NO159655B - NEW IMIDAZOPYRROLOPYRIDINE AND QUINOL INDIA AND HERBICIDE BLENDING CONTAINING THE SAME. - Google Patents

Description

The present invention relates to new intidazopyrrolopyridine (and quinoline) diones with the formulas (III) and (VII) below:

where

R x is C 1-04 alkyl;

R 2 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl;

Y and Z are each hydrogen, C 1 -C 8 alkyl or C 1 -C 6 alkoxy, or

Furthermore, the invention relates to a herbicidal mixture comprising an inert solid or liquid diluent together with a herbicidally effective amount of the compounds defined above, as well as the use thereof for the control of monocots and dicots, annuals, perennials or aquatic plants.

A general method for the preparation of compounds of formula (III) is the reaction of an anhydride of formula (XVI) below with a correspondingly substituted α-aminocarbonitrile of formula (XVII) below which gives a mixture of the monoamides of the acid of formula (IX) and formula (X).

This reaction is carried out at a temperature between approx. 20°C and 70°C, and preferably between approx. 35°C and 40°C in an inert solvent such as tetrahydrofuran, methylene chloride, ether, chloroform, toluene or the like. The acids thus formed are then cyclized to the corresponding pyrrolopyridine-acetonitrile, shown by formula (XI) by heating the reaction mixture with an excess of acetic anhydride in the presence of a catalytic amount of sodium acetate or potassium acetate.

In general, the above reaction is carried out by treating the reaction mixture with acetic anhydride, acetyl chloride, thionyl chloride or the like and heating the mixture to a temperature between approx. 20°C and 100°C. Hydration of the thus formed pyrrolo-pyridine acetonitrile of formula (XI) is carried out by treating the acetonitrile with a strong acid such as sulfuric acid. This reaction gives the pyrrolopyridine or quinoline acetamide of formula (XII). Although the addition of an immiscible solvent such as methylene chloride, chloroform or the like is not essential for carrying out the above-described reaction, the addition of such a solvent to the reaction is generally preferred. The reaction is usually carried out at a temperature between approx. 10°C and 70°C.

The cyclization of the compound of formula (XII) below, pyrrolopyridine or quinoline acetamide, gives the tricyclic imidazopyrrolopyridine and quinoline ions of formula (III).

The product of this reaction is predominantly imidazopyrrolopyridine or quinolindiones (III) (85%) together with the isomer of formula (Illa).

The cyclization reaction is preferably carried out at a temperature of from 80 to 150°C in the presence of a base such as sodium or potassium hydride or an acid such as an aromatic sulphonic acid and a solvent which will form an azeotropic mixture with water and permit its virtually instantaneous removal from the reaction mixture as it forms. Solvents that can be used include toluene, benzene, xylene and cyclohexane. Bases that can be used are alkali metal hydroxides, alkali metal hydrides, alkali metal oxides, tertiary amines such as diisopropylethylamine, 1,5-diazabicyclo[3,4]nonene-5,1,5-diazobicyclo[5,4,0]undecene- 5,1,4-diazabicyclo[2,2,2]octane, tetramethylguanidine, potassium fluoride and quaternary ammonium hydroxide such as trimethyl-benzylammonium hydroxide and strongly basic ion exchange resins.

Finally, acidic reagents that can be used herein include aromatic sulfonic acids such as p-toluenesulfonic acid, beta-naphthalene sulfonic acid, naphthalene disulfonic acid and the like.

The above-mentioned reactions are shown in reaction core I below, where Y, Z, ^ and R 2 are as defined above.

Another general method for preparing compounds of formula (III) is to react a quinolinic anhydride of formula (XVI) with a correspondingly substituted alpha-aminocarboxylic acid such as alpha-methylvaline of formula (XIX), preferably in a ketone solvent such as acetone under a nitrogen cover which gives an isomeric mixture of acids of formula (XX) and (XXI). The mixture is then treated with acetic anhydride and a catalytic amount of sodium acetate at a higher temperature to give dihydrodioxo-pyrrolopyridine or the quinolinic acid of formula (XXII). Reaction of the acid thus formed with a thionyl halide such as thionyl chloride or thionyl bromide in the presence of an organic solvent such as toluene, xylene, benzene or the like at a higher temperature, i.e. 80°C to 150°C, gives the acid halides of formula (XXXIII)

so- corresponds to the acid of formula (XXII). Treatment of this acid halide with an excess of ammonia then gives dihydrodioxopyrrolo-pyridine or the quinoline acetamide of formula (VI). The reaction is preferably carried out in the presence of an i-t aprotic solvent.

Reaction of the acetamide of formula (IV) with 1,8-diazabi-cyclo[5,4,0]undec-7-ene in an inert organic solvent such as toluene or xylene at a higher temperature between approx. 80°C and 125°C give the imidazopyrrolopyridine or quinoline ions of formula (III). These reactions are illustrated in reaction core II.

In another general method, compounds with

formula (III) is prepared by reacting 2-carboalkoxynicotinoyl or quinolinoyl chloride with formula (XIV) below, preferably as the methyl ester and preferably in the form of the hydrochloride salt with the corresponding aminocarboxamide shown by formula (XIII). The reaction gives a carbamoyl compound of formula (XV) and is preferably carried out in an inert gas blanket such as nitrogen. The reaction mixture is generally kept at a temperature below 30°C during the reaction time.

The thus formed carbamoyl compound of formula (XV) below can then be dispersed in an inert non-protic solvent such as xylene or toluene and heated to approx. 50=C to 130°C with 1,5-diazabicyclo-[5,5,0]undec-5-ene. The reaction gives a mixture of imidazopyrrolopyridine or the quinolindione isomers of formula (III) and formula (Illa).

Preparation of the diones of formula (III) and (Illa) by the above-described route is graphically illustrated in reaction core III below.

where , R0, Y and Z are as defined above.

Good luck dude. the acids r.ed formula (I) are converted into 5-H-imidazo-[1', 2': 1, 2] pyrrolo [3, 4-b] pyridir. or the quinoline-3(2H),5-dinones of formula (VII) by reaction with dicyclohexylcarbodiimide (DCC). The reaction is preferably carried out using approx. an equimolar amount of carbodiimide in the presence of a chlorinated hydrocarbon solvent at a temperature between ca. 20°C to 32°C. The reaction can be illustrated graphically as follows:

5H-imidazo[l',2':1,2]pyrrolo[3,4b]pyridine and the quinoline-3(2H),5-diones of formula (VII) are isomers of imidazopyrrolopyridine and the quinolinediones of formula (III) which are mentioned above.

2-(2-imidazolin-2-yl)pyridines of formula (I) and the 2-(2-imidazolin-2-yl)quinolines of formula (II) and the imidazopyrrolo-pyridinediones of formula (III) and the imidazopyrroloquinolinediones of formula (VII ) according to the present invention are highly effective herbicidal agents which can be used for the control of an exceptionally wide variety of herbaceous and woody annual and perennial monocotyledonous and dicotyledonous plants. Furthermore, these compounds are herbicidally active in controlling grass species that are typical of both dry and wet land areas. They are also applicable as water herbicides and have a unique ability to effectively control the above-mentioned plants when applied to their foliage or soil or water containing seeds or other growing organs of the plants such as root tubers, rhizomes or shoots in quantities from approx. 0.016 to 4.0 kg/ha, and preferably in amounts from approx. 0.032 to 2.0 kg/ha.

It is of course clear that application volumes over

The 4.0 kg/ha amount can also be used to effectively kill unwanted plant species, but application amounts of toxic agent above the level necessary to kill unwanted plants should be avoided, as the application of excessive amounts of toxic agent is costly and serves no appropriate function in the environment.

Among the plants that can be controlled with the compounds of this invention are: Elatine triandra Sagittaria pygmaea Scirpus hotarui Cyperus serotinus Eclipta alba

Cyperus difformis Rotala indica Lindernia pyridoria Echinochloa crus- galli Digitaria sanguinalis Setar ia viridis Cyperus rotundus Convolvulus arvensis Agropyron repens Datura stramonium Alopecurus myosuroides Ipomoea spp.

Sida sponosa

Ambrosia artemisii folia Eichhornia crassipes Xanthium pensylvanicum Sesbania exaltata Avena fatua

Abutilon theophrasti Bromus tectorum Sorghum halepense Lo1 ium spp.

Panicum dichotomiflorum Matricaria spp. Amaranthus retroflexus Cirsium arvense and Rumex Japonicus

The pyrrolopyridine acetonitrile of formula (XI), the pyrrolopyridine acetamides of formula (VI), the pyrroloquinoline acetonitrile of formula (XXXX) and the pyrroloquinoline acetonitrile of formula (XXXVIII) are useful as intermediates for the production of the above-mentioned herbicidal imidazopyrrolopyridine diones of formula ( III) and the imidazopyrroloquinolinediones of formula (VII).

The imidazopyrroloquinolinediones of formula (III) and formula

(VII) can also be formulated as wettable powders, liquid concentrates, emulsifiable concentrates, granular formulations and the like.

Wettable powders can also be produced by grinding together approx. 20-45% by weight of a finely divided carrier such as kaolin, bentonite, diatomaceous earth, attapulgite or the like, 45 to 80% by weight of the active compound, 2 to 5% by weight of a dispersing agent such

such as sodium lignosulfonate and 2 to 5% by weight of a nonionic surfactant such as octylphenoxy polyethoxyethanol, nonylphenoxy polyethoxyethanol or the like.

A typical flowable liquid can be prepared by mixing approx.

40% by weight of the active ingredient with approx. 2% by weight of a gelling agent such as bentonite, 3% by weight of a dispersing agent such as sodium lignosulfonate, 1% by weight of polyethylene glycol and 54% by weight of water.

A typical emulsifiable concentrate can be prepared by dissolving approx. 5 to 25% by weight active ingredient in approx. 65 to 90% by weight N-methylpyrrolidone, isophorone, butylcellosolv, methyl acetate or the like and disperse approx. 5 to 10% by weight of a nonionic surfactant such as an alkylphenoxy polyethoxy alcohol. This concentrate is dispersed in water for application as a liquid spray.

When the compounds according to the invention are to be used as herbicides where soil treatments are included, the compounds can be prepared and applied as granular products. Production of the granular product can be achieved by dissolving the active compound in a solvent such as methylene chloride, N-methylpyrrolidone or the like and spraying the thus prepared solution onto a granular carrier such as corncob grains, sand, attapulgite kaolin or the like.

The granular product thus produced generally comprises approx. 3 to 20% by weight of the active ingredient and approx. 97

to 80% by weight of the granular carrier.

The following examples are presented primarily for the purpose of illustrating certain more specific details thereof. Unless otherwise stated, all parts are parts by weight.

EXAMPLE 1

A)

Preparation of 5,7-dihydro-a-isopropyl-a-methyl-5,7,-dioxo-6H-pyrrolo[3,4-b]pyridine-6-acetamide

298 g of finely divided nitrile are added in portions to 330 ml of concentrated sulfuric acid under careful stirring so that the temperature does not exceed 72°C. After the addition, the temperature is adjusted to 60 to 65°C and held there for 1 1/2 hours. The mixture is cooled, quenched with ice and finally diluted to approximately 4 litres. After adding 454 g of sodium acetate and cooling at 0°C for 2 hours,

the mixture is filtered, the solid is collected and washed ten times with 500 ml of water containing sodium

acetate followed by water to remove all the sulfuric acid. The fixed •

substance is dried, and this gives 289 g of the product, m.p. 176-178 C. Material formed in a similar manner and analytically pure, had m.p. 188-190°C.

Using the appropriate pyrrolopyridine-acetonitrile in the above procedure, the following pyrrolo-pyridineacetamides are prepared.

B)

Preparation of 3-isopropyl-3-methyl-5H-inidazo-[11,2',:1,2]-yrrolo[3,4,6]pyridine-2-(3H),5-dione

A mixture of 50 g of amide and 450 ml of toluene is heated under a Dean-Stark water separator to remove traces of water. To the cooled mixture is added 10.1 g of a 50% suspension of sodium hydride in mineral oil and the mixture is heated under reflux for 23 hours. The hot solution is filtered, concentrated in vacuo, after which the residue is crystallized. The mineral oil is removed by decantation and the solid is washed with hexanes and dried in vacuo, yielding 45.5g of product which, by NMR analysis, is approximately 90% of the desired isomer II and 10%

of the undesired isomer IIa.

A pure sample of isomer II can be obtained by recrystallization of the impure product from hexane-methylene chloride, m.p. 107-115°C.

The cyclization can be achieved with either the basic reagent sodium and potassium hydroxide or the acidic reagent n-toluenesulfonic acid in a toluene solvent. It should be understood that a mixture of products corresponding to structure II and IIa above is obtained, and these are usually not purified, but used directly for the production of the derived nicotinic acid esters.

Using the appropriate pyrrolopyridine carboxamide, the following imidazopyrrolopyridines are prepared.

EXAMPLE 2 Preparation of 2-isopropyl-2-methyl-1-5l-imidazo-•LL',2':1,2]pyrrolo[3,4-b]pyridine-3-(2H),5-dione

To a solution containing 50.9 g of dicyclohexylcarbodiimide in 600 ml of dry methylene chloride, 60 g of the acid are added while stirring at such a rate that the temperature does not exceed 32°C. After stirring at room temperature for 2 1/2 hours, the mixture is filtered and the filtrate is concentrated to give a white solid. This solid is recrystallized from methylene chloride to give 57.4 g of the dione, m.p. 125-128.5°C. An analytically pure dione melts at 132-134°C. According to the above method and by using a correspondingly substituted acid, the following compounds are obtained:

EXAMPLE 3

A)

Preparation of 1,3-dihydro-q-isopropyl-a-methyl-1,3-dioxo-2-H-pyrrolo-'[3,4-b]quinoline-2-acetamide

1,3-dihydro- -isopropyl- -methyl-1,3-dioxo-2-H-pyrrolo 3,4-b quinoline-2-acetonitrile (0.44 g, 0.0015 mol) is dissolved in conc. sulfuric acid (5 ml) at room temperature and stirred overnight. The reaction mixture is poured onto crushed ice (50 ml) and a white precipitate forms which is filtered off, washed with water, aqueous sodium bicarbonate and water and then vacuum dried. This gives 0.34 g (74%) of product, m.p. 237-239°C (dec.). Anal. calculated for <C>17<H>17<N>3<0>3<:> C, 65, 58; H, 5.50; N, 13, 50, Found: C, 65. 03; H, 5, 63; N, 13,19.

The following compounds are prepared in the same manner as described above.

B)

■<>>Preparation of cis- and trans- 1, llb- dihydro- llb, hydroxy-3- isopropyl- 3- methyl- 5- H- iTnidazo[ 1' , 2 ' : 1, 2 jpyrrolo- [ 3, 4 - b] - quinoline-2(3H),5-dione

A solution of 1,3-dihydro-o-isopropyl-α-methyl-1,3-dioxo-2-H-pyrrolo-[3,4-b]quinoline-2-acetamide (0.5 g, 0.0016 mol) is heated under reflux in xylene for 2 3 hours. On cooling, a white solid precipitates, 0.17 g, m.p. 191-192°C, and a further yield of 0.1 g, m.p. 187-189°C, is formed by diluting the filtrate with hexane. Anal.

calcd for C 17 H 17 N 3 O 3 : C, 65.58; H, 5.50; N,13,50.

Found: C, 66.08; H, 5.65; N, 13.00.

Herbicide assessment of test compounds after emergence

The apparent herbicidal activity of the compounds according to the present invention is demonstrated by the following tests, whereby a number of monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. During the tests, seedlings are grown in temporary bins for approx. 2 weeks. The test compounds are dispersed in 50/50 acetone/water mixtures containing 0.5% TWEEN<R> 20, a polyoxyethylene sorbitan monolaurate surfactant from Atlas Chemical Industries, in sufficient quantity to provide an equivalent of approx. 0.016 to 10 kg per hectare of active compound when applied to the plants through a spray nozzle operating at 2>8 kg/cm 2 for a predetermined time. After spraying, the plants are placed in greenhouse benches and cared for in the usual way, as in normal greenhouse practice.

From 4 to 5 weeks after treatment, the seedlings are examined and assessed in accordance with the assessment system provided below. The data obtained are set out in Table XI below.

In most cases the data is for a single test, but in several cases average values have been obtained

from more than one test.

Plant species used

Herbicide assessment of test compounds before emergence

The preemergence herbicidal activity of the compounds of the present invention is exemplified by the following tests in which a number of seeds of various monocotyledonous and dicotyledonous plants are separately mixed with plant soil and planted on top of approximately 2.54 cm of soil in separate pots. After planting, the pots are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide an equivalent of approx. 0.016 to 10 kg per,

hectare of test compound per pot. The treated pots are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse practices. From 4 to 5 •weeks after the treatment, the tests are finished and each pot is examined and rated in accordance with the rating system indicated earlier. The herbicidal effect of the active ingredients according to the present invention appears from the test results listed in Table XII below.

When more than one test is involved for a given compound, average data are given.

Claims (3)

1. Connection, characterized by the following formula: where R 1 is C 1 -C 4 alkyl; R 2 is C 1 -C 1 alkyl or C 3 -C 6 cycloalkyl; Y and Z are each hydrogen, C 1 -C 8 alkyl or C 1 -C 8 alkoxy; or 2. Herbicide mixture, characterized in that it comprises an inert solid or liquid diluent and a herbicidally effective amount of a compound with the following formula: where Rlt R2, Y and Z are as defined in claim 1. 3. Use of the herbicidal mixture in claim 2 for the control of monocots and dicots, annuals, perennials or aquatic plants.