DE1567199A1 - Sulphite esters, processes for their preparation and insecticidal agents containing them - Google Patents

Description

DR. R. POSCHENRIEDER

DR. Ε / BOETTNER
DIPL-ING. H.-J. MÜLLER

. SSZSSS * ^ ,, .. ,, "1567199

Lucile-Grahn-SUaHe 38 Γ1 £ * J U Il "* ⁿ

Teleion 443755

Caae 2454

üniroyal, Inc., New York (V.St.A,)

1230 Avenue of the America a. .

Sulphite esters »Process for their production and insecticidal agents that contain them

The invention relates to new © SuIfitester, method iu their production and insuktiaiäJi means that contain these. In particular, the Irfinduag is concerned Did sulfiteaters of alkynyl alcohols bend us! Glycol ethers.

The new chemical compounds bind teauchfear as Ineektiside, heeonders but extermination of mites »you can also be used as plasticizers »

The chemical substances according to the invention are by the following general formula

shown. In this formula, H is an eliphatiacher radical, sB · alkyl, cycloalkyl, alkenyl, oyamoalkyl or a haloalkyl _{radical e} or R iat eia aroBatiseher radical, 2B.B "Phe2? Yl- or naphthyl-, or ®ia fhenyl" or a Haphthyl <- (aryl) radical with one or more Subetit "· = ducks in the aryl nucleus, BB, alkyl" cycloalkyl _v haloalkyl, alkoxy, nitro and Halogsni R "is a acjcliscteer Alkinylreeti iat η 2 to 10 and m is 1 up to 10 · If m

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909886/1740

is greater than 1, the repeating alkyl groups may be the same or different. Examples of R are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, eeo-butyl, tert-butyl, amyl, hexyl, 2-ethylhexyl, _t octyl, decyl , Isodecyl, bodecyl, cyclohexyl, allyl, methallyl, 2-cyanoethyl, 2-chloroethyl, 2,2,2-trichloroethyl, If-chloropropyl, / - · chlorobutyl, ^ -Triehloramyl -, phenyl, 1 ~ naphthyl ~, 2-naphthyl, p-toluyl, o-toluyl, isopropylphenyl, terto-butylphenyl, tert ^ -amylphenyl, sonylphenyl, cyolohexylphenyl, chloromethylphenyl, methoxyphenyl . Nitro phenyl, bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl radicals. Examples of R * are acyclic alkynyl radicals with 3 to 10 carbon atoms, such as ^c _n H _2n _3 ~ ^{Reöte ln} which η b ± M 10 is BB propargyl, 1- (3-butynyl) -, 2- (3 ~ butynyl) -, 2- (2-methyl-3 ^ butynyl) -, 1- (2-heptynyl) - and 1 - (3-Noninyl) -reete. Examples of the "OC _n H _2n -GrUpPe are ethyleneoxy, trimethyleneoxy, tetraethyleneoxy, propyleneoxy, 1,2" dimethylethyleneoxy,

The preparation of the chemical compounds according to the invention is carried out by the selected Alkynyl alcohol with the separately prepared chlorosulfinate of the selected glycol ether is implemented, which by Umeettung of the selected glycol ether with thionyl chloride can be produced. The glycol ether, which is a glycol monoether, can be prepared by adding the selected aliphatic or aromatic monohydroxy compound, i.e., an alcohol (alkanol or alkenol) or Phenol with 1 to 10 moles of the selected alkylene oxide is reacted per mole of alcohol or phenol. tuck

909885/1740 bath

Production is explained by the following reaction equations with the same meanings of R, R * and m ₉ as in the general formula above, and for simplification, ethylene oxide (na 2) is used as alkylene oxide

(1) H-OH + m CH ₂ -CH ₂ ^ O

{2} H4 .0CH ₂ CH _{2) M} + 0H SOCIg- ^ E - (- OCHg) _n -OSCl + HCl

0 0

(3) n -4 OCH ₂ CHg) _n -OSCi + HOi ⁹ ^ R-4-OCH ₂ -CH ₂ ) _n -osoR ^f + aa

Reaction (1) above is known and a smooth reaction. Hit a "Hol Alkylenozyd per Hol alcohol or Phenol essentially gives the result a one-off Compound that contains an alkyl moiety «Hit two «Tor Hehr Hol alkylene oxide per mole of alcohol or phenol a Kiaohung τοη Uasetzusgaprodukten with different numbers of Alkylenojcydeinhelten is obtained. if a connection old of a certain view! If alkylenozydeinhelten are desired, the mixture can be fractionated. If the substances according to the invention as Ineectiiide are used, it is sufficient if aan Mixtures of compounds having different numbers of alkylene oxide units from 1 to 10. The following Reaction of p-tert-butylphenol with propylene oxide is an example of the known preparation of the starting glycol ether according to reaction (1) above;

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90988 5/1740

p-tert-Butylphenol (300 g, 2.0 mol) and 4 g sodium hydroxide are added, and the mixture is heated to 150 ° C. In the course of 2 hours, propylene oxide is (279 al, "232 g, 4.0 mol) hinsugegeben, wherein the reaction temperature is maintained at 150 to 160 C ^4" The mixture is cooled, the catalyst is neutralized with dilute Chlorwaaseretoffeäure added and the Umsetsungeprodukt in benzene . The benzene is removed and the product obtained is ^{heated to 90 11} C (0.5 mm) in order to remove the last traces of volatile substances. The crude reaction product weighs 509 g (95 * 796) · Eb is a mixture of compounds of the structure

(OCH ₂ CH) _B 0H

where m ■ is 1, 2, 3, 4, 5, and so on. The mix will distilled, and the following tractions are collected:

η - 1, Kp 107 - 128 * C (1m) 32 ^

a - 2, Kp 128 - 153 ¹ C (1 ms) 47 Ji

a - 3 »Kp 163 - 184 ¹ C (1am) U %

Backrest 7 *

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

BAD OfUGINAL 909885/1740 ^ö

m - 1, Kp 116 - 120 ⁰ C (1 mm)
m «2, Kp H6 - 153 ⁰ C (1 ma)
α a 3, Ep 175 - 177 ⁰ C (1 mm).

The preparation of the chlorosulfinates of the glycol ethers according to equation (2) is carried out at a temperature between -5 ¹ C and 3O ¹ Ct, preferably close to ⁰ C, and the yield of chlorosulfinate is almost quantitative. This is shown in Example 1 below.

The sulfite esters are prepared in the presence of an HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine, and in a solvent such as benzene, xylene or solvent naphtha. The Beaktionetemperatn "is generally between -1O ⁰ C and 50 ⁰ C, preferably close to ⁰ ° C. This is geeeigt in the following example. 1

Examples of sulfite diesters according to the present invention are ι

Pro pargyIme thoxy ä t hy Isulfi t

Propargyläthoxyäthylsulfit

Propargyl butoxyethyl sulfite

Propargyl tert-butoxyethyl sulfite Propargyl-2-ethylhexoxyethyl sulfate Pr ο pe, ygy Ihexad ecoxy ä thy 1 sul f i t

Propargylcyclohexoxyethyl sulfite Per pargy 1 phenoxy ethyl sul fi t

Propargyl-o-toloxyethyl sulfite

Propargyl-m- (n ~ propyl) - "phenoxyethyl sulfite Propargyl-p-tert " <«Amylphenoxyethyl sulfite Propargyl-p-chlorophenoxyethyl sulfite

909885/1740

Pro pargyl ~ 2 ~ ethylhexoxyi8opropyl sulfite Propargyl-p-tert-butylphenoxyiaopropyl sulfite Propargyloctoxyisopropoxyisopropyl sulfite Propargyl-O-tert-butylphenoxyisopropoxyisopropyl sulfite

Propargyl-m-nitrophenoxydiieopropoxyieopropyl sulfite PrapargyldecoxytetralBOpropoxyisopropyl sulfite PropargyliBodecoxy-n-propylflulfite Propargyl-p-toloxyootyl sulfite

2- (3 ~ butynyl) hexadecoxyisopropyl sulfite.

2- (3-Butynyl} -p-tert »-butylphGnoxyethoxyisopropyl sulfite

1- (2-Butiny1) -o-ehlorphenoxytriäthoxyäthylsulfi t 1- (3-hexynyl) p -isopropylphenoxyhexoxyhexyl sulfite.

It has been found that the effectiveness of acaricides is greatly improved if these have an aftereffect that prevents recontamination from occurring adjacent, untreated fields occurs. Corresponding tests were carried out in which the plants were sprayed very well with the active ingredient to be tested and the mites were found one day later were brought to the plants. They became plants thin 4 days after contamination on surviving animals checked. The results of the experiments in which tert-butylphenoxyr ~ isopropyl-2-chloroethyl sulfite was used as a comparative substance, Bind in the following Table reproduced:

Aftermath after 1 day test 175: 116

Host off % destruction at ppm

1000 200 100 50

tert-butylphenoxy

iflopropyl-2-chloro-

ethyl sulfite 99.7 79.8 65 42

Propargyl-p-tert.-

butylphe noxy-2-

butyl sulfite 100 99 t 5 69 48 _BAD ORSGINAL

Active ingredient 1000 200 100 50

Propargyl-p-tert.-

aoylT> henoxy ~ 2-butyl-

sulfite "100 ^ S ₀ 6 91 a4 72

1- (2-butynyl) -p-tert.-

butylphenoxy-isoprc-

pylaulfite 100 99 «7 58 25

1- (2-butynyl) -1- (p-

tert-butylphenoxy) -

2-butyl sulfite 100 99.4 99 * 3 83

Theater 173-124

tert β-butylpfaenoxy-

iBopropyl-2-chloro

ftthylaulfite 100 89 ₄ θ 51 ₉ 2 -

Propargyl-p-t-butylphenoxy-isopropoiy-

ieopropyl sulfite 99.4 98 _t 0 94.9 77.2

The comparison of the above table was carried out under Qewächheußbedlngusjgea, at which the temperatures were between 23 ° C and 31 ° 0. The differences in the results due to the tur

Kachwirlcung after 1 day - "Test JJH-129 -.... Temperatur 29.4 ⁰ C yirkBtoff ^

200 100 50

tert-butylphenoxy

isopropyl-i? -chloroethyl ~

Sulphite 87 ο 1 45

9 0 9 8 8 5/1740

94, 5 89 1 61 , 7 100 99 θ 92 , 6 99 4th 99 1 89

»· ■ ■ ^ Destruction at ppm active ingredient .- .. .200 J [OO 50

Propargyl-p-tert-butyl-

phenoxy-iaopropoxyieo-

propylaulfite 93 * 7 87.2 47.2

Propargyl-p-tert-butylphenoxy-isopropyl sulfite 26 55 15

173-131 - temperature 18 _t 3 ° C

tert-butylphenoxy isopropyl-2-chloroethyl aulfite

Propargyl-p-tert-butyl-

phenoxy-iaopropoxyieo propylaulfite

Propargyl-p-tert-butylphenoxy-iaopropylulflt

From the above values it follows that propargyl-ptert. -butylphenoxy-isopropylsulf it was relatively ineffective at high temperatures, but was much more effective at lower temperatures than tert Butylphenoxy-ieopropyl-2-chlorofithyl sulfite.

It is often difficult to do this in field conditions to treat entire foliage with the active ingredient, in particular the lower leaf surfaces where the Mites especially sit. A test technique was therefore developed to test the ability of the active ingredient to to distribute on the lower leaf surface and kill the mites there, to determine. In these experiments, bean plants were grown at the two leaf stage used or cotton plants that were about six weeks old and had 6 to 8 leaves. This plant

9G988S / 1740

ζβη were contaminated with mites, and it was one day before spraying, bringing the mites to the top leaf surface. These mites move then calibrate further on the lower surfaces of the leaves =, These lower surfaces of the test sheets were then provided with rings of glue and a plastic film covered. The plants were then sprayed with the active ingredients in such a way that the upper leaf flaps were well moistened. When the active ingredient had dried on the sheet, the plastic film was removed, and the mites were counted for the first time, then, the mites were counted again after four days, and the percentage destruction of the mites was calculated * The results obtained are compiled in the following table.

Deep action on bean leaves (ppm)

read Test Test Test -74 173 * 232 17 3 * 1 81.173 ~ £ ÖÖ " ffPOO ~ 2WÖ ~ " 2000

l TT active ingredient 195-74 173 * 232 17 3 * 1 81. - "2 0ÖÖ " ~ WÖ ~

tert «, - butylphenoxy-

isopropyl-2-chloroethyl

sulfite 28 24 23 48

1- (2-butynyl) -1- (p-tert-butylphenoxy) -2 ~ butyl sulfide 71 - '-

1- (2-Butynyl) -p-tert. ~ - - ~ 45

butylphenoxy-i sopropyl-

sulfite

Propargyl-p-tert-butyl- - 44 phenoxy-2-butyl sulfite

9098 85/1740

Hl -

Test Ttet Teat Test Active Substance 195-74 173-232 173-181 173-223

3000 zoOö 2000 ΤΌ "

Propmrgyl-p-ieopropylphenoxy-2-butyl sulfite - 46

Propargyl-p-tert, -butylphenoxy-iaopropyl sulfite - - 52

Propargyl-o-toloxyieo-

propoxy isopropyl sulfite - - - 88

Propargyl-p-toloxyieopro-

pyliulfite. - - 99.8

Propargyl-p-toloxyleo-

propoxy-ieopropyl sulfite - - - 96.2

In the case of the comparators, Bdt tert-butylphenoxyi8opropyl-2-chloroethyl sulfite, it was found that Prop * rgyl-pt «rt-aeylphenoxy-2-butyl sulfite, propargyl p-tert-butylphenoxy-ieopropoxyi-propyl sulfite, propellyl-p-tert-butylphenoxy-2-butyl sulfite and 1- (2-butynyl) -1- (p-tert. -butylphenoxy) -2-butyl sulfite have greater effectiveness in killing mites by aftereffect.

It has also shown that 1- (2-butynyl) -1- (pt-rt-butylphenoxy) -2-butyl sulfite, 1- (2-butynyl) -p-tert-butylphenoxy-iaopropyl sulfite, propargyl-p ~ tert, t -butylphenoxy-2-butylaulfit, propargyl-p-iaopropylphenoxy-2-butylaulfit, propargyl-p-tert -butylphenoxy _{β-iaopTO-pylaulfit,} propargyl-o-tolcxyieopropoxy-isopropyleulfIt ,.

909885/1740 BAD

Propargyl-p-toloxyisopropylsulphite and Propergyl-p-toloxylsopropoxy-isopropylsulphite "have a greater effect due to the migration to the" foliage and thereby bag the kilben more in protected places than tert-butylphenoxy-isopropyl-Z-chloroethylsulphite "

Example t explains the preparation of the compounds according to the invention.

example 1 Production of ProparCTl ~ p-tert »~ Putylphepoxyl8Opropyl-

BUlfit

p-tert-butylphenoxyisopropylchloroulfinate is produced as shown in line (2) above, and p-tert-butylphenoxyieopropyl alcohol or propylene glycol-bono-p-tert "" butylphenyl ether produced as follows is based on equation (1) as described above (104 g, 0.5 mol) becomes in 150 ■! Bensol dissolved, and the solution is abgektthlt OK to 5 ⁰ C. Mused is thionyl chloride (49 * 4 With 74f4 gff 0.625 Hol) hinsugegeben in the course of one hour, added dropwise, wherein the Reaktionetemperatur wird- kept below 5 ⁶ C The mixture is allowed to warm to room temperature and allowed to stand for 15 hours · The Bensol is under distilled off under reduced pressure at room temperature and the residue is ^{warmed to 35 °} C. in order to drive off the last traces of the solvent. The yield is 141.3 g (97.3 #) of a pale yellow oil, which is almost colorless and which is proportionate is stable when stored in the refrigerator «

BAD ORjGiNAL 90988 5/17 40

The propargyl-p ^ terte-butylphenoxyisopropyl sulfite is, as described in equation (3) above, prepared as follows! Propargyl alcohol (3.2 ml, 3.1 g _f 0.055 Hol), 4 * 1 ml (4 »0 g, 0.05 mol) pyridine and 30 ml xylene are added and the solution is cooled to OK to 5" C. in the course ron, a solution of 14 * 5 g (0.05 Hol) p «~ Terto Butylphenoxyisopropyl ~ chloro ~ oulfInat added in 10 ml of xylene Hinuten 10, wherein the reaction temperature below 5 * C. the mixture is 1/2 hour stirred and washed twice with 25 ml of water each time. The mixture is then stirred for one hour with 50 ml of 2N NaOH. The xylene solution is washed several sharks with saturated salt solution until the water is neutral to pH paper. The xylene is removed under reduced pressure and the residue is heated to an internal temperature of HO ⁰ C (0.2 mm) in order to remove volatile substances. The reaction product is then filtered through Dicalite (a diatomaceous earth filter aid) and yields 13 »9 g (89» 7 yield) of an amber-colored oil * Analysis: calculated for ⁰ IgH ₂₂ O ^ S S _f 10.33 g. Found: S, $ 10.58 »

The following substances were produced using analogous processes. You will be using the values of the sulfur analysis specified.

Propargyl - p-tert ~ _n butyldii80proporylsopropylBulfit. Calculated S, 7.5256 * Found «6

Propargyl-p-terto-amylphenoxyethyl sulfite, calculated S, 10.33 i> « Found: 9 * 78 $>«

9 0 9 8 8 5/1 7 k 0 BAD OBiGiNAL

Propargyl-p-tert »-butylphenoxyiBopropoxyisopropyl sulfite. Calculated S, 8.70 % » Found: 8" 61 # "

Propergyl-p-toloxyiaopropyl sulfite - Calculated 8, £ 11.95 <> Found: 11.19 # -

Propargyl-1 ^ p-Isopropy1phenoxy-2 ~ buty1buIfi t-, Calculated S, 10.33 fi « Found: 9 * 14 # *

Calculated S, 9.89 # - Found: 8 _V 72 ί> »

Propargyl-1-p-tert "-amylphenoxy-Z -butyloulfite Calculated $ 3. 9.47 " Found: θ

Propargyl-3-p-tert _n -butylphenoxy-2-butyl sulfite, Calculated S, $ 9.89> Found: 8.92 ^ o

Propargyl-1-ρ-tert "-butylphenoxy-2-amylsulfite, calculated S, $ 9.48 >> Found: $ 8.58»

Propargyl'-o-toloxylsopropoxyioopropyl sulfite » Calculated S, 9.82 ^. Found: 9.11 # -

Propargyl-p-tolyloxyiaopropoxyiaopropyl sulfite " Calculated S "9" 82 36 "Found: 8.74 ^.

Propargyl-p'-isopropylphenoxyethoxyethyl sulfite. Calculates S ₀ 9 «82 fi. Found: 8.99 ^ S-

Propargyl-p-ioopropyiphenoxyisopropoxyiaopropyl sulfite Calculated S, 9.05%, Found: 8 _c 60 56-

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Propargyl-l ~ (lp-ieopropylpheno3Cy-'2 ~ butoaqr) -2-butyO Calculated S, θ, 42 £ ₉ Found »7.60 £»

Propargyl-2-ethy1. ~ 4-tert '"-' butylpheiiojrieopropoxy i no pro py 1 eul f i t -.

Calculated 8 «£ 8.38 * Found» 7.74 Hη

1- (3-butynyl J

Calculated S, 9.88 1 ·, Found! 9 * 89? Ί *

2 ~ (3-Butynyl) -p-tert «-aey! Phenoxyethylsulfitο Calculated S, 9 ₃ Θ8 ^. Found »9» 38 j6.

i- (3-Hexinyl) -p-tert-aylphenoxyethy1eulfite, calculated S ₄ £ 9.10 * found £ 8.75

Calculated 8.8 _V £ 38 * Found «7.57 ^,

1- (2-But iny 1) -p- tert <. -amylphenoxyethyl sulfite * Calculated S, $ 9.88, found »8.98 i» *

Ζ * (2-methyl-i'-butynyl) «p-tert« -butyl phenoxy! eopropyl aul fit Calculated S ₁₁ 9 «48 fi. Found »8.64 ^ n

Example g

The following explanations explain the insecticidal effectiveness of the substances according to the invention in tests against larvae of Aedes aegyptj (L-.) Mosquitoes. Larvae in the fourth stage were used. These larvae normally reach this stage in 5 days at 27 ^° C (80 ^° F ) after brooding,

BAD ORKiINAt 909885/1740

1 ml of acetone and 100 ml of water are added to 10 ng of each tested substance in order to obtain a concentration of 100 parts per Hillion (ppm) eu and one portion is also diluted to 10 ppm. Equal parts of 25 ml of each chemical substance tested at concentrations of 100 ppm and 10 ppm eu and controls without the chemical subetanes and controls with pure water are placed in test tubes and 5 to 25 larvae are added; each experiment is carried out twice. These test tubes are kept in the dark at 2 \ "C (70 ⁰ P) for 72 hours» At the end of this period, the dead and living larvae are counted and the mortality is calculated as a percentage all larvae alive (mortality £ 0) λ The percentage mortality of the larvae treated with the chemical substances according to the invention is shown in the following table?

Chemical substance f> Mortality

IQO PPM 10 ppm

Propargyl-p-tert - »- butyl-

phenoxyisopropyl sulfite 100 100

Propargyl-p-tertη-butyl-

phenoxyisopropoxyisopropyl

Sulfite 100. 50

Prepargyl-p-tert. "Butylphenoxydiieopropoxyisopropyl sulfite 100 41

example J>

The following shows the effectiveness of the inventive sweeteners chemical substances for the destruction of mite

909885/1740

Swel leaf-stage pinto beans grown in 4-inch boxes (10 cm, 4 ") under greenhouse conditions at 21 ⁰ D bio 24 C (70 ⁰ P-75 ⁰ P) were used, in each The basket consisted of three plants with a total of six leaves for each test, the test with the chemical substances and the control tests were each carried out in duplicate.Aqueous suspensions of chemioohen subotans were prepared by adding 0.2 g of substance to one drop (0.03 g) a handeleüblichen surfactant dispersions! ttele (Isooetylphenylpolyäthoxyäthanol) and T ml of acetone were added and were then gewaeohen in 200 ml of water, while stirring, to form eu to prepare a dispersion, and then with water eu the gewUaechten concentrations ron 1000 ppm and 200 ppm has been diluted.

Si · plants were using the dispersions of chemical Sub camouflage sprayed at different concentrations, and the control plants were treated with aqueous solutions sprays containing the surfactants and acetone without the chemical substances * The spraying was done carried out in such a way that the upper surfaces of the leaves were very well moistened. The plants were then placed in the Greenhouse brought back to you. The following day (20 - 24 Hours later) rings with a non-toxic adhesive for the organisms to be tested, such as on fly papers and around rings of trees are used around the edges of the upper surfaces of the leaves in order to confine the mites to the upper surface of the leaves. The mites were placed on the leaves treated in this way by strongly interleaving the bean leaflets with white-spotted adult mites Tetranycbus telarius L.

909885 / 17A0

within the edge of the glue on the leaves of the IU-testing plants were infected. You number of the transferred mites was found on the same day. The number ranged from 3Q to 300 kilograms on six sheets. The plants were kept in the greenhouse for a further four days. Sann became the living Mites «that were on the leaves, finally counted. You percent annihilation was using found the following formula:

Destruction - 1Oo / i ~ ^ Fick ¹ ** «» ^Number ! »» End «Mites> U j original number

You extermination of the mites by the substances according to the invention at different concentrations is in shown in the table below (the control treatments with no chemical substances showed approximately £ 20 mortality) *

90 9 8 85/1740

Chemical substance $> destruction at

Propargyl ~ p-tert-o-butylphenoxyiaopropyl sulfite

Propargyl-p-tert-butylphenoxy isopropoxyisopropyl sulfite

Propargyl-p-tert -, ~ butyl phenoxy diisopropoxyieopropyl sulfite

Propargyl-p-tert-amylphenoxyethyl sulfite

Propargyliaodecoxyethyl sulfite

Propargyl "O-" tert -butyl phenoxy ieopropoacyissopropyl sulfite

1- (3 "-Butynyl) -p-tert, -amylphenoxyethyl sulfite

2- (3-butynyl) -p - tert _n -amylphenoxyethyl sulfite

anylphenoxyethyl sulfite 3-hexynyl-p-tert- _n- amy 1- jfeinoxyäthylBulfit

2- (3-butynyl) -o ~ tert, -butyl phenoxyiBopropoxyisopropyl sulfite

1- (2-Butynyl) -p-tert-phenoxyethyleul ti t

1000 ppm 200 ppa 99 99 99 90 100 100 47 25th 100 100 100 96 100 99 100 84 76 30th 100 75 100 99

_Bft D

909885/1740

Active ingredient

Propargyl-p-toloxyisopropyl sulfite

Propargyl-1-p-iBopropylphenoxy-2-butyl sulfite

Propargyl-p-terte-amylphenoxyIbo » propyl sulfite

Propargyl ~ l ~ p ~ tert ₀ -butylphenojcy-2-butyl sulfite

Propargyl-1-p-tert-amylphenoxy-2-buty1eulfite

Propargyl-3-p-terto-butylphenoxy-2-butyl sulfite

Eropargyl-1-p-terto-butylphenoxy-2-amy1buIfi t

Propargyl-o-toloxyiBO " propoxyisopropyl sulfite

Propargyl-p-toloxyieopoxyieopropyl sulfite

ftpopergyl-p-iBopropylphenoxyethoxyethyl sulfite

Propargyl-p-ieopropylphenoxyiBopropoxyieopropyl sulfite

Propargyl-l- (l-p-ieopropylphenoxy-2-butoxy) -2r-butyl sulfite

Propargyl-2-Λβthyl-4-p-tert ο -

butylphenoxyiBopropoxyloopropyl-

eulfite 99

Belaplol 4

The example shows the effectiveness of the chemical substances according to the invention and kills mites, Bean plants (pinto beans) at the two leaf stage in 4 inch baskets under greenhouse conditions

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ψ annihilation at 200 ppm 1000 ppm 78 98 100 100 97 100 77 97 1Q0 100 (M 64 99 100 96

1567ΫΒ9

at 21 <€ when 2A ⁹ C (7O ⁰ P to 75 ⁰ P) were sucked, were used for the experiments. For each test there were two pods with a total of 4 leaves in each basket. These tests were carried out twice «

The untreated sheets were provided with adhesive rings, and 40 to 50 nilbe were placed on each sheet in a manner similar to that in Example 3% .

They were then old aqueous solutions of the plants chemical substances with concentrations of 50 ppm and 20 ppm, prepared as in Example 3, were sprayed so that the upper surfaces of the leaves were well wet.

The plants were then allowed to dry and the mites counted. The plants were kept in the greenhouse for 3 days. Then those left behind on the leaves became living Counted mites. Percent destruction was found using the formula from Example 3.

The destruction of the mites by the invention chemical substances is valid in the table below.

Active ingredient υ Annihilation at

50 ppm 20 DP «

Propargyl-p-tert-butylphenoxyleopropyl sulfite 100 84

Propargyl-p-tert, -butyl-

phenoxyibopropoxyisopropyl

Sulfite 95 87

l- (2-butynyl) -p ~ tert "-butyl-

phenoxyiBopropyl sulfite 87 85

909885/1740 ■ »« «. Times

As shown in the above experiments, the compounds of the invention are special as acaricides useful, especially for the destruction of motile forms of phytophageal planar mites «

Compared to the commercially available material for killing spider mites, namely 4-chlorophenyl-2,4,5-triehlophenyl sulfone, they have the advantages that they also kill mites that are already present on the foliage, while the commercial preparation only prevents them from creeping out prevented by young animals »

The following comparative experiments were carried out with the two-spotted mite Tetranycus telarius Llnne, preparations with the chemicals according to the invention were prepared as an aqueous emulsion by weighing 0.2 g of the active ingredient, adding a drop of emulsifier and 1 ml of acetone as solvent and the goose "in a vessel was washed with 200 ml of water. The vessel was then shaken, an emulsion containing 1000 ppm of the active ingredient being obtained. The comparison substance 4 ^ chlorophenyl-1,2,4 »5-triehlorphenylaulfon was used as a finished commercial ^{preparation (n} Tedlon-25W ⁿ ), and 0.4 g of the 25 #ig active material were suspended in 100 ml of water. These 1000 ppm preparations were then used as basic preparations, aliquots of which were taken and diluted to 100 ppm, 50 ppm and 20 ppm for the test spray with water. Bean plants (pinto beans) at the stage of 2 leaves were used as guest plants The upper surfaces of the primary leaves were put on with a ring of glue, and kilbs were placed on them by very strong

BATH 909885/1740

«22 ^

contaminated leaflets were applied within the adhesive rings one day before spraying. The contaminated Plants were then sprayed with the preparations to be tested, 50 ml being applied within 20 seconds and the spray nozzle about 120 cm (48 ") from the Plants was placed in such a way that the plants were very well moistened on a rotating turntable. The treated plants were then placed in a greenhouse and the first count was taken immediately, and after 1 days the last count was made Surviving mites carried out. Each treatment was carried out with two different pots of the plants, with each pot having two plants and four trial leaves contained. The percentage destruction was calculated “as stated above”. *

The values obtained are shown in the table below specified »

Percentage destruction

the Kilben

100 pp * 50 pp «20 ppm

42 39

100

91

87

98

84

55

85

89

Active ingredient

4-chlorophenyl-2 _f 4 «5-trichlorophenylaulfone

Pro pargyl-p-tert-butylphenoxyisopropyl sulfite

Propargyl-p-tert-amylphenoxy-2-butylsttlfit

1 "(2-butynyl) ~ p-tert-butyl-phenoxyisopropyl sulfite

Propargyl-p-tert * -butylphenoxy " isopropoxyisopropyl sulfite

BATH

909885/1740

From these values it is clear that the reference substance of the trade is much less effective for killing the motile forms of mites than the active ingredient according to the invention.

The chemical compounds according to the invention can be used in various ways for the extermination of insects.They can be applied to places which are to be protected against insects, namely as dusts when they are mixed with powdered solid carriers or adsorbed on them, such as the various mineral silicates, e.g. mica, talc, pvrophillite and clays, or they can be liquids or Sprays can be applied when they are in a liquid carrier, for example in solution in a suitable solvent such as acetone, benzene or kerosene, or egg in a suitable non-terminating medium, see B. water, be dieperglert. For shedding plants (this Expression also includes the parts of the plant), which the Are exposed to attack by insects, the chemical substances according to the invention are preferably in applied aqueous emulsions containing a surface-active dispersant, which can be an anionic, a nonionic or a cationic surface-active agent. These surfactants are known, and reference is made to them U.S. Patent 2,547,724, columns 3 and 4, in which Examples of these are given in one place. You can use substances according to the invention with surface-active substances Dispersants with or without organic solvents as insecticidal concentrates for the following Addition of water to be mixed to aqueous sus-

909885/1740

Pensions of the substances of the desired concentration share out. You chemical substances according to the invention can be old powdered solid carriers, such as Hineralsilioaten, together with a surface-active The pearling agents are mixed so that the powders are wettable can be obtained, which can be applied directly to the sites protecting against insects BU, or which can be poured up with water to create a suspension of the chemical substances (and the powdered solid carrier) in water, which is used in this form «. The inventive chemical Substances can be applied to the sites protecting against insects by the aerosol method. Solutions for the aerosol treatment can be prepared by the former subetans directly la aerosol carrier, which is a liquid under pressure from «* at ordinary temperature (e.g. 2CW) and atmospheric« Pressure an oasis, can be dissolved, or the aerosol solution can the Ohio Subetans first is dissolved in a less volatile solvent and dvaa this solution with the more volatile, liquid one Aerosol carrier is mixed · The chemical substances Can also mix it with carriers who are themselves active are, s.B. other insecticides, fungicides, or bactericides can be used.

909885/1740

Claims (3)

Claims _β sulfite ester of the general formula in which, an alkyl group having 1 bie 12 carbon atoms, a cyclohexyl group, a phenyl group, a naphthyl group, "an alkylphenyl group in which the alkyl group of up to 9 carbon atoms, or has a Cycslohexylphenyl Group, R ^{1 is} an acyclic alkynyl group with 3 to 10 carbon atoms, η 2 to 10 and m 1 to 10. 2. Propargyl-p-tort -butylphenoxyisopropoxyisopropyl sulfite 3. Propargyl-p-tert-butylphenoxydiisopropoxyieopropyl sulfite. \ * Propargyl-p-tert-amylphenoxyethyl sulfite. 9 0 9885 / 17A0 New documents (Art. 7 91 para. 2 No. I sentence 3 of amendment _8ge3 . _V. ^. _M: r 26 τ ο 2 ~ (3-butynyl) ~ p-tert »-atnylphenoxyethyl sulfite 6e 1- (3-butynyl) «- p-tert _e -t) utylphenoxyi8opropoxyisopropyl sulfite 7 · Process for the preparation of mixed sulfite esters of general formula in which R an alkyl, cycloalkyl, alkenyl, haloalkyl ", aryl, alkaryl, cycloalkaryl, haloalkaryl, alkoxyaryl» _B nitroaryl or haloaryl radical, R »an acyclic * alkynyl radical and η 2 to IO and m 1 to 10 iet, characterized in that a glycol monoether of the formula in which R, m and η have the meanings given above, is reacted at a temperature between -5 ° and ⁰ 4-30 C with thionyl chloride and the obtained Chlorsulfinat further in the presence of an HCl acceptor in a solvent * corresponding to the R AJdnylalkohol is implemented at a temperature between -10 ° and 50 * 0 8 «Insecticidal agent, characterized in that it contains a compound of the general formula 0 ) 909885/1740 in which R is an alkyl, cycloalkyl, alkenyl, Halo-alkyl-, aryl-, alkaryl-> Cycloalkaryl, halo * · genalkaryl, alkoxyaryl, nitroaryl or haloarylreat, R «is an alkynyl radical and η 2 bis and a is 1 to 10, all active ingredients » Xneektisldee gown according to claim 8, characterized by core draws attention to the fact that it contains a compound as an active ingredient which is produced by the reaction of a glycol monoether formula been at a temperature between -5 ° and +3 (W with thionyl .; chlorld and receive UmsetEung the obtained ChlorBulfinats in the presence of an HCl acceptor in a solvent with the R * corresponding alkynyl alcohol at a temperature between -10 ° and 50 ⁰ C. · is- 90988 5/174