BE847340A - NEW CYCLOALCANAPYRAZOLESHERBICIDES AND THEIR PREPARATION, - Google Patents

Description

       

  New herbicide cycloalcanapyrazoles

  
and their preparation Recently, in the published German patent application

  
 <EMI ID = 1.1>

  
boasts:

  

 <EMI ID = 2.1>


  
where R can be an aryl, aralkyl or benzyl substituent optionally substituted by 1 to 5 halogen atoms or a hydroxy, nitro, cyano, thiocyanato, carboxy, alkyl group

  
or halogenated alkyl, alkoxy, (lower alkyl) thio orphenyl. R can also be optionally substituted by a group having

  
 <EMI ID = 3.1>

  
The phenyl group may contain one or more halogen atoms, nitro groups, lower alkyl groups or lower alkoxy groups.

  
A typical example of the compounds described in the aforementioned application is the compound of Structure 1:

  

 <EMI ID = 4.1>


  
Although the compounds described in the above application are active herbicides, the need still exists for even better herbicides. weeds are very damaging to important crops like rice and wheat and they reduce yields. In the current global situation, where food shortages are acute, it is very important that the maximum possible yields are obtained from crops such as rice or wheat. Thus, there is a need for a particularly effective herbicide which will kill as many weeds as possible without causing

  
significant damage to the desired crop plants, for example rice or wheat.

  
According to the present invention * compounds have been discovered which are very active herbicides and yet cause only minimal damage to certain desired crop plants, for example rice and wheat, and especially to the main food crop in the world, rice.

  
the preparation and utility as a fungicide of 2- (4-

  
 <EMI ID = 5.1>

  

 <EMI ID = 6.1>


  
 <EMI ID = 7.1>

  
ones are described as antipyretics in German patent 668,628 [assigned to P. Beierdorf and Co. AG, Chem.

  
 <EMI ID = 8.1>

  

 <EMI ID = 9.1>


  
 <EMI ID = 10.1>

  
describes herbicides having the general formula

  

 <EMI ID = 11.1>


  
in which

  
 <EMI ID = 12.1>

  
 <EMI ID = 13.1>

  
substituted, an alkoxy or phenoxy radical or a phenyl radical and

  
 <EMI ID = 14.1>

  
hydrogen, an alkyl, optionally substituted phenyl or alkinyl group,

  
 <EMI ID = 15.1>

  
East

  

 <EMI ID = 16.1>


  
 <EMI ID = 17.1>

  
and Hal represents chlorine, bromine or iodine.

  
1-Phenyl-3,4-trimethylenepyrazolone is described in U.S. Patent No. N [deg.] 1.685.407 as being useful as an intermediate for the preparation of dyes and compounds

  
 <EMI ID = 18.1>

  

 <EMI ID = 19.1>
 

  
 <EMI ID = 20.1>

  

 <EMI ID = 21.1>


  
 <EMI ID = 22.1>

  
and the method of using these compounds as selective herbicides, as well as general herbicides, having both pre- and post-emergence activity.

  

 <EMI ID = 23.1>


  
or

  
n is 3, 4 or 5;

  
 <EMI ID = 24.1>

  
Q is fluorine, chlorine, bromine or iodine;

  
X is fluorine, chlorine, bromine, iodine, a cyano, methoxy or nitro group;

Y is hydrogen, fluorine or chlorine;

  
Z is hydrogen, fluorine, chlorine or a methoxy group, with the conditions that <EMI ID = 25.1> chlorine or bromine, Z and V must both be hydrogen and Y must be hydrogen or fluorine; -

  
 <EMI ID = 26.1> fluorine, chlorine or bromine and Z must be hydrogen.

  
Of these compounds of Formula I, it is preferred for their

  
high herbicidal activity or for their attractive cost price or for these two reasons both compounds in which, independently:
.1) n is 3 or 4;

  
2) Q is chlorine or bromine;

  
 <EMI ID = 27.1>

  
4) Z and V are both hydrogen;

  
5) Y is hydrogen or fluorine; or

  
6) X is fluorine, chlorine, bromine or a cyano or methoxy group.

  
Among the compounds of formula I in which n is 4, those in which Q is chlorine or bromine are preferred.

  
Particularly preferred are compounds in which

  
 <EMI ID = 28.1>

  
prefers compounds in which, independently:

  
1) Z and V are both hydrogen;

  
 <EMI ID = 29.1>

  
3) X is fluorine, chlorine, bromine or a cyano or methoxy group.

  
Particularly preferred are compounds in which

  
 <EMI ID = 30.1>

  
and Z and V are both hydrogen.

  
Among those compounds of formula I in which n is 4,

  
 <EMI ID = 31.1>

  
are both hydrogen, preferred by virtue of their high herbicidal activity or favorable cost or for both of these reasons both compounds in which, independently

  
1) Y is hydrogen or fluorine; or

  
2) X is fluorine, chlorine, bromine or a cyano or methoxy group.

  
Particularly preferred are compounds in which

  
 <EMI ID = 32.1>

  
Z and V are both hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, or a cyano or methoxy group.

  
Most preferred on account of their excellent herbicidal activity or very favorable cost or for. these two reasons both the compounds of formula I in which n is 4, Q is chlorine or bromine, IL is hydrogen,

  
Z and V are both hydrogen, Y is hydrogen, or

  
fluorine and X is chlorine or bromine.

  
Among the compounds of formula I in which n is 3,

  
preferred are compounds in which Q is chlorine or bromine.

  
Particularly preferred are compounds in which

  
 <EMI ID = 33.1>

  
Among the compounds of formula I in which n is 3-,

  
 <EMI ID = 34.1>

  
the compounds in which, independently

  
 <EMI ID = 35.1>

  
2) Y is hydrogen or fluorine; or

  
3) X is fluorine, chlorine, bromine or a cyano or methoxy group.

  
Most preferred are compounds in which

  
 <EMI ID = 36.1>

  
Z and V are both hydrogen.

  
Among the compounds of formula I in which n is 3,

  
 <EMI ID = 37.1>

  
are both hydrogen, preferred on account of their higher herbicidal activity or more favorable cost or for both of these reasons both compounds in which, independently

  
1) Y is hydrogen or fluorine; or

  
2) X is fluorine, chlorine, bromine or a cyano or methoxy group.

  
Particularly preferred are compounds in which

  
 <EMI ID = 38.1>

  
Z and V are both hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, or a cyano or methoxy group.

  
Due to their excellent herbicidal activity * or their very advantageous cost or for these two reasons both the compounds of formula I are very particularly preferred.

  
 <EMI ID = 39.1>

  
Among the compounds of formula I, on account of their high herbicidal activity or their advantageous cost or for these two reasons both compounds in which Y is hydrogen or fluorine and Z and V are both of . hydrogen.-

  
Particularly preferred are compounds in which Y is hydrogen or fluorine and Z and V are both hydrogen in which, independently

  
1) Q is chlorine; or

  
2) X is chlorine or bromine. Of these compounds of formula I, on account of their higher herbicidal activity or their more advantageous cost or for both these reasons, both the compounds in

  
which Y is hydrogen or fluorine, Z and V are both

  
hydrogen and Q is chlorine.

  
Particularly preferred on account of their excellent herbicidal activity or very advantageous cost or for these

  
two reasons for both compounds of formula I in which

  
Y is hydrogen or fluorine, Z and V are both

  
hydrogen, Q is chlorine and X is chlorine or bromine.

  
Especially preferred on account of their remarkable herbicidal activity or their favorable cost or both.

  
reasons for both the following compounds:

  
1) 3-chloro-2- (4-chloro-2-fluorophenyl) -4,5,6,7-

  
tetrahydro-2H-indazole; melting point 88-89.5 [deg.] C;

  
 <EMI ID = 40.1>

  
2H-indazole; melting point 86-88 [deg.] C;

  
5) 3-chloro-2- (4-chloro-2-fluorophenyl) -2,4,5,6-tetra-

  
 <EMI ID = 41.1>

  
Synthesis of compounds

  
The new cycloalcanapyrazoles of formula I in the

  
 <EMI ID = 42.1>

  
felt by Equations A and B:

  

 <EMI ID = 43.1>


  
 <EMI ID = 44.1>

  
Q is Br or Cl;

  
R is an alkyl group of 1 to 3 carbon atoms;

  
f is 0 or 1; and

  
A is an anion of the corresponding HA acid having a constant

  
 <EMI ID = 45.1>

  
The preparation of condensed pyrazolones .3 is known in the published technical documentation; for example, the preparation of 2-aryl-1,2,4,5,6,7-hexahydro-3H-indazol-3-ones

  
 <EMI ID = 46.1>

  
suitable hydrazine 1 in a suitable solvent, such as a lower alcohol, or an aromatic hydrocarbon, and, optionally, in the presence of an acid acceptor, such as a tertiary organic amine or an alkali metal hydroxide or alcoholate, and the reaction mixture is heated at reflux for 0.5 to 24 hours. pyrazolone &#65533; 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 carried out by recrystallization, sublimation or other conventional techniques known to those skilled in the art. This same process can be used to prepare the compounds of formula .3

  
 <EMI ID = 47.1>

  
 <EMI ID = 48.1>

  
by combining the appropriate aryl hydrazine with 2-oxo-cyclo-

  
 <EMI ID = 49.1>

  
such as toluene or chlorobenzene. The reaction mixture is heated to reflux and simultaneously the water is removed to obtain a hydrazone. The cyclization giving the pyrazolones .2 in which n is 3 is then carried out by adding 1 to 3 equivalents of an alkali metal alcoholate such as sodium methoxide to the hydrazone solution and heating for 1

  
 <EMI ID = 50.1>

  
to prepare pyrazolones of the formula &#65533; where n = 3.

  

 <EMI ID = 51.1>
 

  
Alternatively, the hydrazone can be isolated and then cyclized by treatment with two equivalents of n-butyllithium in a

  
 <EMI ID = 52.1>

  
period from 2 to 18 hours.

  
Pyrazolones &#65533; in which n is 3 are isolated by pouring the reaction mass into water, separating the organic layer and acidifying the aqueous layer with a

  
 <EMI ID = 53.1>

  
aqueous acidified, the desired product is obtained by filtration, centrifugation, extraction or other similar techniques.

  
The new cycloalkanapyrazoles of formula I in which Q is chlorine are obtained by heating the condensed pyrazolones &#65533; with phosphorus oxychloride

  
(formula 4, Q is chlorine). When Q is bromine in formula 1, phosphorus oxybromide (formula 4,

  
Q is bromine) in the presence of an N, N-dialkoylaniline and dimethylformamide (Equation B).

  
The use of an inert organic solvent such as methylene chloride or toluene is optional; however, it is preferred not to use any solvent other than oxychloride

  
or phosphorus bromide. The mixture is heated to 100-180 [deg.] C,

  
 <EMI ID = 54.1>

  
and the solvent is removed on a rotary evaporator or by distillation. The product obtained is pyrazole of formula I

  
and can be purified by distillation, sublimation or crystallization from a suitable solvent.

  
The compounds of formula I in which Q is iodine are prepared from the corresponding aminopyrazoles by diazotization with nitrous acid and reaction with potassium iodide according to the process of the Spanish patent

  
 <EMI ID = 55.1>

  
required are prepared from the appropriate alpha-cyanocyclohexanone or alpha-cyanocyclopentanone by reaction with the appropriate aryl hydrazine in a solvent such as toluene. The overall sequence for preparing the compounds of formula I

  
 <EMI ID = 56.1>

  
A2 and B2:

  

 <EMI ID = 57.1>


  
The required alpha-cyano ketones can be prepared by a number of methods well known in the art. For example, alpha-cyanocyclohexanone is prepared from alpha-chlorocyclohexanone and sodium cyanide according to R. Meyer in Helv. Chim. Acta, 16, 1291 (1933).

  
 <EMI ID = 58.1>

  
and a strong base such as a lithium dialkoylamide followed by acid hydrolysis in accordance with German patent 591,269

  
[IT. 28, 117 (1934) 3. Alpha-cyanocycloaliphatic ketones can also be prepared from cycloalkanone enamines and cyanogen chloride according to the method of M.E.

  
 <EMI ID = 59.1>

  
pyrazole with nitrous acid in fluoboric acid (equation A,) according to the method of E. D. Bergmann,

  
 <EMI ID = 60.1>

  
 <EMI ID = 61.1>

  

 <EMI ID = 62.1>


  
Beta-keto esters 2 intermediates are commercially available or are prepared by methods described in the published technical literature (see G. Stork et al.,

  
 <EMI ID = 63.1>

  
represented in Equations C, D and E:

vs.

  

 <EMI ID = 64.1>
 

D.

  

 <EMI ID = 65.1>


  
 <EMI ID = 66.1>

  
6 (pyrrolidine can also be used) in a suitable solvent, such as benzene, toluene or chlorobenzene, with simultaneous removal of the water resulting from the reaction by azeotropic distillation (Equation C). Chloroformate

  
 <EMI ID = 67.1>

  
solvent for a period of 1 to 10 hours in the presence of a suitable tertiary organic amine such as triethylamine
(Equation D). The tertiary amine hydrochloride which is formed as a by-product in the reaction is removed by filtration.

  
 <EMI ID = 68.1>

  
nique, is transformed into beta-keto ester 2 by hydrolysis with an aqueous mineral acid (e.g. hydrochloric acid)

  
 <EMI ID = 69.1>

  
again ; purified-by -Under reduced pressure, - sublimation or crystallization.

  
 <EMI ID = 70.1>

  
indazol-3-ones (3a and 3b) is produced; subsequent treatment with a phosphorus 4 oxyhalide will produce a mixture containing both methylated 3-halo-2-aryl-tetrahydroindazoles

  
in position 4 and in position 6 according to the present invention.

  
If the mixture of isomeric methyl cyclohexanones is separated,

  
then 2a and 2b will lead to 3a and 3b respectively when we

  
treats them with an arylhydrazine.

  

 <EMI ID = 71.1>


  
In the case of 2- or 4-methylcyclohexanones, the synthesis of the beta-keto ester is more specific and one isomer is predominantly produced, as summarized schematically in Equations F and G. 2-methylcyclohexanone produces

  
 <EMI ID = 72.1>

  
4-methylcyclohexanone produces 5-methyl-3-halo-4,5,6,7- <EMI ID = 73.1>

  

 <EMI ID = 74.1>


  
The necessary alkyl-2-oxocyclopentanecarboxylates can be prepared by previously described methods.

  
 <EMI ID = 75.1>

  
(1967).

  
The preparation of aryl hydrazines 1 from anilines is well described in the published technical documentation: see

  
 <EMI ID = 76.1>

  
Sons, New York, page 442 and H. Kindler et al., French patent 1,419,092. A general process is illustrated in Equation H:
H.

  

 <EMI ID = 77.1>


  
Aniline 11 is diazotized at approximately -5 to 5 [deg.] C with sodium nitrite in aqueous acid (HA, where A is defined as above) such as hydrochloric acid; the resulting solution is mixed with an aqueous solution of sodium bisulfite at 0-20 [deg.] C, heated at 50-80 [deg.] C for 0.5-2 hours and then acidified with mineral acid to give salt

  
 <EMI ID = 78.1>

  
often directly from the reaction mixture and can be isolated by filtration or other conventional techniques.

  
In most cases, hydrazine can be used without further purification.

  
Certain hydrazines used in the preparation of compounds defined by the present invention are new; for example, 4-chloro-2-fluorophenylhydrazine hydrochloride is a novel compound which can be prepared by the method described above. The following new hydrazines can also be prepared by this process:

  
4-Bromo-2-fluorophenylhydrazine hydrochloride 2-fluoro-4-methoxyphenylhydrazine hydrochloride 2,4,6-trifluorophenylhydrazine hydrochloride 2-fluoro-4-nitrophenylhydrazine hydrochloride 4-cyano-2-fluorophenylhydrazine hydrochloride

  
Also useful for preparing aryl hydrazines, the method described by M.S. Gibson et al., J. Chem. Soc. (VS)
1970, 2106 and M.S. Gibson et al., J. Chem. Soc. (VS),

  
1974, 215.

  
Representative starting anilines for these hydrazines are prepared as described below. 4-Chloro-2fluoro-aniline, for example, can be prepared from 2'-fluoroacetanilide [G. Schiemann and H.G. Baumaarten, Chem.

  
 <EMI ID = 79.1>

  
below:

  

 <EMI ID = 80.1>
 

  
 <EMI ID = 81.1>

  
in several hours (for example 5) at atmospheric pressure.

  
The resulting product is 4'-chloro-2'-fluoroacetanilide.

  
Step B

  
) Chlorofluoroacetanilide is heated to reflux in a mixture of a lower alcohol (50%) (eg ethanol) and concentrated hydrochloric acid (50%) for several

  
 <EMI ID = 82.1>

  
atmospheric. The solvent mixture is removed under a

  
 <EMI ID = 83.1>

  
from 20 to 50 [deg.] C to leave a residue of the hydrochloride salt of 4-chloro-2-fluoroaniline.

  
Step C

  
 <EMI ID = 84.1>

  
of 4-chloro-2-fluoroaniline with a solution of an alkali metal hydroxide, such as 50% sodium hydroxide under ambient conditions, 4-chloro-2-fluoroaniline is extracted into a non- organic solvent miscible with suitable water such as ethyl ether or methylene chloride. Crude 4chloro-2-fluoroaniline is isolated by elimination of. organic solvent under reduced pressure of 100 to 300 mm from

  
 <EMI ID = 85.1>

  
2-Fluoro-4-bromoaniline can be prepared by bromination of 2-fluoroaniline [prepared as in Chem. Berichte,

  
 <EMI ID = 86.1>

  
in the following equation:

  

 <EMI ID = 87.1>
 

  
Bromination of anilines using N-bromosuccinimide in an inert organic solvent such as methylene chloride is well known to those skilled in the art. See for example

  
 <EMI ID = 88.1>

  
bromination of 2-fluoroaniline is an exothermic reaction which occurs at 0 [deg.] C over several hours, for example 5 or

  
more. The resulting reaction mixture is washed with water several times and dried with a suitable drying agent such as sulphide.

  
 <EMI ID = 89.1>

  
by removing the organic solvent under reduced pressure of 100-300 mm Hg at 20-50 [deg.] C.

  
2,4,6-trifluoroaniline is prepared by reducing

  
 <EMI ID = 90.1>

  
the procedures described by G. Schiemann and M. Seyhan, Chem. Berichte, 70, 2396 (1937).

  

 <EMI ID = 91.1>


  
 <EMI ID = 92.1>

  
can be prepared by the method described by G. Scheimann and

  
 <EMI ID = 93.1>

  
be prepared from 4-bromo-2-fluoroaniline by treatment with cuprous cyanide in N-methyl-pyrrolidone using known procedures; L. Friedman and others,

  
 <EMI ID = 94.1>

  
at reflux for several hours and then poured over de'la. ice and sodium cyanide. The resulting solution is heated to 50 to 80 [deg.] C for a period of 1 to 3 hours, cooled and extracted with toluene; the toluene extract is washed with water, dried with a suitable desiccant and evaporated to give 4-amino-3-fluorobenzonitrile.

  
 <EMI ID = 95.1> <EMI ID = 96.1>

  
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

  
 <EMI ID = 97.1>

  
The following non-limiting examples further illustrate the process for synthesizing the compounds of the present invention. All parts are by weight.

  
 <EMI ID = 98.1>
 <EMI ID = 99.1>
(a) Preparation of 4-chloro-2-fluoroaniline

  
71 parts of liquid chlorine are added to a solution of 140 parts of 2'-fluoroacetanilide in 500 parts of glacial acetic acid, over 1 hour, at 25-27 [deg.] C, while cooling in ice water. Stirred for 4 hours at 25-27 [deg.] C, while 4'-chloro-2'-fluoroacetanilide precipitates. After collecting the product by filtration, the filtrate is poured onto 2000 parts of ice. The resulting second portion of precipitated product is collected by filtration, combined with the first portion and recrystallized from 700 parts of methanol at -45 [deg.] C to

  
 <EMI ID = 100.1>

  
form of white crystals melting at 152-155 [deg.] C.

  
A mixture of 119 parts of 4'-chloro-2'-fluoro-

  
 <EMI ID = 101.1>

  
and the solvent is removed under reduced pressure of 300 mm Hg to give the wet solid hydrochloride salt of 4-chloro2-fluoroaniline.

  
 <EMI ID = 102.1> sodium, with stirring, until a pH of 11. The

  
resulting two-phase mixture is extracted four times; 500 parts of methylene chloride are used for each extraction. The combined organic extracts are dried

  
with anhydrous sodium sulfate and the solvent is removed under reduced pressure of 300 mm Hg to leave 89 parts of

  
 <EMI ID = 103.1> hydrazine

  
20.0 parts of 4-chloro-2-fluoroaniline are dissolved in
80 parts of water and 34 parts of concentrated hydrochloric acid. The solution is cooled to 0-10 [deg.] C and added dropwise.

  
 <EMI ID = 104.1>

  
ture of the reaction between 0 and 10 [deg.] C. After the end of the addition of nitrite, the solution is stirred for thirty minutes at

  
 <EMI ID = 105.1>

  
amounts of sulfamic acid. When a negative test is obtained with a sulfonated reagent, the diazonium salt is ready for reduction. For a description of the sulfone assay, see H.E. Fierz-David et al., Fundamental Processes of Dye Chemistry translated from Austrian 5th Edition by P.W. Wittam, Interscience Publishers, Inc., New York, 1949, page 243.

  
In a separate container, 35.4 parts of sodium bisulfite and 32.2 parts of 30% sodium hydroxide solution are dissolved in 140 parts of water. The solution is heated to

  
 <EMI ID = 106.1>

  
over a period of about 1 hour. The mixture is heated to 70 [deg.] C

  
and 0.3 part of sodium hydrosulfite is added. We adjust the pH

  
to 1.2 with 30 parts of concentrated hydrochloric acid; then an additional 90 parts of concentrated hydrochloric acid is added. The reaction mixture is heated for

  
 <EMI ID = 107.1> <EMI ID = 108.1>

  
15.8 parts of 2-fluoro-4chlorophenylhydrazine hydrochloride, 13 parts of 2-carbethoxycyclohexanone are dissolved
(purchased from Aldrich Chemical Company) and 8.1 parts of triethylamine in 100 parts of ethanol. The reactants are heated at reflux for 24 hours. We pour the mass

  
of crude reaction in 1000 parts of water. The resulting gummy product solidifies and is filtered off and dried to give 16.1 parts of crude product mp 163-170 [deg.] C. This material is used without further purification in the next step.

  
 <EMI ID = 109.1>

  
10.0 parts of 2- (4-chloro-2-fluorophenyl) 1,2,4,5,6,7-hexahydro-3H-indazol-3-one and 7.3 parts of oxy- are mixed.

  
 <EMI ID = 110.1>

  
six o'clock. The reaction mixture is dissolved in 100 parts of chloroform. The organic solution containing the product is washed successively with three portions of 25 parts each of 10% sodium hydroxide and then washed with 50 parts of water. The chloroform solution is dried with 2-10 parts of anhydrous sodium sulfate and then filtered. The solvent

  
is removed under reduced pressure on a rotary evaporator. The resulting thick oil is purified by sublimation at 100 <1> 2000 under a pressure of 0.5-1.5 mm to give 7.8 parts of white crystalline material with a melting point of 88-89.5 [ deg.] C.

  
Preparations of other novel anilines used herein; invention are as follows:

  
 <EMI ID = 111.1>

  
160 parts of solid N-bromosuccinimide are added portionwise over a 2 hour period to a 100 part solution.

  
 <EMI ID = 112.1>

  
dark red is washed four times; 200 parts of cold water are used for each wash. The red organic phase is dried with anhydrous sodium sulfate and evaporated under 300 mm Hg to give 164 parts of oily 4-bromo-2-fluoroaniline

  
 <EMI ID = 113.1>

  
6.8 parts of 4-bromo-2-fluoro aniline are dissolved in
75 parts of N-methylpyrrolidone. This solution is treated with 4.1 parts of cuprous cyanide. We heat the mixture

  
 <EMI ID = 114.1>

  
reaction on a mixture of 200 parts of ice and 15 parts of sodium cyanide. This mixture is then heated in a boiling water bath for 2 hours at 60-700C. This aqueous solution is then processed by extraction with four portions

  
 <EMI ID = 115.1>

  
Product is dried over sodium sulfate and stripped to give 2.6 parts of the desired product, mp 71-73 [deg.] C.

  
Using the procedure of Example 1 with many

  
2-carbethoxycyclohexanone, the appropriate hydrazine acid salt and phosphorus oxychloride, the following compounds of formula I are prepared:

  

 <EMI ID = 116.1>
 

  

 <EMI ID = 117.1>


  
Using the procedure of Example 1 with a methyl substituted 2-carbethoxycyelohexanone, the appropriate aryl hydrazine and phosphorus oxychloride, the following compounds can be prepared:

  

 <EMI ID = 118.1>
 

  

 <EMI ID = 119.1>


  
EXAMPLE 2:

  
 <EMI ID = 120.1>

  
hexahydrocycloheptapyrazole

  

 <EMI ID = 121.1>


  
By substituting 2-carbethoxycycloheptanone [prepared

  
 <EMI ID = 122.1>

  
available from the Aldrich Chemical Company) in the procedure of Example 1 (c), 2- (4-

  
 <EMI ID = 123.1>

  
(melting point 224-225 [deg.] C). By reacting this pyrazolone with phosphorus oxychloride according to the procedure of Example 1 (d), 3-chloro-2- (4-chlorophenyl) 2,4,5,6,7,8 is obtained. -hexahydrocycloheptapyrazole (melting point 59-61 [deg.] G).

  
Following the procedure of Example 2, using the appropriate aryl hydrazine hydrochloride (instead of

  
 <EMI ID = 124.1>

  
phosphorus, the following compounds of formula 1 can be prepared:

  

 <EMI ID = 125.1>


  
EXAMPLE 3: <EMI ID = 126.1>

  
Dissolved 795 parts of 4-chloro-2-fluorophenylhydrazine and 6.6 parts of methyl 2-oxocyclopentanecarboxylate.
(purchased from Aldrich Chemical Company) in 200 parts of toluene. The reactants are heated at reflux for 1 to 2 hours while removing the water which is formed. The reaction mixture is cooled to 100 [deg.] C and a mixture is added dropwise.

  
 <EMI ID = 127.1>

  
25 parts of methanol, removing the methanol in the form of its azeotrope with toluene. The reaction mixture is heated until the internal temperature reaches 110 [deg.] C.

  
The reaction mixture is then cooled and poured into
200 parts of ice water. The organic layer is separated and the aqueous layer is washed twice with ethyl ether. Cold dilute hydrochloric acid is added with stirring to the aqueous layer until a pH of 2. The resulting oily product solidifies and is filtered off, dried and recrystallized from acetonitrile. to give

  
3.3 parts of crystalline material, tan color, point

  
 <EMI ID = 128.1>

  
Alternatively, the above pyrazolone is prepared as follows. 16.0 parts of 4-chloro-2fluorophenylhydrazine and 14.2 parts of methyl 2-oxocyclopentanecarboxylate are dissolved in 100 parts of benzene. The reaction mixture is heated under reflux for 1 to 2 hours removing the water which is formed. The reaction mixture is cooled and the solvent is removed under reduced pressure on a rotary evaporator. The resulting brown oil is dissolved in 150 parts

  
 <EMI ID = 129.1>

  
add 2 equivalents of n-butyllithium in cyclohexane
(purchased from Foote Mineral Company) at such speed that

  
the internal temperature is maintained at 0-5 [deg.] C. The reaction mixture is allowed to warm to room temperature, then

  
reflux it for 18 hours. The reaction mixture is cooled and poured into 200 parts of ice water. The organic layer is separated and the aqueous layer is washed twice.

  
with ethyl ether. Cold dilute hydrochloric acid is added to the aqueous layer until a pH of 2 is reached. The resulting oily product solidifies and is separated by filtration, dried and recrystallized from acetonitrile to give 17.5 parts of crystalline material, color of.

  
 <EMI ID = 130.1> phosphorus chloride according to the procedure of Example

  
 <EMI ID = 131.1>

  
Using the procedure of Example 3 with the appropriate methylated 2-oxocyclopentanecarboxylate, the appropriate hydrazine and phosphorus oxychloride, the following compounds of formula I can be prepared:

  

 <EMI ID = 132.1>
 

  

 <EMI ID = 133.1>


  
 <EMI ID = 134.1>

  
hydro-3H-indazol-3-one [from Example 1 (c)] with 3.0 parts of N, N-diethylaniline and 5.0 parts of dimethylformamide - under nitrogen atmosphere, 6.3 parts of oxy-

  
 <EMI ID = 135.1>

  
2 hours, After cooling to room temperature, the reaction mixture is extracted by extraction with 100 parts of ethyl ether, washed with water, dried over anhydrous magnesium sulfate and concentrated on a rotary evaporator. Recrystallization from methanol / water gives

  
 <EMI ID = 136.1>

  
Using the procedure of Example 4 with the appropriate condensed pyrazolones .3, which can be prepared by the method taught in Example 1 or in Example 3, the following compounds can be prepared:
 <EMI ID = 137.1>
 
 <EMI ID = 138.1>
 <EMI ID = 139.1> minutes. 2.5 parts of 2-cyanocyclohexanone, prepared from commercial 2-chlorocyclohexanone and potassium cyanide [R.E. Meyer, Helv.

  
 <EMI ID = 140.1>

  
than. After heating at reflux for 2 hours, followed by stirring at room temperature overnight,

  
the reaction mixture is evaporated to remove toluene and is treated with water, extracted with ethyl ether, dried over anhydrous magnesium sulfate and concentrated. Recrystallization from ethanol / water gives 2.6 parts

  
 <EMI ID = 141.1> tetrahydro-2H-indazole

  
Has 2.5 parts of 3-amino-2- (4-chlorophenyl) -4,5,6,7-

  
 <EMI ID = 142.1>

  
concentrate and 15 parts of water cooled to 0 [deg.] C, are added

  
drop by drop a solution of 0.8 part of nitrite

  
sodium in 5.0 parts of water and the mixture is stirred for

  
an hour and a half. Excess nitrous acid is destroyed using sulfamic acid. Then add slowly

  
1.7 parts of potassium iodide in 5.0 parts of water to diazonium solution. After stirring at 0-25 [deg.] C for 2 hours, the precipitate is collected by filtration and dried. Recrystallization from ethanol / water gives 1.7 part of the product, melting point 83 [deg.] C (decomp.).

  
Using the method of Example 5 with alpha-

  
 <EMI ID = 143.1>

  
react the appropriate alpha-chlorocyclohexanone or alpha-chlorocyclopentanone with sodium cyanide in accordance with

  
 <EMI ID = 144.1>

  
can prepare the following compounds of formula I:

  

 <EMI ID = 145.1>
 

  

 <EMI ID = 146.1>


  
EXAMPLE 6:

  
 <EMI ID = 147.1>

  
tetrahydro-2H-indazole a) Preparation of 2- (4-chloro-2-fluoro- fluoborate <EMI ID = 148.1>

  
To 50 parts of 48% fluoboric acid at 0-5 [deg.] C, a solution of 2.5 parts of sodium nitrite in 10 parts of water and a suspension of 8.7 parts is simultaneously added.

  
 <EMI ID = 149.1>

  
indazole in 30 parts of acetic acid in small portions, so that the mixture always contains an excess of nitrite

  
 <EMI ID = 150.1>

  
Excess nitrous acid is destroyed using sulfamic acid. the precipitates are collected, washed with water, with ethyl ether and dried, giving 9.0 parts of the product. The IR spectrum indicates that no amino compound remains and there is

  
 <EMI ID = 151.1> of 10 parts of potassium fluoride in 100 parts of fluoboric acid is photolysed by a Hanovia high pressure mercury vapor lamp of 200 watts at 0 [deg.] C for one hour and

  
at room temperature for fifteen hours. The reaction mixture is worked up by extraction with ether, washed with water,

  
dried over anhydrous and concentrated magnesium sulfate. The desired product is isolated by dry column chromatography (silica gel, elution with methylene chloride), by preparative thin layer chromatography (silica gel, development with 5 parts of Et 20: 100 parts of hexane) and by chromato-

  
 <EMI ID = 152.1>

  
W HP in particles of 0.149 to 0.177 mm at 250 [deg.] C). The product is found by gas chromatography to be pure and it is analyzed by mass spectroscopy (M + = 268 and m / e + 240 in

  
 <EMI ID = 153.1>

  
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:

  

 <EMI ID = 154.1>
 

  

 <EMI ID = 155.1>


  
Compositions

  
Useful compositions of the compounds of Formula 1 include sprinkling powders, granules, lozenges, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, etc. Many of these compositions can be applied directly. . The sprayable compositions can be diluted in suitable media and used at spray volumes of between a few liters and several hundred liters per hectare. Compositions of high concentration are used mainly as intermediates for further dilution. The compositions, in general, contain

  
 <EMI ID = 156.1>

  
More particularly, they will usually contain these ingredients in the following approximate proportions:

  

 <EMI ID = 157.1>


  
Lower or higher proportions of active ingredient may 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 advantageous and are obtained by incorporation into the composition or by tank mixing.

  
Typical solid diluents are described by Watkins

  
et al in "Handbook of Insecticide Dust Diluants and Carriers", 2nd Edition, Dorland Books, Caldwell, N.J. Usable diluents include finely divided or granular solids classified as attapulgites,

  
vegetable substances, calcites, diatomites, dolomites, gypsum, kaolinites, limestone, mica, montmorillonite-type materials, phosphates,

  
pyrophyllites, sulfur, sand, talcs, tripolites, vermiculite and plastics. These synthetics can include precipitated hydrated silicon dioxide, precipitated hydrated calcium silicate,

  
precipitated calcium carbonate and synthetic organics. The most absorbent thinners are preferred for wettable powders and the densest for powders

  
to sprinkle. Typical liquid diluents and solvents are described by Marsden in "Solvents Guide", 2nd Edition, Interscience, New York, 1950. A solubility of less than 0.1% is preferred for suspension concentrates; concentrates in solution are preferably stable against phase separation at 0 [deg.] C. Found in "McCutcheon's Detergents and Emulsifiers 1975 Annual", MC Publ. Corp., Ridgewood, New Jersey, E.U.A. , as well as in Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co. New York, 1964, lists surfactants and recommended uses. All the compositions can contain small proportions of additives to reduce foaming, cake setting, corrosion, microbiological growth, etc.

  
or to visually mark the area that has been treated.

  
It is sometimes advantageous to add ingredients which reduce the volatility of some of the compounds according to the present invention. These additives can include film-forming materials such as polyvinylpyrrolidones having molecular weights of between about 20,000 and about 100,000; polyvinyl alcohols having molecular weights of between about 20,000 and about 150,000; and poly-

  
 <EMI ID = 158.1>

  
examples of film-forming additives. Any material which forms a film on the solid active ingredient in the preparation

  
of the composition or on the active ingredient when it is sprayed and dried from a liquid composition can be used. Other techniques for reducing volatility can include incorporating the compounds according to the present invention into resins, waxes, gums, rubbers, etc., and then preparing compositions, as described above, for these combinations.

  
Solutions are prepared by simply mixing the 1 ingredients. Fine solid compositions are prepared by mixing and usually grinding as in a hammer or fluid power mill. We prepare suspensions

  
 <EMI ID = 159.1>

  
on the surface of the vehicle, a binder is used to hold the active ingredient on the surface. The binder must bind the ingredient

  
 <EMI ID = 160.1>

  
normal transport and handling. Useful binders include materials which are at least partially soluble in any liquid used in the preparation of the granules and which adhere to the surface of the granules. Water soluble binders are preferred. the binders which can be used include, without limitation, water-soluble polymers such as polyvinyl alcohols having molecular masses of between approximately 20,000 and approximately 150,000; of

  
 <EMI ID = 161.1>

  
between about 20,000 and about 100,000; and polyoxyethylenes having molecular weights of between about 100,000

  
 <EMI ID = 162.1> ligninsulfonates, starches, sugars and certain surfactants listed in "McCutcheons' Detergents and Emul-

  
 <EMI ID = 163.1>

USA.

  
The active material can be sprayed in the form of a solution in a suitable solvent, which may or may not be removed from the composition. If the active ingredient is a liquid, it can be sprayed on the vehicle or mixed directly with it. If it is a solid material, it can be melted and applied directly in the liquid state. If granules of very low mechanical strength are desired, the active ingredient can be applied to the vehicle by spraying. Granules can also be prepared by agglomeration techniques. For example,

  
 <EMI ID = 164.1>

  
be mixed and agglomerated by known techniques of

  
 <EMI ID = 165.1>

  
fluid bed or tank granulator. The active ingredient and diluent can also be mixed with other formulation ingredients and pelletized. The pellets can then be ground to a desired size of granules. The pellets can be formed by agglomeration techniques. See

  
 <EMI ID = 166.1>

  
1967, pages 147 et seq., And "Perry's Chemical Engineer's Handbook", 4th edition, McGraw-Hill, N.Y., 1963, pages 8-59 et seq.

  
For further information concerning the technique of preparation of the compositions, see for example:

  
 <EMI ID = 167.1> <EMI ID = 168.1>

  
Granules

  

 <EMI ID = 169.1>


  
The active ingredient is heated to about 90 [deg.] C and sprayed onto dust free attapulgite granules and preheated in a double cone mixer. The granules are then allowed to cool and packaged.

  
EXAMPLE 8:

  
Solution

  

 <EMI ID = 170.1>


  
The ingredients are combined and stirred to form a &#65533; solution, which can be used for low volume applications.

  
EXAMPLE 9:

  

 <EMI ID = 171.1>


  
The ingredients are mixed, passed through the grinder to

  
 <EMI ID = 172.1>

  
is extruded into cylinders of about 3mm in diameter which are cut to produce pellets of about 3mm in length. The latter can be used directly after drying - or the dried pellets can be ground so that they pass through a sieve having 0.84mm openings. The rejection grams are separated by a sieve having openings.

  
 <EMI ID = 173.1>

  
the fines: are recycled. All the compounds according to the present invention; can be formulated in this way EXAMPLE 10:

  
Emulsifiable concentrate

  

 <EMI ID = 174.1>


  
The ingredients are combined and stirred until complete dissolution. A fine mesh filter is included in the conditioning operation to ensure the absence of any undissolved foreign matter in the. product.

  
EXAMPLE <1> 1:

  
Aqueous suspension

  

 <EMI ID = 175.1>


  
The ingredients are ground together in a sand mill to produce particles having substantially all sizes of less than 5 microns.

  
EXAMPLE 12:

  
Wettable powder

  

 <EMI ID = 176.1>


  
Ingredients - are thoroughly mixed, passed through an air grinder to produce a lump

  
 <EMI ID = 177.1>

  
sieved through a sieve of 0.3 mm mesh opening before packaging.

  
 <EMI ID = 178.1>

  

 <EMI ID = 179.1>


  
The surfactant is sprayed onto the active ingredient in a mixer and the mixture is passed through a 0.42 mm mesh sieve before packaging. The concentrate can then be mixed with other materials for practical use.

  
EXAMPLE 14:

  
Low concentration granules

  

 <EMI ID = 180.1>


  
Forty grams of a solution containing 2.5% of 3-

  
 <EMI ID = 181.1>

  
methyl are atomized slowly on a fluidized bed of attapulgite granules (197 g). Fluidization of the granules is continued after atomization is complete and until all methyl alcohol has evaporated from the granules. The granules are packaged for use.

  
EXAMPLE 15:

  
Extruded pellets

  

 <EMI ID = 182.1>


  
The ingredients are mixed, passed through a hammer mill and moistened with about 10-12% water. The mixture is then extruded into cylinders of about 3 mm in diameter which are cut to lengths of about 3 mm. These pellets can be used directly after drying or the dried pellets can be ground so as to pass through a sieve with 0.84 mm opening. The granules <EMI ID = 183.1>

  
packaged for use and fines are recycled. EXAMPLE 16:

  
Granules-

  

 <EMI ID = 184.1>


  
 <EMI ID = 185.1>

  
Checked on the dusted and preheated granules in a bicone mixer. The granules are allowed to cool and packaged for use.

  
 <EMI ID = 186.1>

  
Low concentration granules

  

 <EMI ID = 187.1>


  
The ingredients are mixed, passed through a hammer mill and placed in a fluidized bed granulator. Water is sucked into the fluidized bed of powder until small granules are formed. The suction of the water is then stopped, but the fluidization is continued to dry the granules formed. The granules are removed from the granulator and sieved so that they pass through a sieve of

  
0.84 mm mesh opening. Granules rejected by a 0.42 mm mesh sieve are packaged for use. Granules larger than 0.84 mm are crushed and recycled. Fine particles smaller than 0.42mm are also recycled.

  
EXAMPLE 18:

  
Extruded pellets
 <EMI ID = 188.1>
  <EMI ID = 189.1>

  
hammers and then moistened with about 12% water. The numid mixture is extruded in the form of cylinders of approximately

  
 <EMI ID = 190.1>

  
lozenges are dried and packaged. They are applied directly.

  
 <EMI ID = 191.1>

  
Low concentration granules

  

 <EMI ID = 192.1>


  
 <EMI ID = 193.1>

  
This solution is atomized very slowly onto 190.1 g of a rapidly tumbling bed of attapulgite granules. After the application of the active ingredient is completed, the composition is mixed for a few more minutes. Dimethylformamide is not eliminated from the composition. The granules are packaged for use.

  
EXAMPLE 20:

  
Emulsifiable concentrate

  

 <EMI ID = 194.1>


  
The ingredients are combined and stirred until complete dissolution. The solution is filtered through a fine mesh filter before packaging to remove any undissolved foreign matter.

  
 <EMI ID = 195.1>

  
Low concentration granules
 <EMI ID = 196.1>
 preformed sand granules with coarse sizes

  
particles between 105 and 297 microns 94.9%

  
0.5 g of 3-chloro-2- (4-chloro-2-fluorophenyl) 4,5,6,7-tetrahydro-2H-indazole and 25 g of ligninsulfonate are dissolved

  
of sodium in 50 g of water. This solution is sprayed slowly onto a tumbling bed of sand granules (474.5 g). When spraying is complete, the tumbling granules are heated to remove water. The resulting granules are packaged for use.

  
The compositions may contain, in addition to the active ingredients according to the present invention, other conventional chemicals for agriculture 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-dichloro-5-isopropoxyphenyl) -1,3,4-

  
oxadiazol-2-one;

  
(2) 6-methylthio-2,4-bis (ethylamino) -s-triazine;

  
 <EMI ID = 197.1>

  
(4) 2,4-dichlorophenoxyacetic acid and esters and salts thereof.

  
Combinations with herbicides for wheat:

  
(1) 2,4-dichlorophenoxyacetic acid and esters and salts thereof;

  
 <EMI ID = 198.1>

  
(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-methyl-

  
 <EMI ID = 199.1>

  
2-methyl-4-chlorophenoxyacetic, its salts or esters, 4 amino-6-tert-butyl-3-methylthio-as-triazin-5 (4H) -one, oxides of aryl and 4-nitrophenyl such as 2,4,6trichlorophenyl and 4-nitrophenyl oxide and 2,4-dichlorophenyl and 4-nitrophenyl oxide, to control a wide range of weeds.

  
The agricultural chemicals mentioned above are examples of compounds which may co-exist with the active compounds and should not be construed as limiting the invention in any way.

  
EXAMPLE 24:

  
For practical use, granules can be prepared from the following ingredients:

  

 <EMI ID = 200.1>


  
The active ingredients are mixed and then heated

  
 <EMI ID = 201.1>

  
preheated in a bioone blender. The treated granules are then allowed to cool and they are packaged *

  
 <EMI ID = 202.1>

  
rice, in particular "paddy" rice, wheat and peanuts. These compounds are also useful for post-emergence control against weeds in certain crops,

  
for example rice. In addition, the compounds according to the present invention can be used in directed treatments for the pre- or post-emergence control of weeds in various crops including soybeans, peanuts, cotton, garden peas and rice. planted in rows.

  
The compounds according to the invention are useful for controlling weeds in transplanted crops.
(transplanted), such as sweetbread, tobacco, tomatoes, cabbage, potatoes, lettuce, celery, pepper and eggplant. The treatment can be applied to the soil surface before transplanting and the plants transplanted into the treated soil, or the active compound can be incorporated into the soil before transplantation and the plants transplanted into the treated soil. The treatment can also be applied after transplanting if care is taken to keep the foliage of cultivated plants free from the chemical (Table IV).

  
The precise amount of the compounds of formula I to be used in any given situation will vary depending on the particular end result desired, the use concerned, the species of crops and weeds, the soil to which

  
this is the composition used, the mode of application,

  
current atmospheric conditions, the density of

  
foliage and the like. Since so many variables play a role, it is not possible to indicate a suitable application rate for all situations. In general, the compounds according to the invention are used

  
at a rate of approximately 0.015 to approximately 15 kilograms per hectare,

  
preferably from about 0.03 to about 10 kilograms per hectare. Lower rates within this range will generally be chosen on relatively light soils, land with low organic matter content, for selective weed control in crops, where in cases

  
where maximum persistence is not required.

  
The herbicidal activity of the compounds according to the present invention was discovered in greenhouse tests, as explained below.

  
Test according to procedure 1

  
Seeds of crabgrass Bigitaria spp., Houndstooth

  
 <EMI ID = 203.1>

  
Cassia fora, garden volubilis (Ipomoea sp.), Lampourde (xanthium sp.), Sorghum, corn, soybeans, rice, wheat and tigernuts tubers are planted in a growing medium and treated in pre-emergence with chemicals dissolved in a non-phytotoxic solvent. At the same time, cotton plants having

  
 <EMI ID = 204.1>

  
kidney beans with the third trifoliate leaf in progress

  
development, crabgrass with two leaves, fowl with two leaves, wild oats with one leaf, cassia with three leaves (including cotyledonary leaves) garden twist with four leaves (including

  
 <EMI ID = 205.1>

  
(including cotyledonary leaves), sorghum with three leaves, corn with three leaves, soybean with two cotyledonal leaves, rice with two leaves, wheat with one leaf, and tiger nut with three to five leaves. The treated plants and controls are kept in a greenhouse for

  
sixteen days, then all species are compared to controls and the response to treatment is visually assessed. The results are expressed on a scale from 0 = no damage to 10 = complete destruction. The letters used have the following meanings B = burn, G = growth retardation, C = necrosis / chlorosis, E- = inhibition of emergence and H = effect

  
training; X = axillary stimulation.

  

 <EMI ID = 206.1>


  

 <EMI ID = 207.1>
 

  

 <EMI ID = 208.1>


  

 <EMI ID = 209.1>
 

  

 <EMI ID = 210.1>


  

 <EMI ID = 211.1>
 

  

 <EMI ID = 212.1>


  

 <EMI ID = 213.1>
 

  

 <EMI ID = 214.1>


  

 <EMI ID = 215.1>
 

  

 <EMI ID = 216.1>


  

 <EMI ID = 217.1>
 

  

 <EMI ID = 218.1>


  

 <EMI ID = 219.1>
 

  

 <EMI ID = 220.1>


  

 <EMI ID = 221.1>
 

  

 <EMI ID = 222.1>


  

 <EMI ID = 223.1>
 

  

 <EMI ID = 224.1>


  

 <EMI ID = 225.1>
 

  

 <EMI ID = 226.1>


  

 <EMI ID = 227.1>
 

  

 <EMI ID = 228.1>


  

 <EMI ID = 229.1>
 

  

 <EMI ID = 230.1>


  

 <EMI ID = 231.1>
 

  

 <EMI ID = 232.1>


  

 <EMI ID = 233.1>
 

  

 <EMI ID = 234.1>


  

 <EMI ID = 235.1>
 

  

 <EMI ID = 236.1>


  

 <EMI ID = 237.1>
 

  

 <EMI ID = 238.1>


  

 <EMI ID = 239.1>
 

  

 <EMI ID = 240.1>


  

 <EMI ID = 241.1>
 

  
 <EMI ID = 242.1> the biological activity of the compounds according to the present invention. The results illustrate the herbicidal efficacy of the compounds with selectivity for two important crops, rice and

  
 <EMI ID = 243.1> downy brome (Bromus tectorum) and seine brome (Bromus secalinus). In addition, wild mustard seeds

  
(Brassica arvensis), Kochia (Kochia scoparia) and black grass

  
fields (Alopecurus myosuroides) are included in some cases, as well as established plants (post-emergence) of some or all of the above mentioned species. The plants are kept in a greenhouse and visual assessments of plant responses (as described in Table I) are

  
usually done about three weeks after application.

  

 <EMI ID = 244.1>


  

 <EMI ID = 245.1>
 

  

 <EMI ID = 246.1>


  

 <EMI ID = 247.1>
 

  

 <EMI ID = 248.1>


  

 <EMI ID = 249.1>
 

  

 <EMI ID = 250.1>


  

 <EMI ID = 251.1>
 

  

 <EMI ID = 252.1>


  

 <EMI ID = 253.1>
 

  

 <EMI ID = 254.1>


  

 <EMI ID = 255.1>
 

  

 <EMI ID = 256.1>


  

 <EMI ID = 257.1>
 

  

 <EMI ID = 258.1>


  

 <EMI ID = 259.1>
 

  

 <EMI ID = 260.1>


  

 <EMI ID = 261.1>
 

  

 <EMI ID = 262.1>


  

 <EMI ID = 263.1>
 

  

 <EMI ID = 264.1>


  

 <EMI ID = 265.1>
 

  

 <EMI ID = 266.1>


  

 <EMI ID = 267.1>
 

  

 <EMI ID = 268.1>


  

 <EMI ID = 269.1>
 

  

 <EMI ID = 270.1>


  

 <EMI ID = 271.1>
 

  

 <EMI ID = 272.1>


  

 <EMI ID = 273.1>
 

  
It will be appreciated that, in general, these compounds at a low concentration practically eliminate unwanted vegetation, eg houndstooth, but have relatively little effect on crop plants, eg rice. In

  
wheat, good results are obtained at a low dose against wild oats, seine bromine, downy bromine and, when tested, wild mustard, Kochia and

  
black grass, with little effect. on the wheat crop.

  
The following table, Table 3, is presented to further illustrate the biological activity of the compounds according to the present invention. The results illustrate the herbicidal efficacy of the compounds with the selectivity for rice in a "paddy" crop.

  
We build a "paddy" for rice using

  
a bin containing soil and houndstooth seeds
(Echino-chloa crusgalli) and japonica rice plants which have been transplanted into "paddy" soil at the two stage.

  
three-leafed.The water level is maintained a few centimeters above the surface of the earth. The test samples are applied directly to the water of the

  
"paddy" and plant response evaluations are carried out approximately three weeks later.

  

 <EMI ID = 274.1>


  

 <EMI ID = 275.1>
 

  

 <EMI ID = 276.1>


  

 <EMI ID = 277.1>
 

  

 <EMI ID = 278.1>


  

 <EMI ID = 279.1>
 

  
It will be appreciated that these compounds at a low application rate practically eliminate unwanted vegetation, eg houndstooth, but have relatively little effect on rice.

  
Oven to demonstrate utility on transplanted cultivated plants, 30 x 30 x 15 cm metal containers are filled to a height of 13 cm with fumigated Fallsington sandy loam. The following weed seeds are mixed throughout the top 2.5cm layer of soil in each container: houndstooth (Echinochloa

  
 <EMI ID = 280.1>

  
The following treatments are carried out by spraying the surface of the soil before planting and also by incorporation into the soil (2.5 cm) before planting

  

 <EMI ID = 281.1>


  
Compound A is dissolved in acetone and the solution is applied at a spray volume of 560 liters per hectare. Immediately after treatment; the following plants are transplanted: pepper (Delaware Belle,

  
 <EMI ID = 282.1>

  
height). Four plants are transplanted into each container. The containers are placed in the greenhouse and watered by hand as needed. Eighteen days after treatment, visual assessments of plant responses are recorded

  
 <EMI ID = 283.1>

  

 <EMI ID = 284.1>


  

 <EMI ID = 285.1>
 

CLAIMS

  
 <EMI ID = 286.1>

  

 <EMI ID = 287.1>


  
in which

  
n is 3, 4 or 5;

  
 <EMI ID = 288.1>

Q is fluorine, chlorine, bromine or iodine;

  
X is fluorine, chlorine, bromine, iodine

  
or a cyano, methoxy or nitro group;

Y is hydrogen, fluorine or chlorine;

  
Z is hydrogen or fluorine; and

  
V is hydrogen, fluorine, chlorine or a

  
methoxy group; with the conditions that
(a) when n is 5, R must be hydrogen,

  
Q must be chlorine or bromine, Z and V must all be

  
two of hydrogen and Y must be hydrogen or fluorine;
(b) when n is 3 or 4 and Q is fluorine or <EMI ID = 289.1>

  
hydrogen or: fluorine; <EMI ID = 290.1>
(d) when V is other than hydrogen,

  
X must be fluorine, chlorine or bromine and Z must be

  
 <EMI ID = 291.1>


    

Claims (1)

2. Compounds according to claim 1, characterized in that n is 4 ... 3. Compounds according to claim 1, characterized <EMI ID = 292.1> 6. Compounds according to claim 1, characterized in that n = 4 and Q is chlorine or bromine. 7. Compounds according to claim 1, characterized in that n = 4 and Q is chlorine. 8. Compounds according to claim 1, characterized <EMI ID = 293.1> hydrogen. 9. Compounds according to claim 1, characterized <EMI ID = 294.1> 10. Compounds according to claim 1, characterized <EMI ID = 295.1> 11. Compounds according to claim 1, characterized in that n = 3 and Q is chlorine or bromine. 12. Compounds according to claim 1, characterized <EMI ID = 296.1> drogenous. 13. Compounds according to claim 1, characterized in that n = 3, Q is chlorine and R1 is hydrogen. 14. Compounds according to claim 1, characterized in that Q is chlorine, Z and V are hydrogen, and Y is hydrogen or fluorine. 15. Compounds according to claim 1, characterized in that n = 4, Q is chlorine, R is hydrogen, Z is hydrogen and V is hydrogen. 16. Compounds according to claim 1, characterized in that n = 4, Q is chlorine, R is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, or a cyano or methoxy group. 17. Compounds according to claim 1, characterized in that n = 4, Q is chlorine, R1 is hydrogen, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine. 18. Compounds according to claim 1, characterized <EMI ID = 297.1> hydrogen and V is hydrogen. 19. Compounds according to claim 1, characterized <EMI ID = 298.1> hydrogen, V is hydrogen, Y is hydrogen or fluorine and X is fluorine, chlorine, bromine or an <EMI ID = 299.1> hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine. 21. Compounds according to claim 1, characterized <EMI ID = 300.1> hydrogen and V is hydrogen. 22. Compounds according to claim 1, characterized <EMI ID = 301.1> hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is fluorine, chlorine, bromine, or a cyano or methoxy group. 23. Compounds according to claim 1, characterized <EMI ID = 302.1> hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine. 24. Compounds according to claim 1, characterized in that Q is chlorine, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine or bromine. 25. Compounds according to claim 1, characterized in that n = 3, Q is bromine, Z is hydrogen, V is hydrogen, Y is hydrogen or fluorine, and X is chlorine. or bromine. 26. Compounds according to claim 1, characterized <EMI ID = 303.1> 4,5,6,7-tetrahydro-2H-indazole, 1,3-chloro-2- (4-chlorophenyl) 4,5,6,7-tetrahydro-2H-indazole, 1,3-bromo-2 - (4-chloro-2fluorophenyl) -4,5,6,7-tetrahydro-2H-indazole, 1,3-chloro2- (4-bromo-2-fluorophenyl) -4,5,6,7-tetrahydro- 2H-indazole, <EMI ID = 304.1> cyclopentapyrazole, and 1,3-chloro-2- (4-chlorophenyl) -2,4,5, 6-tetrahydrocyclopentapyrazole. 27. A composition useful for controlling unwanted vegetation, essentially comprising a compound according to any one of claims 1 to 26 and at least one component selected from (a) a surfactant and (b) a solid or liquid diluent. 28. A method of controlling unwanted vegetation, characterized in that a herbicidally effective amount of a compound according to any one of claims is applied to the place where this unwanted vegetation grows. <EMI ID = 305.1> 29. A method of controlling undesirable vegetation in rice, characterized in that an effective amount is applied to the place where this undesirable vegetation grows. from the herbicidal point of view of a compound according to claim 1. 30. A method according to claim 29, characterized in that the unwanted vegetation is houndstooth. 31. The method of claim 29, characterized in that the compound is 3-chloro-2- (4-chloro-2-fluoro- <EMI ID = 306.1> what rice is "paddy" rice. 33. A method of controlling undesirable vegetation in wheat, characterized in that a herbicidally effective amount of a compound according to claim 1 is applied to the place where the undesirable vegetation grows. 34. The method of claim 33, characterized in that the compound is 3-chloro-2- (4-chloro-2-fluorophenyl) - <EMI ID = 307.1> 4,5,6,7-tetrahydro-2H-indazole. 35. A method of controlling undesirable vegetation in transplanted crops, characterized in that a herbicidally effective amount of a compound according to claim 1 is applied to the location where such undesirable vegetation grows. 36. The method of claim 35, characterized in that the compound is 3-chloro-2- (4-chloro-2-fluorophenyl) -4,5.6,7-tetrahydro-2H-indazole or 3-chloro-2- (4- <EMI ID = 308.1> 37. Process for preparing a compound of the formula <EMI ID = 309.1> <EMI ID = 310.1> Q is chlorine or bromine; X is fluorine, chlorine, bromine, iodine or a <EMI ID = 311.1> Y is hydrogen, fluorine or chlorine .; Z is hydrogen or fluorine; and V is hydrogen, fluorine, chlorine or a methoxy group; with the conditions that <EMI ID = 312.1> must both be hydrogen, and Y must be either hydrogen or fluorine; <EMI ID = 313.1> 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; characterized in that a compound of the formula is reacted <EMI ID = 314.1> <EMI ID = 315.1> subsequently with at least one equivalent of a phosphorus oxyhalide of the formula <EMI ID = 316.1> in which is chlorine or bromine. 38. Process for preparing a compound of the formula <EMI ID = 317.1> in which n is 3 or 4; <EMI ID = 318.1> X is fluorine, chlorine, bromine, iodine or a cyano, methoxy or nitro group; Y is hydrogen, fluorine or chlorine; Z is hydrogen or fluorine; and V is hydrogen, fluorine, chlorine or a methoxy group; <EMI ID = 319.1> be hydrogen and Y must be hydrogen or fluorine; characterized in that a diazonium salt of the formula <EMI ID = 320.1> <EMI ID = 321.1> <EMI ID = 322.1> in which n is 3 or 4; <EMI ID = 323.1> X is fluorine, chlorine, bromine, iodine or a cyano, methoxy or nitro group; Y is hydrogen, fluorine or chlorine; Z is hydrogen or fluorine; and V is hydrogen, fluorine, chlorine or a methoxy group; <EMI ID = 324.1> must be hydrogen and Y must be hydrogen or fluorine; characterized in that a diasonium salt of the formula is decomposed <EMI ID = 325.1> in the presence of fluoboric acid with at least one equivalent of an ionic fluoride. 1-