CA1071216A - Cycloalkanapyrazole herbicides - Google Patents

Abstract

ABSTRACT OF THE INVENTION

Herbicidal cycloalkanapyrazoles of the formula:

(I) where n is 3, 4 or 5;
R1 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 n is 5, R1 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 n is 3 or 4 and Q is fluorine or iodine, R1,Z and V must be hydrogen and Y must be hydrogen or fluorine;

(c) when n is 3 and R1 is methyl, Q must be chlorine or bromine, Y must be hydrogen or fluorine and Z and V must both be hydrogen;
and, (d) when V is other than hydrogen, X must be fluorine, chlorine or bromine and Z must be hydrogen.

Description

BACXGROUND O~ T~ INV~TION

Recently, in German Offenlegung~schrift

2,165,651 a group of lsoindole-1,3-diones which are useful a~ herblcide~ wa~ disclosed. The general formula for the isoindole-1,3-diones disclosed in the Offenlegung~chrift ls a~ follows:

Il .

-R
C/ ~.
O ' wherein R may be an aryl, aralkyl or benzyl ~ubstituent optlonally ~ubstituted with 1 to ~ halogen atoms or a hydroxy, nitro, cyano, thiocyanato, carboxy, aIkyl or halogenated alkyl, alkoxy, lower alkylthio or phenyl group. R may also be optlonally substltuted wlth a group ha~ing the configura-tlon -O-CH ~ where A i~ a phenyl or a naphthyl group. The phenyl group may contaln one or more halogen atom~, nitro groups, lower alkyl group~ or lower alkoxy groups.
TMical of the compounds disclosed in the Offenlegungsschrlft is the compound o~ ~tructure 1:

~ \ N ~ Cl (1) o

- 3 -''"`i' ~ .

'Z~6 Although the compounds di~closed within the O~fenlegungsschrift are active herbicides, the need still exist~ 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 situatlon, wherein ~ood shortage~ are acute, it i8 mo~t lmportant to harve~t the maximum pos~ible ylelds of crop~ sueh as rlce or wheat. ThU8, a need exl~ts for a particularly e~fect-ive herbicide whlch will destroy as many weeds a3 pos~ible wlth-out cau~ing ~lgnlf~cant damage to de~lred crops, e.~., rice or wheat.
According to the lnstant lnvention, compounds have been discovered whlch are hlghly actlve herblcldes and yet cau~e minlmal damage to certaln deslred crops, e.g., rice and wheat, and especially the ma~or ~orld food crop, rice, e preparatlon and fungicldal utllity of the 2-(4-chlorophenyl)-1,2,4,5,6,7-hexshydroindazol-3(3H)-one is dlsclosed in T~keda Chem. Ind. Paper, Chem. Abs., 67, 11542h (1967), 0 C~3~1 2-Aryl-4,5,6,7-tetrahydro-1-alkyl-lH-lndazol-3(2H)-ones are claimed as antipyretics ln Ger. 668.628 ~signed to P. Boierdorf & Co. AG, Chem. Abs., 33, 51312 (1939 ~ and U.S.P.
2,104,348 rasslgned to E.R. ~quibb Co,, Chem, Abs., 32, 1869 (1938 ~.

~ Ar ., I

, /~ - 4 _ German Orfenlegung~schrfit 2,409,753 discloses herbicldes hav1ng the general formula R2 ~--R'3' ln which Rl is hydrogen, an alkyl, cycloalkyl or aralkyl radlcal, a phenyl group whlch may be substitu~ed or an acyl radlcal havlng the ~ormula -C0-R6 or -C0-N -R~

R6 ls hydrogen, an alkyl radical which may be substltuted, an alkoxy or phenoxy radical or a phenyl radical and 7 8 R and R are the same or different and can be hydrogen, alkyl, phenyl which may be substituted or alkinyl, R is an alkyl radical which may be substituted, a cycloalkyl radlcal or a phenyl radical which may be substi-tuted or a heterocycllc radical with 0, N or S atoms in the ring, R3 ls hydrogen, chlorlne, bromlne or a low-molecular-welght alkyl radical, R4 ls the radical -S-R5, -So-R5 or -So2-R5 and R ls an al~yl radical, cycloalkyl radical, aralkyl radical or a phenyl group whlch may be substituted or a hetero-cycllc radlcal with 0, N or S in the rlng.
An intermediate for preparing these herbicides by reaction with a mercaptan having the general formula RsSH is R2 ~31 N a where Rl, R2, R3 and R5 have the previously given meanings and Hal represents chlorine, bromine or iodine.

. -4A -';'lZ16 l-P~enyl-3,4-trime~hylenepyrazolone ls disclosed in U.S. 1,685,407 (1928) with utility as an in*ermediate for making dyes and medicinal compounds. C. Mannich in Arch;
Pharm. 267, 699-702 tl929) and in Brit. 260,577 describes the preparatio~ of l-phenyl-3J4-trimethylenepyrazolones. :
, ~,r~

R. P. Wllliams et al. in J. Med. Chem. 13, 773 (1970) reports the preparation and evaluation as anti-inflammatory agents compounds of the following type:

U y~l~x 20 X- H, Br, F.

DESCRIPTION OF THE INVENTION

. 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.
Rll Q

(CH ~ X (I) ;. Z V

- ` iO'7~;Z16 where n is 3, 4 or 5; ~:
Rl is hydrogen or methyl;
Q is fluorine, chlorine, bromine or iodine;
X is fluorine, chlorine, bromine, iodine, cyano, methoxy or nitro;
Y i8 hydrogen, fluorine, or chlorine;
Z is hydrogen or fluorine; and V is hydrogen, fluorine, chlorine or methoxy with the proviso that (a) when n is 5, Rl 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 n is 3 or 4 and Q is fluorine or iodine, Rl, Z and V must be hydrogen and Y must be hydrogen or fluorine;
~c) when n is 3 and Rl is methyl, Q must be chlorine or bromine, Y must be hydrogen or fluorine and Z and V must both be hydrogen;
and, (d) when V is other than hydrogen, X must be fluorine, chlorine or bromine and Z must be hydrogen.

Of those compounds of Formula I, preferred for their high herbicidal activity or favorable cost or both, are those compounds where, independently, 1) n is 3 or 4;
2)Q is chlorine or bromine;
3) Rl is hydrogen or methyl;

4) Z and V are both hydrogen;

~071Z~6 , .

5) Y is hydrogen or fluorine; or,

6) X is fluorine, chlorine, bromine, cyano or methoxy.
Of those compounds of Formula I where n is 4, pre-ferred are those where Q is chlorine or bromine.
More preferred are those compounds where n is 4, Q
i8 chlorine or bromine, and Rl is hydrogen~
Of those compounds of Formula I where n is 4, Q is chlorine or bromine and Rl 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 i8 chlorine or bromine, Rl is hydrogen and Z and V are both hydrogen.
Of those compounds of Formula I where n is 4, Q
i5 chlorine or bromine, Rl 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 4, Q is chlorine or bromine, Rl is hydrogen, % and V are both hydrogen, Y is hydrogen or fluorine and X is fluorine, chlorine, bromine, cyano or methoxy.
3o -- 7 _ 12~6 . ;
Most preferred for their excellent herbicidal activity or highly favorable cost or both are those compounds of Formula I where n is 4, Q is chlorine or bromine, Rl 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 n is 3, pre-ferred are those compounds where Q is chlorine or bromine.
More preferred are those compounds where n is 3, Q
0 i8 chlorine or bromine, and Rl is hydrogen.
Of those compounds of For~ula I where n is 3, Q is chlorine or bromine and R1 is hydrogen, preferred are those compounds where, independently, 1) 2 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, Rl is hydrogen and Z and V are both 2 hydrogen.
Of those compounds of Formula I where n is 3, Q is chlorine or bromine, Rl 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, Rl is hydrogen, Z and V are both i~)'7iZ16 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 n is 3, Q is chlorine or bromine, Rl 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.
More preferred are those compounds where Y is hydrogen or fluorine and Z and V are both hydrogen where, independently, 1) Q is chlorine; or, 2) X is chlorine or bromine.

Of those compounds of Formula I, preferred for their higher herbicidal activity or more favorable cost or both, are tho~e compounds where Y is hydrogen or fluorine, Z and V are both hydrogen and Q is chlorine.
Most preferred for their excellent herbicidal acti-vity or highly favorable cost or both are those compounds of Formula I where Y is hydrogen or fluorine, Z and V are both hydrogen, Q is chlorine, and X is chlorine or bromine.
Specifically preferred for their outstanding herbi-cidal activity or favorable cost or both are 1) 3-Chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole; m.p. 88-89.5C;
2) 3-Chloro-2-(4-chlorophenyl)-4,5,6,7-tetra-3 hydro-2H-indazole; m.p. 81-84;

-- g ~071216 : .
3) 3-Bromo-2-(4-chloro-2-fluorophenyl)-4,5,6,7- ;
tetrahydro-2H-indazole; m.p. 95-98&; ~
4) ~-Chloro-2-(4-bromo-2-fluorophenyl)-4,5,6,7- ~ :
tetrahydro-2H-indazole; m.p. 86-88C;
5) 3-Chloro-2-(4-chloro-2-fluorophenyl)-2,4,5,6- .
tetrahydrocyclopentapyrazole; m.p. 101.5-104C; and, 6) 3-Chloro-2-(4-chlorophenyl)-2,4,5,6-tetra-hydrocyclopentapyrazole; m.p. 114.5-117C.
10 : ~ .
SYNTHESIS OF THE COMPOUNDS
The novel cycloalkanapyrazoles of Formula I where Q i8 Cl or Br are prepared in two steps as shown by Equations A and ~:

A
Y
H ~ NHNH2 ~ C-OR ~ Y H
,~J_ z ~ f HA + (C~ (C~ 3 B.

(CI~X + P003 ~ (CHz)~ X

Z V Z V

~7~2~6 , where Rl, n, X, Y, V and Z are a3 derined above, Q 18 Br or Cl;
R is a~$yl of 1 to 3 carbon atom~;
f is 0 or 1, and A i~ an anion o~ the corre~pondin~ acid HA
having an ionlzation con~tant Or at least 1 x 10 7, e.g. H2S04 or HCl.
-~ The preparatlon Or the annelated pyrazolones 3 i9 known in the llterature, ~or exu~ple, the preparatlon of 2-aryl-1,2,4,5,6,7-hexahydro-3H-inaazol-3-ones (3, n = 4) 18 described in N. Dleckmann, Ann., 317, 102 (1901). me ~-keto ester 2 1B
combined with the approprl~te aryl hydrazine acid ~alt 1 ln an appropriate solvent, such as a lower alcohol, or aromatlc hydrocarbon, and, optionally, ln the pre~ence of an acid acceptor, ~uch BB a tertiary organic amlne or alkali metal hydroxide or alkoxide and the reactlon mlxture 18 heated at re-lux rOr 0.5-24 hours. me pyrazolone 3 is lsolated by conven-tlonal techniques such as by pourlng the reactlon mass lnto ~ater ~na rllterlng the product. The crude product 18 usually 20 of surficlent purity to be used dlrectly ln the next step. If necessary, further purlflcatlon can be accompll~hed by re-crystalllzatlon, sublimatlon, or other conventlonal technlques known to tho~e skilled ln the art. This ~ame procedure can be u~ed to prepare those compounds of rormula ~ ln ~hlch n ~ 5, ffle pyrazolones ~ ~here n 1~ 3 are prepared by com-blning the appropriate argl hgdrazlne ~ith the appropriate alkyl 2-oxocyclopentanecarboxylate ln a sultable solvent such as toluene or chlorobenzene. ffl e reactlon i8 heated at reflux and ~ater 18 slmultaneously removed to yield a hydrazone.
Cycli~atlon to the pyra~olones 3 ~here n 18 3 i8 then efrected .

~7~ .6 by adding 1-3 equivalent~ of an alkall metal alk~xide such a~
~odium methoxide to the hydrazone solution and heating for 1-5 hour~ at 80-130C.
Methods taught in Arch. Pharm., 267, 699-702 (1929) and J. Med. Chem., 13, 773 (1970) are also u~eful in pre-paring p~razolones of formula 3 in which n = 3.

" Y H
-OR ~ X

Q
p-OR
R ~ I ~ I H ~ R~
H \ ~ X NH ~ ~ X

~ ~ hydrazone Alternatively, the hydrazone may be isolated and subsequently 1~ cyclized by treatment with two equivalents o~ n-butyl lithium ln a solvent such as THF at temperatures of 0-60C for a period of 2-18 hours.
me ~yrazolones 3 where n 18 3 are l~olated by pour-lng the reactlon mass into water~ separatlng the organlc layer and acidlfyine the aqueous layer with a mineral acld, i.e., HCl, H2S04. From the acidifled aqueous layer the desired product i8 o~tained by filtration, centrifugation, extraction or other ~lmilar techniques.

iE)7~2~6 m e novel cycloalkanapyrazole~ of Formula I where Q
18 chlorlne are obtained by heating the annelated pyrazolones 3 with phosphorous ox~chloride (formula 4, Q i8 chl~rine).
When Q 15 bromine ln Formula 1, pho~phorou~ oxybromide (formula 4, Q i~ bromine) in the presence of an N,N-di~lkylaniline and dimethylformamide is used (Equatlon B).
- The use of an inert organic solvent such a~ methylene chloride or toluene i8 optional; however, lt 1~ preferred that no solvent other than the phosphorou3 oxychlorlde or bromide be used. The mlxture 18 heated at 100-180C, preferably 140-150C., for a perlod of 1-10 hours. m e crude reaction mixture ls dl~solved in an lnert organlc solvent (e.g., CHC13, CH2C12, or toluene), and the Qolutlon 18 washed wlth dilute aqueouY base (e.~., NaOH or KOH) ~ollowed with water. me organlc phase 18 drled, and the solvent is removed on a rotary evaporator or by distillatlon. The product obtalned i8 the pyrazole of Formula I and may be purl~ied by dlstlllatlon, subllmatlon or crystal-llzation rrom an approprlate solvent.
Compounds o~ Formula I where Q 18 iodlne are pre-pared ~rom corresponding aminopyrazoles vla dlazotlzatlon with nitrous acld and reactlon with potassium lodide accordlng to the method of Spanlsh Patent No. 394,208 ~ hem. Abst., 83, 972834 (1975~. me requlred aminopyrazole~ are prepared from the appropriate ~-cyanocyclohexanone or ~-cyanocyclopentanone by reaction wlth approprlate aryl hydrazine in a solvent such as toluene. The overall ~equence ror preparlng compounds of Form-ula I where Q i~ iodine is ~llustrated by equation A2 and B2:

~9'7lZ~6 A2 ~ B2 (CH / ~ H2~H

Rl R

(CH2~ Y 1. ~N02 (CH2~K) </
N' \ I ~ 2. KI N ~ ~/ \~ X
\~,X z>~V

The required d-cyanoketones can be prepared by a number Or ; methods well known ln the art. For example, ~-cyanocyclo-hexanone 18 prepared from ~-chlorocyclohexanone and sodlum cyanlde accordlng to R. Meyer in Helv. Chim. Acta, 16, 1291 (1933). ~-Cyanocyclopentanone i~ prepared from adlponitrlle and a strong base such as a llthium dlalkylamlde follo~ed by acid hydrolysls according to ~er. 591,269 (Jan., 1934~ ~.A.
28, 117 (1934~ Cyanocycloaliphatlc ketone~ can also be prepared from cycloal~anone enamines and cyanogen chlorlde according to the method of M. E. Kuehne, J. Am. Chem. Soc., 81, 5400 (1959).
Compounds Or Formula I where Q i~ fluorine are prepared aa shown ln equatlons A3 and B3 ~rom photolysis of correspondlng 3-diazonlum fluoborate (equatlon B3 107~Z16 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, J. Am. Chem. Soc., 78, 6037 (1956).
A3 and B3 ' Rl ~H2 Y ~ ll N~BF4 Y

~CU~--~ ~ (~X

wlth KF ) (CH ~ I z ~ V X

Intermediate B-keto esters 2 are commercially available or ~re prepared by methods well described in the literature: G. Stork et 81., J. ~m. Chem. Soc., 85, 207 (1963). The general procedure is shown in Equations C, D
and E, 2iG
`'~ C.

(C~ +~` Hll~O ~ 'C~3L,~o + H20 , D- O -~
: R O R "
(C ~ ~ + ROC-Cl ~ (-N ~ ~ ~

: 7 8 9 ~ .
R
(CH ~ . HCl ~\ /--\ - ' N O

E. O
i -- " O
~ C-OR ~ C-OR
(CH ~ /~~~\ ~ (CH

Enamlne 7 18 prepared by heating ketone 5 and morpholine 6 (pyrrolldine may also be used) ln an approprlate solvents, such as benzene, toluene, or chlorobenzene, with simultaneous removal Or water from the reactlon by azeotropic distillation (Equation C). The alkyl chloroformate 8 i9 added to the enPmlne 7, and thls mixture ls heated at a temperature from 70C to the boillng point of the ~olvent for a period o~ 1-10 hours. The enamine hydrochloride lO which ls produced as a by-product in the reaction is removed by :' ;

.

1~ 7~Z~6 flltration. me morpholine enamine 9, ~hich ls contained in the organlc ~iltrate, is converted to the ~-keto e~ter 2 by hydrolysi~ wlth aqueous mineral acid (e.~., hydrochloric acld) at temperatures ranging from ambient to 75C (Equa-tion ~). The product 1~ isolated by conventional techniques such as extractlon lnto a suitable organic solvent followed by evaporation o~ the solvent. m e product may be ~urther purified by fractional distillatlon under reduced pressure, ~ubllmation, or crystallization.
The u3e of 3-methylcylohexanone 5a lead~ to a mix-ture of methyl-substltuted p -keto esters (2a and 2b). If this mlxture of methyl-sub~tituted P -keto esters i3 reacted with an aryl hydrazineJ a mixture of 4- and 6-methyl-substi-tuted-2-aryl-1,2,4,5,6,7-hexahydro-3H-indazol-3-ones (3a and 3b) is produced; subsequent treatment with phosphorous oxyhalide ~ will produce a mixture containing both the 4- and 6-methyl-substltuted-3-halo-2-aryl-tetrahydroindazoles of this inventlon. I~ the mixture o~ isomeric methyl cyclohexa-nones is 8ep~rated, then 2a and 2b ~ill lead to 3a and 3b re~pectively when treated with an arylhydrazine.

C ~ +

5a 2a 2b aryl hydrazlne Ar + ~ -Ar 3a 3b 1~71~Z16 : 3a 3b ,. ~ /

-Ar ~ ~ -Ar In the case of the 2- or 4-methylcyclohexanones, the ~-keto ester synthesis i8 more specific and predominately one isomer is produced, as summarized schematically in Equations 10 F and G. 2-Methylcyclohexanone produces 7-methyl-3-halo-2-aryl-4,5,6,7-tetrahydroindazole, and 4-methylcyclohexanone produces 5-methyl-3-halo-4,5,6,7-tetrahydroindazoles.

~ ~ COzR ~ ~ r -- .
Q

CH ~ CH ~ ____3 _~ ~ -Ar The required alkyl-2-~xoc~clopentanecarboxylates can be prepared by methods previously described and by methods described in Organic Reactions, lS, 1-203 (1967).

3o ~C~7 l~Z~6 ' The preparatlon of aryl hydrazine~ 1 from anilines is well documented in the literature: G.H~ ~oleman, Or~anic Syntheses, Coll. Vol, I, J. Wiley ~ Son~, New York, p. 442 and H. Kindler et al., Fr. 1,419,092. A general procedure 18 illustrated in Equation H:
H. y Y

H ~ / 2 1) N N02/~A~ H ~ -NH2 f HA
X ~ 3) HA ~ ~z The anlline 11 ls diazotized at about -5 to 5C
wlth sodium nltrite in a~ueous acid (HA, where A i8 defined ~8 above) such as hydrochloric acid; the result~ng ~olution 1~ mixed wlth an aqueous sodium blsulfite solution at 0-20C, heated to 50-80C ior 0.5-2 hr. and then acldified with the mineral acid to give the aryl hydrazine acld salt 1. The hydrazlne salt often crystallizes directly from the reaction mixture and can be isolated by iiltration or by other con-ventional techniques. In most instances the hydrazlne can : be used without further purlfication.
Certaln hydrazine~ used ln preparing compounds de-iined by thls invention are novel; e.g., 4-chloro-2-fluoro-phenylhydrazine hydrochloride 1B a novel compound whlch can be prepared by the method descrlbed above. The followlng novel hydr~zlnes can also be prepared by thls method:
4-bromo-2-iluorophenylhydrazine hydrochloride 2-fluoro-4-methoxyphenylhydrazine hydrochloride 2,4,6-tri~luorophenylhydrazine hydrochloride 2- Muoro-4-nitrophenylhyarazine hydrochloride 4-cyano-2-fluorophenylhydrazine hydrochloride Al~o useful for preparing aryl hydrazlne~ ls the method descrlbed by M.S. Gibson et al., J. Chem. Soc. (e) 1970, 2106 and M.S. Gibson et al., J. Chem. Soc. (C), 1974, 215.

Representative aniline ~tarting materials for these hydrazines are prepared a3 de3crlbed belo~. 4-Chloro-2-fluoroanilineJ for example, can be prepared from 2'-fluoro- -acetanilide ~G. 8chiemann and H. G. Baumaarten, Chem. Berichte, 70, 1416 (1937~ by the reactlon sequences shown below:

O O
~H-C-CH3 ",~ H-C-CH3 Cl CH3COOHCl - ~ - / ~ Step A

~NH-C-CH3 ~NH2- HCl C ~ CH3CH20~-H20 ~ Step B

C ~ NH2-HCl Cl ~ H2 Step C

~te~ A
Chlorination of acetanilide~ ln acetlc acld i~
well known to tho~e skilled ln 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 chlor-ination of acetanilide. The chlorlnation of 2'-fluoro-~071'~6 acetanilide ta~es place at 25-30C over several hours (e.g. 5) at atmospheric pressure. The resulting product i8 4'-chloro-2'-fluoroacetanilide.
c Step B
The chlorofluoroacetanilide is refluxed in a mixture of a lower alcohol (50%) (e.g. ethanol) and concen-trated hydrochloric acid (50%~ for several hours (e.g. 5 or re) at 70-90C and atmospheric pressure. The solvent mixture is removed at a reduced pressure of 100 to 300 mm.
10 Hg and at a temperature of 20-50C.to leave a residue of the hydrochloride salt of 4-chloro-2-fluoroaniline.
Step C
After basification of an a~ueous 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 20 of the organic solvent under a reduced pressure of 100 t~
300 mm.Hg at 20-50C.
2-Fluoro-4-bromoaniline can be prepared by bromination of 2-fluoroaniline ~prepared in Chem. Berichte, 70, 1416 (1937)~ with N-bromosuccinimide as shown in the following equation.
o C / Br~ NH2 _ 21 --1C~7~Z~6 Bromination of anilines using N-bromo-succinimide in ~n inert organic solvent such as methylene chloride i~ well known to those skilled in the art, e.g., J. B. Wommsck et al., J. Het. Chem., 6, 243 (1969).
Bromination of 2-fluoroaniline is an exo~hermic reaction that takes place at 0C over several hours, e.g. 5 or more. The resulting reaction mixture is washed with water several times and dried with ~n appropriate drying agent such 8S
~nhydrous 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 20-50C.
2,4,6-Trifluoroaniline is prepared by reduction of l,3,5-tr~fluoro-2-nitrobenzene [V. I. Siele and H. J.
Matsugams, U. S. Department Commerce, Office Serv., P B
Rept. 145, 510, p. 1 (1960) or Chem. Abst.,~15394c (1962)~
using the procedures described by G. Schiemann and M. Seyhan, C _ . Berichte, 70, 2396 (1937).

F F
J \ ~ NOz ~ NHz F ~ F F ' \ - ~F

2,4-Difluoroaniline is known to the art and can be prepsred by the procedure described in G. Scheimann and M. Seyhan C _ . Berichte,70, 2396 (1937).

~3'71Z~

4-Amlno-3-fluorobenzonitrile, u~ed in the prepara-tion o~ 4-cyano-2-fluorophenylhydrazlne hydrochloride, can be prepared from 4-bromo-2-fluoroanillne by treatment with cuprous cyanide in N-methylpyrrolidone using known pro-cedure3: ~. Friedman, et al., J. Org. Chem., 26, 2522 (1961). ~he reaction mixture i8 heated to re~lux for ~everal hours and then poured onto lce and sodium cyanlde.
m e resulting ~olution i~ heated between 50-80C for a perlod of 1-3 hour~, cooled, and extracted with toluene;
the toluene extract i8 wa~hed wlth water, dried with a suitable drying agent, and evaporated to give 4-amino-3-fluorobenzonitrlle.
2-Fluoro-4-methoxy~nll~ne, u~ed ln the prepara-tion of 2-fluoro-4-methoxgphenylhydrazlne hydrochlorlde, i8 known and can be prepsred by the method of H. Hodgson, et al., J. Chem. Soc., 1268 (1940).
2-Fluoro-4-nitroaniline, used to prepare 2-fluoro-4-nltrophenylhydrazlne hydrochlorlde, i8 also a known com-pound and can be prepared accordlng to the method of J. B.
Dlc~ey, U.~. Patent 2,436,100.

.

- 107~Z16 The following examples further illustrate the method for synthesis of compounds of this invention. All parts are by weight and all temperatures in degr~es centigrade.

, ExamPle 1 PreParation of 3-Chloro-2-(4-chloro-2-fluorophenyl)-4,5,6~7-tetrahYdro-~M-indazole lO Cl O~CI

(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 soo parts glacial acetic acid, during one hour, at ?5-27 , with ice-water cooling. While stirring for 4 hours at ~5-~7 , 4'-chloro-2'-fluoroacetanilide precipitated. After collecting ., the product by filtration, the filtrate was poured over ~000 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 119 parts of 4'-chloro-2Lfluoroacetanilide a~ white crystals melting at 152-155 .

.

10712~6 A mixtu-Le of 119 parts of 4'-chloro-?'-fluoro-acetanilide 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 extràcts were dried with anhydrous sodium sulfate and the 801vent removed under a reduced pressure Or 300 mm. Hg to leave 89 parts of light brown, oily 4-chloro-~-fluoroaniline, nD 5 : 1.5541.

(b) Preparation of 4-Chloro-2-fluorophenYlhYdrazine HYdrochloride 20.0 Parts of 4-chloro-2-fluoroaniline was dissolved in 80 parts of water and 34 parts of concentrated hydrochloric acid, The solution was cooled to 0 -10 and 3?.? parts of 30% 80dium nitrite was added dropwise maintaining the tempera-ture of the reaction between 0-10~. After the addition of nitrite was completed, the solution was stirred for thirty minutes at 0-10. Excc s~ nitrite was destroyed by addition of small amounts of sulfamic acid When a negative ~07~Z~6 test with sulfone reagent was obtained, the diazonlum salt ~ -wa~ ready for reduction. For a description of the ~ulfone test, see H. E. Fierz-David et al., Fundamental Proce~es of ~ Chemi~try translated from 5th Austrlan Ea. by P. W.
Wittam, Interscience Publishers, Inc., New York, 1949, p. 243.
In a separ~te vessel 35.4 parts o~ sod~um biful-~ite and 32.2 parts of 30~ sodlum hydroxide solution were dissolved ln 140 parts of water. me solutlon wa~ heated to 40. '~he diazonium salt was added to the bi~ulfite ~olu-tlon over a perlod of about 1 hour. The mixture was heated to 70 and 0.3 parts of sodlum hydrosulfite was added. The pH waa ad~ustea to 1.2 with 30 part8 of concentrated hydro-chlorlc acid; then an additlonal 90 parts of concentrated hydrochlorlc acid ~as added. The reaction mlxture was heated for 1.5 hours at 70, cooled slowly, and stlrred overnlght at room temperature.
Puri~ication was achleved by heating the reaction mixture to 70 and filterlng. me ~lltrate was cooled to 10 at which tlme 4-chloro-2-~luor~phenylhydrazine hydro-chloride precipitated. Thls product was flltered and dried to yleld 10.7 part~ of yellow crystalllne solid, m.p. 223, (c) Pre~aration of 2-(4-Chloro-2-~luoropheny1)-1,2,4,5,6,7-hexahrdro-3H-indazol-3-one 15.8 Part 8 of 2-~luoro-4-chlorophenyIhydrazlne hydrochlorlde, 13 parts of 2-carbetho~ycyclohe~anone (pur-chas~d from Aldrich Chemical Company) and 8.1 parts of tri-ethylamine were dlssolved ln 100 parts of ethanol, The ~'7~Z ~ 6 reactantz were heated at reflux ~or twenty-four hours. me crude reaction mass was poured into 1000 parts of water.
The re~ulting gummy product solidified and was filtered and dried to yield 16.1 parts Or crude product with m,p. 163-170.
This material was used without further puri~ication in the next step.
By ~ubstituting 4-chlorophenylhydrazine hydrochloride ln the above procedure for 4-chloro-2-~luorophenylhydrazine hydrochloride, 2-(4-chloropheny1)-1,2,4,5,6,7-hexahydro-3H-lndazol-3-one was prepared, m.p. 183.5-185 (Lit 186-187 , Chem. Abs., 67, 11452h).
(d) Preparation of 3-Chloro-2-(4-chloro-2-~luoroPhenyl)-4,5,~,7-tetrahydro-2H-~ndazole 10.0 Parts o~ 2-(4-chloro-2-fluorophenyl)-1,2,4-5,6,7-hexahydro-3H-indazol-3-one and 7.3 parts Or phosphorous oxychlorlde were mixed and heated to 130-150 for 8iX hours.
The reactlon mixture wa~ dissolved in 100 parts of chloroform.
The organlc solution containlng the product was washed success-ively with three portion~ o~ 25 part~ each of 10~ sodium hydroxlde and then washed with 50 part~ water, The chloro-form ~olution was dried with 2-10 parts of anhydrous ~odlum sulrate and then filtered, me solvent was removed under a reduced pressure on a rotary evaporator, The resulting thick oll was purified by sublimatlon at 100-120 at ~71216 0.5-1.5 mm. pressure to y~eld 7.8 parts of white crystalline material with m,p. 88-89.5.
~ Preparations o~ other novel anilines used in this invention are as follows:
PreParation of 4-Bromo-2-fluoroaniline 160 Parts of solid N-bromosuccin~mide ~ere added in po~t~ons over a 2-hour period to a solution of 100 parts of 2-fLuoroaniline in 400 parts of methylene chloride cooled to 0~. Ater stirring for 20 minu~es~ the dark red 10 mix~ure was washed four times; 200 part~ of cold water were used for each washing. The red organic phase was dried w~th anhydrous sodium sulfate and evaporated under 300 mm.Hg to 164 paxts of brown, oily 4-bromo-2-fluoroaniline, n25: 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 lOO ml portions of toluene. The toluene extracts were combined and washed with four 300-mi portions of water followed by 100 ml of saturated NaCl, The toluene ~0'71Z~i 801ution of the product was dried over sodium ~ulfate a~d ~tripped to give 2.6 parts of the desired product, m.p. ?1 73 .
. Usin~ the procedure of Example 1 with 2-carbethoxy-cyclohexanone, the appropriate hydrazine acid salt and phosphorous oxychloride, the following compounds of Formula I are prepared:

O~vx _Q_ Y X V Z m.pC

Cl H Cl H H 81-84 Cl H Br H H 86-88 Cl H N02 H H 10~-105 Cl H CH90 H H oil, ir bands (760 cm~l, 835 cm~l) Cl Cl Cl H H oil, ir bands (735 cm~l, 820 cm~l) Cl H Cl Cl H 69-71 C~ H F Cl H 70-72 ~07~2~6 `
Q Y X V Z m.p.C

- Cl F Br H H 86-88 Cl F CH30 H H
Cl F W2 H H 108-109,5 Cl F CN H H 113-116 Cl F F H H ~ 5 _ 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 ; Cl H F H H 35-37 Cl Cl Br H H 78-79 ' Cl F F F H
,' Cl F I H H 83.5-87 Cl Cl Cl H F 93.5-101 Cl F F H F 57.5-62 Cl Cl F H H 75-78.5 Cl H I H H 91-103 Cl Cl Cl OCH3 H 107-110 Cl F Cl Cl Using the procedure of Example 1 with a methyl ~ubstltuted 2-carbethoxycyclohexanone, the pppropriate aryl hydrazine, and phosphorous oxychloride, the following compound~ may be prepared:

N ~ X

7 Z V

_ 3o _ ;' ``

~71Z~6 Rl Q Y X V Z m p. C
7-CH3- Cl F F F H
7-CH3- Cl F F II F
7-CHb- Cl F Cl . ~ ~ 58-61.5 7-C~- Cl F Br ~ E
7-C~b- Cl F F H H
7-CHb- Cl ~ Cl H H ir835 ds ~570 3 7-CHs- Cl H OCH~ H H nD251,5839 7-CEb- Cl F F H F
5-CH~- Cl F Cl H H 85-88 5-CH~- Cl H Cl H H 96.5-99 6-C~b- Cl F Cl H H 4~.5-44.5 6-CHo Cl F I H H 1~7~an~516 6-CHb- Cl H Cl Cl H
6-CEa- Cl ~ Cl H H 75-76 6-C~- Cl H CN H H 103-105 6-CHb- Cl ~ OC9~ H ~ nD25--1.5839 6-oHb- Cl H ~02 H H 89-91,5 4-CEb- Cl H Cl H H 47.5-52 - f`or ~lxture f 4-CHb Cl F Cl H H 41-45 ~, ~a~ rOr ~ture 6-CH 3- Cl F I H H
6-CH ~- Cl Cl Cl OCH 3 H
Example 2 Prepara tion of 3 -Chloro -2 - (4 -chlorophenyl) -2, 4 ~ 5, 6, 7, 8 -hexahYdrocycloheptapyrazole I Cl '(~ ~-Cl 3-o -1~7:1LZ16 By substituting 2-carbethoxycycloheptanone ~ re-pared by the method of G. Stork, et al., J. Am. Chem. Soc., 85, 207 (1963~ and p-chlorophenylhydrazine hydrochloride (available from Aldrich Chemlcal Compæny) in the procedure o~ Example l(c), 2-(4-chlorophenyl)-1,4,5,6,7,8-hexahydro-cyclohept~pyrazol-3(2H)-one (m,p. 224-225) WAS prepared.
s By react~ng this pyrazolone with phosphorous ~xychloride according to the procedure of Example l(d), 3-chloro-2-(4-chlorophenyl)-2,4,5~6,7,8-hexahydrocycloheptapyrazole 10 (m.p. 59-61) wa~ obtained.
Following the procedure o~ Example 2, using the : appropriate aryl hydrazine hydrochloride (~or ~-chloro-phenylhydrazine hydrochloride) and phosphorous oxychloride, the ~ollowing compound~ o~ FormNla I may be prepared:
O~ X

i Q Y x v z m.p.c Cl F Br H H 82.5-83.0 Cl F F H H
Cl F OCH3 H
Cl F CN H H
Cl P N02 H H
Cl F Cl H H 68-69.5 Cl H CN H H 95-102 Cl H Br H H 53-55 Br F Cl H H
Br F Br H H

.

lO~lZ16 Example 3 (a) Praparation of 2-(4-chloro-2-fluorophenyl)-1,4,5,6-tetrahydrocyclopentapyrazol-3(2H)-one 7.~ Parts of 4-chloro-2-~luorophenylhydrazine and 6.6 parts o~ methul 2-oxocyclopentanecarboxylate (purch&sed ~rom Aldrich Chemical Company) were disæolved in 200 parts toluene. The reactants were heated at reflux for 1-2 hours remo~ing water that wa~ formed. The reaction mlxture was cooled to 100C,, and a ~olution of 5,0 parts o~ sodium methoxide dissolved in 25 parts methanol ua~ added drop-wise, removing methanol as it~ azeotrope with toluene, The reaction mixture WaB heated until the internal temper-ature 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 ~olldiried and was riltered, dried and recrys-talllzed ~rom acetonitrile to yield 3.3 parts of tan crys-talllne material, m.p. 157-160.
Alternatively~ the above pyrazolone was prepared by the rollowing procedure. 16.0 PartQ of 4-chloro-2-rluorophenylhydrazine and 14.2 parts Or methyl 2-oxocyclo-pentanecarboxylate were dissolved ln 100 part~ o~ benzene.
The rcactlon mlxture was rerluxed for 1-2 hours removing water that was ~ormed. The reaction mixture ~as cooled, ~nd the solvent was removed under reduced pressure on a rotary evaporator. me resulting brown oil was dissolved in 150 part~ o~ anhydrous tetrahydrofuran and the solution 3 was cooled to 0 under a nitrogen atmosphere. To the cold reaction solutlon, 2 equivalents o~ n-butyllithium in hexane (purchased from Foote Mineral Company) were added i~7~Z16 at such a rate that internal temperature was ma~ntai~ed at0-5. me reaction mixture was allowed to warm to ambient temperature, then heated at reflux ~or 18 hours. me rePc-tion mixture was cooled and poured into 200 parts ice water~
me organ~c layer was separated, and the aqueous layer waæ
washed twice with diethyl ether. Cold, dilute hydrochloric acid was added to the aqueous layer until pH 2 wa~ attained.
The resulting oily produ¢t solidified, and was ~iltered, dried, and recrystallized ~rom acetonitrile to y~eld 17.5 parts o~ tan crystalline material, m.p. 165-167.
By sub~tituting 4-chlorophenylhydrazine i~ the former procedure for 4-chloro-2-~luorophenylhydrazine, 2-(4-chlorophen~rl)-1,4,5J6-tetrahydrocyclopentapyrazol-3(21I)-one was prepared, m.p. 193.5-195.
(b) Preparation of 3-chloro-2-(4-chloro-2-fluorophenyl)-2,4~5,6-tetrahydrocyclopentapyrazole By reacting 2-(4-chloro-2-fluoropheny1)-1,4,5,6-tetrahydrocyclopentapyrazol-3(2~)-one with pho~phorouP
oxychloride accordlng to the procedure of Example l(d), 3-chloro-2-(4-chloro-2-fluoropheny1)-2,4.5,6-tetrahydro-cyclopentapyrazole (m.p. 102-104) Wa8 obtained.
U8ing the procedure of Example 3 with the appro-prlate methylsubstituted 2-oxocyclopentanecarboxylate, the appropriate hydrazine and phosphorQus oxychloride, the following compounds of Formula I can be prepared:
~ ~X

- ~7~Z~6 Rl Y X V Z m.p.C
~ _ _ _ _ H H Cl H H 114.5-117 ~-H Cl Cl H H 119-123 H H Br H H 120-121 H Cl Br H H 113-119 H F Br H H 105-106.5 H F F H H 110-119 :~

H F F H F ~-H Cl Cl Cl H
H H Br Cl H

H F CN H H

H H CN H H 126.5-128 . H H Cl Cl H 95-98 H H F Cl H
4-CH3 F Cl H H
4-CH3 H Cl H H
~5-CH3 F Cl H H ~ ir bandsll590, 90S, t 4-CH3 F Cl H H r 990 cm 5-CH3 H Cl H H
6-CH3 H Cl H H
. 6-CH3 F Cl H H 88-93 H F I H H
H Cl Cl OCH 3 H
7-CH3 F Cl H H

lC~ 71Z~6 Example 4 Preparation of 3-bromo-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole , :
To 5.0 parts of 2-(4-chlorophenyl)-1,2,4,5,6,7- -hexahydro-3H-indazol-3-one [from Example l(c)~ with 3.0 ~arts of N,N-diethylaniline and S.0 parts of dimethyl-~Q~amide under nitrogen atmosphere was added 6.3 parts o~ pho~phorous oxybromide. The mixture was heated to 1~0 -170 for two hours. ~fter cooling to room temperature, ~e reaction mixture was extracted with 100 parts of diethyl e~ber, washed with water, dried over anhydrous magnesium ~ulfate and concentrated on a rotary evaporator. Recrystal-Li~ation from methanol/water gave 2.7 parts of product, m.p. 101-102.
Using the procedure of Example 4 with the appro-pri~te annelated pyrazolones 3, which can be prepared by a method taught in Example 1 or Example 3, the following compounds can be prepared:
R

(C112~ X

Z V

n Rl Y X V Z mp C
-3 H F Cl H H 106-110 3 H H Cl Cl H : .
3 H H Cl H H 109-112 3 H Cl Cl H H
3 H F F H H ~:

3 H F Br H H
3 4-CH3 F Cl H H
3 6-CH3 F Cl H H :

4 H F Cl H H 95-98 4 H F Br H H

4 H Cl Cl H H 101-102 4 H F No2 H H

4 H H Br H H 84-87 4 H H F H H 70~7 3 4 H H Cl Cl H
4 5-CH3 F Cl H H

4 H Cl Cl OCH3 H

107~Z~6 n R1 Y X V Z
:
4 7-CH3 F Cl H H

H F Cl H H 59-60 Examr~le 5 Preparation of 3-idO~2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole B) Preparation of 3-amino-2-(4-chloropheny )-4,5,6,7-tetrah2dro-2H-indazole A mlxture 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., 16, 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 snhydrous magnesium sulfate and concentrated.
aecryst811izstion from ethanol/water gave 2.6 parts of the compound, m.p. 140-142.
b) Preparation of 3-lodo-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole To 2.5 parts of 3-amino-2-(4-chlorophenyl)-4,5,6,7-~etrahydro-2H-indazole in 2.5 parts of conc. sulfuric acid ~nd 15 psrts of water cooled to 0 was added dropwise a - ~7~Z~
solution of 0.8 parts Or ~odium nitrite in 5.0 parts of water and the mixture was stirrea ~or one and a hal~ hours.
Excess nitrous acid was destro~ed using ~ul~amic acid.
1.7 Part~ o~ potas~ium iodide in 5.0 parts of water wa~
then added slowly to the diazonium solution. After ~tirring at 0-25 ~or two houxs, the precip~tate wa~
collected by filtration ~nd dried. Recrystallization ~rom ethanol/water gave 1.7 part~ o~ the product, m.p~
83 (decomp,), U~ing the methoa of Example 5 with the appro-priate ~-cyanoketone which i~ conveniently prepared by reacting the approprlate A-chlorocyclohexanone or 4rchloro-cyclopentanone with sodium cyanlde. According to the method o~ Meyer, Helv. Chim. Acta., 16, 1291 (1933), the ~ollowing compound~ of Formula I can be prepared.

(CH2)~ X

Z V
n Rl Y X V Z m.p.C
3 H F Cl H H 106d 3 H H Cl H H
3 H F Br H H

.. -Z~6 n ~ Y X V Z la.p, C - .
4 E F ~ 133-135 . 4 H ~ Br 4 ~ ~ ~ 0 ~ ~
4 ~ H ~2 ~ E
4 ~ H C~ H
4 H P I ~ H

h~mpl~ 6 Pr~paratlon o~ 3-tluoro-2-(4-chloro-2- n uorophonyl)-4,5,6,7-totr~hrdro-2~-lnd~ol~
a~ Pro~ar~tlon Or 2-(4-chloro-2-fluoroph~nyl)-4,5,6,7-tctra-hydro-2E-lnda~olc-3-dla~onlum nuOOorate '. ~o ~0 part~ ot 48% n uoboric acid at 0-5 ~ add~d ~ ult~neou~ly a ~olution ot 2,5 part~ ot sodiu~ nitrltc in 10 ; part~ o~ ~ator and a ~UJp~n don o~ 8.7 parts of 3-~lno-2-(~-chloro-2-nuorQphcnyl)-4,5,6,7-totr~hydro-2~-ln~olo in 30 ~art- Or acctlc acid ~n ~ all ~ortlon~, 80 that th~ mi~turo al~a~ contain~d an e~c-ss Or n~trlto ~ .~. Berg~ann, 8.
B~rkovic and R. I~n, J. Am. Ch~m. ~oc. 78. 6037 (1956)~.
ter the add~tion, th~ r~action m~ztur- ~8J ~tirrc~ at 0-10-r ono hour an~ 10-25- ~or halr an hour. ~e~ nitrou~
~cid ~a~ d ~troyo~ ud n~ ~ulramic acld. Tho proclpitato- ~or-collact d, ~hed ~ith ~ator, Qth~l othor and drio~, ~ieldlng 9.0 ~art~ Or th~ product. Iho lr indicatod that no amino co~-~ound ~a~ lort and lt ~ho~o~ -~ ab~or~tlon at 2200 cm~l. Tho co~poun~ ~a~ u~ed ~ithout ~urthcr rccry~t~lllzatlon.
b) ~ro~aration Or 3-nuoro-2-(4-chloro-2-fluorophcn~ 4,5,6,7-totrahydro-2~-inda~ol~
A mlxtur~ of 9.0 ~art~ Or 2-(4-chloro-3-n uorophonyl)-4,5,6,7-t~tr~h~dro-2~-lnda~ole-3-dia~onlum fluoborat~ and 10 - ~10 -~o71Z~.6 ~:

parts of potassium fluoride in 100 parts of fluoboric acid was photolyzed by a 200 W Hanovia 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 con-centrated. The desired produet was isolated by dry-column chromatogràphy (silica gel eluted with methylene chloride), preparative thin layer chromatography (silica gel developed with S parts of Et20: 100 parts of hexane) and preparative 10 gas chromatography (15~ OV-17 on 80/100 mesh chromosorb W HP at 250). The product was shown to be pure by GC and was analyzed by mass spectroscopy (M = 268 and m/e + 240 due to the loss of C2H4). nmr ~ 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 ~ollowing compounds can be prepared:

R, F

~1~
n ~ / ~X

n Rl Y X V Z

3 H F Cl H H
3 H H Cl H H
3 H F Br H H

3 H H Br H H

4 H H Cl H H
4 H F Br H H

11~71Z16 n Rl Y X Y Z

4 H H Br H H

Formulations U~eful ~ormulat~ons Or the compounds of Formula I lnclude dusts, granules, pellets, solutlons, suspensions, emulslons, wettable powder~, emulsiriable concentrates - and the llke. Many Or these may be applied directly.
Sprayable rormulatlons can be extended ln suitable media and used at spray volumes Or Prom a ~ew llter~ to several hundred llters per hectare. Hlgh stren~th composltlons are primarlly used a~ intermedlates for further formula-tlon. The formulations, broadly, contaln about 0.05% to 99% by weight of actlve lngredlent(~) and at least one of ; (a) about 0.1% to 20% ~ur~actant(s) and (b) about 1% to 99.95% solld or llquid dlluent(~). More speclrlcally, they wlll u~ually contaln these ingredients ln the rollowing approxlmate proportlons:

. .

7 ~'~1 6 Percent by Weight Active Ingredient ~iluent(s~ Sur~actant( 5 Wettable Powders 5-90 1-94 1-10 Oil Su~pensions, Emulsion~, Solutions (including Emulsifi-; able Concentrates~ 5-50 4-95 0-15 Aqueous Su~pensions5-50 40-94 1-20 Dust~ 0.0~-25 7-99.95 -5 Granules and Pellets 0.05-95 1-99,95 0-15 Hlgh Strength Compositions 90-99 0-10 0-2 Iower or higher levels of active ingredient can, 10 Or course, be present depending on the intended use and the physical properties of the compound. Higher ratios o~ sur~actant to active ingredient are sometimes desirable, and are achleved by incorporation into the ~ormNlation or by tank mixing.
Typical solid diluents are described in Watkins, ; et al., "Handbook o~ Insecticlde DUBt Diluents and Car-rier~", 2nd, Edn., Dorland Books, Caldwell, N.J. Suitable diluen~s lnclude finely divlded or granular solids clas~i-fied as attapulgites, botanicals, calcites, diatomites, dolomites, gypsum, kaollnltes, llmestones, mica, montm~r-illonolds, phosphates, pyrophyllites, sulrur, sand, talc~, tripolites, vermicullte, and synthetics. These synthetic~
can include precipated, hydrated silicon dioxide, pre-clpated, h~drated calcium silicate, pxecipitated calclum carbonate and synthetlc organics. The more absorptive diluents are preferred for ~ettable po~ders and the denser one for dusts, Typical liquid diluents and solvent~ are d~scribed in Marsden, "Solvents Guide", 2nd. Ed., iO7~2~6 Interscience, New York, 1950. Solubility under 0.1% i~ pre-~erred for ~u~pension concentrate~; ~olution concentrates are preferably stable again~t phase separation at 0C. "McCutcheon~
Detergents and Emulsi~iers 1975 Annual", MC Publ. Corp., Ridge-wood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agent~", Chemical Publ. Co., New York, 1964, li~t surfactant~ and recommended u~es. All ~ormulation~ ~an contain minor amounts of additives to reduce ~oam, caking, cor-rosion, microbiological gro~th, etc., or to make viæually the area that has been treated.
It 1B sometimec desirable to add ingredients to reduce the ~olatility o~ some o~ the compoundg of this invention.
Those additives can include film forming materials such as polyvinylpyrrolidones of molecular weights from about 20,000 to about 100,000; polyvinylalcohols o~ molecular weights from about 20,000 to about 150,000; and polyoxyethylenes of molecular weights rrom about 100,000 to about 6 x 106~ ~hese are a ~ew examples of rilm forming additives. Any material which forms a rllm over solld active ingredient in the rormulation prepara-tion or a fllm over the active when sprayed and dried ~rom aliquid formulation can be uRed. Other method~ to reduce vola-tility may include the incorporatlon of the comFounds of this invention into resins, ~ases, gums, rubbers, or the like, and then preparing rormulatlons, as has been de~cribed abo~e, for the~e combinations.
Solutions are prepared by simply mlxing the ingred-lents~ Fine solid compositions are made by blending, and usually, grinding as in a hammer or fluld energy mill, Su~pension~ are prepared by wet milling (~ee, ror example, Littler, U.S. Patent 3,060,V84), Granules may be made in ~eYeral ~ays, For example, the acti~e ingredient may be sprayed onto preformed granular lO~lZ~6 carriers. Suitable preformed granular carriers include tbose suitable diluents listed earlier having a particle siæe 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 remalns on the surface of the carrier, a binding agent is used to hold 10 the active ingredient on the surface. The binding agent - -t should bind the active in~redient to the surface well enough so that not more than 10% of the active 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, water-soluble polymers such as polyvinylalcohols of molecular weights from about 20,000 to about 150,000;polyvinylpyrrolidones of molecular weights from about 20,000 to about 100,000; and polyoxyèthylenes of molecular weights from about 100,000 to about 6 x 106. Other suitable binders include, llgninsul~onates, starches, sugars, and certain surface active agents listed in McCutcheons' Detergents and Emulsifiers 1975 Annual", M C
Publ. Corp., Ridgewood, New Jersey.
The active may be sprayed as a solution in a suitable 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 3 be melted and applied directly as a liquid. If very low strength granules are desired, the active may be vaporized :' i~7121 6 .
onto the carrier, Granules may al80 be prepared by agglo-meration techniques. For example, the acti~e ingredient and a ~inely di~ided ~olid diluent may be mixed and agglomerated by techni~ue~ known in the art such as ~pr~ying with a liquid in a fluidized bed or pan granulator. The active ingredient and diluent may slso be mixed with other ~or~ulation ingredi-ents and pelletized. The pellets mag then be crushed to a desired granular size. Pellets may be made by agglomeration techniques. See J.E. Brownlng, "Agglomeration", Chemical Engi-10 neering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Ehgi-neer 18 Handbook", 4th. Edn., McGraw-Hill, N.Y., 1963, pp. 8-59~.
For ~urther information regarding the art o~ ~ormula-tion, ~ee ~or example;
H. M. ~oux, U.S. Patent 3,235,361, Feb. 15, 1966, Col. 6, L~ne 16 through Col. 7, Line 19 and Example~ 10 through 41.
R. W. Luckenbaugh, U.S. Patent 3,309,192, March 14, 1967, Col. 5 Llne 43 through Col. 7 Line 62 and Ex. 8, 12, 15, 39 41, ~2, 53, 58, 132, 138-140, 162-1~4, 166, 167, 169-182.
H. Gy~in and E, Knu~li, U.S~ Patent 2,891,855, June 23, 1959, Col. 3 Line 66 through Col. 5 ~ine 17 and ~xamples 1-4.
~. C. Klln~man, UWeed Control as a Sclence", John Wiley & Sons, Inc., New York, 1961 PP. 81-96.
J. D. FrYer and S. A. Evans, "Weed Control 3 Handbookl', 5th Edn. Blackwell Scienti~ic Public~tions, O~ord, 1968, pp. 101-103.

107~16 Granule 3-chloro-2-(4~chlorophenyl)-4,5,6,7- 10%
tetrahydro-2H-indazole attapulgite granules (low volatile matter, 0.71-0,30 mm, diameteri i . e ., TJ.S.S. #2~-50 mesh sleve 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.

E~AMPLE 8 Solution 3-chloro-2-(2,4-difluorophenyl)-4,5,6,7- 20 tetrahydro-2H-indazole dimethylformamide 80~

The ingredients are combined and stirred to produce a 801ution, which can be used for low-volume applications.

~071Z~6 ~ Extruded Pellet " 3-chloro-2-(4-chloro-2-fluorophen 4,5,6,7-tetrahydro-2H-indazole anhydrous sodium sulfate 10%

crude calcium ligninsulfonate 5%
' 10 sodium alkylnaphthalenesulfonate 1%
polyoxyethylene (4 x 106 average molecular 1%
calcium/magnesium bentonite wt.) 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 a~ter drying, or the dried pellets may be cr~shed to pass a U.S.S. No. 20 sieve (0.84 m~.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 ln this manner.

i~37~Z~6 Example 10 Emulæifia le Concentrate 3-chloro-2-(4-chlorophenyl)-4,5,6,7- 25 tetrahydro-2H-in~azole blend of oil ~oluble sul~onateæ and 4%
polyoxyethylene ethers xylene 71%

The ingredients are combined and stirred until BolUtion iB complete. A fine ~creen filter iB included in packaging operation to insure the absence o~ any extraneous undissolved mater1al in the product.

Example 11 Aqueous_ uspension ._ 3-chloro-2-(4-chlorophenyl)-4,5,6,7-50,0 tetrahydro-2H-lndazole polyacrylic acid thickener 0,3 dodecylphenol polyethylene glycol0,5 ether disodlum phosphate 1.0%
; 20 monosodium phosphate 0.5%
polyvinylalcohol 1.0%
pentachlorophenol 0,4 ~ater 46.3%

The lngredlents are ground together in a sand mill to produce p~rticles essentially all under five microns ln slze.

' `' ~'71Z~6 Example 12 Wettable Powder ~: 3-chloro-2-~4-chloro-2-fluoro- 50 phenyl)-4,5,6,7-tetrahydro-2H-indazole sodium alkylnaphthalenesulfona~2 2%
sodium lignin~ul~onate 2~
synthetlc amorphous sllica 3%
kaolinite 43~
The lngredients are thoroughly blended, passed through an air mill to produce an average particle ~ize under 15 mlcrons, reblended, and slfted through a U S.S. No. 50 sleve (0.3 mm, opening) before packaging, Example 13 Hlgh-Stren~th Concentrate 3-chloro-2-(4-chloro-2-rluorophenyl)- 99 4,5J6,7-tetrahydro-2H-indazole trlmethylnonyl polyethylene glycol l~
ether The surrsctant 18 sprsyed upon the active ingredient ln a blender ~nd the mixture slrted through a U.S.S. No. 40 sieve (0.42 mm. openlngs) prior to p~cksging. The concentrate may be ~ormul~ted ~urther ~or practical use.

- 1073LZ~

Example 14 Low Strength Granule 3-chloxo-2-(4-chloro-2-fluorophenyl)- 0.5%
'~ 4 3 5,6,7-tetrahydro-2H-indazole polyvinylpyrrolidone 1 attapulgite granules (low volatile 98.5 matter, 0.59-0,25 mm.J i.e, USS#30-60 mesh size) ~ ~
Forty grams of a solution containing 2.5~ 3-chloro-2-(4-chloro-2-~luorophenyl)-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).
Fluldlzation of the granules i8 contlnued after atomization is complete and until all the methyl alcohol is evsporated ~rom the granules. The granules are packaged for use.

Example 15 Extruded Pellet . . ~ .
3-chloro-2-(4-chlorophenyl~- 25 2,4,5,6-tetrahydrocyclopentapyrazole anhydrous sodium sul~ate 10 crude calclum lignlnsulfonate 5 sodium alkylnaphthalenesulfonate 1 calclum~magnesium bentonite 59~
The lngredients are blended, hammer milled and moistened wlth about 10-12% water. me mixture is then extruded as cyllnders about 3 mm.in dismeter ~hich are cut to be sbout 3 mm.
long. These pellets may be used dlrectly after drying or the dried pellet~ may be cru~hed to pass a USS #20 sieve (o.84 mm.
openlng). The pellets retained on a USS #40 sieve (0.42 mm.
openings~ mRy be packaged ~or use and the ~ines recycled.

.

~` 1071Z16 l3xa~ple 16 ar~ule:

3-chloro-2-(4-chloro-2-~luorop~eD~ 2%
2,~,5,6-tetrahydrocyclopentapgrazo e a~apulglte granules (~.o~ ~olatile matter~ 98%
0.71-0.30 ~b~ i.e. US~#25-50 me8h ~ie~os~

The ~cti~e ingrodient ~8 ~ar~ed to appr~lm~tel~
110 an~ aprayad upon the dedusted ana pr~armed granules ln a double cone blender. The granules are allo~ed to 10 cool an~ aro ~ac~ag~d ror w e.

----` 107~lZ16 Low Stren~th Granule 3-chloro-2-(4-chlorophenyl)-2,4,5,6- 0.2%
tetrahydrocyclopentapyrazole 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 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 recyled. Flnes sm~ller than 0.42 mm are also recycled.

; 20 EXAMPLE 18 Extruded Pellet 3-chloro-2-(4-chlorophenyl)-4,5,6,7- 0.1%
tetrahydro-2H-indazole anhydrous sodium sulfate 10%
; crude calcium ligninsulfonate 5%

; sodium alkylnaphthalenesulfonate 1~
polyoxyethylene (4 x 10 average molecular wt.)1%
calcium/magnesium bentonite 82.9~

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.

107~Z~6 Theæe ~mall pellets are dried and pac~aged. They ~re applied directly, Example 19 low Strength Granule 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole O.05%
dimethylformamlde 5%
attapul~ite granules (low volatile matter3 94.95%
0.59-0.25 mm, i.e. USS ~30-60 mesh æize) One-tenth of a gram of 3-chloro-2-(4-chloro-2-fluoro-phenyl)-4,5,6,7-tetrahydro-2H-lndazole i~ dissolved in 9.9 grams of dimethylformamide. m læ solution i8 Yery BlOWly atomized onto 190.1 grams Or a rapidly tumbling bed Or the attapulgite granules. After application of the active i8 complete, the formulation 18 blended for a few additional minutes. The dimethylformamide i8 not removed from the rOrmulatiOn~ me gr~nules are packaged for use.
Example 20 Emulslriable Concentrate 3-chloro-2-(4-chloro-2-fluorophenyl)- 20%
4,5,6,7-tetrahydro-2H-lndazole blend of oil-solublo sulfonate with polyoxyethylene ethers 6%
20aromatic hydrocarbon solvent with 8 Tag 74 closed cup rlash point bet~een 100 and 115F.
me ingredlents are combined and stirred until solution is complete. m O ~olution 18 filtered through a ~ine screen ~ilter prior to packaging to remove any extraneous undl~olved material.

, 1~71Z16 Low Stren~th Granules 3-chloro-2-(4-chloro-2-fluorophenyl)- 0.1%
4,5,6,7-tetrahydro-2H-indazole sodium ligninsulfonate 5~

preformed sand granules havlng a particle 94.9%
size distribution from VSS sieve No.
140 (105 microns) to USS Sieve No. 50 (297 microns) 0.5 gm. 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole and 25 gm sodium ligninsulfonate are dissolved in 50 gm water. This solution is slowly sprayed onto a ~umbllng bed of the sand granules (474.5 gms.). After sPraYin~ ls 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 this invention, other conventional agricultural chemicals such as fertilizers, plant growth modifiers or herbicides.
For example, the compounds of Formula I can be com-bined with the following herbicides:
~1) 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one;
(2) 6-methylthio-2,4-bis(ethylamino~-triazine;
~3) 3-isopropyl-(lH~benzo-2,1,3-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-trichloroallyl)-diisopropylthiocarbamate;
~3) Methyl 2{ 4-(2,4-dichlorophenoxy(phenoxy)]-propanoate;
3 t4) 1,2-dimethyl-3,5-diphenyl-lH~pyrazolium methyl sulfate;

~5) 4-chloro-2-butynyl 3-chlorocarbanilate.

iC~71Zl~

The compounds Or Formula I can also be comb~ned wlth other herbicides and are particularly useful in combi-nation wlth bromacil ~3-(sec-butyl)-5-bromo-6-methyluracil], diuron ~3-(3,4-dlchlorophenyl)-1,1-dimethylurea], 3-cyclohexyl-l-methyl-6-dimethylamino-s-trlazlne-2,4(1H,3H)-dlone, paraquat ~l,l'-dimethyl-4,4'-bipyridinum lon3, m-(3,3-dimethylureido) phenyl tert-butylcarbamate, 2-methyl-4-chlorophenoxyacetic acid, lts salts or e~ters, 4-amlno-6-tert-butyl-3-methylthio-a~-trlazln-5(4H)-one, aryl 4-nltrophenyl ethers such a~
2,4,6-trlchlorophenyl 4-nltrophenyl ether and 2,4dichloro-phenyl 4-nitrophenyl ether for controlling a broad spectrum o~ weed~.

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.

For industrial use, a granule may ~e made from 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-5%
2H-indazole 3-cyclohexyl-1-methyl-6-dimethylamino-s- 5~/0 triazine-2,4(1H,3H)-dione #25-50 attapulgite ~ranules (low volatlle90/o matter~ 0.71 mm.-0.30 mm. d~ameter) \
~ - 56 -1~712~6 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.

_ llit~
The compounds of Formula I are useful for the selective preemergence control Or undesired vegetation, _ ~L barnyardgrass, ln crops such as rlce, in particular paddy rlce, wheat, and pea-nuts. These compounds also have utlllty for the postemergence ¢ontrol o~ weeds ln certain crops, for example, rice. Further-more, compounds Or thls invention can be used as directed treat-ments ror the pre- or post-emergence control Or weeds in various crops lncluding soybeans, peanuts, cotton, garden beans and row-planted rlce.
The compounds of this lnvention are useful for the control Or weeds in transplanted crops such as rice, tobacco, tomatoes, cabbage, sweet potatoes, lettuce, celery, peppers, and eggplant. The treatment may be applled to the soll ~ur~ace prlor to transplantlng and the c~op transplanted 1071Z~6 through the treated soil or it may be soil lncorporated prior to transplanting and the crop set in the treated ~oil. It may also be applied after the crop ls transplanted if care is taken to keep the chemical off the crop follage (Table I~).
The precise amount of the compounds of Formula I
to be used in any given situation will vary accordi-l, to 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, folia~e density and like factors. Since so many variables play a role, it is not possible to state a rate of appllcation suit-able for all sltuatlons. Broadly speaking, the compounds of the lnventlon are used at levels of about 0.015 to about 15 kllograms per hectare, pre~erably about 0.03 to about lO
kllograms per hectare. The lower rates ln thls range will generally be selected on llghter 90il9, 80119 low ln organic matter ~ontent, ~or selective weed control ln crops, or in 81tuatlons where maximum perslstance 18 not neces8ary.
Herbicldal activlty o~ compounds of this lnvention ~a8 dlscovered in ~reenhouse tests, as explained below:
Procedure Test l ~=
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avcna fatua), Cassia tora, morningglory (Ipomoe_ sp.), cocklebur (Xanthium 9P- ) ~ sorghum, corn, soybean, rice, ~leat and nutscdge tubers were planted in ^" 1~)7~21~;

.
a growth medium and treated preemergence with the chemicals :
dis~olved in a non-phutotoxic solvent. At the same time, cot-ton having five leaves (including cotyledonary ones), bush beans with third trifoliolate leaf expanding, crabgrass with two leaves, barnyardgra~s with two leaves, wild oats with one leaf, ca~sla with three leaves (including cotyledonary ones), morning-glory with four leaves (including the cotyledonary ones), cock-lebur with ~our leaves (including the cotyledonary ones), sor-ghum with three leaves, corn with three leaves, soybean with two cotyledonary leaves, rice with two leaves, wheat with one lea~, and nutsedge with three-five leaves were sprayed. Treated plants and controls were maintained in a greenhouse for sixteen days, then all ~pecies were compared to controls and visually rated ; for response to treatment.
'.
Ratlngs for compounds tested by this procedure are recorded ln Table 1. Plant response was expressed on a scale ~ extending from 0 - no inJury to 10 - complete klll. Letter 8ymbol8 used had the folloulng meanings: ~ = burn, G =
growth retardation, C = necrosis/chlorosis, E = emergence inhibition, and H = formative effect, X - axillary stimulation.

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~ ~ //z ~) - 76-)'7~6 Table 2 i8 presented to further illustrate the biological activity of the compounds of this invention.
The data illustrate the herbicidal efficacy o~ the com-pounds with selectivity for two important crops, rice and wheat.

me test compound~ were applied in a non-phyto-toxlc ~olvent to 80il pots containing seeds of an inter-mediate hybrid rice, japonica rice, barNyardgrass (Echi-nochloa crusgalli), morning glory (Ipomoea 8p. ), wheat, wild oats (Avena fatua), downy brome (Bromus tectorum) and cheat (Bromus secal~nus). In addition, wild mustard (Brassica arvensis), Kochia (Kochia scoparia) and black-grass (Alopecurus myosuroide~) seeds were included in some instances, as were established plantings (postemergence) of some or all of the species ment$oned above. The plants were maintained in a greenhouse (glasshouse), and visual plant respon~e ratlng8 (as de8cribed in Table 1) were generally taken about three weeks after application.

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LZ~6 It should be noted that, in general, these compounds at a low concentration virtually eliminated the undesirable vegeta- -tion, e,g., barnyardgrass, but had relatively little effect on the crops, e.g., rice, In wheat, wild oats, cheat, downy brome, snd, where tested, wild mustard, Kochia, and blackgra~s were con--trolled at a low rate with little effect on the wheat crop~
me following table, Table 3, i8 pre~ented to addition- -ally illustrate the biological activity of the compounds of the pre8ent 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 barnyard~rass (Echinochloa crusgalli) seeds, and ~aponica rice plants which were transplanted into the paddy soil when in the two to three-leaf stage. The water level was main-tained a few centimeters above the soil surface. Test samples were applied directly into the paddy water, and plant response r~tlng8 were taken about three week~ later.

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~07~Z16 It should be noted that these compounds at a low application rate virtually eliminated the undesirable vege-tation, e , barnyardgrass, but had relatively little ef~ect on rice.
To demon trate utilit~ on transplanted crops, metal containers 30 x 30 ~ 15 cm. were filled to a depth of 13 cm.
with fumlgated ~allsington ~andy loam soil. me ~ollowing weed seed~ were mixed throughout the top 2.5 cm. of soil in each container: barnyardgrass (_chinochloa crusgalli), crab-grass (Dlgitaria sa~ alls), giant foxtail (Setaria ~aberii)Jimsonweed (Datura ~tramonium~, velvetlear (Abutilon theo-phrasti) and morningglory (Ipomoea purpurea~. -The following treatments were applied as a pre-plant soil surrace spray and also pre-plant soil incorporated (2-5 cm.) Control Compound A 3-chloro-2-(4-chloro-2- 0.016 kg/ha fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole Compound A 0.12 kg/ha Compound A 1.0 kg/ha Compound A was dissolved in acetone and the ~olution applied at a spray volume of 560 l/ha. Immediately after treat-ment the ~ollowlng crops were transplanted: pepper (Delaware Belle, plants 12.5 cm tall), tomato (Bonny Best, plant~ 10 cm tall), cabbage (Wisconsin Golden Acre, plants 12.5 cm tall) and tobacco (Coker 319, plants 10 cm tall). Four plants were transplanted ~071216 into each container. The containers were placed in the green-house and watered by hand as needed. Eighteen days after treat-ment the visual plant response ratlngs in Table 4 were recordea.

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Claims (78)

WHAT IS CLAIMED IS:
.

1. A compound of the formula where n is 3, 4 or 5;
R1 is hydrogen or methyl;
Q is fluorine, chlorine, bromine or iodine;
X is fluroine, 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 n is 5, R1 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 n is 3 or 4 and Q is fluorine or iodine, R1, Z and V must be hydrogen and Y must be hydrogen or fluorine;
(c) when n is 3 and R1 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 bromine and Z must be hydrogen.

2. A compound of Claim 1 wherein n is 4.

3. A compound of Claim 1 wherein n is 3.

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.

6. A compound of Claim 1 wherein n is 4 and Q
is chlorine or bromine.

7. A compound of Claim 1 wherein n is 4 and Q is chlorine.

8. A compound of Claim 1 wherein n is 4, Q is chlorine or bromine and R1 is hydrogen.

9. A compound of Claim 1 wherein n is 4, Q is chlorine and R1 is hydrogen.

10. A compound of Claim 1 wherein n is 4, Q is bromine and R1 is hydrogen.

11. A compound of Claim 1 wherein n is 3 and Q is chlorine or bromine.

12. A compound of Claim 1 wherein n is 3, Q is chlorine or bromine and R1 is hydrogen.

13. A compound of Claim 1 wherein n is 3, Q is chlorine and R1 is hydrogen.

14. A compound of Claim 1 wherein Q is chlorine, Z
and V are hydrogen and Y is hydrogen or fluorine.

15. A compound of Claim 1 wherein n is 4, Q is chlorine, R1 is hydrogen, Z is hydrogen and V is hydrogen.

16. A compound of Claim 1 wherein n is 4, Q is chlor-ine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydro-gen or fluorine and X is fluorine, chlorine, bromine, cyano or methoxy.

17. A compound of Claim 1 wherein n is 4, Q is chlor-ine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine and X is chlorine or bromine.

18. A compound of Claim 1 wherein n is 4, Q is bromine, R1 is hydrogen, Z is hydrogen and V is hydrogen.

19. A compound of Claim 1 wherein n is 4, Q is bromine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, cyano or methoxy.

20. A compound of Claim 1 wherein n is 4, Q is bromine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine.

21. A compound of Claim 1 wherein n is 3, Q is chlor-ine, R1 is hydrogen, Z is hydrogen and V is hydrogen.

22. A compound of Claim 1 wherein n is 3, Q is chlor-ine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, cyano or methoxy.

23. A compound of Claim 1 wherein n is 3, Q is chlorine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine.

24. A compound of Claim 1 wherein Q is chlorine, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine and X is chlorine or bromine.

25. A compound of Claim 1 wherein n is 3, Q is bromine, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine and X is chlorine or bromine.

26. The compound of Claim 1,3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

27. The compound of Claim 1,3-chloro-2-(4-chloro-phenyl)-4,5,6,7-tetrahydro-2H-indazole.

28. The compound of Claim 1,3-bromo-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

29. The compound of Claim 1,3-chloro-2-(4-bromo-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

30. The compound of Claim 1,3-chloro-2-(4-chloro-2-fluorophenyl)-2,4,5,6-tetrahydrocyclopentapyrazole.

31. The compound of Claim 1,3-chloro-2-(4-chloro-phenyl)-2,4,5,6-tetrahydrocyclopentapyrazole.

32. 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.

33. 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.

34. 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.

35. 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.

36. 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.

37. 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 6.

38. 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 7.

39. 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 8.

40. 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 9.

41. 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 10.

42. 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.

43. 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 12.

44. 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 13.

45. 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 14.

46. 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 15.

47. 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 16.

48. 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 17.

49. 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 18.

50. 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 19.

51. 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 20.

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 21.

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 22.

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 23.

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 24.

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 25.

57. 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.

58. 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 27.

59. 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.

60. 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 29.

61. 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.

62. 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.

63. A method for the control of undesirable vegetation in rice consisting essentially of applying to the locus of such undesirable vegetation a herbicidally effective amount of a compound of Claim 1.

64. The method of Claim 63, wherein said undesirable vegetation is barnyard grass.

65. The method of Claim 63, wherein the com-pound is 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

66. The method of Claim 63, wherein the com-pound is 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

67. The method of Claim 65, wherein the rice is paddyrice.

68. The method of Claim 66, wherein the rice is paddyrice.

69. A method for the control of undesirable vegetation in wheat which comprises applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of Claim 1.

70. The method of Claim 69, wherein the compound is 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

71. The method of Claim 69, wherein the compound is 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

72. A method for the control of undesirable vegetation in transplanted crops consisting essentially of applying to the locus of such undesirable vegetation a herbicidally effective amount of the compound of Claim 1.

73. The method of Claim 72, wherein the com-pound is 3-chloro-2-(4-chloro-2-fluorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

74. The method of Claim 72, wherein the com-pound is 3-chloro-2-(4-chlorophenyl)-4,5,6,7-tetrahydro-2H-indazole.

75. A process for making a compound of the formula where n is 3, 4 or 5;
R1 is hydrogen or methyl;
Q is chlorine or bromine;
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 n is 5, R1 must be hydrogen, Z and V
must both be hydrogen and Y must be hydrogen or fluorine;
(b) when n is 3 and R1 is methyl, Y must be hydrogen or fluorine and Z and V must be hydrogen; and, (c) when V is other than hydrogen, X must be fluorine, chlorine or bromine and Z must be hydrogen;
by reacting a compound of the formula where n, R1, X, Y, Z and V are as previously defined;
with at least one equivalent of a phosphorous oxyhalide of the formula where Q is chlorine or bromine.

76. A process for making a compound of the formula where n is 3 or 4;
R1 is hydrogen;
X is fluorine, chlorine, bromine, iodine, cyano, methoxy or nitro;
Y is hydrogen or fluorine;
Z is hydrogen; and V is hydrogen;
by reacting a diazonium salt of the formula where n, R1, X, Y, Z and V are as previously defined and S is Cl, HSO4, H2PO4 or other counter ion corres-ponding to an acid HS used for preparation of the diazonium salt with at least one equivalent of an ionic iodide.

77. A process for making a compound of the formula where n is 3 or 4;
R1 is hydrogen;
X is fluorine, chlorine, bromine, iodine, cyano, methoxy or nitro;
Y is hydrogen or fluorine;
Z is hydrogen; and V is hydrogen;
by decomposing a diazonium salt of the formula in the presence of fluoboric acid with at least one equivalent of an ionic fluoride.

78. A process for making a compound of the formula where n is 3, 4 or 5;
Q is fluorine, chlorine, bromine or iodine;
R1 is hydrogen or methyl;
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;
said process being selected from the group consisting of (A) when Q is chlorine or bromine and with the proviso that (a) when n is 5, R1 must be hydrogen, Z and V
must both be hydrogen and Y must be hydrogen or fluorine;
(b) when n is 3 and R1 is methyl, Y must be hydrogen or fluorine and Z and V must be hydrogen; and (c) when V is other than hydrogen, X must be fluorine, chlorine or bromine and Z must be hydrogen;
said process comprises reacting a compound of the formula with at least one equivalent of a phosphorous oxyhalide of the formula POQ3;

(B) when n is 3 or 4, Q is iodine, R1, Z and V are all hydrogen and Y is hydrogen or fluorine, said process comprises reacting a diazonium salt of the formula where S is Cl, HSO4, H2PO4 or other counter ion corresponding to an acid HS used for the preparation of the diazonium salt with at least one equivalent of an ionic iodide; and (C) when n is 3 or 4, Q is fluorine, R1, Z and V are all hydrogen and Y is hydrogen or fluorine, said process comprises decomposing a diazonium salt of the formula in the presence of fluoboric acid with at least one equivalent of an ionic fluoride.