DE1567130A1 - Herbicidal agents with derivatives of 2,6-dichlorothiobenzamide as active ingredient - Google Patents

Description

DR. ING. F. "WUKSTHOFF DIPL ·. ING. G. PTJI-S DR-B-V-PEOHMAIiIi

8 MtTNGHBN 9

SOHWEI & FIRST HATE 2

22 06 Sl

TELEGBAMMADHESSE i PBOIEOTPATBST

1A-31 311

Description of the patent application

SHELL ΠΓΤΕΒΝΑΤΙΟΙίΑΙιΕ RESEARGH IVIAAT S GHAPPIJ N.V., 30, Garel van Bylandtlaan, Hague, The Netherlands.

concerning

"Herbicidal agents with derivatives of 2,6-dichlorothio-

benzamids as v / irkotoffe "

The invention relates to novel derivatives of 2,6-dichlorothiobenzamide with herbicidal action or to herbicidal compositions which contain these compounds and are suitable for combating weeds.

The derivatives of 2,6-dichlorothiobenzamide according to the invention have the general formula

BAD OBiGlNAt

009830 / 18S4

- 2 - 1A-31 311

wherein R represents an alkyl or Hai ο g enalky! group which preferably 1 Ms contains 6 carbon atoms, and X is a Means alkyl, aryl or alkaryl sulfate or sulfonate ion. Examples of the sulfonate ion are the methanesulfonate ion, the thahsulfonate ion and the benzenesulfonate ion and the toluenesulfonate ion, for example the p-toluenesulfonate ion. Examples of the sulfate ion are methyl sulfate, ethyl sulfate, isopropyl sulfate and the if onyl sulf ation.

If a halogenoalkyl group is represented by R, then is these are preferably a chlorine or bromoalkyl group, e.g. a 2-chloroethyl, 3-bromopropyl or 2-chlorobutyl group.

The compounds of the invention are particularly active as pre-emergence herbicides. The methyl sulfate salt of S-methyl-2, b-dichlorothiobenzimidate combines high herbicidal effectiveness with low toxicity towards warm-blooded animals. Among the inventions _;; It is therefore preferred according to compounds.

The compounds can be used in a manner known per se for herbicides, i.e. they can be used in a mixture be applied with an inert diluent that

BATH

009830/1864

156713C

~ 3 - 1A-31 311

may also contain a surfactant. the The invention therefore comprises a herbicidal preparation which consists of a compound according to the invention and a carrier or a surfactant or both additives. ■

The carrier can be a pesticide, a liquid or be a compressed gas. Examples of suitable solid carriers are clays, silicates, synthetic hydrated ones Silicas, resins, waxes, polymeric synthetics, carbon and sulfur. Examples of liquid carriers are water, alcohols, ketones, aromatic hydrocarbons, chlorinated hydrocarbons and the like Petroleum fractions, such as gas oil (kerosene). Examples of usable Compressed gases are those normally used in aerosols, e.g. trichloromonofluoromethane or dichlorofluoromethane.

The surfactant can be anionic, cationic or non-ionic and can be in the form of an emulsifier, a wetting agent, a dispersing agent or a 'Thickeners are present. Examples of suitable surface-active agents Means include alkylarylsulfonates, alkylii-ulfat.emit more than 10 carbon atoms, alkylphenols

ORIGlNAL BATHROOM

009830 / 18SA '

15-671 3C

4- 1Α-3Ϊ 311 '

£ t ^ lezLOxyd - condensates, sorbitol esters: · of ?,! Fatty acids ,. MfcylanriLIIsulfonate and comaensates from -iLtfi.yI.en.oxyd and 'Feitsäureesternu

. Bie "erfindungsgeiaälßeiK herbicides tönnert vorliegeni as a Benetz cash powder _r a s dust form o> the gramtillerten SübsiiaiEZ ^ einas- concentrate, a solution, a emulgierftareaa. Concentrate, a standard emulsion, a Invertemalsloja or aerosol; they can also be in any garbage can be used as capsules.

Combinations of the compounds according to the invention with each other or with other substances, for example with known pesticides and / or fertilizers are provided.

The active ingredients according to the invention are used in A method of controlling weeds, which consists in looking at the weed in question and / or its Environment applies a compound according to the invention or a herbicide in which such an active ingredient is contained.

O Ο 9 8 3 07 1 8 5 U bad ORiGiNAL

15S7130

- 5 - U-31 311

The compounds according to the invention can be fused with the aid of Clay produced in a process known per se in chemistry be .. For example, they can be produced by one 2,6-Dichlorthiοbenzamid with the appropriate ester an oxygen acid of sulfur (0: x ^ sulfur acid.) τίμιο etzt. According to the invention, the novel connections the general formula

Ί.

produced by reacting 2,6-diehlorthiobenisamide with a compound of the formula RX, wherein R and X the © bige Have meaning * If, for example, Dime.thyläulfait is used with the 2,6-Diehlorthiobenzamiä; um, ώαίι receives the following Link!

NS*

6 - 1A-31 311

The reaction can be carried out in the absence of a reaction medium, but is preferably carried out within

an inert reaction medium which is organic or ang.B. Acetone or water.

may be organic, / In some Pällen gives better yields if the reaction at a higher temperature, suitably to 10O ⁰ G, takes place in the range of 60, for example, "at the reflux temperature of the reaction mixture.

The following examples serve to illustrate the invention in all of its aspects. Parts by weight (G.-T.) and column parts (V.-T ») are in the same ratio to one another like the kilogram to the liter.

example 1

Manufacture of S-methyl-2,6-pichlorothiobenzimidate methyl sulfate.

Eq
% GL " ^fc CH, SO-,

Cl

(1) Without reaction medium

2,6-Mchlorthiobenzamid (20.6 G, -T /) and dimethyl sulfate (12.6 G.-T.) were together for 3 hours at 100 ⁰ C and then

BATH ORIGINAL

009830 / 13S4

- 7 - '1Α ^ ΐ 311

Maintained at room temperature for 16 hours. The mixture was triturated with acetone (50%) and filtered. The desired product (28 parts by weight) with a melting point of 188 - ISg ⁰ G was obtained in a yield of 85%.

(2) With water as the reaction medium

2,6-Dichlorthiobenzamid (20.6 G .- $.), Dimethyl sulfate (12.6. G.-Τ ') and distilled water (80 G.-T.) were stirred "at 80 IDIS 90 ⁰ G "until a solution was formed which was filtered hot. When the filtrate cooled, a solid separated out, which was filtered off, washed with acetone (50 V.T.) and dried. The sought product ^ 18.5 3rd part) ι F. 189-190 ⁰ C, was obtained in 56 $ yield.

(3) With acetone as the reaction medium

2,6-dichlorothiobenzamide (20.6 parts by weight), dimethyl sulfate (1 ^, 6 parts by weight) and acetone (150 parts by weight) were mixed and refluxed for one hour. It different from a white solid which is filtered and first with acetone and then washed with ether "are looking .The product (28 Gc-T.), F. 189-190 ⁰ G, was obtained ° / cent yield in 85.

009830/185

- 8 - 1Α-31 311

Analysis:

For C ₉ H ₁₁ Cl ₂ IIO ₄ S ₂ SC 32.5; H 3.3; N 4.2; S 19.3; 0121, ^ p

Found: C, 32.2; H 3.4? ΪΓ 4.5; S 19.0; $ 0.21.1

Example 2

Production of S-Ätb.yl-2,6-dic3ilortliio "benzimidate-Ätliylsulfat.

SC ₂ H ₅

C ₂ H ₅ SO

2,6-dichlorothiobenzamide. (20 parts by weight), diethyl sulfate (20 parts by weight) and acetone (100 parts by weight) were mixed and refluxed for 12 hours. The acetone was driven off from the reaction mixture and the residue was recrystallized from ethyl acetate. The above product, -F. 149 - 151 ⁰ C.

Arolyse:

Calculated for C ₁₁ H ₁₅ Cl ₂ MO ₄ S ₂ : C 36.7; H 4.2; N 3.9, S 17.8, C1

Found: C 36.5; Ii 4.3; N, 3.9; S 17.8; Cl

BATHROOM OBlQINAL 009830/1854

1A-31 311

Example 3 Production of S-A * thy 1-2,6-dichlorothiobenzimidate methane

sulfonate.

GH., SO,

2,6-Diohlorthiobenzamid (21 G-. -11 ..) and ethyl methanesulfonate (12,5 G-T.) were heated together for 3 hours on the water bath. The mixture was cooled and acetone was added which precipitated a white crystalline material on standing. The pesticide (22 G .- (D.) Was filtered and washed with acetone and then with ether. Yield 66 _for P. 176-178 ° C.

Analysis:

Calculated for G ₁₀ N ₁₅ NO ₅ S ₂ GI ₂ JG 36.4; H 3.9 .; S 19.4; Cl 21.5

Found? C 36.4; H 4.0; S 19.2; Cl 21.5

In the same way, the following compounds were made manufactured j

009830/1864

156713t:

1A-31 311

F. 166 - 168 ⁰ C (68 §S):

Analysis:

Bereclinet for C ₁₆ H ₁₇ NO ₅ S ₂ C1 ₂ : C47.3; E4.2; 10.4; S 15.8; Cl

Found:

047.1; H4.4; * T3.4; S 15.7; Cl 17,

F. 133 - 134 ⁰ C (64 ⁰ Pi.

Analysis:
Calculated for
Found:

: C 49, "; H 4.8; S 14.9; Cl 16, 5 \ C 49.5?; II 4.9; S 14.3; Cl 1½, 3: ■ '<

009S30 / 1864 BAD

15671 SC

11 - 1A-31 311

Example 4 ■

Production of S-n-butyl-2,6-dichlorothiobenzimidate methane

sulfonate.

Cl

. \ CH ₃ SO ₃

SCIl CH CH GH

2,6-DiehlorthiObenzamid (20.6 G.-T.) and butyl methanesulfonate (15.2 G.-T.) were heated for 2 hours at 10O ⁰ C. The mixture was dissolved in acetone (50 V.T.) and left to stand overnight. It separated white crystals a "b, after filtering and washing, the desired product (15 G.-T.), I. 110-112 ⁰ C, yielded Another portion was (8 G.-T.) of the product. obtained when the filtrate is poured into ether (100 V, -TV). Total yield $ 64.

Analysis:

Calculated for C ₁₂ H ₁₇ Cl ₂ WO ₅ S ₂ : C 40-2; H 4.7; 13.9; S17.9; C119.8 %

Found; C 4O.3; H 4.5; F3,9; S17,9; C12O, O $ '

The following connections are made in the same way:

BAÖ OfflGlNAL

0 0 9830/1854

1A-31 311

F. 141 - 143 ⁰ C.

Analysis:

Calculated for C ₁₇ H ₁₉ Cl ₂ NO ₅ S ₂ : C, 48.6; H 4.5; N 3.3; S $ 15.2

Found: C, 48.4; H 4.4; F 3.2; S 15.2 <ji

Example 5

Herste Settin g of S-methyl-2,6-dichlorthiotienzimidat ethanesulphonate.

C ₂ H ₅ SO ₅

2,6-dichlorothiobenzainide (21 parts by weight), methyl ethanesulfonate (12.5 parts by weight) and acetone (150 parts by weight) were refluxed together for 20 hours. The reaction mixture was then cooled, whereby white crystals separated out, which were filtered and washed with acetone and then with ether. Yield 17 G.-T., F. 174-176 ⁰ C.

"BAD OKlGMAL

0 9 8 3 0/1854

1567 "1 3 O

1A-31 311

Analysis:
Calculated for Found: ₅ S ₂ : C3b, 4; H3.9; 3 \ T4.2; S19.4; C1 21.5 C36.4; H4, Q; H4.2; S1 9.2; C1 21, 7th

In the same way the following expression was made manufactured: .

P. 178 - 180 ⁰ C.

Analysis :, Calculated for C found:

₂ : C44.4; H3.4; N3.7; S 16.9;, C1 18.8 ^ C44.3iH3.4; K3.7iS 17.2; Cl 19.0 ⁰ A

Example 6 Preparation of S-n-Bropyl-2, b-dichlorothiobenzimidate-p-'Eoluo.l

sulfonate.

SCH ₂ CH ₂ CH ₅

BATH ORIGINAL

0098 30/186

-H-

1A-31 311

2,6-Diehlorthiobenzamid (12 parts by weight) and n-propyl-p-toluenesulfonate (22 parts by weight) were heated together for 3 hours on the water bath, the reaction mixture was cooled and washed with ither. It resulted in a sticky solid. A small amount of acetone was then added, whereupon a white solid separated out, which was filtered off and washed with acetone. Yield 15 G -.- TF 141-143 ⁰ C.

Analysis:
Calculated for foundj

₂ : C 48.0 j H 4.5; 3 15.2j Cl 16.9 C 48.7; H 4.7? S 14.9; -Cl 1ο, 9

The following connection is made in the same way
manufactured:

F. 129 - 131 ⁰ C.

Analysisj
Calculated for found »

CH, .-

CH ₂ GH ₂ GH ₂ Cl

SC-,

₅ S ₂ : C 44.9? II 3.9; S 14, Ij Cl 23.4 C 4b >> 2j H 4.2; S 14.2; Gl 2? _t y

009830 / t854

BAD ORiCHNAL

156713

1A-31 311

Example 7 * Production of S-methyl-2,6-dichloro-benzimidate-p-toluene-

sulfonate.

2,6-Dichlorthio'benzamide (20 -Gr ..- !.) > Methyl p-toluenesulfonate (18 parts by weight) and acetone (100 parts by weight) became common Refluxed for 6 hours. The reaction mixture was then left to stand at room temperature for 16 hours Product, mp 161-163 ° C, crystallized from the Solution. Yield 12 parts by weight

Analysis;

Calculated for 'C ₁₅ H ₁₅ Cl ₂ IO ₃ S ₂ JC 45.9; H 5.8; S 16.3; Cl 18.1 ° / o

Found: C, 45.6; H 3.7; S 16.6; Cl $ 18.0

Example 8 Production of S- (2-chloroethyl) -2,6-dichlorothiobenzimidate

-p-toluenesulfonate.

0098 30 / 18B4

- 16 - 1Δ-31 311

2,6-dichlorothiobenzamide (21 parts by weight) and 2-chloroethyl p-toluenesulfonate (23.5 parts by weight) were heated on the water bath for 6 hours. The reaction mixture was cooled and ether added. A small proportion of solid separated out and was filtered off. When the piltrate stood overnight, yellow crystals separated out, which were filtered off, combined with the first portion and washed with acetone. Yield 6 parts by weight, i ¹ . 154 - 156 ⁰ C.

Analysis:

Calculated for C ₁₆ H ₁₆ Cl ₅ O ₅ NS ₂ : C, 43.6; H 3.6; Cl 24.2 io

Found: C, 43.8; H 3.9; Cl 24.5 tf

Example 9 Production of an emulsifiable concentrate.

An emulsifiable concentrate was made by mixing the following ingredients:

S-methyl-2,6-dichlorothiobenzimidiate

Methyl sulfate

(Example 1) 20.2 <f ° G.-T./V.-T.

Surface active agent

(Tensiofix D 120) 5.0 # G.-T./V.-T,

Carrier (N-Methy! Pyrrolidon) · to 100 V.-T.

009830/1854 BAD OfiiGiNAL

- 17 - ΪΑ-31 311

(Tensiofix D 120 is a commercially available surface-active Medium and consists of an alkylaryl polyether alcohol).

Example 10 Manufacture of a wettable powder.

A usable powder was made by mixing the following ingredients:

S-methyl-2,6-dichlorothiobenzimidate

Methyl sulfate 50.5 % w / v

Surface active agent

ITonipol CS 50 ⁺ 9.5 % G.-T./V.-T,

Aerosol Oil / B ⁺⁺ · 0.5 $ G.-T./V.-T.

Carrier (clay GTY) ⁺⁺⁺ 39.5 f ° G.-T./V.-T.

IJonipol CS 50 is a water-soluble, non-ionic surface-active agent (polyethylene glycol ether).

⁺⁺ Aerosol OT / B is a surface-active and wetting agent made from liatrium dioctyl sulfosuccinate.

⁺⁺⁺ TOn GTY is a kaolinite china clay.

BATH ORIGINAL

9830/1864

- 18 - 1A-31 311

Example 11 Testing of herbicidal effectiveness.

The compounds according to the invention are essentially herbicides which are given before the seeds emerge and their degree of effectiveness was determined by the following method:

In sterile compost soil (John Innes compost) were sown the following seeds: oats, ryegrass, sweet corn, peas, sugar beet, flax and mustard. Was used to spray the floor the following preparation used, whereby the sprayed amount corresponded to a volume of 56 l / ha:

Acetone 40 vol. - ^

Water 60 vol .-;>

Surface active agent

(Triton X-155) 0.5 wt .- ^

Active ingredient varying amounts

(Triton X-155 is a commercially available surfactant. Agents made from alkylaryl polyether alcohol). Comparison attempts were also carried out.

ORIGlNAL BATHROOM

00983071854

1A-31 311

After 12 days, the phytotoxic effect of the compound in question was determined by determining the decrease in the fresh weight of the stems and leaves of the emerged plants compared to the control plants, and drawing up a regression curve in which the obstruction to wakefulness was plotted against the dosage of the compound used . The growth to a disability of 90 fo necessary dosage (ie that smenge weight of the compound, wherein a reduction in Prischgewicht the leaves and stems of the plants of 90 ° was achieved Ό /) is given in the table below in kg / ha *

Tabel

S-R

Dose for $ 90> - growth retardation in kg / ha

M = corn; H = oats, RG = grass; E = pea, L = flax; S = mustard; ZR = sugar beet

β- -, ■ ■;. -; ■ X 2 M - H <ο RG 6th E. ■ L. S. 78 ZR CH ₅ SO ₄ 2 , 24 <Q45 <ο , 45 5 , 94 1 , 0 0, 12th <0.45 Γ'ΙΤ ' SO ₅ G ₂ H ₅ , 0 iOA5 , 45 , 6 0 , 67 1, <0.45

<0.45 4.93 1.23 1.12 0. -56

BAD ORfGJM _AL

009830 / 18B U

1A-31511

Table - continued

Cl GD

SR dose for 90 ° ß> stunted growth in kg / ha

M = corn; H = oats, RG = Ray £ ras; E = pea, I = linen; S = mustard; ZR = sugar beet

MH RG E IS ZR

2.58 <0.45 0.9 5.8 0.78 1.68 0.67

C ₂ H ₅ CH ₅ SO ₅ 3 , 5 ίο , 45 <Ο , 45 4th , 4 0, 56 1, 12 0, 56 C ₂ H ₅ C ₂ H ₅ SO ₄ CVJ , 2 , 45 <Ο , 45 7th , 0 · <ο, 45 0, 5640, 45

C ₂ H ₅

2.13 <0.45 <0.45 4.0 0.67 2.0 40.45

CH ₂ CH ₂ Cl

3.25 <0.45 0.67 8.4 1.0 2.0 0.67

C ₅ H ₇

3.6 <0.45 * 0.45 7.6 O ', 9 1.12 <0.45

CH ₂ CH ₂ CH ₂ Cl

3.6 <0.45 0.56 4.7 0.9 <0.45 <0.45

η [^ ₁ SQ CH

■ ■ - ^ j

BAD Of? IG! NAL

0098 3 0/185 /;

Table ~ Port setting

RX

M H RG E Ϊ S ZR

O ₄ H ₉ SO ₃ GH ₃ 1.45 <0.45 <0.45 6.3 1.57 1.23 0.67

1.45 <0.45 <0.45 8.3 1.23 1.34 <0.45

1.57 <0.45 <0.45 5.7 <0.45 0.67 <0.45

Patent claims ι

ORIGINAL INSPECTED

30/186

Claims (4)

. G. Pulse .·. 4 ir> ανν 22 / Λ _ - 22 - / Λ ^. . .. 1Α-31 311 MUNICH β - ■ '■' "a r Cj Λ patent claims 1. Herbicidal agents, characterized by a content of a compound of the general formula where R stands for an alkyl or Iialogenalkylgruppe and X stands for an alkyl, aryl or alkaryl sulfate odex »-sulfonation 3" tlvt ;, as an active ingredient. 2. Herbicidal agents according to claim 1, characterized by a content of a compound according to the above general formula, wherein E is an alkyl or Halogenalkyl group with 1 to 6 carbon atoms stands as an active ingredient. 3. Herbicidal agents according to claim 1 or 2, characterized by a content of a compound of the above general formula, in which R stands for a chloro or bromoalkyl group, as active ingredient. BATH ORIGINAL 009830/1864 - 25 -. 1A-31 311 4.. Herbicidal agents according to one of the claims 1 Ms 3> geke η n ζ ei c.1l ^; ii et by a content of one or more of the following compounds as active ingredient; S-methyl-2, e-diclilortliioljenzimidat-Methy! Sulfate, S-Hethyl-2, ö-Dichlortiiiolaenzimidat-Äthansulfonat, S-methyl-2, b-diclilortliiolaenzimidat-Benzolsulfonat, S-methyl-Sje-dicBlorthiobenzimidat-p-Toluenesulfonat, S-iithyl-2, G-diciilorthiol-deiizimidate-methanesulfonate, S-ethyl-2, o-dicKLortniolDenzimidat-ethyl sulfate, S-I thyl-2, ö-dichlorotliiobenzimidate-p-toluenesulfonate, S- (2-chloroethyl) -2,6-dichlorothiol-benzimidate-p-toluene-sulfonate, S- (n-Propyi) -2,6-äiclilGrthio'benzimidat-p-Toluenesulfonat, S- (3-chloropropyl) -2,6-dichlorothio "benzimidate-p-toluene sulfonate, S- (n-Butyl) -2, b-diciilortliioTaenzimidat-Methanesulfonat, S- (n-butyl) -2,6-diehlorthio'benzimidate benzenesulfonate, S- (n-B.utyl) -2, o-dichlorothiobenziiniaate-p-toluenesulfonate. SAD ORIGINAL 0098 30/185 4