NZ235768A

NZ235768A - 2-(imidazolyl, benzimidazolyl or triazolyl)-pyridine-3-carboxylic acid derivatives; preparation processes and herbicidal compositions

Info

Publication number: NZ235768A
Application number: NZ235768A
Authority: NZ
Inventors: Georges Axiotis; Michel Euvrard; Francois Guigues; Fatemeh Tad; Christopher John Pearson
Original assignee: Rhone Poulenc Agrochimie
Priority date: 1989-10-20
Filing date: 1990-10-19
Publication date: 1992-06-25
Also published as: IE903691A1; IL96058A0; HU906524D0; HUT55378A; BR9005406A; CA2027347A1; JPH03151377A; PT95636A; CN1051040A; MA21980A1; FR2653432A1; AU629057B2; ZA908351B; EP0429372A1; FI905180A0; YU196990A; AU6469990A; KR910007910A; TR26798A; OA09318A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £35768 No: Date: 235 7 .. iQ..oa,n0 :. ' Jf'5JUN..!99? J35,' MA % if^fS 9 X W h# ii ^"'sU'u NEW ZEALAND PATENTS ACT, 1953 -"1 —i • ! 1 ! . 1 V 'l 1 - ^ ^ I ' COMPLETE SPECIFICATION HERBICIDES DERIVED FROM 2-AZOLYL NICOTINATE tyWe RHONE-POULENC AGROCHIMIE, a French body corporate, of 14-20 Rue Pierre Baizet 69009 Lyon France hereby declare the invention for which ^we pray that a patent may be granted to n^/us, and the method by which it is to be performed, to be particularly described in and by the following statement -1- (followed by page la) v * C- - 235 7 6 8 iq PH 89042 The invention relates to novel compounds, to their use as herbicides, particularly in the form of a herbicidal composition, and to a method of controlling weeds with the aid of these compounds or these 5 compositions. US 4,638,068 discloses herbicides which are derived from 2-(2-imidazolin-2-yl)-pyridines and -quinolines, such as imazapyr or 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (Pest. 10 Manual, 8th edition, page 473). It is an object of the present invention to propose novel compounds which can be used pre- or post-emergence as herbicides. It is another object of the present invention to 15 propose compounds which can be used pre- or post-emergence as broad-leaf herbicides. It is another object of the present invention to propose compounds which can be used pre- or post-emergence as selective herbicides in maize and a large 20 number of other monocotyledon crops (wheat, barley, rice). General definition of the invention Compounds of the formula I: ISD / D 8 2 PH 89042 in which: A is the hydrogen atom or an R7S02- group, Rx is a hydrogen atom, an optionally substituted alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical, an optionally substituted aralkyl radical, it being possible for the aryl or aralkyl radicals also to contain 1 to 4 hetero atoms in the ring which are selected from amongst the oxygen atom, the sulphur atom or the nitrogen atom (for example furyl, thienyl or pyridyl), R2 is selected from amongst the radicals of the formula XxM, M being an organic or inorganic cation and X2 being the oxygen atom or the sulphur atom, X2R5, R5 having one of the meanings of R: or being an alkyl which is optionally substituted by an alkenyl, alkynyl, in particular allyl, propargyl or 2-butenyl group, the alkyl being optionally substituted by an alkenyl or alkynyl which preferably does not contain more than 8 carbon atoms, and X2 being the oxygen atom or the sulphur atom, NR3R4, R3 and RA being identical or different and selected from amongst the hydrogen atom, the optionally substituted alkyl radicals, the optionally substituted cycloalkyl radicals, the optionally substituted aryl radicals, the optionally substituted aralkyl radicals or the OR6 radicals, R6 having one of the meanings given for Rlf R7 is an optionally substituted alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical or an optionally \ A 235768 3 PH 89042 substituted aralkyl radical, NRaRg, Re and Rg being identical or different and having one of the meanings given for Rx or they can form, together with the nitrogen atom to which they are bonded, a heterocycle 5 which contains 1 to 3 hetero atoms (preferably containing 4 to 6 ring members), W is an =N- or =CR10-group, R10 having one of the meanings indicated for Rlf or Rx and R10 together with the atoms to which they are attached can form a ring which, in combination with the 10 imidazole ring, forms an aromatic system of two fused rings, Rx and R10 constituting either a chain having three atoms where one is sulphur or oxygen and the two others are carbon, or a chain of four carbon atoms which contains two double bonds or a chain of four 15 atoms containing 1 to 3 nitrogen atoms and 3 to 1 carbon atoms, these chains being optionally substituted by one to 4 Y: radicals selected from amongst the optionally substituted alkyl radicals, optionally substituted alkoxy or alkylthio radicals, halogen 20 radicals, dialkylamino radicals, two radicals selected from amongst the alkoxy radicals, alkylthio radicals or alkyl radicals together in the 4, 5 position or the 5, 6 position, which, with the carbon atoms to which they are attached, can form an aliphatic ring having 5 or 6 25 atoms and having not more than two hetero atoms selected from amongst oxygen or sulphur, such as 1,3-dioxolo[4,5-e]benzimidazole; 5,6-dihydrofuro [2,3-e]benzimidazole; 4,5 235768 4 PH 89042 dihydrofuro[3,2-e]benzimidazole; 4,5-dihydrothieno[3,2-e]benzimidazole; Y is an optionally substituted alkyl radical, an optionally substituted alkoxy or alkylthio radical, a halogen atom, and, furthermore, if n is equal to 2 or 3, the Y radicals which are adjacent in the a and /9 positions of the nitrogen atom, together with the carbon atoms to which they are attached, can form a fused phenyl ring group (benzo group), or can form an aliphatic ring containing 5 or 6 atoms (optionally heterocyclic), and not more than 2 non-adjacent hetero atoms selected from amongst the oxygen or sulphur atoms, such as the 3,4-dihydropyrano[3,2-b]pyridine or 2,3-dihydropyrano[3,2-b]pyridine or 2H-3,4-dihydropyran[3,2-b]pyridine; 2H-3,4-dihydrothiopyran-[3,2-b]pyridine or 2,3-dihydrofuro[3,2-b]pyridine groups, n is a positive integer or zero, lower than 4, it being understood that, if n is higher than 1, the Y groups can be identical or different. In the above description, the alkyl radicals can be linear or branched and have preferably 1 to 6 carbon atoms.' The cycloalkyl radicals have preferably 3 to 7 carbon atoms. The aryl radicals have preferably between 6 and 10 carbon atoms (preferably phenyl). The aralkyl radicals have preferably between 7 and 11 carbon atoms (preferably benzyl). 235 7 68 > A ■ r 5 PH 89042 From amongst the substituents which are suitable for the abovementioned radicals, there will be mentioned, particularly, the halogen atoms (CI, Br, F), ' the hydroxyl radical, the C1-C4-alkyl radicals (apart 5 from the abovementioned alkyl radicals), the Ci-C,,-alkoxy radicals, the mono- or polyhalogenated C^C,,-alkyl radicals (apart from the abovementioned alkyl radicals), the mono- or polyhalogenated alkoxy radicals, cyano and nitro. 10 Amongst the fused aromatic rings which have been mentioned further above in the case of the imidazoles, the following rings may be mentioned: benzimidazole, lH-thieno[2,3-d]imidazole, lH-thieno[3,4-d]-imidazole, lH-furo[2,3-d]imidazole, lH-furo[3,4-d]-imidazole, 1H-15 purine, lH-imidazo[4,5-b]pyrazine, lH-imidazo[4,5-c ]pyridine, lH-imidazo[4,5-b]pyridine. The cations are preferably selected from amongst the alkali metals (Na, K, Li), the ammonium salts of the formula NRnR12R13R14, Rn, R12, R13 and Ru being 20 selected from amongst the hydrogen atom, the C^Cs-alkyl radicals which are optionally substituted by a hydroxyl ) radical, aralkyl (particularly benzyl), it being possible for not more than two of the radicals Rn to R14 to correspond to the aralkyl group. 25 Because of the biological properties or the possibilities of synthesis, those compounds of the formula (I) will be preferred in which: - A is the R7S02- group, R7 preferably being NR8R9, 235768 6 PH 89042 advantageously NMe2, - and/or n = 0 or 1, - and/or Rx is an aryl radical which optionally contains a nitrogen atom and which is optionally substituted, Rx preferably being a phenyl or 2-pyridyl radical, - and/or R2 is the hydroxyl radical, allyloxy radical, propargyloxy radical or OM, M. preferably being NRi1R12R13Rn, - and/or W is -N= or -R10C=, R10 being selected from amongst the hydrogen atom, the phenyl radical or the tert.-butyl radical, or R10 together with Ri and the two carbon atoms to which they are attached forms a phenyl ring which is optionally substituted by one or two groups selected from amongst the alkoxy, haloalkoxy (OCF3), alkyl, halogen and haloalkyl groups. Preparation process The invention also relates to preparation processes for the compounds of the formula (I). In what follows, the substituents Ri to R12, Y and W have the same meanings as in Claim 1. The compounds of the formula (I) in which A is the R7S02- group and R2 is an X2R5 radical where R5 is other than the hydrogen atom, can be prepared by reacting a sulphonyl chloride or sulphamoyl chloride of the formula R7S02C1 with a compound of the formula (I) in which A is the hydrogen atom and R2 has the abovementioned meaning (X2R5, R5 radicals being other than H), in the presence of an acid acceptor such as 235768 7 PH 89042 10 15 -\ J 20 potassium carbonate, triethylamine, 1,8-diazabicyclo[5.9.0] undec-7-ene or sodium hydride, preferably in an anhydrous medium, in an aprotic polar solvent such as, for example, ethers such as THF, or nitriles, at a temperature which is generally between 25"C and the reflux temperature of the solvent. The compounds of the formula (I) in which A is the hydrogen atom are prepared by treating a compound of the formula (II): with an alkali metal alcoholate or alkaline earth metal alcoholate of the formula R5X2M', M' being the metal cation, in an aprotic polar solvent, at a temperature which is generally between 0°C and the boiling point of the solvent, or with an alcohol of the formula R2OH in a polar organic solvent in the presence of an acid acceptor, such as pyridine or triethylamine. Another process for obtaining the compounds of the formula (I) in which A is the hydrogen atom, where R2 * X2H consists in reacting a compound of the formula co (III) III H 235768 8 PH 89042 10 15 y where R2 = X2H in a protic solvent such as methanol, in the presence of gaseous HC1, with an alcohol of the formula R5OH, following a well-known esterification process. The compounds of the formula (II) are obtained by-reacting thionyl chloride with compounds of the formula (III), using the thionyl chloride as a solvent, and at the reflux temperature of the latter. Three routes allow the compounds of the formula (III) to be obtained. If w is the trivalent nitrogen atom -N=, the compounds of the formula (III) can be obtained by treating an alkali metal salt or alkaline earth metal salt of a compound of the formula (IV): in water at a temperature between 25°C and 100°C. The alkaline earth metal salt or alkali metal salt of the formula (IV) is prepared by reacting the corresponding base with the compound of the formula (IV). Likewise, the reaction can be effected starting from a compound of the formula (IV) by reacting an 23 5 7 9 PH 89042 5 10 15 alkali metal base or alkaline earth metal base, of normality IN, such as sodium hydroxide solution or potasium hydroxide solution, at a temperature between 25°C and 100°C. The compounds of the formula (IV) can be prepared by reacting a hydrazide of the formula Ri-CONHN^ with a cyanonicotinate of the formula (V), described in FR-A-2,598,708 filed by RHONE-POULENC AGROCHIMIE, or in the reference L.I.M. Spiessens, M.J.O. Anteunis Bull Soc. Chim. Belg. 89, 205, (1980). in which Ru is an alkyl radical, in the presence of an alkali metal alcoholate or alkaline earth metal alcoholate in a protic polar solvents such as methanol or ethanol, at a temperature between 258C and the boiling point of the solvent. If W is =CR10-, R10 not being attached to Rlr the compounds of the formula (III) can be obtained by treating a compound of the formula (VI): 0 VI 7C9> 10 PH 89042 with an inorganic base, soda or potash, between 25°C and 100°C, in an inert solvent medium. The compounds of the formula (VI) are prepared by reacting an a-halogenated ketone of the formula Br-HCRiQ-CO-Ri with a compound of the formula (VII): in the presence of an acid acceptor, such as alkali metal carbonates, catalysed by alkali metal halides, in a polar solvent such as acetone or DMF. The compounds of the formula (VII) are prepared from compounds of the formula (V), in a manner known from the literature (reference: A.D. Dunn J. Heterocyclic Chem, - 21, 965, (1984)). If W is=CR10-, R10 forming a ring with R^ the compounds of the formula (III) can be obtained by cyclizing compounds of the formula (X) 0 VII (Y) n in fen organic solvent such as ethoxyethanol, under reflux. r; '? "7, / 11 PH 89042 The compound of the formula (X) is obtained by reducing a compound of the formula (XI) in an aqueous basic or organic solution in the presence of hydrogen and of a hydrogenation catalyst, such as platinum oxide, between 20 and 60°C , C0„H (XI) 10 The compound of the formula (XI) is obtained by condensing the compound of the formula (VIII) with a 2-nitroaniline of the formula (XII) in an organic solvent, such as chloroform or tetrahydrofuran between 20"C and the boiling point of the solvent 15 <V ■'-€C NO. NH, <xii>xirTT<vx \* The compounds of the formula (II) wher^ Rx and R together form an aromatic ring can be obtained by reacting a quinoline anhydride of the formula (VIII) A a 12 23 5 7 PH 89042 (VIII) with orthophenylenediamine of the formula (IX) (IX) Y1 having one of the meanings of Y and being an 5 integer from 1 to 4, first by heating to temperatures from 110° to 190°, preferably from 130° to 150°, either without solvent or in an inert solvent which has a higher boiling point, such as xylene or dichlorobenzene, and subsequently by treating the 10 reaction mixture with acetic anhydride at boiling point for 1 to 3 hours. The compounds of the formula (VIII) and (IX) are obtained in a known manner. If it is desired to obtain the compounds of the 15 formula (I) in which R2 is X2H, the compound of the formula (I) where R2 is X2R5, R5 being other than H, is hydrolysed by an inorganic base, for example lithium hydroxide, in a mixture of water and alcohol, such as methanol, at a temperature between 0°C and 25°C. 20 If it is desired to obtain the compounds of the formula (I) in which R2 is XiM, the corresponding base 13 PH 89042 is reacted in a knovm manner with the acid form of the compound of the formula (I) where R2 = X2H. v In the case where it is desired to obtain the compounds of the formula (I) in which R2 is NR3R<,, an amine of the formula HNR3R<, is reacted with the compound of the formula (II) in an appropriate aprotic polar solvent. The resulting compounds of the formula (I) are then treated with sulphonyl chloride or sulphamoyl chloride as stated previously. Compounds of the invention of formula (I) where A is the hydrogen atom, can also be used as intermediates in the preparation processes of the compounds of the formula (I) in which the substituents Rx to R1A, Y, n and W have the same meaning as in formula (I) described above. Generally speaking and without wanting to be tied down by any scientific interpretation, the filing company is of the opinion that it is the carboxylic acid in free or salt form which is active. COR2 groups which are not anticipated in the present description and which, on hydrolysis, give the carboxylic acid in free or salt form are also part of the present invention. Examples of the preparation of compounds according to.* £ w J" Q -: i/^ * the invention /V Example 1 \ " 8 MAY 1992 * Isopropylamine salt of 3-(3-carboxy-2-pyridyl)-2-N,N-is," - , -•' COoi b8 ■■ C 5 10 EX W Ri Rt M m.p. ( *C) 0 3,4, 5-triCl 2-thienyl NMe 2 >-NH3 168 3 N 2,4-diC1 ph NMe2 >-NH3 120 4 N ph NEt2 >-NH3 8' ! 1 5 CH ph NMe 2 >-NH3 134 6 N ph NMe 2 H3NCH2CH2 OH i 77 14 PH 89042 dimethylsulphamoyl-5-phenyl-l, 2,4-triazole. 25 ml of isopropylamine are added at ambient temperature to 1 g of 3-(3-carboxy-2-pyridyl)-2-N,N-dimethylsulphamoyl-5-phenyl-1,2,4-triazole acid. After the mixture has been stirred for one hour, a solid precipitates. The amine is evaporated, and the resulting solid is washed with heptane. m.p. = 180°C. Starting with corresponding acids, whose synthesis will be described hereinafter, the following other compounds of the formula (la) have been prepared: N V 235788 10 15 15 PH 89042 Example 7 3-(3-Carboxy-2-pyridyl)-2-N,N-dimethylsulphamoyl-5-phenyl-1,2,4-triazole acid. 1 g (0.02 mol) of lithium hydroxide, dissolved in 10 ml of water, are added to 1.7 g (0.0044 mol) of 3-(3-carbomethoxy-2-pyridyl)-2-N,N-dimethylsulphamoyl-5-phenyl-1,2,4-triazole, dissolved in 30 ml of methanol and kept at 0°C. The mixture is then concentrated, the solution is brought to pH 2 using HC1, and the resulting white precipitate is washed with water and dried. Yield = 0.77 g m.p. = 200°C In the same manner, we have obtained the following acids of the formula (lb) starting with corresponding methyl esters: 5 C O OH lb / FU N V s7sq / 235768 16 PH 89042 EX W R1 R7 i m.p. (* C ) j 8 N 4-OMe ph NMe 2 170 9 N 3-C1 Ph NMe 2 i i 205 | ! 10 N 3,4,5-triCl 2-thienyl NMe 2 230 11 N 2,4 - diClph NMe 2 200 j 1 ! 12 N tBu NMe 2 ! 169 13 N 4-pyridyl NMe 2 197 14 i N ph NEt2 167 15 N Ph pyrrolidine 160 I 16 CH ph NMe 2 209 17 i N 2-pyridyl i I N'ME2 1 146 Example 18 3-(3-Carbomethoxy-2-pyridyl)-2-N/N-dimethylsulphamoyl-5-phenyl-l,2,4-triazole. 12.7 g of anhydrous potassium carbonate are added 5 to 16.4 g (0.0527 mol) of 3-(3-carbomethoxy-2-pyridyl)-5-phenyl-l,2,4-triazole, dissolved in 50 ml of anhydrous acetonitrile. The batch is refluxed for 2 hours. 8.9 ml (0.062 mol) of N,N-dimethylsulphamoyl chloride are added to the reaction mixture, which is > S 235768 17 PH 89042 cooled to ambient temperature. After 1 hour at this temperature, the batch is refluxed. Another equivalent of N,N-dimethylsulphamoyl chloride is added to the reaction mixture after 5 5 hours' refluxing. The batch remains under reflux for 10 hours. After the reaction mixture has been cooled, the solid is filtered off. The filtrate is evaporated and chromatographed on silica gel (eluent ethyl 10 acetate/heptane 3/7) to give 6.1 g of (Ic) (m.p. = 134°C) and 5.7 g of 3-(3-carbomethoxy-2-pyridyl)-1-N,N-dimethylsulphamoyl-5-phenyl-l,2,4-triazole (m.p. = 100°C). The compounds of the formula Ic 5? JH w T- 3 Ic 15 are obtained in the same fashion. 18 235768 PH 89042 EX W Ri R7 R2 m.p.('C) 19 N ph NMe 2 OEt honey I 20 N" benzyl NMe 2 OMe honey 21 N 3-CI ph NMe 2 OMe 120 22 N 3-OMe ph NMe 2 OMe 134 23 M 2 , 4-Cl ph NMe 2 OMe 120 24 N ph 2-Cl ph OMe 134 25 N ph 2 , 6-diclph OMe 174 26 N 3,4,5-triCl 2-thienyl NMe 2 OMe 180 27 N ph NMe 2 NMe 2 67 28 N ph NEt2 OMe 97 o 23 5 7 19 PH 89042 Example 29 3-(3-Carbomethoxy-2-pyridyl)-5-phenyl-l,2,4-triazole. 50 g of 3-(3-carboxy-2-pyridyl)-5-phenyl-l,2,4-triazole are dissolved in 800 ml of methanol. The 5 mixture is refluxed, and gaseous hydrochloric acid is introduced until the reaction is complete. The reaction mixture is cooled, and the methanol is evaporated. A saturated sodium bicarbonate solution is added to the resulting oil until the mixture is 10 neutral. A solid precipitates. It is filtered off, washed with water and dried. Yield = 49.6 g m.p. = 150°C Example 30 3-(3-N,N-Dimethylcarboxamide-2-pyridyl)-5-phenyl-l,2,4-15 triazole. 5.5 g of 3-(3-carboxy-2-pyridyl)-5-phenyl-l,2,4-triazole (0.022 mol) are added to 7 0 ml of thionyl chloride. After the mixture has been refluxed for 8 hours, the thionyl chloride is evaporated. 5.2 g of 20 (II) are obtained. m.p. = 228°C The latter is dissolved in 50 ml of anhydrous THF, and the solution is kept at 0°C. Dimethylamine is introduced into the solution until the reaction is 25 complete. The solvent is evaporated. Normal hydrochloric acid is added until the mixture is neutral. Extraction with CH2C12, followed by drying and evaporation of the 23 5 7 20 PH 89042 solvent, gives a syrupy substance which crystallizes with diisopropyl ether. The resulting solid is filtered off and washed with heptane. Yield = 5.3 g m.p. = 156°C The compounds of the formula (Ilia) were obtained in the same manner as described in Examples 29 and 30, using the appropriate reagents: CoR-a, Kfi, (Ilia) 23 5 7 6 8 21 PH 89042 EX V P.i Rj m.p.( *C) j 31 2,4-diCl Ph OMe 190 32 tf ph 0(CH2 )2 -N*Q> w 171 33 N' P ^ ON=C-C(Me)2 (SHe ) 154 34 N ph CEt 133 35 N P h 0- < 145 36 N P H SCH2-CO:Me 117 37 N 4-OMe ph OMe 204 CO c> CH P h OMe 126 35 N P h N(CH3)3 242 40 N ph NH? 260 41 N ph NHOH 260 235768 22 PH 89042 Example 42 3-(3-Carboxy-2-pyridyl)-5-phenyl-l/2,4-triazole. 93 g of (6H) 5-oxo-2-benzoyl-7-hydrazopyrrolo-[3,4-b]pyridine (0.27 mol) are placed in 1.8 litres of 5 normal potassium hydroxide. The batch is refluxed for 3 hours. After the reaction mixture has been cooled, concentrated hydrochloric acid is added until the pH is 2. The solid which has precipitated is filtered off, washed with water and dried. 10 Yield = 57 g m.p. = 242°C The following compounds of the formula (Illb) (where n = 0) were obtained in the same manner starting with appropriate starting materials: (Illb) H ] y 23 235768 PH 89042 EX Y W Ri m.p. ( ' C) 43 H N 2,4-diCl ph 260 44 H N 3,4,5-triCl 2-thienyl 260 45 H N benzyl 120 4 6 H N 4-pyridyl >250 47 H N 4 - OMe ph >250 48 H N 3-C1 ph >250 49 H N 2-Cl ph 230 5 0 H N 3,5-diCl ph >250 51 H N 2 - pyridyl 220 52 H N 2 - N02 ph >250 53 H N 4 - CF3 ph 230 54 H N 2-Me ph 220 55 H N 4-Me ph >250 235768 24 PH 89042 1 EX Y w Rl m.p.("C) 1 i j 5 6 1 H N 2-CMe ph 220 1 i i i H N 4-tBu ph 120 t 58 5-CH3 N ph 250 59 5-OCH3 N ph >250 60 H N C(CH3 )3 198 61 H N H 230 62 H N OH 250 63 H N 3-CF3 ph >250 64 H N 3,4-OMe ph >250 65 H N 3,5-CF3 ph >250 66 i H N 3-OMe ph 240 i H N styryl 120 23 5 7 6 P 25 PH 89042 EX Y W Ri m.p.( '.C) 63 H N Cl-^O^-OCHj Me IS 5 69 K N 2-F ph >250 70 H N (CHs h -CH 166 71 H N benzyl 158 72 H N CHi 212 73 H N 2,5-diCl ph >250 Example 74 2-(3-Carboxy-2-pyridyl)-5-phenylimidazole. 11 g of 5-oxo-7-imino-6-acetophenonepyrrolo-(3,4-b)pyridine (0.041 mol) are added to 80 ml of normal sodium hydroxide. The mixture is diluted with 50 ml of water. The batch is heated at reflux for 2 hours. After the mixture has been cooled, 100 ml of normal hydrochloric acid are added thereto. A solid precipitates, and it is filtered off, washed with water and dried. Yield = 7.5 g m.p. = 267°C 2,5 3 7 6 8 26 PH 89042 Example 7 5 Preparation of 2-(1-N.N-dimethvlsulphamovl-2-benzimidazolvl)-3-carboxvpvridine A solution of 0.9 g (0.021 mol) of lithium 5 hydroxide, hydrated in 10 ml of water, is added to a suspension of 2.5 g (0.007 mol) of 2-(1-dimethyl-sulphamoyl-2-benzimidazolyl)-3-carbomethoxypyridine in 30 ml of methanol at ambient temperature and with stirring. Stirring is continued until the solid is 10 completely dissolved, that is to say, for three hours. The methanol is eliminated by evaporation in vacuo, the residue is taken up in 50 ml of water, and the mixture is acidified with 15 ml of normal hydrochloric acid solution. The white precipitate which has formed is 15 filtered off, washed with water and dried. 2.25 g of white crystals which melt at 220cC are obtained (yield: 93 % of theory). The following compounds were obtained in the same fashion using the appropriate starting compounds: 0 ti p f* 2 3 5 7 6 27 PH 89042 ex y y« y2 y3 m.p.(°C) 76 h h ch3 ch3 210° 5 77 h h h cf3 212° 78 h h cf3 h 190° 79 h CI h h 190° 80 h h ci cf3 210° h h cf3 ci 10 81 h h f f 210° 82 h h h cn 195° (d) 83 h h cn h 193° (d) 84 h h ci h 174° 85 h h h ci 176° 15 86 h ch3 h h 165° 87 h h ch3 h 174° h h h ch3 88 h h no2 h 198° 89 h h h no2 >250° 20 90 h och3 h h 128-131 91 h ch3 ch3 h 157-158 92 h h ocf3 h 152 93 ch3 h h h 205-206 25 and the following two compounds; 235768 N- 28 PH 89042 o EX z2 m.p.(°C) 94 CH N 180° 5 95 N CH 198° Example 96 Preparation of 2-(l-N,N-dimethvlsulphamovl-2-benzimidazovl)-3-carbomethoxvpvridine 10 14.6 ml (0.13 mol) of dimethylsulphamoyl chloride are added to a suspension of 8.45 g (0.03 mol) of methyl 2-benzimidazolylnicotinate and 9.2 g (0.066 mol) ) of potassium carbonate in 100 ml of anhydrous acetonitrile. 15 The mixture is refluxed for 4 hours with vigorous stirring. The solvent is evaporated, the residue is x taken up in 100 ml of water, and the mixture is extracted with 100 ml of ethyl acetate. The organic phase is decanted off, dried and evaporated. The 20 resulting product is purified by chromatography on silica. 6.0 g of yellow solid which melts at 180°C are obtained (yields 50 % of theory). 235768 29 PH 89042 The following compounds were obtained in the same fashion with the appropriate starting compounds ex y Yi R2 m.p.(°C) 97 h 4,5-diCH3 OCH3 189-191 98 h 5-OCF3 OCH3 135-137.5 99 h h och2c»ch 187-188.5 100 h h och2cf3 oil 101 h h och2ch=ch2 105-107 102 6-ch3 h och3 165-167 103 h h 0(ch2^ch3 68-69.2 123 h h och3 180 124 h 5-CF3 0CH3 165 125 h 6-CF3 och3 150 126 h •u 1 n och3 127 h 5C1,6-CF3 och3 210 h 5-CF3, 6-Ce 0CH3 128 h 5,6-diF OCH3 160 129 h 5-C1 0ch3 158 130 h 6-Cl och3 142 131 h 5-CH3 och3 148 \ ^ 235768 30 PH 89042 H 6-CH3 OCH3 148 132 H 5-CN OCH3 173 133 H 6-CN OCH3 214 134 H 4-CH3 OCH3 165 135 H CSJ O z 1 in OCH3 168 136 H 6-N02 OCH3 150 The following compounds, are obtained in the same fashion. 10 137 138 / Example 104 Preparation of methyl 2-benzimidazolvl-3-pyridine 15 carboxvlate. 10.4 g (0.047 mol) of pyrido[2',3':3,4]pyrrolo-[1,2-a]benzimidazol-5-one suspended in a solution of 0.100 g of potassium hydroxide in 30 ml of methanol are heated to reflux for 1 hour 30 minutes with stirring. 20 After the mixture has been cooled, the precipitate which has formed is filtered off, washed with water and dried. Zi Zi F° CH N 158° N CH 188° 23 5 7 10 15 31 PH 89042 8.35 g of a white solid which melts at 200eC are obtained (yield: 70 % of theory). Example 105 Preparation of methyl 2-M-methoxv-2-benzimidazolvl)-pyridine-3-carboxvlate 8 ml of triethylamine are added to a stirred solution of pyrido[2',3':3,4]pyrrolo[l,2-a]-7-methoxybenzimidazol-5-one (17.4 g) in 260 ml of dichloromethane at ambient temperature. After half an hour, 2.1 ml of methanol are added, and the solution is stirred for 14 hours, washed with water, dried and evaporated. The resulting product is purified on column to give 10.5 g of a gum. The following compounds were obtained in the same fashion with pyrido[2'3':3,4]pyrrolo[l,2-a]benzimidazol-5-one and the appropriate alcohols: EX Y r2 m.p.(°C) 106 H 4,5-diCH3 och3 141-143 107 H 5,(6) -OCF3* och3 146.5 108 H H 0CH2CSCH 187.5-189 20 ^ r> 235768 32 ph 89042 o ex y Y* *2 m.p.(°C) 109 h h och2cf3 177-179 5 110 h h och2ch=ch2 157 111 6ch3 h och3 150-151 112 h h 0(ch2)5ch3 131-133 139 h h och3 200 140 h 5,6-di ch3 och3 150 10 141 h 5-cf3 och3 72 142 h 5-cl,6-CF3 och3 180 143 h 4-Cl och3 140 144 h 5-Cl och3 154 145 h 5,6-di-F och3 15 146 h 5-CH3 och3 80 147 h 5-cn OCH3 >280 The following compound, No. 148, is obtained in the same fashion with the appropriate starting material; c -- 2.1 0\ 20 (* 50:50 mixture of isomers) •9 C -7 / *\ h j C, ->J ^ / \ 33 PH 89042 Example 113 Preparation of pvridor2'.3':3.4lpvrrolor1.2-a]-benzimidazol-5-one 2 9.6 g (0.2 mol) of quinoline anhydride and 21.5 g 5 (0.2 mol) of diamine orthophenylene which are finely ground and intimately mixed are heated on an oil bath at 150°C in a round-bottomed flush rotating about an axis inclined at 45° to the horizontal for 1 hour 15 minutes until the release of water and gas has ceased. 10 After cooling, 50 ml of acetic anhydride are added, and the mixture is heated under reflux for 3 hours. After the mixture has been cooled again, the precipitate which has formed is filtered off and then washed with diethyl ether. 15.1 g of a yellow solid are 15 obtained. The filtrate is diluted with 100 ml of toluene and rendered neutral as far as pH = 6 by stirring with a saturated sodium bicarbonate solution. After decanting, drying and evaporation, a yellow oil is obtained to which acetone is added. The precipitate 20 which has formed is filtered off and dried. A second lot of 2.1 g of yellow solid is obtained. A total of 17.2 g'of product is obtained which melts at 225°. (Yield: 38.9 % of theory). The following compounds were prepared in the same 25 fashion: pyrido[2'3':3,4Jpyrrolo[1,2-a]-7-methoxy-benzimidazol-5-one. m.p. = 180°C (Example 114) pyrido[2'3':3,4]pyrrolo[l,2-a]-7,8-dimethyl-benzimidazol-5-one. m.p. = 196-198<'C (Example 115) 23 5 7 6 8 ■ C1 34 PH 89042 pyrido[2',3':3,4]pyrrolo[1,2-a]-(8 or 9)-trifluoro-methoxybenzimidazol-5-one. m.p. = 140-151°C (Example 116) 2-methyl-pyrido[2',3':3,4]pyrrolo[1,2-a]benzimidazol-5-5 one. m.p. = 265.5-268.4°C (Example 117) ; 2 3 5 7 6 10 35 PH 89042 Example 118 Preparation of benzvltrimethvlammonium 2-(l-N,N-dimethvlsulphamovl)-2-benzimidazolvl)pvridine-3-carboxylate. 0.48 g of N-benzyltrimethylammonium hydroxide are added to a stirred solution of 1 g of 2-(l-N,N-dimethylsulphamoyl-2-benzimidazolyl)pyridine-3-carboxylic acid in 10 ml of methanol. After the mixture has been stirred for 1.5 hours at ambient temperature, the solvent is evaporated to give a yellow oil which on trituration with hexane gives 1.3 g of product in the form of ice-cream. The following salts of the same acid are obtained in the same fashion. 15 EX Salt (+) 119 (ch3)2ch nh3 120 (c2h5), n 121 c12h26 nh3 20 122 K 25 Example a (6H) 5-oxo-2-benzoyl-7-hydrazo[3,4-6]pyrrolopyridine. 50 g of benzhydrazide and 500 g of ethyl 2-cyano-nicotinate (0.286 mol) are added to a solution of 62.8 g of potassium tert.-butanolate in 1.7 litres of methanol. 23 5 7 36 PH 89042 After 2 hours at ambient temperature, the mixture is heated to reflux for 3 hours. A yellow precipitate is obtained which, after filtration and washing with methanol, leads to 93 g of a solid which corresponds to the dipotassium salt of (VI). This compound is characterized in the salt form, m.p. = 282 °C The following compounds of the formula (IVa) (where n = 0) were obtained following this procedure: ° \\ u (lva, EX Ri m.p.(* C) b 2-Me ph c 4 - tBu ph d 4 — CF3 ph e 2 - N02 ph f styryl 283 3 2-Cl ph >250 h 3-C1 ph >250 i 4-OMe ph 200 j benzyl 230 k 3,4,5-triCl 2-thienyl 260 1 2,4-diCl P'h 260 m 2 - pyridyl >300 2 3 5 7 6 8 \ 37 PH 89042 EX Ri m.p.{* c ) | i n 3-pyridyl >300 o 4-Cl ph >260 j P CH3 261 q 4 - pyridyl >300 r 4 - Me ph s H3C-0 227 t H i : V ( CH3 )2 CH . w (CH3 ) 3 C X 2,4 - diCl ph 38 PH 89042 Example y 5-Oxo-7-imino-6-acetophenonepyrrolo[3,4-6]pyridine. 1.47 g (0.001 mol) of (VII) is placed in 100 ml of acetone. 0.2 g of potassium iodide and 3 g of potassium carbonate are added. After the mixture has been stirred for 1/2 hour at ambient temperature, 2.2 g of bromoacetophenone are added. The reaction mixture is stirred for 16 hours. After the solid has been filtered off, the filtrate is evaporated. The resulting honey substance is crystallized from ethyl ether. Yield = 1.8 g m.p. = 172°C The invention likewise relates to the use of the compounds of the formula (I) as herbicides. The following can be mentioned as weeds which can be controlled or destroyed by the compounds of the formula (I), by way of example: Graminaceae/Cvperaceae Echinochloa crus-galli, Lolium multiflorum, Sorghum halepense, Alopecurus myosuroides, Digitaria sanguinalis, Panicum miliaceum, Setaria viridis, Setaria faberie, et cetera. Dicotyledons: Ipomoea purpurea, Abutilon theophrasti, Xanthium pennsylvanicum, Solanum nigrum, Viola Tricolor, Galium aparine, Veronica spp, Sinapis arvensis, Stellaria media, Polygonum spp, et cetera. The use of the compounds of the formula (I) is 23 5 7 39 PH 89042 mostly in the form of a herbicidal composition containing one or several agriculturally acceptable -s carriers. In fact, the compounds according to the invention 5 are rarely used on their own for practical purposes. These compounds are mostly part of compositions. These compositions, which can be used as herbicidal agents, contain a compound according to the invention as described above as the active substance, in a mixture 10 with solid or liquid carriers which are agriculturally acceptable. Inert customary carriers and customary surface-active agents, in particular, can be used. These compositions are likewise part of the invention. These compositions can also contain a wide range 15 of other ingredients such as, for example, protecting colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, sequestering agents, etc... More generally, the compounds used in the invention can be combined with all solid or liquid additives which 20 correspond to customary formulation techniques. Generally speaking, the compositions according to the invention usually contain from 0.05 to 95 % (by weight), approximately, of a compound according to the invention, one or more solid or liquid carriers, and, 25 if appropriate, one of more surface-active agents. The term "carrier" in the present text is understood as meaning an organic or inorganic substance, natural or synthetic, with which the 7 7 r: -e \ ■» - «x, V./< sj J V \ 40 PH 89042 compound is combined to make possible its application to the plant, to grains or to the soil. This carrier is therefore generally inert, and it must be agriculturally acceptable, particularly by the treated 5 plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, particularly butanol, etc...). The surface-active agent can be an emulsifier, 10 dispersant or wetting agent of the ionic or nonionic type, or a mixture of such surface-active agents. For example the following may be mentioned: salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic acids or naphthalenesulphonic acids, 15 polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (particularly alkylphenols or arylphenols), salts of esters of sulphosuccinic acids, taurine derivatives (particularly alkyl taurates), phosphoric 20 esters of alcohols or of polyoxyethylated phenols, esters of fatty acids and of polyols, and derivatives of the previous compounds having sulphate, sulphonate and phosphate functional groups. The presence of at least one surface-active agent is generally 25 indispensable since the compound and/or the inert carrier are not water-soluble and the vehicle for application is water. The compositions for agricultural use, according 23 5 7 41 PH 89042 to the invention, can therefore contain active ingredients according to the invention within very wide limits, ranging from 5 x 10~5 % to 95 % (by weight). Their content of surface-active agent is advantageously 5 between 5 % and 40 % by weight. These compositions according to the invention are themselves in very diverse, solid or liquid forms. As solid composition forms, the following may be mentioned: dusting powders for dusting (having a 10 compound content which can be up to 100 %) and granules, particularly those obtained by extrusion, by compacting, by impregnating a granulated carrier, by granulation using a powder (the compound content in these granules being between 0.5 and 80 % in those 15 latter cases). The wettable powders (or powders for spraying) are generally prepared in such a way that they contain 20 to 95 % of active ingredient, and they generally contain, in addition to the solid carrier, from 0 to 20 30 % of a wetting agent, from 3 to 20 % of a dispersant, and, if required, from 0 to 10 % of one or more stabilizers and/or other additives, such as penetrants, adhesives, agents which prevent clot formation, colorants, etc... 25 To obtain powders for spraying or wettable powders, the active ingredients are intimately mixed with the additional substances in appropriate mixers, and the mixture is ground using mills or other N- f* 42 PH 89042 appropriate grinders. By this means powders for spraying are obtained whose wettability and suspendability are advantageous; they can be suspended with water in any desired concentration/ and these 5 suspensions can be used very advantageously, in particular for application to the leaves of plants. In place of wettable powders, pastes can be produced. The conditions and circumstances of production and use of these pastes are similar to those 10 of the wettable powders or powders for spraying. The following are various compositions of wettable powders (or powders for spraying) by way of example: Example Fl: - active ingredient (compound No. 1) 50.00 % 15 - ethoxylated fatty alcohol (wetting agent).. 2.50 % - ethoxylated phenylethylphenol (dispersing agent) 5 . 00 % - chalk (inert carrier) 42.50 % Example F2 20 - active ingredient (compound No. 1) 10.00 % - branched-type synthetic C13-oxo alcohol, ethoxylated by 8 to 10 ethylene oxide (wetting agent) 0.75 % - neutral calcium lignosulphonate 25 (dispersant) 12.00 % - calcium carbonate (inert filler) to 100 % Example F3: This wettable powder contains the same ingredients as in the preceding example, in the Z6o > n 43 PH 89042 proportions given hereinafter: - active ingredient 75.00 % - wetting agent 1.50 % - dispersant 8.00 % 5 - calcium carbonate (inert filler) to 100 % Example F4 - active ingredient (compound No. 1) 90.00 % - ethoxylated fatty alcohol (wetting agent).. 4.00 % - ethoxylated phenylethylphenol (dispersant). 6.00 % 10 Example F5 - active ingredient (compound No. 1) 50.00 % - mixture of anionic and nonionic surfactants (wetting agent) 2.50 % - sodium lignosulphate (dispersant) 5.00 % 15 - kaolin clay (inert carrier) 42.50 % The compounds according to the invention can be formulated in the form of water-dispersible granules, which is likewise within the framework of the invention. 20 These dispersible granules, whose apparent density is generally between about 0.3 and 0.6, have a particle size which is generally between about 150 and 2,000, and, preferably, between 300 and 1,500 microns. The content of active ingredient of these granules 25 is generally between about 1 % and 90 %, and, preferably, between 25 % and 90 %. The rest of the granules is essentially composed of a solid filler and optionally surface-active 9 7. r-; 7 C. \J sj * 44 PH 89042 adjuvants which impart water-dispersibility properties to the granules. These granules can essentially be of two different types, depending on whether the filler selected is water-soluble or not. If the filler is 5 water-soluble, it may be mineral, or preferably, organic. Excellent results have been obtained using urea. In the case of an insoluble filler, the latter is preferably mineral, such as, for example, kaolin or bentonite. It is therefore advantageously accompanied 10 by surface-active agents (2 to 20 % by weight of the granules) of which more than half is, for example, composed of at least one essentially anionic dispersant, such as alkali metal polynaphthalenesulphonate or alkaline earth metal 15 polynaphthalenesulphonate, or an alkali metal lignosulphonate or alkaline earth metal lignosulphonate, the rest consisting of nonionic or anionic wetting agents, such as an alkali metal alkylnaphthalenesulphonate or alkaline earth metal 2 0 alkylnaphthalenesulphonate. Moreover, other adjuvants such as antifoam agents can be added; although this is not essential. The granules according to the invention can be prepared by mixing the ingredients required, followed 25 by granulation according to a variety of techniques which are known per se (cutting apparatus, fluidized bed, atomizer, extrusion, etc...). The process is generally finished by crushing, followed by sieving at 235 7 v- O 45 PH 89042 the desired particle size, within the abovementioned limits. The granules are preferably obtained by extrusion, following a procedure as indicated in the examples 5 hereinafter. Example F6: Dispersible granules 90 % by weight of active ingredient (compound No. 1) and 10 % of urea in head form are mixed in a mixer. The mixture is subsequently ground in a toothed 10 roll crusher. This gives a powder which is moistened with about 8 % by weight of water. The moist powder is extruded in a perforated roll extruder. This gives granules which are dried, then crushed and sieved in such a way that, respectively, only those granules are 15 retained which have a size between 150 and 2,000 microns. Example F7: Dispersible granules The following constituents are mixed in a mixer: - active ingredient (compound No. 1) 75.00 % 20 - wetting agent (sodium alkylnaphthalenesulphonate) 2.00 % - dispersant (sodium polynaphthalenesulphonate) 8.00 % - water-insoluble inert filler (kaolin) 15.00 % 25 This mixture is granulated in a fluidized bed in the presence of water, and then dried, crushed and sieved in such a way as to obtain granules of a size between 0.15 and 0.80 mm. 23 5 7 \ 46 PH 89042 These granules can be used on their own or in a solution or dispersion in water so as to obtain the desired dose. They can also be used for preparing combinations with other active ingredients, 5 particularly fungicides, the latter being in the form of wettable powders, or granules or aqueous suspensions. The compounds of the formula (I) can also be used in the form of powders for dusting, a composition 10 comprising 50 g of active ingredient and 950 g of talc can also be used, a composition comprising 20 g of active ingredient, 10 g of finely divided silica and 97 0 g of talc can also be used, and these constituents are mixed and ground, and the mixture is applied by 15 dusting. The following may be mentioned as forms of liquid compositions or designed to give liquid compositions during application: solutions, in particular water-soluble concentrates, emulsifiable concentrates, 20 emulsions, concentrated suspensions, aerosols, wettable powders (or powders for spraying), or pastes. The emulsifiable or soluble concentrates mostly comprise 10 to 80 % of active ingredient, the emulsions or solutions which are ready for use contain, as far as 25 they are concerned, 0.001 to 20 % of active ingredient. In addition to the solvent, the emulsifiable concentrates can contain, if required, 2 to 20 % of appropriate additives, such as stabilizers, 23 5 7 6 i * 47 PH 89042 surfaceactive agents, penetrants, corrosion inhibitors, colorants or the adhesives mentioned above. Using these concentrates, it is possible to obtain emulsions of any desired concentration by dilution with 5 water, these emulsions being particularly suitable for application to the crops. What follows is the composition of several emulsifiable concentrates, by way of example: Example F8: 10 - active ingredient 400 g/1 - alkali metal dodecylbenzenesulphonate 24 g/1 - nonylphenol oxyethylated with 10 molecules of ethylene oxide 16 g/1 - cyclohexanone 200 g/1 15 - aromatic solvent to 1 litre According to another formulation of an emulsifiable concentrate, the following are used: Example F9: - active ingredient 250 g 20 - epoxidized vegetable oil 25 g - mixture of alkylaryl sulphonate and of an ether of polyglycol and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g 25 The concentrated suspensions, which can likewise be applied by spraying are prepared in such a way as to obtain a stable fluid product which does not form deposits, and they generally contain from 10 to 75 % of 23 5 7 48 PH 89042 active ingredient, from 0.5 to 15 % of surface-active agents, from 0.1 to 10 % of thixotropic agents, from 0 to 10 % of appropriate additives such as antifoams, corrosion inhibitors, stabilizers, penetrants and 5 adhesives, and, as a carrier, water or an organic liquid in which the active ingredient is sparingly, soluble or insoluble: certain solid organic substances or mineral salts can be dissolved in the carrier to help prevent sedimentation, or as antigels for water. 10 What follows is a composition of a concentrated suspension, by way of example: Example F10: - compound 500 g - polyethoxylated tristyrylphenol phosphate.. 50 g 15 - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g 20 - water 316.5 g The aqueous dispersions and emulsions, for example ^ the compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with the aid of water, are within the general 25 framework of the present invention. The emulsions can be of the water-in-oil type or oil-in-water type, and they can have a thick consistency, like that of "mayonnaise". 2 3 5 7 6 8 49 PH 89042 With regard to the compositions suitable for storage and transport, they contain more advantageously from 0.5 to 95 % (by weight) of active substance. The present invention also relates to a method of 5 weeding (particularly areas where monocotyledons are grown, in particular maize, wheat, barley, rice) which consists in applying an effective quantity of a compound of the formula (I) to the plants to be destroyed. 10 During application to an area under cultivation, the application rate should be sufficient for controlling the occurrence of weeds without causing substantial permanent damage to said crops. By effective dose there is understood, precisely in this 15 context, the dose which allows this result to be obtained. The products and compositions according to the invention are preferably applied to the weeds to be eliminated when the latter display green foliage, 20 advantageously dicotyledons. Nevertheless, it will also be possible to use a method of weeding which consists in applying an effective quantity of a compound of the formula (I) to areas or terrains where it is desired to prevent the 25 germination or the development of plants which have not yet germinated (pre-emergence application). The method can be carried out in such a way that the crop is sown before or after treatment. 23 5 7 -\ 50 PH 89042 The application rate of active ingredient is generally between 1 and 8,000 g/ha. The examples below illustrate the invention: Example A - Herbicidal application, before emergence of 5 plant species Into 7 x 7 x 8 cm pots filled with light agricultural soil there is sown a number of grains, determined as a function of the plant species and the size of the grain. 10 The pots are treated by being sprayed with slurry in a quantity which corresponds to an application rate by volume of 5 00 1/ha and which contains the active ingredient at the desired concentration. The treatment with the slurry is hence carried out 15 on grains which are not covered by soil (the term slurry is used generally to denominate the compositions which are diluted in water, such as they are applied to the plants). The slurry used for the treatment is a solution or 2 0 suspension of the active ingredient in a mixture of acetone/water in a ratio of 50/50, in the presence of 0.05 %-by weight of Cemulsol NP 10 (surface-active agent) composed of polyethoxylated alkylphenol, particularly polyethoxylated nonylphenol) and 0.04 % by 25 weight of Tween 20 (surface-active agent composed of an oleate of the polyoxyethylated sorbitol derivative). In the case of a suspension, the latter is obtained by mixing and grinding the ingredients in a 235768 51 PH 89042 micronizer in such a way as to obtain an average particle size of less than 40 microns. After the treatment, the grains are covered by a layer of soil of thickness approximately 3 mm. 5 The pots are then placed into troughs designed to receive irrigation water, by means of subirrigation, and kept for 24 days at ambient temperature and 70 % relative humidity. Assessment of the herbicidal activity 10 The readings are carried out in the following fashion: After 24 days, a percentage destruction (D) is determined from the number of shoots in the treated pot in relation to the number of plants in the untreated 15 pots (controls) . On the remaining treated plants, the percentage size reduction (SR) in relation to the control plants is determined. The percentage of the foliar volume which is not destroyed by the product is therefore given by the 20 formula: noo-pi x noo-SRi = a 100 This figure A is translated into an assessment of 0 to 5 according to the following scale: 2 T ol 0 / 52 PH 89042 Assessment 0 to 10 5 (complete destruction) 4 10 to 30 30 to 50 3 50 to 70 2 70 to 90 1 90 to 100 0 (no effect) The results obtained are presented after Example B for application rates of 4,000 g/ha. Example B - Herbicidal application after emergence of the plant species Into 7 x 7 x 8 cm pots filled with light agricultural soil there is sown a number of grains, determined as a function of the plant species and the size of the grain. The grains are then covered by a layer of soil of thickness about 3 mm, and the grains are left to germinate up to the point where they have grown into a plantlet of convenient stage. The stage for treatment in the case of Gramineae is the stage "formation of second.leaf". The stage for treatment in the case of dicotyledons'is the stage "cotyledons spread out, first true leaf developing". The pots are then treated by spraying the slurry in a quantity corresponding to an application rate by volume of 500 1/ha and containing the active ingredient in the desired concentration. The slurry has been prepared in the same manner as 235768 53 ph 89042 in Example A. The treated pots are then placed into troughs designed to receive irrigation water, by means of subirrigation, and kept for 24 days at ambient temperature and 70 % relative humidity. Assessment of the herbicidal activity The readings are carried out in the following fashion: After 24 days, a percentage destruction (D) is determined from the number of shoots in the treated pot in relation to the number of plants in the untreated pots (controls). On the remaining treated plants, the percentage size reduction (SR) in relation to the control plants is determined. The percentage of the foliar volume which is not destroyed by the product is therefore given by the formula: This figure A is translated into an assessment of 0 to 5 according to the following scale: noo-pi x noo-sri = a 100 Assessment 0 to 10 5 (complete destruction) 4 10 to 30 30 to 50 3 50 to 70 2 70 to 90 1 90 to 100 0 (no effect) a r» 23 5 7 54 PH 89042 The results obtained are presented after Table A for application rates of 4,000 g/ha. The plant species used in these Examples A and B are: 10 15 ABBREVIATIONS LATIN NAME ENGLISH NAME ECH Echinochloa crusgalli Japanese millet LOL Lolium multiflorum Rye grass CYP Cyperus esculentus Earth almond DIG Digitaria sanguinalis Hairy finger grass IPO Ipomea purpurea Purple morning glory SIN Sinapis alba White mustard SOL Solanum nigrum Black nightshade ABU Abuliton theophrasti China jute \ J 235 7 68 55 PH 89042 EXAMPLE A: PRE-EMERGENCE ACTIVITIES (4 kg/ha) COMPOUND No. ECH LOL DIG IPO SIN ABU SOL CYP 5 1 2 2 3 4 5 1 5 5 2 3 3 4 5 4 0 1 0 3 5 5 5 5 5 2 3 2 6 1 - 1 4 3 1 5 4 10 7 3 2 1 5 3 2 5 5 8 2 3 1 5 2 3 1 2 9 4 2 5 5 5 5 5 3 10 2 1 4 4 4 0 3 0 14 3 - 4 5 1 1 1 2 15 24 3 2 4 5 2 1 5 1 33 4 3 5 4 1 1 2 2 36 4 2 5 5 2 1 5 1 37 3 3 3 5 2 5 1 0 41 4 3 4 5 1 1 0 2 20 42 3 2 - 5 4 5 - 4 43 4 3 4 3 2 1 1 2 47 5 3 4 5 2 1 1 3 48 4 5 4 5 2 5 1 4 49 4 3 4 3 2 3 2 4 25 235768 56 PH 89042 EXAMPLE A: PRE-EMERGENCE ACTIVITIES (4 kg/ha) COMPOUND No. ECH LOL DIG IPO SIN ABU SOL CYP 5 50 4 1 4 5 3 4 0 0 53 4 3 4 4 4 4 1 0 54 4 4 4 4 3 4 4 4 55 4 4 4 3 3 5 5 1 10 56 4 3 4 3 3 3 2 4 57 4 4 4 4 3 4 5 0 59 3 2 3 5 1 1 0 0 63 4 2 4 5 5 5 1 3 64 4 3 4 4 4 1 1 1 15 66 3 1 5 4 1 0 0 4 67 3 3 5 5 2 5 1 0 69 - 3 4 5 2 2 1 3 73 4 4 4 5 5 4 3 4 75 1 - 2 4 5 2 5 4 20 78 3 - 1 3 5 0 5 4 7? 1 - 0 4 3 1 5 5 84 - - 4 4 5 2 5 5 87 0 - 0 3 5 1 5 3 121 0 - 2 4 4 1 5 0 25 - 2 3 5 7 6 8 57 PH 89042 EXAMPLE A: PRE-EMERGENCE ACTIVITIES (1 kg/ha) (continuation) COMPOUND No. ECH LOL DIG IPO SIN ABU SOL CYP 119 0 - 0 4 4 1 4 1 122 0 — 1 4 2 1 3 5 o 3 r; 58 PH 89042 5 10 15 20 25 EXAMPLE B: POST-EMERGENCE ACTIVITIES (4 kg/ha) COMPOUND No. ECH LOL DIG IPO SIN SOL 1 0 0 0 3 5 5 3 0 0 0 2 2 3 4 3 - 3 2 2 1 6 0 - 0 4 5 5 7 1 1 1 4 5 5 9 2 0 2 3 4 3 12 0 0 0 3 4 4 15 3 3 3 2 1 1 24 0 0 0 3 3 3 42 2 1 - 4 4 - 43 4 3 3 4 5 3 44 2 0 1 3 4 1 45 3 2 3 3 2 3 48 3 2 3 3 2 1 50 3 0 2 3 0 0 54 2 3 3 0 1 3 67- 0 0 2 3 2 2 73 3 2 2 3 3 3 75 0 - 0 4 5 5 84 0 - 0 3 5 5 87 0 - - 4 5 5 121 3 — 2 4 5 5 235768 > 59 PH 89042 5 EXAMPLE B: POST-EMERGENCE ACTIVITIES (1 kg/ha) (continuation) COMPOUND No. ECH LOL DIG IPO SIN SOL 119 0 - 0 3 4 5 122 2 - 1 4 5 5 10 Example C - Selectivity trial in grown crops after emergence of the plant species Into 7 x 7 x 8 cm pots filled with light agricultural soil there is sown a number of grains, determined as a function of the plant species and the 15 size of the grain. The grains are then covered by a layer of soil of thickness about 3 mm, and the grains are left to germinate up to the point where they have grown into a plantlet of convenient stage. The stage for treatment 20 in the case of Gramineae is the stage "formation of second leaf". The stage for treatment in the case of dicotyledons is the stage "cotyledons spread out, first true leaf developing". The pots are then treated by spraying the slurry in 25 a quantity corresponding to an application rate by volume of 500 1/ha and containing the active ingredient in the desired concentration. The slurry has been prepared in the same manner as 60 PH 89042 in Example A. The treated pots are then placed into troughs designed to receive irrigation water, by means of subirrigation, and kept for 24 days at ambient temperature and 7 0 % relative humidity. Assessment of the herbicidal activity The readings are carried out in the following fashion: After 24 days, a percentage destruction (D) is determined from the number of shoots in the treated pot in relation to the number of plants in the untreated pot (controls). On the remaining treated plants, the percentage size reduction (SR) in relation to the control plants is determined. The percentage of the foliar volume which is not destroyed by the product is therefore given by the formula: noo-pi x noo-sri = a 100 This figure A is translated into an assessment of 0 to 5 according to the following scale: Assessment 0 to 10 5 (complete destruction) 10 to 30 4 30 to 50 3 50 to 70 2 70 to 90 1 90 to 100 0 (no effect) 2 3 5 7 61 PH 89042 In this way, a product is considered selective with respect to the crop if the recorded fiqure A is 0 or 1. The results obtained are presented in Example C 5 for application rates between 0.5 and 4 kg of active ingredient per hectare, depending on the products. The plant species used in this example are: 1) For weeds 10 ABBREVIATIONS LATIN NAME ENGLISH NAME SOL Solanum nigrum Black nightshade IPO Ipomea pupurea Purple morning 15 glory SES Sesbania exaltata Indigo weed XAN Xanthium Common pennsylvanicum cocklebur VI0 Viola tricolor Wild pansy 20 SIN Sinapis alba White mustard POL Polygonum Black bindweed - convolvulus CON Convolvulus Field bindweed arvensis 25 CHY Chrysanthemum Corn marigold segetum O 7 f" "7 62 PH 89042 2) For the crops ABBREVIATIONS LATIN NAME ENGLISH NAME TRZ Triticum aestivum Wheat ZEA Zea mays Maize ORY Oryza sativa Rice 235768 63 PH 89042 SELECTIVITY TRIAL IN GROWN CROPS HERBICIDAL POST-EMERGENCE ACTIVITY i i i r Compound (No. Dose applied in kg/ha R I E 1 Z | A -t" 0 R Y I P 0 X A N V | S I P | C I I I I I I . 0 I 0 I . I 0 1 N I L N C H Y 10 15 20 6 1 9 7 19 75 84 79 87 119 122 2 1 0.5 2 4 1 1 2 2 0.5 1 0 !0 1 0 ! i 0 ' 0 0 I I x! 0 I 0 I I °! 0 I 5 4 3 4 4 5 4 4 4 3 5 4 4 3 4 2 5 3 1 2 3 5 4 r -15 - I 3 " I5 - I5 4 I 2 I ~ 1 I- 0 |- 3 r 3 I- 4 ' 5 I 3 I 4 4 | 5 ! 5| 2 5 I 5 5 4 5 5 5 i 25 As can be seen from the table of results of this Example C, numerous products have an excellent post-emergence activity against dicotyledons, while showing an excellent selectivity for 1 or 2 or 3 of the crops tested: wheat, maize, rice. 2 3 5 7 6 8 64 PH 89042 Method of use of herbicidal compounds: Herbicidal activity: a) General Appropriate quantities of the test compounds were 5 dissolved in acetone to give solutions equivalent to application rates of 250, 1,000 or 4,000 g of test compound per hectare (g/ha). These solutions were applied from a standard laboratory herbicide sprayer using flat fan jet travelling at 2.9 km/h, and 10 delivering the equivalent of 540 litres of spray fluid per hectare (method 1) and 290 litres (method 2). Method 1 b) Weed control: Pre-emeraence application Weed seeds were sown on the surface of John Innes 15 No. 1 potting compost (7 parts by volume of sterilized loam, 3 parts by volume of fine grit) in 70 mm square, 75 mm deep plastic pots. The quantities of seed per pot were as follows:- Weed species Approximate number seeds/pot 20 1) Broad-leafed weeds Abutilon theophrasti 10 Sinapis arvensis 20 Chenopodium album 60 Ipomoea purpurea 10 25 2) Grass weeds Avena fatua 15 Echinochloa crus-galli 20 235768 65 PH 89042 3) Sedges Cyperus esculentus 3 The compounds of the invention were applied to the uncovered seeds as described in (a) above and the seeds 5 were covered with 25 ml of sharp sand after spraying. A single pot of each weed species was allocated to each treatment with unsprayed controls and controls sprayed with acetone alone. After treatment, the pots were kept in the greenhouse and were watered overhead. Visual 10 assessment of weed control activity was made 17-20 days after spraying. The results were expressed as the percentage reduction in growth or kill of the weeds, in comparison with the plants in the control pots. c) Weed control: Post-emergence application 15 Weed species were grown and then transplanted at the seedling stage into John Innes No. 1 potting compost in 70 mm square, 75 mm deep plastic pots, except for Avena Fatua, which was sown directly in the test pot and not transplanted. The plants were then 20 grown in the greenhouse until ready for spraying with the test compounds. The number of plants per pot, and the growth of the plant at spraying were as follows:- 10 Weed species 66 Number of plants per pot 1) Broad leafed weeds Abutilon theophrasti 3 Sinapis arvensis 4 Chenopodium album 4 Ipomoea purpurea 3 2) Grass weeds Avena fatua 15 Echinochloa crus-galli 4 3) Sedges Cyperus esculentus 3 o ** r, 7 PH 89042 Growth stages at spraying 1-2 leaves 2-leaves 2-4 leaves 1-2 leaves 1-2 leaves 2-3 leaves 3-leaves The test compounds were applied to the plants as 15 described in (a) above. A single pot of each weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After spraying, the pots were watered overhead, commencing 24 hours after spraying. Visual assessment of the control 20 of the growth of the weeds was made 17-20 days after spraying. The results were expressed as the percentage reduction in growth or kill of the weeds in comparison with the plants in the control pots. Method 2 25 d) Weed control: Pre-emeroence The seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil from Boarded Barns \ r> 23 5 7 / 67 PH 89042 Farm or similar soil type from a suitable source. The quantities of seed per pot were as follows:- Weed species 5 1) Broad-leafed weeds Abutilon theophrasti Amaranthus retroflexus Galium aparine Ipomoea purpurea 10 Sinapis arvensis Xanthium strumarium 2) Grass weeds Alpercurus myosuroides Avena fatua 15 Echinochloa crus-galli Setaria viridis 3) Sedges Cyperus esculentus Crop 20 1) Broad-leafed Cotton Soya 2) Grass Maize 25 Rice Wheat Approx. number of seeds/pots 10 20 10 10 15 2 15 10 15 20 3 3 2 6 6 The compounds of the invention were applied to the soil surface, containing the seeds, as described in »-n (L, vj xJ / \) 68 PH 89042 (a). A single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After treatment the pots were kept in a 5 greenhouse, and watered overhead for 3 days, and then by controlled subirrigation. Visual assessment of crop damage was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the 10 plants in the control pots. e) Weed control: Post-emeraence The weeds and crops were sown directly into John Innes potting compost in 75 mm deep, 70 mm square pots except for Amaranthus which was pricked out at the 15 seedling stage and transferred to the pots one week before spraying. The plants were then grown in the greenhouse, until ready for spraying with the test 20 25 compounds. The number of plants per pot were as follows:- Weed species Number of plants Growth per pot staae 1) Broad leafed weeds Abutilon theophrasti 3 1-2 leaves Amaranthus retroflexus 4 1-2 leaves Galium aparine 3 1st whorl Ipomoea purpurea 3 1-2 leaves Sinapis arvensis 4 2 leaves Xanthium strumarium 1 2-3 leaves ^ -4^, 69 2) Grass weeds Alopecurus myosuroides 8-12 Avena fatua 12-18 Echinochloa crus-galli 4 ■ Setaria viridis 15-25 3) Sedges Cyperus esculentus 3 23 5 7 PH 89042 1-2 leaves 1-2 leaves 2-3 leaves 1-2 leaves 3 leaves 10 15 Crops 1) Broad leafed Cotton Soya 2) Grass Maize Rice Wheat Number of plants per pot 2 2 2 4 5 Growth stage 1 leaf 2 leaves (1st trifoliate) 2-3 leaves 2-3 leaves 2-3 leaves The test compounds were applied to the plants as 20 described in (a). A single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone. After treatment the pots were kept in a greenhouse, and watered overhead once after 24 hours 25 and then by controlled subirrigation. Visual assessment of crop damage and weed control was made 20-24 days </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 23 5 7 70 PH 89042 after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots. 5 When applied pre-emergence at 4,000 g/ha (method IB) compounds 101, 92, 100) gave at least 90 % reduction in growth of one or more of the weed species. When applied post-emergence at 4,000 g/ha (method IC) compounds (101, 92, 100) gave at least 90 % 10 reduction in growth of one or more of the weed species. When applied pre-emergence at 4,000 g/ha (method 2D) compounds (118, 91, 90, 103, 93, 99) gave at least 90 % reduction in growth of one or more of the weed species. 15 When applied post-emergence at 4,000 g/ha (method IE) compounds 118, 91, 90, 103, 93, 99) gave at least 90 % control of one or more of the weed species. ; ) 23,r/7t - 71 - WHAT WE CLAIM IS: 1. A compound of the formula I r "R2. I fyji fU II N w A / in which: 5 A is the hydrogen atom or an R7S02- group, is a hydrogen atom, an optionally substituted alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical, an optionally substituted aralkyl radical, it being possible for the aryl or aralkyl radicals also to 10 contain 1 to 4 hetero atoms in the ring which are selected from amongst the oxygen atom, the sulphur atom or the nitrogen atom, R2 is selected from amongst the radicals of the formula X^M, M being an organic or inorganic cation and X^ being the oxygen atom or the sulphur atom, X2Rs, R5 15 having one of the meanings of R^ or being an alkyl which is optionally substituted by an alkenyl or alkynyl group, and X2 being the oxygen atom or the sulphur atom, NR3R4, R3 and R4 being identical or different and selected from amongst the hydrogen atom, the optionally substituted alkyl 20 radicals, the optionally substituted cycloalkyl radicals, the optionally substituted aryl radicals, the optionally y * 8 MAY 1992;z&7{&;-12-;substituted aralkyl radicals or the 0R6 radicals, R6 having one of the meanings given for Rj_, R7 is an optionally substituted alkyl radical, an optionally substituted cycloalkyl radical, an optionally substituted aryl radical 5 or an optionally substituted aralkyl radical, or R7 is a NRgRg group, R8 and R9 being identical or different and having one of the meanings given for Rj^ or they can form, together with the nitrogen atom to which they are bonded, a heterocycle which contains 1 to 3 hetero atoms, W is an =N-;1;10 or =CR10- group, R10 having one of the meanings indicated for Rlr where R^ and R10 together with the atoms to which they are attached can form a ring which, in combination with the imidazole ring, forms an aromatic system of two fused rings, R^ and R10 constituting either a chain having three 15 atoms where one is sulphur or oxygen and the two others are carbon, or a chain of four carbon atoms which contains two double bonds or a chain of four atoms containing 1 to 3 nitrogen atoms and 3 to 1 carbon atoms, these chains being optionally substituted by one to four Y^ radicals which are 20 the same or different and are selected from optionally substituted alkyl radicals, optionally substituted alkoxy radicals, halogen radicals, and dialkylamino radicals or, two of the radicals Ylf which are alkoxy radicals, alkylthio radicals or alkyl radicals together, in the 4, 5 position or 25 the 5, 6 position, from, with the carbon atoms to which they are attached, an aliphatic ring having 5 or 6 atoms and having not more than two hetero atoms seJ ^ ^ - 7* iy;ito9, - 73 - oxygen or sulphur, Y is an optionally substituted alkyl radical, an optionally substituted alkoxy or alkylthio radical, or a halogen atom, it being possible if n is 2 or 3 for two Y radicals in adjacent positions a and B to the 5 nitrogen atom, together with the carbon atoms to which they are attached to form a fused phenyl ring, or an aliphatic ring (optionally heterocyclic) containing 5 or 6 atoms containing not more than 2 non-adjacent hetero atoms selected from oxygen or sulphur atoms, n is 0, 1, 2 or 3 it 10 being understood that, if n is higher than 1, the Y groups can be identical or different.
2. A compound according to Claim 1, in which the alkyl radicals have 1 to 6 carbon atoms.
3. A compound according to Claim 1 or 2, in which 15 the cycloalkyl radicals have from 3 to 7 carbon atoms.
4. A compound according to Claim 1, 2 or 3 in which the aryl radicals have 6 to 10 carbon atoms.
5. A compound according to any one of the preceding claims in which the aralkyl radicals have between 20 7 and 11 carbon atoms.
6. A compound according to any one of the preceding claims in which the optionally substituted radicals or moieties are optionally substituted by a halogen atom, the hydroxyl radical, the C-^-^-alkyl radicals (apart 25 from where the optionally substituted radical is an alkyl radical), the C1-C4-alkoxy radicals, the jmono- or polyhalogenated C1-C4-alkyl radicals (apart from where the--, 2 7(/?> - 74 - optionally substituted radical is an alkyl radical), the mono- or polyhalogenated ^-04 alkoxy radicals, cyano and nitro.
7. A compound according to any of the preceding 5 claims in which the cation M is selected from amongst the alkali metals (Na, K, Li), the ammonium radicals of the formula NR11R12Ri3Ri4«■ Rii/ Ri2' R13 and R14 bein9 selected from amongst the hydrogen atom, C^-Cg-alkyl radicals which are optionally substituted by a hydroxyl radical, and 10 aralkyls not more than two of the radicals R^ to R14 being aralkyl.
8. A compound according to any one of the preceding claims in which - A is the R7S02- group, and R7 is NR8R9, 15 - and/or n = 0 or 1, - and/or Rx is an optionally substituted phenyl or 2-pyridyl radical, - and/or R2 is a hydroxyl, allyloxyl, or propargyloxy radical or OM, wherein M is NR11R12R13R14< 20 - and/or W is -N= or -R10C=, Rio selected from the hydrogen atom, the phenyl radical or the tert,-butyl radical, or R10 together with Ri and the two carbon atoms to which they are attached forms a phenyl ring which is optionally substituted by one or two groups selected from 25 alkoxy, haloalkoxy, alkyl, halogen and haloalkyl groups.
9. A compound according to claim 1 hereinbefore indentified in any one of Examples 1 to 147. 2 3<57&g - 75 -
10. A process for the preparation of a compound according to Claim 1, which comprises -1) in the case where A is an R7S02- group, reacting a sulphonyl chloride or sulphamoyl chloride of the formula 5 R7S02C1 with a compound of the formula (I) in which A is the hydrogen atom, in the presence of an acid acceptor, - 2) in the case where A is the hydrogen atom and R2 is an X2R5 radical where R5 is not H, reacting a compound of the formula (II) wherein, W,Y,R, and n have the meanings 10 defined in claim 1: with an alkali metal or alkaline earth metal compound of the formula R5X2M', M' being a metal cation and R5 being other than the hydrogen atom:, or with an alcohol of the formula 15 R5OH in the presence of an acid acceptor, - 3) in the case where A is the hydrogen atom, R2 is X2R5 and R5 is other than a hydrogen atom, esterifying a compound of the formula (III) 0 II (III) iy^7C?> - 76 - where R2 is an X2H radical and W,Y,R and n are as defined in claim 1, with an alcohol of the formula R50H. - 4) in the case where R2 is X2H Uydrolysing the compound of formula (I) where R2 is X2R5, and R5 is other than H. 5-5) in the case where R2 is XjM the action of the corresponding base on the acid form of the compound of the formula (I), - 6) in the case where R2 is NR3R4, reacting an amine of the formula HNR3R4 with a compound of the formula (II) , and 10 if desired, treating with a compound of the formula R7SO2CI. 15 1 to 9 when prepared by a process according to claim 10 or 11. active ingredient, a compound according to any one of Claims 1 to 8 or 12 in association with an agriculturally 20 acceptable diluent or carrier and or an agriculturally acceptable surface-active agent.
11. A process according to claim 10 which is substantially as hereinbefore described in any one of Examples l to 147.
12. A compound according to any one of claims
13. A herbicidal composition, comprising, as
14. A composition according to claim 13 comprising from 0.05 to 95% by weight of a compound of formula I. 25
15. A composition according to claim 13 which is substantially as hereinbefore described in any one Examples F1 to F10.
16. A method of controlling the growth of weeds at a locus which comprises applying thereto a compound as claimed in any one of claims 1 to 8 or 12.
17. A method according to claim 16 in which 5 maize, wheat, barley or rice are grown at the locus.
18. A method according to claim 16 or 17 in which the compound of formula I is applied post-emergence of the weeds.
19. A method according to claim 16 which is 10 substantially as hereinbefore described. tv, i twjpniiThoir Authorised Aq®0'8' --fl r V 2 y -8 MAY 1992 m< </div>