IL46284A - Alkylaminosulfonyloxy butynyl carbamates their preparation and herbicidal compositions containing them - Google Patents

Description

0'Βδ3ΐ »3*&ιη »o iK¾»a la ioij OK ' ^K οηηκ New alkylaminosulfonyloxy butynyl barbamates, their preparation and herbicidal compositions containing them BASF AKTIENGESELLSCHAFT C:- 44258 46284/2 The present invention relates to new, substituted butynyl carbamates having a herbicidal action, herbicides containing these compounds, and the use of these compounds as herbicides.

It is known (German Printed Application DAS 1,137,255) to use 4-chlorobutyn-2-yl-N- ( 3-chlorophenyl ) -carbamate as a herbicide. However, its action is poor.

We have, now found that a butynyl carbamate of the formula where R^" denotes phenyl optionally substituted with CF3 or 2 alkoxy or with one or two halogens and R denotes hydrogen, alkyl (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl) or haloalkyl ( β-chloroethyl) , has a good herbicidal action.

The new substituted butynyl carbamates of the formula I may be prepared by reaction a 4-hydroxybutyn-2-yl carbamate o.z. 30,291 of the formula H 0 V' N-C-0-CH2-C=C-CH2OH II, where R has the above meanings, with an aminosulfonyl halide of the formula 2 where R has the above meanings and X denotes halogen (e.g. chloro and bromo). This method of manufacture is preferred.

The new butynyl carbamates of the formula I may also be prepared by reacting a compound of the formula where R has the above meanings, with an isocyanate of the formula R1NCO V, where R1 has the above meanings, or with phosgene and an amine of the formula R½H2 VI, where R has the above meanings .

The compounds of the formulas II, III and IV are generally known, or may be prepared as follows. Formula II compounds may be produced by reacting a 1 ,^-butynediol with an isocyanate of the formula V, or with phosgene and an amine of the formula VI. Formula III compounds may be manufactured for instance by the process described in Liebig's Ann. Chem., 729, 10-51, 1969. o.z. 30,291 Formula IV compounds may be prepared by reacting a l^-butyne-diol with a compound of the formula III, R2NHS02X, X denoting.-halogen.

The following examples illustrate the invention.

EXAMPLE 1 At 0° to 5°C and while stirring, 20.8 parts by weight of methylaminosulfonyl chloride (approx. 90%) and 16.6 parts by weight of triethylamine were simultaneously added to a solution of 23.95 parts by weight of 4-hydroxybutyn-2-yl-N- (3-chloro-phenyD-carbamate in 650 parts by weight of methylene chloride. 30 minutes after completion of the reaction the mixture was treated with ice water, dilute aqueous hydrochloric acid, water, sodium bicarbonate solution and again with water. The methylene chloride solution was dried with magnesium sulfate and concentrated; there was obtained 33 parts of crude product having a melting point of 99° to 102°C. After recrystallization from a mixture of 1,2-dichloroethane and benzene the compound melts at 103° to 105°C.

The compound, -methylaminosulfonyloxybutyn-l-yl-N- ( 3-chlorophenyl) -carbamate, has the following formula: 0 CI The following compounds of the formula I were prepared in analogous manner to that described in Example 1, starting from the appropriate 4-hydroxybutyn-2-yl substituted carbamate and an appropriate aminosulfonyl chloride. o.z.30,291 3 ClCgH^ 103 -105 3 ClCgH^ C2H5 I.538O 3 C1C6H4 C3H7 3 ClCgH^ i-C3H7 84. 86 3 C1C6H4 CH2CH2C1 3 CF3C6H1 H 3 CF3C6Hlj CH, 3 CF3C6Hi| C2H5 3 CF^H^ C3H7 3 CF3C6Hl| i-C3H7 3 CF3C6Hi( CH2CH2C1 CH.

C6H5 3 BrCgH^ CH. 3j4 C12C6H4 CH. 3 CHjCgHjj CH- 3 CPjCgH,, CH. 59 - 63 CH, 91 - 93 C6H5 3^ C12C6H3 CH- 122 - 125 3,4 C12C6H3 C2H5 113 - 115 3^4 ,C12C6H3 i-C3H7 136 3 CHjCgH^ CH, 90 - 92 3 CH3OC6H 58 - 61 O.Z. 30,291 The new compositions have a strong herbicidal action and may therefore be used as weedkillers or for controlling the ^ ■ growth of unwanted plants. Whether the new active ingredients are used as total or selective agents depends in essence on the amount of ingredient used per unit area.

By weeds and unwanted plant growth are meant all mono-cotyledonous and dicotyledonous plants which grow in loci where they are not desired.

The agents according to the invention may therefore be used for controlling for instance Gramineae, such as Cynodon spp. Dactylis spp.

Digitaria spp. Avena spp.

Echinochloa spp Bromus spp.

Setaria spp. Uniola spp.

Panicurn spp. Poa spp.

Alopecurus spp. Leptochloa spp.

Lolium spp. Brachiaria spp.

Sorghum spp. Eleusine spp.

Agropyron spp. Cenchrus spp.

Phalaris spp. Eragrostis spp.

Apera spp. Phragmites communis etc . ; Cyperaceae, such as Carex spp. Eleocharis spp.

Cyperus spp. Scirpus spp. etc. ; dicotyledonous weeds o.z. 30,291 Malvaceae, e.g. , Abutilon th60prasti Hibiscus spp.

Sida spp. Malva spp. etc . j .

Compositae, such as Ambrosia spp. Centaurea spp.

Lactuca spp. Tussilago spp.

Senecio spp. Lapsana communis Sonchus spp. Tagetes spp.

Xanthium spp. Erigeron spp.

Iva spp. Anthemis spp.

Galinsoga spp. Matricaria spp.

Taraxacum spp. Artemisia spp.

Chrysanthemum spp. Bidens spp.

Cirsium spp. etc . ; Convolvulaceae, such as Convolvulus spp. Cuscuta spp.

Ipomoea spp. Jaquemontia tamnifolia etc . ; Cruciferae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp.

Capsella spp. Draba spp.

Sisymbrium spp. Coronopus didymus Thlaspi spp. Lepidium spp.

Sinapis arvensis Raphanus spp. etc . ; Geraniaceae, such as Erodium spp. Geranium spp. etc . ; Portulacaceae , such as Portulaca spp. etc . ; Primulaceae, such as Anagallis arvensis Lysimachia spp. etc . ; Rubiaceae, such as Richardia spp. Diodia spp.

Galium spp. etc.; Scrophulariaceae , such as Linaria spp. Digitalis spp.

Veronica spp. etc . ; Solanaceae, such as Physalis spp. Nicandra spp.

Solanum spp. Datura spp. etc . ; Urticaceae, such as Urtica spp.

Violaceae, such as Viola spp. etc . j Zygophyllaceae, such as Tribulus terrestris etc. ; Euphorbiaceae, such as Mercurialis annua Euphorbia Umbelliferae* such as Daucus carota Ammi majus Aethusa cynapium etc . ; o.z. 30,291 Commelinaceae , such as Commelina spp. etc . ; Labiatae, such as Lamium spp. Galeopsis spp. etc . ; Leguminosae, such as Medicago spp. Sesbania exaltata Trifolium spp. Cassia spp.

Vicia spp. Lathyrus spp. etc . ; Plantaginaceae , such as Plantago spp. etc . ; Polygonaceae, such as Polygonum spp. Pagopyrum spp.

Rumex spp. etc . ; Aizoaceae, such as Mollugo verticillata etc . ; Amaranthaceae , such as Amaranthus spp. etc . j Boraginaceae , such as Amsinckia spp. Anchusa spp.

Myostis spp. Lithospermum spp. etc . ; Caryophyllaceae, such as Stellaria spp. Silene spp.

Spergula spp. Cerastium spp.

Saponaria spp. Agrostemma githago Scleranthus annuus etc . ; o.z. 30,291 Chenopodiaceae , such as Chenopodium spp. Atriplex spp.

Kochia spp. Mcnolepsis nuttalliana Salsola Kali. etc . ; Lythraceae, such as Cuphea spp. etc . ; Oxalidaceae, such as Oxalis spp.

Ranunculaceae , such as Ranunculus spp. Adonis spp.

Delphinium spp. etc . ; Papaveraceae, such as Papaver spp. Fumaria offinicalis etc . ; Onagraceae, such as Jussiaea spp. etc . ; Rosaceae, such as Alchemillia spp. Potentilla spp. etc . ; Potamogetonaceae, such as Potamogeton spp. etc . ; Najadaceae, such as Najas spp. etc . ; Equisetaceae Equisetum spp. etc . ; Marsileaceae, such as Marsilea quadrifolia etc . ; Polypodiaceae, Pteridium quilinum O.Z. 30,291 Alismataceae, such as Alisma spp. Sagittaria sagittifolia etc .

The herbicides according to the invention may be employed in cereal crops such as Avena spp. Sorghum Triticum spp. Zea mays Hordeum spp. Panicum miliaceum Secale spp. Oryza spp.

Saccharum offinicarum and in dicotyledon crops such as Cruciferae, e.g.

Brassica spp. Raphanus spp.

Sinapis spp. Lepidium spp.

Compositae, e.g.

Lactuca spp. Carthamus spp.

Helianthus spp. Scorzonera spp.

Malvaceae, e.g.

Gossypium hirsutum Leguminosae, e.g.

Medicago spp. Phaseolus spp.

Trifolium spp. Arachis spp.

Pisum spp. Glycine max.

Chenopodiaceae, e.g.

Beta vulgaris Spinacia spp.

Solanaceae, e.g.

Solanum spp. Capsicum annuum Nicotiania spp. o.z. 30,291 Linaceae, e.g.

Linum spp. L Umbelliferae, e.g.

Petroselinum spp. Apium graveolens Daucus carota Rosaceae, e.g. Pragaria Cucurbitaceae, e.g.

Cucumis spp. Cucurbita spp.

Liliaceae, e.g.

Allium spp.

Vitaceae, e.g.

Vitis vinifera Bromeliaceae, e.g.

Ananas sativus.

The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 15 (and more), preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before or after planting, before sowing, and before, during or after emergence of the crop plants and unwanted plants.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

O.Z. 30,291 For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaph-thalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophcrone, etc., and strongly polar solvents such as dimethyl-formamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols , heptadecanols , and octadecanols , salts of sulfated fatty o.z. 30,291 alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, ^ condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol , ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tri-butylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil ,polyoxyethylene alk l ethers, ethoxy-lated polyoxypropylene , lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose .

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths, such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90% by weight of active ingredient.

There may be added to the compositions or individual active ingredients (if desired, immediately before use (tank-mix) ) oils of various types, herbicides, fungicides, nemato- o.z. 30,291 cides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g. ,silicones ) , growth regulators, antidotes and^* other herbicidally effective compounds such as substituted anilines substituted aryloxycarboxylic acids and salts, esters and amides thereof, substituted ethers substituted arsonic acids and their salts, esters and amides substituted benzimidazoles substituted benzisothiazoles substituted benzothiadiazinone dioxides substituted benzoxazines substituted benzoxazinones substituted benzothiadiazoles substituted biurets substituted quinolines substituted carbamates substituted aliphatic carboxylic acids and their salts, esters and amides substituted aromatic carboxylic acids and their salts, esters and amides substituted carbamoylalkylthiol- or -dithiophosphates substituted quinazolines substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides substituted cycloalkylcarbonamidothiazoles substituted dicarboxylic acids and their salts, esters and amides substituted dihydrobenzofuranyl sulfonates O.Z. 30,291 substituted disulfides substituted dipyridylium salts substituted dithiocarbamates substituted dithiophosphoric acids and their salts, esters and amides substituted ureas substituted hexahydro-lH-carbothioates substituted hydantoins substituted hydrazides substituted hydrazonium salts substituted isoxazole pyrimidones substituted imidazoles substituted isothiazole pyrimidones substituted ketones substituted naphthoquinones substituted aliphatic nitriles substituted aromatic nitriles substituted oxadiazoles substituted oxadiazinones substituted oxadiazolidine diones substituted oxadiazine diones substituted phenols and their salts and esters substituted phosphonic acids and their salts, esters and amides substituted phosphonium chlorides substituted phosphonalkyl glycines substituted phosphites substituted phosphoric acids and their salts, esters and amides O.Z. 30,291 substituted piperidines substituted pyrazoles ^ substituted pyrazole alkylcarboxylic acids and their salts, esters and amides substituted pyrazolium salts substituted pyrazolium alkyl sulfates substituted pyridazines substituted pyridazones substituted pyridine carboxylic acids and their salts, esters and amides substituted pyridines substituted pyridine carboxylates substituted pyridinones substituted pyrimidines substituted pyrimidones substituted pyrrolidine carboxylic acid and its salts, esters and amides substituted pyrrolidines substituted pyrrolidones substituted arylsulfonic acids and their salts, esters and amides substituted styrenes substituted tetrahydrooxadiazine diones substituted tetrahydroxadiazole diones substituted tetrahydromethanoindenes substituted tetrahydroxadiazole thiones substituted tetrahydrothiadiazine thiones substituted tetrahydrothiadiazole diones substituted aromatic thiocarbonylamides substituted thiocarboxylic acids and their salts, esters and amides o.z. 30,291 substituted thiol carbamates substituted thioureas ^ substituted thiophosphoric acids and their salts, esters and amides substituted triazines substituted triazoles substituted uracils, and substituted uretidine diones .

The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.

These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.

EXAMPLE 2 In the greenhouse, various plants were treated at a growth height of from 2 to 18 cm with 0.5 kg per hectare of each of the following active ingredients, each being dispersed or emulsified in 500 liters of water per hectare: I 4-methylaminosulfonyloxybutyn-2-yl-N-(3-chlorophenyl)- carbamate II 4-ethylaminosulfonyloxybutyn-2-yl-N-(3-chlorophenyl)- carbamate III 4-chlorobutyn-2-yl-N-(3-chlorophenyl) -carbamate (comparative agent).

After 2 to 3 weeks it was ascertained that compounds I and II had a better herbicidal action than III, combined with the same crop plant compatibility. o.z. 30,291 The results are given below: Active ingredient I II III Crop plants : Beta vulgaris 0 0 0 Triticum aestivum 0 0 0 Unwanted plants : Avena fatua 80 80 80 Alopecurus myosuroides 85 80 50 Poa annua 80 75 40 Lolium multiflorum 75 70 30 0 = no damage 100 s complete destruction EXAMPLE 3 In the greenhouse, loamy sandy soil was filled into pots and sown with the seeds of various plants. The soil was then immediately treated with 2 kg per hectare of each of the following active ingredients, each being dispersed or emulsified in 500 liters of water per hectare: I 4-methylaminosulfonyloxybutyn-2-yl-N- ( 3-chlorophenyl)- carbamate II 4-ethylaminosulfonyloxybutyn-2-yl-N- (3-chlorophenyl)- carbamate III 4-chlorobutyn-2-yl-N- (chlorophenyl )-carbamate (comparative agent).

After 3 to 4 weeks it was ascertained that active ingredients I and II had a better herbicidal action than III, combined with the same crop plant compatibility.

O.Z. 30 , 291 The results are given below: Active ingredient I II III Crop plants : Beta vulgaris 0 0 0 Triticum aestivum 10 10 10 Unwanted plants: Avena fatua 50 55 HO Alopecurus myosuroides 70 75 55 Poa annua 80 80 50 Lolium multiflorum 70 70 45 0 = no damage 100 = complete destruction

Claims (9)

46284/2 WHAT WE CLAIM IS:.

1. A butynyl carbamate of the formula where R1 denotes phenyl optionally substituted with CF3 or alkoxy or one or two halogens arid R denotes hydrogen, alkyl or haloalkyl.

2. A herbicide containing a butynyl carbamate of the formula where R1 denotes phenyl optionally substituted with CF3 2 or alkoxy or one or two halogens and R denotes hydrogen , alkyl or haloalkyl.

3. A herbicide containing a solid or liquid carrier a butynyl carbamate of the formula where denotes phenyl optionally substituted with CF^ 2 or alkoxy or one or two halogens and R denotes hydrogen, alkyl or haloalkyl. 46284/2

4. A process for producing a herbicide wherein a solid liquid carrier is mixed with a butynyl carbamate of the formula where R1 denotes phenyl optionally substituted with CF3 or alkoxy or one or two halogens* and R2 denotes hydrogen, alkyl or haloalkyl.

5. A process for controlling the growth of unwanted plants wherein the plants or the soil are treated with a butynyl carbamate of the formula where R1 denotes phenyl optionally substituted with CF3 or alkoxy or one or two halogens and R 2 denotes hydrogen, alkyl or haloalkyl.

6. A process for producing a butynyl carbamate of the formula where R1 denotes phenyl optionally substituted with CF3 2 or alkoxy or one or two halogens and R denotes hydrogen, o.z. 30,219 alkyl or haloalkyl, wherein a -hydroxybutyn-2-yl carbamate of the formula where R has the above meanings, is reacted with an amino-sulfonyl halide of the formula H 0 \ " / NSX, / » R2 0 2 '' where R has the above meanings and X denotes halogen, wherein an aminosulfonyl butynyl alcohol of the formula 0 H HOCH,-C=C-CH0-OS-N^ , where R has the above meanings, is reacted with an isocyanate of the formula R-'NCO, where R has the above meanings, or with phos ene and an amine of the formula R1NH2, where R has the above meanings.

7. A butynyl carbamate prepared by the process as claimed in claim 6.

8. 4-methylaminosulfonyloxybutyn-2-yl-N- (3-chlorophenyD-carbamate.

9. 4-ethylaminosulfonyloxybutyn-2-yl-N- ( 3-chloropheny1 ) -carbamate .