DE2136494A1 - New thiol carbamic acid esters and processes for their preparation and their use as herbicides and acaricides - Google Patents

Description

New thiol carbamic acid esters and processes for their preparation and their use as herbicides and acaricides

The present invention relates to new thiol carbamic acid esters, a process for their preparation and their use as herbicides and acaricides.

So far, to combat the chicken millet, an in Rice fields occurring weeds, used pentachlorophenol. This connection is not only great, however Irritant effect on the human mucous membranes, and difficult to use, but also extremely toxic to Fishes. The time and range for the application of this compound are therefore limited. To combat Marsh rushes, a weed that occurs at the same time as barnyardgrass, becomes 2-methyl-4-chlorophenoxyacetic acid but it is not very effective for this purpose.

The compounds of the present invention are thiol carbamic acid esters the general formula

78 -1-

109B .8-671 977

ι-ι V

wherein R is hydrogen or methyl, η 1 or 2 and

X is hydrogen, halogen, lower alkyl or lower alkoxy and the radicals X are identical or different

can be when η is 2.

The or each radical X is preferably hydrogen, chlorine, bromine, methyl, ethyl, isopropyl, methoxy or isopropoxy. These new compounds have proven to be excellent herbicides and are particularly well suited for the Control of barnacles, rushes and broad-leaved weeds.

The present invention also relates to a process for the preparation of compounds of the general formula (I), where (a) a benzyl mercaptan of the general formula

(II)

wherein M is hydrogen, ammonium or a metal equivalent

means with a methylpiperidinocarbamoyl halide

the general formula

H / V ^CH q

HaI-CN H Λ ^ö (III)

Hal a halogen * preferably chlorine, means in reaction

is brought, or (b)

Nit 78 -2-

109886/1977

a benzyl thiocarbonyl halide of the general formula

. R 0

/ \ cH-SC-Hal (IV) X _n

Hal is a halogen, preferably chlorine, with a methylpiperidine of the general formula

HN WJ

CH,

(V)

the

is reacted, or (c) a benzyl halide 'general formula

(VI)

Shark is a halogen,

with carbonyl sulfide, COS and a methylpiperidine of the above given general formula (V) is implemented in the presence of an acid binder.

In the above formulas (il) to (Vl) have X, η and R have the meaning given for formula (I). M is preferably the ammonium radical or an alkali metal atom, in particular a sodium or potassium atom.

As examples of the benzyl mercaptans of the general Formula (II) are benzylntercaptan, 2-chlorobenzyl mercaptan, 4-chlorobenzyl mercaptan, 4-bromobenzyl mercaptan, 3,4-dichlorobenzyl mercaptan, 4-methylbenzyl mercaptan, 4-ethylbenzyl mercaptan, 4-isopropylbenzyl mercaptan, 2,5-dimethylbenzyl mercaptan, 3,4-dimethylbenzyl mercaptan, 4-methoxybenzyl mercaptan, 4-isopropoxybenzyl mercaptan, 3-chloro-4-

Nit 78

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109886/1972

methoxybenzyl mercaptan, 3-chloro-4-isopropoxybenzyl mercaptan, 3-methyl-4-isopropoxybenzyl mercaptan, α-methylbenzyl mercaptan and called their sodium, potassium and ammonium salts.

Examples of the compounds of the general formula (III) are 2-methylpiperidinocarbamoyl chloride, 3-methylpiperidinocarbamoyl chloride and called 4-methylpiperidinocarbamoyl chloride.

If appropriate, the reaction of process variant (a) be carried out in the presence of an acid binder. For this purpose, an alkali metal carbonate or -bicarbonates such as sodium bicarbonate, potassium carbonate or sodium carbonate, an alkali metal alcoholate such as potassium or sodium methylate or ethylate or an aliphatic, aromatic or heterocyclic tertiary base such as triethylamine, diethylaniline or pyridine is used will.

The reaction of process variant (b) should in general be carried out in the presence of an acid binder will. Excess methylpiperidine can be used for this purpose. It is therefore beneficial to have 2 moles of methylpiperidine to be used per mole of benzyl thiocarbonyl halide. As an acid binder in process variant (c), before ^ preferably an alkali is used.

The reaction in each of the process variants mentioned above can be carried out in an inert organic solvent or diluent be performed. For this purpose, if necessary halogenated aliphatic and aromatic hydrocarbons such as gasoline, methylene chloride, chloroform, Carbon tetrachloride, benzene, chlorobenzene, toluene and xylene »ethers such as diethyl ether, dibutyl ether, oxane and Tetrahydrofuran; low-boiling alcohols such as methanol,

Nit 78 -4-

109886/197 7

Ethanol and isopropanolj ketones such as acetone, methyl ethyl ketone, Methyl isopropyl ketone and methyl isobutyl ketone and low aliphatic nitriles such as acetonitrile and propionitrile are suitable *

The compounds of the present invention excel not only through strong herbicidal effectiveness when used before the chicken millet emerges, but also in 1 - 3 * Leaf stage under flood conditions; compared to rice plants, they show only low phytotoxicity. This is noteworthy because the current commercial herbicides against the chicken millet only exist or are effective after rising. Besides, they are Compounds of the present invention because of their low levels Phytotoxicity to rice plants suitable and mean for controlling weeds occurring in water a great manpower saving as they have one or two Weeks after the rice plants have been released, and currently none for this phase effective control method exists.

The compounds of the present invention exhibit such potent herbicidal activity when taken from the roots the weeds are absorbed in that they are considered nonselective or seceltive herbicides against weeds, even against those which occur in rice fields, depending on the application, but especially when treating the soil before it rises the seeds, can be applied. In addition, the compounds according to the invention are effective when applied to plants are also called acaricides, especially against the double-flecked spider mite.

The compounds according to the invention show in comparison to others made in a similar manner. Connections with similar structural formula a special herbicidal effective

NiLt JB -5 ~

1GSo 86 Λ197

on. The active ingredients according to the invention have at Use in large quantities (e.g. 5 - 40 kg of active ingredient per hectare), non-selective herbicidal activity. Will you however, applied in low concentrations (e.g. 1.0 5 kg / ha), they are excellent selective herbicides Effectiveness on, making them as anti-sprouting, and above especially as weedkillers.

The compounds according to the invention, which herbicidal activity against the plants listed below show excellent selective herbicidal effectiveness, when applied in the correct amount mentioned above (e.g. 1.05 - 5 kg / ha). They can therefore be used as herbicides be used in areas cultivated with the following arable products.

dicot weeds mustard (Sinapis) cress (Lepidium) stickwort (Galium) sternini ere (Stel 1 aria) chamomile (Matricaria) French herb (Ga1ino soga) goose foot (Chenopodium) nettle (Urt i ca) ragwort (Senecio) foxtail (Amaranthus Purslane (Pörtulaca)

dicot arable crops Cotton ( Go ssyρium) Carrots (Daucus) Beans (Phaseolus) Potatoes (Solanum) Coffee (Coffea) Sugar beet (Beta) Cabbage (Brassica) Spinach (Spinacia)

monocot weeds timothy grass (Phleum) bluegrass (Pos) fescue grass (Festuca) fingergrass (Digitaria)

monocot arable products Maize (Zea) Rice (Oryza) Oats (Avena) Barley (Hordeum)

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109886/1977

monocot weeds dicot arable products

Birdweed (Eleusine) Wheat (Triticum)

Bristle grass (Setaria) Millet (Panicum)

Chicken millet (Echinochloa) Sugar cane (Saccharum) Trespe (Bromus)

The plant species listed above are representative examples of those identified in Latin Called genera. The active ingredients according to the invention can not only be used against these, but also against others, similar plant genera are used.

The active compounds according to the invention can be converted into the customary Preparations such as aerosols, fumigants, solutions, emulsions, emulsion concentrates, slurries, Powders (including wettable and soluble powders), pastes, tablets and granules can be transferred. These preparations can be made in the usual way, for example by mixing the active ingredients with excipients, i. liquid, solid or gaseous diluents or carriers, optionally using surface-active agents Agents such as emulsifiers and / or dispersants are produced. If water is used as an extender, organic solvents can also be used as auxiliaries will.

Liquid diluents or carriers are preferred aromatic hydrocarbons such as xylene, toluene, benzene, dimethylnaphthalene or aromatic petroleum fractions, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloromethylene, chloroethylene, trichlorethylene, dibromoethylene or carbon tetrachloride, aliphatic Hydrocarbons such as η-hexane, cyclohexane, gasoline, Petroleum ether, soluble petroleum fractions or paraffins, (e.g. mineral oil fractions such as petroleum, light oil, medium

Nit 78 -7-

109 8.86 / 1 977 _{> {}

heavy or heavy oil) alcohols such as methanol, ethanol, Propanol, butanol or ethylene glycol ,. Ketones such as Acetone, isophorone, methyl ethyl ketone or cyclohexanone or strongly polar solvents such as amides, in particular Dimethylformamide or dimethylacetamide, sulfoxides, especially dimethyl sulfoxide, or acetonitrile, as well as water are used »Also ethers such as diethyl ether, dioxane or Ethylene oxide, ether alcohols such as ethylene glycol monomethyl ether and esters such as ethyl and amyl acetates can be added be used.

Solid diluents or carriers are preferred the powders of natural minerals such as kaolins, clays, talc, chalk, pyrophilite »mica, gypsum, calcite, Vermiculite, dolomite, apatite, sulfur »pumice stone, attapul gite, Montmorillonite or diatomaceous earth or the powders of artificial minerals such as highly dispersed silica * aluminum oxides or silicates are used. It can also use ground vegetable substances, inorganic salts such as potassium carbonate and synthetic resins such as phenol resins, urea resins and polyvinyl chloride can be used.

As gaseous diluents or carriers are propellants for aerosols, which under normal temperatures and pressure conditions exist in a gaseous state, such as Freon.

Preferred examples of emulsifiers include ampholytic, cationic, nonionic and anionic Emulsifiers such as the alkylamines, e.g. laurylamine, stearyltrimethylammonium chloride or alkyldimethylbenzylamoonium chloride, polyoxyethylene alkylamines, polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g., alkyl aryl polyglycol ethers, alkyl sulfonates and aryl sulfonates, e.g. Sodium Laurylsulfonate or Alkylnaphthalenesulfonatej too

Nit 78 -8-

109886/1977

the dispersants preferably used Lignin, sulphite waste liquors and methyl cellulose.

Organic substances, stabilizers, adhesives such as soap, calcium caseinate, sodium alginate, polyvinyl alcohol, Cleaning agents, coumarone (or indene), resins or polyvinyl butyl ether, flammable substances such as zinc dust or dicyandiamide, substances that give off oxygen, such as perchlorates, nitrite, or dichromates, substances, which reduce phytotoxicity, such as zinc sulfates, Ferric chloride or copper nitratej substances that affect the biological Prolong the effect, e.g. cMorinated terphenyls »emulsion stabilizers, vde 2 B casein, gum tragacanth, carboxymethyl cellulose, or polyvinyl alcohol or synergistic agents can be used.

In general, the preparations contain 0.1-95% by weight, preferably 0.5-90% by weight of the active ingredient of the general formula Z.

The compounds according to the invention can be used together if necessary with other agricultural chemicals such as insecticides, acaricides, nematocides, antiviral agents, herbicides, plant growth regulators and moisturizers Agents (to which organic phosphoric acid esters, carbamates, dithio (or thiol) carbamates, chlorinated compounds » Dinitro compounds, organosulfur and organometallic compounds, Antibiotics, substituted diphenyl ethers and urea triazines include) and fertilizers are used.

The ready-to-use preparations can be in any usual way, e.g. by spraying, such as spraying liquids » Fogging, atomizing, dusting, scattering, sprinkling, shaking up, smoking and soil treatments, such as e.g. mixing, splashing, vaporizing and spraying and Surface treatment such as painting by applying tapes and strips »dipping and applying catching materials be used·

NIt 78 -9-

109886/1977

When actually used, the content of active ingredient in the ready-to-use preparations is usually between 0.0001 and 20 %, preferably between 0.005 and 10 %. The active ingredient content can be varied depending on the type of preparation and method used, the purpose, time and place of application and the stage of growth of the weeds and / or acarids.

The compounds according to the invention can also be used according to the known ultra-low-volume method, which allows concentrations of active ingredient between 95 and 100 % .

The dosage per unit area is usually 3-1000 g, preferably 30-600 g, per 10 ar, based on the active ingredient. To However, these quantities can be exceeded or undercut as required, which is sometimes necessary »

The present Irfindung also relates to a herbicidal or acaricidal composition which, as an active ingredient, is an according to the invention Contains compound together with a diluent or carrier. If a liquid diluent is used, this preferably contains a surface-active substance

The present invention also relates to a method for combating weeds or mites, which consists in applying a compound according to the invention either alone or in the form of a preparation to the weeds or mites or to the habitat of the weeds or mites old '. ^: ~ ^r: - ~ ": Active ingredient contains a compound according to the invention mixed with a» diluent or carrier * _.:

The present invention also relates to a method for _; Soil treatment to protect the agricultural products from weeds or mites, which are found in the soil with a compound according to the invention either immediately before or after the arable products have emerged

Nit 78 -10-

10 9 8 86/1977 orksinally inspected

mixed with a diluent or carrier. .

It has been shown that by using the invention Products the yield of arable products is improved.

The invention is explained in more detail with the aid of the examples given below. The individual connections in the Production Examples (i) - (vii) and Test Examples A-D are similar to those in Production Examples 1-3 listed numbers.

example 1

0
/ VcH ₂ -SCN H) (3)

1.8.1 g (0.1 mol) of the sodium salt of 4-chlorobenzyl mercaptan are mixed with 150 ml of acetone. 16.2 g (0.1 mol) of 2-methylpiperidinocarbamoyl chloride are gradually added dropwise to this mixture with stirring at room temperature. After the end of the dropwise addition, the reaction is brought to an end by refluxing for 2-3 hours. The acetone is distilled off and 300 ml of benzene are added. The benzene layer is removed and washed with 1 # hydrochloric acid solution, 1% sodium hydroxide solution and water, and then dried over anhydrous sodium sulfate. After the benzene has been distilled off, the distillation is continued under reduced pressure, 26.5 g of 4-chlorobenzyl4 ^ 2-methyl-piperidino) thiol carbainate being obtained. This connection is subsequently referred to as No. 3 designated. Boiling point 168-172 ° C / 0.5 mm Hg. Yield: 93.3 %. Refractive index ng = 1.5779.

CH ₀ -SCN H) (14)

Nit 78 -11-

109886/1977

27.9 g (0.1 mol) of S-chloro - ^ - isopropoxybenzylthiocarbonyl chloride are dissolved in 200 ml of acetone. The solution is cooled to ^{0-5 ° G.} 19.6 g (0.2 mol) of 2-methylpiperidine dissolved in 100 ml of acetone are added dropwise to this solution with stirring. After the end of the dropwise addition, the mixture is allowed to react for one hour and then left to stand for 12 hours at room temperature. The precipitated amine salt is then filtered off from the acetone layer of the reaction mixture. The filtrate is washed with 1% sodium hydroxide solution, 1% hydrochloric acid and water and then dried over anhydrous sodium sulfate. After the acetone has been distilled off, the distillation is continued under reduced pressure, 31.0 g of 3-chloro-4-isopropoxybenzyl-1- (2-methylpiperidino) thiol carbamate being obtained. This connection is referred to in the following with the number. Boiling point: 193 - 198 ° C / 0.5 mm Hg, refractive index »rip 1.5628. Yield! 91 %.

The compounds according to the invention listed below were prepared by methods which are similar to those described in Examples 1 and 2 described.

Table 1

Connection number

formula

Physical properties Boiling point ° C / mm ^ - Hg (refractive index n ^)

/ "Melting point ° C__7

160-165 / 0 · 5 (1.5724)

170-173 / 0.4 (15? 85)

Nit 78

-12-

109886/1977

ORIGINAL

Connection number

formula

Br

Il

, -S-C-NH

Physical properties Boiling point ° C / mrn _2Q Hg (refractive index n _D ) ^ / "" Melting point C _7

172-130 / 0.2 (1.5957)

Cl

CH ₂ -SC-Ii H

Il G

// v \ Il

CRj ~ (/ j \ - (M ₂ -SG-

160-164 / 0.6 (1.5658)

\ VcH ₂ -sc-;

168-173 / 0, (1.5657)

NV-CH ₂ -SC-

165-170 / 0.4 (1.5566)

CH,

.CH

172-175 / 0.4 (1.5670)

CH,

CH,

3Λ-

CH ₂ -SC-:

178-182 / 0.6 (1.5700)

WIT 78

-13-

109886/197 ORIQSNAL INSPECTED

Connection number

Formula Physical properties Boiling point C / mm ₂ 0 ^H ^ (refractive index n «)

// "Melting point ° C_7

169-172 / 0.6 (1.5711)

Il f3

180-183 / 0.3 (1.5560)

Cl

CH-

-S-C-Ii η 195-199 / 0.4 (1.5803)

. 185-187 / 0.6 J (1.5526)

¹⁶ & \ V GH-SCN H

145-150 / 0.3 (1.5666)

Nit 78

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109886/1977

INSPECTED

Connection number

formula

Physical properties Boiling point ° C / mm ₂ n Hg (refractive index η-)

^ / "Melting point ° C_7

H \ - CH,

oil

Example (i)

15 parts by weight of compound no. 3.80 parts by weight of a mixture of kieselguhr and kaolin (1: 5) and 5 parts by weight an emulsifier "Runnox" (a polyoxyethylene alkylaryl ether) are mixed and ground into a wettable powder. This preparation can be mixed with water

can be diluted to the desired concentration and then sprayed.

Example (ii)

30 parts by weight of compound no. 6, 30 parts by weight of xylene, 30 parts by weight "Kawakasol" (aromatic hydrocarbons having a high boiling point) and 10 parts by weight of Sorpol ^{M M} (a Polyoxyäthylenalkylaryläther) are mixed and transferred under stirring in an emulsifiable concentrate. The preparation can be diluted with water to the desired concentration and then sprayed on.

Example (iii)

2 parts by weight of compound no. 8 and 98 parts by weight of one Mixtures of talc and clay (1: 3) are mixed and ground to a dust. This preparation is made by dusting upset.

Nit 78

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109886/197 7

Example (iv)

1.5 parts by weight of compound no. 11, 2 parts by weight of an organic phosphoric acid ester, 0.5 part by weight isopropyl hydrogen phosphate and 96 parts by weight of a mixture of talc and clay (1: 3) are mixed and made into a dust grated. This preparation is applied by dusting.

Example (v)

10 weight parts of compound no. 13, 10 parts by weight of bentonite, 78 parts by weight of a mixture of talc and clay (1 s 3rd) and 2 parts by weight of lignium sulfate are mixed. This Mixture is added 25 parts by weight of water, it is then kneaded and granulated into 375-750 / u (20-40 mesh) transferred, which are dried at 40 - 50 C. This preparation is applied by sprinkling.

Example (vi)

5 parts by weight of compound no. 14 are dissolved in a suitable organic solvent and added to 95 parts by weight Clay granules with a diameter of 0.2 to 2 mm are sprayed on in a rotary mixer and then at a Dried at a temperature of 40 to 50 C to obtain a preparation in the form of granules. This is through Scatter applied.

Example (vii) : · .Λ:.

0.5 part by weight of compound no. 15.20 parts by weight / ¹¹ VeIsicol AR-50 "(aromatic hydrocarbons with high boiling point) and 79.5 parts by weight" Deobase "(odorless kerosene) are mixed and converted into an oily preparation

Nit 78 -16-

1 0 98 8 6/1977

transferred, which can be applied by spraying.

The new compounds according to the invention are in comparison compared to known compounds of similar structure due to their improved action and their low toxicity warm-blooded animals and therefore of great usefulness.

The effectiveness of the active ingredients according to the invention is based on Reason for the examples given below, which show the results of tests against various plants, weeds and mites.

Example A.

Test against weeds occurring in rice fields under flooding conditions for soil treatment (pot test).

Production of the active ingredient preparation

Carrier: 5 parts by weight of acetone or talc Emulsifier: 1 part by weight of benzyloxy polyglycol ether

1 part by weight of active ingredient and the abovementioned amounts of emulsifier and carrier were mixed and poured into one emulsifiable concentrate or a wettable powder. The mixture became the desired one with water Concentration diluted.

Test procedure

Wagner pots (1/5000 a) were filled with rice field soil. Two rice seedlings (Kinmaze) at the three or four leaf stage were placed in each pot. After rooting of the saplings, the seeds of barnacles and broad-leaved weeds were sown in the pots and rushes

NIT 78 -17-

109886/1977

were planted in the soil of the pots. Then each pot was placed 6 cm deep under water. The active substance was applied to the pots in certain amounts by means of a pipette in the form of the above formulation. After application, the water level was lowered by 2 - 3 cm per day within 2 days and became then left at a height of 3 cm. After 4 weeks, the herbicidal effect and the phytotoxicity on the test rice plants were determined rated and classified according to the following scale:

Herbicidal effect (compared to the untreated

Control area):

5: more than 95 % destroyed

4: more than 80 and up to 95 % destroyed

3: more than 50 and up to 80 % destroyed

2: more than 30 and up to 50 % destroyed

1: more than 10 and up to 30 % destroyed

0: 10 % or less destroyed

Phytotoxicity: (compared to untreated

Control area):

5: more than 90 % damage (fatal) 4: more than 50 and up to 90 % damage 3: more than 30 and up to 50 % damage 2: 10 to 30 % damage

Ii less than 10 % damage 0: no damage

The results can be seen in the table below:

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" Table 2

Test against weeds occurring in rice fields under flood conditions for soil treatment (pot test)

Connect
manure
No. Really
material
salary
(g / ioa Yeasticidal effect Chicken
millet swamp
bull broadleaf ^fl)
rige weeds Phytoto
xicity 1 200
150
100 5
5
5 5
4th
4th 5
4th
4th rice
plants 2 200
150
100 5
5
4th 5-4
4th
4th 5
4th
4 " ooo 3 200
150
100. 5
5
5 5
5
5 5
5
5 ooo. 4th 200
150
100 5
5
5. 5
5
4th 5 '
5
5 ooo 5 200
150
100 5
"4
, 4 5
. ' 4th
■ 4 · 5
4th
4th ooo 6th 200
150
100 5
5
5 5
5
5 '- 5
5
5. : - -
ooo 7th 200
150
100 5
5
5. . .5
5
4-5- 5
5
5 0
0
⁰ . .- 8th 200
150
100 5 ·
5
5. ' 5
5
5 5
5
5 0 '
0
0 9 · 200
150
100 5
5
4-5 5
4th
4th 5
5
5 ooo 10 200
150
100 5
5
4-5 5
5
4th 4th
4 ·. . ooo 0
0
0

Nit 78

-19-

1 09886/1977

Table 2

removal)

Test against weeds occurring in rice fields under flood conditions for soil treatment (pot test)

Connect
manure Effective
material- - Chicken Herbicides effect • Phytoto
xicity SIr. held
(g / 10a 11- · millet swamp broadleaf ⁽¹⁾ rice 200 5 bull rige weedsex plants 150 5 5 . 5 0 11 100 .5 5 5 0 200 5 5 5 0 150 5 5 . 5 0 12th 100 5 5 5. 0 200 5-: ' 5 5. 0. · 150 CJl 5 5 0 13th 100 5 5 5 0 200 5 4-5 5 0 150 5 5 5 0 14th IQO • 5 5 5 0 200 ■ '& ■ ·' ·· ■ 5 5 0 150 5 5 • 5 .0 15th 100.. · '5. 4-5 5 0 200 ^ ■. ■
• 5 . ' . 4. · 4th ■ ο · 150 " 5 • 5 ^: • 5 · 0 '- 16. 100 5 4-5 . . 5 0 200 ' 5. '· 4th 5 0 150 · 5 · .5 5 0 17 .. 100 5 . 4th 5 0 200 ■ 5 4th 5 0 150 5 · 5 · 5 0 18th 100 5 4-5 4-5 0 200 5 4th 4th 0 Ver 150
100 4th
• 3 4th 4th 1 "« $ * . 4th
3 3
2 0
0 Inconvenient ■ o hands!
te .0 • 0 0 Contr area

Nit 78

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109886/1977

on «HAL INSPECTED

Notes: '** " L \ Q

(1) Broad-leaved weeds: Monochoria, Rotala indica

and Lindernia phxidaria

(2) Comparison: p-chlorobenzyl-N ^ -diethylthiol carbamate

(See Published Japanese Patent Application Sho 43-29025)

fi - ^. Q CH "

Ci ^ VcH ₀ SC-NCr ² H ⁵ ^ ¹⁹ )

Example B;

Test against weeds occurring in rice fields under flood conditions when treating the stems and leaves (pot test)

Test procedure

Wagner pots (1/5000 a) were filled with rice field soil. Two rice seedlings (Kinmaze) each about 15 cm high in the Three or four leaf stages were placed in each pot. After the seedlings were rooted, the seeds of barnyard grass and broad-leaved weeds were sown in the pots and "rushes planted in these. Then the pots were put under water. When the millet in each When the pot had reached the two-leaf stage (on the 7th to 9th day after sowing), the pot was 6 cm deep under water set. The active ingredients were in the preparation as described in Example A using a pipette in a specific Amount applied. After application, the water level was decreased by 2 - 3 cm / day within a period of 2 days and then held at a height of 3 cm. To The herbicidal activity and the phytotoxicity against the rice plants were evaluated for 4 weeks and as in Example A listed classified.

The results are shown in Table 3.

With 78 -21-

71877

Tabel

Test against weeds occurring in rice fields under over-,
Flood conditions when treating the stems and leaves. . (Pot test) -

• Connect
manure
«R. Really
material
salary
(g / ioa Herbicidal effect Chicken
millet swamp
bull broadleaf ^fO
rige weeds Phytoto
xicity 1. 200
150 '
100 5
4th
4th 4-5
4th
3-4 5
4th
3-4 rice
plants .2 200
150
100 5
4-5
4th 4-5
4th
4th • 5
4th
4th 000 3 200
150
100 5 · '
5
5. ·. ■ 5
4-5
4-5 5
5
4-5 000 • 4th 20Ό
150
100 5 '■ .-.
• 5 " 5
5 ■
4th .5
- 5th
5 Ό
0
0 5 οοό
omo
CNl »Η ιΗ. 5 ·. · - '
.. A '.
3-4 ·. 4-5
4th
- ".3-4 _ ■ -; ■ ' 4-5
4th
3-4
t 0
0
. 0 200; .
150
100 - -5 ■■■ '■'
5
5 ·· .- ■ '·. 5 :. . '.
4-5
4-5;. '".;. • 5 '"
• 5
4-5. . 0
0
• 0 ' 7 ·. 200
150 '
100 'S- ■ "
• 5:. '
• · 5 . '-5 - ^; ■ '.
• 4-5 '-
"■ 4.". ■. ■ - '· 5
. - 5 ·, ■ '
• 4-5 ooo 00. 200
150
100 '5 · ^;
5 ·
• ■ ^5,. ' 5
■ 4-5 ·
. ■ 4 " . ^: 5
.5
4th 000 9 2Ό0
150
100; 5
4-5
• 4 . 5
• 4
4th 5
5
5 OOP 10 200
150
10Ö • 5
4-5
4th 5
4th
4th .5. '
4th
4th PPO OPO

Nit 78

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9 8 8 6/1977

ORDINAL INSPECTED

2T36A94

Table 3 (continued)

Test against weeds occurring in rice fields under flooding conditions when treating the stems and leaves

. (Pot test). , ·

Connect
manure • Really
material Chicken Yeasticides effect Phytoto
xicity • tfr. salary
(g / 10a millet swamp wide bloom- ⁽¹⁾ rice 200 5 bull rige weeds plants 150 5 5 5 0 11 100 5 5 5 0 200 5 4th '4 0 * 150 · 5 5 5 · 0 ' 12th 100 5 ■ · 4-5 5 .0 200 5. · . 4-5 4-5 0 150 ' 5 5. 5 0 13th 100 5 ·. 4-5 4-5 0 200 '"5' ■ 4-5 ' 4 · Ό 150 . "■ 5 '. · . 5 5 0 14th 100 5 ". ..; ■ · ' 5. 5 0 200 " 5 4-5 "5 • o • 150 · * 4-5:. ■ • ■ 5 ": ··. ·. 5, ■ 0 15th 100 4-5 " 4 · ■ '' 5 ο - . 200 5. '' '4 ··. 4th 0 ' • 150 4-5- ·. 5 · ^: 5 0 16 100. 4th • 4 4th 0 · · ■ 200 '5 4th .4 0 - 150 .4-5. '5 5 0 17th 100 4th 4 '■ 4-5 0 200 5 4th 4th 0 150 5 5 5 0 18th 100 4-5 4-5 4 ' 0 '4 4th 0
t

• Nit 78

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ORK35NAL iWSPEOTED

it

Table 3 (continued)

Test against weeds occurring in rice fields under flooding conditions when treating the stems and leaves

(Pot test)

Connect
manure
No. Really
material
salary
(g / 10a) Herbicidal effect Swamp--
bull broadleaf ^ ¹ *
rige weeds Phytoto
xicity
rice
plants Ver
same 200
150
100 Chicken
millet 3-4
3
2 4-5
4th
3 1
0
0 Inconvenient
trade-
te con
troll
area - 3-4
3
2 0 0 0 0

Remarks:

(1) broad-leaved weeds; Monochoria, Rotala

indica and Lindernia phxidaria

(2) Comparison of benzyl-Ν, Ν-diethylthiolcarbamate

(French Patent No. 1,328,112)

Example C;

Test against different plants during soil treatment

Test procedure

The seeds of test plants were placed in pots of 20 χ 30 cm sown and after 24 hours a preparation prepared as in Example A in amounts of 20, 10, 5, 2.5 or 1.25 kg / ha sprayed on the soil in the pots. 3 weeks after the spraying was «tea? gchadervegrad assessed and according to the classified according to the following scale.

Phytotoxicity

0: no phytotoxicity Nit 78

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1: slight damage or delay in growth 2: significant damage or inhibition of growth 3: severe damage and poor development or

only 50 JIi emerged 4: plants partially destroyed or after emergence

only 25 % risen 5: Plants completely dead or not risen

The test results are shown in Table 4.

With 78 »25»

109886/1977

Tabel At Test against different plants during soil treatment

IZ ι] I. as ta dl * Ω SO §? CU Τ C: Τ » Q CA »Υ 11 r ro P (D Η · (D φ (D C. H* ο 3 * ο OK Ρ H 3 * H Ρ · H Η · 3 (Ii 3 (D ο I. VT ω χ N ο » (A. sj H-" Φ (+ 0) H ΙΟ § ^ * · <n ι— · 0 » (D <+ O H C. (D (0 (D so t + r + c + 3 (D H ¹ 3 * Η « Η » ι (A. O O H-- Η · ω C. Ρ · O (Ω H" (D H TT D) (D 3 " H H" ^% · ™ Τ1 χη H CU (Ω I (D (D ο> (0 3 3 "
Q) N O 4th 4th 5 so 20th 4th 4th 4th 2 2 4th 5 5 5 5 5 5 co 10 1-2 2 1-2 0 0 2 5 5 5 5 5 5 co No. 3 5 0 0 0 0 0 0 5 5 5 5 5 5 CD 2.5 0 0 0 0 0 0 5 5 5 5 5 5 1.25 0 0 0 5 5 0 5 4-5 4-5 4th 4-5 4-5 CD 20th 5 5 5 2 2 5 5 5 5 5 5 5 -a
•• «3 10 1-2 2 3 0 0 1-2 4th 5 5 5 5 5 comparison 5 0 0 0 0 0 0 3 5 5 5 5 5 (D 2.5 0 0 0 0 0 0 2 4th 4th 4th 4th 3 1.25 0 0 0 0 2 2 2 2 2

Remarks:

(1) Comparison: Benzyl-N, N-diethylthiol carbamate
(French Patent No. 1,328,112)

CaI CO

Example D:

Test with two-spotted spider mites Preparation of the test preparation:

Solvent 3 parts by weight of dimethylformamide Emulsifier: 0.1 part by weight of alkylaryl polyglycol ether

One part by weight of active ingredient is used with the above Amount of solvent that corresponds to the amount of. Contains emulsifier, mixed. The resulting emulsion concentrate is converted into an aqueous preparation by dilution with water, - which the active ingredient in a contains the prescribed concentration.

Test procedure?

A kidney bean plant planted in a 6 cm diameter pot has 50 to 100 adults and no fully developed specimens of the two-spotted spider mite were inoculated and after 2 days one as described above became Preparation by means of a spray device applied to the pot in amounts of 40 cm.

To. After leaving in a glass house for 10 days, the pot treated in this way was examined in order to evaluate the control effect, which was classified according to the scale given below)
3t no live adults, nymphs or eggs 2t less than 5 % live adults, nymphs or eggs in the

Compared to the untreated control area, 5 - 50 % live imagines, nymphs or eggs in the

Compared to the untreated control area Ot More than 50 % live imagines, nymphs or eggs in the

Comparison to the untreated control area

The results are shown in Table 5.

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Table 5: Test against two-spotted spider mite

Control effect in the case of an active ingredient
concentration of TpM Connection
number 1000 300 100 1
2
3
4th
5
6th
7th
8th
9
10
11
12th
13th
14th
15th
16
17th
18th 3 3 3
3-2 2
3 2 2
3 2 1
3 2 2
3 2 1
3 3 3
3 3 3
3 2 1
3 2 1
3. 2 1
3 3 3
3 3 3
3 2 2
3 2 2
3 2 2
3 2 2
3 2 2 Celtans
(D 3 2.0 Untreated 0

Remarks:

(1) Keltaneί Commercially available wettable

Powder containing bis (chlorophenyl) trichloroethane

Nit 78

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Claims (6)

Patent claims: Thiocarbamic acid esters of the formula R 0> CH, II! - ^ -CH-SCN _x H> (I) in which R stands for hydrogen or methyl, η stands for the numbers 1 or 2 and X is hydrogen, halogen, lower alkyl or lower alkoxy and the radicals X are the same or, can be different if η stands for the number 2. 2) Process for the preparation of thiol carbamic acid esters according to claim 1, characterized in that one
a) a benzyl mercaptan or a salt thereof of the formula R -CH-SM '(II) in which R, X and η have the meaning given above and M * for hydrogen, ammonium or a metal equivalent stands, with a methylpiperidinocarbamoyl halide of the formula / - v ^ ⁰¹ * HaI-C-IT H> (III) in which shark stands for halogen, if appropriate in the presence of an inert solvent and if appropriate in the presence of an acid binder Nit 78 - 29 - 109886/1977 implements or b) a benzylthiocarbony halide of the formula R 0 -CH-S-C-Cl (IV) in which R, X and η have the meaning given above with a methylpiperidine of the formula (V) if appropriate in the presence of an inert solvent and if appropriate in the presence of an acid binder implements. 3) Herbicidal agents, characterized by a content of Thiol carbamic acid esters according to claim 1, 4) methods of controlling unwanted plant growth, characterized in that one thiol carbamic acid ester according to claim 1 can act on the unwanted plants or their habitat. 5) Use of thiol carbamic acid esters according to Claim 1 for combating unwanted plant growth. 6) Process for the preparation of herbicidal agents, characterized in that thiol carbamic acid esters according to Claim 1 mixed with extenders and / or surface-active agents. Nit 78 - 30 - \
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