DE2154443A1 - Phosphorylated 1,2,4-thiadiazole derivatives, processes for their preparation and their use as pesticide agents - Google Patents

Description

DR. ING. F. "WUKSTHOFF DR.E.v.I »ECHMAN2f DR. ING. D. BEHHEXS DIPI..I1CG. R. GOETZ PATElTTAITWJtI ₁ TE

8 MUNICH 9O

SCHWBIOERST BREED 3 TELEPHONE (0811) S 24 OTO

FHOTECTPATESTT MUJfCHSK

1A-40 355

Description of the patent application

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ N.V. Carel van Bylandtlaan 30, The Hague, Netherlands

concerning

Phosphorylated 1,2,4-thiadiazole derivatives, method too their manufacture and their use as pesticides

' Middle

The invention relates to new phosphorylated 1,2,4-thiadiazole derivatives, the method of manufacture and pesticidal agents containing these compounds.

The invention relates to phosphorylated 1,2,4-thiadiazole derivatives of the general formula

₁ O Ϊ

S-A-Z

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each a _t optionally substituted in the alkyl group R. and Rp a j A by alkyl or aryl groups, alkylene group; and Z denotes an optionally substituted 1,2,4-thiadiazole ring which is bonded to group A in the 3- or 5-position. Examples of suitable substituents on the thiadiazole ring are halogen atoms, alkyl, alkoxy, alkylthio, dialkylamino and aryl groups.

Preferred phosphorylated 1,2,4-thiadiazole derivatives are those of Formula I in which R ^ and Rp, respectively represent an alkyl group having 1 to 6 carbon atoms such as a methyl or ethyl group; A is an alkylene group with 1 to 6 carbon atoms, preferably a methylene group means which are optionally substituted by alkyl groups having 1 to 6 carbon atoms or by phenyl groups is, for example, a methylene, ethylidene or benzylidene group; and Z is a 1,2,4-thiadiazole ring, which is bonded to group A in the 3- or 5-position and which is optionally by chlorine atoms, alkyl, alkoxy or Alkylthio groups of 1 to 6 carbon atoms, e.g. Methyl, ethyl, methoxy or methylthio groups Dialkylamino groups with up to 12 carbon atoms, e.g. substituted by diethylamino or phenyl groups is.

A particularly preferred compound is

3-dimethoxyphosphinothioylthiomethyl-1,2,4-thiadiazole.

The phosphorylated 1,2,4-thiadiazole derivatives of Formula I are prepared by a process in which a 1,2,4-thiadiazole derivative of the general formula

Shark - A - Z II

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in the Hal a halogen atom, preferably a chlorine or Bromaton ^ means with an alkali salt, conveniently a sodium or potassium salt, a dithiophosphoric acid derivative the formula:

R ₁ O g

ρ P - SH

R ₂ CT

implements. The reaction is preferably carried out in an organic solvent, conveniently a ketone such as acetone or Methyl isobutyl ketone carried out.

The phosphorylated 1,2,4-thiadiazole derivatives according to the invention are interesting as pesticides and show efficacy against a wide variety of Insects and spiders. The invention therefore also relates to pesticidal agents containing a carrier and / or a surfactant and, as the active ingredient, at least one phosphorylated 1,2,4-thiadiazole derivative according to the invention. The invention also relates to a method for combating insect and / or spider pests, where a pesticidally effective amount of an inventive phosphorylated 1,2,4-thiadiazole derivative applies.

The term "carrier" as used herein means a material that can be inorganic or organic and synthetic or natural with which the active Compound mixed or prepared to apply it to plants, seeds, the soil or others

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objects to be treated or their storage, transport or handling. The carrier can be a Be solid or a liquid. Each usually used in the preparation of pesticides, herbicides, or fungicides The material used can also be used here as a carrier.

Suitable solid supports are natural and synthetic clays and silicates, for example natural silicon oxides such as diatomaceous earth; Magnesium silicates, for example talc; Magnesium aluminum silicates such as attapulgites and vermiculites; Aluminum silicates such as kaolinites, montmorillonites and mica; Calcium carbonates; Calcium sulfate; synthetic hydrated silicas and synthetic calcium or aluminum silicates; Elements such as; B. carbon and sulfur; natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrofoam polymers and copolymers; solid polychlorophenols; Bitumina; Waxes such as beeswax, läraffin wax and chlorinated mineral waxes, as well as solid fertilizers such as superphosphate.

Examples of suitable liquid carriers are water, Alcohols such as isopropanol; Glycols; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether; aromatic hydrocarbons such as benzene, toluene and xylene; Petroleum fractions such as kerosene; light mineral oils; chlorinated hydrocarbons such as e.g. carbon tetrachloride, perchlorethylene, trichlorethylene, orethane, as well as liquefied normally gaseous compounds. Mixtures of different liquids are also common suitable.

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The surfactant can be an emulsifier or a dispersing or wetting agent; it can be nonionic or ionic. Any surface active agent normally used in the preparation of pesticides, herbicides or fungicides can also be used here. Examples of suitable surface-active agents are sodium or calcium salts of polyacrylic acids and lignosulfonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; Fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; Condensates of these compounds with ethylene oxide and / or propylene oxide; Condensation products of fatty alcohols or alkylphenols, for example p-octylphenol or p-octyl cresol with ethylene oxide and / or propylene oxide; Sulfates or sulfonates of these condensation products; Alkali or alkaline earth salts, preferably sodium salts _; of sulfuric or sulfonic acid esters containing at least 10 carbon atoms in the molecule, e.g. sodium lauryl sulfate, sodium sec-alkyl sulfate, sodium salts of sulfonated! Castor oil and sodium alkylarylsulfonates such as sodium dodecylbenzene sulfonate and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The agents according to the invention can be prepared as wettable powders, dusts, granulates, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually composed so that they 25, 50 or 75 wt .-% of active ingredient and usually in addition to solid carrier, 3 to 10 parts by weight of a dispersing agent A ⁰ and, if necessary, 0 to 10 wt .-% of stabilizer ( en) and / or other additives

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such as containing penetrants or tackifiers «Dusts are normally produced as a dust concentrate with a similar composition to that of the wettable powders but without dispersants. Field diluted with other solid carriers to obtain an agent which normally contains 1/2 to 10% by weight of active ingredient. Granules are usually prepared so that they have a size 152 mm from 1.676 to 0 _s and may be prepared by Agglomeration or impregnation techniques. Granules normally contain 1 to 25% by weight of active ingredient and 0 to 10% by weight of additives such as stabilizers, modifiers for slow release of the active ingredient and binders. Emulsifiable concentrates normally contain, in addition to the solvent and, if necessary, a second solvent, 10 to 50 % (w / v) active ingredient, 2 to 20 % (w / v) emulsifiers and 0 to 20 % (w / v). ) suitable additives such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are so composed that a stable, non-settling, flowable product is obtained and normally contain 10 to 75% by weight of active ingredient, 0 to 5 % of dispersing agent and 0.1 to 10 % by weight of suspending agent such as protective colloids and thixotropic agents, 0 to 10 wt .-% of suitable additives such as antifoams _$ corrosion inhibitors, stabilizers, penetrants and tackifier, and as carrier, water or an organic liquid in which the active ingredient is substantially insoluble. Certain organic solids or inorganic salts can be dissolved in the carrier to prevent sedimentation or as antifreeze agents for water.

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The invention also relates to aqueous dispersions and emulsions, e.g. agents, 'obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention can be obtained with water. These Emulsions can be in the form of a water-in-oil or an oil-in-water emulsion and can be thick Have a mayonnaise-like consistency.

The agents according to the invention can also contain other ingredients, e.g. other compounds with pesticides, contain herbicidal or fungicidal properties.

The invention is illustrated in more detail by the following examples, in which the NMR spectra of the compounds measured in deuterochloroform solution and the position of the bands is given in ppm based on tetramethylsilane.

example 1

S-methyl ^ -dimethoxyphosphinothioylthicmethyl-i, 2,4-thiadiazole

0.9 g of 3-bromomethyl-5-methyl-1,2,4-thiadiazole was dissolved in 25 ml of dry methyl isobutyl ketone. To the solution were 1.4 g Kaliumdimethyldithiophosphat added and the mixture stirred for 7 h at 50 to 60 ⁰ C. The solvent was then removed under reduced pressure and a 2N sodium hydroxide solution was added to the residue. The alkaline mixture was extracted with ether and the ether extracts dried over anhydrous magnesium sulfate and evaporated. The residue was chromatographed over silica gel with chloroform as the eluent to give the desired product as an oil.

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Nuclear Magnetic Resonance Spectrum 2.81 ppm, singlet (CH ₃ ); 3.78 ppm doublet (OCH ₃ ); 4.28 ppm, singlet (CH ₂ ).

analysis

Calculated for Found

; C 26.7; H 4.1;

N 10.4%; C 26.3; H 4.2;

N 10.1%

Example 2

3-dimethoxyphosphinothioylthiomethyl-i, 2,4-thiadiazole

1.0 g of 3-chloromethyl-1,2,4-thiadiazole, 1.33 g of sodium dimethyldithiophosphate and 0.12 g of potassium iodide in 25 ml of dry acetone were added together for 24 h stirred at room temperature. The mixture was then poured into 100 ml of dilute sodium hydroxide solution and washed with Ether extracted. The ether extracts were dried and the solvent removed under reduced pressure. Of the The residue was chromatographed over silica gel with 5% acetone in petroleum ether as the eluent, the desired product received as an oil.

Nuclear Magnetic Resonance Spectrum 3.74 ppm, doublet (OCH ₃ ); 4.18 doublet (CH ₂ ); 9.70 ppm, singlet (Ring-H).

analysis

Calculated for Found

C 23.5; H 3.5; N 10.9% C 23.8; H 3.4; N 10.8%

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Example 3

Corresponding to those given in Examples 1 and 2 Further compounds were produced, their physical properties and analytical values in the procedure Table 1 below.

Table 1 ;

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Table 1

Compound NMR Spectrum (ppm)

analysis

5-dimethoxy> phosphinothioylthiomethyl-3-methyl-1,2,4-thiadiazole

2.66 singlet (CH,) Ber..for

3.80 doublet (OCH ,?

4.45 singlet (CH ₀ ) Found

rH. ,,

PN ₀ S 1 O ₀ : C, 26.7; H 4.1; ^ ⁵ ^ N 10.4; P 11.5%: C 28.4; H 4.4; N 10.2; P 10.6%

3- (1- (Dirnethoxypho sphinothioylthio) ethyl) -5-ethyl-1,2,4-thiadiazole

1.49 triplet (CH, CH _O ) calc. For 1.83 doublet (CH ^ CH) ^ oil 3.13 quadrupled? (CH ₀ ) found 3.75 doublet (OCH,) * 3.80 doublet (OCIK) 4.64 wide multiplet (CH)

, S ₃ O ₂

: C, 32.2; H 5.1;

N 9.4%

C 34.4; H 5.3;

N 9.4%

-α 5-chloro-3-dimethoxyphosphino- 01 3 , 77 Doublet (OCH- Calculated for C ₁ -H ₈ PN ₀ S, Found 0 Cl: C 20.7 ; H 2 ,8th; -λ thioylthiomethyl-1,2,4- 4th , 18 Doublet (CH ₀ , DO c. O ² N 9.6; P 10 .6% 0ΐ thiadiazole : C 22.2 ; H 3 , 0; N 9.1; P 9, 7;% ' )

3-diethoxyphosphinothioylmethyl-1,2,4-thiadiazole Oil 1.36 triplet

(OCH ₂ CH ₃ )
4.2 double

plett (OCH ₀ CH,)
9.75 SinguletF "^ ^

(Ring H)

For
Found

C 29.6; H 4.6; N 9.8; P 10.9% C 30.6; H 4.5; N 9.7; P 10.7%

3-pimethoxyphosphinothioyl-thio-

thiomethyl-5-niethoxy-1 »2,4-thiadazole oil

3.80 doublet

((CH, 0) _o P)
4.10 DUbIeVtT (CH ₂ ) Found
4.19 singlet (ring

OCH,)

For CiH ^ EN ₉ SO,

; C 25.2; H 3.8; ^ _{N 9j8} . ρ _10, 8% ( "

ι C 25.2; H 3.7; j>. N 9.5; P 10.8% 4>.

CO

Table 1 (continued)

link

NMR spectrum (ppm)

analysis

5- (1- (Dimethoxypho sphlnothioylthlo) ethyl) -3-methyl-1,2,4-thiadiazole

1.86 doublet (CH ₃ CH) 2.66 singlet "TRing oil. CH,)

3.78 Dusslet (OCH,) 4.8 double quadruple

For
Found

C 29.6; H4.6; N 9.9%

C 30.9; H 4.8; N 10.096

3- (φ- (dimethoxylphosphinothioylthio) benzyl) -1,2,4-thiadiazole

3.57 doublet (OCH,) 3.51 doublet (OCH ^) oil 5.78 doublet (SCH?

7.1-7.4T complex multi-7.4-7:, 7} plets (C ₆ H ₅ ) 9.7 singlet (RiHg ^ H)

Calculated for CL ₁ H ₁ , PN ₉ S, O
Found

C 39.8; H 3.9; N 8.4%

C 40.2; H 4.2;

N 8.5%

3-diethoxyphosphinothioylthiomethyl-5-methoxy-1,2,4-thiadiazole

1.32 doublet triplet

Oil 4.0-4, ^ + complex multiplet (CH ₃ CH ₂ , CH ₃ O, SCH ₂ )

For CoH.
ö 1

Found

PN ₉ S, 0,: C, 30.6; H
d $ 5 ₆

: C, 30.7; H 4.8; N 8.4%

5- (j & - (Dimethoxyphosphinothioylthio) -benzyl) -3-methyl 1,2,4-thiadiazole

2.67 singlet (CH,) 3.72 double doublet oil (CH, O)

5.85 Dubiett (CH) 7.2-7.6 complex multiplet (C ₆ H ₅ I

For C.
Found

: C 41.6; H 4.3; _{N 8j1} . ρ _{9) 0} %

: C, 43.0; H 4.2; N 8.0; P 8.3%

Table 1 (continued)

Verb induing

NMR spectrum (ppm) analysis

S-diethylamino-O-diniethoxyphosphinothioylthiomethyl-

1,2,4-thiadiazole

1.25 triplet (CH, CH ₂ ) 3.48 quadruplet

(CH ₃ CH ₂ )

. 3.78 dowels "(CHUO

4.02 doublet (CH | S

Ber.für C _q H _iq PN, S, 0 _9: C, 33.0; H 5.5;

^{S1S 5i} > N 12.8; P 9.5%

Found: C, 34.1; H 5.6;

N 12.5; P 9.1%

NJ O CO

5-dimethoxyphosphinothioyl- "thiomethyl-3-phenyl-1,2,4-thiadiazole oil

3.80 doublet (CH, O) 4.53 doublet (CHg) 7.46) complex mufti-8.26 jplets (C ₆ H ₅ ) calc _{. For C 1.} , H ₁ , PN ₉ S ^ O ₉ : C 39.8; H 3.9;

'' ^{ ° * -> * N 8.4% Found: C 39.9; H 4.3;

N 8.1%

3-dimethoxy-phosphinothioylthiomethyl-5-phenyl-1,2,4-thiadiazole

3.80 doublet (CH ^ O) 4.36 doublet (CH2) oil 7.507 complex multi-7.95 jplets (C ₆ H ₅ ) calc. For C Found

C 39.8; H 3.9; _4ό

C 40.2; H 4.0; N 8.2%

3-dimethoxyphosphinothioyl-

thio ~ methyl-5-methylthio-

1,2,4-thiadiazole oil

2.74 singlet (SCH,) 3.80 doublet (CH 1 O) ^-3 4.24 doublet (CH ₁ ) Calculated for C 1 -C H 1, PN ₅ S 1 O ₅ : C 23.8; H 3.6;

^b11 ^^ N 9.3% Found: C 24.2; H 3.9;

N 9.4%

5- (1 - (damn thoxyphosphino thioylthio) ethyl) -3-ethyl-1,2,4-thiadiazole oil

1.34 triplet 1.83 doublet (ClH 2.92 quadruple P

(CH _x CH ₉ ) 3.74 DubieTt (OCH,) 4.70 multiplet °

(CHCH ₃ ) Calc. For Found

\ C 32.2; H 5.1;

N 9.4% C 32.4; H 5

N 9.3%

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Example 4

Insecticidal effectiveness

The insecticidal activity of the compounds according to the invention was examined as follows: ■

I. An acetone solution of 1.0 wt -.% Of the test compound was prepared and mounted in a micrometer syringe. Two to three day old adult female close-up flies (Musca domestica) were anesthetized with carbon dioxide and a 1 / ul drop of the solution to be examined was brushed onto the ventral side of each fly. 20 flies were treated in this way. The treated flies were placed in glass containers for 24 hours each containing a small amount of granulated sugar as food for the flies and the percentage of dead or moribund flies recorded.

II. Amount of 0.1 ml of a solution of 0.1

the compound to be investigated in acetone was mixed with 100 ml of water in a beaker. 20 five to six Day-old mosquito larvae (Aedes aegypti) in the fourth stage of development were placed in the beakers and left standing for 24 hours. The percentage of dead and moribund larvae was noted.

III. The compounds were prepared as solutions or suspensions in water containing 20% by weight Acetone and 0.05 wt. Triton X 100 prepared as a wetting agent. The preparations contained 0.2% by weight of the compound to be investigated. Turnips and broad beans, each trimmed back to a leaf, were on the underside of the leaf sprayed with the above preparation.

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The spraying was carried out with a spray device, which emitted 450 l / ha (40 gallons per acre) with the plants resting on a sliver under the sprayer moved through. Ten 8-day-old cabbage moth larvae (ELutella maculipennis) in the fourth stage of development or ten adult 1 to 2 week old mustard beetles (Phaedon cochleariae) were placed on the sprayed leaves of each turnip and ten aptere 6-day-old lice (ifegoura viciae) on the sprayed leaves of every drink Bean plant put on. The plants were enclosed in glass cylinders with a Cotton cap were provided. Mortality was determined after 24 hours.

IV, When compared to the studies of effectiveness Glass house spider mites (Tetranychus urticae) were cut into disks from leaves of green bean plants and in the under III. sprayed manner described. One hour after the spraying, the disks with ten adults became Inoculates mites. Mortality was determined 24 hours after inoculation.

ψ V. In the tests on larvae of white butterflies (Pieris brassicae), disks were made

Cabbage leaves cut and on the under III. sprayed manner described. Ten larvae, 8 to 10 days old in the third stage of development were placed in double Petri dishes placed on the panes. Mortality was determined 24 hours after putting on.

The results of these tests are given in Tables 2 and 3 where A complete kill, B is a part ^{we see} ifbtötung and C no kill of the test

means used insects.

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I «

Tabel

(BD) ₂ P

-S-

link X ^; '; Y. M. domestic " A. aegypti P. cochlearia " Insecticides effectiveness H. vicia " T_j.
uTvfcicae R. H P. maculipennif P. brassicae CH ₃ CH ₃ C ₂ H ₅ A. A. A. A. A. H Cl. B. A. A. B. A. A. A. CH ₃ H H- C. C. B. B. - • A A. CH ₃ H H A. A. A. B. - A. A. C ₂ H ₅
I. H OCH ₃ . A. B. A. A. A. A. A. i CK ₃ ^C 6 ^H 5 H A. A. C. B. - A. A. I CH ₃ H OCH ₃ A. A. A. B. A. A. A. "2 ^H 5 H N (C ₂ H ₅ ) ₂ A. A. B. A. A. A. A. CH ₃ H ^C 6 ^H 5 C. B. A. B. - A. A. CH ₃ H SCH ₃ C. C. C. A. A. "A. A · CH ₃ C. B. A. C. - A. A. C. - ■

Table 5

σ link -3 X H Y M. domestica A. aegypti Insecticidal effectiveness P. maculipetinis P. brassicae M. viciae T. urticafc CU
QO
NJ R. CH ₃ CH ₃ P. cochleariae cn, ^C 6 ^H 5 CH ₃ B. A. A. A. A. A. CH ₃ H CH ₃ C. B. A. A. A. A. A. η- '
f-3 CH ₃ ^C 6 ^H 5 B. A. A. A. A. A. A. • U
f'3 ^C 2 ^B 5, C. "A - A. C. - A. B. , B. C. A. A. A. A. A. A.

Claims (11)

Claims 1. Phosphorylated 1,2,4-thiadiazole derivatives of the general formula R ₂ O -S-A-Z in which R ^ and Rp each represent an alkyl group; A one, if applicable alkyl- or aryl-substituted, alkylene groupj and Z denotes an optionally substituted 1,2,4-thiadiazole ring which is bonded to group A in the 3- or 5-position is. 2. Compounds according to claim 1, characterized in that R. and Rp each represent an alkyl group having 1 to 6 carbon atoms; A is an alkylene group having 1 to 6 carbon atoms, optionally substituted by alkyl groups is substituted by 1 to 6 carbon atoms or phenyl groups; and Z is a 1,2,4-thiadiazole ring which is bonded to group A in the 3- or 5-position and optionally by chlorine atoms, by alkyl, alkoxy or alkylthio groups having 1 to 6 carbon atoms Dxalkylamino groups with up to 12 carbon atoms or phenyl groups can be substituted. - 18 - 209820/1154 215U43 - 18 - 1A-40 355 3. Compounds according to claim 2, characterized in that A is a methylene group which is optionally substituted by alkyl groups having 1 to 6 carbon atoms; and Z is a 1,2,4-thiadiazole ring which is connected to A in the 3- or 5-position and optionally with chlorine atoms or alkyl or alkoxy groups 1 to 6 carbon atoms can be substituted. 4. Compounds according to claim 2, characterized in that R ^ and R _{2 represent} a methyl or ethyl group; and A is a methylene, ethylidene or benzylidene group; and Z denotes a 1,2,4-thiadiazole ring which is connected to A via the 3- or 5-position and can optionally be substituted by chlorine atoms, methyl, ethyl, methoxy, methylthio, diethylamino or phenyl groups. 5. 3-Dimethoxy-phosphinothioylthiomethyl-i, 2,4-thiadiazole, 6. A method for the preparation of compounds according to claim 1, characterized in that a 1,2,4-thiadiazole derivative of the general formula Shark - A - Z in which Hai means a halogen atom with an alkali salt of a dithiophosphoric acid derivative of the formula S R ö " ^> P - SH R ₂ CT implements. - 19 - 209820/1154 - 19 - 1A-40 355 7. The method according to claim 6, characterized in that one starts from a connection in the shark a (word or bromine atom means. 8. The method according to claim 6 or 7, characterized in that one is used as the alkali metal salt Sodium or potassium salt used. 9. The method according to claim 6 to 8, characterized in that the reaction in one organic solvents. 10. The method according to claim 9 , characterized in that the organic solvent used is a ketone, especially acetone or methyl isobutyl ketone. 11. Pesticide compositions containing a carrier and / or a surface-active agent and as an active ingredient at least one of the compounds according to claims 1 to 5. 6285 209820/115