CA1066294A - 1,2-dialkyl-3,4,5-trisubstituted pyrazolium salts as herbicidal agents - Google Patents

Abstract

A B S T R A C T
1,2-dialkyl-3,4,5-trisubstituted pyrazolium salts which are useful as herbicidal agents having the following formula:
wherein R1 is alkyl C1-C5, allyl or benzyl; R2 is alkyl C1-C5; R3 is or naphthyl; R5 is ; R4 is alkoxy C1- C22, alkenyloxy C3-C4, halogen substituted alkenyloxy C3-C4, alkynyloxy C3-C4, -O-(CH2)n-W, alkyl-thio C1-C22, alkylsulfonyl C1-C22, , , , , , and ;

R6 is hydrogen, methyl or phenyl; U and V each are hydrogen halogen, alkyl C1-C4, alkoxy C1-C4, NO2 or CF3; W is halogen, cyano, carbalkoxy C1-C7, alkoxy C1-C7, alkylthio C1-C7, alkyl-sulfonyl C1-C7, benzylthio or benzylsulfonyl; Z and Z' each are hydrogen, halogen, alkyl C1-C12, alkoxy C1-C4 or phenyl;
X is an anion which is not phytotoxic and selected from the group consisting of an organic or inorganic acid; m is 1, 2 or 3; and n is 1, 2, 3, or 4.

Description

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, lS This invention relates to novel 1,2-dialkyl--3,4,5-trisubstituted pyrazolium salts represented by the structure:
(1) 1 _ - ..
Rl x-m ~ R3 1 . m wherein Rl is alkyl Cl-C5 straight chain or branched, allyl benzyl; R2 is alkyl Cl-C5 straight chain or branch-ed; R3 is ~ ~ .

~ or naphthyl R5 ic ~ Rg i~ ~
30 alkoxy Cl-C22 straight chain or branched, alkenyloxy ~ ;

.

- 2 ~ ~ . .

. .. ' : :
,' :' ' ' . . .: :' ' ' ~66'~
C3-C4, halogen substltuted alkenyloxy C~-C4, alkynyloxy C3-C4, -O-~CH2)n-W, alkylthio C1_C22J alkylsulfonyl C1_C22, V V

, -S-CH

V V V

-SO2-CH2 ~ -S ~ ~ -S2 ~ and V
-OCH ~

R6 is hydrogen, methyl or phenyl; U and V each are hydrogen, halogen, alkyl Cl-C4, alkoxy Cl-C4, NO2 or CF3; W is halogen, cyano, carbalkoxy Cl-C7, alkoxy Cl-C7, alkylthio Cl-C7, alkylsulfonyl Cl-C7, benzylthio or benzylsul-fonyl; Z and Z' each are hydrogen, halogen, alkyl Cl-C12; alkoxy Cl-C4 or phenyl; X is an anion which is no~ phytotoxic and selected from the group consisting of halides such as chloride, bromide, and iodide, triodide; tri~ : .
bromide; tetrafluoroborate; hydroxide; acetate; sulfate; hydrogen sulfate;
methyl sulfate; benzene sulfonate; perchlorate; Cl-C4 alkyl benzene sulfonate, :
. : . .
preferably p-toluene sulfonate; hydrogen phosphate; Cl-C4 alkane sulfonate;

o ,R8 1Rl l ,~ ~ ' -O-C-C-R9 and -O-C-CH-O-~ Cl R7 Rlo .
where R7 and R8 are halogen; Rg is halogen, methyl, halomethyl or dihalo-methyl; Rlo is chlorine or methyl; and Rll is hydrogen or methyl, m is 1, 2 ~ .
or 3; and n is 1, 2, 3 or 4.
In another aspect, the inven~ion provides a method for the control of undesirable broadleaf weeds and grass weeds comprising contacting said .~ :~
weeds with a herbicidally effective amount of a compound having the formula~
:" . ' .
~ - 3 ~ ~ :
" ~ ~ .

.': . ' '' ' '- ~ . . , , ' . ~

~L066Z94 ., .

4 ~ ~ m 1' 2' R3, R4, R5, m, x and n are as defined above Illustrative of the anions which are suitable for use in the present invention are halides such as chloride, bromide, and iodide;
triodide; tribromide; tetrafluoroborate; hydroxide; acetate; sulfate;
hydrogen - 3a -,, ~ ~! , -. :

~' ' '' , . ' ' ' ' ' , ~ ' ' , ' .

~066Z94 1 sulfate; methyl sulfate; benzene sulfonate; perchlorate;
Cl-C4 alkyl benzene sulfonate, preferably p-toluene sul-fonate; hydrogen phosphate; Cl-C4 alkane sulfonate;

O R 8 , , ,1 1 ~\
-0-C-C-R~ and -0-C-CH-O ~ ~ Cl, r`
Rlo where R7 and ~8 are halogen; Rg is halogen, methyl, halo-methyl or dihalomethyl, Rlo is chlorine or methyl; and Rll is hydrogen or methyl.
Preferred compounds of this invention have the above structure, wherein Rl and R2 are each methyl or ethyl; R3 and R5 are each phenyl; R4 is OCH3, ethoxy, OC H7-n, 2-propynyloxy~ OC4Hg-n, Cl3H27 -' C16 33 -O(CH2)2Br, OC~2CH=CHCl, O-CH2-C=CH2, CH2OC7H15~n, SC4Hg-_, or the moiety: Cl (`~2 ~ , .
where Y is hydrogen, 4-methyl, 3-chloro-4-chloro or 4-CF3;
m is l; and X is methyl sulfate, bromidej chloride, io-dide, perchlorate, phosphate, hydrogen phosphate, hydro-gen sulfate or _-toluene sulfonate.
Further, especially preferred compounds have the above structure, where Rl and R2 each represent methyl; R3 and R5 are each phenyl; R4 is methoxy, ethoxy, or 2-propynyloxy; m is l; and X is methyl sulfate, chlor-ide, perchlorate, bromide, iodide, hydrogen, sulfate or p-toluene sulfonate.
The invention is a modification of or an im-.. ; : , ,

3~06629~
1 provement in the invention forming the subject matter of our Canadian Patent 1020165 issued November 11, 1977.
This patent describes 1,2-dialkyl-3,5-diphenylpyra-zolium salts and their use as herbicidal agents, particularly as herbicidal agents effective for the selective control of wild oats (Avena spp. ) in the presence of certain small grains These salts are uniquely effective for selective control of wild oats, but exhibit only minimal herbicidal activity against other economically irnportant grass weeds such as barnyard grass, foxtail and crabgrass.
It has now been found that the substitution in the

4-position of the pyrazolium ring in place of hydrogen, parti-cularly by alkoxy, markedly alters the spectrum of postemer-gence herbicidal activity of the desired pyrazolium compounds.
15 Such alteration chanqes the biological activity of the latter compounds by providing them with a much broader spectrum of broadleaf weed and of grass control and the most noteworthy changes are seen in the pronounced improvement in Sesbania, mustard, pigweed, morningglory and barnyard grass control and ~ -20 the selectivity obtained when said compounds are used for ~ -grass control in the presence of rice.
In accordance with ~his invention compounds having the structure:

(I) ~ , x-m .. .
~7, .
".

~3662~4 Rl, R2~ R3, R4, R5, X and m are as described above, can be prepared by N-alkylation o~ a formula (II) pyrazole or O-alkylation of an alkali metal salt of a pyrazolium hydroxide (III). These reactions may be graphically illustrated as follows:
Method A

~S ~ ~ Alkylat1on~ ~ g ~

(II) (I) ; . :

Method B
. .
. . . , :

R~ Alkylation> j~g~R~

(III) m ~ .:

wherein Rl, R2, R3, R4, R5, m and X are as described . :~
~above.
In accordance with the procedure of Method A, a pyrazole such as depicted by formula II can be alkylat-25 ed in toluene, xylene or similar solvent, with one or ~:~
more equivalents of an alkylating agent such as dimethyl sulfate, methyl ioxide, methyl bromide or ~-methyl tolu-ene sulfonate. This reaction is generally carried out at a temperature between 70C. and 150C., and preerably, 30 at.a temperature.between.70C.-and-130C. .

. ' " .
- 6 - .

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1 An alternative method for the preparation of the formula (I) pyrazolium salts, wherein R4 is as here-inbefore defined is described above and identified as Method B. This preparative method involves the alkylation of an alkali metal salt of the formula (III) pyrazolium salt and is generally carried out in the presence of an aprotic solvent such as dimethylformamide (DMF), dimethyl-sulfoxide (DMS0), xylene, toluene, benzene, or the like, at a temperature between about 25C. and 100C. In prac-tice, the 4-hydroxy-1,2-dialkyl-3,5-disubstituted pyra-zolium salt is initially treated with an alkali metal hydroxide or Cl~C4 alkali metal alkoxide, preferably sodium or potassium hydroxide or sodium or potassium methoxide, in the presence of an aprotic solvent at an elevated temperature, e.g. 50C. to 80C.; then cooled and thereafter treated with an alkylating agent as des-cribed above.
As indicated above, the compounds of this in-vention are highly effective herbicidal agents. They are effective for the control of many broadleaf weeds and grass weeds and differ in biological activity from the 1,2-dialkyl-3,5-diphenylpyrazolium salts which are not substituted in the 4-position of the pyrazolium ring. They differ in their superior effectiveness for -control of broadleaf weeds such as Sesbania, mustardl pigweed and morningglory and of grass weeds such as barn-yard grass, crabgrass and foxtail, and are generally highly selective for the control of grass weeds in the presence of rice. Ho~ever, they are less effective than the pyrazolium compounds of the above-referred-to ~66;~94 1 Klingsberg et al. Netherlands Application as wild oat herbicidal agents.
In practice, it is found that the compounds of this invention are generally most effective when applied to the foliage of undesirable plants at rates between about 0.25 and 10 pounds per acre, calculated as the cat-ion.
Advantageously, many of the formula (I) pyra-zolium salts demonstrate a high degree of water solubil-ity and lend themselves to the preparation of aqueousconcentrates. Among the preferred salts in this regard are the methyl sulfates, hydrogen sulfates, sulfates, chlorides and bromides. In practice, the aqueous concen-trates may be applied directly as a liquid spray to the 15 foliage of undesirable plants or they may be further di- ~-luted with water and applied as dilute aqueous sprays to said undesirable plants.
Water-miscible concentrates are prepared by dis-solving from 15~ to 95~ of the compound in 85% to 5~ of a water-miscible solvent, such as water itself or another polar water-miscible solvent, such as 2-methoxyethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, formamide and dimethylformamide.
Application for the material is made by addin~ a prede-termined quantity of the water-miscible concentrate to a spray tank and applying the mixture as such or in combin-ation with a suitable diluent such as a further quantity of water or one of the above polar solvents. Generally, addition of a surfactant to the mixture is also desirable.
The surfactant is preferably a nonionic surfac-_ ~ _ . ,.. . :

: : . ' . ' ', , ,' ' ~', , ' ,: .
, , . , .. . : , z9~

1 tant such as an alkylphenol ethylene o~ide condensate, and is used at the level of about 0.17% to 5~ by volume.
Herbicidal concentrates containing su-factants can be formulated as aqueous sprays containing approxi~
mately 30~ by weight of the appropriate salt, from about 25~ to 50% by weight of water and the remainder of said formulation (20% to 45% by weight) of a selected surfac-tant.
Other formulations which may be prepared with the ~:
compounds of this invention include dusts, dust concen-trates and wettable powders.
Dusts are generally prepared by grinding to- .
gether about 1% to 25% by weight of the active agent with from about 99% to 75% by weight of a solid diluent such as kaolin, attapulgite, diatomaceous earth, or the like.
Dust concentrates are prepared in similar fashion except-ing that about 25% to 95% by weight of the active compound ~
is ground with about 75% to 5% by weight of the diluent. . .
Wettable powders are prepared in the same man-ner as the dust concentrates excepting that about 1~ to5% by weight of a dispersing agent such as sodium ligno-sulfonate, or the sodium salt of condensed naphthalene sulfonic acid is blended with the mixture and about 1%
to 5% of a surfactant is also blended with the formula-tion.
In practice, the wettable powder is dispersedin water and applied as a liquid spray to the foliage of undesirable plants. ~pplication rates should be suffic-ient to provide about 0.25 to 10 pounds per acre of the pyrazolium cation, although 0.5 to 5 pound~ per acre of -~066294 ~
1 said cation is generally satisfactory to control undesir-able broadleaf weeds and undesirable grass plants.

This invention is further illustrated by the examples set forth below.

Example 1 Preparation of 4-Methoxy-1,2-dimethyl-3,5-diphenylpyra-_ zolium perchlorate Method A
.__ - ' . .

10 ~

OC~3 ~ ~
C~3 N~

~ ~3 ClO~
OCH
,.......... .................................................................. ..... ... .....

4-Methoxy-l-methyl-3,5-diphenylpyrazole (2.5 g., 0.0095 mole) in molecular sieve-dried toluene (80 ml.) is heated to 50C. and dimethyl sulfate (2.5 g., 0.02 mole) is added. The mixture is stirred and heated under reflux for 6 hours, cooled and set aside overni~ht.
Water (100 ml.) is then added and this aqueous layer sep-arated and treated with 10~ aqueous perchloric acid.
After 30 minutes, 0.6 g. (16~) of a white powder is filt-ered off with a melting point of 135-136C.
AnalYSis calculation for C18HlgN2cl05 C, 57.05; H, 5.06; N, 7.40. Found: C, 56.96; H, 5.17;
N, 7.40.

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.

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.. . ..
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1 Example 2 Preparation of 4-Methoxy-1,2-dimethyl-3,5-diphenylpyra- -zolium perchlorate :
Method B

~ C10 ~ C1049 4-Hydroxy-1,2-dimethyl-3,5-diphenylpyrazolium perchlorate (7 g., 0.02 mole) in DMSO (2.5 ml.) is added to 5% sodi~n hydroxide (0.84 g., 0.02 mole) in DMSO (100 ml.), dropwise with stirring~ The mixture is warmed to 60C. for 5 minutes, then stirred at room temperature for 4 hours. The reaction mixture (75 ml.) is treated with methyl iodide (0.43 g., 0.013 mole) and the mixture is stirred at roorn temperature for 16 hours, then heated at 40C. for 2 hours. On pouring into water, a solid precipitates with melting point 88C. One crystallization from methanol gives the product with melting point 132--132.5C. in 53% yield.
Example 3 Preparation of 4-Methoxy-1,2-dimethyl-3,5-diphenylpyra-zolium methyl sulfate ~H3 h~r"i' ,r~
\ /
()CH3 \===J

: ` ;
\
~L0~i62~1 C113 -:

~;~g> C115S04(~) ~-Methoxy-l-methyl-3,5-diphenylpyrazole (20 g., 0.076 mole) is suspended in dimethyl sulfate (23 g.) at 20C. and the mixture is stirred and the reaction temp-erature raised to 130C. At 70C. the mixture becomes a homogeneous solution and at 130C. some darkening occurs.
After maintaining the reaction at 130C. for 1 hour, it is cooled and the mixture poured into toluene (250 ml.).
The toluene layer is decanted off and further toluene is added, decanted off, and this sequence repeated a third time. The residual oil, obtained from the above treat-ment, is then treated with acetone (10 ml.) which hasbeen dried over anhydrous potassium carbonate. This yields a crystalline product which is filtered off and washed with ether. The acetone filtrate is evaporated to give 27.5 g. of oil, dissolved in water, and extracted with chloroform. The chloroform layer is evaporated to a small volume and then ether added. A white precipitate is obtained; combined yield 22 g. (74%) of melting point 104.5-105~C. is obtained.
Example 4 r Compounds of the present invention are prepared in accordance with the procedure of Examples 1 or 2 above with appropriate substitution of reactants. Compounds prepared are listed in Table I below, with identification of process used, reagent, yield where determined and char-acterization of product obtained.
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Additional exemplary matter is presented here- ;
inbelow to illustrate and/or describe the preparation of the useful and nov~l pyrazoles, represented by the struc-ture:
(II) wherein Rl, R2, R3, R4 and R5 are as previously defined.
Example 5 General Method for Preparation of 4-Hydroxy-l-methyl-3,5--di(substituted-phenyl)pyrazoles _ _ The procedure of M. J. Nye and W. P. Tang, Can.
J. Chem. 51: 338 (1973), is followed. A mixture of 2--acetoxy-1,3-di(substituted-phenyl)-1,3-propanedione and methylhydrazine are allowed to react in _-propanol. Upon isolation of the product as described, the subject com-pounds are obtained. The compounds are listed in Table II below:

1~66~9~ :
- TABLE; II
. CH3 ,, Z'~ . ~
Z
.
. _ ._.A~
. Melting Z_Z'__ . Po nt 2-chloro .
..... - : ..... _.__ .
4-chloro H 179-181 :
.... , .... _ ~ . ..
3-chloro . 3 chloro 128-132 . 13-8.5 . . . ~ .. _ . .... . .. _ . , , 3-methyl H 131-135 . . . . ._ .
4-methyl H 168-170 . . ._ .. . _ . . . . .
. 3-methyl 3-methyl 143-145 ~ .. . ... . ~ . v . . _ . . ~ ~ .
4-methyl 4-methyl 182-184 .... _ . . ~ ... .... ___ 4--(n-dodecyl) H 96-106.
_ ~,. _ .... :. - .
. 4-(n-butoxy) H 152-170 . ~.
.... __ .. ..... _ 4-phen~l H 1~5-201 . ~ . .
... .... _ CU~ 15~173 .. __ _....... . ... _ . .
Cll~ a4-ss ¦

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. . . . .

~(~6~Z94 1 Example 6 Preparation of l-Benzyl-3~5-diphenyl-4-pyrazolol, ace-tate (ester) . . _ _ _ . _ _ _ .
Sodium acetate (5.13 g., 0.626 mole) is added 5 to a mixture of 2~hydroxy 1,3-diphenyl-1,3-propanedione, ~-acetate (8 g., 0.0283 mole), benzyl hydrazine dinydro-chloride (6.1 g., 0.0313 mole) and l-propanol (80 ml.).
The reaction mixture is stirred and heated slowly to 80C~
After heating for 2 hours, the mixture is poured into water. The solid formed, 11 g. (105%), is isolated by filtration and recrystalli~ed from methanol to give a white crystalline solid, melting point 103-103.5C.
Analyses calculated for C24H20N2O2 C, 78.24;
H, 5.47; N, 7.60. Found: C, 78.45; H, 5.66; N, 7.73.
Example 7 Preparation of l-~enzyl-3,5-diphenyl-4-pyrazolol A solution of sodium hydroxide (1.5 g., 0.0375 mole), methanol (30 ml.) and water (30 ml.) is added to l-benzyl-3,5-diphenyl-4-pyrazolol, acetate (6.9 g., 0.019 mole) and the mixture stirred and refluxed for one hour.
A white solid forms and is isolated by filtration, treat-ed with dilute hydrochloric acid, washed with water and dried to give a white solid, 6.36 g., melting point 194--195C.
Analyses calculated for C22HlgN2O C~ 80-95;
H, 5.56; N, 8.58. Found: C, 80.87; H, 5.67; 1~, 8.53.
Exam~le 8 General Metl~ods for Preparation of 4-Alkoxy-l-methyl-3,5--diphenylpyra-zoles and 3,5-di(substituted-phenyl)p~razoles Method A

.' ' ' . ' "' ' ' ::

2S~
1 A mixture of 1-methyl-3,5-diphenyl-4-pyrazolol (0.04 mole) (or the appropriate substituted-phenyl pyra-zole), benzyltriethylammonium chloride (1 g.), the approp-riate alkyl halide (0.08 mole) and aqueous sodium hydrox-ide (0.08 mole) in 46 ml. water) is stirred vigorously and heated at 60-70C. for 24 hours. The reaction is followed by glc.
The cooled reaction mixture is extracted with methylene chloride. The methylene chloride layer is sep-arated, washed with 10% aqueous sodium hydroxide solution,then washed well with water, dried (Drierite) and stripped ln vacuo.
Method B
A mixture of l-methyl-3,5-diphenyl-4-pyrazolol (0.06 mole~, sodium methoxide (0.06 mole) and methanol (200 ml.) is stirred and refluxed for 2 hours. The re-action mixture is then evaporated to dryness and azeo-tropically dried with toluene. The toluene is removed in vacuo and the residue dissolved in dry DMF (250 ml.).
The appropriate alkyl ester of _-toluenesulfonic acid (0.06 mole) is added, and the reaction mixture stirred overnight at room temperature. The reaction is followed by glc. The reaction mixture is heated at 50-75C. as required to complete the reaction.
The cooled reaction mixture is poured into water and extracted with ether. The ether layer is sep-arated, washed with 10~ aqueous sodium hydroxide solution, washed well with water and then stripped ln vacuo.
Method C
A mixture of l-methyl-3,5-diphenyl-4-pyrazolol . .

1q:1166~
1 (O.02 mole), DMF (50 ml.) and potassium t-butoxide or sodium methoxide (0.02 mole) is stirred and heated at 50C. for one hour. The appropriate aliphatic halide (0.04 mole) is added and the mixture heated at 55-60C.
for 2 to 3 hours.
The reaction mixture is poured into water and made alkaline with 1% aqueous sodium hydroxide solution.
Crude solid products are isolated by filtration. In the case of oils, the products are isolated by extraction with chloroform. The chloroform layer is separated, wash-ed with water and stripped in vacuo.
Compounds prepared by these methods are listed in Tables III and IV.

.. ..
.. ~ . . , , , .. . . .

~ 66294 1 TAELE Ill ~ .
4 ;:~
. Melting ._ ~. .
R Point Recrystallizing 4 C _ Method _ Solvent _ CH3 8B^89 (CH3O)2~2 . _ NaOII
(CH3)2~H- 114-llg A Hexane . . . . :.-- ~ . ,, ' ', (~H3)2CH~Hz- 60-61 A Hexane . .. __ . .. . ___ C2}l5cH~cH3)- 93-94 AMethanol .__ ... ------ ~ ., . CH3 (C~12) 4 - 68 : : A Hexane ., .. . _ ..
CH3(CH2)5- oil A Chromatogr~phed .
. on silica gel . . . : with benzene~
followed by recrys~allization . from hexane . . .__ _ _ CH3(CH2)6- oil A Chromatographcd, silica gcl, . _ toluenc .C~13(C112)7- oil AChrom3to~ra~hcd, silica gel, toluene . _ _ _ ~.. .
(C~(CI-12)9- oil B Chrom~tographcd, . Si ~. iC;? g~l, ' .tolucnc .__ _ ... ._ . .. _ .

.

.

.:

11066;~4 TABLE~ III (continued) N\
\:==/ ~ ' o 1~4 Melting R I'o:int Recrystalli~ing 4 C Method Solvent . oil B Silica gel, _ CH3(CH2)15- oil B Silica gel, toluene C}l3~CH2)17- waxy B Silica gel, o~,l toluene .
_ ~
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1 Example 9 General Method for Preparation of 4-Benzyloxy-l-methyl--3,5-diphenylpyrazoles ~ mixture of 4-hydroxy-1-methyl-3,5-diphenyl- ~
5 -pyrazole (0.04 mole), sodium methoxide (0.045 mole) and ~ -dry DMF (100 ml.) is stirred and heated to 60C. The reaction mixture is cooled to room temperature and the substituted-benzyl halide (chloride or bromide) (0.05 mole) added dropwise. If the substituted-benzyl halide is a solid, a solùtion is prepared using dry DMF (50 ml.).
Stirring is continued and the reaction mixture heated at 55-60C. until the reaction is complete. The reaction is followed by tlc (CHC13/silica gel). The mixture is then cooled and poured into an excess of water. The aqueous mixture is made alkaline by the addition of li~
sodium hydroxide and extracted with ether. The ether layer is separated, washed well with water, dried and -stripped in ~a_uo.
The compounds prepared by this method are list-ed in Table V.
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1 Example_10 Preparation of 3-(p-Chlorophenyl)-4-methoxy-1-methyl-5--phenyl [and 5-(~-Chlorophenyl)-4-methoxy-1-methyl-3--phenyl]-~yrazole A mixture of 3-(_-chlorophenyl)-1-methyl-5- --phenyl [and 5-(p-chlorophenyl)-1-methyl-3-phenyl]-4-py-razolol (7.9 ~., 0.0278 mole) and 20~ aqueous sodium hy-droxide solution (200 ml.) is stirred and heated to 60C.
Dimethyl sulfate (20.7 ml., 0.222 mole) is added to the -turbid yellow solution. An exotherm is observed and the temperature of the reaction mixture rose to 80C. Stirr-ing is continued and the mixture is allowed to cool to room temperature. A buff-colored gum is formed. The aqueous layer is decanted away from the gum and the gum washed well with water until neutral. The yellow gum, 5.5 g., is dissolved in ether and filtered through a bed of neutral alumina. The filtrate is stripped ln vacuo to give a clear yellow oil, which upon standing became a solid. The crude product is slurried with pentane. The product is isolated by filtration and obtained as a white crystalline solid, 2 g. (24~), melting point 100-103C.
Analyses calculated for C17Hl5N2ocl C, 68.33;
H, 5.06; N, 9.38; Cl, 11.86. Found: C, 68.18; H, 4.89;
N, 9.39; Cl, 12.10.
Example 11 General Method for the Preparation of l-Substituted-4--benzyloxy-3,5-diphenYl~Yrazoles . _ _ . _ _ . _ ~7....

A mixture of 4-benzyloxy-3,5-diphenylpyrazole (0.0278 mole), potassium t-butoxide (0.0306 mole) and 2-propanol (90 ml.) i~ stirred well at room temperature until a clear solution forms. The appropriate alkyl (or 11066;~:99~ ~
1 arylalkyl) halide ~0.0337 mole~ is added dropwise. The reaction mixture is stirred for one to two days at room temperature and then is heated at 50C. for 2 to 4 hours.
The mixture is poured into water and extracted with chloroform or toluene. The chloroform or toluene layer is separated, washed well with water, dried and stripped ln ~
vacuo to give an oil or a solid. ;
The compounds prepared by this method are list-ed in Table VI. ~ ~
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- ~)66Z94 1 Example 12 Preparation of 4-(n-Propoxy)-3,5-diphenylpyrazole A mixture of 3,5-diphenyl-4-pyrazolol (10 g., 0.042 mole), sodium methoxide (2.27 g., 0.042 mole) and methanol (60 ml.) is heated at 60C. for 2 hours. Then l-bromopropane (5.17 g., 0.042 mole) is added slowly (5 -minutes) at 60C. The reaction mixture is then held at 60C. until the reaction is complete by tlc. The mixture is poured into water and the solid forrned is isolated by filtration. Recrystallization of the solid from acetoni-trile affords white crystals, 7.4 g. (63%), melting point 142-1~2.5C.
Analyses calculated for C18H18N2O: C, 77.67;
H, 6.52; N, 10.07. Found: C, 77.46; H, 6.60; N, 9.97. ;;
Example 13 Preparation of 4-(Benzyloxy)-3,5-diphenylp~razole A mixture of 3,5-diphenyl-4-pyrazolol (10 g., 0.042 mole), sodium methoxide (2.27 g., 0.042 mole) and -~
methanol (60 ml.) is heated at 60C. for 2 hours. Then benzyl chloride is added slowly at 60C. A white solid forms. Heating is continued overnight at 60C. The reaction mixture is examined by glc and tile reaction is found to be complete. The mixture is poured into water and the solid isolated by filtration. The solid is wash-ed well with water, dried and recrystallized from aceto-nitrile to give pale yellow crystals, melting point 152--152.5C.
Analyses calculated for C22H18N2O: C, H, 5.56; N, 8.58. Found: C, 80.77; H, 5.71; N, 8.69.
Example 14 ~L~6629~
1 Preparation of l-Methyl-3,5-diphenyl-4-n-propoxypyrazole .. . . . . .
Sodium hydride (57~, 0.92 g., 0.022 mole) is added slowly to a suspension of l-methyl-3,5-diphenyl-4--pyrazolol (5 g., 0.02 mole) in anhydrous ether (100 ml.).
An off-white precipitate forms. After stirring for 45 minutes, the solid is removed by filtration, added to dry DMF (30 ml.) and treated with l-iodopropane (5 ml., O.05 mole). The reaction mixture is stirred, heated at 60C.
for 14 hours and then poured into ice water (600 ml.).
After standing ~or 24 hours in the refrigerator, a tacky yellow solid is formed. Recrystallization from hexane ~
at -20C. affords an off-white solid, melting point ~-56-57C.
Analyses calculated for ClgH20N2O C, 78.05;
H, 6.90; N, 9.58. Found: C, 78.04; H, 6.90; N, 9.49.
Example 15 Preparation of 4-n-Butoxy-l-methyl-3,5-diphenylpyrazole .~
A mixture of l-methyl-3,5-diphenyl-4-pyrazolol (25 g., 0.1 mole), sodium hydroxide (56 g., 1.4 mole) and water (800 ml.) is stirred until all the sodium hy-droxide dissolved. The reaction mixture was heated, filtered and the filtrate stirred vigorously, and l--iodo-butane (22.8 ml., 0.2 mole) added dropwise. The reaction mixture is refluxed for 22 hours. Acetonitrile (700 ml.) is added to the reaction mixture to give a homogeneous solution and more l-iodobutane (10 ml., 0.09 mole) added.
After refluxing for 3 hours, the reaction mixture is cooled, extracted with ether and the ether layer separ-ated. The ether layer is washed well with water, dried and stripped ln vacuo to give a viscous orange oil, 24.35 ':

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The oil is dissolved in hexane (35 ml.), filt-ered through neutral alumina and the filtrate stored over-night at 0C. Pale yellow crystals formed and are iso-lated by filtration and dried to give a solid, 7.0 g.

(23~), melting point 48-49.5C.

Analyses calculated for C20H22N2O C, 78.40;

H, 7.24; N, 9.14. Found: C, 78.61; H, 7.53; N, 9.25.

Example 16 Preparation of 4-[(Heptyloxy)methoxy]-l-methyl-3,5-di-phenylpyrazole .. . . ~
Anhydrous hydrochloric acid gas is bubbled through a well stirred solution of l-heptanol (5.8 g., 0.05 mole), para-formaldehyde (l.S g., 0.05 mole) and methylene chloride (100 ml. ) at -20C. An exotherm is observed.
The temperature is maintained at ~20C. to -10C. during the addition. When the exotherm subsides, the addition of gas is discontinued and the reaction mix-ture allowed to warm up to 5-10C. The reaction mixture is washed with chilled water (100 ml.) and the organic layer separated. The organic layer is filtered through calcium chloride and added to a solution of the sodium salt of l-methyl-3,S-diphenyl-4-pyrazolol in DMF. The 4-pyrazolol solution is prepared by stirring l-methyl--3,5-diphenyl-4-pyrazolol (lO g., 0~04 mole) with sodium methoxide (2.16 g., O.04 mole) and dry DMF (lOO ml.).
The combined reaction mixture is stirred for 1 1/2 hours and then poured into water (S00 ml.). The mixture is stirred for 15 minutes and then allowed to ~066;~9~
1 settle. The upper aqueous layer is decanted and the low-er organic layer diluted with methylene chloride. The methylene chloride solution is washed with 10% aqueous sodium hydroxide (200 ml.) and then with water (100 ml.).
The organic layer is separated and stripped in vacuo.
The oil residue is slurried with water (100 ml.) and ex-tracted with hexane. The hexane layer is separated and stripped ln vacuo to give an oil, 11 g. (75%).;
AnalySeS calculated for c24H20N2O2: C~ 76-15;
H, 7.99; N, 7.40. Found: C, 75.21; H, 8.02; N, 6.99.
Example 17 ~ -Preparation of 4-tert-Butoxy-l-methyl-3,5-diphenylpyra-zola 4-Bromo-l-methyl-3,5-diphenylpyrazole (31.3 g., 0.1 mole) and dry tetrahydrofuran (250 ml.) are stirred under a nitrogen atmosphere and cooled to -30C. to -40C.
A solution of _-butyllithium (50 ml., 2.4 moles) is add-ed and the deep red solution formed is stirred ~or 1/2 hour and allowed to warm to -20C. The reaction mixture is cooled to -60C., and a solution of tert-butylperoxy-benzoate (19.4 g., 0.1 mole) and dry tetrahydrofuran (50 ml.) added dropwise over a 1/2 hour period. During the addition, the reaction mixture became dark and then lighk-er in color. The mixture is stirred for 1/2 hour at -60C.
and a solid is formed. The mixture is poured into 10~
aqueous hydrochloric acid (400 ml.) and the mixture stir-red for 10 minutes. The upper organic layer is separated, washed consecutively with 10% aqueous hydrochloric acid (100 ml.), with water, with 4% aqueous sodium hydroxide solution (2 x 200 ml.) and finally with water. The or-~0662g4 1 ganic layer is separated and treated with hexane (200 ml.).
A solid forms, and is removed by filtration.
Stripping of th~ mother liquor in vacuo affords an oil. The oil is chromatographed on silica gel with toluene. A major component is isolated and recrystalliz-ed from hexane to give 4-tert-butoxy-1-methyl-3,5-diphenyl-pyrazole, 1.0 g. (3.4%), melting point 106-107.5C.
Analyses calculated for C20H22N2O: C, 78.40;
H, 7.34; N, 9.14. Found: C, 78.37; H, 7.22; N, 9.10.
Example 18 Pxeparation of 4-(2-Iodoethoxy)-l-methyl-3,5-diphenylpyra-zole A mixture of 4~-(2-bromoethoxy)-1-methyl-3,5--diphenylpyrazole (3.57 g., 0.01 mole), potassium iodide 15 (16.6 g., 0.1 mole) and acetone (50 ml.) is stirred and refluxed for 24 hours.
The reaction mixture is cooled, filtered and evaporated in vacuo to dryness and the residue dissolved ~ -in chloroform. After washing with water, the chloroform layer is separated and evaporated _ vacuo to dryness.
The solid residue is slurried with hexane, removed by filtration and then dried. Recrystallization from a mix-ture of benzene and hexane yields a solid melting point 68-69C.
Analyses calculated for C18H17N2OI: C, 58.48;
H, 4.24; N, 6.93; I, 31.39. Found: C, 54.32; H, 4.51;
N, 6.81; I, 30.54.
Example 19 Preparation of 3,5-Diphenyl-l-methyl-4-[2-(methylthio)-ethoxv]~vrazole , ' ' ~6~;~9~

1 An aqueous solution of sodium methylmercaptide is prepared by saturating a solution of sodium hydroxide (1.2 g., 0.03 mole) in water (35 ml.) with methyl mer-captan. The sodium methylmercaptide solution is added dropwise to a well stirred solution of 4-(2-bromoethoxy)--l-methyl-3,5-diphenylpyrazole (7.14 g., 0.02 mole), benzyltriethylammonium chloride (1 g.) and DMF (100 ml.).
During the addition an exotherm is obs~rved and the tem-perature rose to 37C. The reaction mixture is stirred overnight at room temperature and then poured into ice water (450 ml.). The mixture i5 stirred for one hour and then extracted with chloroform. The chloroform layer is separated and stripped in vacuo to give an oil. The oil is slurried with water (100 ml.) and extracted with tolu-ene. The toluene layer is separated and stripped invacuo to give an oil, 5.4 g. (83%).
Analyses calculated for ClgH20N2OS: C, 70.35;
H, 6.22; N, 8.64; S, 9.87. Found: C, 70.38; H, 6.22;
N, 8.74; S, 9.86.
~ le 20 Preparation o~ 4-[2-(Benzylthio)ethoxy]-3,5-diphenyl-1--methylpyrazole The product is prepared in a similar manner to the previous compound using benzyl mercaptan instead of methyl mercaptan. The oil obtained from the chloroform layer is purified by eluting on silica gel with toluene.
The product is obtained as an oil, 6.3 g. (78.8%).
AnalySeS calculated for C2sH24N2S C~ 74-98;
H, 6.04; N, 7.00; S, 7.99. Found: C, 74.87; H, 6.11;

30 N, 6.88; S, 7.96. -: . .

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10662~4 1 Example 21 Preparation of 4-[2-(Heptyloxy)ethoxy]-l-methyl-3,5-di-phenYl~yrazole ,, ~
Sodium hydride (0.89 g., 57%, 0.02 mole), is added to a solution of 2-[(1-methyl-3,5-diphenyl-4-pyra-zolyl)oxy]-ethanol (5.9 g., 0.02 mole) and dry DMF (50 ml.). The reaction mixture is stirred and heated to 80--90C. The stirred mixture is allowed to cool. This mixture is added to a solution of l-bromoheptane (9 g., 0.05 mole) and dry FMD (75 ml.). After heating at 80--90C. for 4 hours, the stirred reaction mixture is pur-ed into water.
The aqueous mixture is stirred for 15 minutes and then extracted with chloroform. The chloroform layer is separated, washed with water, filtered tnrough sodium chloride, and evaporated to dryness in a hood. The resi-due is slurried with hexane (400 ml.). A solid forms and is removed by filtra~ion. The filtrate is evaporated to drynessO The rasidue is dissolved in a mixture of chloroform and toluene (1:1) and chromatographed on silica gel. The product is obtained as an oil, 2.5 g., (31.9~).
AnalySeS calculated for C25H32N2O2- C~ 7 H, 8.22; N, 7.14. Found: C, 76.35; H, 8.35; N, 6.99.
Example 22 5 Preparation of 4-[2-(benzylsulfonyl)ethoxy~-3,5-diphenyl--l-methYl~vrazole .. _ ----- ~
A solution of 2 chloroperbenzoic acid (6.09 g., 85%, 0.03 mole) and dry chloroform (75 ml.) is 'added dropwise at 10-15C. to a well-stirred solution of 3,5--diphenyl-4-[2-(benzylthio)ethoxy]-1-methylpyrazole (4.1 . , . ,, , .. . , ,, , '.

3 1)66Z~4 1 g., 0.0102 mole) and dry chloro~orm (100 ml.). After complete addition, the reaction mixture is stirred over-night at room temperature.
The mixture i5 poured into 5~ aqueous sodium hydroxide solution (200 ml.) and stirred for 1 hour. The chloroform layer is separated, washed with water and stripped to dryness ln vacuo. The residue is dissolved in toluene and eluted on silica gel. The purified product is obtained as a solid and is recrystallized from a mix-ture of benzene and hexane (3:7) to give 1.5 g. (34%),m.p. 101C. to 102C., Ag IR 44,369.
AnalySiS calculated for C25H24N2So3 ~ ;
H, 5.59; N, 6.~8; S, 7.40. Found: C, 70.41; H, 5.95;
N, 6.06; S, 7.08.
~Example 23 Preparation of l-Methyl-4-(~-nitrophenoxy)-3,5-diphenyl-_ pyrazole A solution of 4-hydroxy-1-methyl-3,5-diphenyl-pyrazole (10 g., 0.04 mole), potassium t-butoxide (4.5, 0.04 mole) and dry DMF (150 ml.) is stirred and heated to 60C. The green fluorescent solution is cooled to room temperature and ~-chloronitrobenzene (6.0 g., 0.038 mole? is added. The dark green solution is heated at 60C. ~or 24 hours and then poured into waterj made alk-alkine with lN sodium hydroxide and extracted with ether.The ether layer is separated, washed well with water, dried and stripped in vacuo to give a bright yellow solid 12.9 g. (86.5~), m.p. 85C. to 110C. The solid is chrom-atographed on silica gel with benzene to give a yellow crystalline solid 11.3 g., m.p. 74C. to 100C. Recrys-.~ .

- 62 _ .

-~662g~

1 tallization from methanol (185 ml.) affords white crys-tals 5.5 g. (37%) m.p. 120C. to 122C.

Analysis calculated for C22H17N3O3: C, 71.15;

H, 4.61; N, 11.32. Found: C, 70.55; H, 4.65; N, 11.20.

A second crop 2.35 g. (15.8%), m.p. 119C. to 120C. is obtained by chilling the mother liquor.

Example 24 Preparation of 4-(~-Aminophenoxy)-l-methyl-3,5-diphenyl-pyrazole .. . .. .. . . ..
Hydrazine hydrate (3 ml., 60% solution) is added to a well-stirred mixture of l-methyl-4~ nitro phenoxy)~3,5-diphenylpyrazole (2.56 g., 0.0069 mole), 5%
Pd on carbon (0.4 g.) and absolute ethanol (40 ml.). Gas bubbles form immediately and an exotherm (ca. 50C.) is observed. After the reaction subsides, the reaction mix-ture is refluxed for 2 hours. The reaction mixture is cooled slightly and ~iltered to remove the catalyst. The filtrate is stripped in vacuo to give a white solid 2.4 g.
(100%), m.p. 167C. to 169C. Recrystallization from ben-zene (20 ml.) affords a white solid m.p. 167C. to 168C.
Analysis calculated for C22HlgN3O: C, 77.39;
H, 5.61; N, 12.31. Found: C, 7~.39; H, 5.85; N, 11.99.

Example 25 Preparation of 4-(~-Chlorophenoxy)-l-methyl-3,5-diphenyl-PYrazole A solution of sodium nitrite (3.1 g. t 0. 0442 -mole) in water (10 ml.) is added slowly at 0C. to 5C.
to a well-stirred, chilled solution of 4-(p-aminophenoxy)--l-methyl-3,5-diphenylpyrazole (15.1 g., 0.0442 mole) in concentrated hydrochloric acid (50 ml.).

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1~66Z94 1 This cold reaction mixture is added at 0C. to 5C. to a well-stirred, chilled solution of cuprous chlor-ide (4.85 g., 0. oas mole) in concentrated hydrochloric acid (50 ml.). The reaction mixture is held at 0C. for a half hour, then allowed to warm up to room temperature and finally heated on a steam bath for a half hour. The reaction mixture is cooled and the solid isolated by fil-tration.
The tan solid 16.1 g. is chromatographed on silica gel with chloroform to give a white solid 9.7 g.
(54.9%), m.p. 99C. to 102C. -~
Analysis calculated for C22H17ClN20 C, 73.22;
H, 4.75; N, 7.77; Cl, 9.83. Found: C, 72.98; H, 4.61;
N, 7.67; Cl, 9.78.
Exam le 26 Preparation of 4-(n-Butylthio)-1-methyl-3,5-diphenylpyra-zole A mixture of 4-bromo-1-methyl-3,5-dlphenylpyra- ;;
zole (21 g., 0.0671 mole), copper(l)salt of butanethiol (12.58 g., 0.08 mole), pyridine (10 ml.) and quinoline (100 ml.) is stirred and heated at 175C~ to 180C. for 8 hours. The reaction mixture is cooled, poured into di-lute hydrochloric acid (500 ml.) and extracted with ben- ~ -zene. The benzene layer is separated and stripped ln vacuo to give a brown oil. The oil is slurried with~pet-r~leum ether (b.p. 40C. to 60C.), filtered and the fil-trate stripped in vacuo to give a brown syrup 21 g., (97%), ~95% pure by glc.
Analysis calculated for C20H22N2S C, H, 6.88; N, 8.69. Found: C. 73.91; H, 6.75; N, 8.74.

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1~)66Z94 1 Example 27 Preparation of l-Methyl-3,5-diphenyl-4-(phenylthiol)py-razole A mixture of 4-bromo-1-methyl-3,5-diphenylpyra-zole (21.84 g., 0.07 mole), copper(l)salt of benzenethiol (14.67 g., 0.085 mole), pyridine (10 ml.) and quinoline (100 ml.) is stirred and heated at 175C. to 185C. (re-flux) for 8 hours. The reaction mixture is allowed to stand overnight at room temperature. The mixture is poured into dilute hydrochloride acid and extracted with benzene. The benzen~ layer is separated and stripped ln vacuo to give a brown syrup. The syrup is extracted with a hot mixture of n-hexane and n-heptane and filtered.
The cooled filtrate yields a gray colored solid m.p.
109C. Recrystallization from n-hexane affords white .
crystals 17.35 g. (72.4~), m.p. 109C. to 110C.

Analysis calculated for C22HlsN2S: C, 77.17;

H, 5.30; N, 8.18; S, 9.35. Found: C, 77.05, I~, 5.16;

N, 8.20; S, 9.43.

Example 28 :
Preparation of 4-(_-Butylsulfonyl)-l-methyl-3,5-diphenyl-pyrazole A solution of m-chloroperbenzoic acid (10.15 g., 85%, 0.05 mole) in dry chloroform (100 ml.) is added ;
25 to 4-(n-butylthio)-1-methyl-3~5-diphenylpyrazole (6.5 g., 0.02 mole) in dry chloroform t50 ml.) and the reaction mixture stirred overnight at 10C. to 12C. The mixture -is poured into 10% aqueous sodium hydroxide (200 ml.) and extracted with chloroform. The chloroform layer is 30 separated, dried and stripped in vacuo to give a light- ~ ;
'.,. '~' - . . ~ -, . : . ,: . ' ' : : :

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~QG62~4 1 -orange oilO The oil is chromatographed on silica gel with benzene. The fractions containlng the product are combined, stripped ln vacuo, extracted with methanol~
filtered, stripped in vacuo and then recrystallized from hexane to give a white fluffy solid 4.37 g. (61%), m.p.
92.5C. to 93C.
Analysis calculated for C20H22N2SO2: C, 67.78;
H, 6.26; N, 7.91; S, 9.04. Found: C, 68.01; H, 6.30;
N, 7.98, S, 9.14O
Example 29 Preparation of l-Methyl-3/5-diphenyl-4-(phenylsulfonyl)-~vrazole . . -At a temperature of 9C. a solution of m-chloro-perbenzoic acid ~10.15 g., 85%, 0.05 mole) in dry chloro-form (50 ml.) is added to a solution of 4-(phenylthio)-1--methyl-3,5-diphenylpyrazole (6.84 g., 0.02 mole) in dry chloroform (50 ml.). The reaction mixture is stirred for 3 hours at 9C. and then overnight at room temperature.
A heavy precipitate orms. The mixture is treated Witil 2% aqueous sodium hydroxide and extracted with chloroform.
The chloroform layer is separated and stripped in vacuo to give an oil. Trituration of the oil with cyclohexane affords crystals 6.8 g. (91%), m.p. 135C. to 141C. Re-crystallization from a mixture of benzene and pentane gave white crystals, m.p. 149C. to 150C.
Analysis calculated for C22H18N2SO2: C, 70-58;
H, 4.85; N, 7.48; S, 8.55. Found: C, 70.86 H, 5012;
N, 7.23; S, 8.39.
Example 30 The postemergence herbicidal activity of the .. . ... . . .
.
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~6294 1 compounds of the present invention is demonstrated by the following tests, wherein a variety of monocotyledonous and dicotyledonous plants are treated with test compounds dispersed in aqueous acetone mixtures. In the tests, seedling plants are grown in jiffy flats for about two weeks. The test compounds are dispersed in 50/50 acetone/-water mixtures containing 0.5~ Tween~ 200 a polyoxyethyl-ene sorbitan monolaurate surfactant by Atlas Chemical Industries, in sufficient quantity to provide the equiv-alent of about 0.5 lb. 10 lbs. per acre of active com-pound when applied to the plants through a spray noæzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices. Two weeks after treat-ment, the seedling plants are examined and rated accord-ing to the rating system provided below. The data ob-tained are reported in Table VII, where it can be seen that the compounds are effective for the control of a var-iety of broadleaf weeds and grass weeds and with selectedaompounds effective for controlling barnyardgrass. The specificity of certain aompounds is demonstrated by the ~-findings that wheat, barley or rice are not injured or only very mildly affected by selected compounds at rates ;
which provide effective control of the broadleaf weeds and grasses, particularly barnyardgrass.

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~ Difference in Growth Rating Systcm: from the Chcck*
0 - No efect O
1 -,Possible effect 1-10 2 - Slight effect 11-25 3 - Moderate effect 26-4Q
5 - Definite injury 41-60

6 - Herbicidal effect ' 61-75

7 - Good herbicidal effect 76-90

8 - Approaching complete kill 91-99

9 - Complete kill 100.
.

10 4 - Abnormal growth; that is, a definite physiological malformation but with an over-all effect less than 5 on the rating'scalè.
-- ..
,*Based on visual determination of stand, size, vigor, ' '' chlorosis, growth malformation and over-all plant appearance.
.
Plant~Abbrev _tions: . .
S~ - Sesbania (Sesbania exaltata) - ~'' -' LA - Lambsquarters (Chenopodium album) . ' MU - Mustard (Brassica kaber?
PI - Pigweed (Amaranthus retroflexus) BA - Barnyardgrass (Echinochloa crusgalli CR - Crabgrass (Digitaria sanguinalis) ,:
GRF - Green foxtail (Setaria viridis) WO - Wild oats (Avena fatua) VL - ~elvetleaf (Abutilon theophrasti) TW - Teaweed (Sida spinosa) RAG - Ragweed (Ambrosia artem iifolia) WH - Wheat (Triticum vulgare) MG - Morningglory (Ipomoca purpurea) BR - Barlcy t}lordcum vul~,are) RI - Rice (Oryza sativa) ', ;,' ~L~66Z94 ~ ~oo ~oo ~oo ooo ooo '.
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Claims (27)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the formula:
wherein R1 is alkyl C1-C5, allyl or benzyl; R2 is alkyl C1-C5; R3 is and naphthyl; R5 is ; R4 is alkoxy C1-C22, alkenyloxy C3-C4, halogen substituted alkenyloxy C3-C4, alkynyloxy C3-C4, -O-(CH2)n-W, alkyl-thio C1-C22, alkylsulfonyl C1-C22, , , , , and R6 is hydrogen, methyl or phenyl; U and V each are hydrogen, halogen, alkyl C1-C4, alkoxy C1-C4, NO2 or CF3; W is halogen, cyano, carbalkoxy C1-C7, alkoxy C1-C7, alkylthio C1-C7, alkyl-sulfonyl C1-C7, benzylthio or benzylsulfonyl; Z and Z' each are hydrogen, halogen, alkyl C1-C12, alkoxy C1-C4 or phenyl;
X is an anion which is not phytotoxic and selected from the group consisting of halides such as chloride, bromide, and iodide; triodide; tribromide; tetrafluoroborate; hydroxide;

acetate; sulfate; hydrogen sulfate; methyl sulfate; benzene sulfonate; perchlorate; C1-C4 alkyl benzene sulfonate, pre -ferably p-toluene sulfonate; hydrogen phosphate; C1-C4 alkane sulfonate;
and where R7 and R8 are halogen; R9 is halogen, methyl, halo-methyl or dihalomethyl; R10 is chlorine or methyl; and R11 is hydrogen or methyl, m is 1, 2 or 3; and n is 1, 2, 3, or 4.

A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-methoxypyrazolium perchlorate .

3. A compound according to Claim 1, 1,2 dimethyl--3,5-diphenyl-4-methoxypyrazolium bromide.

4. A compound according to Claim l, 1,2-dimethyl--3,5-diphenyl-4-methoxypyrazolium iodide.

5. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-methoxypyrazolium methyl sulfate.

6. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-ethoxypyrazolium methyl sulfate.

7. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-propoxypyrazolium methyl sulfate.

8. A compound according to Claim 1, 4- allyloxy -1, 2-dimethyl-3,5-diphanylpyrazolium perchlorate.

9. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-(2-propynyloxy) pyrazolium sulfate.

10. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-(2-propynyloxy) pyrazolium methyl sulfate.

11. A compound according to Claim 1, 4-butoxy -1,2--dimethyl-3,5-diphenylpyrazolium methyl sulfate.

12. A compound according to Claim 1, 4-n-butoxy--1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate.

13. A compound according to Claim 1, 4-sec-butoxy--1,2-dimethyl-3,5-diphenylpyrazolium perchlorate.

14. A compound according to Claim 1, 4-sec-butoxy--1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate.

15. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-pentyloxypyrazolium perchlorate.

16. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-pentyloxypyrazolium methyl sulfate?1/2H2O.

17. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-hexyloxypyrazolium methyl sulfate.

18. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-tridecyloxypyrazolium methyl sulfate.

19. A compound according to Claim 1, 1,2-dimethyl--3,5-diphenyl-4-n-hexadecyloxypyrazolium methyl sulfate.

20. A compound according to Claim 1, 4-[(3-chloro-allyl)oxyl]-1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate.

21. A compound according to Claim 1, 4-[(2-chloro-allyl)oxyl]-1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate.

22. A compound according to Claim 1, 4-benzyloxy-1,2--dimethyl-3,5-diphenylpyrazolium methyl sulfate.

23. A method for the control of undesirable broad-leaf weeds and grass weeds comprising contacting said weeds with a herbicidally effective amount of a compound having the formula of Claim 1:
wherein R1, R2, R3, R4, R5, m, X and n are as defined above.

24. A method according to Claim 23, wherein the compound is applied to the foliage of undesirable plants at the rate of from 0.5 pound to 10 pounds per acre of pyrazolium cation.

25. A method for the control of undesirable broad-leaf weeds and grass weeds comprising applying to the foliage thereof a herbicidally effective amount of a compound accord-ing to Claim 1.

26. A method according to Claim 23, wherein the compound is 1,2-dimethyl-3,5-diphenyl-4-methoxypyrazolium perchlorate.

27. A method according to Claim 23, wherein the compound is 1,2-dimethyl-3,5-diphenyl-4-methoxypyrazolium perchlorate.