg in the form of 2 μl of an acetone solution were applied to the back of the tracks. Each dose was tested on 25–50 tracks. The processed} 51e tracks (12-15 in each batch) are distributed in 0.5-liter plexiglas glasses, covered with a cloth, at 25 ° C and 18-hour daylight illumination. As feed

 the caterpillars were given cabbage leaves.

the caterpillars were given cabbage leaves.

The effect of the active substances was assessed after the skin was dropped or pupated. The percentage of non-active was determined.

incapable caterpillars with morphogenetic damage. The so-called intermediate forms between the larva and the pupa were divided into categories according to the five-dimensional scale (O-normal pupa; 4-larva-like shape with pupal organs characteristic for the pupa) and the average damage caused by individual doses of the active substance was determined. To determine the activity of the compounds, the LD values were calculated from these values (dose causing 50% inhibition), and the EDj value was determined from the percentage of damage caused to the caterpillars using a linear regression analysis (50% effective dose ), The results are shown in Table. one.

Table 1

On the scale of intermediate forms between larvae and pupae (0-4) there is an average dose, causing the appearance of a medium form (2).

causing disturbances in the development of an average of 50% of the caterpillars. Example 5. From the active beginning 1, a moisturizing powder of the following composition was obtained, vol.%:

Active start 50 Kaolin 40

Sulphite liquor 5 Aliphatic alcohol sulphate5 With the use of water, aqueous suspensions of an agent have been obtained with an active principle content of 0.01; 0.001 0.0001 vol.% "They were then applied finely by the Herobrinnen manual spraying machines on the branches of the home plum infected with the caterpillars of the American cabbage seedling and the last stage of development

but).

Experience has shown that even when treated with an aerosol liquid with the most

0

g

0

five

With a low content of the active principle, most of the pupae viable (morphological) developmental anomalies were observed in the treated specimens, and in untreated groups, the intact specimens.

Example 6. Laboratory-instruments on the Californian shield (Quadraspidiotus perniciosus).

The surface of the pumpkin was sprayed with an acetone solution containing 5 mmol of the active substance (application sigmaaerosol). After the liquid had dried, the fruit was infected with 50-60 calypus larvae at the first stage of development and kept under conditions of a long day at. After 3 months, the number of rooted insects was determined and, taking into account the data of the control experiment, calculated the total number of animals for each experiment using the Henderson – Tilton equation for percent of the compounds.

The results are shown in Table. 2,

table 2

thirty

Active substance

Activity according to GendersonTilton,%

five

one

7

eleven

12

14

Phenoxycarb

100 100 100 100 100 100

0

five

0

five

Example 7. Laboratory experiments on Blustella gennanica Prussians Experiments were started with a resistant culture obtained from insect females with 75% egg shell (ootheca) and continued with the offspring that hatched soon after the release of the shell (30 larvae from the female caldera). The active substance was mixed in cockroach feed (10 parts Kuke dog food, 4 hours sunflower seeds, 1 part yeast). The active substances were administered in the form of an acetone solution. Their final concentration was 50 ppm. Insects were kept in the dark in 200 ml beakers, covered with linen, into which water was also poured for drinking. The effect of the tested compounds was in slowing the formation of the epithelial membrane

ki, mortality of larvae during molting, an increase in the period of development and the emergence of transitional forms of larvae-imago (adultoidy), the color of the latter corresponded to the color of adults

five

eight

9

ten

eleven

12 13

Phenoxycarb Test Experience

80-100 the first and the last

--37 Melanized 30 -37 Coloring for adults

individuals

- Sixth molt Only up to the sixth stage

--37 Melanized 25. -38--36 coloring adults

individuals

60 Sixth Moult Only to the sixth stage

--47 Melanized

--43 Coloring adults

individuals

25-100 First and pta Only up to p of this - molting stage

h -T 1 "-1

Example 8. Laboratory experiments on the larvae of the flies of the red-headed Sarcophaga bullata. The larvae of the flies were kept under long day conditions on an agar nutrient medium based on bovine liver. After the insects at the last stage of development of the larvae became able to shuffle, they were held for 2 days to synchronize. on wet filter paper with. The test active substances in the form of an acetone solution in quantities of 4 μl at a dose of 5 and 0.5 μg / insect were applied to the body of the larvae. The activity of the compounds was assessed by mortality of the pupae (in percent) after 12 days. The results are shown in Table. four.

cut or was dark (melanism), which is characteristic of larvae.

The results are shown in Table 3.

Table 3

Table 4

As can be seen from the table. 1-4, the compounds according to the invention have a higher activity compared to the known compound phenoxycarbamide-2- (4-phenoxy-phenoxy) -ethylcarbamic acid ester. Received

f Vo-f WasNgSNgK

Where

ry-ocHjCHj when Rj is C, -C4-alkyl, characterized by a compound of the general formula

By the fact that SOUOSNgSNg-in-SOOV

Claims (1)

the compounds belong to the group of weakly toxic. Invention Formula The method of obtaining derivatives of carbamic acid esters of the general formula XOOR X-N-COOR2 where R, has the indicated meanings, is reacted with a compound of the general formula S (Y), where both Y is halogen or one is halogen, and the other is a group of formula -N, / N COOR, where X is R, C, -C-alknl; With g-C, 2-al kil.