CA1125301A - Herbicidally active n-(2-propynyl)-carbanilic acid (3-aliphatic hydrocarbon-oxy- or - thio- carbonylaminophenyl) esters and their manufacture and use - Google Patents

Abstract

ABSTRACT

(I) (wherein R represents C1-C4 -alkyl, C3-C4-alkenyl or C3-C4-alkynyl and X represents O or S) and their manufacture.
The novel compounds of the general formula I have a herbicidal action, especially a selective herbicidal action, and accordingly may be made up with suitable carriers into herbicidal preparations and may be used for protecting living plants and crop areas against weeds.

Description

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The present invention i~ concerned with new N-t2-Propynyl)-carbanilic acid (3-aliphatic hydrocarbon-oxy- or thio-carbonylaminophenyl) e~ters, with proce~ses ~or the manu~acture of these compounds and also with their use as herbicidal agents, especially selective herbicidal agents.
The herbicidal action of carbanilic acid (3-alkoxycarbonylaminophenyl) esters and diùrethane~ is already known (German Patent Speci~ication NoO 1,567,115).
These compound~ have a su~ficient selectivity only in beta beet crop~. Furthermoret these compounds ex-hibit large gaps in activity.
The problem upon which the pre~ent invention i~
based has been to provide a weed~controlling agent which ~urthermore acts again~t weeds that are difficult to control, especially accompanied by a complete toler-abil.ty towards important agricultural crops. This problem ls solved according to the p~esen~ inventio~ by the compounds o~ the general ~o~mula I, a~ defined below.
The present i~vention accordingly provides compounds o~ the general ~ormula I

(I) NH-C-X~R

O
in which R represents a Cl-C4-alkyl~ C3-C4-alkenyl or C~-C4-alkynyl group and X represents an oxygen or sulphur atom~
~he compounds o~ the present invention surprising-ly exhibit a greater selective herbicldal action than do known constitutionally analogous compounds having the ~ame direction o~ action~
~ further technically more important advantage of the compounds of the present invention lie~ in th~ir practical u~e, a~ the~ can be u~ea ~3 new h0rbicide~
again8t those resistant weedQ and a secondary flora that can no longer be adequately controlled by the herblcide~ kr,own i~ practice owing to the development o~ a resistance by the weed~.
The compound~ of the pre~ent invention are di~-tinguished by a broad leaf-herbicidal action~ They can be used for controll~ng dicotyledonous weedsO
~he csmpounds control by the post-emergence methods weed~ in arable land, ~or example 9tellaria media, Matricaria chamomilla, Lamium amplexicaule, Centaurea cyanus, Amarantus retroflexus, Solanum saccharoides, Eschholtzia californica, Ipomoea purpurae, Setaria italica and other weeds.

For controlling seed weeds there are generally used application quantities within the range of from 1 kg to 5 kg of active substance perhectare. In this way the characterized active substances are surprisingly selective in commercial plant crops, Eor example cotton, potatoes, maize, wheat and 10 rice. When two or more compounds of -the general formula I
are used, the range of 1 to 5 kg refers of course to the total application ~uantities of these compounds.

The present invention accordingly also provides a 15 herbicidal preparation which comprises a compound of the general formula I, in admixture or conjunction with a suitable carrier. The preparation may of course contain one or more compounds of the general formula I~

The present invention further provides a method of protecting a living plant against weeds~ wherein the area in the vinicity o~ the living plant is treated with a compound of the general formula I.

The present invention further provides a method of protecting a crop area against weeds, wherein the crop area is treated with a compound of the general formula I.

The present invention further provides a pack which comprises a compound of the general formula I together with instructions for its use as a herbicide.

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The compounds of the presen-t invention may be used either singly or in the form of mixtures with one another or with other active substances. If desired, other plant-protec-ting agents and/or pesticides may be added, depending on -the desired aim.

If a broadening of the range of action is intended, other herbicides may also be added. As suitable herbicidally-active co-components there may be mentioned, for example, active substances from the groups of triazines, aminotriazoles, anilides, diazines, uracils, aliphatic carboxylic acids and aryloxycarboxylic acids, hydrazides, amides, nitriles and esters of such carboxylic acids, carbamic acid esters, thiocarbamic acid esters, ureas, 2,3,6-trichlorobenzyloxy~
isopropanol, thiocyanate-containing agents and other additives.
Among other additives there are to be understood, for example, non-phytotoxic additives which are capable of producing, with herbicides, a synergistic increase in action, for example wetting agents, emulsifiers, solvents and oily additives.
The active compounds of the present invention or mixtures containing them are advantageously used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface-active agents for example wetting, adhesive, emulsifying and/or dispersing agents.

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Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethyl Eormamide, and also mineral oil fractions.

Suitable solid carriers are, for example, mineral earths, for example, tonsil, silica gel, talcum, kaolin, attaclay, limestone and silicic acid, and vege-table products, for example meals.

As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylene-alkylphenol ethers, naphthalenesulphonic acids and salts thereof, phenolsulphonic acids and sal-ts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzenesulphonic acids and salts thereof.

The proportion of the active substance or sub-stances in the various herbicidal preparations may vary withinwide limits. For example, the preparations may contain approximately 5 to 95% by weight of active suhstance(s), approximately 95 to 5% by weight of liquid or solid carrier and also, if desired, up to 20% by weight of surface-active agent(s).

The active compounds may be applied in the usual ~ - 6 ~

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manner, for example with water as carrier in quantities of spray liquor of approximately 50 to 1000 litre~ per hectare. It i~ also possible to apply the active com-pounds by the so-called low-volume and ultra-low-volume method~ as ~ell as to apply them in the form of so-called microgran~es.
~ mong the compounds of the present invention that are distinguished by an out~tanding æelective herbici-dal action there should be mentioned more especially tho~e of the general formula I in which R represents a methyl, ethyl, i~opropyl, allyl~ propynyl, isobutyl~
sec.-butyl, sec~-butenyl or ~ecO-butynyl group and X
represents an oxygen or ~ulphur atom~
~he new compound~ of the general formula I may be manufactured, for e~ample, by the process of the pre-~ent invention, a~ def~ned below.
~ he Pr~sent invention accordingly ~urther prov~o~
~ p~oce~s ~or the manufacture of the compound~ of the general formula I, wherein a) a compound of the ge~eral formula 0 -C~Cl d, , 11 N~-C X-R
~,.

~ 3 in which R and X have the meanings given above, is . reacted with N-(2-propyn~ aniline of the formula ~CH2-C-CH
H N
\,~ , .

in the presence o~ an acid acceptor, ~or example with the addition of an excess of the amine or of an inr organic bas~, ~or example a ~odium hydroxide solution, ~odium carbonate or pota~sium carbonate, or a tertiary organic ba~e, ~or exarnple trlethylamine, or b~ a compound o~ the general ~ormula . . 0~ .

~--a--X--R ~ ' O

in ~hich ~ and ~ have the meanings given above, i~
reacted in the presence o~ a tertiary organic base~
for example triethylamine or pyridi~e, or is reacted ~ the ~orm o~ an alkali ~alt thereof w~th N-phenyl~
N-(2 propynyl)-carbamo~-l chloride of the formula - 9 ~ z~

C=C-~2 ~ -C0-Cl each reaction of variant (b) bein~ carried out at a temperature within the range o~ from 0 to 100Co Thc compound~ of the general formula I formed by the variant (a) or ~b) may be isolated in the usual manner.
~ hs compound~ o~ the pre~ent in~ention are ~olu-ble i~, *or example, isophorone, cyclohexanone, ace-tone, tetrahydro~uran, dimethylformamide and dimethyl sulphoxide and sparingly ~oluble in, for example, water, benzene and tolue~e~
The ~ollowing ~xamples illustrate the invention.
~xampl~ 1 illustrates the manufacture of the com-po~nd~ o~ the p~e~ent i~entio~ and ~xample~ 2 and 3 illuHtrate the pos~ible way~ of using the ^om~ou~ds o~ the present invention, the compou~d3 in ~ample~

2 and 3 being u~ed in the ~orm o~ preparations thereo~.
~B~
~(2-Propynyl~carbanilic acid (3-methoxycarbonyl-amino~hen 1) e~ter Into a solutio~ o~ 39~4 g tO03 mole) o~ N- t2-5~

propynyl)~aniline in 75 ml o~ ethyl acetate were intro-duced dropwise, while stirring and cooling to 8 to 12C, a ~olution of 68 9 7 g (0.3 mole) o~ chloro-formic acid (~-methoxycarbonylc~minophenyl) e~ter in 150 ml of ethyl acetate and siml~taneously a solution o~ 41.4 g (0.~ mole) of potas~ium carbonate in 150 ml of water. Stirring was continued for 30 minutes at 10C, and then the organic phase wa~ separated and, wlth the addition o~ ice, wa~hed with dilute hydro~
chloric acid and water. A~ter drying the mixture ~ith magne~ium sulphate it wa~ concentrated by evapor-ation under reduced pre~ure, and ~hen 500 ml of iso- -propyl ether were added, ~hereupon the reaction pro-duct crystallized out~
Yield: 6709 g - 69.8% of the theore~ical yield~
~elting point: lGdC.
The following compounds of the present invention may be prepared in an analogou~ manner.
Phy~ical constant ~ame o~ the compound ~-(2-Propynyl~-carbanilic acid C3-(methylthio-carbonylami~o)~
phenyl] ester M.p.: 130C
~ (2 Propynyl)-carbanilic acid ~-(ethylthio-carbonylamino)- -phenyl~ e~ter M.p.: 99C
~-(2-Propynyl)-carbanilic acid [~-(Z propynyloxyca~bonyl-amino)-phenylJ ester N.p~: 118C

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Name of the compound Phy~ical con~tant N-(2-Propynyl)-carbanilic acid ~3~(2-methylpropoxycarbonyl-amino)-phenyl3 ester M.p.: 108C
N-(2-Propynyl)-carbanilic acid (3-ethoxycarbonylaminophenyl) ester ~l.p.: 101 to 10~C
N-(2-Propynyl)-carbanilic acid [3~ methylethoxycarbonyl-amino) phenyl]- ester M.p~: 78 - 79C
N-(2-Propynyl)-carbanilic acid ~3~ methyl-2-propen~loxy-carbonylamino)-phenylJ e~ter M.p.; 96 97C
~ . .
In a serie~ of tests carried out in a greenhouse, the compounds, o~ the present invention listed in the ~able below were each sprayed in the form o~ an aqueous e~ulsion or suspension by the post-emergence method at a rate of applicatio~. of 5 kg o~ acti~e substance per hectare in 500 lltres of water per hectare, on ~,o Solan um and Bra~aica aa 'he tes~v plants,.
~ hree ~eP~s after the treatment the results there-o~ were evaluated and e~pres~ed by a numerical scale having the values 0, 1, 2, 3 and 4, the value 0 at one end o~ the ~cale representing no action and the value 4 at the other end representing de~truction of the plant.
The results show that i~ general destructio~ of the plants was achieved.

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Compound of the invention Solanum Bra~ioa , N-(2-Propynyl)-carbanilic acid [3-(methylthio-carbonylamino)_ phenyl] ester 4 4 N-(2-Propynyl)-carbanilic acid [3-(ethylthio-carbonyla~ino)-phenyl] ester 4 4 N-(2-Propynyl)-carbanilic acid [3-(2-propynyloxycarbonyl-amino)-phenyl] ester 4 4 N-(2-Propynyl)-carbanilic acid [3-(2-methylpropoxycarbonyl-amino)-phenyl] ester 4 4 ~-(2-Propynyl)-carbanilic acid .-(3-et~oxycarbonylaminophenyl) eæter 4 4 ~-(2-Propynyl)-carbanilic acid t~ methylethoxycarbonyl-amino) phenyl] ester . 4 4 N-(2-Propynyl)-carbanilic acid [~ (l-methyl-2-propen~lo~y-carbonylamino)-phenylJ ester 4 4 Untreated ~ O
O = no action 4 = destruction of the plant ~8~ , I~ a series of test~ carried out in a greenhouse~
the plants listed in the Table below were treatea after their emergence with the compound of the pre~ent i~-vention and the known compound used for comparison, ~n each caæe in the form o~ an aqueous emulsion apply-~ng 1 kg of active substance per hectare in 500 litrea of water per hectare. For thi~ purpo~e9 the aqueous

3~

emulsion wa~ in each case sprayed uniformly over the plant~.
Three weeks after the treatment the results there-of were evaluated and expressed by a numerical scale extending from O to 10 9 the value O representing total de~truction of the plant and the value 10 re-presenting no damageO
The compound of the present invention exhibited an outstanding sèlective herbicidal action, whereas the known compound did not.

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Claims (24)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED
AS FOLLOWS:

1. A compound of the general formula I

( I) in which R represents a C1-C4-aIkyl, C3-C4-alkenyl or C3-C4-alkynyl group and X represents an oxygen or sul phur atom.

2. A compound as claimed in claim 1, wherein R
represents a methyl, ethyl, isopropyl, allyl, propynyl, isobutyl, sec.-butyl, sec.-butenyl or sec.-butynyl group and X represents an oxygen or sulphur atom.

3. N (2-Propynyl)-carbanilic acid (3-methoxy-carbonylaino?phenyl) ester.

4. N-(2-Propynyl)-carbanilic acid [3-(methylthio carbonylamino)-phenyl] ester.

5. N-(2-Propynyl)-carbanilic acid [3-(ethylthio-carbonglamino)-phenyl] ester.

6. N-(2-Propynyl)-carbanilic acid [3-(2-propynyl-oxycarbonylamino)-phenyl] ester.

7. N-(2-Propynyl)-carbanilic acid [3-(2-methyl-propoxycarbonylamino)-phenyl] ester.

8. N-(2-Propynyl)-carbanilic acid (3-ethoxycarbonyl-aminophenyl) ester.

9. N-(2-Propynyl)-carbanilic acid [3-(1-methyl-ethoxycarbonylamino)-phenyl] ester.

10. N-(2-Propynyl)-carbanilic acid [3-(1-methyl-2-propenyloxycarbonylamino)-phenyl] ester.

11. A process for the manufacture of a compound of the general formula I given in claim 1, in which R and X have the meanings given in claim 1, wherein a) a compound of the general formula in which R and X have the meanings given above, is reacted in the presence of an acid acceptor with N (2-propynl)-aniline of the formula or b) a compound of the general formula in which R and X have the meanings given above, is reacted in the presence of a tertiary organic base or is reacted in the form of an alkali salt thereof with N-phenyl-N-(2-propynyl)-carbamoyl chloride of the formula each reaction of variant (b) being carried out at a temperature within the range of from 0 to 100°C.

12. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 1.

13. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 2, 3 or 4.

14. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 5, 6 or 7.

15. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 8, 9 or 10.

16. A method as claimed in claim 12 wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 5 kg per hectare.

17. A method as claimed in claim 12 wherein two or more compounds of the general formula I are used for the treat-ment in a total amount within the range of from 1 to 5 kg per hectare.

18. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 1.

19. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 2, 3 or 4.

20. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 5, 6 or 7.

21. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 8, 9 or 10.

22. A method as claimed in claim 18 wherein a single compound of the general formula I is used for the treatment in an amount within the range of from l to 5 kg per hectare.

23. A method as claimed in claim 18 wherein two or more compounds of the general formula I are used for the treat-ment in a total amount within the range of from 1 to 5 kg per hectare.

24. A method as claimed in claim 18 wherein the crop is a cotton, potato, maize, wheat or rice crop.