DE1567198C - Sulfurous phenyl phenoxyalkyl esters and their uses A, 5 \ m Uuwoyal Uic, New Yolk, N Y (V St A) - Google Patents

Description

R _{1 is} hydrogen, an o-methyl, p-methyl, isopropyl, tert-butyl, tert-amyl or nonyl radical,

R ₂ denotes hydrogen, an o- or p-methyl radical, an i-propyl, tert-butyl, tert-amyl or a nonyl radical and
π = 2 to 10.

2. Use of the compounds according to claim 1 as insecticides.

The invention relates to new organic esters of sulphurous acid, namely phenylphenoxyalkyl esters.

The new compounds are particularly useful as insecticides for killing mites. You can can also be used as plasticizers.

The new sulphurous phenylphenoxyalkyl esters have the following general formula:

O - C _n H

2 η

R _{1 is} hydrogen, an o-methyl, p-methyl, isopropyl, tert-butyl, tert-amyl or nonyl radical;

R ₂ denotes hydrogen, an o- or p-methyl radical, an i-propyl, tert-butyl, tert-amyl or a nonyl radical and
η = 2 to 10. .

The preparation of the compounds according to the invention is carried out by a corresponding Reacts phenol with the separately prepared chlorosulfinate of a corresponding phenoxyalkanol, which can be obtained by reacting the glycol ether in question with thionyl chloride. The glycol ether, which is a glycol monoether, can be prepared by using the phenol in question, is reacted with 1 to 10 moles of the alkylene oxide in question per mole of phenol. This manufacture will illustrated by the following reaction scheme, where A and B are those in the general given above Formula contained, correspondingly substituted phenyl radicals, for simplicity is ethylene oxide («= 2) used as alkylene oxide:

(1) A-OH + CH ₂ -CH ₂

O
> A - O - CH, - CH, -. OH

(2) A - O - CH ₂ - CH ₂ - OH + SOCl ₂

Il

- »A-O-CH ₇ -CH ₂ -OS-Cl + HCl

(3) AO-CH ₂ -CH ₂ -OS-Cl + HO-B

^ AO-CH ₂ -CH ₂ -OSOB

The reaction (1) above is well known and a smooth reaction. With 1 mole of alkylene oxide per mole of phenol is the result is essentially a single compound containing an alkylene oxide moiety. With 2 or more moles of alkylene oxide per mole of phenol, however, will be a mixture of reaction products obtained different numbers of alkylene oxide units. To obtain the for the production of the invention Compounds required phenoxyalkanols with an alkylene oxide unit, the mixture can be fractionated.

The preparation of the chlorosulfinate of the glycol ethers according to equation (2) is at a Temperature between -5 and 30 ° C, preferably close to 0 ° C, carried out, and the yield of chlorosulfinate is almost quantitative.

The production of the sulfuric acid ester is carried out in the presence of an HCl acceptor such as pyridine, di-, methylaniline or trimethylamine, carried out and is carried out in a solvent such as benzene, or xylene Solvent naphtha. The reaction temperature is generally between -10 and 50 ° C, preferably close to 0 ° C. This is shown in the following example. •. Examples of sulfite diesters according to the present invention Invention are:

40

45 phenyl phenoxyethyl sulfite,

Phenyl-o-tolyloxyethyl sulfite, Phenyl-p-tert-amyl-phenoxyethyl-sulnt, Phenyl-p-tert-butyl-phenoxy-isopropyl-sulfite, p-Toluyl-p-tert-butyl-phenoxy-isopropyl-sulfite.

example

The following describes the preparation of o-toluyl-p-tert-butyl-phenoxy-isopropyl-sulfite explained. The other new compounds can also be made using the same procedure.

a) p-tert-butyl-phenol is reacted with propylene oxide according to the above reaction (1).

p _: tert-Butyl-phenol (300 g, 20.0 mol) and 4 g of sodium hydroxide are combined, and the mixture is heated to 150.degree. Propylene oxide (279 ml, 232 g, 4.0 moles) becomes over the course of 2 hours. added, the reaction temperature being kept at 150 to 160 ° C. The mixture is cooled, the catalyst neutralized with dilute hydrochloric acid and the reaction product taken up in benzene. The benzene is removed and the product obtained 9O ⁰ C (0.5 Torr) heated to the last traces of volatile substances to be removed. The crude reaction product has

a weight of 509 g (95.7%). It is a mixture of compounds of structure

(CH ₃ J ₃ C

(OCH ₂ CH) ₁₁₁ OH
CH ₃

where m = 1, 2, 3, 4, 5, etc. The mixture is distilled and the following fractions are collected: '

m = 1, bp 107 to 128 ° C (1 Torr) ... 32%

m = 2, bp 128 to 153 ° C (1 Torr) ... 47%

m = 3, bp 163 to 184 ° C (1 Torr) ... 14%

Residue 7%

Mean cuts taken from these fractions give the pure compounds as follows:

m = 1, bp. 116 to 120 ⁰ C (1 Torr)
m = 2, bp 146 to 153 ° C (1 Torr)
m = 3, b.p. 175-177 ° C (1 torr).

b) ρ - tert. - Butyl - phenoxy - isopropyl - chlorosulfinate is prepared as follows according to the above reaction (2).

Propylene glycol - mono - ρ - tert. - butyl - phenyl ether or ρ -tert. - Butyl - phenoxy - isopropanol (104 g, 0.5 mol) is dissolved in 150 ml of benzene and the solution is cooled to 0 to 5 ° C. Then thionyl chloride (45.4 ml, 74.4 g, 0.625 mol) was added dropwise over the course of one hour, the reaction temperature is kept below 5 ° C. The mixture is then allowed to warm to room temperature and let it stand for 15 hours. The benzene is under reduced pressure at room temperature distilled off and the residue is warmed to 35 ° C (0.8 torr) to remove the last traces of solvent expel. The yield is 141.3 g (97.3%) of a light yellow oil, which is almost colorless and is relatively stable when stored in the refrigerator.

c) ο - toluyl - ρ - tert. - butyl - phenoxy - isopropyl sulfite is prepared according to the above reaction (3) as follows:

o-cresol (5.9 g, 0.055 mol), 4.1 ml (4.0 g, 0.05 mol) Pyridine and 30 ml of xylene are combined and the solution is cooled to 0-5 ° C. in the A solution of 14.5 g (0.0.5 mol) of p-tert-butyl-phenoxy-isopropylchlorosulfinate is obtained in the course of 20 minutes added in 10 ml of xylene, the reaction temperature being kept below 5 ° C. The mixture is stirred for 1 hour and washed twice with 25 ml of water each time. Then the mixture Stirred with 50 ml of 2N NaOH for 1 hour. The two layers are separated and the xylene layer becomes Washed several times with saturated saline solution until the washing water is neutral to pH paper. The xylene is removed under reduced pressure and the residue is brought to an internal temperature of Heated to 135 ° C (0.7 torr). The reaction product is then filtered through a diatomaceous earth filter aid and gives 13.9 g (77% yield) of a reddish yellow oil.

Analysis for C ₂₀ H ₂₆ O ₄ S:

Calculated ... C 66.26, H 7.23, S 8.85%;
found .... C 67.44, H 7.68, S 8.13%.

Nonylphenyl - ρ - tert. - butyl - phenoxy - isopropyl sulfite was produced by an analogous process. The analysis gave: "" ^ ./; ^; '.'

Calculated: S ^"6.75%; found: S 6.77%.
. This compound has the formula

(CH ₃ ) ₃ C

(CH ₂ ) ₈ CH ₃

Application example A

The following explanations explain the insecticidal effectiveness of the substances according to the invention in tests against larvae of Aedes aegyti (L.) mosquitoes.

Fourth instar larvae were used.

These larvae typically reach this stage in 5 days at 27 ° C after hatching.

To 10 mg of each substance to be tested, 1 ml of acetone and 10 ml of water are added to achieve a concentration of 100 parts per million (ppm).

Equal parts of 25 ml of each compound to be tested and control experiments at concentrations of 100 ppm without the connection and control tests with pure water are placed in test tubes, and it will be. 5 to 25 larvae added; each attempt is carried out twice. These test tubes are kept in the dark at 21 ° C for 72 hours.

At the end of this period of time, the dead and living larvae are counted and the mortality becomes calculated in percent. In the control experiments all larvae were alive (mortality 0%). the percentage mortality of the larvae treated with the compounds according to the invention is given in shown in the following table:

Chemical substance % Mortality ⁴⁵ o-toluyl-p-tert-butyl-phenoxy-
isopropyl sulfite
Nonylphenyl-p-tert-butyl-
phenoxyisopropyl sulfite 100
47

Application example B

This example shows the effectiveness of the compounds according to the invention for destroying Mites.

Two leaf stage pinto beans grown in 10 cm baskets under greenhouse conditions grown at 21 to 24 ° C were used. In each basket there were three plants in total six sheets for each exam. The tests with the compounds according to the invention and the control tests were each carried out twice. Aqueous suspensions of the compounds were prepared by adding a drop (0.03 g) of a commercially available surface-active dispersant to 0.2 g of the substance (Isooctylphenyl-poly-ethoxy-ethanol) and 1 ml of acetone and then washed in 200 ml of water. It was stirred to make a dispersion to build. Then was with water on the

desired concentrations of 1000 and 200 ppm ^diluted::: ■> ■ ■■■■■■■ ·.. '■ *. . ;

The plants were with the dispersions of Compounds sprayed at various concentrations, and the control plants were sprayed with sprayed aqueous solutions containing the surfactant and acetone without the invention Connections included. The spraying was carried out so that the upper surfaces of the leaves have been very well moistened. The plants were then returned to the greenhouse. The following Day (20 to 24 hours later) rings with a non-toxic to the organisms to be tested Adhesives such as B. for fly paper and for ringing trees is used to brought the edges of the top surfaces of the leaves to confine the mites to the top leaf surface. The mites were placed on the leaves treated in this way by making the bean leaflets strong with two-spotted adult mites, Tetranychus telarius L., within the edge of the glue the leaves of the plants to be tested were infected. The number of mites transferred was on noted the same day. The number ranged from 30 to 300 mites on six leaves. The plants were kept in the greenhouse for a further 4 days. Then the live mites that were on the Scrolls were, finally, numbered. The percent destruction was calculated using the following formula found:

% Annihilation = 100.

Final number of living mites)

1 -

Original number

The destruction of the mites by the compounds according to the invention at various concentrations is shown in the following table (the control treatments without the inventive Compounds showed approximately 20% mortality):

Application example C

Extermination of living mites

The active ingredients listed below were applied to living mites and those after a Day surviving mites were counted.

-. ■. ■ \. 6 .. % Annihilation at. 200 ppm 1000 ppm ■■■■ · '; -. ■, ■■ 99 5 o-Tolyl-p-tert-butyl-phenoxy- 100 isopropyl sulfite 95 o-Tolyl-p-tert-amyl-phenoxy- 100 ethyl sulfite 97 o-Tolyl-p-tert-amyl-phenoxy- 98- IO 2-butyl sulfite 99 o-Tolyl-p-tert-butyl-phenoxy- 100 2-butyl sulfite 97 o-tolyl-2-methyl-phenoxy- 96 ethyl sulfite 95 15th o-tolyl-2-methyl-phenoxy- 99 2-butyl sulfite 97 o-Tolyl-3- (4'-tert-butyl- 100 phenoxy) -2-butyl sulfite 95 20th o-Tolyl-1- (4'-tert-butyl- 100 phenoxy) -2-pentyl sulfite 96 p-fluorophenyl-p-tert-butyl- 100 phenoxy-isopropyl-sulfite 25th 9 C o-toly 1-1 - (o-tolyloxy) -2-decy 1- 96 sulfite

Connection according to the invention % Annihilation at 200 ppm 45 50 82. 55 71 1000 ppm o-toluyl-p-tert-butyl-phenoxy- 92 95 88 isopropyl sulfite 100 Nonylphenyl-p-tert-butyl- phenoxy-isopropyl-sulfite 59 p-tert-butyl-phenyl-p-tert-amyl- phenoxyethyl sulfite 99 · o-toluyl-p-tert-amyl-phenoxy- ethyl sulfite 100 Phenyl-p-isopropyl-phenoxy- ethyl sulfite 94, Phenyl-p-tert-butyl-phenoxy- isopropyl sulfite

Comparative experiments

Testing the effectiveness of the substances
on the destruction of mite eggs

Comparative substance: The commercial product 2- (p-tert-butyl-phenoxy) -isopropyl-2-chloroethyl sulfite,

(CH ₃ ) 3CC ₆ H ₄ OCH ₂ C (GH ₃ ) H OS O ₂ CH ₂ CH ₂ Cl.

Pests: Eggs of two-spotted mites (Tetranychus telarius Linne).

Plants: pinto beans at the two-leaf stage, grown under greenhouse conditions:

Manufacture of the spray ■.

The sprays were as aqueous emulsions or suspensions with a concentration of 1000 ppm produced by weighing 0.2 g of the substance and adding a drop of an emulsifier and 1 ml Acetone was added as a solvent. This was then washed into distilled water, made up to 200 ml and then stirred to form an emulsion or suspension. Other dilutions were made by adding distilled water.

Proceedings .

Adult mites were on the surfaces of the primary 2 days before the spray application Leaves of pinto beans brought where they laid their eggs. They were held in place by fly glue which was attached to the edge of the sheet. The sprays were dripped onto two plants a spray gun for 20 seconds (50 ml in 20 seconds). The spray gun was about 120 cm away from the plant and directed in such a way that> it wets the surface of the leaves well. To after spraying the plants were in the greenhouse brought back. An area from one of the infested leaves was selected for each pot,

namely one that had about 50 mite eggs. This area was coated with fly glue. The movable forms were removed by hand and the eggs contained in the enclosed area were counted microscopically. -yVyVi '' · - \:. ^.,: ■ -;,; ;.: .., ·, ■■; .., ■. ·. _ / 'V -' -, '■■. - ■ "■■ - ■■ - * '■■ ■ ■ ■ _ _ß - ■ · _■:;. ■ ■; ■ · -v ^ - * -.-) / ■. - .V ^. i "'' ¹ : · ^; ] '

After a week, the eggs that had not hatched were counted again. As on the untreated plants often there are many unhatched eggs, the percent destruction is calculated using the following formula received:. '. ■ ·.

,% hatched eggs __% hatched eggs

··.,. ' , "; ■■". · ■■ the control after treatment

Corrected percentage egg destruction = -% hatched eggs of the control

100

% eggs hatched =

Final count of unhatched eggs. Original number of eggs 100

Egg destruction

% Destruction at 200 ppm

2- (p-tert-butyl-phenoxy) -isopropyl-2-chloroethylene sulfite 21

o-Tolyl-p-tert-butyl-phenoxy-

isopropyl sulfite 100

o-Tolyl-p-tert-butyl-phenoxy-

butyl sulfite 100

o-Tolyl-2-methyl-4-tert-butyl-, phenoxy-isopropyl-sulfite 100

The following table contains the phytotoxicity values some compounds according to the invention and the comparison compound 2- (p-.tert-butyl-phenoxy) -isopropyl-2-chloroethyl sulfite.

35

40 The following table contains the labeling data for the compounds named in the preceding tables.

20 running No.

connection % -Phyto-
toxicity
opposite to
Tomatoes
a con
centering
of 2000 ppm o-Tolyl-pt-butyl-phenoxy-isopropyl-
sulfite 50 *)
0
0
0
0
2
0
0
0
20th o-Tolyl-pt-butyl-phenoxy-2-butyl-sulfite.
o-Tolyl-pt-butyl-phenoxy-2-pentyl-sulfite
o-Tolyl-pt-amyl-phenoxyethyl-sulfite ...
o-Tolyl-pt-amyl-phenoxy-2-butyl-sulfite.
o-Tolyl-2-methyl-4-t-butyl-phenoxy-
isopropyl sulfite
o-Tolyl-p-isopropyl-phenoxy-2-butyl-
sulfite ..... '. m-tolyl-pt-butyl-phenoxy-isopropyl-
sulfite o-Toiyl-l- (o-tolyloxy) -2-decyl-sulfite ....
2-chloroethyl-p-tert-butyl-phenoxy-
isopropyl sulfite

45

55

*) The higher phytotoxicity of o-tolyl-p-t-butyl-phenoxyisopropyl-sulfite compared to tomatoes (compared to the comparison, compound) is due to its 5 times greater ability to destroy more than compensated for by mite eggs. Added to this is the ability of this sulfurous acid ester to be used in one application Concentration of 100 ppm to induce 100% larval mortality of Aedes aegypti mosquitoes. The mortality of Mites applied to bean leaves treated with 1000 ppm of this sulfurous acid ester is 100%. the Mortality from mites on at 200 ppm. this sulfur gj acid ester-treated bean leaves were applied is 92% (at 100ppm - 83%; at 50ppm - 81%). The direct treatment living mites with 200 ppm of this sulfurous acid ester leads to a mite mortality of 99%.

1.

3.

4th

5.

6th

10.

11. Connection + identification

o-Toluyl-p-tert-butyl-phenoxy-isopropyl sulfite

IR spectrum: refractive index nf = 1.5279; 3.4, 6.6, 6.7, 6.85, 8.0, 8.3,

8.4, 8.6, 9.0, 9.6, 10.9, 11.4, 11.8, 12.1, 13.2, 13.9, 14.7 µ

Nonylphenyl-p-tert-butyl-phenoxyisopropyl-sulfite
Refractive index nf = 1.5203

p-tert-Butyl-phenyl-p-tert-amyl-phenoxyethyl-sulfite

IR spectrum: 3.4, 6.6, 6.85, 8.0, 8.2, 8.4, 8.6.9.85, 11.1, 11.9, 12.1, 13, 6, 14.2 µ

o-Toluyl-p-tert-amyl-phenoxyethyl-sulfite IR spectrum: 3.4, 6.6, 6.7, 6.85, 8.0, 8.25, 8.4.8.55.9.05.11.11.11.8.12, 05,12,95,13,15, 13,9,14,65 µ

o-Toluyl-p-tert-amyl-phenoxy-2-butyl-sulfite IR spectrum: 3.4, 6.6, 6.7, 6.8, 8.0, 8.2, 8.4, 8.55, 9.0, 11.2, 11.8, 12, 05, 13.15, 13.9, 14.75 µ

o-Toluyl-p-tert-butyl-phenoxy-2-butyl-sulfite IR spectrum: 3.5, 6.7, 6.8, 6.9, 8.1, 8.3, 8.5, 8.6, 9.1, 11.2, 11.8, 12, 1, 13.2, 13.9, 14.8 µ

o-Toluyl-2-methyl-phenoxyethyl-sulfite ^ IR spectrum: 6.7, 6.9, 8.0, 8.3, 8.6, 8.9,

9.05, 9.8, 11.1, 11.8, 13.3, 14.0, 14.2 µ o-Tolyul-2-methyl-phenoxy-2-butyl-sulfite

IR spectrum: 6.7, 6.85, 8.05, 8.3, 8.55, 8.9, 9.05, 9.5, 11.2, 11.8, 13.3, 14, 0.14.75 µ

o-Toluyl-3- (4'-tert-butyl-phenoxy) -2-butyl sulfite

IR spectrum: 3.4, 6.6, 6.7, 8.05, 8.3, 8.4, 8.55, 9.05, 11.2, 11.8, 12.05, 13, 2, 13.9, 14.75 µ

o-Toluyl-1- (4'-tert-butyl-phenoxy) -2-pentyl sulfite

IR spectrum: 3.4, 6.6, 6.7, 6.85, 8.0, 8.25, 8.45, 8.55, 9.0, 11.2, 11.8, 12.1, 13.2, 13.95,

14.75 µ ■. ;

o-Toluyl-p-iso-propylphenoxy-2-butyl-sulfite IR spectrum: 3.4, 6.6, 6.7, 6.85, 7.8, 8.05, 8.25, 8.55, 9.05, 9.6, 11.2, 11, 8, 12.1, 13.2, 13,9,14,75 µ

309 608/224

A 567

ίο

continuation

Serial No.

Connection + identification

12. o-Toluyl-1- (o-tolyloxy) -2-decyl-sulfite .. · ■■■ ·

IR spectrum: 3.4, 6.7, 6.8, 8.0, 8.2, 8.5, 9.0, 11.2, 11.8, 13.2, 14.7 μ .- - ''. . 'V

13. Phenyl-p-isopropyl-phenoxy-ethyl-sulfite

IR spectrum: 3.45, 6.7, 6.8, 8.1, 8.3, 8.5, 8.7, 9.8, 11.2, 12.1, 13.0, 14, 6μ

14. Phenyl-p-tert-butyl-phenoxy-isopropyl-

sulfite

IR spectrum: 3,4,6,6,6,7,8,0,8,2,8,4,8,65, 10.9, 11.4, 12.0, 13.0, 13.2, 14.5 µ

The new sulfurous acid esters can be used in various ways for the use of insects will. They can be applied to places that should be protected against the insects, namely as dusts when they are mixed with powdered solid * carriers or adsorbed on them, z. B. the various mineral silicates, e.g. B. mica, talc, pyrophillite and clays, or they can be used as Liquids or sprays are applied when in a liquid carrier, e.g. B. in solution in a suitable solvent, such as acetone, benzene or kerosene, or they can be in a suitable one non-dissolving medium, e.g. B. water, be dispersed. For the protection of plants (where this expression also includes the plant parts) which are exposed to attack by insects are those according to the invention chemical substances are preferably used in aqueous emulsions that have a surface-active substance Contain dispersants, which is an anionic, a nonionic or a cationic surface-active Means' can be. These surfactants are known and will be See U.S. Patent 2,547,724, columns 3 and 4, for details of which examples are specified. The compounds according to the invention can be used with surface-active dispersants with or without organic solvents as insecticidal concentrates for the subsequent addition of water be mixed to produce aqueous suspensions of the substances of the desired concentration. The compounds according to the invention can be mixed with powdered solid carriers, such as mineral silicates, be mixed together with a surfactant dispersant to make wettable powders can be obtained, which can be applied directly to the areas to be protected against insects, or which can be poured up with water to create a suspension of the chemical substance (and the powdered solid carrier) in water, which is used in this form. The invention Compounds can be applied to the areas to be protected against insects by the aerosol method be applied. Solutions for aerosol treatment can be prepared by the compound directly in the aerosol carrier, which is a liquid under pressure but at ordinary temperature (e.g. 20 ° C) and atmospheric pressure. Gas, can be dissolved, or the aerosol solution can be prepared by first dissolving the compound in a less volatile solvent and then this Solution is mixed with the more volatile, liquid aerosol carrier. The compounds according to the invention can also be used in mixtures with carriers that are themselves active, e.g. other insecticides, Fungicides or bactericides.

Claims (1)

■ '■; ■. Patent claims: 1. Sulfurous acid phenyl-phenoxyalkyl-ester of general formula 0-QH _7n -OSO- ₂ ίο wherein