DE2021822A1 - Acylated trifluoromethylurea carbamates and their use as herbicides - Google Patents

Description

LAWYERS

DR-JUR-DIPL-CHEM-WALTERBEIL ALFRED HOEPPENER
DR. JUR. DIPt-CHEM. H.-J. WOLFF DR. JUR. HANS CHR. AX

623FRANKFURTAMAAAIN-HIGHEST ADELONSTRASSE 58

t May ■ "; J

Our number 16 273

Stauffer Chemical Company, New York, Ν.Ϊ., Y.St.A,

Acylated Irifluo: C methyl urea carbainates and their use as HerTpigicle

The invention relates to certain new acylated urea carbamates, which are useful as herbicides. The invention Compounds can be prepared by reacting suitable carbamoyloxyphenylureas with trifluoroacetic anhydride and conform to the formula

O {) 9 B4 7/2 O r. «:

2021

In this formula mean

R. and R ₅ independently of one another are alkyl radicals with 1 to about 8 carbon atoms, cyclohexyl, lower alkenyl with about 3 to 4 carbon atoms, phenyl or substituted phenyl - the substituents being lower alkyl groups -, lower alkoxy, nitro or halogen,

R and R ₂ independently of one another are hydrogen, alkyl groups with 1 to about 8 carbon atoms, cyclohexyl, lower alkenyl with about 3 to about 4 carbon atoms or trifluoroacetyl, where in each case at least one of the groups R or Rp must be irifluoroetyl;

R. hydrogen, methyl or - if only one of the two groups R or Rg! Represents erifluoraoetyl - OJrifluoraoetyl.

Suitable carbamoyloxyphenylureas which can be used as starting material are those in which R, R ₂ and R ^ in the ion indicated above are each independently hydrogen.

The various groups mentioned preferably have the following meanings? The alkyl groups are preferably those with 1 to about 8 carbon atoms and the lower ACyl groups are those with 1 to about 4 carbon atoms; in both cases, both a straight-chain and a branched-chain configuration can be present. Examples of alkyl and lower alkyl groups are methyl, ethyl, n-propyl _f isopropyl, η-butyl, sec. Butyl, n-hexyl, Isoanyl, n-heptyl, _t isooctyl, n-octyl, inter alia, Examples of lower alkenyl groups having 3 to about 4 carbon atoms are solohe with at least one double bond in the

009847/2002

2-position, namely allyl, 2-methylallyl, 2-butenyl and others If a lower alkenyl group occurs in a substituted phenyl, it can be a vinyl radical. The term "halogen" includes fluorine, chlorine, bromine and iodine.

The compounds of the invention are active herbicides with general applicability. This is to say that certain members of the class have herbicidal effects against a large number of plant species exhibit, To reduce and the compounds according to the invention are sufficient to eliminate undesired vegetation Quantities applied to the soil in which the plants grow.

"Herbicide" in the present context is a Understood compound that prevents or affects plant growth. Under one to influence plant growth "sufficient" amount means the amount which has a noticeable influence on plant growth. Be under an "influence on plant growth" understood all deviations from natural development, e.g. extermination, delay, defoliation, dehydration, regulation, wilting, cultivation, stimulation, Dwarf growth, among other things, "Plants" include both germinating seeds and emerging little plants as well as already formed ones Plants including the roots and the above-ground parts understood.

The compounds according to the invention can be prepared by various methods depending on the nature of the starting materials and desired products. The following The general method described is applicable to the preparation of any of the compounds described herein. After that, will an appropriately N-monosubstituted carbamoyloxyphenylurea treated with trifluoroacetic anhydride.

009847/2002

If appropriate, sulfuric acid can be used as a catalyst for the reaction. Implementation will in general carried out in a suitable solvent such as benzene. After the reaction has ended, the solvent is removed and the product separated. After the crude product has been separated off, the product is worked up in in a conventional manner, for example by distillation in the case of liquids and by recrystallization in the case of solid substances.

The N-monosubstituted carbambyloxyphenylurea used as the starting material can in turn after a Process for the synthesis of orbamates and urea derivatives, which is described in British Patent 1,106,064.

The compounds according to the invention can be used the procedure described in detail in the following example. Following the example the compounds that can be prepared in the manner indicated are compiled in a table.

example

Reaction of 1- (3'-N-methyl-carbamoyloxyphenyl) -5-methylurea with irifluoroesslgic anhydride

The starting material has 3 reactive hydrogen atoms. In the present example, the reaction of the reactants is described in a molar ratio of about 1s1. It is possible for each hydrogen atom to take part in the reaction alone or at the same time during the reaction several active hydrogen atoms take part in the conversion. This is done so that at least one trifluoroacetyl group at one of the sites with a reactive hydrogen atom

009847/2002

_ '5 -

is present in the product. In the reaction product are present in different amounts: 1- (3'-N-methyl-JN "-trifluoroacetyl-carbamoyloxy-phenyl ^ -methylurea, 1 - (3 '-N-methyl-N-trifluoroacetyl-carbamoyloxy-phenyl) -3-trifluoroacetyl-3-methylurea and 1- (3 ^I -F-methylcarbamoyloxyphenyl) -1,3-di-trifluoroacetyl-3-methylurea

15.6 g (0.07 mol) of 1- (3'-lT-methylcarbamoyloxy-phenyl) -3-methyl-urea are * 15 g of trifluoroacetic anhydride in 10 ml of benzene containing 5 drops of sulfuric acid, "is sawn *. The clear solution which forms after the addition of the anhydride is heated to reflux for 30 minutes, then diluted with more benzene, then washed with sodium bicarbonate solution and water and dried P. ^{receives 84-87 °} C. as the yield. The herbicidal activity of this product is explained in the following “Tests for testing the herbicidal effect”, the compound being listed as compound no.

If the reaction between Srifluoroacetic anhydride and Carbamoyloxyphenylurea carried out in a molar ratio of 2: 1, the result is a product believed to be It can be found that there are on average at least 2 trifluoroacetyl groups per molecule contains. It is therefore a mixture of ■ 1- (3 '~ li- "methyl-N-trifluoroacetyl-carbamoyl-' oxy-phenyl) -3-trifluoroacetyl-3-metaylurea and 1- (3'-F-methyl-carbanioyloxyphenyl)-1,3-ai-trifluoraeetyl-3-methylurate. The herbicidal 'effect of this product, which ala compound Hr. 2 denotes; is is also in that. following report "Tests to test the herbicidal effect" explained. . '

OS) OO /. 7/20 0 2 ' _BAD original

Typical compounds by the formula

are included, according to the methods described above can be produced and processed into weed killers are the following;

R,

GOOP ₃ n-butyl hydrogen methyl hydrogen COGP ₃ n-propyl hydrogen methyl hydrogen GOOP ₃ n-hexyl methyl methyl hydrogen COOP., Feopentyl methyl . methyl hydrogen Isopropyl hydrogen Isopropyl hydrogen GOCP ₃ methyl hydrogen ethyl hydrogen COCP ₃ n-octyl methyl methyl hydrogen COCP ₃ 2-methylallyl methyl methyl hydrogen COCP ₃ t-butyl. methyl 'Methyl hydrogen COCP ₃ t-butyl hydrogen Isopropyl hydrogen CQCP ,. methyl Ityl ethyl hydrogen COOPv t-Biityl hydrogen t-butyl hydrogen COOP ₃ methyl Allyl methyl hydrogen COOP ,, Iaopentyl ethyl methyl hydrogen COOP ', Isopropyl methyl Cyclohexyl hydrogen COOP ₃ Allyl methyl methyl hydrogen COOP., Cyclohexyl hydrogen methyl hydrogen

009847/2002

R ₂

COCF, Phenyl - * hydrogen methyl hydrogen ■ hydrogen P. p-tolyl hydrogen ethyl hydrogen hydrogen GOGF ₅ Methoxyphe
nvl hydrogen methyl hydrogen hydrogen COOP, »• j <* -
m-Hitro- hydrogen methyl hydrogen hydrogen phenyl Trifluorine COCP ₅ p-chlorine
phenyl hydrogen methyl acetyl COGP ₅ n-butyl Trifluoroacetyl methyl hydrogen COCP ₅ n-propyl Trifluoroacetyl methyl Trifluorine
acetyl COCP ₅ methyl Trifluoroacetyl ethyl . ■. ■.
Trifluoro COOP- methyl Trifluoroacetyl ethyl aeetyi P. COCP ₅ Phenyl Trifluoroacetyl methyl COCF- Phenyl Trifluoroacetyl methyl COCF _x t-butyl methyl ■ -
methyl P.

Attempts to test the Hertalztd effect

As already mentioned above, the connections described a phytotoxic ^ effect which makes them weed killing and make weed control appropriate. The compounds according to the invention are as follows in terms of their action been checked.

Preventive weed control

On the day preceding the intended treatment, seeds of seven different plant species were grown in each Rows sown j where one type of plant was used for each row and the row across the entire width of the Planter has been pulled. Hairy fingers were used as seeds - grass (Digitaris sanguinalis (Ij.) Scop.), yellow foxtail

00984772002

(Setarla glauca (L.) Beauv.), Water grass (Echinochloa crusgalli (L.) Beauv.), Californian red oat (Avena sativa (L.), wire-haired foxtail (AmaranthUB retroflexus (L.), Mustard (Brassica; juncea (L.) .) Cobs.) And rabbit sorrel (Rumex crispus (L.). Sufficient quantities of seeds were used in each case so that there were about 20 to 50 seedlings per row after emergence, the number depending on the size of the plants A spray solution was prepared by dissolving 50 mg of the compound to be tested in 3 ml of a solvent, for example acetone, which contained 1-6 of the surfactant "Tween 20" (polyoxyethylene sorbitan monolaurate), On the following day (Dag each planter was sprayed with the test compound in an amount of 9.07 kg per 303 liters of solution per 400 m (20 lbs per 80 gallons of solution per acre). The solution was applied with a suitable spray device the floor surface scraped up ht. The planting trays were then placed in a Sewäeheham® having a temperature of 27 ⁰ G and regelaESIg "watered. Two weeks later, the degree of weed control was determined, in which one the extent of germination uaä of -Wacbjstuais each seed type" in the treated Pflansensehalen with Comparing the growth of weeds in various control planters that were not bandaged. The following system was used for assessment!

- β no significant influence (0-15 #ige

Fight)

+ = weak influence (25-35 $ control) ++ = moderate influence (55-65 $ control)

+++ = strong influence or destruction (85-100 $ ige

Fight)

To show the total activity against all seven weed species a so-called activity index is used. This is the sum of the number of + markia.

009847/2002

so that an activity index of 21 a complete control of all seven types of weeds. Compound no. 1 has an index value of 21 while the compound Fr. 2 has an index value of 19.

Weed control after the plants have emerged?

Seeds of five species of weeds, namely hairy pingergrass, watergrass, California red oat, mustard, and sorrel and a useful plant, namely pinto beans (Phäseolus vulgaris) were in the further forward at

the preventive weed control described in the manner described in plant trays. The planters were then placed in a greenhouse at a temperature of 22.2-29.4 ° C and watered daily with a hose. About 10 to 1 day after planting out, as soon as the primary leaves of the bean plants had expanded almost completely and the first three-lobed leaves were just beginning to form, the plants were sprayed. The spray solution was prepared in which one 50 of these weighed amount of test compound in mg 5 ml of acetone containing 1 i> "Tween 20" (polyoxyethylene sorbitan monolaurate), and dissolved zusetzte then 5 ml of water. The solution was sprayed onto the leaves using a sprayer. The concentration of the spray solution was 0.5% and the amount applied was about 9.07 kg per 4000 m ² when all of the spray solution was retained on the plants and on the soil; however, some of the spray solution was lost, so it can be estimated that about 5.72 kg was applied per 4000 m.

Bean plants were used to discover defoliants and plant growth regulators. The beans were up on two or 3 plants per bowl thinned out, internally the

009847/2002

redundant weaker plants several days before Treatments were cut off. The treated plants were returned to the greenhouse and placed on top care that the treated leaves were not sprayed with water within three days of treatment. The water was applied to the ground as a weak stream from an irrigation hose, being here too care was taken that the foliage was not moistened.

The extent of the influence was determined 1 day after the treatment. The rating system was again the same as described for the previous test, where the ratings (-), (+), (++) and (+++) were used for the different degrees of influence. the The type of influence was also recorded. The maximum of the activity index when completely eradicated of all Unkrantarten is 18 for this test, where it are in turn the Suaae of the Plus-Karken, the could be obtained from the six plant species used in the experiment. The connection ITr. 1 had an index value of 18; also, compound # 2 showed one Indian value of 18.

The compounds according to the invention can be used as preventive Herbicides as well as herbicides for already emerged plants are used and in different whites and in different, consentrations are applied. Pure the In practical application, the compounds according to the invention are processed into weedkillers, in which one they are mixed in sufficient quantities with extenders and carrier materials, as is usually the case for the purpose facilitate the dispersion of the active ingredients for agricultural purposes happens. Of course, it must also be ensured that the type of preparation and the

009847/2002

Application of the preparation can influence the effect of the material as a herbicide. For example, the active herbicidal compounds can become relatively coarse ^! ■ can be processed into granulates, wettable powders, emulsifiable concentrates, dusts, solutions and various other known types of preparations, depending on the desired type of application. The most suitable forms of application both for preventive application and for application after the plants have emerged are wettable powders, emulsifiable concentrates and granules. Such preparations can contain one hand, very small amounts of only about 0.5 $> and on the other hand, up to about 95 wt. #, Or more of active ingredient. The amount to be applied depends on the type of seeds or plants to be controlled; in general the amount is between 0.45 and 22.7 kg per 4-000 a.

Wettable powders lie in the pore of very fine particles that easily dispersed in waeeer or a dispersant can be »The wettable powder is eventually deposited on the floor either as a dry dust or as a Dispersion in water or another "liquid applied. Typical carrier materials for wettable powders are For example, Fuller's earth, Eaolin, Clays, and silicic acid other easily wettable organic or inorganic extenders. Wettable powders are usually made in such a way that that they contain about 5 to about 95% of the active ingredient as well as a small amount of a hate speech, Dispersing or emulsifying agent, which does the wetting and dispersing is facilitated.

The emulsifiable consentrates are homogeneous liquid preparations that can be dissolved in water or other dispersions.

0038A7 / 2002

lubricants are dispersible; they can consist entirely of the active compound mixed with a liquid or solid emulsifying agent; however, it can also be a mixture with a liquid carrier material such as xylene, heavy aromatic petroleum hydrocarbons, isophorone or other non-volatile organic solvents. For use as herbicides, these concentrates are dispersed in water or other liquid carrier materials and usually sprayed onto the area to be treated. The percentage by weight of the active ingredient can vary widely depending on the type of application; generally it is about O _V 3 to 95 wt. # active material, based on that weed control agents.

Granules in which the active toxic agent is in relatively coarse particles are generally applied without dilution to the area to be weeded. Typical carrier materials for granules are sand, fuller's earth, bentonite, vermiculite, perlite and other organic and inorganic materials which can absorb the toxic agent or to which the toxic agent can be applied. Granules are generally made to contain from about 5 to about 25% of the active ingredient; they can also contain smaller amounts of other components, such as surface-active agents such as wetting agents, dispersants or emulsifiers, oils, e.g. heavy aromatic petroleum hydrocarbons, kerosene or other petroleum fractions or vegetable oils and / or adhesives such as dextrins, glue or synthetic resins.

Typical NetE diapering or emulsifying agents used for agricultural preparations are suitable for example alkyl and alkylarylsulfonates and sulfates

009Ü47 / 2002

as well as their sodium salts, polyhydric alcohols as well as other types of surface active agents which are used in large numbers are commercially available. If a surfactant is used, it should be in amounts of 0.1 to 15% by weight present in the herbicide be.

Dusts, which are free-flowing mixtures of the active ingredient with finely divided solid substances such as talc, clays, flour and other organic and inorganic solid substances that act as dispersants and carrier materials for the toxic material are used, are particularly suitable when the preparations to be introduced into the ground.

Pastes that are homogeneous suspensions from the finely divided solid toxic agents in a liquid carrier material - the latter can be water or oil be - are used for special purposes. Also such Preparations generally contain the active agent in amounts of about 5 to 95 percent by weight; besides can wetting agents, dispersants and emulsifiers may be present in small amounts to facilitate dispersion. Before use, the pastes are usually diluted and sprayed onto the surface to be treated.

Finally, further forms of preparations which can be used for weed control are simple solutions of the active agent in solvents in which it is completely soluble in the desired concentration; Suitable solvents for this are, for example, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized spray solutions, e.g. aerosols, in which the active agent is dispersed, can also be used by evaporation of the carrier material.

009847/2002

low boiling solvent, e.g. B. Freons, sit down the active agent in finely divided form.

The phytotoxic preparations according to the invention are applied to the plants in the usual way. Dusts and liquid preparations can be applied, for example, with motor-driven or hand-operated atomizers. The preparation can also be dusted or sprayed onto the plants from airplanes, because they are already in very small quantities are effective. To influence or prevent the growth of germinating seeds or budding seedlings, according to a typical example, powder or liquid preparations are introduced into the soil in the usual way, to a depth of at least one inch below the surface of the soil. It is not necessary that the phytotoxic Agent mixed with the soil particles; it is sufficient if the agent is sprayed or poured onto the floor will. The phytotoxic agents according to the invention can also be added to the water with which the fields are watered will. By this procedure, a penetration of the agent is achieved in the soil, namely in the Measure of how water is absorbed by the ground. Dusts, granules and liquid preparations that first hit the ground have been applied, can in the usual way, for. B. by raking, hoeing, etc., can be incorporated into the ground.

The phytotoxic preparations according to the invention can contain other additives, such. B. fertilizers, pesticides and the like, and can also be used in admixture with other phytotoxic agents. Other phytotoxic agents, which could be used in connection with the phytotoxic agents according to the invention are, for example, 2,4-dichlorophenoxyacetic acids, 2.4 »5-2richlorophenoxyacetic acid, 2-Methyl-4-Chlorphöaoxyessigsäure as well as the Salsa, Ester and amies of these associations; 'uriazine derivatives such as 2,4-bis-

009847/2002

(3-methoxypropylamino) -6-methylthio-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S-triazine and 2-ethylamino-4-isopropylamino-6-methylmercapto-S-triazine; Harnet off derivatives such as 3- (3,4-dichlorophenyl) -1,1-dimethylurea and 3- (p-chlorophenyl) -1,1-dimethylharastoffj acetamides such as H _f H-diallyl-a-chloroacetamide, N- (a-chloroacetyl ) -hexamethyleiiimi! i and N, N-diethyl-a-bromaoetamide and the like, benzoic acids such as 3-amino-2,5-dichlorobenzoic acid; Th.iocar "bamate. Such as S-Propyldipropyltliiocarbamat, S-ethyl-dipropylthiooarbaiaat, S-Äthylcyclohexyläthylthiocarbamat, S-Äthylhexmhydro-IH-azepin-1-carbothioate and the like .. Suitable fertilizers, for example, used like in combination with the active phytotoxic agents ammonium nitrate, urea and superphosphate.Other valuable additives can e.g. consist of materials in which plants can form roots and grow, such as compost, dung, humui, sand and the like.

00984 7/20 0

Claims (1)

1. j Acylitrte UreaoarbanataerlTate aar Ια which R ₁ and R, independently of one another, alkyl radicals with 1 to about 8 carbon atoms, cyclohexyl, lower alkenyl with about 3 to 4 carbon atoms, phenyl or substituted phenyl - where the substituents are lower alkyl groups -, lower alkoxy, nitro or halogen, R and R ₂ independently of one another are hydrogen, alkyl groups with 1 to about 8 carbon atoms, cyclohexyl, lower alkenyl with about 3 to 4 carbon atoms or trifluoroacetyl - where in each case at least one of the groups H or R ₂ must be trifluoroacetyl -, R ^ hydrogen, methyl or - if only one of the two groups R 'or R _{2 is} trifluoroacetyl - trifluoroacetyl mean. 2. A compound according to claim 1, characterized in that R is trifluoroacetyl, R _{1 is} methyl, R _{2 is} hydrogen, R, methyl and R. are hydrogen. 3 .. connection after. Claim 1, characterized in that R trifluoroacetyl, R ₂ trifluoroacetyl, R ₁ methyl, 009847/2002 R, methyl and R ^ represent hydrogen. 4, herbicide, also consisting of a reaction product of frifluorine acid anhydride and a carbaeoyloxypheny / urea the formula in which R ₁ and R ₃ independently of one another are alkyl formates with up to about 8 carbon atoms, cyclohexyl, lower alkenyl with about 3 to 4 carbon atoms, phenyl or substituted phenyl - the substituents being lower alkyl groups -, lower alkoxy, nitro or Halogen, R and R ₂ independently of one another are hydrogen, alkyl groups with 1 to about 8 carbon atoms, cyclohexyl or lower alkenyl with about 3 to 4 carbon atoms - where at least one of the groups R and R ₂ must be hydrogen - and R * denote hydrogen or methyl. 5. Herbicide according to claim 4t, characterized in that R ₁ and R _{5 represent} methyl and R ₉ Rg and R * represent hydrogen. Tttr Stauffer Chemical Company, Hew Xork, H. Y., V. St. A. RecgWanwalt 009847/2002 ORIGINAL INSPSCTED