NZ206856A

NZ206856A - Imidazo-pyrrolopyridine(and quinoline)diones and herbicidal compositions

Info

Publication number: NZ206856A
Application number: NZ206856A
Authority: NZ
Inventors: M Los
Original assignee: American Cyanamid Co
Priority date: 1980-06-02
Filing date: 1981-05-29
Publication date: 1985-11-08

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £06856 ~\q - • • priority Date(s): .«"■ • ■ • • • • QR-6 -%\ Complete Specification Filed: Class: p.8 NOV 1985 , Publication Date: j'^ 7"7 P.O. Journal, No: " NO NEW ZEALAND Under the provisions of Regth? lation 23 (I) the j £aj£C. 'Specification has been ante-date4 to 19<SLi 4C '+B* ^ * w V <3 ® PATENTS ACT, 1953 Divided frcm No. 197247 No.: Date: COMPLETE SPECIFICATION IMIDAZOPYRROLOPYRIDINE (AND QUINOLIN&) DIONES *P?We, AMERICAN CYANAMID COMPANY, a corporation organized and existing under the laws of the State of Maine, United States of America, and having its executive offices at Wayne, New Jersey, United States of America hereby declare the invention for which XK/ we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - /'H' p* 4s" ' : ■ ■ n ' - ^ 4 - - .y -•/ 28,221/B - 2- i The present invention relates to novel imidazo-pyrrolopyridine (and quinoline) diones represented by the structures (III) and (Vll)below: ^ V V \ /li:I.)' r * V\ /* I g T I ^ V VI 1 R. 2 I - 20*6856 - 3 - wherein is C1-C4 alkyl; R2 is C1-C4 alkyl or c3-c5 cycloalkyl; and when and R2 are taken together with the carbon to which they are attached they may represent C3-C6 cycloalkyl optionally substituted with methyl; X is hydrogen, halogen, hydroxyl or methyl, with the proviso that when Y and Z are taken together to form a ring and YZ is represented by the structure: -(CH2)n-, where n is 3 or 4, X is hydrogen; Y and Z each represen-t members selected from the group consisting of hydrogen, halogen, C4-c5 alkyl, hydroxy-C^-C^ alkyl, ci~cg alkoxy, C^_C4 alkylthio, phenoxy, (4-c4~haloalkyl, nitro, cyano, C4-c4 alkylamino, aifC^-C^ alkyl)amino C1-C4 alkylsulfonyl group, or phenyl optionally substituted with one (4-c4 alkyl, C1-C4 alkoxy or halogen; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure: -(CH2)n-, where n is an integer selected from 3 and 4, provided that X is hydrogen; or L M Q R_ I 1 1 l7 C=C-C=C-, where L, M, Q and are each hydrogen, halogen, C^-C^ alkyl, C^-C^ alkoxy, C^-C^ alkylthio, C^-C^ alkylsulfonyl, halo- alkyl, NC>2, CN, phenyl, phenoxy, amino, C2~C4 alkylamino, di(C^-C^ alkyl)amino, chlorophenyl, methylphenyl, or phenoxy substituted with one CI, CF^, NC>2 or CH^ group, with the proviso that only one of L, M, Q or R^ may represent a substituent other than hydrogen, nalogen, alkyl or C][-C4 alkoxy; and the N-oxides thereof, and when R^ and R^ are not the same, the optical isomers thereof. 206856 One group of the formula (III) compounds has the formula: 0 o wherein Y is hydrogen, alkyl, C^-C^ alkoxy, cyano, nitro or halogen; R1 is C-j-C^ alkyl; R2 is Cx-C4 alkyl or C^-Cg cycloalkyl; and when and R2 are taken together with the carbon to which they are attached, they can represent C_-Cr cyclo- 3 6 alkyl optionally substituted with methyl, and when R^ and R2 are not the same, the optical isomers thereof. One general method for the preparation of the formula (III) compounds involves the reaction of an anhydride of formula (XVI) hereinbelow, with an appro- :.j priately substituted a-aminocarbonitrile of formula (XVII), hereinbelow, to yield a mixture of the mono-amides of the acid of formula (IX) and formula (X). This reaction is carried out at a temperature between about 20°C and 70°C and preferably between about 35°C and 40°C in an inert solvent, such as tetrahydro-furan, methylene chloride, ether, chloroform, toluene or the like. The thus-formed acids are then cyclized to the "corresponding pyrrolopyridine acetonitrile, depicted by formula (XI), by heating the reaction mixture _ ,-L A A ^ * X.' Vf. 2.0 5* - 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, 5 acetyl chloride, thionyl chloride or the like and heating said mixture to a temperature between about 20°C and 100°C. Hydration of the thus-formed pyrrolopyridine acetonitrile formula (XI) is carried out by treating said acetonitrile with a strong acid such as sulfuric 10 acid. This reaction yields the formula (XII) pyrrolopyridine or quinoline acetamide. Although the addition of a non-miscible solvent such as methylene chloride, chloroform or the like is not essential to the conduct of the above described reaction, addition of such a 15 solvent to the reaction is generally preferred. Said reaction is usually carried out at a temperature between about 10°C to 70°C. The cyclization of the formula (XII), hereinbelow, pyrrolopyridine or quinoline acetamide yields 20 the tricyclic formula (III) imidazopyrrolopyridine and quinoline diones. The product of this reaction is predominantly the imidazopyrrolopyridine or quinoline diones (III) (85%) together with the isomer of formula (Ilia). 25 The cyclization reaction is preferably conducted at a temperature of from 80°C to 150°C in the presence of a base such as sodium or potassium hydride or an acid such as an aromatic sulfonic acid and a solvent which will form an azeotropic mixture with water, per-30 mitting virtually immediate removal thereof from the reaction mixture as it is formed. Among the solvents which may be employed are toluene, benzene, xylenes and cyclohexane. Bases which may be used include alkali metal hydroxides, alkali metal hydrides, alkali metal 35 oxides, tertiary amines such as diisopropyl ethylamine, 1,5-diazabicyclo[3.4]nonene-5,1,5-diazobicyclo[5.4.0]- 2-OGS 56 (, J? - X- undecene-5,1,4-diazabicyclo[2.2.2]octane, tetramethyl-quanidine, potassium fluoride and quaternary ammonium hydroxide, such as trimethylbenzyl ammonium hydroxide and strongly basic ion exchange resins. 5 Finally, acidic reagents which can be employed herein include aromatic sulfonic acids, such as £-toluene-sulfonic acid, beta-naphthalenesulfonic acid, naphtha-lenedisulfonic acid, and the like. The above reactions are graphically illustrated on Flow Diagram I below, when X, Y, Z, and R2 are as defined above. 15 20 25 30 35 % - JS- FLOW DIAGRAM I V\J I L> ^ v* g (xvi) nh2-c-cn (xvii) I L *1- 2^ v conh—c—cn (ix) tn A /=o'»4-«' i I ^ •v •. ^ V\ V (ch3c0)20 cooh (x) V\J , V- -CN (XI) % ' Z^v I h h2so4 V FLOW DIAGRAM T (CONTINUED) v\J I IL /V 4 I -conh. Qaae v Vv\ I o /V V\. ? 1? /? «3 (xii) (III) • V 1N ! I ' s / ^ v y A 1 I s (Ilia) Another general method for the preparation of the formula (III) compounds involves the reaction of a quinolinic anhydride of formula (XVI), with an appropriately substituted alpha-aminocarboxylic acid such 5 as alpha-methylvaline represented by formula (XIX), preferably yin a ketonic solvent such as acetone under a blanket of nitrogen to yield an isomeric mixture of the formula (XX) and formula (XXI) acids. The mixture is then treated with acetic anhydride and a catalytic amount 10 of sodium acetate at an elevated temperature to give the dihydrodioxopyrrolopyridine or quinoline acid formula (XXII). Reaction of the thus-formed acid with a thionyl halide, such as thionyl chloride or thionyl bromide, in the presence of an organic solvent such as toluene, 15 xylene, benzene or the like, at an elevated temperature, i.e., 80°C to 150°C, gives the formula (XXIII) acid halide corresponding to the formula (XXII) acid. Treatment of this acid halide with excess ammonia then yields the formula (IV) dihydrodioxopyrrolopyridine or quinoline 20 acetamide. The reaction is preferably carried out in the presence of an aprotic solvent. Reaction of the formula (IV) acetamide with 1,8-diazabicyclo[5,4,0]undec-7-ene in an inert organic solvent such as toluene or xylene at an elevated temperature 25 between about 80°C and 125°C gives the formula (III) imidazopyrrolopyridine or quinoline diones. These reactions are illustrated as Flow Diagram II. 30 35 zo , - 5 -J - FLOW DIAGRAM II 10 15 V\_J /V~I (xvi) f COOK V\./ /v\ I1 CONH-HJ-COOH nh2-C-cooh (XIX) \r VA r s-co z/'V T* 3NH—<^—COOH •-COOH *2 20 25 (XX) (XXI) (CH3C0)20 vsAil •k * ' I z'V 8 A2 -COOH 30 (XXII) 35 Jt- - y- FLOW DIAGRAM II (CONTINUED) (xxiii) (IV) 10 15 20 25 30 x - Sf - FLOW DIAGRAM II (CONTINUED) tobu X V f? Yv > T I "T ►—R. z^v" v\ (III) + isomer £ 35 13 - - In another general procedure,,the formula (III) compounds can be prepared by reacting the 2-carboalkoxy-nicotinoyl or quinolinoyl chloride of formula (XIV), here in below, preferably as the methyl ester and preferably 5 in the form of the hydrochloride salt, with the appropriate aminocarboxamide depicted by formula (XIII). The reaction yields a carbamoyl compound of formula (XV), and is preferably carried out in an inert blanket of gas such as nitrogen. The reaction mixture is generally 10 maintained at a temperature below 30°C during the reaction period. (XV), hereinbelow, can then be dispersed in an inert non-protic solvent such as xylene or toluene and heated 15 to about 50°C to 130°C with 1,5-diazabicyclo-[5.5.0]un-dec-5-ene. The reaction yields a mixture of the formula (III) and formula (Ilia), imidazopyrrolopyridine or quinoline dione isomers. 20 diones, by the route described above, is graphically illustrated in Flow Diagram III below. The thus-formed carbamoyl compound of formula Preparation of the formula (III) and (Ilia) u> FLOW DIAGRAM III f £0C1 25 .hcl coor (XIV) (xiii) 30 II 2 •*. . • V N coor 35 (XV) 10 15 - 14 - FLOW DIAGRAM III (CONTINUED) DBU xylene A * J * , V fi 1N LCC*. r'V V V (III) 206856 20 25 I I ! > \ y*\ /vy 1 1 I 2 (Ilia) 30 wherein R^, R2, X, Y and Z are as defined above. 206856 - 15 - In accordance with the process of New Zealand Patent Specification No. 197247, 2-(2-imidazolin-2-yl)-pyridine and quinoline esters of formula (lb), hereinbelow, wherein A is COOR^ and R^ represents a substituent other than hydrogen or a salt-forming cation, and R^, RX, Y and Z are as described above, can be prepared by reacting an imidazopyrrolopyridine or quinoline dione, represented by formula (III), hereinabove, with an appropriate alcohol and corresponding alkali metal alkoxide at a temperature ranging between substantially 20°C and substantially 50°C. In these reactions, the alcohol can function both as reactant and solvent. As such, a secondary solvent is not required. However, when an expensive alcohol is employed in the reaction, a less expensive secondary solvent, such as dioxane, tetrahydrofuran or other non-protic solvent, may be added to the reaction mixture. The amount of non-protic solvent added to the reaction mixture may be widely varied. The overall reaction can be graphically illustrated as follows: ? S h WvJ-, I II J I 2 /V' V\ * vvi > (III) Y .• COOR, • » ' " P /v\a./; 1 i 2 (lb) K*—* ^ ^0 where is an alkali metal, and X, Y, Z, R^, R2 and R3 are as defined above. ,/ 206856 - 16 - The mixture of compounds of formula (III) and formula (Ilia) prepared according to Flow Diagrams I, II and III can be converted to formula (lb) , by reaction, as discussed above, with an alkali metal alkoxide and alcohol. The formula (I) acids where A is COOH may be prepared by treatment of an aqueous solution of the formula (lb) ester with a strong base. In practice the formula (lb) ester is"generally treated with one equivalent of base in aqueous solution, and the mixture heated to between 20°C and 50°C. The mixture is then cooled and adjusted to pH 6.5 to 7.5 and preferably pH 7, with a strong mineral acid. Such treatment yields the desired acid. The reaction can be illustrated as follows: 1 ) \ S \ / • • I / v\ a A : •—r_ JUL 1. Base /H^O 2. Acid \A / COOH ■ „L4 " where is other than hydrogen or a salt-forming cation, and , X, Y and Z are as defined above. The formula (I) acids may then be converted to the formula (VII) 5-H-imidazo [ 1 1 , 2 ' : 1,2 ] pyrrolo [f3 , 4 , b] pyridine or auinoline-3 (2H) ,5-diones by reaction with^b* - A r.^.4 206856 - 17 - dicyclohexylcarbodiimide (DCC). The reaction is preferably conducted using approximately an equimolar amount of carbodiimide in the presence of a chlorinated hydrocarbon solvent at a temperature between about 20°C to 32°C. The reaction may be graphically illustrated as follows: . f .COOB y f S V\/ V V \ A-'wf ^ A-vy j-O 'i-' v0 (i) •' <vii) The formula (VII) 5H-imidazo[l',2':1,2]pyrrolo-[3,4-b]pyridine and quinoline-3(2H),5-diones are isomers of the formula (III) imidazopyrrolopyridine and quinoline diones referred to above. Formula (III) and formula (VII) imidazopyrrolo-pyridinediones and imidazopyrroloquinolinediones of the present invention are exceedingly effective herbicidal 25 agents useful for the control of an exceptionally wide variety of herbaceous and woody annual and perennial monocotyledonous and dicotyledonous plants. Moreover, these compounds are herbicidally effective for controlling weeds indigenous to both dry land and wet land 30 areas. They are also useful as aquatic herbicides and are unique in their effectiveness in controlling the above-said plants when applied to the foliage thereof or to soil or water containing seeds or other propagating organs of said plants such as tubers, rhizomes or stolons, 35 at rates of from about 0.016 to 4.0 kg/ha, and preferably at rates from about 0.032 to 2.0 kg/ha. 206 2 5b (9 - >5 - It is, of course, obvious that rates of application above the 4.0 kg/ha level can also be used to effectively kill undesirable plant species; however, rates of application of toxicant above the level neces-5 sary to kill the undesirable plants should be avoided since application of excessive amounts of toxicant is costly and serves no useful function in the environment. Among the plants which may be controlled with the compounds of this invention are: 10 Elatine triandra Sagittaria pygmaea Scirpus hotarui Cyperus serotinus Eelipta alba 15 Cyperus difformis Rotala indica Lindernia pyridoria Echinochloa crus-gal1i Digitar ia sanguinalis 20 Setaria viridis Cyperus rotundus Convolvulus arvensis Agropyron repens Datura stramonium 25 Alopecurus myosuroides Ipomoea spp. Sida sponosa Ambrosia artemisiifolia Eichhornia crassipes 30 Xanthium pensylvanicum Sesbania exaltata Avena fatua Abutilon theophrasti Bromus tectorum 35 Sorghum halepense Lolium spp. Panicum dichotomiflorum 206856 -19- Matricaria spp. Amaranthus retroflexus Cirsium arvense and Rumex Japonicus. The formula (III) and formula (VII) imidazopyrroloquinolinediones ,-can be formulated as wettable powders, flow concentrates, emulsifiable concentrates, granular formulations and the like. Wettable powders can be prepared, by grinding together 20% to 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 as sodium 1 ignosulfonate, and 2% to 5% by weight of a nonionic surfactant, such as octylphenoxy polyethoxy ethanol, nonylphenoxy polyethoxy ethanol or the like. A typical flowable liquid can be prepared by admixing about 407o by weight of the active ingredient with about 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 547« by weight of water. A typical emulsifiable concentrate can be prepared by dissolving 5% to 25% by weight of the active ingredient in substantially 65% to 90% by weight of N-methyl-pyrrolidone, isophorone, butyl cellosolve, methylacetate or the like and dispersing therein substantially 5% to yew "<i. o % ■ /V 29 AUGI985.' 206856 - 20 - 107o by weight of a nonionic surfactant -such as an alkyl-phenoxy polyethoxy alcohol. This concentrate is.dispersed in water for application as a liquid spray. When the compounds of the invention are to be 5 used as herbicides where soil treatments are involved, the compounds may be prepared and applied as granular products. Preparation of the granular product can be achieved by dissolving the active compound in a solvent such as methylene chloride, N-methylpyrrolidone or the 10 like and spraying the thus prepared solution on a granular carrier such as corncob grits, sand, attapulgite, kaolin or the like. The granular product thus prepared generally comprises substantially 3% to 20% by weight of the active 15 ingredient and substantially 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 noted, all parts 20 are by weight. 25 30 35 / 206856 - 21 - 10 EXAMPLE 1 Preparation of 5 ,7-Dihydro-dL-isoprooyl-t3.-methyl-5,7-dioxo-6H-pyrrolo[3,^-b ]pyridine-6-ace toni trile To a stirred solution containing 212 g quinolinic anhydride in 950 ml methylene chloride is added at a moderate rate 167 g of 2-amino-2,3-dimethylbutyronitrile . The mixture had reached the boiling point of the solution after about one quarter of the aminonitrile had been added and the rate of addition is adjusted to maintain this temperature. After the addition the solution is heated under reflux for a further ^ hours. The solution is cooled, filtered and concentrated to a thick oil. This oil is dissolved in 950 ml acetic anhydride, 6 g anhydrous sodium acetate added and "*5 the mixture distilled until the vapor temperature reached ll8°C when the heating was continued under reflux for 3 hours. The mixture is concentrated in vacuo the residue dissolved in 500 ml toluene and again concentrated. This is repeated. The 20 residue is slurried with a mixture of ether and hexane and the crude product which crystallizes collected (3^9 g). This is dissolved in 700 ml methylene chloride and filtered through a column containing 700 g silica gel and the product eluted 25 with methylene chloride. Concentration of the eluant gave 258 g of the desired product. An analytically pure sample with mp 95-96°C can be obtained by the recrystallization of the product from ether-methylene chloride. Using the appropriate amino nitrile and quinolinic anhydride in the above procedure, the following pyrrolopyridines are prepared: 35 206856 - 22 - rl 12 x y Z mD°c ch3 ch3 h h h 119 - 123 ch3 c2h5 h h H 95 - 97 ch3 _A h h h 69 - 73 ch3 ch2ch(ch3)2 h h h oil -(ch2)5- h h H 85 - 87 c2h5 c2h5 h h h 71 - 72.5 ch3 ch(ch3)2 ch3 k h 129-5 - 131.3 ch3 ch(ch3)2 h h och3 108 - 110 ch3 ch(ch3)2 h h ci 94 - 9o 206856 - 23 - EXAMPLE 2 Preparation of 5 ,7-Dihydro-3s.-isopropyI-l-nethyl-5 ,7 ,-dioxo-6H-pyrrolo[3,4-blpyridine-6-acetamide To 330 ml concentrated sulfuric acid is 5 added portion wise with thorough stirring 298 g finely divided nitrile so that the temperature did not go about 72°C. After the addition the temperature is adjusted to 60-65°C and maintained there for 1 1/2 hours. The mixture is cooled, quenched with 10 ice and finally diluted to approximately 4 liters. After adding 454 g sodium acetate and cooling at 0°C for 2 hours the mixture is filtered, the solids collected and washed twice with 500 ml water containing sodium acetate followed by water to 15 remove all the sulfuric acid. The solid is dried to give 289 g of product, mp 176-178°C. Material made in a similar way and analytically pure had mp 188-190°C. Employing the appropriate pyrrolopyridine-20 acetonitrile in the above procedure, the following pyrrolopyridineacetamides are prepared. 25 "2 1 ——C / ONH V 5 k £1 *2 X Y ch3 ch3 h H ch3 • C2H5 H H ch3 -a H H z mp°C H 203-5 H 158 - 16 1 H 195 - 198 /V w. 2 29 AUG 1935." 206856 - 24 -EXAMPLE 3 Preparation of 3-Isopropyl-3-methyl-5fl-imidazo-f1 *,2*,:1, 2]pyrrolo [3,4,5.] pyridine-2-(3H)« 5-dione A mixture of 50 g amide and -450 ml 5 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 heated under reflux for 23 hours. The hot solution is 10 filtered, concentrated in, vacuo where upon the residue is crystallized. The mineral oil is removed by decantation and the solid washed with hexanes and dried iji vacuo to give 45.5 g product which, by nmr analysis, is approximately 90? the desired 15 isomer II and 10J the undesired isomer Ila. A pure sample of.isomer II can-be obtained by recrystallizing the crude product from hexane-methylene chloride mp 107-115°C. The cyclisation can be achieved by either 20 the basic reagent sodium and potassium hydroxide, or the acidic reagent £-toluenesulfonic acid in a toluene solvent. It should be understood that a mixture of products corresponding to Structures II and Ila above is obtained and in general these are 25 not purified but used directly for the preparation of the derived nicotinic acid esters. Employing the appropriate pyrrolopyridine carboxamide, the following imidazopyrrolopyridines are prepared. 30 35 - - 10 15 20 t ff r/Y'Y T- -R z^v#—V1"0 2 ll Iz x y z mP°c ch3 ch3 h h h ch3 c2h5 h h h ch3 -a h h h -ch-CH2CH2CH2CH2- h h h 125 3 ch3 ch(ch3)2 h h och3 147 25 30 35 206856 - 26 -EXAMPLE 4 , Preparation of 3-IsoDropyl-5-H-imidazo[2f, 2': 1,2]-pyrrolo[3,4-6]pyridine-2(3H)-dione A mixture containing 52 g of 3-C(1-Carbamoyl-1,2-dimethylpropyDpicolinate, 1.77 ml 1,5-diazabicyclo-[5 .4.0]-undec-5-ene(DBU) in 400 ml xylene is heated under reflux under a Dean-Stark water separator for 2 hours. The mixture is concentrated in vacuo and the residue is chromatographed on 400 g basic alumina. The mixture of desired products is eluted with methylene chloride and used without further purification. 0 c. - 27 -EXAMPLE 5 Preparation of 5 ,7-Dihydro-^-isoproDyI-3L-methyI -5 ,7-dioxo-6^il-pyrrolo[ 3,4-ii3pyridine-6-acetic acid (-isomer) 10 20 25 30 /\ R ? n n ch t i3 ,• cooh i j /° + nh2-v-c00h > ?h3 \/~l Ucu3)2 ^.-CONH-i-COOH 3 ' ch( cr h(ch3)2 *3 a j "w ch(chj COOH 3 2 /\ ft ch [ [l >4-coo:-V/*1 chcch. 15 I ^-f-cooa « VI H(CV7 To a stirred suspension of 18.4 g of the anhydride in 760 ml of dry acetone is added, under nitrogen, 16.2 g of (+) -methylvaline. After stirring at room temperature for 48 hours, the mixture is filtered and the filtrate concentrated to give the crude intermediate. This material is dissolved in 500 ml acetic anhydride, a catalytic quantity of sodium acetate added and the mixture stirred at room temperature for 5 hours. After heating under reflux for 1.5 hours,' the mixture is concentrated. The residue is dissolved in ethyl acetate and washed with water. The dried extract is concentrated to give a dark syrup. A sample is dissolved in ethyl acetate, treated with charcoal, 206856 28 filtered and concentrated. The residue is crystallized from methylene chloride to give the 25 product, mp 122 - 125°C U]D = -7.73°C (c = 0.100,THr). By essentially the same procedure and using the appropriate starting quinolinic anhydride 5 and amino acid the following acids are prepared 10 15 20 -ch3 CH3 CK2CH(CH3)2 CH3 CK(CH3)2 *2 ck(ch3)2 tsp° C 126 - 127 +6.93 (c = 0.100,THF) 174 - 176 196.5 - 198.5 183 - 186 25 30 35 206856 - 29 - EXAMPLE 6 Preparation of 5 ,7-Dihydro-^-isopropyl-j.-methyl-5 ,7-dioxo-oil-pyrrolo [ 3, ^-.tjcyridine-6-acetamide f r>-T-* ^ fVv&oc! - \/"3 iH(CH3)3 I II /\J f 1 II >4 VI * VI a(CH3), H3 -conh nh3 2 h(ch3)3 To a mixture containing 32 g of (-)-acid in 375 ml of toluene is added 2 ml of dinethyl-formamide followed by 13 ml of thionyl chloride. After heating at reflux for 1.25 hours, the mixture is concentrated i_n vacuo. The residue is dissolved in 350 ml of tetrahydrofuran, cooled to 0°C and a slight excess of gaseous ammonia bubbled through the mixture. The solvent is removed i_n vacuo to leave a solid which is washed with water and air-dried A portion of this solid is crystallized twice from ethyl acetate (with charcoal treatment) to give the desired product as a white crystalline solid, rap 188-189°C U]pD = + 3.59 (c = 0.0791, DMSO) By essentially the same procedure and using the appropriate acid, the * following amides are prepared. - 30 - 06856 y\J J, I II >-f-c°NHs vi K 10 15 20 25 Rj ch3 *2 ch(ch3)2 ch3 ch2ch(ch3)2 -chch2ch2ch2ch2-ch3 mp°C 189-5 - 192 p -3-02 (c = 0.0744,DKSO) 176 - 178 186 - 188 30 .35 - 31 - 206856 EXAMPLE 7 Preparation of 3-Isopropyl-3-niethyl-5H-imidazo [ 1', 2 ' : 1, 2] pyrrolo[3,4-b]pyridine-2-(3H), 5-dione ^"\ f? ch viuokh a j 1 Xf "v—a 4«ch ) i ii ap 32 •vs-jj2pcy2 isoaer The cyclization of the araide is accomplished by heating 7.83 g of araide in 150 ml of toluene and 0.45 ml of 1,8-diazabicyclo[5,4,0]undec-7-ene under a Dean-Stark water Separator for 2 hours as described in Example 4 . If EN >> *s\\ j!\j 2 9 AUG1985 r, O / %$$ \ 206856 32 EXAMPLE 8 „ Preparation of 2-Isopropyl-2-cethyl-5.H.-imidazo-C1' , 2' : 1 12]pyrrolo[3 ,4-ft.]pyridine-3C2H),5-dione To a solution containing 50.9 g of dicyclo- hexylcarbodiimide in 600 ml of dry methylene chloride is added, while stirring, 60 g of the acid at such a rate that the temperature does not exceed 32°C. After stirring at room temperature for 2.5 hours, the mixture is filtered and the filtrate concentrated to give a white solid. This solid is recrystallized from methylene chloride to give 57.4 g of the dione, mp 125-128.5°C. The analytically pure dione melts at 132-134°C. 206856 10 - 33 -EXAMPLE 9 Preparation of 1, 3-Dihydro-g-isopropyl—a-methvl-1, 3-dioxo-2-H-pyrrolo- [3,4-b.l qui noli ne-2-acetoni tr ile Procedure A •AA Ajr- /Vv!\J" i t o > ii >-c-cn —> i i ii V-t-cn v\/ ■n/1h(c„3,2 vvykcv, Anthranil (59.6 g, 0.5 mol) is added dropwise 15 under nitrogen, with stirring, over a 45 minute period, to a refluxing solution of a- isopropyl-a-methyl-2 , 5-d i oxo-3-pyrroline-l-acetonitr ile in o-dichlorobenzene (450 ml). After 18 hours the reaction mixture is cooled and methylene chloride added. This solution is passed through 20 a 3 inch silica gel column, by eluting with methylene chloride. The eluate is concentrated to 500 ml and hexane added. A precipitate forms and is filtered off and air dried, to yield the product 110.6 g, (75%) as a light brown solid. Crystallization from ethyl acetate-hexane 25 gives pale yellow crystals, mp 195-196°C. Anal, calcd. for ci7h15N302: c' 69.61; H, 5.15; N, 14.33. Found: C, 69.37; H, 5.15; N, 14.43. Employing similar conditions the compounds of Table I are prepared. 30 35 29AUG19853) // 206856 34 Procedure B Cyclization of o-formylani1ino-maleimides 5 :—cn —> *\ *\ * / \ h(ch ) v i c:h(ch ) 3 2 11 3 2 :—cn ,u A solution of N-(1-cyano-l,2-dimethylpropyl)- 2-(o-formylanilino) maleimide (7.19 g, 0.023 mol) in xylene (300 ml) containing £-toluenesulfonic acid (0.3 g, 0.0016 mol) is heated at reflux for 4 hours using a Dean-Stark trap to collect the eliminated water. The 15 reaction is cooled, evaporated under reduced pressure and dissolved in hot ethyl acetate which is passed through a 3 inch silica gel column. The ethyl acetate fractions eluted are combined to give a solid, mp 195-195.5°C, 5.51 g, (81%) of 1,3-dihydro-a-isopropyl-a-methyl-l,3-20 dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetonitrile. Other compounds prepared by this procedure are listed in Table I. 25 30 i ? i. Table I v ? ff "V'YYyp yVV I i 8 CN r1 r2 x l m Q r ch3 ch(ch3)2 h i! no2 h ii ch3 ch(ch3)2 h h h no2 ii C»3 ch(ch3)2 h no2 h ii ii cii3 cii(cii3)2 h H H h no ch3 ch(ch3)2 H Br h 11 11 ch3 ch(ch3)2 H ci ii ii ii ch3 cii(ch3)2 h ii cf3 ii cn 3 c!!(ch3)2 ii If ii ci ii Procedure mp°C A 230-232 A 260-261 A A A,n 139.5-142 n n inn u> Ul rv> o CN CD CJ1 On Table I cont'd r1 r2 x l m q r7 ch3 ch{ch3)j h h cii3 ii h ch3 ch(ch3)2 h h h c»3 h ch3 ch(ch3)2 ii h ii h ch3 ch3 ch(ch3)2 h h •°cii3 h ii cn3 ch(ch3)2 h h ii ch3 ch3 ch3 ch(ch3)2 h ii ch3 h ch3 ch3 ch(ch3)2 ii ch3 h ii c«3 cii3 ch(ch3)2 h ii ii CI cii3 ch3 ch(ch3)2 h CI ii ii ch3 ch3 ch(ch3)2 ii ii ci ii cii3 CH3 ch(ch3)2 H CI h ii 0cii3 ch3 c3h7 11 ii ii ii ii ch., A c2h5 h ii ii h ii Procedure mp°C D D 186-190 D D II D n n n n n A A o On CO Ul On Table I cont'd R1 R2 X ch3 n-c4»9 h ch3 £-c4h9 h ch3 i-c4h9 h ch3 t-c4h9 h ch3 cyclopropyl II ch3 ch2ch=ch2 h ch3 cyclohexyl h (ch2)5 h m R. ch. ch. ch. ch(ch3)2 ci ch(ch3)2 ch3 chich3)2 f ch(ch3)2 och3 ch(ch3)2 oh A A A A A A A i U) I ro CD On CO c_n On Table I cont'd r1 r2 x l m 0 CH3 CH(CH3)2 II H CI Procedu re mp°C 202.5-203.5 u> CO r-o O On OO en On 206856 25 39 - EXAMPLE 10 preparation of 1,3-Dihydro-a-isopropyl-q-methyl-l. 3-dioxo-2-H-pyrrolo [3 ,4-h.iqui noline-2-acetamide /VV\ /Vv\ f3 t II I ^N-c-CN > T I II V-i-CONH VVY1(ch3)2 VVY ch(ch ) j 3 2 i 32 10 1,3-Dihydro-a-isopropyl-a-methyl-l,3-diojco-2-g-pyrrolo [3,4-fc. lquinoline-2-acetonitrile (0.44 g, 0.0015 mol) is dissolved in conc. sulfuric acid (5 ml) at room temperature and stirred overnight. The reaction 15 mixture is poured onto crushed ice (50 ml) and a white precipitate forms and is filtered off/ washed with water, aqueous sodium bicarbonate and water and then vacuum dried. This gives 0.34 g (74%) of product, ,mp 237-239°C (dec.). Anal, calcd. for C^H^N^C^: C, 65.58 ; H, 5.50; 20 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. 30 4-° - 7A - 2 06 8 5 Table II * * 9 B a/vvj1 tTt I II ^N—C—CONH ^vvn/a I i 2 Rl R 2 X L M Q R7 mp°C ch3 ch(ch3 2 B B NO2 B B 225-227(c 10 ca3 ch(ch3 2 H B B N02 B 237-238 CH3 ch(ch3 2 H no2 B B B ^3 ch(ch3 2 H Br B H B 197-198 ch3 ch(ch3 2 H B CI H B 216-217 15 ch3 ch(ch3 2 h B cF3 H h ca3 ch(ch3 2 H B B CF3 B ch3 ch(ch3 2 H B B CI B 232-234 20 ch3 ch(ch3 2 b b B b .CI 207.5-208.5 ch3 ch(ch3 2 B B cb3 b B 226-227 CH3 ch(ch3 2 B B B cb3 B 256-260 CH3 ch(ch3 2 B b b b cb3 25 ch3 ch(ch3 2 B b och3 B b 225-280 ch3 ch(ch3 2 B B B cb3 cb3 ch3 ch(ch3 2 B B cb3 B CH3 208-214 30 15 20 25 L\ %K - Table II (cont'd) 10 CH, C,B- H H H H H 222-224 ri r 2 x l m q r? ch3 ch(ch3)2 h ch3 b b ch3 ch3 ch(ch3)2 h b b ci ch3 ch3 ch(ch3)2 h ci b b ch3 ch3 ch(ch3)2 b b ci b ch3 ch3 ch(ch3)2 h ci b b och3 ch3 c3h7 h b b b h ch3 c2h5 b b b b h ch3 c4h9 b b b b h ch3 ®-c4h9 b b b b h ch3 1-c4h9 b b b b h ch3 1"c4h9 b b b b. b ch3 h h b b h ch3 ch2ch»ch2 b b b b h ch3 • • h b b b b (ch2)5 b b b b b ch3 ch(ch3)2 ci b b b b ch3 ch(ch3)2 ch3. b b b b ch3 ch(ch3)2 f b h h h ch3 ch(ch3)2 och3 h b h b mp°C 195-197 202-205 30 206856 - 42 - Table II cont'd rx r2 x ch3 ch(ch3)2 oh ch3 ch(ch3)2 OAc ch3 ch(ch3)2 h L M Q h h h h h h ci h h r7 mp°C h h H 198-199 (dec.) 206856 43 EXAMPLE 11- Preparation of 2-(5 - Isopropy1-5-methyl-4-oxo-2-imidazol i n-2-yl)-3-cuinolinecarboxylic acid Procedure A 1,3-dioxo-2-H-pyrrolo [3,4-b] quinoline-2-acetamide (5.76 g, 0.0185 mol) in dry xylene (600 ml) is added a 50% oil dispersion of sodium hydride (1.33 g, 0.0278 mol) and the mixture is heated to reflux, whereupon the reaction mixture becomes homogeneous. After 3 hours at reflux the reaction is set aside at room temperature overnight and then methanol (15 ml) containing sodium methcxide (0.1 g) is slowly added and warmed at reflux for 1 hour. The mixture is filtered while hot and the organic solvents stripped to give an oil and solid. A methylene chloride-water mixture is shaken with the above residues, until they dissolve. The aqueous layer (200 ml) is separated and slowly acidified with acetic acid ( 5 ml). A precipitate of the product is formed and is collected by filtration to give 3.91 g (72%) of mp 219-224^. Recrystallization from hexane-ethyl acetate gives mp 219-222°C (dec.). Anal, calcd. for C17H17N3C>3: C, 65. 58; H, 5.50; N, 13.50. Found: C, 65.09; H, 5.50; N, 13.59. 5 10 To a slurry of 1,3-dihydro-a-isopropyl-i-methyl- 20 25 206856 44 This example is used to prepare the following examples. However to avoid ester formation, rather than filter off the insolubles and strip down the xylene one may simply add methanol followed by water (caution hydrogen may be evolved) to the xylene layer. 15 20 25 Table III COOH v } *yyy -vvw: & r.\ r r x l m 0 r ch3 ch(ch3)2 h h ii no2 h ch3 ch(ch3)2 h ii no2 ii h ch3 ch(ch3)2 ii no2 h h h ch3 ch(ch3)2 h h ' h h no ci?3 ch(ch3)j h Dr h ii ii ch3 ch(ch3)2 h h ci h h ch3 ch(ch3)2 h h ii ci ii ch3 ch(ch3)2 ii ii ii h ci O Jz ch(ch3)2 ci h ii 11 ii m Procedure mp°C a 247-251 a 241.5-242 a a a A a 238-240 a cn K> CD ON oo en ON Table III cont'd R R X L M Q R Procedure mp°C ch3 ch(ch3 2 ' h ci h h h a 255-256(dec.) ch3 ch(ch3 2 h h cf3 ii ii a ch3 cutely 2 h h ii cf3 ii a • ch3 ch(ch3 2 h h f ii h a ch3 ch(ch3 2 h h ch3 ii h a ch3 ch(ch3 2 h h ii ch3 h a i ch3 cii(ch3 2 h h ii h ch3 a CTl ch3 ch(ch3 2 ch3 h ii ii h a 1 cn2 cn(cn3 2 h h 0cii3 h ii a ch3 ch(ch3 2 h ii scn3 h ii a ch3 ch(ch3 2 ii h so2ch 3 " h (perac id on above) ch3 ch(ch3 2 f h H H H A ch3 ch(ch3 2 H If H Cfl3 ch3 a O CN CD un V X i Table iii (cont *d) r R x l m q r ch3 ch(ch3 2 h h ch3 ii ch3 ch3 ch(ch3 2 ii ch3 h h ch3 ch3 ch(ch3 2 h ii h ci cii3 ch3 ch(ch3 2 h ci •. h h ch3 ch3 ci!(ch3 2 °c»3 h ii ii ii ch3 ch(ch3 2 oh ii ii h ii ch3 ch(ch3 2 OAc h h ii H ch3 ch(ch3 2 h ii ci h ch3 ch3 ch(ch3 2 h ci ii ii OCH ch3 C3H7-n 1! ii h ii ii ch3 C2lI5 h ii H ii ii cn3 C4H9-n h ii ii ii h Tf }0 C JL-sec s 1! h h ii ii Procedure A A A A A A A A A A A C> T»/ mp°C i •Ck -J I f\J> o CS 00 ui On Table III (cont'd) Table III (cont'd r r x l M Q ch3 C4H9-iso h II II ii ch3 C4H9-tert h h II h ch3 • h II II II ch3 chch=ch2 h II II ch3 • — • / \ • • \ / h H h h (CH2)5 h H II II CH3 CH(CH3)2 H H H F CH3 CH(CH3)2 II H II CN ch3 CH(CH3)2 H H H N (Clf 3 ) 2 ch3 ch(ch3)2 h h ii nh2 ch3 cii(cii3)2 ii ii ii i Procedure A A A A A A A (reducti on Q A NT- . • j \ ^ \ co i no2) ro CD ON OO en On 206856 49 EXAMPLE 12 Preparation of 2-Isopropvl-2-methyl-5-H-imidazof1' , 2 ' : 1, 2]-pyrazolo 3,4-b quinoline 3(2H),5-dione, 2-isopropyl-2-methvl ^ in methylene chloride under nitrogen is added to a stirred suspension of 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylic acid, (5.24 g, 0.0168 mol) in methylene chloride at room temperature overnight. Since reaction was incomplete a further 0.3 g of cicyclo-20 hexylcarboaiimide was added and the mixture stirred for a further 48 hours. The reaction mixture is evaporated to a yellow solid and is purified by chromatography on a silica gel column. The product elutes with acetonitrile-methylene chloride as a white solid, which 25 is crystallized from toluene as mp 225-227°C. Anal. Procedure A 10 Dicyclohexylcarbodiimide (3.47 g, 0.0168 mol) calcd. for ci7Hi5N3°2: C' 69.61; Found: C, 69.76, H, 5.31; N, 14.13. C, 69.61; H, 5.15; N, 14.33. 30 / 206856 - 50 - EXAMPLE 13 Procedure B Preparation of cis and trans 1,llb-Dihydro-llb-hydroxy-3-isopropyl-3-methyl-5-H-imidazo[1',2':1,2]pyrrolo f3,4-b]quinoline-2(3H),5-dione r'VYvL.- A^rr CH vv\/1<ch)2 vvysf3 15 3 2 ;hcf4—8 ca(ca ) H o a solution of 1,3-dihydro-a-isopropyl-a-methyl-1,3-dioxo-2-H-pyrrolo[3,4-b]quinoline-2-acetamide (0.5 g, 0.0016 mol) was heated under reflux in xylene for 23 hours. On cooling, a white solid 0.17 g, mp 191-192°C precipitates and a further crop of 0.1 g, mp 187-189°C is formed by dilution of the ,filtrate by hexane. Anal, calcd. for C^H^N^: C, 65.58; H, 5.50; N, 13.50. Found; C, 66.08; H, 5.65; N, 13.00. Other tricycles are obtained by procedures similar to' Procedures A and B above. / o -' /? ' ' ^ ■ - y 5/ - z? - Examples of Tricycles: V ? ff fl % -r' yy y *-vv ~ •\/, ■iv 10 15 20 q m ch3 x,l,m,r7 a h r1 - ch3 r2 * ch(ch3)2 q 9 ci x,l,m,r7 V h r1 - ch3 r2 9 ch(ch3)2 m a ch3 x i lrq tr7 a h r1 9 ch3 r2 9 ch(ch3)2 M 9 ci x rl r qtr? 3 h r1 - ^3 r2 9 ch(ch3)2 q ■9 cf3 x,l,m,r7 8 h r1 9 ch3 r2 » ch(ch3)2 M 9 n(ch3)2 x,l # q»r7 a h r1 9 ch3 r2 - ch(ch3)2 M 9 och3 x r l c q >r7 a h * r1 9 ch3 r2 S ch(ch3)2 x 9 oh l»m»Q»r7 a h r1 9 ch3 r2 9 ch(ch3)2 25 30 x,l,m,r,q » h 10 15 20 sx - >gr - R1 R2 ch, c2h5 ch3 c3h7 CH3 c4h9- n ch3 c4h9- sec ch3 c4h9- iso ch3 (ch2)5 CH3 < > 25 30 1 c. - 53 -" EXAMPLE 14 Post-Emercence Herbicidal Evaluation of Test Compounds The postemergence herbicidal activity of the compounds of the present invention is demonstrated by the .5 following tests, wherein a variety of monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in acrueous acetone mixtures. In the tests, seedling plants are grown in jiffy flats for about two weeks. The test compounds are dispersed in 50/50 acetone/ water mixtures 10 containing 0.5% TWEENY 20, a polyoxyethylene sorbitar. mono-laurate surfactant of Atlas Chemical Industries, in sufficient quantity to provide the equivalent of about .016 kg of 10 kg per hectare of active compound when, applied to the plants through a spray nozzle operating at 40 psi for a ?re-15 determined time. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. From 4 to 5 weeks after treatment,-the seedling plants, are examined and rated according to the rating system provided belcw. 20 The data obtained are recorded in Table XI below. Ratine System % Difference in Growth •from the Check* 0 - 1 - 25 2 ~ 3 - 5 - 6 - 7 - 30 8 " 9 - 4 - 35 In/most cases the data are for a single test, but in several i stances, they are average values obtained from more than one test. 0 1-10 11-25 26-40 41-60 61-75 No effect Possible effect Slight effect Moderate effect Definite injury Herbicidal effect Good Herbicidal effect 76-90 Approaching complete kill 91-99 Complete kill 100 Abnormal growth, that is, a definite physiological malformation but with an over-all effect less than a 5 on the rating scale. 10 15 Barnyardgrass Green foxtail Purple Nutsedge Wild Oats Quackgrass Field Bindweed Cocklebur Morningglory Ragweed Velvetleaf Barley Com Rice Soybean Sunflower Wheat - xc - Plant Soecies Used (Echinochloa crusqalli) (Setaria" viridis) (Cyperus rotundus L.) (Avena Fatua) (Agropvron repens) (Convolvulus arvensis L.) (Xanthium per.svlvanicum) (Ipomoea purpurea) (Ambrosia arteraisiifolia) (Abutilon Theophrasti) (Hordeum vulcare) (Zea mays) (Oryza Sativa) -(Glycine max) (Helianthus annus) (Triticum aestivum) 20 25 30 35 Table XI POST-tMfBStltt USTS — RATCS HI KC/IU COMPOUNDS RA1( 6P£fll *r33^ fOX t lut siocc who Otis QUICK CRASS no o irmtttj COCKl cctn xxx n biiglt RIC.lt (0 VllVt TllAF 3 BAR ir ia coflm fkio R1CC. IUTO SOlftt All UI SU!*t R XXX 3-1 sopropyl-3-methyl-l3H|-Imidazo(I',2s1,2]pyrrolo-{3,4-b]pyrldlne-2-(3H),5-d loae t u<c at ta .SOS ».9 * « 7.8 1 0 1.0 *.0 4.0 .iso 1.0 t 0 7.0 1 0 8.0 1.0 J.O .lis 4.0 • 0 J.O 4 0 4.0 *.0 3.0 .Oil ).» 4 0 4.0 I 0 0.0 t.O t.O .0 it 1.0 4 • 1 0 0.0 1.0 t.O 7.1 * 0 t.O « 0 1.0 1 0 * 0 4.0 4.0 0 1.0 7 0 4.0 ♦ 0 0 0 1.0 4.0 « 0 1.0 7 0 t.O • 0 t 0 t.O 1.0 I 0 f.O I 0 7.0 < 0 1 0 0.0 t.O 4 • • .0 I 0 4.0 1 0 1 0 Ln Ln ro o cr\ oo (j1 on Compound 3-Isopropyl-8-methoxy-3-methyl-5H-imidazo-[1',2':1,2lpyrrolo-[3,4-b]pyridine-2-(3H),5-dione BARNY GREEN BATE APDC-R FOX 8. .000 9.0 9.0 1. .000 6.0 a.o .500 6.0 8.0 .250 4.0 7.0 .125 2.0 <♦.0 .063 2.0 4.0 .032 0.0 3.0 5-d-Hydroxy - 3<*--isopropyl-3-methyl-5H-imidazo[1',2* : 1,2]-pyrrolo[3,'l-b]pyridin-2-(3H)dione 2-Iaopropy1-2-methyl-5-M-imidazo[ 1 ' ,2' : 1, 2 ] -pyrrolo[3,'l-b]pyridlne-3(21!) ,5-dione 4.000 9.0 9.0 1.0C0 9.0 9.0 .500 9.0 9.0 .750 . 7.0 7,0 .125 S.O 7.0 .063 3.0 7.0 .032 0.0 4.0 8.000 9.0 9.0 1.000 9.0 9.0 .500 9.0 9.0 .250 9.0 9.0 .125 9.0 9.0 .063 9.0 9.0 .032 9.0 9.0 w £ 10 flr *°\ fable XI (Continued) POST-EMERGENCE TESTS — RATES IN KG/HA P HUT WILD QUACK FID B MRtlGL RAGWE VEIVE S BAR noPN COTTO RICE, SOYB SEDGE OATS G3A5S INDU'D RY SP ED TLEAF LY LA FIELD II NATO AM A 9.0 9.0 9.0 0.0 a.o a.o 9.0 8.0 9.0 8.0 7.0 8.0 2.0 2.0 a.o 6.0 9.0 7.0 4.0 7.0 3.0 6.0 7.0 2.0 0.0 2.0 4.0 2.0 7.0 7.0 1.0 4.0 1.0 4.0 3.0 2.0 0.0 1.0 1.0 1.0 6.0 7.0 1.0 1.0 0.0 2.0 2.0 1.0 0.0 0.0 0.0 1.0 6.0 6.0 1.0 1.0 0.0 2.0 1.0 0.0 0.0 0.0 2.0 4.0 1.0 1.0 0.0 1.0 1.0 0.0 0.0 0.0 0.0 1.0 3.0 0.0 9.0 9.0 9.0 3.0 9.0 9.0 9.0 0.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 9.0 9.0 7.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 9.0 9.0 6.0 9.0 9.0 9.0 a.o a.o 9.0 a.o 7.0 a.o 7.0 9.0 6.0 7.0 7.0 9.0 a.o a.o 6.0 a.o 4.0 7.0 7.0 7.0 4.0 7.0 7.0 a.o a.o 7.0 7.0 6.0 4.0 7.0 5.0 7.0 1.0 4.0 6.0' 7.0 7.0 6.0 2.0 1.0 3.0 4.0 3.0 3.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9,0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0, 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 9.0- 9.0 9.0 9.0 0.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 9.0 . . 9.0 9.0 9.0 0.0 9.0 9.0 9.0 9.0 9.0 7.0 ro o CK OO cn On Coinppund 7-Ethy]-2-isopropy1-2-inethy l-5H-imidazo-f1',21 :1,2 ] pyrrolo-[3,'l-b]pyridine-3-(2H) , 5-d ione pate 1.000 .500 . 2S0 .125 .063 .032 TABLE XI (Continued) POST-EMERGENCE TESTS — RATES IN KG/HA Anocn 9.0 9.0 9.0 9.0 7.0 7.0 GREEK P HUT MILD QUACK FLO B WJHGi RAGWE VELVE S BAR CORK RICE. SOYSE SIM IF L FOX SEOGE OATS GRASS mono RT SP EO TLEAF LY LA FIELD IIATO Alt AO R XXX 9.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 7.0 9.0 a.o 7.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 a.o 6.0 9.0 a.o 7.0 9.0 9.0 9.0 7.0 9.0 9.0 7.0 6.0 9.0 a.o 7.0 9.0 0.0 a.o a.o 4.0 9.0 9.0 7.0 5.0 9.0 e.o 7.0 '9.0 6.0 7.0 a.o 4.0 9.0 9.0 7.0 4.0 9.0 7.0 4.0 4.0 2.0 7.0 2.0 3.0 9.0 3.0 3.0 9.0 7.0 2-Isopropy1-2-rnethy l-5H-imidazo-[ 1 1 , 2' : 1 ,2]pyprolate,1'- b]quinoline-3-C 211) , 5-d ione 4.000 1.000 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0- 9.0 9.0 9.0 9.0 a.o a.o 9.0 9.0 9.0 9\ 0 9.0 9.0 4.0 4.0 9.0 9.0 9.0 9.0 UI ^ c., <0 *0\ r .o f ro o On OO UI On 206856 - 58 -' EXAMPLE 15 Preemercence Herbicidal Evaluation of Test Compounds The preemergence herbicidal activity of the compounds of the present invention is exemplified by the 5 following tests in which the seeds of a variety of monocotyle donous and dicotyledonous plants are separately mixed with potting soil and planted on top of approximately one inch ' of soil in separate pint cups. After planting, the cups are sprayed with the selected aqueous acetone solution containing 10 test compound in sufficient quantity to provide the equivalent of about 0.016 to 10 kg per hectare of test compound per cup. The treated cups are then placed on greenhouse benches, watered and caired for in accordance with conventicr.a ■greenhouse procedures. From 4 to 5 weeks after treatment, 15 the tests are terminated and each cup is examined and rated according to the rating system-set forth above." The herbicidal proficiency of the active, ingredients of the present invention is evident from the test results which are records'* ■ in Table XII below. Where more than one test is involved for 20 given compound, the data are averaged. 25 30 Table 'XII Compound a 3-laopropyl-3-m*thyl-(3-llf-ioildaro fl' ,2 ':1,2} pyrrolo(3,«,6-)pyri-d lne-2 (3-II),5-dione put-(ttreciiirr Ttjrj -- nuti in kg/ha ftlTt Bip nr XBOCR £01 (H f 0* r t*rr SIOGC HIIO qms Oi UCK 60»1J f LfJ B nmtjo COCKl (BUB yxx n picir OtCWt to VClVf HHf 1 out IT LA COOH riiio Pier, NATO sotnt Ml UI soire R rvx S Wi( »T td l.» 1.0 0.0 0.0 t.l t.O 1.0 0.0 7.0 7.0 7.0 l.t t.O 7.0 1.0 Ul r t & g f\) O ON OO LJ1 On1 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> Compound 3-Isopropyl-8-methoxy-3-methyl-5H-imidazo-[11,2':1,27pyrrolo-[3i4-b]pyridine-2-(3H ) ,5-d i one 5_a._Hydroxy-3i- i sopropy1-3-methyl -5H-imidazo[ 1 ' ,2':1,2]-pyrrolo[3,4-b]pyridin-2-(3H )d ione
2-Isopropyl-2-me thy 1 -5-H-imidazo[ 1 ' ,2' : 1 ,2]-pyrrolo[3,4-b]pyridine-3(2H),5-dione RATE Table XII (Continued) pre-emcrgence tests -- rates ih kg/ha. BARNY GPEfN P HUT WHO AFUGR FOX SEOGE OATS quack FID B nntlGl ragwe velve s BAR CORU COTTO RICE, SOrBE gi'ass Ililiro ry sp ED ueaf IY LA M e ID H IUTO ill ad 6. 000 9.0 9.0 9. 0 9. 0 9. 0 9. 0 a.o 9. 0 .500 1.0 a.o 9. 0 fe. 0 U . 0 9. 0 9. 0 o. 0 3. 0 6. 0 I. 0 , 0 7. 0 0. 0 .250 1.0 a.o 9. 0 2 0 3. 0 9. 0 1 . 0 0. 0 0 . 0 6. 0 0. 0 <1. ,0 4. 0 0. ,0 . ICS 0.0 6.0 3. 0 0. 0 0. 0 a. 0 0. 0 0. 0 0. 0 2. 0 0. 0 0. 0 3. 0 .063 0.0 0.0 1. 0 0. 0 0 . 0 a. 0 0. 0 0. 0 0, 0 0. 0 0. 0 0 . 0 2. 0 0 . , 0 .03? 0.0 0.0 0. 0 0 . 0 a. 0 0. 0 0. 0 0. 0 0.0 0. 0 0 . 0 2. 0 .016 0.0 0.0 0. 0 0. 0 0. 0 0 0. 0 0. 0 0. 0 0. 0 0. 0 0 . ,0 1. 0 0 . .0 0.000 9.0 9.0 9. 0 9. 0 . 9. 0 9. 0 9. 0 9. 0 9. 0 .500 9.0 9.0 a. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 .:so a.o 9.0 0. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 9. 0 1. 0 9. 0 9. 0 9. 0 . irs a.o 9.0 7. 0 9. 0 7. 0 9. 0 9. 0 9. 0 9. 0 9. 0 5. 0 a. 0 7. 0 7. 0 . 06 J 1.0 9.0 J. 0 7. 0 . 0 9. 0 9. 0 9. 0 9. 0 a. 0 <«. 0 7. 0 6 . 0 3. 0 .0 32 0.0 9.0 0 . 0 0 3. 0 9. 0 a. 0 7. 0 7. 0 7. 0 1. 0 2. 0 4 . 0 1. 0 .016 0.0 7.0 0. 0 i. « 0 2.0 9.0 a. 0 5. 0 <t. 0 6 . 0 1. 0 1. 0 U . 0 0. 0 0. 000 9.0 9.0 9, 0 0. 0 9. 0 9. 0 0. 0 O. 0 a. 0 .500 9.0 9.0 9, ,0 9. 0 9.0 9.0 9. 0 9, .0 9. 0 9. 0 9. .0 9 .0 9. 0 V , ,u .:oo 9.0 9.0 9, , 0 9. 0 9, 0 9. 0 9. 0 9, .0 9. 0 9. 0 », 0 9 .0 9 , .0 ' ' 9. ,0 . 1C5 a.o 9.0 9, , 0 9. 0 9. 0 9, 0 9.0 9, ,0 9. 0 9. 0 9, . 0 9 .0 9. . 0 9 .0 ,0<>3 9.0 9.0 9 .0 9. .0 9, 0 9 .0 9, .0 6 .0 9, 0 9. 0 9 .0 9.0 9 .0 9 .0 , 050 1.0 9.0 1 .0 9. .0 9, 0 9, ,0 a.o 0. .0 9. 0 9. 0 9, .0 a.o 9.0 s .0 .016 1.0 9.0 0 .0 9, .0 3. .0 9.0 2, ,0 0.0 7. 0 a. 0 9 .0 7 .0 9.0 1 .0 c\ o ro o CT\ CD CJ1 On 206856 - 61 - WHAT WE CLAIM IS: 1. A compound of the following formula: Y I ! s*l J ff \ / V. / n y .1 • j) I i ! I 2 or YNCr£ /v*~Vv / v VI Rl wherein Rl is C1-C4 alkyl; R2 is C1-C4 alkyl or C3-C6 cycloalkyl; and when Ri and R2 are taken together with the carbon to which they are attached they may represent C3-C6 cycloalkyl optionally substituted with methyl; X is hydrogen, halogen, hydroxyl or methyl, with the proviso that when Y and Z are taken together to form a ring and YZ is represented by the structure: -(CH2)n"j where 11 is 3 or 4, X is hydrogen; Y and Z are each hydrogen, halogen, C^-Cg alkyl, hydroxy-C^-C^ 'alkyl, C^-Cg alkoxy, (4-C4 alkylthio, phenoxy, C1-C4 haloalkyl, nitro, cyano, C1-C4 alkylamino, di(C^-C^ alkyl)amino or Cj-C^ alkylsulfonyl group, or phenyl optionally substituted with one C1-C4 alkyl, C1-C4 alkoxy or halogen; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure: -(CH2)n-, where n is an integer of 3 or 4, provided that X is hydrogen; or L M Q R7 I I I 1 -C=C-C-C-, where L, M, Q and R7 are each \o ft* hyd rogen, halogen, (4-C4 alkyl, C1-C4 alkoxy, / ay 2Q6856 62 C^-C^ alkylthio, C^-C^ alkylsulfonyl, haloalkyl, NC>2, CN, phenyl, phenoxy, amino, alkylamino, diCC.^-^ alkyl) amino, chlorophenyl, methylphenyl, or phenoxy substituted with one CI, CF^ t N02 or CH^ group, with the proviso that only one of L, M, Q or may represent a substituent other than hydrogen, halogen, C^-C^ alkyl or C^-C^ alkoxy; or an N-oxide thereof, and when R^ and are not the same, an optical isomer thereof. 2. A compound according to Claim 1 having the wherein Y is hydrogen, C^-C^ alkyl, C^-C^ alkoxy, cyano, nitro or halogen; is C^-C^ alkyl; R2 is C^-C^ alkyl or C^-Cg cycloalkyl; and when and R^ are taken together with the carbon to which they are attached, they can represent C^-Cg cycloalkyl optionally substituted with methyl, and when R^ and R^ are not the same, an optical isomer thereof. 3. A compound according to Claim 1 wherein said compound is
3-isopropyl-3-methyl-5H-imidazo[ 1' , 2 ' : 1, 2] -pyrrolo[3,4,b]pyridine-2(3H),5-dione, 2-isopropvl-2-methyl-5H-imidazo[ 11 , 2 ' : 1, 2] -pyrrolo[3,
4-b]pyridine-3(2H),
5-dione, or 2-isopropyl-2-methyl-5H-imidazo[l',2':l,2]-pyrrolo[3,4-b]quinoline-3(2H),5-dione. structure o 0 / 206856 63 4. A method for the control of monocotyl-edonous and dicotyledonous annual, perennial and aquatic plant species comprising: applying to the foliage of said plants or to soil or water containing seeds or other propagating organs thereof, a herbicidally effective amount of a compound of the following formula: wherein , R^, X, Y and Z are as defined in Claim 1. edonous and dicotyledonous annual and perennial plant species comprising: applying to the foliage of said plants or to soil containing seeds or other propagating organs thereof, a herbicidally effective amount of a compound of the following formula: ? 5. A method for the control of monocotyl- o o wherein R^, R2 and Y are as defined in Claim 2. / 206856 - 64 -
6. A herbicidal composition comprising an inert solid or liquid diluent and a herbicidally effective amount of a compound of the following formula: , 1 i h ^ a /"v. i •i s V-]— r'y v\ or wherein R^ , R2, X, Y and Z are as defined in Claim 1.
7. A herbicidal composition comprising an inert solid or liquid diluent and a herbicidally effective amount of a compound of the following formula wherein R^, R2 and Y are as defined in Claim 2.
8. A solid herbicidal composition according to Claim 6 or Claim 7, comprising from 20% to 45% by weight of a finely divided solid inert carrier; from 45% to 80% by weight of the herbicidally effective compound; from substantially 2% to 5% by weight of a dispersing agent and from substantially 2% to 5% by weight of a surface active agent.
9. A liquid herbicidal composition according to Claim 6 or Claim 7, comprising from 5% to 25% by weight of the herbicidally effective compound; from substantially 65% to 90% by weight of an inert organic solvent and from substantially 5% to 10% by weight of a surface active agent. 206856 - 65 -
10. A granular herbicidal composition according to Claim 6 or Claim 7, comprising from substantially 80% to 97% by weight of an inert granular carrier and from substantially 3% to 20% by weight of the herbicidally effective compound. DAVi'irj Tru.j 2.7/1 CAY Cr '9^^" A , J. F A R K & SO: m PLZR M-S- t <zc~ AGENTS FOR THE APPLICANTS !(■■ i Y>, ivry </div>