DE1417402C - 4 chlorine 2 oxobenzthiazohnyl (3) acetic acid, their salts and their esters with methyl, ethyl, propyl or 2 (2 butoxyathoxy) ethyl alcohol and their use - Google Patents

Description

'I c = o

their salts and their esters with methyl, ethyl,

their salts and their esters with methyl, ethyl, propyl or 2- (2-butoxyethoxy) ethyl alcohol.

Propyl or 2- (2-butoxyethoxy) ethyl alcohol. The 4-chloro-2-oxobenzthiazo according to the invention

. 2. Use of the compounds according to alinyl (3) acetic acid compounds show a very

Claim 1 as active ingredients for weed control. 15 substantial herbicidal effects compared to the important ones

Weeds such as knotweed (Polygonum persicaria),

Stickwort (Galium aparine) and chickweed (Stellaria

The invention relates to 4-chloro-2-oxobenzthiazo media). In particular, it works with sets of lynyl (3) acetic acid, its salts and certain esters 140 to 350 g / ha (based on the free acid), adhesives and their use for phytotoxic purposes. 20 effective control of herb and chickweed in clover The control of weeds by chemical d. H. with amounts that do not damage the clover Substances are now causing both in arable farming and in horticulture. This observation is a valuable one common practice. Despite extensive theoretical contribution to chemical weed control. . the Work in the field of chemical weeds - for example most commonly used herbicides, combat, however, all currently available 25 namely 2,4-dichlorophenoxyacetic acid (2,4-D) and Herbicide still has any flaws. This is true to have 4-chloro-2-methylphenoxyacetic acid (M C P A) especially for selective herbicides, i.e. the herbicides, against sticky herb none at all, against bird soft, applied to crops and weeds, miere and knotweed only have a minor effect, only the weeds without damaging the useful plants a- (4-chloro-2-methylphenoxy) propionic acid (C M P P; intended to destroy. The spectrum of herbicidal activity 30 published documents of the Belgian patent of the available selective herbicides, however, 561 485) is very effective against sticky herb not completely off, so that there is still a need for chickweed and chickweed in cereal seeds, but must for the better Herbicides. control of these weeds in clover in abundance From U.S. Patents 2,693,408, 2,653,865,. of at least 1680 g / ha are used, what 2,637,647 and 2,468,075 and the British patent 35 inevitably caused noticeable damage to the clover 766 690 it is known that certain thiazole leads. The compounds of the invention are derivatives possess herbicidal properties. After that no plant toxins for cereals, but not for either U.S. Patent 2,468,075, benzthiazolyl clover, when applied in the amounts ether of the general formula that are required to remove the aforementioned weeds

40 combat, and if its application in one

^, \ / N stage of growth of cereals takes place in

which the already known selective

• O - Y - COOH "..... ,,,

Herbicides are normally used.

The present invention is therefore

45 also the use of 4-chloro-2-oxobenzthiazo-

in which X is a hydrogen atom or one or more vinyl (3) acetic acid, their salts or their esters

Halogen atoms and Y is a divalent hydrocarbon with methyl, ethyl, propyl or 2- (2-butoxy-

represent substance group, by reaction of a salt ethoxy) ethyl alcohol as active ingredients for weed

of 2-hydroxybenzothiazole with, for example, a fight.

Obtain the salt of chloroacetic acid. By comparison 50 to the salts of 4-chloro-2-oxobenzothiazolinyl (3) -

the infrared and UV spectra as well as observable · acetic acid include the salts with inorganic and

processing of the behavior of these substances in Coleoptile organic bases, z. B. metal salts, such as those with

Straight growth test related to the sodium, potassium and ammonium, and the salts with

Examination of the plant growth regulating effect of organic amines.

and by testing the herbicidal properties 55 For use, the inventive However, it was found that the compounds not only as ready-to-use compounds, called the reaction available compounds no- but also as highly concentrated preparations, which away from benzothiazolyl ether, but rather 2-oxobenzthiazo- dilute with water or before using them Iinyl-3-alkanoic acids are and accordingly require another diluent, geFormula 60 will be delivered.

Y - COOH- The type of diluent or carrier

I punch depends on the physical properties

of the active ingredient. The use can be for example

X-

= O

in the following form:

x '/ ^ o / a) Dispersible Solutions. A dispersible

- Solution comprises a solid, insoluble in water. compound to be used according to the invention,

3 4

The total amount is de

medium, ζ. B. Acetone, with the addition of a dispersing component per unit area of the to

Giving agent, so that when diluted with treating culture most important. One has stuck-

Water an aqueous dispersion is formed. put that for the control of knotweed,

b) Miscible oils. A miscible oil comprises a 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid or the compound which is in solid form or its salts or the esters mentioned in one which is insoluble in 5 stickyweed and chickweed the use of water may be in liquid form, e.g. B. dissolved in an amount of 280 to 1120 g / ha, on the free acid beWasser immiscible solvent, such as a dragged, is suitable. A . low acid equivalent, high-boiling hydrocarbon, with the addition of ^10, ie around 280 to 560 g / ha is sufficient to combat an emulsifier, so that with water an emul of stickweed and chickweed; Knotweed seems to be sion being formed. In the case of liquid, but to be more resistant in water; an acid equivalent of insoluble compounds, the solution of at least 560 g / ha is an effective control agent. The consumer may prefer ^{fun S.} It is expedient to use an acid equivalent of about 560 g / ha, also obtained with a concentrated emulsion, in order to ensure that approximately the same volume of water is supplied from a miscible oil by adding control of all three weeds. show grains being made. Such concentrated emulsions advertising not plant poisoning when the before spraying the plants with the inventive compounds in the correct water diluted be applied ^ao stage of plant growth.

c) Dispersible powders. "A dispersible powder of summer cereals should be sprayed _{together aqinv-alent V (} , _{n 280 g / ha} ) at an early stage of growth comprising a water-insoluble inventive stage (ie 1 to 5 leaves) with an acidic compound to be used Klebmit solid inert diluent, to combat, such as kaolin ^k f ^ut and chickweed. at higher and a dispersant. ^{25 M} .engen. ^{al so} _u. ^to knotweed and cleavers bird

_1X ",". ,,. ., ", -" · ^ miere at the same time, it is preferable to

d) dust. Em herbicidal dust inventions comprises a _spraying up to the hinausdungsgemaß 5-leaf stage to be used in conjunction to-en _zuschieb to damage to the crop plants together with a solid, pulverulent extenders _{sdbst VÖM be avoided. As in the case of probably} .

■ medium, such as kaolin or a normal artificial _{30 known} . _selective hormone-type herbicides

fertilizer. ^^ ^ ₃₅ Do not spray after the rising

e) Aqueous solutions. The water soluble. invented cereal crops.

Compounds according to the invention can be used for A simultaneous use of MCPA

Positioning of solutions in water _and CMPP or its derivatives are used for

• will. _{35 the} spectrum of activity is easily possible.

: borrowed.

The dispersible solutions, miscible oils, The very high herbicidal effect on adhesives

dispersible powder and aqueous solutions chickweed, chickweed and knotweed, which

may also contain a wetting agent. have proper connections is very over-

4-Chloro-2-oxobenzothiazolinyl- (3) -acetic acid is surprising because the closely related 2-oxobenzothiazoein solid, water-insoluble compound and can be vinyl- (3) -acetic acid compounds, as they are for example to a) dispersible solutions, b) miscible manner are known from US Pat. No. 2,468,075, oils, c) dispersible powders and d) dusts do not have such a high effect as from the post-processed will. The mentioned esters of the 4-chlorine standing data emerges.

2-oxobenzothiazolinyl- (3) -acetic acid are also used in 45 The determination of the herbicidal effect of VerWasser insoluble and, depending on the alcohol content, are resistant to sticky herb, chickweed and knot resistant or liquid. As a result, they can be done the same way in the following way: Way the free acid will be processed. In the case of quadruple lots of sticky herb, chickweed and the salts of 4-halo-2-oxobenzothiazolinyl (3) -acetic knotweed were sprayed with aqueous emulsions acid, the soluble salts, e.g. B. the alkali and 50 of 2-oxobenzothiazolinyl- (3) -acetic acid, 4-chloro simple Alkyl and oxyalkylammonium salts to form 2-oxobenzothiazolinyl- (3) -acetic acid or their ethyls) aqueous solutions are processed. It can be ester or olamin appropriate with aqueous solutions of the diethan be, the consumer a salt in solid salts of these acids. The sprays are in ab-form with or without the addition of a wetting agent in graduated amounts, corresponding to an acid equivalent deliver. This salt is then mixed with water, applied 55 free acid of 280, 560 and 1120 g / ha, to be used for spraying on the plants in a volume of water of 225 l / ha, to get ready-made solution. The plants were grown in under normal conditions

The concentration of the active ingredient grown in pots and the evaluation was made

which he in the intended use month after treatment; the respective effect

on weed control crops 60 was classified according to the following scale:

is applied depends on the culture concerned _{Λ Tr} . ,,, .....

and the weeds to be treated, also 0 - No noticeable effect

of the type of machine used for spraying 1 - Doubtful effect

is used because one generally has both spray .2 - Limited effect, which, however, neither to machines for small volumes as well as those for 65 a permanent loss of size, growth large volume used, which spray ability or pigmentation leads to another

with different concentrations of the effective, significant morphological change

Require component. From the weed-leads standpoint.

3 - Effect between paragraphs 2 and 4.

4 - A noticeable effect on plant growth resulting in loss in size, growth ability or pigmentation or a significant permanent change caused in the morphology of the plant without causing its death.

5 - Effect between paragraphs 4 and 6.

IO 6 - Severe action on the growth of the plant, which leads to the death of the plant at the end of the trial period of one month.

The results obtained with 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid and their ethyl esters and obtained with 2-oxobenzothiazolinyl (3) acetic acid are listed in Table I below:

Table I.

connection

Sticky herb: 280 560 1120 Chickweed: 280 560 1120 sow Cnoteric Acid equivalent 2 . 3 4th Acid equivalent 0 0 0 reaquiv g / ha 4th 5 6th g / ha 5 6th 6th 280 g / ha 5 6th 6th 6th 6 * 6th 0 560 4th 2 2 5 4th

Comparison connection

2-oxobenzothiazolinyl (3) acetic acid

(U.S. Patent 2,468,075)

Compounds According to the Invention
4-chloro-2-oxobenzthiazoIinyl (3) acetic acid
Ethyl ester of the above acid

The following tests were also carried out:
Four approaches of various weeds and crops were with A. aqueous solutions of the diethanolamine salt of 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid, B. aqueous emulsions of certain esters of the specified acid and C. aqueous solutions of the diethanolamine salt of 5-bromo -2-oxobenzothiazolinyl- (3) -acetic acid sprayed. In each

Case the application ratio corresponded to 1120 g / ha free acid, and the test compound was in one Water volume applied according to 225 l / ha. The plants were taking in rearing dishes standardized'.conditions raised and one month after the treatment of a visual examination subjected, the evaluation being carried out as indicated above:

Herbicidal effectiveness

connection

Sticky
herb Weeds
Chicken-
colon Redshank
(Redshank) peas fruit
wheat 6th 6th 6th 1 0 6th
6th
6th
6th 6th
6th
6th
6th 5
5
6th
5 1
1
0
0 0000 0 ^% 1 1 - -

oats

Compounds According to the Invention

A. 4-Chloro-2-oxobenzothiazolinyl- (3) -acetic acid (I)

B. Esters of I:

methyl

ethyl

Propyl

2- (2-butoxyethoxy) ethyl

Comparison connection

C. 5-Bromo-2-oxobenzothiazolinyl- (3) -acetic acid ..
(U.S. Patent 2,468,075)

The compounds of the invention can, for. B. by reacting 4-chloro-2-oxobenzothiazoline with a compound X - CH ₂ - Y, where X is a halogen atom and Y is the carboxylic acid group or a salt or an ester thereof, in the presence of an alkaline condensing agent, where the group Y can optionally be converted into another desired group in a manner known per se.

In detail, for example, ^ chlorine ^ -oxobenzothiazoline with a haloacetic acid ester, for example an alkyl ester of chloroacetic acid, such as. Ethyl chloroacetate, implemented. This reaction gives the corresponding 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid ester. This ester can be converted into the 4-chloro-2-oxobenzothiazolinyl (3) -

acetic acid are transferred. Reactive derivatives of this acid, e.g. B. the acid chloride, can then after known processes can in turn be converted into the desired ester.

The preparation of compounds according to the invention is described below by way of example :

Preparation example A

For the preparation of the ethyl ester of 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid was a mixture of 186 g of 4-chloro-2-oxobenzothiazoline, 180 g of ethyl bromoacetate, 140 g of potassium carbonate and 1 liter of acetone IV heated under reflux for 2 hours. The reaction mixture was filtered and the acetone was removed from the filtrate by evaporation. Included

7 8

an oil was obtained which, during the treatment, was heated at a temperature of 105 °. After 300 ml of ethanol crystallized out. The solid body with the addition of 300 ml of water, the isobutanol was isolated and recrystallized from ethanol. Extract with ether. The aqueous phase was acidified to the ethyl ester of 4-chloro-2-oxobenzthiazo and then made alkaline with sodium bicarbonate in the form of a crystalline solid 5. The insoluble 4-chloro-2-oxobenzothiazoline body with a melting point of 78 to 79 °. was filtered off; the filtrate gave on acidification (analysis: 48.4 ° / o C, 3.8 ° / o H and 5.2% N; the formula. light yellow resin, which solidified quickly. Two Um-C ₁₁ Hi ₀ ClNO ₃ S requires 48.6% C, 3.7% H and crystallizations from ethyl acetate gave 5.2% N.) 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid. Melt production ^{example B 10 point 193} ° - ·

ι · ι mc vr * 'ι j * c Example of use 1
200 ml of a 1.075 η sodium hydroxide solution were added dropwise and with stirring to a mixture heated under reflux of a herbicidal dust ethyl (3) ethyl acetate and 200 ml of methanol were added to 2.5 parts by weight of 4-chloro-2-oxobenzothiazohin. In the course of 30 minutes, vinyl (3) acetic acid was intimately distilled off with 97.5 parts by weight of Kao-180 ml of methanol, whereupon the reaction mixture was mixed.

mixture was poured into 11 water after removal use example 2 '

The filtrate was formed with a slight precipitate.

acidified until the color changes from Congo red. 20 For the use of ^ -Chlor ^ -oxobenzthiazo-

Cooling gave a crystalline lower vinyl (3) acetic acid in the form of a dispersible one

blow. The recrystallization from ethyl acetate powder was 20 parts by weight of 4-chloro-2-oxobenz-

gave 4-chloro-2-oxobenzothiazolinyl (3) acetic acid in thiazolinyl (3) acetic acid with 8 parts by weight of one

in the form of a crystalline solid with a dispersant, e.g. B. a condensation product

Melting point of 193 °. (Analysis showed 44.5% C, 25 of formaldehyde and an alkylaryl sulfonate, and

2.4% dog, 6.0% N; C ₉ H _e ClNO ₃ s, requires 44.4% C, 72 parts by weight of kaolin intimately mixed. This

2.5% H and 5.7% N.) Water can be added to the mass in order to

_{TT A} " ,. . “ To obtain ready-to-use herbicidal dispersion.

Preparation example C

5.0 g of 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid 30 use example 3
were refluxed with 15 ml of thionyl chloride to use 4-chloro-2-oxobenzthiazo. The excess thionyl chloride was distilled off under linear (3) acetic acid in the form of a herbicidal solution under reduced pressure. The crude acid were 4 g of 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid chloride was distilled under a pressure of 1 to 2 mm with heating in 50 ml of an aqueous solution (boiling point: 110 to 130 °) and gave thereby 35 dissolved to a content of 0.66 g of sodium hydroxide, an oil which crystallized out when left to stand. The solution was diluted to a volume of 1000 ml by adding water to this 4-chloro-2-oxobenzothiazolinyl- (3) -acetyl chloride. One obtained was refluxed with methanol. In the case of the aqueous solution which cools 0.4% (weight / volume), crystals were obtained which were in the form of 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid from methanol. have been recrystallized; the methyl ester obtained contained 40 of its sodium salt.
4-Chloro-2-oxobenzothiazolinyl- (3) -acetic acid would have a _T7 . ', ·· ,,,
Melting point from 126 to 127 °. (The analysis gave Use Example 4
46.3% C and 3.2% H; C ₁₀ H ₈ ClNO ₃ S requires the use of ^ -Chlor ^ -oxobenzthiazo-46.7% C and 3.2% H.). Vinyl (3) ethyl acetate in the form of an aqueous υ * ti u ■ ■ 1 Tx 45 emulsion were 4.5 g of 4-chloro-2-oxobenzthiazo preparation example D vinyl (3) ethyl acetate with 50 ml of xylene with a mixture from 10 g of 4-chloro-2-oxobenzthiazo a content of 1 ml of an emulsifier, the linyl (3) acetyl chloride, 5 ξ 2- (2-butoxyethoxy) ethanol, a mixture of lauryl diethanolamide and a 5 g pyridine and 200 ml of ether were prepared for 2 hours polyethylene oxide condensation product, heated under reflux. The reaction mixture was mixed and then diluted successively with ice-cold 5N sulfuric acid, water, to a volume of 1000 ml by adding water,
an aqueous sodium bicarbonate solution and water. . .
washed, whereupon the ether was distilled off. Usage example 5
Resin-like residue was distilled and, in doing so, gave 2- (2-butoxyethoxy) ethyl ester of 4-chloro-2-oxo-55-lynyl (3) -acetic acid ethyl ester in the form of aqueous konbenzthiazolinyl (3 ) -acetic acid <in the form of an oil with centered solutions that are diluted with water with a boiling point of 19070.075 mm. (The analysis suitable to obtain herbicidal solutions for the application gave 52.0% C and 5.6% H; C ₁₇ H ₂₃ ClNO ₅ S requires genes on plants, the following were 52.6 C and 5.7% H.) . Components mixed in the specified quantities:

Preparation _{Example E a} ) 4-chloro-2-oxobenzthia-, 18.5 g of 4-chloro-2-oxobenzthiazoline, in 100 ml of isozolinyl- (3) -acetic acid-

butanol and 30 ml of toluene became 20 g of acid equivalent with 4.5 g of sodium sodium salt

hydroxyd heated, and the water was replaced by azeo water to make up to 100 ml

tropic distillation removed. An Auf- 65 b) diethanolamine salt was obtained
slurry of the sodium derivative. To the cooled 4-chloro-2-oxobenzthiazo-

12.8 g of chloroacetic acid-nalinyl- (3) -acetic acid were 20 g acid equivalent

The trium salt was added and the mixture was filled with water to make up to 100 ml for 3 hours

. 309 620/108

ίο

Usage example 6

In field trials to further evaluate 4-chloro-2-oxobenzothiazolinyl- (3) -acetic acid and its Ethyl ester one took the usual small ones

Surfaces. In experiments 1, 2 and 3 the results are 5 plants.

Attempt 1
Weed: Glutinous herb (Galium aparine)

nisse summarized. The "percentage control" is based on the fresh weight of those above the ground Parts of the weeds in the three main types compared to untreated control

Treated with crowd
Acid equivalent
g / ha Stage of growth '
the weeds Percentage
Combat Ethyl ester
acid 280
560
, 1120
280
560
1120 Sticky herb, about 15 cm
\ 15 cm high, strong j
Sticky herb more than 2 ¹ I ₂ cm
I 2 ¹ I ₂ cm high and flowering j 100
100
100
67
70
85

Attempt 2
Weeds: knotweed (Polygonium persicaria)

Treated with

Amount of acid equivalent

g / ha

Stage of growth
of weeds

Percentage control

Ethyl ester

280

560

1120

Seedling

35 50

55

Attempt 3

could be achieved a 100 ° / ₀ sodium elimination of weeds by applying the ethyl ester in amounts ent-35 speaking acid equivalents of 280, 560 and 1120 g / In this experiment it was not possible, a ha, one of which is carried out by visual inspection of the test Quantitative determination , but was able to convince in practical terms. .

Weeds: Chickweed (Stellaria media)

Claims (1)

1 2 Claims · - The invention relates to 4-chloro-2-oxobenzthiazoIinyl- (3) -acetic acid of the formula 1,4-chloro-2-oxobenzothiazolinyI- (3) -acetic acid der. ' Formula Cl CH ₂ -COOH CH ₂ COOH 5 j I