DE2029387A1 - Benzoisothiazoles and herbicidal agents containing them - Google Patents

Description

PATENT ADVERTISERS £ Ό £ .Ό ÖO [

dr. W. Schalk dipl.-ing. P. Wirth dipl.-ing. G. Dannenberg DR. V. SCHMIED-KOWARZIK · DR. P. WEI NHOLD · DR. D. GUDEL

6 FRANKFURT AM MAIN

OR. ESCHENHEIMER STRASSE 39 ^ iV / ^ K

K.1099

Montecatini Edison SpA
Foro Buonaparte 31, Milan

Tullo Vitali.

Piazza Garibaldi 23, Parma

Riccardo Ponci

Via MontebeHo della Battalgia 4, Pavia

Franco Gialdi

Via Feiice Cavallotti 9 _t Pavia

Benzoisothiazoles and herbicides containing them middle

The present invention relates to herbicides derived from benzoisothiazole derivatives existing means, processes for their production, their use as plant growth regulators and in particular as Herbicides, on preparations containing these herbicides and their use for the same purposes.

.;, x; ^. , .w * 009882/2217

The present invention relates in particular to herbicidal agents, that by substituting a hydrogen atom of the benzene ring with different ones Groups of 3-chloro-1,2-benzoisothiazole are derived.

These compounds can be represented by the following general formula will: ·

CCl

■ /

in which X stands for a halogen atom, an alkyl, nitro or alkoxy group stands.

These compounds are obtained by reacting the corresponding 1,2-benzoisothiazolin-3-ones (Benzo isothiazolone) with acid chlorides, such as PC.1 ^,

Lo or mixtures thereof, if possible in the presence of a tertiary Nitrogen-containing base (such as pyridine or triethylarain) by known methods. After removing excess reagent, the End products by distillation under reduced pressure, by steam distillation or even by extraction with solvents such as petroleum ether, ligroin, etc., separated. .

The following list of compounds is representative of the present Invention and is not a limitation.

009882/2217

BATH ORIGINAL

5- * tthyl-3-chlorobenzoisothiazole; white needles (made from petroleum ether) with a Melting point between 60-02 C (2.1);

y-methyl-S-chlorobenzoisothiazole: small white needles (from petroleum ether) having a melting point between 42- ^ 3 C. (2.1);

3,4-Dichlorberizoisothiazole: white flakes (from alcohol / water) with a Melting point between 123-124 ° C. (2.1);

3 _t 5-dichlorobenzoisothiazole: white needles (from petroleum ether) with a melting point between 90-91 ° C. (2.1);

5- ^ litro-3-chlorobenzoisothiazole small, straw yellow needles (from ethanol) with a melting point between 130-132 C;

5 ^ ethoxy-3-chlorobenzo isothiazole white needles (from petroleum ether) with a melting point between 73-7 ^ C _e ;

1) = Boeshagen and Geiger, Ber. IDl, 2 * 1-72 (1 ° 68)

2) = Vitali, Mossini, Bertaccini and Impiceiatore "H Farmaco" Ed. Sc. 2 ^,

1081 "(1968)

According to the invention it was found that those belonging to the class specified above belonging compounds have a herbicidal activity and as a preliminary and / or IJ achlauf herbicides achieve an extremely high intensity.

When applied to the ground, these compounds are particularly effective against germinating seeds and against small sprouts; Furthermore, they also act on the standing above ground part of the plant _$ with which they come into direct contact, and develop an acute toxicity, so UaB the plants when they have come up with an appropriate dose of the active substance 'in contact die and the vegetation as such is irreparably disturbed.

# 00882/2217

: ■■■■■■■■ · .- ^■::: BAD ORIGINAL

In practice the compounds of the invention are used as weed killers used in widely varying amounts depending on the type of compound, the level and type of weeds being controlled Application method, the type of soil and the type of used Wording depend on.

Since the compounds according to the invention are very active, they are generally sufficient Relatively moderate amounts per hectare of soil for weed control »Shouldn't destroy the plants, only appropriate growth regulation are achieved, much smaller amounts are used.

An average of 1-8 kg of active substance is used to kill weeds applied per hectare.

The following data illustrate the range of action of some of the invention Links; of course are those according to the invention Compounds also, regardless of the method used, for combating other plant species and this information is not a limitation dar ο

With pre-weed killing, the soil became more active with amounts of it Substance between a maximum of 6 kg / ha surface and a minimum of 1 kg / ha 'treated " In the follow-up treatment, the plants were treated with the same amount active substance sprayed per hectare of planted area »

The results were evaluated as follows:

Q09SS2 / 2217

- »5- ■ ■

Follow-up treatment : '

0 = no damage ■

1 = moderate effectiveness

2 = certain effectiveness with partial damage, but in general the

Small plant viability not affected

3 ⁼ considerable effectiveness with plant damage; which the further-ent

oiler ''

Development of the larger part / small plants was significantly impaired

^ = Necrosis with impairment of plant viability up to its Die

If there was an effectiveness between two evaluations, both values were given; the first value means the clearest effect.

The tests were carried out on the following plants:

A = Amaranthus retroflexus L.

B = Artemisia vulgaris L.

C = Chi? no podium album L.

D = Convolvulus sepium L.

E = Echinochloa crus-galli RS ₀

F = Setaria glauca L.

G = Vicia sativa L.

H = A vena sativa L.

I = Beta vulgaris L.

L = Phaseolus vulgaris L.

M = Pisum sativum L.

N - Solanum lycopersicum L.

O = Triticun vulgar L.

P = Zea Mays L.

009882/2217 ¹ ^

' BATH

- ο ->.

As mentioned, the compounds according to the invention can be successfully used in small, quantities to be distributed over wide areas are used for weed control »For a uniform distribution of the active substance, preparations be used that mix the active compound with a large one Contains an amount of inert substances as a diluent. You can also use formulations to use with a larger amount of active substance, but these must be lightly before their application with water or inert substances be dilutable "

Due to the physical properties and solubility of the invention Compounds, the formulation of these preparations is not difficult tied together. ■

The compounds shown in the table below have the following Formulas:

Verb. I

II j ^ S ,, - Eq

Cl-I

III

S- 3 Λ, J ₁₁ * / *.

000882/2217

Verb. V

- 7 -

N0 ₂ - <- ~. .-Cl

VI

CH ₃ O-

009882/2217

Verb, kg / ha Follow-up treatment

3}

DEFGH IL, M JN

6 444344 33 332232

4 3 2 3 3 4 4 1/232 1/2 1/2 l / 2 2/3 1/2

2; _: 2 2/1 1/2 2/3 3 3 I / 03 2 1 O / ll 1/2 0/1

II 6 ■ '' 4 4 4 4 1/2 4 1/2 1/2 4 3 1 3 3 2/3 4 4 2 4 1 0/1 2 1 1 2/3 1/2 0 1/2 O / l 1

2; 4 1 3 O / l 0/1 1/2 0 O 2 O / l O O / l 0/1 O / l

III 6 '■' 4 ^: 4 4 4 3 4 1/2 2/14 2 2 4 2 2

4 ^i: 4 3 4 2 1/2 1/2 O / l. 1/2 4 1/2 1 3 1/2 1/2

O 2 1/2 1/2 3 0/1 1 1 O 0/1 2. 1. 0/1 1 1 1

6 '■■ · 3 3 4 1 1 1 Ί

y 6-43443 ^ 3,

, 44334232

2 4 3 3 3-232 °°

| VI 6 4 3 4 4- 1/2 1/2 1/2 0/1 3 1/22212 '

4 1/2 1/2 4 3 1 1/2 1 0 2 1 1/2 1/2 O / l 1

² 0/1 i / 2 3 1 Q 0 0 0 1 0/1 0 0 0 0

Preliminary treatment _; . ■

::. ι 64 4 4 "4 4/3 4 4 4 4 4 3 4 3/4 3

X 4 Z ₄ . 4 4 4 3444442432

2 4 4 4 3/4 2 3/4 3/4 ''

14 4/3 4 2/3 12 2

(NJ CD CO OO

Solid or liquid preparations can be used; solid preparations in granulated form are made by thoroughly mixing the active Substance with solid inert carriers, such as bentonite, calcium carbonate, Vermicullite, attapulgite, pyrophyllite, sepiolite, phosphorite, superphosphates etcj or you can use the active substance in a volatile solvent dissolved, spray onto the granular carrier, mix with it and finally dry the grains.

The content of active substance can be within very wide limits, e.g. vary between $ 0.25-30, preferably between $ 0.5-20. the Particle size of the granular carrier can vary between 0.1- ^ · mm but preferably between 0.15-0.7 mm.

Powder preparations for dry spraying are easily obtained by using the active substance with inert carriers, such as talc, diatomite, attapulgite etc., then mixes until the desired particle size is reached is wedded, the concentration of active substance lies • on average between 1-20 # .. "..- ■

The so-called "wettable powders" are obtained by thoroughly mixing the active substance with inert carriers such as diatomites, kaloins, attapulgites, "pyrophyllites, bentonites, synthetic anhydrous silicates, celites, etc., as well as surface-active agents, whereupon the mixture is mixed until the By dispersing these powders in water, aqueous suspensions with the desired concentrations of active substance are obtained. Such aqueous suspensions are sprayed over the soil and onto the plants. In such preparations, the content of active substance varies on average between 10-95 '#.

009882/2217

Liquid emulsifiable preparations are produced by using the active Substance in an inert solvent, preferably in little water is soluble, such as benzene, toluene, etc., dissolves and an emulsifier is added ο If these preparations are mixed with water, emulsions are obtained, in which the solvent phase is dispersed in the aqueous phase and the active substance is kept in solution in the dispersed phase.

In this way you get when sprayed over the ground and on plants a uniform distribution of the active substance in the aqueous preparation. In such preparations, the content of active substance varies greatly as a function of the dissolving power of the liquid medium for the active substance essential. It is generally between 10-50 $ or

In the production of wettable powders and emulsifiable concentrates, anionic, non-ionic and cationic emulsifying and dispersing agents are used

Anionic agents of this type are for example ": Sodium dodecylbenzenesulfonate, Calcium naphthalene sulfonate, lauryl sulfate. Suitable cationic agents are the quaternary ammonium compounds, such as cetylpyridinium bromide, dodecylbenzylmethylamraonium chloride, Bis (hydroxyethyl) benzyldodecylanmonium chloride etc.

As nonionic agents, there can be mentioned the condensation products of ethylene oxide with aliphatic alcohols, amines, fatty acids, alkylphenols η etc.

009882/2217

Choosing the most suitable alloy for a given purpose, Wetting or dispersing agents pose no problem for the person skilled in the art and many such products are commercially available.

Usually the surface-active agents constitute only a small percentage of the preparation, which is generally less than 25 % .

If necessary, other types of herbicides and pesticides (such as insecticides, acaricides, fungicides, etc.) can also be incorporated into the preparations according to the invention _{or the like}

The following examples illustrate the present invention without it to restrict.

Example 1

5-methyl-3-chlorobenzoisothiazole

5.0 g of 5-methylbenzoisothazolone and 6.9 g of PCI-, to which a few drops of POC1 had been added, were reacted with one another in a small flask; the flask was fitted with a reflux condenser and H ₂ Sok valve and was heated ⁰ C. ■ during the reacting for 3 hours in an oil bath at 130-WO.

The adduct obtained by decomposing the reaction mixture with ice water was purified by distillation in a stream of steam. Then the distilled, solid product was recrystallized from petroleum ether. The crystals in the form of white needles would have a melting point between 60-62 ⁰ C ₀ (2.1); the IR analysis (on film) gave the following values: 6.76 (f - strong), 7.52 (m = medium) 7.79 (f), 8.00 (f), 7.50 (m) , 10.18 (m), 11 , ^ U), 12.48 (f), 12.87 (m) and 13.88, u (m). The yield was 85 #.

_B AD ORIGINAL

Example 2

7-methyl-3-chlorobenzoisothiazole

As above, a reaction adduct was prepared from 50 g of 7-methylbenzoisothiazole and 6.9 g of PCI ,, and a few drops of POG1 "; this was decomposed in ice water and then distilled in a steam stiom. The solid distillate was recrystallized from petroleum ether. The crystals in the form of white needles had a melting point of ^ -2-VJ ⁰ C. (2.1); IR analysis (on Fi] jn: 3Λ2 (m), 6.30 (m), 6.75 (f), 6.90 (f), 6.99 (f), 7.22 (m), 7 * 67 (£), 9.18 (f), 11.60 (f), 12.85 (f) and 13.78 m (f). The yield was 81 #.
Example 3

3, h- dichlorobenzoisothiazole

The reaction was carried out in a pear-shaped 50 cc flask equipped with a mechanical stirrer, dropping funnel with tap, thermometer, reflux condenser and H-SO2 valve. In these were 1.5 g of 4-chlorobenzoisothiazolone and 2.5 g of PCl ₁ . given and mixed thoroughly. The mechanical stirrer was turned on, the outside of the reactor was cooled with an ice / salt mixture, and 0.65 g of anhydrous pyridine was added dropwise in order to avoid a sudden drop in temperature (development of white vapors).

Then the whole thing was on an oil bath at 17U ° C within one hour. heated and held at this temperature for a further 7 hours. The reaction mixture, cooled to 70 ° C., was then decomposed by poured it in a thin stream onto 200 g of ground ice.

Then the adduct was extracted with ether and the ether extracts washed with water, dried and evaporated to dryness. The resulting wife back '''' ■ was recrystallized from petroleum ether. · "

009882/2217

1.2 g of white needles with a melting point of 119-121 ° C. were obtained (2). After recrystallization from a water / alcohol mixture, the product lay in the form of white flakes with a melting point of 123-124 C. (3); IR analysis (KBr): 6.37 (m), 6.52 (m), 6.88 (f), 7.94 (f), 8.36 (f), 9.05 U), 10.24 (m), 12.70 (f) and 13.60 / u (m).

Example 4

3,5-dichlorobenzoisothiazole

5t5 g of 5-Ghlorbenzoisothiazolon were mixed with 6.3 g of PCl _1, and 0.5 g Pocio 3 hours at 130-140 ⁰ C. implemented.

The oxychloride was then eliminated by distillation and the residue was poured into ice water. The precipitate was filtered off and distilled in a steam stream! then the distilled solid was recrystallized from petroleum ether _e The product was in the form of white needles with a melting point of 9O-91 ° C prior} IR analysis (KBr): 6.88 (m), 7.99 (£) '9, 09 (m), 9.32 (ra), 10.11 (m), 11.50 (m), 12.20 (m), 12.42 (f) and 12.75 / U (m). The yield was 95 1 °° ■

Example ^

5-nitro-3-chlorobenzoisothiazole

According to Example 3 5.9 g of 5-Nitrobenzoisothiazolon, 9.4 g of PCI and 2.4 g of anhydrous pyridine were mixed, and the mixture after completion of Pyridinzugabe heated for 7 hours 170-18O ⁰ C. The solid obtained by decomposing the reaction adduct in ice was filtered off, washed with water, air dried and finally extracted with boiling petroleum ether.

After the fös'ühgsmitteils had been steamed off, the essentials delivered ^: Extracts ^! 4, ig ■

it is a Schneiapturict

- i4 -

After uracrallization from ethanol, the product was obtained in the form of thin, straw-yellow needles with a melting point of 130-132 Cj. IR analysis (KBr): 6.28 (m), 6.38 (d = weak), 6.61 (f), 6.82 (m), 7.58 (f), 7.92 (f), 9.21 (m), 9.31 (m), 10.03 (d), 11.12 ( d), 11.91 (f), 12.95 (m) and 13.52 ju (m).

Analysis for C ₁ Ji GlN ₂ O ₂ S calcd .: C 39.17 H 1.41 Cl 16.52 $ found : C 39.39 H 1.36 Cl l 6.42 £

Example 6

5-metho: xy-3-chlorobenzoisothiazole

10.8 g of 5-methoxy-benzoisothiazolone and 4.8 ecm of anhydrous pyridine were introduced into a small, pear-shaped flask equipped with a magnetic stirrer, separating funnel, thermometer, reflux condenser and H _{9 SO, valve fitting;} then the reactor was stirred and cooled externally with water so that the temperature of the reaction mass did not exceed 60.degree. rise, 13.8 g of POC1 "dropped in". The mixture was then heated to 130-140 ° C. on an oil bath for 7 hours and then poured into ice. The deposited powder was filtered off, washed with water and distilled in a stream of steam. This gave 8.3 g of a solid product having a melting point of 73-74 ° C., which was recrystallized from petroleum ether. Thin white needles were obtained with a melting point between 73-74 C ₀ J IR analysis (KBr): 6.25 (m), 6.69 (f), 6.99 (m), 7.42 (m), 7.80 (f), 8.02 (m), 8.23 (f), 8.50 (m), 9.78 (m), 11.35 (f), 12.02 (m), 12.30 (itt) and 13.83 ^ u (m). Analysis for CgH ^ CBIOS

Calcd .: C 48.12 H 3.03 Cl 17.76 i found : C 48.14 H 3, U Cl 17.74 ^

Claims (3)

Claims lo herbicide »consisting of or containing one or more compounds the general formula: in which X stands for halogen, or an alkyl, nitro or alkoxy group stands. · 2. Herbicide according to claim 1, characterized in that it is the main active component one or more compounds according to claim 1 contains. 3. Herbicide according to claim 1 and 2, characterized in that it is still there contains other herbicides and / or antiparasitic compounds and / or fertilizers. "^ 5 ™" » Ov £ All l'eil WOT ' Dtektiillpx uiig ν Oll draws that on jle3J.JBodwi «tmtl you 'pertaining vegetation a herbaceous 009 882/2 217 _BAD original