IE43776B1 - 2-(4-substituted-phenyl)-indazoles or-cyclopentano-or-cycloheptano-pyrazoles, and their use in herbicical compositions - Google Patents

Abstract

1519906 Herbicidal compositions E I DU PONT DE NEMOURS & CO 14 Oct 1976 [15 Oct 1975 12 Dec 1975 26 Aug 1976] 42776/76 Heading A5E [Also in Division C2] Herbicidal compositions comprise novel compounds of formula wherein n=3, 4 or 5; R 1 is H or CH 3 ; Q is F, Cl, Br or I; X is F, Cl, Br, I, CN, OCH 3 or NO 2 ; Y is H, F or Cl; Z is H or F and V is H, F, Cl or OCH 3 , with the provisos (a) that when n=5, R 1 =H, Q=Cl or Br, Z=V=H and Y=H or F; (b) when n=3 or 4 and Q=F or I, R 1 =Z=V=H and Y= H or F; (c) when n=3 and R 1 =CH 3 , Q=Cl or Br, Y=H or F and Z=V=H and (d) when V#H, X=F, Cl or Br and Z=H, together with one or more known herbicides as listed (see Example 22) and at least one of (a) a surface active agent and (b) a solid or liquid diluent.

Description

This invention concerns 2-(4-substituted-phenyl)-indazoles or -cyclopentano- or -cycloheptano- pyrazoles having herbicidal activity.

Recently, in German Offenlegungsschrift 2,165,551 a group of isoiridole-1,3-diones which are useful as herbicides was disclosed. The general formula for the isoindole-1,3-diones disclosed in the Offenlegungsschrift is as follows: wherein R may be an aryl, aralkyl or benzyl substituent optionally substituted with 1 to 5 halogen atoms or a hydroxy, nitro, cyano, thiocyanato, carboxy, alkyl or halogenated alkyl, alkoxy, lower alkylthio or phenyl group. R may also be optionally substituted with a group having the configuration —0—CH^A where A is a phenyl or a naphthyl group. The phenyl group may contain one or more halogen atoms, nitro groups, lower alkyl groups or lower alkoxy groups.

Typical of the compounds disclosed in the Offenlegungsschrift is the. compound of Structure 1: Although the compounds disclosed within the Offenlegungsschrift are active - 2 10 herbicides, the need still exists for even better herbicides. Weeds are very damaging to important crops such as rice and wheat and they decrease crop yield. In the current world situation, wherein food shortages are acute, it is most important to harvest the maximum possibTe yields of crops such as rice or wheat. Thus, a need exists for a particularly effective herbicide which will destroy as many weeds as possible without causing significant damage to desired crops, e.g., rice or wheat.

According to the present invention, compounds have been discovered which are highly active herbicides and yet cause minimal damage to certain desired crops, e.g,, rice and wheat, and especially the major world food crop, rice; The preparation and fungicidal utility of the 2-(4-ch1orophenyl)1,2,4,5,6,7-hexahydroindazol-3(3H)-one is disclosed in Takeda Chem. Ind. Paper, Chem. Abs., 67, 11542h (1967). 2-Aryl-4,5,6,7-tetrahydro-l-alkyl-lH-indazol-3(2H)-ones are claimed as antipyretics in German Patent No. 668,628 {Chem. Abs., 33, 51312 (1939)} and U.S. Patent No. 2,104,348, {Chem. Abs,, 32 18691 (1938)}. - 3 4 27 7 6 German Offenlegungsschrift 2,409,753 disclosed herbicides having the general formula R“ R1 in which R1 is hydrogen, an alkyl, cycloalkyl or aralkyl radical, a phenyl group which may be substituted or an acyl radical having the formula —CO—R6 or R7 R8 R6 is hydrogen, an alkyl radical which may be substituted, an alkoxy 10 or phenoxy radical or a phenyl radical and R7 and R8 are the same or different and can be hydrogen, alkyl, phenyl which may be substituted or alkynyl, Rz is an alkyl radical which may be substituted, a cycloalkyl radical or a phenyl radical which may be substituted or a heterocyclic radical with 0, N or S atoms in the ring.

R3 is hydrogen, chlorine, bromine or a low-molecular-weight alkyl radical, R4 is the radical —S—R8, ——SO—R8 or —SO2—R8.and R8 is an alkyl radical, cycloalkyl radical, aralkyl radical or a - 4 phenyl group which may be substituted or a heterocyclic radical with 0, N or S in the ring.

An intermediate for preparing these herbicides by reaction with a mercaptan having the general formula R5SH is where R1, R2, R3 and R5 have the previously given meanings and Hal represents chlorine, bromine or iodine. l-Phenyl-3,4-trimethy1enepyrazolone is disclosed in U.S. Patent No. 1,685,407 (1928) with utility as an intermediate for making dyes and medicinal compounds. C. Mannich in Arch. Pharm. 267, 699—702 (1929) and in British Patent No. 260,577 describes the preparation of 1-phenyl3,4-trimethylenepyrazolones.

R, P. Williams et al. in J.. Med. Chem. J3, 773 (1970) reports the 15 preparation and evaluation as antiinflammatory agents compounds of the following type: - 5 7 7 & , **> 4 n X = H, Br, F.

This invention relates to the novel compounds of Formula I and to agricultural compositions containing them, and to the method of use of these compounds as selective, as well as general, herbicides having both pre- and post-emergence activity. where n_ is 3, 4 or 5; Ri is hydrogen or methyl; Q is fluorine, chlorine, bromine or iodine; X is fluorine, chlorine, bromine, iodine, cyano, methoxy or nitro; Y is hydrogen, fluorine, or chlorine; Z is hydrogen, or fluorine; and V is hydrogen, fluorine, chlorine or methoxy with the proviso that (a) when ii is 5, R, must be hydrogen, Q must be chlorine or bromine, Z and V must both be hydrogen and Y must be hydrogen or fluorine; (b) when ii is 3 or 4 and Q is fluorine or iodine, Ri, Z and V must be hydrogen and Y must be hydrogen or fluorine; (c) when n is 3 and Rx is methyl, Q must be chlorine or bromine, Y must be hydrogen or fluorine and Z and V must both be hydrogen; and -6 f o r· .·» β ο > f ο (d) when V is other than hydrogen, X must be fluorine, chlorine or bromine and Z must be hydrogen.

Compositions of the invention for the control of undesirable vegetation comprise a compound of Formula I and at least one of (a) a surface active agent, and (b) a solid or liquid diluent.

Included within the compounds of Formula I are those wherein £ is or 5, Ri is hydrogen or methyl, Q is chlorine or bromine,X is fluorine, chlorine, bromine, cyano, methoxy or nitro , Y is hydrogen, fluorine or chlorine; and Z and V are each hydrogen or fluorine, at least one being hydrogen, with the proviso that at least one of X, Y and Z is other than hydrogen. Also included within the compounds of Formula I are those wherein Q is chlorine, bromine or iodine; X is not iodine; V is hydrogen, fluorine or chlorine; with the provisos that at least one of X, Y and Z is other than hydrogen; and at least one of X, Y, V and Z is hydrogen.

Of those compounds of Formula I, preferred for their high herbicidal activity or favourable cost or both, are those compounds where, independently, 1) n is 3 or 4; 2) Q is chlorine or bromine; 3) R] is hydrogen or methyl; 4) Z and V are both hydrogen; ) Y is hydrogen or fluorine; or, 6) X is fluorine, chlorine, bromine, cyano or methoxy.

Of those compounds of Formula I where ii is 4, preferred are those where Q is chlorine or bromine.

More preferred are those compounds where n is 4, Q is chlorine or - 7 ci ( 6 bromine, and Rx is hydrogen.

Of those compounds of Formula I where is 4, Q is chlorine or bromine and R! is hydrogen, preferred are those compounds where, independently, 1) Z and V are both hydrogen; 2) Y is hydrogen or fluorine; or 3) X is fluorine, chlorine, bromine, cyano or methoxy.

More preferred still are those compounds where n is 4, Q is chlorine or bromine, Rx is hydrogen and Z and V are both hydrogen.

Of those compounds of Formula I where is 4, 0 is chlorine or bromine, Rj is hydrogen and Z and V are both hydrogen, preferred for their higher herbicidal activity or more favorable cost or both, are those compounds where, independently, 1) Y is hydrogen or fluorine; or, 2) X is fluorine, chlorine, bromine, cyano or methoxy.

More preferred are those compounds where in is 4, Q is chlorine or bromine, Rj is hydrogen, Z and V are both hydrogen, Y is hydrogen or fluorine and X is fluorine, chlorine, bromine, cyano or methoxy.

Most preferred for their excellent herbicidal activity or highly favorable cost or both are those compounds of Formula I where £ is 4, Q is chlorine or bromine, is hydrogen, Z and V are both hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine.

Of those compounds of Formula I where £ is 3, preferred are those compounds where Q is chlorine or bromine.

More preferred are those compounds where £ is 3, Q is chlorine or ’5 bromine, and Rj is hydrogen. - 8 4 £ 7 7 6 Of those compounds of Formula I where £ is 3, Q is chlorine or bromine and Ri is hydrogen, preferred are those compounds where, independently, 1) Z and V are both hydrogen; 2) Y is hydrogen or fluorine; or, 3) X is fluorine, chlorine, bromine, cyano or methoxy.

Most preferred are those compounds where n_ is 3, Q is chlorine or bromine, RA is hydrogen and Z and V are both hydrogen.

Of those compounds of Formula I where ji is 3, Q is chlorine or bromine, Ri is hydrogen and Z and V are both hydrogen, preferred for their higher herbicidal activity or more favorable cost or both, are those compounds where, independently, 1) Y is hydrogen or fluorine; or, 2) X is fluorine, chlorine, bromine, cyano or methoxy.

More preferred are those compounds where n is 3, Q is chlorine or bromine, Ri is hydrogen, Z and V are both hydrogen, Y is hydrogen or fluorine and X is fluorine, chlorine, bromine, cyano or methoxy.

Most preferred for their excellent herbicidal activity or highly favorable cost or both are those compounds of Formula I where £ is 3, Q is chlorine or bromine, Ri is hydrogen, Z and V are both hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine.

Of those compounds of Formula I, preferred for their high herbicidal activity or favorable cost or both, are those compounds where Y is hydrogen or fluorine and Z and V are both hydrogen.

Most preferred are those compounds where Y is hydrogen or fluorine and Z and V are both hydrogen where, independently, - 9 7 ‘ΐ 6 1) Q is chlorine; or 2) X is chlorine or bromine.

Of those compounds of Formula I, preferred for their higher herb' cidal activity or more favorable cost or both, are those compounds whe Y is hydrogen or fluorine, Z and V are both hydrogen and Q is chlorine Most preferred for their excellent herbicidal activity or highly favorable cost or both are those compounds of Formula I where Y is hydi gen or fluorine, Z and V are both hydrogen, Q is chlorine, and X is chlorine or bromine.

Specifically preferred for their outstanding herbicidal activity o favorable cost or both are 1) 3- Chloro -2-(4- chloro - 2 - fluorophenyl) - 4,5,6,7 tetrahydro - 2H - indazole; m.p, 88—89.5°C; 2) 3 - Chloro -2-(4- chlorophenyl) - 4,5,6,7 - tetrahydro - 2Hindazole; m.p. 81—84°C; 3) 3 - Bromo -2-(4- chloro - 2 - fluorophenyl) - 4,5,6,7 - tetra hydro - 2H - indazole; m.p. 95—98°C; 4) 3 - Chloro -2-(4- bromo - 2 - fluorophenyl) - 4,5,6,7 - tetra hydro - 2H - indazole; m.p. 86—88°C; ) 3 - Chloro -2-(4- chloro - 2 - fluorophenyl) - 2,4,5,6, tetrahydrocyclopentapyrazole; m.p. 101.5—1O4°C; and, 6) 3 - Chloro -2-(4- chlorophenyl) - 2,4,5,6 - tetrahydrocyclopentapyrazole; m.p, 114.5—117°C. - 10 SYNTHESIS OF THE COMPOUNDS The novel cycloalkanapyrazoles of Formula I where Q is Cl or Sr are prepared in two steps as shown by Equations A and B: 4 I where Rls η, X, Y, V and Z are as defined above; Q is Br or Cl; R is alkyl 0f1 to 3 carbon atoms; f is 0 or 1; and A is an anion of the corresponding acid HA having an ionization constant of at least 1 x IO-7, e.g. H2SO^ or HC1.

The preparation of the annelated pyrazolones _3 is known in the litera ture; for example, the preparation of 2-aryl-l,2,4,5,6,7-hexahydro-3H15 indazol-3-ones (3, n = 4) is described in W. Dieckmann, Ann., 317, 102 (1901). The s-keto ester Z is combined with the appropriate aryl hydra- 11 43776 zine acid salt 2 in an appropriate solvent, such as a lower alcohol, or aromatic hydrocarbon, and, optionally, in the presence of an acid acceptor, such as a tertiary organic amine or alkali metal hydroxide or alkoxide and the reaction mixture is heated at reflux for 0.5—24 hours. The pyrazolone 3 is isolated by conventional techniques such as by pouring the reaction mass into water and filtering the product. The crude product is usually of sufficient purity to be used directly in the next step. If necessary, further purification can be accomplished by recrystallization, sublimation, or other conventional techniques known to those skilled in the art. This same procedure can be used to prepare those compounds of formula 2 in which _n = 5.

The pyrazolones 2 where ji is 3 are prepared by combining the appropriate aryl hydrazine with the appropriate alkyl 2-oxocyclopentanecarboxylate in a suitable solvent such as toluene or chlorobenzene. The reaction is heated at reflux and water is simultaneously removed to yield a hydrazone. Cyclization to the pyrazolones 2 where is 3 is then effected by adding 1—3 equivalents of an alkali metal alkoxide such as sodium methoxide to the hydrazone solution and heating for 1—5 hours at 80—130°C.

Methods taught in Arch. Pharm. 267, 699—702 (1929) and in 2- Med.

Chem., 13. 773 (1970) are useful in preparing pyrazolones of formula 2 in which π = 3. - 12 crude reaction mixture is dissolved in an inert organic solvent (e.g., CHC13, CH2C12, or toluene), and the solution is washed with dilute aqueous base (e.g., NaOH or KOH) followed with water. The organic phase is dried, and the solvent is removed on a rotary evaporator or by distillation. The product obtained is the pyrazole of Formula I and may be purified by distillation, sublimation or crystallization from an appropriate solvent.

Compounds of Formula I where Q is iodine are prepared from corresponding aminopyrazoles via diazotization with nitrous acid and reaction with potassium iodide according to the method of Spanish Patent No. 394,208 {Chem. Abst., 83, 972834 (1975)}. The diazonium salt intermediate will contain a chloride, bisulfate, dihydrogen phosphate or other counter ion corresponding to the acid used for preparation of the diazonium salt. The required aminopyrazoles are prepared from the appropriate a-cyanocyclopentanone by reaction with appropriate aryl hydrazine in a solvent such as toluene. The overall sequence for preparing compounds of Formula I where Q is iodine is illustrated by equation A2 and Bz: Alternatively, the hydrazone may be isolated and subsequently cyclized by treatement with two equivalents of n-butyl lithium in a solvent such as THF at temperatures of 0—60°C for a period of 2—18 hours.

The pyrazolones 2 where £ is 3 are isolated by pouring the reaction mass into water, separating the organic layer and acidifying the aqueous layer with a mineral acid, i ,e., HC1, H2SOi,. From the acidified aqueous layer the desired product is obtained by filtration, centrifugation, extraction or other similar techniques.

The novel cycloalkanopyrazoles of Formula I where Q is chlorine are obtained by heating the annelated pyrazolones 2 with phosphorus oxychloride (formula 4, Q is chlorine). When Q is bromine in Formula 1, phosphorous oxybronride (formula 4, Q is bromine) in the presence of an N,N-dia1ky1aniline and dimethylformamide is used (Equation B).

The use of an inert organic solvent such as methylene chloride or toluene is optional; however, it is preferred that no solvent other than the phosphorous oxychloride or bromide is used. At least one equivalent of the oxyhalide reagent will generally be used. The mixture is heated at 100—180°C, preferably 140—150°C., for a period of 1—10 hours. The - 13 4 3 7 7 6 The required α-cyanoketones can be prepared by a number of methods well known in the art. For example, α-cyanocyclohexanone is prepared from α-chlorocyclohexanone and sodium cyanide according to R. Meyer in Helv. Chim. Acta. 16, 1921 (1933). α-Cyanocyclopentanone is prepared from adiponitrile and a strong base such as a lithium dialkylamide followed by acid hydrolysis according to German Patent No. 591 ,269 (dan., 1934) tC.A. 28, 117 (1934)}. u-Cyanocycloaliphatic ketones can also be prepared from cycloalkanone enamines and cyanogen chloride according to the method of Μ. E. Kuehne, 2· Am. Chem. Soc., 81 , 5400 (1959).

Compounds of Formula I where Q is fluorine are prepared as shown in equations A3 and B3 from decomposition (especially photolysis) of corresponding 3-diazonium fluoborate (equation S3) which in turn are obtained by diazotization of 3-aminopyrazoles with nitrous acid in fluoboric acid (equation A3) according to the method of E. D. Bergmann, £· Am. Chem. Soc., 78, 6037 (1956).

A3 and B3 - 15 .37 7 6 Intermediate β-keto esters 2 are commercially available or are prepared by methods well described in the literature: G. Stork et al., J. Am. Chem. Soc., 85, 207 (1963). The general procedure is shown in Equations C, D and E: C.

Ri * \_y Rl /Vj o Ri Hi \ + R0C-C1-+Al/ C O «W 8 _r Λ/·θκ \_y + HZO Enamine T_ is prepared by heating ketone £ and morpholine £ (pyrrolidine may also be used) in an appropriate solvent, such as benzene, toluene, or chlorobenzene, with simultaneous removal of water from the reaction by azeotropic distillation (Equation C). The alkyl chloroformate 8 is added to the enamine 1_, and this mixture is heated at a temperature from 70°C to the boiling point of the solvent for a period of 1—10 hours. The enamine hydrochloride TO which is produced as a by-product in the reaction - 16 4 S 7 7 6 is removed by filtration. The morpholine enamine £, which is contained in the organic filtrate, is converted to the β-keto ester 2 by hydrolysis with aqueous mineral acid (e.g., hydrochloric acid) at temperatures ranging from ambient to 75°C (Equation E). The product is isolated by conventional techniques such as extraction into a suitable organic solvent followed by evaporation of the solvent. The product may be further purified by fractional distillation under reduced pressure, sublimation, or crystallization.

The use of 3-methylcyclohexanone 5a leads to a mixture of methyl10 substituted β-keto esters (2a and 2b). If this mixture of methyl-substituted β-keto esters is reacted with an aryl hydrazine, a mixture of 4and 6-methyl-substituted-2-aryl-l,2,4,5,6,7-hexahydro-3H-indazol-3-ones (k> and 3b) is produced; subsequent treatment with phosphorous oxyhalide 4 will produce a mixture containing both the 4- and 6-methyl-substituted15 3-halo-2-aryl-tetrahydroindazoles of this invention. If the mixture of isomeric methyl cyclohexanones is separated, then 2a and 2b will lead to 3a and 3b respectively when treated with an aryl hydrazine.

In the case of the 2- or 4-metbylcyclohexanones, the g-keto ester synthesis is more specific and predominately one isomer is produced, as summarized schematically in Equations F and G. 2-Methylcyclohexanone produces 7-methyl-3-ha1o-2-aryl-4,5,6,7-tetrahydroindazole, and 4-methylcyclohexanone produces 5-methyl-3-halo-4,5,6,7-tetrahydroi ndazoles.

The required alkyl-2-oxocyclopentanecarboxylates can be prepared by methods previously described and by method described in Organic Reactions, , 1—203 (1967).

The preparation of aryl hydrazines 1_ from anilines is well documented - 18 4 3 7 7 5 in the literature: G. H. Coleman, Organic Syntheses, Col 1. Vol. J. Wiley & Sons, New York, p. 442 and H. Kindler et al., French Patent No. 1,419,092. A general procedure is illustrated in Equation H: in aqueous acid (HA, where A is defined as above) such as hydrochloric acid; the resulting solution is mixed with an aqueous sodium bisulfite solution at 0—20°C, heated to 50—80°C for 0.5—2 hr. and then acidified with the mineral acid to give the aryl hydrazine acid salt _l_. The hy10 drazine salt often crystallizes directly from the reaction mixture and can be isolated by filtration or by other conventional techniques. In most instances the hydrazine can be used without further purification.

Certain hydrazines used in preparing compounds defined by this invention are novel; e.g., 4-chloro-2-fluorophenylhydrazine hydrochloride is a novel compound which can be prepared by the method described above. The following novel hydrazines can also be prepared by this method: 4-bromo-2-fluorophenylhydrazine hydrochloride 2-f1uoro-4-methoxyphenylhydrazine hydrochloride 2,4,6-tri f1uorophenylhydrazi ne hydrochlori de 2-fluoro-4-nitrophenylhydrazine hydrochloride 4-cyano-2-fluorophenylhydrazi ne hydrochlori de - 19 Also useful for preparing aryl hydrazines is the method described by M. S. Gibson et al., k Chem. Soc.(C) 1970, 2106 and M. S. Gibson et aL, J. Chem. Soc. (C), 1974, 215.

Representative aniline starting materials for these hydrazines are 5 prepared as described below, 4-Chloro-2-fluoroaniline, for example, can be prepared from 2Z - fluoroacetanilide {G. Schiemann and H. G. Baumaarten, Chem. Berichte, 70, 1416 (1937)} by the reaction sequences shown below: - 20 Step A Chlorination of acetanilides in acetic acid is well known to those skilled in the art and may be carried out under the conditions taught in W. W. Reed and K. J. P. Orton, J. Chem. Soc., 91, 1543 (1907) for the chlorination of acetanilide. The chlorination of 2••-fluoroacetanilide takes place at 25—30°C over several hours (e.g. 5) at atmospheric pressure. The resulting product is 4''-chloro-2>-fluoroacetanilide.

Step B The chlorofluoroacetanilide is refluxed in a mixture of a lower alco10 hoi (50%) (e.g. ethanol) and concentrated hydrochloric acid (50%) for several hours (e.g, 5 or more) at 70—90°C and atmospheric pressure. The solvent mixture is removed at a reduced pressure of 100 to 300 mm. Hg and at a temperature of 20—50°C to leave a residue of the hydrochloride salt of 4-chloro-2-fluoroaniline.

Step C After basification of an aqueous solution of the hydrochloride salt of 4-chloro-2-fluoroaniline with an alkali metal hydroxide solution, such as 50% sodium hydroxide at ambient conditions, the free 4-chloro-2-fluoroaniline is extracted into a suitable water-immiscible organic solvent such as ethyl ether or methylene chloride. Crude 4-chloro-2-fluoroaniline is isolated by removal of the organic solvent under a reduced pressure of 100 to 300 mm. Hg at 20—50°C. 2-Fluoro-4-bromoaniline can be prepared by bromination of 2-fluoroaniline {prepared in Chem. Berichte, 70, 1416 (1937)} with N-bromosuccin25 imide as shown in the following equation. - 21 10 Bromination of anilines using N-bromosuccinimide in an inert organic solvent such as methylene chloride is well known to those skilled in the art, e.g., J. B. Wommack et al_., £. Het. Chem., 5, 243 (1959). Bromination of 2-fluoroaniline is an exothermic reaction that takes place at 0°C over several hours, e.g. 5 or more. The resulting reaction mixture is washed with water several times and dried with an appropriate drying agent such as anhydrous sodium sulfate. The 4-bromo-2-fluoroaniline is recovered by removal of the organic solvent under a reduced pressure of 100 to 300 mm.

Hg at 20—50°C. 2,4,6-Trifluoroaniline is prepared by reduction of 1,3,5-trifluoro2-nitrobenzene (V. I. Siele and H. J. Matsugama, U.S. Department Commerce, Office Serv., P. B. Rept. 145, 510, p.l (1950) or Chem. Abst., 56, 15394c (1962) using the procedures described by G. Schiemann and M. Seyhan, Chem. Berichte, 70, 2396 (1937). - 22 2,4-Difluoroaniline is known to the art and can be prepared by the procedure described in 6. Scheimann and M. Seyhan Chem. Berichte, 70, 2396 (1937). 4-Amino-3-fluorobenzonitrile, used in the preparation of 4-cyano-25 fluorophenyl hydrazine hydrochloride, can be prepared from 4-bromo-2-fluoroaniline by treatment with cuprous cyanide in N-methylpyrrolidone using known procedures: L. Friedman, et al., £. Org. Chem., 26, 2522 (1961).

The reaction mixture is heated to reflux for several hours and then poured onto ice and sodium cyanide. The resulting solution is heated between 50—80°C for a period of 1—3 hours, cooled, and extracted with toluene; the toluene extract is washed with water, dried with a suitable drying agent, and evaporated to give 4-amino-3-fluorobenzonitrile. 2-Fluoro-4-methoxyam'line, used in the preparation of 2-fluoro-4methoxyphenylhydrazine hydrochloride, is known and can be prepared by the method of H. Hodgson, et al_., J. Chem. Soc., 1268 (1940). 2-Fluoro-4-nitroaniline, used to prepare 2-fluoro-4-nitrophenylhydrazine hydrochloride, is also a known compound and can be prepared according to the method of U.S. Patent 2,436,100.

The following examples further illustrate the method for synthesis of compounds of this invention. All parts are by weight and all temperatures in degrees centigrade.

Example 1.

Preparation of 3 - Chloro -2-(4- chloro - 2 - fluorophenyl) - 4,5,6,7 tetrahydro - 2H - indazole Cl - 23 *3776 (a) Preparation of 4-Chloro-2-fluoroaniline Seventy-one parts of liquid chlorine were added to a solution of 140 parts of 2''-fluoroacetanilide in 500 parts glacial acetic acid, during one hour, at 25—27°, with ice-water cooling. While stirring for 4 hours at 25—27°, 4'-chloro-2'-fluoroacetanilide precipitated. After collecting the product by filtration, the filtrate was poured over 2000 parts of ice. The resulting second portion of precipitated product was collected by filtration, combined with the first portion and recrystallized from 700 parts of methanol at -45° to yield Π9 parts of 4>-chloro-2z-fluoroacetanilide as white crystals melting at 152—155°.

A mixture of 119 parts of 4'-chloro-2'-fluoroacetanilide in 475 parts of ethanol and 200 parts of 37% hydrochloric acid was refluxed for 17 hours and the solvent removed under a reduced pressure of 300 mm. Hg to yield the moist, solid hydrochloride salt of 4-chloro-2-fluoroaniline.

The moist, solid hydrochloride salt of 4-chloro-2-fluoroaniline was cooled to 10° in an ice-acetone bath and 50% aqueous sodium hydroxide was added dropwise, with stirring, until pH 11 was obtained. The resulting two-phase mixture was extracted four times; 500 parts of methylene chloride was used for each extraction. The combined organic extracts were dried with anhydrous sodium sulfate and the solvent removed under a reduced pressure of 300 mm. Hg to leave 89 parts of light brown, oily 4-chloro-2fluoroaniline, nQ25 = 1.5541. (b) Preparation of 4-Chloro-2-fluorophenylhydrazine Hydrochloride .0 Parts of 4-chloro-2-fluoroani1ine was dissolved in 80 parts of water and 34 parts of concentrated hydrochloric acid. The solution was - 24 43776 cooled to 0—10° and 32.2 parts of 30% sodium nitrite was added dropwise maintaining the temperature of the reaction between 0—10°. After the addition of nitrite was completed, the solution was stirred for thirty minutes at 0—10°. Excess nitrite was destroyed by addition of small amounts of sulfamic acid. When a negative test with sulfone reagent was obtained, the diazonium salt was ready for reduction. For a description of the sulfone test, see Η. E. Fierz-David et al., Fundamental Process of Dye Chemistry translated from 5th Austrian Ed. by P. W. Wittam, Interscience Publishers, Inc., New York, 1949, p.243.

In a separate vessel 35.4 parts of sodium bisulfite and 32.2 parts of % sodium hydroxide solution were dissolved in 140 parts of water. The solution was heated to 40°. The diazonium salt was added to the bisulfite solution over a period of about 1 hour. The mixture was heated to 70° and 0.3 parts of sodium hydrosulfite was added. The pH was adjusted to 1.2 with 30 parts of concentrated hydrochloric acid; then an additional parts of concentrated hydrochloric acid was added. The reaction mixture was heated for 1.5 hours at 70°, cooled slowly, and stirred overnight at room temperature.

Purification was achieved by heating the reaction mixture to 70° and filtering. The filtrate was cooled to 10° at which time 4-chloro-2fluorophenylhydrazine hydrochloride precipitated. This product was filtered and dried to yield 10.7 parts of yellow crystalline solid, m.p. 223°. (c) Preparation of 2 - (4 - Chloro - 2 - fluorophenyl) - 1,2,4,5,6,7 hexahydro - 3H - indazol - 3 - one .8 Parts of 2-fluoro-4-chloropheny1hydrazine hydrochloride, 13 parts - 25 1377 6 of 2-carbethoxycyclohexanone (purchased from Aldrich Chemical Company) and 8.1 parts of triethylamine were dissolved in 100 parts of ethanol.

The reactants were heated at reflux for twenty-four hours. The crude reaction mass was poured into 1000 parts of water. The resulting gummy pro5 duce solidified and was filtered and dried to yield 16.1 parts of crude product with m.p. 163—170°. This material was used without further purification in the next step.

By substituting 4-chlorophenylhydrazine hydrochloride in the above procedure for 4-chloro-2-fluorophenylhydrazine hydrochloride, 2-(4-chloro10 phenyl)-!,2,4,5,6,7-hexahydro-3H-indazol-3-one was prepared, m.p. 183.5— 185° (Lit 186—187°, Chem. Abs., 67, T1452h). (d) Preparation of 3 - Chloro -2-(4- chloro - 2 - fluorophenyl) 4,5,6,7 - tetrahydro - 2H - indazole .0 Parts of 2-(4-ch1oro-2-fluorophenyl)-1,2,4,5,6,7-hexahydro-3H15 indazol-3-one and 7.3 parts of phosphorous oxychloride were mixed and heated to 130°—150° for six hours. The reaction mixture was dissolved in 100 parts of chloroform. The organic solution containing the product was washed successively with three portions of 25 parts each of 10% sodium hydroxide and then washed with 50 parts water. The chloroform solution was dried with 2—10 parts of anhydrous sodium sulfate and then filtered.

The solvent was removed under a reduced pressure on a rotary evaporator.

The resulting thick oil was purified by sublimation at 100—120° at 0.5— 1.5 nrn. pressure to yield 7.8 parts of white crystalline material with m.p. 88—89.5°, Preparations of other novel anilines used in this invention are as follows: - 26 Preparation of 4-Bromo-2-fluoroaniline 160 Parts of solid N-bromosuccinimide were added in portions over a 2-hour period to a solution of 100 parts of 2-fluoroaniline in 400 parts of methylene chloride cooled to 0°. After stirring for 20 minutes, the dark red mixture was washed four times; 200 parts of cold water were used for each washing. The red organic phase was dried with anhydrous sodium sulfate and evaporated under 300 mm. Hg to 164 parts of brown, oily 4bromo-2-fluoroaniline, n^25: 1.5885.

Preparation of 4-Amino-3-fluorobenzonitrile 6.8 Parts of 4-bromo-2-fluoroaniline were dissolved in 75 parts of N-methylpyrrolidone. This solution was treated with 4.2 parts of cuprous cyanide. The reaction mixture was heated to 190° for 2 hours.

The reaction mass was poured onto a mixture of 200 parts of ice and 15 parts of sodium cyanide. This mixture was then heated on a steam bath for 2 hours at 60—70°. This aqueous solution was then extracted with four 100 ml portions of toluene. The toluene extracts were combined and washed with four 300-ml portions of water followed by 100 ml of saturated NaCl. The toluene solution of the product was dried over sodium sulfate and stripped to give 2.6 parts of the desired product, m.p. 71—73°.

Using the procedure of Example 1 with 2-carbethoxycyclohexanone, the appropriate hydrazine acid salt and phosphorous oxychloride, the following compounds of Formula I are prepared: 7 6 Q Y X V Z m.p.°C Cl H Cl H H 81—84° Cl H Br H H 86—88° Cl H N02 • H H 103—105° 5 Cl H ch3o H H oil, ir bands (760 cm'1, 835 cm*1) Cl Cl Cl H H oil, ir bands (735 cm*1, 820 cm1) Cl H Cl Cl H 69—71° 10 Cl H F Cl H 70—72° Cl F Br . H H 86—88° Ci F CH30 H H Cl F no2 H H 108—109.5° Cl F CN H K 113—116° 15 Cl F F H H nDz5=1.5587 Cl Cl Cl Cl H 101—105° Cl H Br Cl H Cl H CN H H 104—106.5° Cl H F Cl H 70—72° 20 Cl H F H H 35—37° Cl Cl Br H H 78—79° Cl F I H H 83.5—87° Cl Cl Cl H F 93.5—101° Cl F F H F - 57.5—62° 25 Cl Cl F H H 75—78.5° C 7 7 6 Q Y X V z m.p.°C Cl H I H H 91—103' Cl Cl Cl 0CH3 H 107—1101 Cl F Cl Cl H Using the procedure of Example 1 with a methyl substituted 2-carbethoxycyclohexanone, the appropriate aryl hydrazine, and phosphorous oxy chloride, the following compounds may be prepared: Ri Q Y X V Z m.p.°C 10 7_CH3- Cl F F F H 7-CH3- Cl F F H F 7-CH3- Cl F Cl H H 58-61.5° 7—CH3— Cl F Br H H 7—CH3— Cl F F H H 15 7—CH3— Cl H Cl H H ir bands 1570 7_CH3- Cl H 0CH3 H H nD25 1.5839 7—CH3— Cl F F H F 5—CHj- Cl F Cl H H 85—88° &——CH 3— Cl H Cl H H 96.5—99° 20 6—CHy- Cl F Cl H H 43.5—44.5° Ri Q Y X V z m.p.°C 6—CH3 6—CH3— Cl Cl F H I Cl H Cl H H ir bands 1600, 870, 825 6—CH3- Cl H C1 H H 75—76° 5 6—CH3— Cl H CN H H 103—105° CH3— Cl H och3 H H ηθ25 = 1.5839 6—CH3— Cl H no2 H H 89—91.5° f4-CHj- [6—CH3- f4_CH3 Cl H Cl H H 47.5—52° for mixture10 (6-CH3 Cl F 'Cl H H 41—45° for mixture 6—CH3- Cl F I H H 6—CH3— Cl Cl Cl och3 H Example 2.

Preparation of 3 - Chloro -2-(4- chlorophenyl) - 2,4,5,6,7,8 - hexa· hydrocycloheptapyrazole By substituting 2-carbethoxycycloheptanone {prepared by the method of G. Stork, et al., Am. Chem. Soc., 85, 207 (1963)} and p-chlorophenyl20 hydrazine hydrochloride (available from Aldrich Chemical Company) in the procedure of Example i(c), 2-(4-chlorophenyl)-l,4,5,6,7,8-hexahydrocyclo- 30 f c 6 heptapyrazol-3(2H)-one (m.p. 224—225°) was prepared. By reacting this pyrazolone with phosphorous oxychloride according to the procedure of Example 1(d), 3-chloro-2-(4-chlorophenyl)-2,4,5,6,7,8-hexahydrocyclohepta pyrazole (m.p. 59—61°) was obtained.

Following the procedure of Example 2, using the appropriate aryl hydrazine hydrochloride (for p-chl orophenyl hydrazine hydrochloride) and phosphorous oxychloride, the following compounds of Formula 1 may be pre- 4S776 Example 3. (a) Preparation of 2 - (4 - chloro - 2 - f1uorophenyl) - 1,4,5,6 - tetrahydrocyclopentapyrazol - 3(2H) - one 7.5 Parts of 4-ch1oro-2-fluorophenylhydrazine and 6.6 parts of methyl 5 2-oxocyclopentanecarboxylate (purchased from Aldrich Chemical Company) were dissolved in 200 parts toluene. The reactants were heated at reflux for 1—2 hours removing water that was formed. The reaction mixture was cooled to 100°C., and a solution of 5.0 parts of sodium methoxide dissolved in 25 parts methanol was added dropwise, removing methanol as its azeotrope with toluene. The reaction mixture was heated until the internal temperature reached 110°. The reaction was then cooled and poured into 200 parts ice water. The organic layer was separated, and the aqueous layer was washed twice with diethyl ether. Cold, dilute hydrochloric acid was added, with stirring, to the aqueous layer until pH 2 was reached. The resulting oily product solidified and was filtered, dried and recrystallized from acetonitrile to yield 3.3 parts of tan crystalline material, m.p. 157—160°.

Alternatively, the above pyrazolone was prepared by the following procedure. 16.0 Parts of 4-chloro-2-fluorophenylhydrazine and 14.2 parts of methyl 2-oxocyclopentanecarboxylate were dissolved in 100 parts of benzene. The reaction mixture was refluxed for 1—2 hours removing water that was formed. The reaction mixture was cooled, and the solvent was removed under reduced pressure on a rotary evaporator. The resulting brown oil was dissolved in 150 parts of anhydrous tetrahydrofuran and the solution !5 was cooled to 0° uhder a nitrogen atmosphere. To the cold reaction solu- 32 43776 tion, 2 equivalents of ji-butyl 1 i thi urn in hexane (purchased from Foote Mineral Company) were added at such a rate that internal temperature was maintained at 0—5°. The reaction mixture was allowed to warm to ambient temperature, then heated at reflux for 18 hours. The reaction mixture was cooled and poured into 200 parts ice water. The organic layer was separated, and the aqueous layer was washed twice with diethyl ether. Cold, dilute hydrochloric acid was added to the aqueous layer until pH 2 was attained. The resulting oily product solidified, and was filtered, dried, and recrystallized from acetonitrile to yield 17.5 parts of tan crystalline material, m.p. 165—167°.

By substituting 4-chlorphenylhydrazine in the former procedure for 4-chloro-2-f 1 uorophenylhydrazine, 2-(4-chlorophenyl)-1,4,5,6-tetrahydrocyclopentapyrazol-3(2H)-one was prepared, m.p. 193.5—195°. (b) Preparation of 3 - chloro -2-(4- chloro - 2 - fluorophenyl) 15 2,4,5,6 - tetrahydrocyclopentapyrazole By reacting 2-(4-chloro-2-fluorophenyl)-1,4,5,6-tetrahydrocyclopentapyrazol-3(2H)-one with phosphorous oxychloride according to the procedure of Example 1(d), 3-chloro-2-(4-chloro-2-f1uorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole (m.p. 102—104°) was obtained.

Using the procedure of Example 3 with the appropriate methyl substituted 2-oxocyclopentanecarboxylate, the appropriate hydrazine and phosphorous oxychloride, the following compounds of Formula I can be prepared: - 33 4 37'· 6 Ri Y X V Z m.p.°C Η H Cl H H 114.5—117° Η Cl Cl H H 119—123° Η H Br H H 120—121° Η Cl Br H H 113—119° Η F Br H H 105—106.5° Η F F H H 110—119° Η H F H H 57—60° Η F F H F Η Cl Cl Cl H Η H Br Cl H Η F CH30 H H Η F no2 H H Η F CN H H H H . CH30 H H Η H no2 H H Η H CN H H 126.5—128° Η H Cl Cl H 95—98° Η H F Cl H 4——CH3 F Cl H H 4—CH3 H Cl H H fc-CH3 F Cl H ir bands 159 [4—ch3 F Cl H ϋ 990 cm-1 5—CH3 H Cl H H 6—CH3 H Cl H H 34 - Rt Y X V Z m.p. °C 6-ΐΗ3 H F Cl Η H 88—93° F I Η H H 7—CH3 Cl Cl 0CH3 H F Cl Η H Example 4.

Preparation of 3-bromo-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H indazole To 5.0 parts of 2-(4-chlorophenyl)-l,2,4,5,6,7-hexahydro-3H-indazol10 3-one {from Example 1(c)} with 3.0 parts of Ν,Ν-diethylaniline and 5.0 parts of dimethylformamide under nitrogen atmosphere was added 6.3 parts of phosphorous oxybromide. The mixture was heated to 130—170° for two hours. After cooling to room temperature, the reaction mixture was extracted with 100 parts of diethyl ether, washed with water, dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator. Re crystallization from methanol/water gave 2.7 parts of product, m.p. 101— 102°.

Using the procedure of Example 4 with the appropriate annelated pyra zolones 2, which can be prepared by a method taught in Example 1 or Example 3, the following compounds can be prepared: - 35 43775 η Ri Υ X V Z m.p. °C 3 Η F C1 H H 106—110° 3 Η Η C1 Cl H 3 Η Η Cl H . H 109—112° 5 3 Η C1 . C1 H H 3 Η F F H H 3 Η F F H F 3 Η F Br H H 3 4—CH3 F Cl H H 3 3 6—CH3 F Cl H H 3 Η F CH3O H H 3 Η F no2 H H 3 Η F CN H H 4 Η F Cl H H 95—98° 5 4 Η F Br H H 4 Η F F H H 4 Η C1 Cl H H 101—102° 4 Η F F H F 4 Η F CH30 H H 0 4 Η F no2 H H 4 Η F CN H H 4 Η Η no2 H H 4 Η Η Br H H 84—87° 4 Η Η F H H 70—73° 5 4 Η Η CH30 H H - 36 m.p. °C H H —CH3 H H H 7—CH 3 H H Cl H H 0CH3 F H H H H H H H F F Cl F F H F H H CN Cl Cl I Cl F Cl H F Cl Η H 59—60 Η H Cl Η H CH3O Example 5.

Preparation of 3-iodo-2-(4-chlorophenyl)-4,5,6,7~tetrahydro-2H-indazole (a) Preparation of 3-amino-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole A mixture of 3.6 parts of 4-chlorophenylhydrazine and 2.0 parts of triethylamine in 20.0 parts of toluene was stirred at room temperature for fifteen minutes. To the mixture was added 2.5 parts of 2-cyanocyclohexanone, prepared from commercial 2-chlorocyclohexanone and potassium cyanide {von R. E. Meyer, Helv. Chim. Acta., T6, 1291 (1933)}, and a few drops of acetic acid. After refluxing for two hours, followed by stirring at room temperature overnight, the reaction mixture was evaporated to remove toluene and was treated with water, extracted with diethyl ether, dried over anhydrous magnesium sulfate and concentrated. Recrystal lizati on from ethanol/water gave 2.6 parts of the compound, m.p. 140—142°. - 37 '{7 6 (b) Preparation of 3-iodo-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2Hindazole ’ ’ To 2.5 parts of 3-amino-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2Hindazole in 2.5 parts of cone, sulfuric acid and 15 parts of water cooled to 0° was added dropwise a solution of 0.8 parts of sodium nitrite in 5.0 parts of water and the mixture was stirred for one and a half hours. Excess nitrous acid was destroyed using sulfamic acid. 1.7 Parts of potassium iodide in 5.0 parts of water was then added slowly to the diazonium solution. After stirring at 0—25° for two hours, the precipitate was collected by filtration and dried. RecrystaTlization from ethanol/ water gave 1.7 parts of the product, m.p. 83° (decomp.).

Using the method of Example 5 with the appropriate a-cyanoketone which is conveniently prepared by reacting the appropriate a-chlorocyclohexanone or ο-chlorocyclopentanone with sodium cyanide. According to the method of Meyer, Helv. Chint. Acta., J6, 1291 (1933), the following compounds of Formula I can be prepared: H 3 H H F Cl Η H 106°d H Cl Η H F Br H H - 38 43776 n Ri Y X V Z m.p. °C 3 H F F H H 3 H F CH30 H H 3 H F no2 H H 3 H F CN H H 4 H F Cl H H 133—135° 4 H F Br H H 4 H F F H H 4 H H CH30 H H 4 H H no2 H H 4 H H CN H H 4 H F I Example 6. H H Preparation of 3 - fluoro -2-(4- chloro - ; 2 - fluorophenyl) - 4,5,6,7 - tetrahydro - 2H - indazole (a) Preparation of 2 - (4 - chloro - 2 - fluorophenyl) - 4,5,6,7 - tetrahydro - 2H - indazole - 3 - diazonium fluoborate To 50 parts of 48% fluoboric acid at 0—5° was added simultaneously a solution of 2.5 parts of sodium nitrite in 10 parts of water and a suspension of 8.7 parts of 3-amino-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazo1e in 30 parts of acetic acid in small portions, so that the mixture always contained an excess of nitrite {E. D. Bergmann, S. Berkovic and R. Ikan, J. Am. Chem. Soc. 78, 6037 (1956)}. After the addition, the reaction mixture was stirred at 0—10° for one hour and 10— 25° for half an hour. Excess nitrous acid was destroyed using sulfamic - 39 377 6 acid. The precipitates were collected, washed with water, ethyl ether and dried, yielding 9.0 parts of the product. The ir indicated that no amino compound was left and it showed —N2 absorption at 2200 cm-1. The compound was used without further recrystallization. (b) Preparation of 3 - fluoro -2-(4- chloro - 2 - fluorophenyl) 4,5,6,7 - tetrahydro - 2H - indazole A mixture of 9.0 parts of 2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole-3-diazonium fluoborate and 10 parts of potassium fluoride in 100 parts of fluoboric acid was photolyzed by a 200 W Hanovia (resistered Trade Mark) high pressure mercury-vapor lamp at 0° for one hour and at room temperature for fifteen hours. The reaction mixture was extracted with ether, washed with water, dried over anhydrous magnesium sulfate and concentrated. The .desired product was isolated by dry-column chromatography (silica gel eluted with methylene chloride), preparative thin layer chromatography (silica gel developed with 5 parts of EtzO: 100 parts of hexane) and preparative gas chromatography {15% 0V—17 on 80/100 mesh Chromosorb (Trade Mark) W HP at 250°). The product was shown to be pure by GC and was analyzed by mass spectroscopy (M* = 268 and ra/e + 240 due to the loss of C2Ht,). nmr 4 1.5 (m, 4H), 2.0—2.2 (2t, 4H), and 7.0 (m, 3H).

Using the method of Example 6 with the appropriate 3-amino compound (Example 5a), the following compounds can be prepared: - 40 43776 n Ri Y X V Z 3 H F Cl H H 3 H H Cl H H 3 H F Br H H 3 H F CN H H 3 H F CH30 H H 3 H H Br H H 3 H H CN H H 4 H H Cl H H 10 4 H F Br H H 4 H F CN H H 4 H F CH30 H H 4 H H Br H H 4 H F N02 H H 15 4 H F Formulations I H H Useful formulations of the compounds of Formula I indue granules, pellets, solutions, suspensions, emulsions, wettable powders and emulsifiable concentrates. Many of these may be applied directly.

Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain for example 0.05% to 99% by weight of active ingredient(s) and at least one of (a) 0.1% to 20% surfact25 ant(s) and (b) 1% to 99.95% solid or liquid diluent(s). More specifically, - 41 4 3 7 7 6 they will usually contain these ingredients in the following approximate proportions: Percent by Weight Active Ingredient Diluent(s) Surfactant(s) Wettable Powders 5—90 T—94 1—10 Oil Suspensions, Emulsions, Solutions (including Emulsifiable Concentrates) 5—50 40—95 0—15 10 Aqueous Suspensions 5—50 40—94 1—20 Dusts 0.05—25 70—99.95 0-5 Granules and Pellets 0.05—95 1—99.95 0—15 High Strength Compositions 90—99 0—10 0—2 Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Edn., Dorland Books, !0 Caldwell, N.J. Suitable diluents include finely divided or granular solids classified as attapulgites, botanicals, calcites, diatomites, dolomites, gypsum, kaolinites, limestones, mica, montmorillonoids, phosphates, pyrophyllites, sulfur, sand, talcs, tripolites, vermiculite, and synthetics These synthetics can include precipitated hydrated silicon dioxide, pre- 42 cipitated hydrated calcium silicate, precipitated calcium carbonate and synthetic organics. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Edn., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. McCutcheon's Detergents and Emulsifiers 1975 Annual, MC Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion or microbiological growth, or to mark visually the area that has been treated.

It is sometimes desirable to add ingredients to reduce the volatility of some of the compounds of this invention. Those additives can include film forming materials such as polyvinylpyrrolidones of molecular weights e.g. from 20,000 to 100,000; polyvinyl alcohols of molecular weights e.g. from 20,000 to 150,000; and polyoxyethylenes of molecular weights e.g. from 100,000 to 6 x 106. These are a few examples of film forming additives. Any material which forms a film over solid active ingredient in the formulation preparation or a film over the active ingredient when sprayed and dried from a liquid formulation can be used. Other methods to reduce volatility may include the incorporation of the compounds of this invention into resins, waxes, gums or rubbers, and then preparing formulations, as has been described above, for these combinations.

Solutions are prepared by simply mixing the ingredients. Fine solid - 43 437 7 6 compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. Patent 3,060,084).

Granules may be made in several ways. For example, the active in5 gredient may be sprayed onto preformed granular carriers. Suitable preformed granuTar carriers include those suitable diluents listed earlier having a particle size range from USS Sieve No. 200 (74 microns) to USS Sieve No. 10 (2000 microns). The preferred particle size is from USS Sieve No. 140 (105 micron) to USS Sieve No. 20 (840 microns). Depending upon the nature of the carrier, the active ingredient may remain on the surface of the carrier or be absorbed into the carrier. Usually when the active ingredient remains on the Surface of the carrier, a binding agent is used to hold the active ingredient on the surface. The binding agent should bind the active ingredient to the surface well enough so that not more than 10% of the active ingredient is removed during normal shipping and handling operations. Suitable binding agents include materials which are at least partially soluble in any liquid used in the manufacture of the granules and which adhere to the granular surface. Water-soluble binders are preferred. Suitable binders include, but are not limited to, Ό water-soluble polymers such as polyvinyl alcohols of molecular weights from 20,000 to 150,000; polyvinylpyrrolidones of molecular weights from 20,000 to 100,000; and polyoxyethylenes of molecular weights from 100,000 to 6 x 105. Other suitable binders include, ligninsulfonates, starches, sugars, and certain surface active agents listed in McCutcheons' Detergents and :5 Emulsifiers 1975 Annual, M.C. Publ. Corp., Ridgewood, New Jersey. - 44 The active ingredient may be sprayed as a solution in a suibable solvent, which may or may not be removed from the formulation. If the active ingredient is a liquid, it may be sprayed onto or mixed with the carrier directly.

If it is a solid, it may be melted and applied directly as a liquid. If very low strength granuels are desired, the active ingredient may be vaporized onto the carrier. Granules may also be prepared by agglomeration techniques.

For example, the active ingredient and a finely divided solid diluent may be mixed and agglomerated by techniques known in the art such as spraying with a liquid in a fluidized bed or pan granulator. The active ingredient and diluent may also be mixed with other formulation ingredients and pelletized. The pellets may then be crushed to a desired granular size. Pellets may be made by agglomeration techniques. See J. E. Browning, Agglomeration. Chemical Engineering, Dec. 4, 1967, pp. 147ff. and Perry's Chemical Engineer's Handbook. 4th Edn., McGraw-Hill, N.Y., 1963, pp. 8~ 59ff.

For further information regarding the art of formulation, see for example: Η. M. Loux, U.S. Patent 3,235,361, Feb. 15, 1966, Col. 6, Line 16 to Col. 7, Line 19 and Examples 10 to 41.

R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5 Line to Col. 7 Line 62 and Ex. 8,12, 15, 39, 41, 52, 53, 58, 132, 138— 140, 162—164, 166, 167, 169—182.

H. Gysin and E. Kniisli, U.S. Patent 2,891,855, June 23, 1959, Col. 3 Line 66 to Col. 5 Line 17 and Examples 1—4.

G. C. Klingman, Weed Control as a Science, John Wiley & Sons, Inc., - 45 λ Ο r? W Π ii ( ί Ο New York, 1961 pp. 81—96.

J. D. Fryer and S. A. Evans, Weed Control Handbook, 5th Edn.

Blackwell Scientific Publications, Oxford, 1968, pp. 101—103.

Example 7.

Granule 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H indazole 10% attapulgite granules (low volatile matter, 0.71— 0.30 mm. diameter; i.e., U.S.S. # 25—50 mesh sieve size) 90% The active ingredient is warmed to approximately 90° and sprayed upon dedusted and pre-warmed attapulgite granules in a double cone blender. The granules are then allowed to cool and are packaged.

Example 8.

Solution 3-chloro-2-(2,4-di fluorophenyl)-4,5,6,7-tetrahydro2H-indazole 20% dimethylformamide 80% The ingredients are combined and stirred to produce a solution, which can be used for low-volume applications.

Example 9.

Extruded Pellet 3-chloro-2-(4-ch1oro-2-fluorophenyl)-4,5,6,7-tetrahydro - 46 4 3 7 7 6 2H-indazole 1% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% polyoxyethylene (4 x 106 average molecular wt.) 1% calcium/magnesium bentonite 82% The ingredients are blended, hammer milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm. diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm. openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm. openings) may be packaged for use and the fines recycled. All compounds of this invention may be formulated in this manner.

Example 10.

Emulsifiable Concentrate 3-chloro~2-(4-chloropheny1)-4,5,6,7-tetrahydro2H-1ndazole 25% blend of oil soluble sulfonates and polyoxy20 ethylene ethers 4% xylene 71% The ingredients are combined and stirred until solution is complete.

A fine screen filter is included in packaging operation to ensure the absence of any extraneous undissolved material in the product. - 47 . 2 7 7 6 Example Π.

Aqueous Suspension 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro2H-indazole 50.0% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1.0% monosodium phosphate 0.5% polyvinylalcohol 1.0% pentachlorophenol 0.4% water 46.3% The ingredients are ground together in a sand mill to produce particles essentially all under five microns in size.

Example 12.

Wettable Powder 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole 50% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 43% The ingredients are thoroughly blended, passed through an air mill to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S.. No. 50 sieve (0.3 mm. opening) before packaging. - 48 Example 13.

High-Strength Concentrate 3-chloro-2-(4-chloro-2-f 1uorophenyl)-4,5,6,7tetrahydro-2H-indazole 99% trimethyl nonyl polyethylene glycol ether 1% The surfactant is sprayed upon the active ingredient in a blender and the mixture sifted through a U.S.S. No. 40 sieve (0.42 mm. openings) prior to packagaing. The concentrate. ma.y be formulated further for practical use.

Example 14.

Low Strength Granule 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7tetrahydro-2H-indazole 0.5% polyvinylpyrrolidone 1 % attapulgite granules (low volatile matter; 0.59— 0,25 inm., i.e. USS #-30—60 mesh size) 98.5% Forty grams of a solution containing 2.5% 3-chloro-2-(4-ch1oro-2fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole and 5% polyvinylpyrrolidone dissolved in methyl alcohol are slowly atomized onto a fluidized bed of attapulgite granules (197 gm). Fluidization of the granules is continued after atomization is complete and until all the methyl alcohol is evaporated from the granules. The granules are packaged for use. - 49 Example 15.

Extruded Pellet 3-chloro-2-(4-ch1orophenyl)-2,4,5,5-tetrahydrocyclopentapyrazole 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesiuni bentonite 59% The ingredients are blended, hammer milled and moistened with about 0 10—-12% water. The mixture is then extruded as cylinders about 3 mm in diameter which are cut to be about 3 mm. long. These pellets may be used directly after drying or the dried pellets may be crushed to pass a USS 4 20 sieve (0.84 mm. opening). The pellets retained on a USS =#40 sieve (0.42 mm. openings) may be packaged for use and the fines re’ cycled.

Example 16.

Granule 3-chloro-2-(4-chloro-2-fluorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole 2% 1 attapulgite granules (low volatile matter; 0.71— 0.30 mm., i ,e. USS =$-25—50 mesh sieves) 98% The active ingredient is warmed to approximately 110° and sprayed upon the dedusted and prewarmed granules in a double cone blender. The granules are allowed to cool and are packaged for use. - 50 Example 17.

Low Strength Granule 3-chloro-2-(4-chlorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole 0,2% 5 anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% finely divided attapulgite clay 83.8% The ingredients are blended, hammer milled and placed in a fluidized 10 bed granulator. Water is aspirated into the fluidized bed of powder until small granules are formed. Water aspiration is then stopped but fluidization is continued to dry the formed granules. The granules are removed from the granulator and screened to pass a USS # 20 sieve (0.84 mm opening). Granules retained on a USS ^40 sieve (0.42 mm opening) are packaged for use. Granules larger than 0.84 mm are ground and recycled. Fines smaller than 0.42 mm are also recycled.

Example 18.

Extruded Pellet 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H20 indazole 0.1% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% polyoxyethylene (4 x 106 average molecular wt.) 1% calcium/magnesium bentonite 82.9% - 51 776 The ingredients are blended, hammer milled and then moistened with about 12% water. The moist mixture is extruded as cylinders about 1 mm. in diameter and about 2 mm. long. These small pellets are dried and packaged. They are applied directly.

Example 19.

Low Strength Granule 3-chl oro-2-(4-chloro-2-fluorophenyl )-4,5,6,7-tetrahydro2H-indazole 0.05% dimethylformamide 5% attapulgite granules (low volatile mater; 0.59—0.25 mm. i.e. USS # 30—60 mesh size) 94.95% One-tenth of a gram of 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7tetrahydro-2H-indazole is dissolved in 9.9 grams of dimethylformamide.

This solution is very slowly atomized onto 190.T grams of a rapidly tumbling bed of the attapulgite granules. After application of the active ingredient is complete, the formulation is blended for a few additional minutes. The dimethylformamide is not removed from the formulation. The granules are packaged for use.

Example 2Q.

Emulsifiable Concentrate 3-chloro-2-(4-ch1oro-2-f1uorophenyl)-4,5,6,7-tetrahydro2H-indazole 20% blend of oil-soluble sulfonate with polyoxyethylene ethers 6% - 52 4 3776 aromatic hydrocarbon solvent with a Tag closed cup flash point between 100 and 115°F 74% The ingredients are combined and stirred until solution is complete. The solution is filtered through a fine screen filter prior to packaging to remove any extraneous undissolved material.

Example 21.

Low Strength Granules 3-chloro-2-(4-chloro-2-f1uorophenyl)-4,5,6,7tetrahydro-2H-indazole 0.1% sodium ligninsulfonate 5% preformed sand granules having a particle size distribution from USS sieve No. 140 (105 microns) to USS sieve No. 50 (297 microns) 94,9% 0,5 gm. 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H15 indazole and 25 gm sodium ligninsulfonate are dissolved in 50 gm water.

This solution is slowly sprayed onto a tumbling bed of the sand granules (474.5 gins). After spraying is complete the tumbling granules are warmed to remove the water. The resulting granules are packaged for use.

Compositions can contain, in addition to the active ingredients of 20 this invention, other conventional agricultural chemicals such as fertilizers, plant growth modifiers or herbicides.

For example, the compounds of Formula I can be combined with the following herbicides: (1) 5-tert-butyl-3-(2,4-dich1oro-5-isopropoxyphenyl)-1,3,4-oxadiazo1-2 25 one; - 53 gT'θ (2) 6-methyl thi o-2,4-bis(ethyl amino)-s.-tri azine; (3) 3-isopropyl-(lH)-benzo-2,l ,3-thiodiazin-4-one-2,2-dioxide; (4) 2,4-dichlorophenoxyacetic acid and related esters and salts.

Combinations with wheat herbicides: (1) 2,4-dichlorophenoxyacetic acid and related esters and salts; (2) S^-(2,2,3-tri chi oroal lyl) -di i sopropyl thi ocarbamate; (3) Methyl 2-(4-(2,4-dichlorophenoxy(phenoxy)}-propanoate; (4) 1,2-dimethyl-3,5-diphenyl-lH-pyrazolium methyl sulfate; (5) 4-chloro-2-butynyl 3-chlorocarbanilate.

The compounds of Formula I can also be combined with other herbicides and are particularly useful in combination with bromacil {3-(sec-butyl)5-bromo-6-methyluracil}, diuron {3-(3,4-dichlorophenyl)-1, 1-dimethylurea}, 3- cycl ohexyl-1-methyl-6-dimethylamino-s-tri azi ne-2,4(1H,3H)-di one, paraquat {1,1'-dimethyl-4,4'-bipyridinum ion}, m-(3,3-dimethy1ureido) phenyl tert5 butyl carbamate, 2-methyl-4-chlorophenoxyacetic acid, its salts or esters, 4- ami no-6-tert-butyl-3-methylthi o-aS-tri azi n-5(4H)-one, aryl 4-ni trophenyl ethers such as 2,4,6-trichlorophenyl 4-nitrophenyl ether and 2,4-dichlorophenyl 4-nitrophenyl ether for controlling a broad spectrum of weeds.

The agricultural chemicals listed above are exemplary of the compounds which can be mixed with the active compounds and are not intended to limit the invention in any way.

Example 22.

For industrial use, a granule may be made from 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H> indazole 5% - 54 43776 3-cyclohexyl-1-methyl-6-dimethylami no-s-tri azi ne2,4(lH,3H)-dione 5% #25—50 attapulgite granules (low volatile matter, 0,71 mm.—0.30 mm. diameter) 90% The active ingredients are mixed and then warmed to approximately 90° and sprayed onto the dedusted and prewarmed granules in a double cone blender. The treated granules are then allowed to cool and are packaged.

Utility The compounds of Formula I are useful for the selective preemergence control of undesired vegetation, e.g., barnyardgrass, in crops such as rice, in particular paddy rice, wheat, and peanuts. These compounds also have utility for the postemergence control of weeds in certain crops, for example, rice. Furthermore, compounds of this invention can be used as directed treatments (i.e. treatments designed to minimise application to the crop plants) for the pre- or post-emergence control of weeds in various crops including soybeans, peanuts, cotton, garden beans and row-planted rice.

The compounds of this invention are useful for the control of weeds in transplanted crops such as rice, tobacco, tomatoes, cabbage, sweet potatoes, lettuce, celery, peppers, and eggplant. The treatment may be applied to the soil surface prior to transplanting and the crop transplanted through the treated soil or it may be soil incorporated prior to transplanting and the crop set in the treated soil. It may also be applied after the crop is transplanted if care is taken to keep the chemical off - 55 the crop foliage (Table IV).

The precise amount of the compounds of Formula I to be used in any given situation will vary according to many factors including the particular end result desired, the use involved, the crop and weed species, and soil involved, the formulation used, the mode of application, prevailing weather conditions and the foliage density. Since so many variables pTay a role, it is not possible to state a rate of application suitable for all situations. Broadly speaking, the compounds of the invention are used at levels of e.g. 0.015 to 15 kilograms per hectare, preferably 0.03 to kilograms per hectare. The lower rates in this range will generally be selected on lighter soils, soils low in organic matter content, for selective weed control in crops, or in situations where maximum persistence is not necessary.

Herbicidal activity of compounds of this invention was discovered in greenhouse tests, as explained below: Procedure Test I Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), Cassia tora, morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice, wheat and nutsedge tubers were planted in a growth medium and treated preemergence with the chemicals dissolved in a non-phytotoxic solvent. At the same time, cotton having five leaves (including cotyledonary ones), bush beans with the third trifoliolate leaf expanding, crabgrass with two leaves, barnyardgrass with two leaves, wild oats with one leaf, cassia with three leaves (including I cotyledonary ones), morningglory with four leaves (including the cotyledonary ones), cock!ebur with four leaves (including the cotyledonary ones), sorghum with three leaves, corn with three leaves, soybean with two cotyledonary leaves, rice with two leaves, wheat with one leaf, and nutsedge with three-'ive leaves were sprayed. Treated plants and controls were maintained in a greenhouse for sixteen days, then all species were compared to controls and visually rated for response to treatment.

Ratings for compounds tested by this procedure are recorded in Table 1, Plant response was expressed on a scale extending from 0 = no injury to 10 = complete kill. Letter symbols used had the following meanings: B = burn, G = growth retardation, C = necrosis/chlorosis, E = emergence inhibition, and H = formative effect, X = axillary stimulation. - 57 42778 39Q3SinN o o o O . o O r— VISSV3 o co o O o X in m 8(18313303 o o t o o X ΟΪ CPl *—· A80199MIN80W o o o o o o CM LU Ο SSV899V83 x rc o x co X UJ o IU IOC IOC Ο Οί SSV89Q8VAN8V8 o x cm σι o x o o o ς. m Γ—’ LU LU Q£ 3318 o in o tx. OC5 cm in o o r-“ o tx SiVO OHM o o o o o o o CM co CO in σι *—' 1V3HM O o o o U O <3· CM CM in CM σι NV39A0S rz x X- X O is r— r— ID t— in N803 OX o oz ox O X X o r— px CM CM co CM 07 CM ID r— W(1H98OS O —J o O O X O r“ CO f*» i— in CM 39Q3Si(lN ca CQ CQ ca co CQ CO CM CM CM CM CM VISSV3 co CQ CQ CQ cQ CQ px 07 LO CO CO CO 809313303 CQ t-* - ca CQ Px CQ σι CQ Px ca . <3* A80199NIN80W co CQ Γ 1 jao ca CQ OB CD px cn Px r— SSV899V83 CO CQ ca CQ CQ CQ m CM 07 «=t ID px w o x SSV83QHVAN8V8 ca - CQ O CQ OB OB CQ LU O' r— Px • σι Q£ tu 3318 CQ ca ID CQ CQ CQ CM co ’’J h- tn o SiVO OHM co in 5B CO *3- CO ca CM co CM iV3HH CO CO CQ CO CQ CO ip 07 CO *a* CM CM . NV38A0S 03 IO CQ ID CQ rx . co ID as CO in N800 co CQ CQ CO CQ CO in m IO ID IO rx wnHaaos co rx CQ 07 CQ LO' CQ - LO as co *4* NOiiOO CO σι CQ Px 1 SB 1 CQ σ» CQ σι CQ σι WV38 Hsna co σι CQ σι SB co • σ 801 .i cd . σι m to - - io in in 38V133H 83d 93 *χ, CM . CM -x. CM X. CM *x. CM CM awnodwoo CM CO in IO 1— { 1— F- 1— H- 1— 3 7 7 6 TABLE 1 (Continued) - 39a3SinN o f*· o CM o Cd r- 1 7C © O VISSVO o CM o o r—· X CM o o r— Cd o o o nna3TOoo CD r** o o O Cd o Cd o o © n ..... .. . -ΓΣ . ... ...________ AHOTOSNINilOW o o o 05 CM ω ο Cd o o © fM. ·” ... . Id cd SSVH98VH3 o o LU o CD CM ο ο Cd o CD co LU o X r— Γ“ r— . . id s SSVHStRIVANHVg o o LU o Cd Ο ο cd o X CQ LU O id P“ r— Γ r- *“ - Σ Id LU 33IH Cd LO o στ 8 Ο ο Cd cn o o CQ fyt Γ“ £U sivo ohm Cd o o o o LO © ο Cd o o Cd h*. Γ“ i— 1V3HH o στ Cd © O Lf> Cd στ Cd στ o Cd CQ r— . .. .. NV38A0S X CD r— LO X σ» X CM ο σ Cd o o o Γ“ r— NHOO Ld X στ o o Cd X CM LO 10C IOC o HOI WflH9H0S o CM a © o LO Cd ο Cd o o LU O r— Γ“_ rr--1 'T—. 39Q3SK1N CO co io co r— 03 C0 co CQ CM ca CM VISSVO ca lo co σι CO CM CO Ο co στ CO CQ co CM ΜΠ93ΊΧ303 co co co © CO LO co ο co o CQ LO CO LD r— «“ r—· .. AH0T99NINH0W co o r— CO o CO 00 ο 1“ CQ O r*· CO o SOI SSVM98VH0 co cn co © CO CM 00 ο CO στ co co co Lf) r— (Μ .. . Id CO CO co co CQ CO X LU ssvagaavANUva o © στ σ o r— LO CD O£ g 33IH co o co στ CO r— CQ Ο CO στ CQ CM CO CM r- . LU 1— LQ sivo ατίΜ co 00 co στ CO *3* cO Ο co στ CO CM CQ LO O Γ— o. 1V3HM CO co co 00 CO CO co ο co 00 CQ CM CO CM NV39A0S co X στ in co Gh CO LO 00 ο co στ 03 <3* CO LO NH03 co στ CO © CO LO ca ο co o £0 r» CO I*«* r“ WfiHSHOS co σ> co o CO LO 8 CO o CQ CM co CQ N01103 co Ch co © CO στ 03 Ο co στ co co X στ r— r— NV39 Hsna co o CO s CQ στ c0 Ο co © CQ co co o r- r— KIV133H H3d 9» CM CM CM CM LO -s. Lf) CM CM CM ONnOdWOO r*s b- 52 στ 1— Oil r— r-“ (— CM f— 3776 39Q3SK1W o o © o o O VISSVO 1 o CM CD LO © o © anaaixooo CD co CD r>. o LU o r—- O I Α90199ΝΙΝ90Η o CD in o o CJ Ol Q bJ Ο ssvaoavao X io x o o o o o X IO CJ r— LU C5 QC LU ssvasaavAwava cj σι o o r-· (ioe CJ co CJ Ol CJ X CM Γ** LU 30IM o CJ CJ CJ CJ CJ LU or LO Ol co LO sf* CM S1V0 OHM o h- CJ o CJ Ol CJ CJ co CJ 1— 1V3HM O o CJ CJ cj CJ N. Ol Ol rx <#· wvaaAos CJ r—» CD in x r- CD CM CJ X N903 cj x X x o x CJ X CJ X CM co Ol o r— to cm 1— CM wnHoaos CD r*. cj Ol o Ol o o oi CJ x <— CO 3903SifiN C0 CM co LO co LO CQ CQ CO CO VISSV0 CO M CO o CO LO co CQ CQ CM co CM 90931X300 co LO CO r-. CO LO CO LO co LO CO CQ AU0199NIN90W CO o r*· co o 1 10B 1 CO O CQ Oi CQ CO SSV99aVH3 CO f-% co o r-“ CO © P~· co x cq σι co CD «— LO CO Γ” LU o ssraaWANava co Ol co o CQ O Γ“ CQ o r— co r** CQ LO LU 33ia co co CO CO CQ CO CD CC. LO Ol o »— LO to CQ Σ. sivo ohm cO CO co CQ CQ 03 LU H* co Ol Ol LO CM CQ O cu 1V3HM co co co I-'. co σι CO LO CQ CM CO r—- NvaaAos co co CQ CO CQ CO LO σι LO LO LO CM N900 co co 03 CO CQ CQ co Ol oi LO «Φ W0H9H0S co cQ co CO CQ CO LO Ol o LO σι LO N0LL03 CO co CD CO © CQ CQ o © Ol CO t- Ch r*. NV39 HS08 CO σι co o co o CO oi CO Ol CO Ol 3 9V133H 93d 9» 2/5 CM CM CM CM LO CM ONOOdWOO cq LO LO H I— 1— l·- P 3 7 7 6 TABLE 1 (Continued) 39Q3SH1N CJ 1“ o © CM © CM © O o VISSV3 o o CJ © © CM © o © CM 1111331)1303 © © © • © © © o o O AH0139NINM0W © © CJ o CJ o CJ o o CD CM O Ld 1— r— l-“ © z Ld SSVH98VH3 CJ σ» © CM LU o CJ co o © CM © CM CD Oi LU X SSVHDOHVANHVfl © o CJ o CJ o © o © © © © © CO LU r— r- r“ ... LU Oi CL 33 ia © CO CJ r*· © © © © © CM © CM © ......... ___... .... -,..—mm. SiVO 01IM CJ o CJ cn CJ © © © © © r*. © r— 1V3HM CJ cn CJ r-> CJ © © © LO © LO © CM NV38A0S © o CJ cn z © © © o z CM X N803 CJ © © ©z © © © © o r-“ σι © co © CM CM LO WI1H9H0S CJ cn CJ cn z © © © i— r*. © r~* © © 3903S1HN 03 © 03 © «Ο © LO co © o VISSV3 © LO 03 <· © © co LO © © CM © © 80831)1303 03 Γ** co co © © © o © CM © © © A80199NIN80W © o co © © o © LO © © © © © © r— 1“** SSV898V83 03 o 03 © © o 5B 8H © co © CM © CM r* r·* . LU CJ Z LU ssvasaavANavs 8 © o © o r— © © i— 8 © LO © CD oi LU X 3318 © cn 03 © © © © © LO © © © © LU |— ω o SIVO OHM co CD ca co © © © © © LO © CM © CM CL 1V3HM CO fifl © © © © © co © © LO CM CM NV38A0S co © © © © © co co © © co © F- N803 co © © © © © © σι co O © LO © CM . —1 —............J —~ *------- .. —. -- H0H9H0S co CQ © © © © © o co o © LO CM © pm pm N01100 03 cn ca cn © o r“ © © 8 © © NV38 HSOa co © © © © © © o © © o © © n*. 1.,1 -1 · 1 LO © lO 38VL33H H3d 9)1 CM CM CM LO CM CM CM CM QNOOdWOO CO © O CM f— CM CM CM 1— l·- 1— I- t— 3 7 7 6 \ νυιι 11 eiueu) 39G3S1I1N © O © O o O VISSV3 o o O CD CO O CD r— CO O ynaaiMDOo o X r— O X X CM © AH0199NINH0W © Lf) X r— O X CM CD m o PREEMERGENCE SSV892W O O CJX r— LO O CD r— in ox i— σι X co ssraaavANHVg O CM o co OX r- o o Γ-· o o O CD cm σι 3319 O CO o . sr o co o LO o CM o sivo ohm o in o co o r-. o σι o Ch o 1V3HM o m o LO o «3· o X co r*w o P*» o NV38A0S X r*. CD CO CD <3* X co CD CO o M900 o σι o l>» O CD r- r*. O CD CM t- O X in co o WnH9H0S ox r- r- o co o «—r cox co co o o 39Q3S10N co CM co ca co co co co VISSV3 CO IO co CM ca in CO co CQ CO. CQ © 90931)1303 co LO CO «3· co 3* ca in ca *3· CQ CM A90199NIN90W CO o iP“ co o P-* CO cr> ca σι ca © ca © ω o x SSV999V93 CQ CO CO CM ca r-“ CQ r*s ca x *3* LO CO ssvasawANwg ca o CO co CO CO co r*. ca σι co LO CD O' bJ 3319 co co CQ in co co co 1 co CM l·—· GO SIVO OHM co co co io co CO co co CM co 1V3HM co co LO co CQ ca CM co CM NV39A0S CO X CO LO co *3* co co ca r- ca o ca «3- N903 co X CO LO. CO LO co CM co LO ca m co LO WnH990S co © co σι £0 CM CO r>. co CQ CM N01100 CQ σι co co ca o ca co ca a σι σι CQ o ps, LO NV38 HSO9 CO a 1— ca cn ca σι CO σι co t-«. ca co 39V133H H3d 9» CM to CM in CM in \ CM CM m CM QNflOdWOO 1 T23 . 1 ί cf CM V- m LO H- 4S776 TABLE 1 (Continued) POSTEMERGENCE | PREEMERGENCE 39Q3S1I1N o O o o © o VISSV3 o © LO © © LO © r~ o X o © LO a o X r— anaaiMOO AHOTONINNOW © CM © o r** © CO © © o X r— ssvasavaa © στ © © r~ LO © © r*“ © © © © © © hx. ssvasaavANava © o r* © CM © στ © X co © © CM © CM 33IH © CO © co © © CM LO © co o © © sivo ατίΜ © σι © στ © © CM © © CM © © 1V3HH 8C X © CM LO © © r— N. © © CM © © r- © r— NV33A0S X LO © CM © CO o O © © r— «Φ N803 X o T* © X CM © X r— στ © X CM CM X CM © © i— U> wiwaos © CO © CM © CM © CM O © r—· MSlflN CO CM CO co CO CM © o © VISSVO CO CO co LO CO CM © r— © CM © anaaTOoo CO LO co to CO Px © CM © © © AH0T99NINM0W CO o r— co o £0 O Γ· © O © o r— © o sswraam ! 4B 1 1 co © (O r- CO x © σι © © r— © ca © © o ssvaooavANava CO o 1*““ © σ» co CM © CM © © © CD 3318 CO σ» 3C ca CO © © © © © •e SIVO GUM co LO © CD CO CM © CM © CM © CM 1V3HM CO CM x © CM LO CO CM © CM © CM © CM NV38A0S CO co © CM CO © © *3 © © © © NM03 co x στ © X CM © CO © © © © © *=3 WGH9H0S co co © CM co στ © CO © © © LO N01103 CO CM CO co co o r—- © στ © r-χ. © στ NV3a Hsna 10B co o r— 86 i © r·». © σ» © 00 3HV133H 83d 9)1 iO •*x. CM 2/5 © 2/5 © CM 2/5 QNilOdWOB r-. CM l·- T28 T29 T30 © H CM © 1- 437'?® TABLE 1 (Continued) 3903SinN o to o o O o c— O LO o VISSV3 CD to 301 1 o CD P-. O o f— o o 8(1331)1303 CD CD CM o Ld O CD CM 301 10C A80TB9NIN80W O CD CM o OX ·— co CD CM o LO o Ld o ssraavas CD Cd ca o ox «—co X LO X 00 Ld O Ld O z Ld O X ·— r— «— SSVTOOWANWa O O o o ca στ O CO 9C Ld O Ld O E r—r~“ *“ (MW Ld Ή3ΙΗ o o ca o o O o Ld X στ . r·*» CM LO CM στ co SLVO QTIM o o {_> στ ca x CM J-* ca to 7C o o o o Γ—· r— 1V3HM o ca x ca x ca o o O co co στ CM to LO to στ στ NV33A0S zz στ x LO o o x i— CM X to o στ ca x «— στ N803 x can; ox O X ox o o στ cm σ> i— Γ-» CM CO CM pv. o στ wiraos CD O ca ca OX O CD o o CM «— στ στ i— LO «— to o o f— 33<33S±nM ca to ca CM co ca co CO LO ca CM VISSV3 co LO ca co co co co to CQ CM 10B CQ στ 8(1931X003 ca ΓΧ ca LO ca LO ca στ CO ca o CQ o A80T99NIN80W co to ca o r— co στ CQ O r— CQ to ca o aoi ί ssraavao co στ CQ O co o r— ca co co hs 301 ca στ ssvasaavANwa ca o CO o ca στ ca στ CQ or CQ O ca o r~ r— «“ »— Ld O 33IM Ci CQ ca s ca CQ ca Ld LO «— cn X Ld sivo otim CO Γ'· ' ca ca «Φ ca co ca CM ca o ca στ x l·—* 1V3HM ca ca ca ca ca ca CO in o to io CM LO «— co to NV39A0S ca co ca r> co X LO LO ca στ ca ca στ CQ X CO to N803 ca co CQ co X CQ CO ca r*. r-. CO lo στ LO στ στ W(1H98OS co Γ-. co o ca co co LO ca LO ca στ ca στ tioiioa CO O co o ca στ CO στ ca co ca o ca στ Γ— r— r— NV3a Hsna co σ ca cn CQ σ» 1 301 ί ca στ ca o r— ca o 38VJL33H 83d 9X LO CM LO \ LO LO CM LO CM CM CM CM CM ONflOdWOO CO co •5fr CO LO CO LO co 1-- cn l·— l·— H J— TABLE 1 (Continued) 39Q3S10N © © «φ lo © lo o © CM © o VISSVO 8 © o © r— © © © CM © »“· r— 1— yns3TO00 ’ © o © X O © © O 1 λΜ0Τ99ΝΙΝΜ0Η © co 1 1 9V : o © X © X o Ixl ssvaoavao 8 I— © © r— © X 30 L © o r-“ © © z LU SSVMQHVANHVa © O © O © © 8 © O © © r— Oi 1 < 1 331« © © © © © © ε LU © © X LO © fY· sivo ohm o © © © © © CL o o o © r- 1V3HH © © © © o © o o CM © r— r— NV39A0S © X © © o r-“ © O X © N«03 © © c· © o t— © CM 8 r~ © © r“ © WflH9«0S 8 © LO © rx. © • X © X © X X X X X X 39Q3S1HN un 'if X LOr*“ § X © X X X VISSVO LO X CM fx. CM X X x X X X «0933)1303 o fx LO fx. CM X X X X X X A«0399NIN«0W o 1—* σ P— o i— o fM o (M X X X X X X X SSVH99VdO o © X © X r-x X X ca X X X ssv«9aavAN«va o © © © r— © P“ X X © X X X X 331« © © io © X CQ © X X X X X X © X sivo aiiM o o p— X X CM © © X X CQ X X X Q£ © IV3HM © X X rx. X CM ε UJ X X X X X X h* στ NV38A0S © X r-x fx. © X o CL X X X X SOL X NM03 o r— © X o p— •KJ· X X X ca X X WfWMOS o © © rx © r~ X X X X X X X N01100 o © X X o P— o X X © X X X NV39 Hsna o © © o © r*· X X 3W133H «3d 9)1 CM CM CM CM CM •x^ CM X © O r— CM CQ ONflOdWOO P X ’Cf’ 1— *ύ· b- TABLE 1 (Continued) 39Q3S10N o © © Ο Ο Ο Ο VISSVO © p~» t Ο © ο © 8993151303 1 o ο ο ο ο A80199NIN80W o © © CM © © ο X SSV898V80 o © X © X © LU a r— στ r— στ © ο Ο LU O X SSV8908VAN8V8 o o 1 00L! 1 © ο ι— © στ X © ο ο r-“ LU © C£ 3318 o px 9C © Γχ © © Ο Ο © LU 2Σ LU txt C£ SIVO OHM O X i— Px © o © στ © © © Ο ο cu 1V3HM © X © © © X ο P- LO στ © © στ X X © X © NV39A0S co στ © στ ο © © X © © X © © © Ο X N803 1— CO ο cm στ CM © © cm στ o ο © © Ο <3 ο W9H980S cn στ t— © r- Γχ ο ο1 : CO © © © © © 3903S19N CM CM © * © VISSVO © © © © © © CM ο CM © Ρχ © © © © © © 8993151303 LO ο γ— px © CM © A80199NIN80W © © © © © © o f— . στ στ στ CM Ο t— © © © © © © SSV899V80 στ στ © © © Ο © © © © © © LU f 1 SSV89Q8VAN8V9 στ Ο στ στ Γχ ο © © © © © © X LU 3318 Γχ στ © Γχ © 03 . © fV © © © © © © UJ s SIVO OHM - CM ο ι—· Γχ Γχ CM στ LU l·—- m © © © © © 1V3HB CM Μ* CM © CM © Cu © © © © ϊ>< © © NV39AGS LO στ © στ © © στ © © © © © © N803 LO Γχ © © CM στ © © © © © © WnH980S Γχ στ Ρχ © © στ © © © © © © N0J100 στ στ στ στ © ο © © © © © © NV39 Hsna o r— στ στ στ © ο © © © © CM 38VI33H 83d 95) CM CM CM *Χχ CM •χ. CM © { © Ρχ CO QMOOdWOO •5J t— . ?£ «cP t- «4· I— - 66 TABLE I (Continued) PREEMERGENCE 3903S1HN © r— © © © r““ VISSV3 CD CO o © in © © o 90331)1000 CD CM © X ΓΟ o © © r- CO A90199NIN90W © o © co o r— o X CQ SSV998V93 X cn CD CO bJ O 8 f— SSV99Q9VAN9V8 © o Γ © Ch © © r~ © X r- © © I— 3019 • © σ» © in © © i— in O © © SIVO 01IM © σ» © CD r- CO X σι © © i— CO © © r“ 1V3HH © • cn © © p- m X σ> © © r- -M © o r— NV38A0S X r— © r- χ in o © © I— CO r· N903 OX i— CO X CO © © r- CO o W0H990S © CD r* LO © CD CM CO © © CM Ch o © © I— 39Q3S10N CO CM CQ r— © © CO <· VISSVO CQ CM CQ CO CQ LO CQ CM co o 90331)1300 CO in CQ n CQ m CO CM co © POSTEMERGENCE A90199NIN90W co σι co o i— CQ o r— CQ oo co tn CQ in CQ © p— 03 O 03 © Γ* SSV998V93 SSV99Q9VAN9V8 CO X r- © 8 03 © i— n co ps. co Ch co O r-· 3319 CO 10 CQ tn 8 co in CQ © SIVO OHM CQ ·*· CQ co r* co CM CQ © 1V3HM CQ co 00 S «f CQ cO CO NV39A0S CQ CO CQ © r— CO CO in CQ © N900 X CQ CM P-- co in 8 CQ co CO o P— W0H990S CQ P*. CQ in 03 O I—· CQ in CQ © N0J.103 CO Q co co m σ> CQ © CQ m CQ © r— NV38 HS08 CQ © CQ co CQ © co co CO © 1— 39V133H 93d 9)1 in CM in *Ss. CM m CM in CM CM QNflOdWOO Ch cf 1— O in h- i— in h- CM in H cn in H- z V 7 6 TABLE 1 (Continued) 3903SJ.I1N © O O O O o O VISSV3 1 1 . O O O o o O 98831X303 o o O 1 o o o A90199MIN90W CD CM o O P“ o o r—· o o LU O SSV998V93 © CQ © CM O o X © X o CD © z r— LU © O' SSV99Q9VAN9V8 O X cq σ> O X r— LO O © O X © © O © o o LU r— 3319 Ο CD o o o o LU «— © © r— o o O' a. S1V0 Q1IM o x o O X o o o CM CO 1—· r— CM © o r~ JLV3HM OX OX o o o O CM CO r- CM © © o NV38A0S X X CD CM O © © CM © o N903 o x o O X O CD O CD o r- I* (— © t— © r— © o WnH990S o O X o o O σι r- LO © © © o o 3903SlflN CQ © © © © © O I—‘ F- r“ VISSV3 CQ © © © © © © r— Γ*» © r— r— CQ 9Π83ΊΧ303 CQ © © © © © © CQ CM © CM CM r~* © A90199NIN90W CQ © © © © © © © o © © CM SSV998V93 CQ © © X © © © © CQ CM © © r-w CM CM . SSV99Q9VAN9V8 CQ © co © © © © © © CM © © 3319 CQ © © © © © © LU CQ © © © O 7Z. I.f S1V0 0ΊΙΜ CQ © © © © © © CD O' CM © © ro r” LU 5T CQ © © © © © © LU l·- 1V3HM r— CM © CM ,L... t/) o CQ © © © © © CL NV38A0S LO © © © 1 © CO © © © © © © N903 LO © © © CQ © - CQ © © © © © © W8H990S CM © P-. «$· © CQ © © © © © © N01103 o r—· © © © © © © CQ © © © © © © NV38 Hsna σι © © © © © © © © © 39V133H 93d 9X CM S. CM CM CM CM CM «3* © © Γ*·. ONflOdWOB LO H © H © 1— © H TABLE 1 (Continued) 39Q3SiON o o © © O O VISSVO o o o O © O 80833)1303 o o o o A80399NIN80W o o © © © o ω © z SSV898V83 © © © LO o co © © © CM © © Cd LU SSV8908VAN8V8 © co © σ» O X co o 1“· © P“ o © 2£Z 3318 © © o © CD a CM © © o © CM © Δ. SiVO 03IM CJ © o o O rx co cn Γ“ O © iVSHM © © X ω LO © o © CM NV38A0S X r*· o o o © j- 6H N803 — © © X o o X LO r- un o r*“ © CM CO © © O W0H980S © o o o r- CQ © © © © 39Q3SI0N CM o CM CQ © © © © © VISSVO pm r— © CM i— © 1 <. s © © © © © 80833)1303 © sr CM r-“ A80399NIN80H © © © © © cn LO cn © © O SSV898V80 © © © © © © LO © r— CM © LU © Z SSV89Q8VAN8V8 © cn © cn © cn © © 3B © p-« LU © Q* 3318 © © m © © © LU X co CM CM CM r* «a· LU SiVO 03IM t£t © © © © © © Ο in © pm ϊ— <3- Q. © © © © © © iVSHM © CM P“ r- r- © © © © © © © NV38A0S © © © © r~ N803 © © X © © © © © cn © © CM © r— © © © © © © H0H980S © © © ·” © © © © © © © NOiiOO CO © © © O CO NV38 HS08 © © © © © £9 cn co © r— © © 3W103H 83d 9)1 © © © © © CM QNOOdWOO co LO cn © © © © CM © © © h- h- H- h- t— - 70 4 37γ6 TABLE 1 - Identification of Compounds (Contd.) - 71 TABLE 1- Identification of Compounds (Contd.) - 72 *277.6 - 73 TABLE 1- Identification o,f Compounds (Contd.) - 74 4 3 7 7 6 TABLE 1 - Identification of Compounds (Contd.) - 75 TABLE 1 - Identification of Compounds (Contd.) •ί» - 76 4 37 7 G - 77 TABLE 1 - Identification of Compounds (Contd.) - 78 4 3 7 7 6 Table 2, is presented to further illustrate the biological activity of the compounds of this invention. The data illustrate the herbicidal efficacy of the compounds with selectivity for the two important crops, rice and wheat.

The test compound^ were applied in a non-phytotoxic solvent to soil pots containing seeds of an intermediate hybrid rice, japonica rice, barnyardgrass (Echinochloa crusgalli), morning glory (Ipomoea sp.), wheat, wild oats (Avena fatua), downy brome (Brorous tectorum), and cheat (Bromus secalinus). In addition, wild mustard (Brassica arvensis), Kochia (Kochi scoparia), and blackgrass (Alopecurus myosuroides) seeds were included in some instances, as were established plantings (postemergence) of some or all of the species mentioned above. The plants were maintained in a greenhouse (glasshouse), and visual plant response ratings (as described in Table 1) were generally taken about three weeks after application. - 79 I rtDLC.

POSTEMERGENCE SSBj6>|3E[{ - . . EL 1(30) pjBqsnw PLTP snupiBoes sniuojj uinuoToaq snuiouf S4E0 Pl IH ------ --------- TBsqH XllOiG6ilj.iuow © X X o ssEjBpJBAuBg X O uo 33iy BBLUOdBp © © X 30Ly 3TBLp3UUaqUI © © OJ PREEMERGENCE SSBU5y3Bl8 BJ.q30)| pjBisnw PLIM snui[B33S sniuoag UMU0T33T snraoug © Q O © O O O © © σ © o x © O © © X SVBO PIS-M O O O O © O 1 o Τ6ΘΙΙΗ o o o o © o o o Kuo|66uiu40W Ο O © © © © LO © © o o ssBjGpjBAuBg © © © O lo in © © X X © © © © 1— fx 33iy BSLUOdsp o © © o © i m o © o o 33Ly 34BLP3UU3TUI o o o o © o X Ο Ο O © ίβ -c 2 ·> LO r- X 04 \ X^ X. \ r— r— i—· OJ Χχ OJ 04 LO X 1— OJ •x. \ Xs. ‘x r— t—· r— r— ONnOdWOO P X {— 3 7 7 6 TABLE 2 (Continued) 1ERGENCE POSTEMERGENCE [ ssbuB^ob (g BLipO» pjeqsnw pl.lm snu.L|Boos snuioug tunuoqosq sniuoug sqso PL.LM 4ΒΘ4Μ Kuol68uluuow ssEuBpusAuuEg eOLH BOLUOdBp 30|.H 34Bipouuaq.ui ssBu6>|OBLg Βίμοοχ puB^snw pllm snuiiBoes sniuoug cd ο o co i CD O r— CD Ο O o co co cn uinuoipaq. sniuoug CD oom i o o O 1 CD O CO CD CJ CJ o in σι LU O. Φ0 PLi-H O O ο o ro TBsqM o o O 1 o o CJ CJ Ο O r— CM Auo[6Buluuom o o o © © © O O O O ssBuBpueAuuBg CD O O 1 CO ο ο ι o CD CD CJ CJ oo σι cb A 33(8 B3j.UOdBp O O O O O O 33 Lg aqeipBiuuaqui ο ο ο o o o O O O O Π3 cn'x UC T(0 CM CO n r« 00 Q· 00 CM \ X r·* r* CO r— CO M* CM Μ X» X, X r· r· r-· r“ ahinodwoo in H- S Ξ 7 7 6 TABLE 2 (Continued) ssEuBxoeig t I I etqoo>| CQ στ CQ στ CQ στ pueqsnw PLi-H o CD © Ld snuLieoes snuioug o o CQ *3* y CD X turucrpsq. snuioug o CQ 00 X co F d 1~ CO o ΦΟ ΡΠΗ o o X X Τβθμη o © o XltoiBBuLuaow I o CD στ sseu6paeAweg o CQ CM X στ aoLH eo.LUodep o a ο 33 LH 3qBLp3UUaq.UI © o Ο sseu6>)3e |_g i i BLqso» o o ο pusisnw pl.lM o © ο LU U snuiLEoas snuioug O o o o o o CD in o o Ld X Ld uinjoq334. snuioug o o o o o o co o ro Ld X STBO PLiM o o o o © o o co r- CD r— V33LIM o o o © o o o o XjolBBuluuoW o o ( © © o o © o ssejBpjBAuEg o o o in o CO co co co στ co o X 33LH B3LU0dBC o o I o o o CD f— o o 33lH 3q.BLp3UU3qUI o o 1 1 © CD CM co co «1 στ 1/32 to CM co nJ r— r— * '‘S r-“ — QNilOdWOO rx. t- 00 b- στ I— 4S776 PREEMERGENCE I POSTEMERGENCE SSBUfiyOEia PL 1)30)) puETsnw PITM snu.HBoas sniuoug uinuoqosq sniuoug steo ΡΜΜ. TBsqM Auo|66uluuow ssEu6puBAuuBg 30iy BOLUOdBp 30iy 3TBl.p3lUU3TUI sseuByoELH Etqoo)) pusqsnM PLi-H snu.LLBOss sniuoug 0 0 rx. O Ο Ο O © © rx. uinuoqosq sniuoug 0 8 © 0 © © © © X sq.EO pl.lh 0 s © © © © r— © 0 TB3l)M 0 O CM © Ο O © r- © © CM Auo|66uluuoh <5 O 00 Ο © O © Ο O sseuEpuEXtiuBg © 0 στ © © O 0 στ © 0 soiy Boiuodsp o 0 O O O 1 0 0 33 iy 3q.BI.p3UU3q.UI 0 1 © © © 1 0 1 ro x: στ-χ. -r- <0 X CM •X. S 1—· r~ © r- X *1- CM Χχ xs Χχ Xs <· x-. »— dNnodwoo © 1— h- Γ—· P CM P \buritinuea; postemergence sseuGpeig EL q30)| pusqsnw PUM snu.L[B33S snraoug wnuoqosq snraoug S4E0 PMM qeaqH Auo|66utuucfyj SSBUGpUB/ilUBg 33 Ly BOLUOdBP 33 Ly 3TB Lp3lUU3q.il I PREEMERGENCE ssBuGyoBig BL 1)30)) pusqsnw PUM snui|B03s snraoug o o © O © O o © i— in cm © Ο Ο Ο r- mnuoqosq snraoug ο o a o © o Ο O f- (Ό r- © © O © «— M· sqeo PUH qB3t)M /iuo|.6Euiuuow © Ο o CM o o o o i— X X X © © © © X o o o o o o O «— X © © © © o o o o o o o ο ο ο o ssEuBpueXuueg © © © CM © © © o co rx. σ» o © © © O »— X 33Ly BOLUOdBp © © o © © o o © © o o 33Ly aqEiparauaqui ο ο o © © o o o o © © fO -C ©x T- ra © r- CO CM X X X © (— X CM X X X X © r- X CM X X X X QNnOdWOO X r*“ h- © 1— . 3 7 r' 6 PREEMERGENCE sseu6>|oe|.g BLqoo» pueqsnw pl.lm snuLieoas sniuoug uinuoqoaq sniuoug sqEQ pii-M q.Eai)M X'uolBBuluuow ssBuBpueAuEg aoLU BaiuodEp 33 iy aqBipauuaqui ssEu6>|0E|.g ειηοοχ puBisnM PLS-M snui|Boas snuioug o O o CD in o © © CD CO o O o uinuoqoaq snuioug © O o CD rx o o o CD CO o O CJ m SdBO PL.LM o o o CD < o o o O © © ΪΕΘΜΜ o o o CD t— © o o O o o o r- XUolBBuluuow o o o O o o o o o o © SSBUfipUBAlUBg o o o cn o o © © © CJ ΟΊ o CD CM CJ o 33 iy BOLUodBp o o O 1 o o o o o O o soLy aq.Bi.pauuaq.ui o o o o o o o o o O o (0 x: Cl X -X ·!nJ CM co X, 1 9L/L •4- x. r—· CM 1—“ 1/32 © t—“ X r-*· CM X r— x> r— CO X^ CM QNnOdWOO Γ» rx r-· H CO r““ F— - 85 TABLE 2 (Continued) ssej6>petg B LL}30>| LU O pjeqsnw PLLM S © cc LU snuLieees snuioug © CO CM © © © © LU b— © uinuoqosT snuioug © cP © © © στ © στ S4«O Pl PM O o © © © iW o o © r— © r— iuo[66uiuuon © © © © © © © στ ssBu6pueAueg o © © t— © px sota eoLuodep o o O © 33 PH 3TBLP3UU3TUI o o O © SSBU6>j3B|.g Βριροχ puBTsnw PLJ-M snuiLB33s snuioug a o o o co ο Ο 1 Ο LU O z uinuoqoaT snuioug o o o σ ο ο ο ο © © ac sTBQ PlPM o o o o ο Ο ι— ο © ο © LU LU OC _ TB3MM O' o © Γ“ o © ο Ο 1 ο yfuoiBBuLUUOW o o o o ο Ο ο ο SSBUGpUBAllUBg o o Px o © ό στ ο ο ο στ ο ο 33Ly BSLUOdBp o o o ο ο ο ο ο 33ly 3TBLP3U1U3TUI o o o cP ο © ο ο ό ίΰ CM tU · CM © r CP CM rO f— r— r· r— Ρ“· r-1 QNIlOdWOO στ P Ο CM Η- 3 7 7 6 TABLE 2 (Continued) ssea6s|3E|,g 1 1 1 1 Biq30)| ca CT\ © O © o r—· © © LU © pueqsnw PL!-M o O © © © o r· LU CD QC UJ snuj.|B39S snuioug m co m Lf) © © © © ail. LU CO O uinuoqsaq snuioug co LO O © sq-eo PL.LM o © CM © © © © qeeqM o o © © © © AjolBEulujoh 1 © © © o r— © O sseuBpuBAuuBg © © LO © © © © 33Ly B3LU0dBp © o O CQ 33 i.y sqBLpBiiuaqui o © o © CM SSBU6)]3B[g 1 1 1 1 61.1)30)1 © un © LO © o r* © O puBqsnw PUH © o © © © O r— snui|B33s snuioug o O o © o © © © © © LU © uinuoqosq snuioug o o © © o © CM © © © © LU © Q£ LU X Ld a Q_ sqeo PL.LM © © © © © O © r— © CO T631JM o o © o o O O o XUolBBuluuow o o o o o o o © CM SSBUfipUBXUUBg o © CM © P% © © © © cm © © © © P“ 33Ly B3LU0dBp o o o © © © © © 33 UJ 3TBip3UIU3qUI o © © o 1 o o © P— ITS © x: CM LO CM © «sp ‘r- «3 QNflOdWOO CM h- CM CM h- 43776 . , ._'__ TABLE 2 (Continued) POSTEMERGENCE ssBu6>jOBi.g b Lipo» pueqsnw p[LN ------ --------------- snuLieaes snuioug uinuoqosq snuioug sqt>o ΡΙΛΜ qeauM XUojBBUiuuow sseuGpuBXuUEg so t,y soiuodBp soig 3q.sLp3uu33.u1 PREEMERGENCE sssuBxosLg BLlpO)! pusqsnw PLLH lilt I t I ( 1 1 I t 1 I I I * I I 1 I I I I I ( 1 snu,L|B03s snuioug © 0 0 0 0 CJ 0 0 O CM © Ol O r— tunu03033 snuioug 0000 CJ © CJ CJ 0 © © σι cn sqeo PLiM CD 0 0 O CM O CJ CJ 0 O CM CM © σ» 3BSIJM 0 0 σ 0 CJ O CJ CJ O r-* r— © Auo|66uluuow © 0 0 0 CD CD Ο Ο O «— CM sseuBpusKuueg CD CD CD © © © h* CJ CJ CJ O CJ σι σι σι © ο r— r— 30ty Botuodsp I © O © CJ 0 0 © Ο 1— 30iy 33BLP3U1U33UI Ο Ο O © CJ CJ © © © «— © ftf cnx Jd \ •Γ» rO CM © © 1— «4* CM \ \ pm pm (-. r» © »*-* CO *4* CM ry f— r*“ r—· anno·» © CM l·- «4* CM l·- 3 7 7 6 PREEMERGENCE POSTEMERGENCE sseaB^eig © CO X X X X © X © X r—· X o t— X © X o 80 L Btqoo» III! 1 801 X o X o X o t— 1 paEqsnw pti-M o O X © X © X o X in X m X © X © «“ f— snuj.|B33S sniuoug CD X © X © X © § © X r*. X to X o 801 uinuoqoaq sniuoug © X © r^. X o X o X © X X X γ*». X X X o X o r“ r— *-· STBO PL.LM o © to © X X © Λ O © CM © to X o X o X o r— r— r- r— TBapM © © © © X X o o LO © O O CM X o Kuo|66uluuow CD © rx X o X © X O X © X © X o X r* 1— r— r— r— sseu6pueKuuBg CD in © to CO © X © r“ X © X © CO o r—· X o t— X © X © aDLH EOLUOdER © o o © © X o o o CO CM X CM ao.LH aq.Bipauuaq.ui o © © © © o © o X LO X to ssBu6)f3Big Ld LO Ld in Ld Ld © © © U1 © © © o © © X © X u o r— BLipOX O © X © o © O © o 1 1 1 r— pueqsnw pum O o © X © to © © 1 1 1 1 1 snuLiEoas snuioug © © X © X © © © o © r*. 3 © © 10C uinuoqoaq sniuoug o © X § © o © © o O © © 10C © o »— © © © © © © © © sqEQ PL.LM o in to © o X CM © © qBaw © © © o o o o CM o o O t— CM Kuoi.66ui.uuon o © o © CM © «ύ* o o o © ssBu6puEKuusg CD LD © cn © © IOC hoc i_ © rs. © X © © © © © o Θ01.Η BOLUOdBp o © © © o o © © © © aoiy aqeipauuaqui o o o o o © o o o © to nJ cn-c cM X to X •e CM •d- •r— i—« CM *“· r— r· X QNnOdWOO T25 T26 377G TABLE 2 (Continued) ssBu6>)3B[g 1 i BLl|00)| co *5t CQ CO puBTsnw PL.LM © ca CM LU snuL|Eoes sniuoug © O IQ © C£ uinuoqosT snuioug o O LU J— co o sqeo PLtM o O 4Βθΐ)Μ © o AuoiG6ulujow i i ssBu6puB/CuuBg CQ © CQ r- aoLy eotuodep o ©: 33 iy 34BLp3UU3q.UI o © ssBj6>(0Big 1 1 I f I i Elipox o © © © © © o © in puBqsnw pi.LM o o CJ o CJ © CJ © r-- © © snuiiBoas sniuoug o o o © © o o o O O © LU © z iunuoq.03) sniuoug o o o © «3* O o o o © © ro © s)E0 PUM o o © © © © CM © © CM o o O © m •ρ» LU LU 1B31JM © © © © O O o o o O AuoiBBuluuow o o o © © © o o o © m sseuBpueXuusg o © © © fx. © © © © ro o © ro © © © © r— SOLy BOLUOdBp o o o o © © © o © O 33 iy 3qBLp3lUU3q.UI o o o o © o © o © © re © co -v r“ CM © jSc ·»fl3 f“ 5!. |— xt .t—» •X, t— A. r— r— T. r-* oNnodWoo £ CO CM © CM I— 3 7 7 6 PREEMERGENCE j POSTEMERGENCE SSBU6>|OELg BLLjOOX pjEqsnw PLi-H sniiL|B33s sniuoug ---------------------------- — tunuoqoaq sniuoug sqeo ΡΜΜ qB3l|M Auoi.66ui.uuow ssBu6puBAuueg ----------------------- --------------— boLy BoquodBp 30 Ly 3qB|.p3UIU3qUI ssBu6>|0Big BL l)00>| pueqsnw pl.lh snuLLEOss sniuoug . © © Ο O CM X © Ο O © © uinuoqosq sniuoug © © ο o x x © © © © t— © στ SW PLLH qB3qH © O © © r- © © ο o cm o © © © o © © © Auol66uluuow © o o © © o o o o ssBu6pUBAuueg © © ο o x στ © © © © i— © στ στ 30Ly BOLUOdBp OIIO Cel 30 ly eqBLpBUUsqui © o o © © © © © j—· 10 στ-c •*X <0 © r— 00 «4* CM X X X X © r- CO CM pe pe |-e QNflOdWOO o X 1- 1“ p 437 7 6 TABLE 2 (Continued) POSTEMERGENCE sssuBpsig BLqooy pueqsnw PLi-H snuLLEnes sniuoug uinuoqoeq sniuoug STEO PLLH qesqH AuolSBuluuow ssBuSpuBAuueg aoLy soLuodep eoi.y aqsLpaiuuaqui PREEMERGENCE ssBuSyoBLg blqoo» pueqsnw PLi-H snuLLBoes sniuoug CD CD © Ο X «Μ· 1 J 1 1 uinuoqoeq snuioug CD © O O X 1 1 i I STEO PLLH © © Ο O CM X 1 1 1 1 qeaiLM © Ο Ο O r- 1 t 1 1 AuolBBuluuow O O O O © © © © © © CM r” r*“ ssBuBpueAuueg © O O O CM o © o o © στ o aoty Boiuodep © © O O O O 1 © aoqy aqeipauiuaqui o o o o ο o i o kg ai/ha CM LO X I— X *d- X X X X i—· p~ r*» CM © X r- <3- CM X X X X r** r- r“ r·· ONROdWOO CM P X X l·- 2 7 7 6 TABLE 2 (Continued) LU O LU CD Οί £ LU J- to o CL· sseu6>|oe(g BLipo» pueqsnw PUM snuLLBoas sniuoug uinuoqoaq snuioug sqso P(LM qeaqM Aio|B6uiuuow ssBuBpueAuuEg aoiy BotuodBp aoiy aqBLpauiuaqui PREEMERGENCE ssBUBqoELg BLipo» pueqsnw PLLM snuiLBoas snuioug 1 1 1 1 CD CJ O O LO CO uinuoqoaq snuioug 1 1 1 1 CD O O O «3* © 1— sqso PL.LM 1 1 1 1 CD © O © CO <3* qBaqM till o o o © KuolBBuluuow CD © ο o co © ο ο o ssEuBpuEAiuEg CJ O CJ Q lo cn © o © CJ CJ o io cn cn aOLH BOLUOdBp O O 1 1 O 1 © o 33 ty aqBipauiuaqui Ο O © 1 o © o o nJ cnx: J* X» (0 CM LO CO 1— *3- CM i— r— r— r— CM LO (V) r~ CO aunodHoo CO LO co μ- 4S776 - 94 ζ *7 I*.· mt * if) - 95 4 3 7 7 6 - 96 4 3 7 7 6 - 97 43776 - 98 43776 TABLE 2 - Identification of Compounds (Contd.) - 99 6 ο I -i ί » TABLE 2 - Identification of Compounds (Contd.) T32 ;l T33 Cl / Cl T34 T35 - 100 4 3 7 7 6 It should be noted that, in general, these compounds at a low concentration virtually eliminated the undesirable vegetation, e.g., barnyardgrass, but had relatively little effect on the crops, e.g., rice.

In wheat, wild oats, cheat, downy brome, and, where tested, wild mustard, Kochia, and blackgrass were controlled at a low rate with little effect on the wheat crop.

The following table, Table 3, is presented to additionally illustrate the biological activity of the compounds of the present invention. The data illustrate the herbicidal efficacy of the compounds with selectivity for rice in paddy culture.

A rice paddy was constructed using a tub containing soil and barnyardgrass (Echinochloa crusgalli) seeds, and japonica rice plants which were transplanted into the paddy soil when in the two to three-leaf stage. The water level was maintained a few centimeters above the soil surface.

Test samples were applied directly into the paddy water, and plant response ratings were taken about three weeks later. - 101 437 7 6 Ο σ» TABLE 3 102 TABLE 3 (Continued) 103 * 3 7 ? θ CJ o CL rcJ **3 TABLE 3 (Continued) 104 ,3776 It should be noted that these compounds at a low application rate virtually eliminated the undesirable vegetation, e.g., barnyardgrass, but had relatively little effect on rice.

To demonstrate utility on transplanted crops, metal containers 30 x 5 30 x 15 cm. were filled to a depth of 13 cm, with fumigated Fallsington sandy loam soil. The following weed seeds were mixed throughout the top 2.5 cm. of soil in each container: barnyardgrass (Echinochloa crusgalli), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), jimsonweed (Datura stramonium), velvetleaf (Aoutilon theophrasti) and morningglory (Ipomoea purpurea).

The following treatments were applied as a pre-plant soil surface spray and also pre-plant soil incorporated (2.5 cm.).

Control Compound A 3-chloro-2-(4-cnloro-2-fluorophenyl)-4,5,6,715 tetrahydro-2H-indazole 0.016 kg/ha Compound A 0.12 kg/ha Compound A 1.0 kg/ha Compound A was dissolved in acetone and the solution applied at a spray volume of 560 1/ha. Immediately after treatment the following crops were transplanted: pepper (Delaware Belle, plants 12.5 cm tall), tomato (Bonny Best, plants 10 cm tall), cabbage (Wisconsin Golden Acre, plants 12.5 cm tall) and tobacco (Coker 319, plants 10 cm tall). Four plants were transplanted into each container. The containers were placed in the greenhouse and watered by hand as needed. Eighteen days after treatment the visual plant response ratings in Table 4 were recorded. - 105 6 >5 V) in *σ in α» co φ i-3 ίΰ στ £ ο &. ιΟ στ s: I Ρ φ 4> ro »— Φ Φ ρ> Ο Ο Ο (ϋ χ ο ο ο © co ο • ♦ ο «ί σι ι© CM Ο CO Ο Ο • Ο Ο © ι— rCD CM Ο Ο * Γχ Ο CQ «— © Ο Ο · ο © «— t3 Ο (Ο $. φ X Φ 4-3 5. «β Ο ί- ιη στ στ ο Ν <0 •σ £ η ο Ο Ο Ο ο 1 X σ CM ιη φ t φ Ο ΙΛ 3 &. ο σ Ι- >τ Ο X CD φ Π3 © C £ S- Ο Ο Ο ο Ο Ρ Ο &. «Ρ“ Φ © ο -μ «Ρ Χχ rd 1 TJ υ Γχ £ •ι— <0 © £Χ Α χ ιη Φ © Ο CM ♦Γ· U. Α Ο Ο Ο Ο η ιΛ *0* t— Ο Ο Φ t γ—· U C *-Χ TABLE 4 φ στ <ο X X (Ο Ο £- «ο Ο (0 3 X £ χ ιη •χ. ·Γ“ *χ. στ στ r-~ «X ύ£, γ— χ _S£ ’Γ— Ο Ο © Ο Ό © m Γ“ £ »™· CM ιη £ CM Ο 3 Ο 1— Ο ο 3 ο (— Ρ J- Ο • * •μ &. Ο • • £ Ρ α. Ο Ο C— £ Ρ £Χ ο Ο *0 £ ε ιο £ ε ι-*· Ο ο f— Ο σ CL Ο Ο ο. ο ο Φ φ i- s- □u Ο- ο ο Γ— >> X ε £ υ σ Φ Ρ X II 4- α. ο ο Φ S- ρ ο to • 3 Α 1“ r~ ιη £ 4- Ο στ Φ I £ £ £ CM Ρ ‘j— •ι—· 1 £ Ρ <0 Ο Ο Φ Ρ U ο £ £ 0 Ο φ Ο. U X Ρ Ο υ φ £ £Χ ι Ο Ο «ο· α. U Χ-» ε α 1 ο CM υ ♦ χ 1 >5 υ 0 II Ρ ro £- •γ-* φ Ο ό > r- Ρ υ 4Φ I! Ο ίθ Μ- © ι— φ II (0 £ £ ο < Ο XΕ *σ Ε in c ο στ σ χ £ ο •ι- ΟII <Ρ Ε to ο X S- ο

Claims (5)

WHAT WE CLAIM IS:1. A compound of the formula where 5 n is 3, 4 or 5; Rx is hydrogen or methyl; Q is fluorine, chlorine, bromine or iodine; X is fluorine, chlorine, bromine, iodine, cyano, methoxy or nitro; Y is hydrogen, fluorine or chlorine; 10 Z is hydrogen or fluorine; and V is hydrogen, fluorine, chlorine or methoxy; with the proviso that (a) when £ is 5, Rj must be hydrogen, Q must be chlorine or bromine, Z and V must both be hydrogen and Y must be hydrogen or fluorine; 15 (b) when £ is 3 or 4 and Q is fluorine or iodine, Rj, Z and V must be hydrogen and Y must be hydrogen or fluorine; (c) when £ is 3 and Rx is methyl, Q must be chlorine or bromine, Y must be hydrogen or fluorine and Z and V must be hydrogen; and (d) when V is other than hydrogen, X must be fluorine, chlorine or 20 bromine and Z must be hydrogen.

1. —6. 34. A composition for the control of undesirable vegetation comprising a compound of claim 1 and at least one of (a) a surface-active agent, and 20 (b) a solid or liquid diluent. 35. A composition for the control of undesirable vegetation comprising a compound of claim 2 and at least one of (a) a surface-active agent, and (b) a solid or liquid diluent. 36. A composition for the control of undesirable vegetation comprising 25 a compound of claim 3 and at least one of (a) a surface-active agent, and (b) a solid or liquid diluent. - 109 7 7 6 37. A composition for the control of undesirable vegetation comprising a compound of claim 4 and at least one of (a) a surface-active agent, and (b) a solid or liquid diluent. 38. A composition for the control of undesirable vegetation comprising 5 a compound of claim 5 and at least one of (a) a surface-active agent, and (b) a solid or liquid diluent. 39. A composition according to claim 34 comprising a compound of any of claims 6—10. 40. A composition according to claim 34 comprising a compound of 10 claim 11, 12 or 13. 41. A composition according to claim 34 comprising a compound of claim 14 or 24. 42. A composition according to claim 34 comprising a compound of any of claims 15—20. 15 43. A composition according to claim 34 comprising a compound of any of claims 21—23. 44. A composition according to claim 34 comprising a compound of claim 25, 45. A composition according to claim 34 comprising the compound of !0 claim 26. 46. A composition according to claim 34 comprising the compound of claim 27. 47. A composition according to claim 34 comprising the compound of claim 28. 5 48. A composition according to claim 34 comprising the compound of - 110

2. A compound of claim 1 wherein £ is 4. - 107 4 3 7 7 6

3. A compound of claim 1 wherein £ is 3. 4. Ξ7 7 G claim 29. 49. A composition according to claim 34 comprising the compound of claim 30. 50. A composition according to claim 34 comprising the compound of claim 31. 51. A composition according to claim 34, substantially as hereinbefore described with reference to any one of Examples 7—22. 52. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 1. 53. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 2. 54. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 3. 55. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 4. 56. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 5. 57. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of any of claims 6—10. - Ill , *! 7 58. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 11, 12 or 13. 59. A method for the control of undesirable vegetation comprising 5 applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 14 or 24. 60. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of any of claims 15—20. 10 61. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount bf a compound of any of claims 21—23. 62. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally 15 effective amount of a compound of claim 25. 63. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of claim 26. 64. A method for the control of undesirable vegetation comprising 20 applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of claim 27. 65. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of claim 28. 15 66. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally - 112 S *Γι )·> J./ fy fcfc ( t 5 effective amount of the compound of claim 29. 67. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of claim 30. 5 68. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of claim 31. 69. A method for the control of undesirable vegetation in rice comprising applying to the locus of such undesirable vegetation a herbicidally 10 effective amount of a compound of any of claims 1—33. 70. The method of claim 69, wherein said undesirable vegetation is Echinochloa crusgalli. 71. The method of claim 69 or 70 wherein the compound is 3-chloro2-(4-chloro-2-f1uorophenyl)-4,5,6,7-tetrahydro-2H-i ndazole. 15 72. The method of claim 69 or 70 wherein the compound is 3-chloro2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-i ndazole. 73. The method of any of claims 69—12 wherein the rice is padtlyrice. 74. A method for the control of undesirable vegetation in wheat which comprises applying to the locus of such undesirable vegetation a herbi20 cidally effective amount of the compound of any of claims 1—33. 75. The method of claim 74, wherein the compound is 3-ch1oro-2-(4chloro-2-f1uorophenyl)-4,5,6,7-tetrahydro-2H-indazole. 76. The method of claim 74, wherein the compound is 3-chloro-2-(4chlorophenyl)-4,5,6,7-tetrahydro-2H-i ndazole. 25 77. A method for the control of undesirable vegetation in transplanted - 113 6 crops which comprises applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of any of claims 1—33. 78. The method of claim 77 wherein the compound is 3-chloro-2-(4chloro-2-f1uorophenyl)-4,5,6,7-tetrahydro-2H-indazole. 5 79. The method of claim 77, wherein the compound is 3-chloro-2-(4chlorophenyl)-4,5,6,7-tetrahydro-2H-i ndazole. 80. The method of claim 63 substantially as exemplified herein. 81. A process for making a compound of claim 1 wherein η, X, Y, Z and V are as defined in claim 1 and Q is chlorine or bromine, which 10 comprises reacting a compound of the formula where £, R ls X, Y, Z and V are as previously defined; with at least an equivalent amount of a phosphorous oxyhalide of the formula P0Q 3 15 where Q is chlorine or bromine. 82. A process for making a compound of claim 1 wherein £ is 3 or 4; Q is iodine and R ls X, Y, Z and V are as defined in claim 1, which comprises reacting a diazonium salt of the formula - 114 Γ776 where £, Rj, X, Y, Z and V are as previously defined and A is Cl, HSOi,, Η 2 ΡΟ 4 or other counter ion corresponding to an acid HA used for preparation of the diazonium salt with at least an equivalent amount of an ionic iodide 83. A process for making a compound of claim 1 wherein Q is fluorine, 5 £ is 3 or 4; and Rj, X, Y, Z and V are as defined in claim 1 which comprises decomposing a corresponding diazonium salt of the formula in the presence of fluoboric acid with at least an equivalent amount of an ionic fluoride. 10 84. A process according to claim 81, 82 or 83 substantially as illustrated in Examples 1—6. 85. A compound of claim 1 where £ is 4 or 5, Rj is hydrogen or methyl, Q is chlorine or bromine, X is fluorine, chlorine, bromine, cyano, methoxy or nitro, Y is hydrogen, fluorine or chlorine and Z and V are each hydrogen 15 or fluorine, at least one being hydrogen, with the proviso that at least one of X, Y and Z is other than hydrogen. 86. A compound of claim 1 wherein Q is chlorine, bromine or iodine; X is not iodine; V is hydrogen, fluorine or chlorine; with the provisos that at least one of X, Y and Z is other than hydrogen; and at least one 20 of X, Y, V and Z is hydrogen. 87. A method for the control of undesirable vegetation comprising - 115 43776 applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of claim 85. 88. A method for the control of undesirable vegetation comprising applying to the locus of such undesirable vegetation a herbicidally

4. A compound of claim 1 wherein Y is hydrogen or fluorine and Z and V are hydrogen. 5. A compound of claim 1 wherein Q is chlorine. 5 6. A compound of claim 1 wherein ji is 4 and Q is chlorine or bromine. 7. A compound of claim 2 wherein Q is chlorine. 8. A compound of claim 6 wherein Ri is hydrogen. 9. A compound of claim 8 wherein Q is chlorine. 10. A compound of claim 8 wherein Q is bromine. 10 11. A compound of claim 3 wherein Q is chlorine or bromine, 12. A compound of claim Π wherein Rj is hydrogen, 13. A compound of claim 12 wherein Q is chlorine. 14. A compound of claim 1 wherein Q is chlorine, Z and V are hydrogen and Y is hydrogen or fluorine. :5 15, A compound of claim 7 wherein R x is hydrogen, Z is hydrogen and V is hydrogen. 16. A compound of claim 15 wherein Y is hydrogen or fluorine and X is fluorine, chlorine, bromine, cyano or methoxy. 17. A compound of claim 16 wherein X is chlorine or bromine. 0 18. A compound of claim 10 wherein Z is hydrogen and V is hydrogen. 19. A compound of claim 18 wherein Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, cyano or methoxy. 20. A compound of claim 19 wherein X is chlorine or bromine. 21. A compound of claim 13 wherein Z is hydrogen and V is hydrogen. 5 22. A compound of claim 21 wherein Y is hydrogen or fluorine, and X - 108 is fluorine, chlorine, bromine, cyano or methoxy. 23. A compound of claim 22 wherein X is chlorine or bromine. 24. A compound of claim 14 wherein X is chlorine or bromine. 25. A compound of claim 1 wherein jn is 3, Q is bromine, Z is hydrogen, 5 V is hydrogen, Y is hydrogen or fluorine and X is chlorine or bromine. 26. 3-Chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2Hindazole. 27. 3-Chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole. 28. 3-Bromo-2-(4-chloro-2-f1uorophenyl)-4,5,6,7-tetrahydro-2H-i ndazole. 10 29. 3-Chloro-2-(4-bromo-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole. 30. 3-Chloro-2-(4-chloro-2-fluorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole. 31. 3-Chloro-2-(4-chlorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole. 32. Compounds of claim 1 as hereinbefore specifically disclosed 15 excepting the compounds of claims 26—31. 33. Compounds of claim 1, substantially as illustrated in Examples

5. Effective amount of a compound of claim 86.