IL29192A - Octahydro-1,2,4-methenopentalenyl urea derivatives,their preparation and herbicidal compositions containing them - Google Patents

Description

o* *3an a*aws> »*t*»tf» 0**1*03111 tnjsrr derivatives, t eir preparation and herbicidal compositions containing them CIBA-0EIQT AS C: 27636 The present invention concerns methenopentalene derivatives of ureas, processes for their production, herbicidal compositions containing these new ureas as active substances, and processes for combatting undesirable plant growth using the new ureas or the compositions containing them.

The new urea derivatives according to the invention have the general formula I represents hydrogen, a lower alkyl, alkenyl or alkinyl cycloalkyl radical, a lower alkoxy radical or the phenyl radical, K represents hydrogen, a lower alkyl or lower alkenyl radical, or and R2 together represent the ethylenoxyethylene radical or a polyrae iylene bridging member.

The new compounds of formula I above have been found to possess excellent herbicidal properites and to be superior, for combatting certain weeds and undesirable grasses, to some known urea derivatives in which one nitrogen atom is substituted with a condensed bicyclic or tricyclic hydrocarbyl radical, such as disclosed in US Patent Specifications ITos. 3,174,843 and 3,276,855. The active substances according to the invention can be used both in the pre-emergenee as well as the post-emergence process for the combatting of undesirable plants i cultivated crops. They are distinguished in particular by their quick onset of action as well as a short after effect.

In the urea derivatives of general formula I, 29192/2 radical having 1 to 5 carbon atoms such as the methyl, ethyl, propyl, butyl or amyl' radicals etc., a lower alkenyl radical such as the allyl or jnethallyl radical, or it can be an alkinyl radical such as the propinyl or l-methyl-2-propinyl radical; as ( ' . cycloalkyl radical it can be a cyclopropyl., cyclobutyl, cyclo-pentyl or cyclohexyl radical; as alkoxy radical it can be e.g. the methoxy, ethoxy, propoxy or butoxy radicals. As lower alkyl radical, the symbol can be one of those radicals mentioned above for R^. The polymethylene bridging member symbolised by R-j^ and R2 together has, e.g. 3 - 6 chain members and is, e.g. the trimethylene , tetramethylene , pentamethylene or hexamethylene '\ ·' ■ ■ · ■ a; group. The new ureas' of formula I are obtained by reacting/functional derivative of octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -car-bamic acid with an amine of general formula II ^Rl • HN - (II) R2 wherein R-^ and Rg have the meanings given in formula I, in the presence of a solvent which is inert to the reaction components.

According to another analogous process, the ureas of general formula I are obtained by reacting octahydro-1, 2, 4-metheno- pentalenyl-( 5)-amine with either: a) a carbamic acid halide of the general formula III wherein Hal represents halogen up to the atomic number 35, and R, and R9 have the same meaning as in formula I , or 29192/2 - 3 - ' b) the components for the formation of such a carbamic acid, halide of formula III, i.e. with phosgene and an amine of formula II, in the presence 'of a condensing agent, and, preferably, in a solvent or diluent which is inert to the reaction components.

The oc'tahydrq-pentalenyl-(5)-ureas of the general formula. I wherein R-^ is a lower aliphatic hydrocarbon radical, a cyclo- alkyl radical or the phenyl radical' and is hydrogen, are also obtained according to the invention by reacting octahydro-1 , 2 , 4- methenopentalenyl-(5)-amine. with an isocyanate of the general formula IV R∑ - NCO (IV) wherein R1 .represents a lower alkyl, alkenyl or alkinyl radical, a .cycloalkyl radical or the phenyl radical.

Reactive functional derivatives of the carbamic acid mentioned are, for example, the following: the isocyanate, the low alkyl esters, particularly the methyl or ethyl ester, also the phenyl ester, as well as mono- and di- substituted amides. ' Tho now ureas of the gcmus-al fo m la I whuroin Η·, Us a lower alkoxy radical, can be produced by subsequent alkylation, in the presence of an acid binding agent, of an N-oc tahydro-1 , 2 , 4- methenopentalenyl- ( 5) -N ' -alkoxy urea or of an N-octahydro-1 , 2 , 4- methenopentalenyl- ( 5) -N ' -hydroxy urea with the usual alkylating agents such as alkyl halides, dialkyl sulphates etc. The N-octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -N 1 -alkoxy ureas can be obtained in their turn by reaction of the octahydro-1 , 2 , 4-methenopentalenyl- (5)-isocyanate with an O-alkyl hydroxylamino [0. Scherer et al., Angew. Chemie, 7J , 851-854 (1963)].

Examples of inert solvents suitable for the modifications mentioned of the process according to the invention are hydrocarbons such as benzene, toluene, xylenes; ethers such as diethyl ether, dioxane, tetrahydrofuran, diethylene glycol mono- methyl ether; chlorinated hydrocarbons such as methylene chlor-5 ide, and low ketones such as acetone or methylethyl ketone.

The reaction of the isocyanate, of a carbamic acid ester or amide (urea) is generally performed without condensing agent. In some cases it can be of advantage to perform the reaction in the presence of, e.g. alkali metal alcoholates or a tertiary o organic base.

] The reaction of octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -amine with a carbamoyl halide or components for the formation of same (phosgene/amine of formula II) is performed' in ' the presence of a condensing agent such as an inorganic base, e.g. alkali metal hydroxide or acetate, hydrogen carbonate, carbonate and phosphate, or in the presence of an organic base, e.g. a tertiary amine such as pyridine, trialkylamine or collidine. Amines of the general formula II which are useful are, e.g. the following: methylamine, dimethylamine , ethylamine, diethylamine , the propylamines and the o butylamines, cyclopropylamine , cyclobutylamine , cyclopentylamine , cyclohexylamine , also aniline, azeridine, pyrrolidine, piperidine in the free form and also as salts of hydrohalic acids, preferably as hydrochlorides.

As isocyanates of general formula IV, the corresponding alkyl isocyanates can be used such as the methyl, ethyl and propyl 5 isocyanates, phenyl isocyanate, the allyl isocyanate., also the cyclopropyl, cyc butyl, and cyclohexyl isocyanate. As carbamic acid halides of formula III, particularly the dialkyl and alkyl- aryl carbamic acid chlorides and bromides such as dimethyl, diethyl, di-isopropyl , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylphenyl carbamic acid chloride, can be reacted according to the present invention.

Both ■ octahydro-1 , 2 , -methenopentalenyl- ( 5) -isocyanate and octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -amine have not been known hitherto. These compounds, which serve as intermediate products, 5 are obtained by degrading functional reactive derivatives of octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -carboxylic acid. The azide and amide can be used as reactive functional derivatives which are degraded according to Curtius or Hofmann to the isocyanate and amine respectively. o The starting isocyanate is produced, preferably, by Curtius degradation of the azide. For this purpose, either the carboxylic acid chloride which is then reacted with alkali metal azide to form the desired carboxylic acid azide; or one of the alkyl esters such the methyl or ethyl ester is converted into the carboxylic acid azide direct with hydrazine hydrate and nitrous acid, preferably in the presence of a solvent or diluent.

The azide is converted into the isocyanate by thermic decomposition in a solvent which is inert to the reaction components such as in an aromatic hydrocarbon such as benzene, toluene, xylenes, o or in a higher boiling ether such as dioxane. The temperature for the decomposition of the azide lies between 20 and 180°C. methenopentalenyl- ( 5 ) -amine by reacting it either with a) glacial acetic acid and acetic acid anhydride, or b) with an alkanol.

In the former case (a), the acetylamine is obtained as reaction product which is converted into the free amine by alkaline sapo-5 nification. In case (b) , the carbamic acid esters corresponding to the alkanols used are obtained which can be converted by acid as well as basic hydrolysis into the amine mentioned. Hydrohalic acids, glacial acetic acid, halogenated acetic acids or mixtures of such acids, e.g.can be used for acid hydrolysis; alkali metal o and alkaline earth metal hydroxides, for example, are suitable for basic hydrolysis., The hydrolysis can be performed both in water as well as in an alkanol such as methanol and ethanol or in diethylene glycol etc.

In addition, oc tahydro-1 , 2 , -methenopentalenyl- ( 5 ) -amine 5 can be obtained by acid amide degradation according to Hoftnann.

For this purpose, the corresponding carboxylic acid amide is heated, e.g. in the presence of an agent giving off bromine or chlorine, in the presence of an alkali metal or alkaline earth metal hydroxide or an acid, . Both water as well as an alkanol are o suitable as solvent, but in cases where the degradation is performed in an alkanol, e. . methanol or ethanol, the corresponding alcoholates are used instead of the hydroxides mentioned.

The new ureas of the general formula I, in the purified state, are colourless and dissolve well in organic solvents; on 5 the other hand, ..they are insoluble in water.

Tests to determine the herbicidal action showed that the following compounds are particularly valuable for the combatting of weeds and undesirable grasses:' N-octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -urea , ta.p. 140-145°C; o N-octahydro-1 , 2 , -methenopentalenyl- ( 5) - ' -methyl urea, m-.p. 116-118°C; ' ' N-octahydro-1 , 2 , -methenopentalenyl- ( 5 ) - 1 -tetramethylene urea , m.p. 169-170°C; N-octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -N ' , ' -diethyl urea , m.p. 86-88°C; N-octahydro-1 , 2 , 4-methenopentalenyl- ( 5) - 1 -pentamethylene urea , m.p. 166-168°C; N-octahydro-1 , 2 , -methenopentalenyl- ( 5 ) -N ' -ethyleneoxyethylene urea, m.p. 173-175°C; N-octahydro-1 , 2 , 4-methenopentaienyl- ( 5) -N ' -methyl-N ' - (1 ' -methy1- 2 ' -propinyl) -urea , m.p,, 105 - 107°C; N-octahydro-1 , 2 , -methenOpentalenyl- ( 5) -N ' -methyl-N ' -methoxy urea, b,p. 109-112 °C/0.06 Torr.

The following examples describe the production of the new ureas of the general formula I. Parts mean parts by weight, the temperatures are given in degrees Centigrade.

Example 1 1. Production of the starting material a) 164 Parts of the known octahydro-1 , 2 , 4-methenopentalenyl- (5)-carboxylic acid [cf. H,K. Hall, J. Org. Chem. 25, 42 (I960)], 1000 parts by volume of benzene and 4 parts by volume of pyri- dine are gently heated on a steam bath. 250 Parts of thionyl chloride are added dropwise within 15 minutes in such a way that spontaneously of SO2 the reaction proceeds b.¾._it«ei.£ with S-Og development/- On completion of the addition of the thionyl chloride, the whole is heated for another 15 minutes on the steam bath, after which all volatile products are removed at room temperature by water jet vacuum. 200 Parts by volume of petroleum ether are added to the residue, the mixture is left to stand for 30 minutes and then filtered. The solvent is removed in the evaporator. The octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -carboxylic acid chloride ob- tained is distilled; it boils at 63-65°/2 Torr. (Yield: 162.7 parts; 88.5$).. b) 93.6 Parts of sodium azide are dissolved in 1720 parts by volume of 50% aqueous acetone and the solution is cooled to 0°. 90 Parts of the octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -carboxylic acid chloride obtained according to (a) are then added within 5-■ 10 minutes. The temperature in the reaction vessel is kept at 0 - 2° by exterior cooling „ On completion of the addition, the whole is stirred at 0° for another 50 minutes, after which the solution is extracted, first with 1000 parts by volume of ice cold benzene and then a second time with 300 parts by volume of ice cold benzene. The combined benzene extracts are then dried with finely pulverised calcium chloride at 0 - 5° . The calcium chloride is filtered off and the filtrate is heated for 22 hours in a steam bath. Nitrogen is developped and the solution foams. pentalenyl- ( 5)-isocyanate boils at 70 - 75°/3 Torr. 2. Production of a urea derivative according to the invention c) 16.1 Parts of octahydro-1 , 2 , -methenopentalenyl- ( 5) -iso-cyanate (cf. example 1 b) in 200 parts by volume of benzene are reacted with 9.7 parts of diethylamine . After removal of the solvent, the crude product is distilled: B.P. 131-1340 /0.004 Torr, After recrystallisation from petroleum ether, N-octahydro -1 , 2 , 4-methenopentalenyl- ( ) -N ' ,N ' -diethyl urea is obtained as colourless crystals which melt at 88 - 89°.

Example 2 a) 16.1 Parts of octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -iso-cyanate (cf. example 1 b) are boiled for 100 minutes in a mixture of 25 parts by volume of glacial acetic acid and 15 parts by volume of acetic acid anhydride. On completion of the CO ^ development, 35 parts by volume of the solvent are distilled off and the residue is poured into 100 parts by volume of water and then stirred for 3 hours. The precipitated crystalline product is taken up in 175 parts by volume of ether, the ethereal solution is washed with 15 parts by volume of water and dried with sodium sulphate. After removal of the ether, the residue is distilled. The octahydro-1 , 2 , -methenopentalenyl- ( 5 ) -acetylamine obtained boils at 120 - 125°/0.05 Torr, and melts at 77 - 80°. b) 26.5 Parts of the acetyl amine obtained above are boiled in a solution of 200 parts by volume of diethylene glycol mono-methyl ether and 42 parts of potassium hydroxide in 50 parts by volume of water. 35 Parts by volume of water are slowly distilled off and the mixture is then refluxed for 8 hours (inner temperature 120°). The mixture is poured into 600 parts by volume of water and the solution is extracted 5 times with 80 arts washed twice with 20 parts by volume of saturated sodium chloride solution each time and then dried over sodium sulphate. After removal of the ether, 18.3 parts of the oily amine are obtained by distillation at 82 - 84°/l2 Torr. As the distillate still contains diethylene glycol monomethyl ether, it is purified as follows: .221 Parts of crude amine are dissolved in 1500 parts by volume of dry ether and hydrogen chloride is introduced into the solution at 0° until no more hydrochloride precipitates „ The octahydro-1 , 2 ,4-methenopentalenyl- ( 5) -amine hydrochloride so iso-lated is washed with ether and dried in vacuo. It melts at 265-270° . c) 117 Parts of the above amine hydrochloride are dissolved in 100 parts by volume of water and the solution is shaken with 200 parts by volume of 4N sodium hydroxide solution. The preci-pitated amine is extracted 4 times with 150 parts by volume of ether each time and the ethereal solution is dried with sodium sulphate. After removal of the ether and distillation, the amine is obtained as a colourless liquid. The octahydro-1 , 2 , -me theno-pentalenyl-(5)-amine boils at 81 - 83°/l2 Torr„ n^°: 1.5160. d) 6.45 Parts of dimethyl carbamic acid chloride are added dropwise to a solution of 8.1 parts of octahydro-1 , 2 , 4-metheno-pentalenyl- ( 5 ) -amine and 6„3 parts of triethylamine in 80 parts by volume of benzene, the addition being made at a temperature of 5 - 10°. The reaction mixture is then stirred for another 2 hours at 25°. The precipitated triethylamine hydrochloride is filtered off and the solution is washed with water. After drying, the benzene is removed in a rotatory evaporator. The N-octahydro-1 , 2 , 4-methenopentalenyl- ( 5) - 1 ,N 1 -dimethyl urea obtained is sublimed at 150°/l Torr and melts at 138 - 140°.

Example 3 16.1 Parts of octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -i so-cyanate (cf. example 1 b) are dissolved in 200 parts by volume of benzene and 7 parts of methoxy-methylamine are added dropwise within 12 minutes in such a way that the temperature does not rise above 5°. The whole is stirred for 20 minutes at 25° and then the solvent is removed in vacuo. The residue is distilled and an oil, boiling at 112-114°/0 „ 07 Torr, is obtained which slowly solidifieso The N-oc ahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -N ' -methyl-N ' -methoxy urea melts at 73 - 76° „ Example 4 8.05 Parts of octahydro-1, 2 , 4-methenopentalenyl- ( 5) -iso-cyanate (cf. example 1 b) are dissolved in 50 parts by volume of tetrahydrofuran and ammonia is introduced into this solution while stirring* The reaction mixture is stirred at room temperature for another 45 minutes and then the solvent is evaporated in vacuo. The N-octahydro-1 , 2 , 4-methenopentalenyl- ( ) -urea which remains melts at 135 - 140° .

Example 5 13.5 Parts of octahydro-152 , 4-methenopentalenyl- ( ) -amine are dissolved in 200 parts of benzene and the solution is added dropwise within 30 minutes to 11.8 parts of phenyl isocyanate in 100 parts of benzene, the addition being made at 20 - 30° while cooling with an ice bath. The reaction mixture is then stirred for 16 hours at 50 - 60° whereupon it is filtered and the residue is recrystallised from ethyl acetate. The N-oc tahydro-1.2 , 4-methenopentalenyl- ( )- ' -phenyl urea obtained melts at 181-182°.

Besides the already mentioned ureas those listed in the following Table are also obtained by the process described in example 1 when equivalent amounts of octahydro-1 , 2 , 4-methenopen- talenyl- ( 5) -isocyanate and a corresponding amine are used: The production of the starting material, octahydro-1 , 2 , - methenopentalenyl- ( ) -amine by way of a carbamic acid alkyl ester as intermediate is described below: Parts of octahydro-1.2 , 4-methenopentalenyl- ( 5 ) -carbo- xylic acid ethyl ester, 40 parts by volume of a 26 by volume aqueous ammonia solution and 5 parts by volume of methanol are heated in an autoclave for 10 hours at 140°. Volatile parts are removed from the reaction product by water jet vacuum. 25 Parts is filtered and the residue is recrystallised from water. The octahydro-1 , 2 , 4-methenopentalenyl- ( 5 ) -carboxylic acid amide obtained melts at 160 - 169° (with decomposition). 16.3 Parts of octahydro-1 , 2 , 4-methenopentalenyl- ( 5) -carbo-5 xylic acid amide are dissolved in 500 parts by volume of methanol 11 Parts of sodium methylate are then added and the whole is left to stand for 30 minutes and then heated in a steam bath for 45 minutes. Acetic acid is then added until the mixture is neutral and all volatile products are removed by evaporation. The resi-o due is shaken with 100 parts by volume of water. The water is decanted. 250 Parts by volume of petroleum ether are added to the insoluble residue, the whole is left to stand for some hours and then filtered. The filtrate is concentrated, and the oily residue is distilled. It boils at 97 - 101°/0.02 Torr. The octa 5 hydro-1 , 2 , 4-methenopentalenyl- ( 5) -carbamic acid methyl ester crystallises and, after recrystallisation from petroleum ether, melts at 84 - 86°. 29 Parts of this carbamic acid methyl ester and 42 parts of potassium hydroxide are boiled in 50 parts by volume of water o and 200 parts by volume of diethylene glycol monomethyl ether as solvent. 35 Parts by volume of water are slowly distilled off; the solution finally boils at 125° „ It is then boiled for 8 hours.; The mixture is poured into 600 parts by volume of water and the solution is extracted 5 times with 80 parts by volume of 5 ether each time. The ether extracts are combined and washed twice with 20 parts by volume of saturated sodium chloride solution each time and then dried over sodium sulphate. After removal of the ether, distillation at 82-84°/l2 Torr yields 18.3 parts of oily amine. This amine still contains diethylene gly-o col monomethyl ether as impurity and is purified by way of the hydrochloride as described in example 2 b and 2 c.

The herbicidal compositions according to the invention are produced in the known way by intimately mixing and milling active substances of general formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be present and used in dusts, sprinkling agents, granulates, coated granules, impregnated granules, homogeneous granules; wettable powders, pastes, emulsions; solutions and aerosols, The concentration of active substance in these composite, tions is, e.g. 0.01 to 80%.

Other biocidal active substances or agents can be admixed with the compositions according to the invention. Thus, the new compositions, in addition to the compounds mentioned of general formula I can contain, e.g. insecticides, other herbicides, fun-15 gicides, bactericides, fungistatica , bacteriostatica or nematoci- des, to widen the range of action.

As herbicides can be mentioned, for instance, halogen-di- arni o- alkoxy-diamino- and alkylthio-diamino-s-triazines , in particular , 2-chloro-4-methylamino-6-isopropylamino-s-tri.azine , 2-2o chloro-4 , 6-diethylamino- s- triazine , 2 -chloro-4 -ethylami.no-6-i so - propylamino-s-triazine , 2 -chloro-4 , 6-diisopropylamino-s- triazine , 2-chloro-4 -ethylamino-6-diethylamino-s-triazine , 2-chloro-4,6- bis-die hylamino-s- triazine , 2-chloro-4-diethylamino-6-isopropyl- amino-s-triazine , 2 -chloro-4 -ethylamino- 6- ( 31 -methoxy-propyl-25 amino)-s-triazine , 2-methoxy- and 2-methyl hio-4-methylamino-6- isopropylamino-s-triazine , 2-methoxy- and 2-methyl hio-4 , 6-di- ethylamino- s-triazine , 2-methoxy- and 2-methylthio-4-ethylamino- 6-isopropylamino-s- tria zine , 2-methoxy- and 2-methylthio- , 6-di- isopropylamino- s-triazine , 2-methylthio-4-isopropylamino-6- ( 3 ' -3o methoxy-propylamino ) -s-triazine , 2-methoxy- 4 , 6-bis- ( 3 ! -methoxy- propylamino) -s-triazine and 2-methylthio- , 6-bis- ( 31 -methoxy- The compositions according to the invention can also contain synthetic fertilisers and trace elements.

The following examples serve to illustrate the application part of the present invention; where not otherwise stated, parts mean parts by weight.

Wettable Powder The following components are used to produce a 50 wettable powder : 50 parts of octahydro-1 , 2 , -methenopentalenyl- ( ) -N ' , ' - dimethyl urea, parts of a dibutylphenyl/ethylene oxide condensate, parts of a naphthalene sulphonic acid/phenol sulphonic acid/formaldehyde condensation product, 40 parts of Champagen chalk.

The active substances mentioned are drawn onto the carriers and then mixed and milled with the additives given.

Wettable powders having excellent wettability and suspendibility are obtained. Suspensions of any concentration desired can be obtained from such wettable powders by dilution with water „ Granulate 90 Parts of a granular carrier, e.g. sand, kaolin, mont-morillonite, are moistened with 1.5 parts of water, isopropanol or polyethylene glycol and mixed with 10 parts of N-octahydro-1,2, -methenopentalenyl- ( 5) -N 1 -methyl urea « - Γ5 - 29192/2 Ύ

Claims (1)

1. CLAIMS New octa the general ormula I wherein represents a lower alkenyl or alkinyl a cyoloalkyl a lower alkoxy radical or the phenyl represents a lower alkyl or lower or and together represent the ethyleneoxyethylene radical or a polymethylene bridging methyl Process for the production of new of the general formula I in Claim which compriaes reacting a reactive functional derivative of acid with an amine of general II 17 wherein and have the same meaning as in Claim Process according to Claim characterised by the use of as reactive functional derivative of Process according to Claim characterised in as reactive functional derivatives of an ester thereof is Process for the production of ureas of the general la I defined in Claim which comprises reacting aine with a carbamic acid halide of the general III wherein Hal represents halogen up to the atomic number and and have the same meaning as in Claim or the components for the formation of such a carbamic acid halide of the general formula phosgene and an amine of general formula the presence of a condensing agent Process for the production of of the general formula I in Claim wherein represents a lower aliphatic hydrocarbon a cycloalkyl radical or the phenyl radical and represents hydrogen9 characterised by reacting with an isocyanate of formula IV wherein represents a lower or alkinyl a radical or the phenyl Composition for combatting undesirable plant characterised in as active it contains at least one urea of the general formula I defined in Claim 1 together with suitable carriers distributing agents other active Process the combatting of weeds and undesirable characterised by the use of ureas of the general formula I defined in Claim 1 or of agents which contain such ureas as active insufficientOCRQuality