CA1067907A - Herbicidal 1,4-diphenyl-3-pyrazolin-5-ones - Google Patents

Herbicidal 1,4-diphenyl-3-pyrazolin-5-ones

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Publication number
CA1067907A
CA1067907A CA264,490A CA264490A CA1067907A CA 1067907 A CA1067907 A CA 1067907A CA 264490 A CA264490 A CA 264490A CA 1067907 A CA1067907 A CA 1067907A
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Prior art keywords
alpha
pyrazolin
tolyl
trifluoro
compound
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CA264,490A
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French (fr)
Inventor
Robert P. Gajewski
James R. Beck
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Eli Lilly and Co
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Eli Lilly and Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18One oxygen or sulfur atom
    • C07D231/20One oxygen atom attached in positions 3 or 5
    • C07D231/22One oxygen atom attached in positions 3 or 5 with aryl radicals attached to ring nitrogen atoms

Abstract

Abstract of the Disclosure Novel 1,4-diphenyl-3-pyrazolin-5-ones which have small alkyl substituents at the 2-position and may have the phenyl rings substituted are described herein. The novel compounds are prepared by alkylating the corresponding 2-unsubstituted pyrazolinones. The compounds are useful as herbicides.

Description

1~)6'79~

HERBICIDAL 1,4-DIPHENYL-3-PYRAZOLIN-5-ONES
This invention belongs to the field of agricul-tural chemistry, and provides new herbicidal compounds to the art. The growth of weeds, which are often defined as plants growing where they are not wanted, has well-known deleterious effects on crops which are infested with such plants. Vnwanted plants growing in cropland, as well as in ~allow land, consume soil nutrients and water, and compete with crop plants for sunlight. Thus, weed plants constitute a drain on the soil and cause measurable losses in the yield of crops.
The compounds of formula I below are new to organic chemistry. Some compounds which have a relationship to the present invention, however, are known in the herbicidal art.
Earlier workers have found herbicides among the pyridazinones, for example, U.S. Patent 3,644,355. Some pyrimidinone herbicides have also been disclosed in the agricultural chemical art, such as the 6-alkyl-2,5~dihalo-3-phenyl-4-pyrimidinones of U.S. Patent 3,823,135.
Some diphenyl-5-pyrazolinones have been disclosed, for example, the 3-methyl-1,4-diphenyl compound of Beckh, Ber. 31, 3164 (1898) and the 2-~lethyl-1,3-diphenyl compound o Knorr et al., Ber. 20, 2549 (1887). A pharmaceutical pyrazolinone is 2,3-dimethyl-1-phenyl--3-pyrazolin-5-one, called antipyrlne, which was formerly used as an analgesic.
Merck Index,~93 (8th ed. 1968).
This invention provides to the agricultural -.:
~chemical art~new compounds of the general formula ~ ;
.: .
~ X-4223A -2-i:: . :
~ .

wherein R is Cl-C3 alkyl;
Rl and R2 independently are hydrogen, chloro, fluoro, bromo, methyl or trifluoromethyl, provided that Rl and R2 do not simultaneously represent hydrogen; and provided that Rl may not be bromo or chloro in the 4-posi-tion.
The compounds of formula (I) are prepared by reacting a compound of the general formula R~ 1l 1 ' \ c =~ H \ ~ (II;

wherein Rl and R2 are defined as before, with an alkylating agent in the presence of a base. ;~
Suitable alkylating agents and bases are alkyl halides, such as an alkyl iodide in the presence of a strong inorganic base, or a dialkyl sulfate under strong basic ~ ~ conditions. I'he most convenient reaction temperature for ;; the alkylation is the reflux temperature of the reaction ~mixture. Alkylations of this typè are frequently preformed and are common in the chemical literature.
In formula (I), the term Cl-C3 alkyl refers to methyl, ethyl, or propyl.

~ X-4223A -3-: :
: ~ , . '.
:: :

: . ! . . :

~0~ 7 Formula (I) above is believed to describe the invention clearly. In order to assure that agricultural chemists understand the invention, however, the following exemplary compounds are presented. It will be understood that the compounds below do not bound the invention, but are merely typical of it.
4-(3-bromophenyl)-2-methyl-1-phenyl-3-pyrazolin-5-one 1-(3-chlorophenyl)-2-ethyl-4-(3-fluorophenyl)-3-pyrazolin-5-one 4-(3-chlorophenyl)-1-(2-fluorophenyl)-2-propyl-- 3-pyrazolin-5-one 1,4-bis(3-bromophenyl)-2-methyl-3-pyrazolin-5-one

2-propyl-1,4-bis(m-tolyl)-3-pyrazolin-5-one 4-(3-chlorophenyl)-2-methyl-1-(a,a,a-trifluoro-_-tolyl)-3-pyrazolin-5-one 2-ethyl-1-phenyl-4-(m-tolyl)-3-pyrazolin-5-one 1-(3-chlorophenyl)-2-methyl-4-(m-tolyl) 3-pyra-zolin-5-one 1-(2-bromophenyl)-2-propyl-4-(a,a,a-trifluoro-m- ; -tolyl)-3-pyrazolin-5-one 4-(3-chlorophenyl)-2-methyl-1-(_-tolyl)-3 pyrazolin-5-one 4-(3-bromophenyl)-1-(2-chlorophenyl)-2-methyl-~;

3-pyrazolin-5-one 2-ethyl-1,4-bis(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one 1-(3-fluorophenyl)-2-methyl-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one X-4223~ -4- `
~-' ' ;..~ ,.... ... .

~'7~

2-ethyl-l-(2-fluorophenyl)-4-(3-fluorophenyl)-3-pyrazolin-5-one 2-ethyl-l-(3-fluorophenyl)-4-(m-tolyl)-3-pyrazolin-5-one

4-(3-bromophenyl)-l-(4-fluorophenyl)-2-propyl-3-pyrazolin-5-one l-(2-bromophenyl)-4-(3-fluorophenyl)-2-propyl-3-pyrazolin-5-one l-(3-bromophenyl)-2-methyl-4 (m-tolyl)-3-pyrazolin-

5-one 2-methyl-4-(m-tolyl)-l-(a,a,-trifluoro-o-tolyl)-3-pyrazolin-5-one :
4-(3-fluorophenyl)-2-methyl-l-.(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one The preferred compounds of formula (I) are those wherein R is Cl-C2 alkyl;
R is hydrogen, chloro, or fluoro; and provided that Rl may not be chloro in the 4-pos1tion;
R is trifluoromethyl.
Such preferred compounds are more particularly .
identified as the following: ..
.
2-methyl-l-phenyl-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-~ ~5-one, 2-ethy1-1-phenyl-4-(a,a,a-trifluoro-m-tolyl)-3-; pyrazolin-5-one, 2-ethyl-1-(4-fluorophenyl)-4- (a,a,a- ~-trifluoro-m-tolyl)-3-pyrazo11n-5-one, 2-ethyl-l-(3-chloro-phenyl)-4-(a,a~,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, :~ 2-methyl-l-(3-chlorophenyl)-4-(,a,~-trifluoro-m-tolyl)-3-pyrazolin-5-one, 2-methy1-1-(2-ah1Oropheny1)-4-(a,,a-trifluoro- -tolyl)-3-pyrazolin-5-one, l-(3-bromophenyl)-30 : : ~
:
~;: X-4223A : -5- :.
., ~

, ~:3679()7 2-ethyl-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, 1,4-bis~3-chlorophenyl)-2-ethyl-3-pyrazolin-5-one, and 2-methyl-l-(4-fluorophenyl)-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
The starting materials for the compounds of f~rmula (II) are made most advantageously by a 2-step process.
First, a methyl or ethyl ester of phenylacetic acid, bearing the R2 substituent on the phenyl ring, is reacted with di(Alk)formamide di(Alk) acetal neat or in dimethylformamide to produce an intermediate substituted ester of atropic acid of the formula (III) below.
R~\ O

C COAIk \~__ / 11 :
(III) HC-- N(Alk) ': ' The term Alk refers to methyl or ethyl. The reaction is ~ ~ -carried out at temperatures from about 80 to about 140C. in -~
: . .
a flask open to the atmosphere.

The intermedlate III is then reacted with a phenyl- -.
hydrazine or a hydrohalide thereof, bearing the R1 sub-stituent, if any, on its phenyl ring, to form the desired starting material of formula (II). When a phenylhydraz1ne in the free base form is used, the reaction is carried out in an aprotic solvent. The aromatic solvents such as benzene and toluene, the aliphatics such as hexane and octane, and the halogenated solvents such as methylene ~chloride and chloroform~are appropriate solvents. Xylenes ~are the preferred solvents. The most convenient reaction temperature lS the reflux temperature of the reaction , :
~ X-4223A ~ , -6-:
,..

, ~, - , . . . ~ . . , ., , ~ . , -79C~

mixture, but other temperatures from room temperature to about 120Co can be used if convenient in a given instance.
When a phenylhydrazine hydrohalide is used, the reaction can be carried ou-t in an aprotic solvent as de-scribed above in the presence of a base. Tertiary organic amines such as triethylamine, pyridine, triethanolamine and the like, and inorganic bases such as potassium carbonate, sodium bicarbonate, alkali metal hydroxides and the like are satisfactory bases.
~ 10 Alternatively, reactions using phenylhydrazine hydrohalides may be performed by first reacting the hydra-zine with the intermediate (III) in a lower alkanol at the reflux temperature of the mixture to exchange the di(Alk)-amino group of (III) with the arylhydrazine molety. The resulting intermediate may then be cyclized by heatlng in an aprotic solvent such as xylene at temperatures from about 50 to about 120C~ Alternatively, the resulting inter-mediate may be cyclized by heating in a lower alkanol at reflux temperature with inorganic bases such as potassium carbonate, alkali metal hydroxides, or alkali metal alkoxides.
All of the starting compounds used to prepare the compounds of formula (III) are commonly known in the chemical art and are readily obtainable.
A few typical preparative examples will be shown to assure that organic chemists can obtain any desired compound of formula (I). All of the products described below were identifled by nuclear magnetic resonance analysis and-elemental microanalysis.

' X-~223~ ~7~

: :
~ ~ , ~L06 ~

Example 1 A 10.9 g. portion of 3-trifluoromethylphenylacetic acid, methyl ester, was combined with 11.9 g. of dimethyl-formamide dimethyl acetal and the mixture was heated over-night on the steam bath. In the morning, the reaction mixture was taken up in methanol and poured over ice. The aqueous mixture was filtered, and the solids were recrystal-lized from aqueous ethanol to produce 4 g. of m-trifluoro-methyl-~-(dimethylamino)atropic acid, methyl ester, m.p.
45-49C.
The ester prepared above was combined with 1.6 g.
of phenylhydrazine in 25 ml. of benzene and the mixture was refluxed overnight. About 25 ml. o~ p-xylene was added and the mixture was refluxed for 2 hours more. The reaction mixture was then cooled, and the resulting solids were separated by ~iltration and identified as 2.6 g. of l-phenyl- ~-4- (a,a,a- trifluoro-m-tolyl)-3 pyrazolin-5-one.
A 1.5 g. portion of the pyrazolinone was dissolved in 50 ml. of methanol, and 0.7 g. of methyl iodide and 0.7 g. of potassium carbonate were added. The mixture was stirred at reflux temperature overnight. The mixture was then poured over ice, and the aqueous mixture was filtered to recover the product, which was recrystallized from ethyl acetate-hexane. The product was 0.85 g. of 2-methyl~l-phenyI-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin~5-one, m.p. 153-155C.
Theoretical~ound C64.15~64.17 H4.12 4.19 N8.80 8.77 X-4223A ~ -8-~ , ' ' ' , 1Clt:;79V7 Example 2 A 9 g. portion of 3-fluorophenylacetic acid, methyl ester, was reacted with 6.5 g. of dimethylformamide dimethyl acetal in 15 ml. of dimethylformamide at 120C. to produce 11.2 g. of the corresponding m-fluoroatropic acid, - methyl ester. The ester was reacted with 5.4 g. of phenyl-hydrazine in 50 ml. of toluene at reflux temperature for 4 - hours. An equal volume of m-xylene was then added, and the mixture was refluxed overnight. The mix~ure was then cooled and decanted, and the solids were triturated with benzene and filtered. The separated solids were slurried in hot benzene-ethyl acetate, and filtered again. The solids were then recrystallized from ethanol to produce 2.9 g. of 1-phenyl-4-(3-fluorophenyl)-3-pyrazolin-5-one, m.p. 189C.
A 2.4 g. portion of the above pyrazolinone was combined with 3.9 g. of methyl iodide and reacted as described in Example 1 above. The product, after recrystallization from-benzene-hexane, was 1.5 g. of 2-methyl-1-phenyl-4-t3-fluorophenyl)-3-pyrazolin-5-one, m.p. 134C.
TheoreticalFound C71.63% 71.35 H4.88 5.01 ~ N10.44 10.17 Example 3 A 3 g. portion of the 2-unsubstituted pyrazolinone of Example 1 was reacted with 10 ml. of propyl iodide to produce 0.45 g. of 1-phenyl-2-propyl-4-(a,~,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, an oily liquid.
' ,' ',~ '.

:

:. . :

~6'~07 Theoretical Found C~5.89~ 65.64 H 4.95 5.09 N 8.09 7.97 Example _ A 2.5 g. portion of the 2-unsubstituted pyrazo-linone of Example 1 was reacted with 1.2 g. of ethyl iodide.
The alkylated product was 1.2 g. of 2-ethyl-1-phenyl-4-(a,a,a-trifluoro-m-toly1)-3-pyrazolin-5-one, m.p. 156-157~C.
TheoreticalFound C65.06% 65.25 H4.55 4.65 N8.43 ~.40 A 17 g. portion of 3-chlorophenylacetic acid, methyl ester, was combined with 12 g. of dimethylformamide dimethyl acetal in lOO ml.~of dimethylformamide and the ~
mlxture was heated in an open flask at the boiling tem- ~ -perature of the mixture for 6 hours. The hot reaction ~20~ mixture was then poured over ice~, and the aqueous mixture was filtered. The solids were recrystallized from benzene-hexane to produce~13 g. of the 3-chloroatropic acid, methyl ester, m.p. 84-86C. ~
A~4.8 g. portion of the above intermediate was reacted~wLth~2~.2 g. of phenylhydrazine to produce 3.5 g. of l-phenyl-4-(3-~chlorophenyl)~-3-pyrazolin-5-one, m.p. 197-199C.
;A 2~g~. portion~o~f~the~above intermediate was alkylated~w1th~2.7 g. of methyl~iodide~to~ produoe~l g. o~
2-methyl-1-phenyl-4-(3-chlorophenyl)-3-pyrazolin-5-one, m.p.
30 ~ 49~-~150C.~

X-42~23A~ -10-~ ;

Theoretioal Found C ~7.4'~% 67.24%
H 4.60 4.38 N 9.84 9.80 Example 6 A 5.5 g. portion of the atropic ester of Example 1 was combined with 3.5 g. of 4-fluorophenylhydrazine hydro-chloride and 2 g. of triethylamine in 50 ml. of benzene.
The mixture was stirred at reflux temperature for 5 hours, after which about half of the benzene was allowed to evapo-rate and an equivalent amount of m-xylene was added. The mixture was then stirred at reflux overnight, and the reabtion mixture was evaporated to dryness under vacuum.
The residue was partitioned between ethyl acetate and water, .
and the organic layer was dried~over sodium sulfate and ..
evaporated to dryness. The residue was chromatographed on silica gel with~ethyl acetate~as the eluant. The product-contai~ning fractions~were~combined~and evaporated to dryness ~ -to produce about 3.5 g. of crude product, which was recrystal-llzed from methanoi to produce 2.7 g. of purified 1-(4-fluoro-;~ ; phenyL?~-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, m.p.
171-173C.

~ ~ . . . :
Two g. of the above intermediate was alkylated w~ith 2.7 g.~ o~ methyl iodide to produce 1.6 g. of 2-methyl-(4-fluorophenyl)-4-(a,~,a-trifluoro-m-tol~yl)-3-pyrazolin-5-one,~m.p. 165C.

Theoretical Found C~ 60.72% 6~ 99% ~ ~

H~ ~ ;3.60 3.5~ . -30~ N ~ 8.3~3 ~8.3Z ~ -X-4223A ~

.

~L06~7~

Example 7 A 3.5 g. portion of the atropic ester of Example 1 was reacted with 2.3 g. of 3-chlorophenylhydra2ine hydro-chloride in the presence of 1.3 g. of triethylamine in m-xylene according to the scheme of Example 6. The product was 2 g. of 1-(3-chlorophenyl)-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, m.p. 182-184C.
A 1.65 g. portion of the above intermediate was alkylated with 2 g. of methyl iodide to produce 1 g. of 2-methyl-1-(3-chlorophenyl)-4-(a,a,a trifluoro-m-tolyl)-3-pyrazolin-5-one, m.p. 130-131C.
Theoretical Found C 57.89% 58.13%
H 3.43 3.59 N 7.94 8.04 Example 8 A 2.2 g. portion of the atropic ester of Example 1 was reacted with 1.3 g. of m-tolylhydrazine hydrochloride in the presence of triethylamine to produce 1.7 g. of l-(m-20 tolyl)-4-(,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, m.p. ~ -158-159C.
A 1.6 g. portion of the above intermediate was .
alkylated with 2 g. of methyl iodide to produce 1 g. of 2-methyl-1-(m-tolyl)-4-(a,a,a-trifluoro-m-tolyl) 3-pyrazolin-5-one, m.p. 153-154C.

Theoretical Found C 65006% 65.19%

H 4.55 4.32 N 8.43 8.33 X-4223A ~ ~-12-:: .

~0~ ~ 9~7 Example 9 A 3.5 g. portion of the atropic ester of Example 1 was reacted with 2.7 g. of ,,a-trifluoro-m-tolylhydrazine hydrochloride in the presence of triethylamine to produce 2.4 g. of 1,4-bis(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, m p. 207-208C~
A 1.8~ g. portion of the above pyrazolinone was reacted with 2 g. of methyl iodide to produce 1.25 g. of 2-methyl-1,4-bis(a,a,a-trifluoro-m= tolyl)-3-pyrazolin-5-one, m.p. 110-111C.
Theoretical Found C 56 2~% 56.04% -H . 2. 62 2.86 N 7.29 7.19 Example 10 A 2.7 g. portion of the atropic ester of Example 1 was reacted with 1.8 g. of 2-chlorophenylhydrazine hydro-chloride in the presence of triethylamine to produce 1 g. of 1-(2-chlorophenyl)-4-(a,a,~-trifluoro-m-tolyl)-3-pyrazolin-.
5-ona, m.p. 236C.

One g. of the above pyrazolinone was alkylated .
with 1 g. of methyl iodide to produce 0.45 g. of 2-methyl- -1-(2-chlorophenyl)-4- (a,a,a~trifluoro-m-tolyl)-3-pyrazolin-5-one~, m.p. 175C.

Theoretical Found ~ ~ ~ C 57 ~7~ 57-3~%

: ~ H 3.40 3.51 .
~ N ~ 7.94 7.93 , . ~
: ~ ., ' .

~;-4223A -13-. ~ ~ ....................... . . .
: ' ' , ' ~lti'7~31Q7 Example 11 A 2.6 g. portion of 1-(3-chlorophenyl)-4-(a,a,~-trifluoro-m-tolyl)-3-pyrazolin-5-one, prepared in Example 7, was alkylated with ethyl iodide to produce 0.25 g. of 2-ethyl-l-(3-chlorophenyl)-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one, an oily liquid.
Theoretical Found C58.95~ 58.89~ -H 3.85 3.61 N 7.64 7.52 Example 12 A 15 g. portion of the atropic ester of Example 1 was allowed to react with 10 g. of 3-fluorophenylhydrazine hydrochloride in methanol at reflux temperature for about 2 -~
days. The solvent was evaporated and the residue parti- ~:
tioned between ethyl acetate and water. The organic layer was separated and concentrated in vacuo to leave a residue. -The residue was recrystallized from a mixture of ethyl acetate and hexane to yield product having a melting point - :
of about 172C. and weighing 2.1 g. The product was iden- ;
tified as 1-(3-fluorophenyl)-4-(a,a,~-trifluoro-m-tolyl~-3-pyrazolin-5-one.
The 2.1 g. of pyrazolinone prepared above was `i ~ -placed in 40 ml. of ethanol together with 15 ml. of ethyl lodide and~l g. of potassium carbonate and the mixture refluxed for about 8 hours. The reaction product mixture was concentrated ln vacuo~and the residue partitioned between ethyl acetate and water. The ethyl acetate layer was separated and dried, and concentrated in vacuo, and the residue~chromatographed on a sillca gel column u~-ng~a X-4223A ~ -14-~, :
.
: : ~

6'79~

mixture of ethyl acetate and hexane in a ratio o~ 1:2. The product which was isolated had a melting point of about 140-141C. and weighed 0.7 g. The product was identified as 2-ethyl-1-(3-fluorophenyl)-4-~a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
Theoretical Found C 61.71% 61.72 H 4.00 4.06 N 8.00 8.00 Example 13 A 4 g. portion of 1,4-bis(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one (from Example 9) was heated with 20 ml. of ethyl iodide, 3 g. of potassium carbonate, and 40 ml. of ethanol at reflux temperature for about 4 hours. The reaction product mixture was concentrated ln vacuo and -extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate, the drying agent filtered off and the filtrate concentrated in vacuo. On standing over-night the residue solidified and was recrystallized from a mixture of hexane and benzene. The solid was chromato-graphed on a silica gel column using a mixture of ethyl acetate and hexane in the ratio of 1:2. The product from -the column was~then recrystallized from a mixture of hexane and benzene to yield product having. a melting point of about 110-111C., and identified as 2-ethyl-1,4-bis(a,a,a-trifluoro- -m-tolyl3-3-pyrazolin-5-one.
Theoretical Found C57.00% 56.63%
H 3.50 3.49 N 7.00 6.85 X-422~3A -15-IL0~7~
Example 14 A 13.7 g. portion of the atropic ester of Example l was allowed to react with 11.2 g. of 3-bromophenylhydrazine hydrochloride in 100 ml. of methanol at reflux temperature overnight. The solvent was evaporated, and the residue was refluxed in 100 ml. of m-xylene and 5 g. of triethylamine for about 16 hours. The reaction mixture was concentrated in vacuo and the residue chromatographed on a silica gel column using 1:1 ethyl acetate-hexane. There was obtained

7.5 g. of product, which was identified as 1-(3-bromophenyl)-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
A 7.5 g. portion of the above pyrazolinone was combined with 4 g. of potassium carbonate and 15 ml. of ethyl iodide in lO0 ml. of ethanol and heated in the same manner as previously described for other similar compounds.
There was obtained 2.0 g. of product having a melting point of about 106C., and identified as 1-(3-bromophenyl)-2-ethyl-4-(a,a~a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
~ Theoretical Found C52.57~ 52.80 .:
N 6.81 6.98 Example 15 A 6 g. portion of 1-(4-fluorophenyl)-4-(a,~,a-~trifluoro-m-tolyl)-3-pyrazolin-5-one (prepared in Example 6) was mixed with 4 g. of potassium carbonate and 15 ml. of ethyl iodide in lO0 ml. of ethanol and refluxed overnight.
There was isolated in the usual manner 1.8 g. of product having a melting Poin~ f about 92C., and identified as .
.

~06 ~9 0!7 2-ethyl-1-(4-fluorophenyl)-4-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
Theoretical Found ; C61.72~ 61.87 4.03 ~.20 N 8.00 8.06 Example 16 A 12 g. portion of the 3-chloroatropic acid, methyl ester (prepared in Example 5 above) was allowed to react wlth 10 g. of 3-chlorophenylhydrazine hydrochloride in 100 ml. of methanol at reflux temperature overnight. There was obtained 10 g. of product having a melting point of about 173-174C., and identified as 1,4-bis(3-chlorophenyl)-3-pyrazolin-5-one.
A mixture of 7 g. of the pyrazolinone prepared above, 4 g. of potassium carbonate, and 15 ml. of ethyl iodide in ethanol was refluxed overnight. There was i90-lated, after recrystallization from ether, 3.0 g. of product havlng a melting point of about 101C., and identified as 20 1,4-bis(3-chlorophenyl)-2-ethyl-3-pyrazolin-5-one.
Theoretlcal Found C61.28~ 61.04%
H 4.24 4.21 N 8.4I 8.55 ExampIe 17 A mixture of 12 g. of the 3-chloroatropic acid, methyl ester (prepared~in Exa~mple 5 above), 13 g. of m-trifluoromethylphenylhydrazine hydrochloride and 100 ml. of methanol was~reflux~ed overnight to yield 4.6 g. of prodùct ~. .

30 having a melting point of about 190-192C., and identified X-4223A ~ -17-. ~ . . .
.. ~ . ' :. .

~06'7~(~7 as 4-(3-chlorophenyl)-1-(a,a,a-trifluoro-m-tolyl)-3-pyrazolin-5-one.
A mixture of 4.6 g. of the pyrazolinone prepared above, 4 g. of potassium carbonate, 15 ml. of ethyl iodide and 50 ml. of ethanol was refluxed overnight. The reaction product mixture was worked up in the customary way to yield 1.8 g. of product having a melting point of about 113-114C.
and identified as 4-(3-chlorophenyl)-2-ethyl-1-(a,~,~-trifluoro-m-tolyl)-3-pyrazolin-5-one.
Theoretical Found C58.95~ 58.84%
H3.85 3.89 N7.64 7.63 Example 18 A 120 g. portion of phenylacetic acid, methyl ester, was combined with 95 g. of dimethylformamide dimethyl acetal in 200 ml. of dimethylformamide, and heated to gentle ~ ;
reflux for about four days, while adding, at intervals, 5 g.
portions of dimethylformamlde until a total of 140 g. addi-tional had been added. At the end of the heating period, the reaction m1xture was allowed to cool to room temperature and was poured over crushed ice. The oily product which separated eventually crystallized. The crystalline product was washed with water, cooled in the refriyerator, filtered off and air drled. The crude product was recrystallized ~from cyclohexane to yield product havlng a melting point of about 58-60C., which was idèntified as ~-(dimethylamino)-atropic acidj methyl~ester. ~ -X-4223A ~ -18- ; ~
., . . ~ .
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......... .. .. . . .

IL ~!67 9 ( ~ 7 Theoretical Found . _ _ C 70.22% 70.47 H 7.37 7.36 N 6.82 6.85 A mixture of 10.5 g. of the atropic acid, methyl ester, 9.1 g. of 3-chlorophenylhydrazine hydrochloride, and 200 ml. of methanol was refluxed overnight. The reaction product mixture was worked up in the usual manner to yield 11 g. of crude 1-(3-chlorophenyl)-4-phenyl-3-pyrazolin-5-one. A sample recrystallized from methanol had a melting point of about 211-212C.
A mixture of 4 g. of the above preparéd pyrazo-linone, 20 ml. of ethyl iodide, 20 ml. of ethyl bromide, 3 g. of potassium carbonate, and 40 ml. of ethanol was refluxed for about 4 hours. The reaction product mixture was worked up to yieId 0.9 g. of an oil, which was iden-tified as 1-(3-chlorophenyl)-2-ethyl-4-phenyl-3-pyrazolin-5-one.
Theoretical Pound C 68.34~ 68.15 H 5.06 4.89 N 9.38 9.29 Example 19 A mixture of 8.2 g. of the atropic acid, methyl :
; e~ster, (prepared in Exampla 18), 8.5 g. of m-trifluoro-methylphenylhydrazine hydrochloride, lOO ml. of benzene and .

~ g.; of triethy~lamine~, was reflu~ed overnight and worked up -~
,, to yield 6.5 g. of 4-pheny1-1-~(a,~,a-trifluoro-m-to1yl)-3-pyrazolin-5-one having a melting point o~ about 210-213C. ~ ~;

30 ~

X-4223A~ -19-.
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A mixture of 2.2 g. of the pyrazolinone prepared above, 2 g. of potassium carbonate, 25 ml. of ethyl iodide and 25 ml. of ethanol was re1uxed for about 3 hours. The reaction mixture was worked up in the usual manner to yield an oll whlch was identified by NMR spectrum as 2-ethyl-4-phenyl-l-(a,a,~trifluoro-m-tolyl)-3-pyrazolin-5-one.
The compounds of formula (I) have been tested in a number of herbicidal test systems to determine the range of their herbicidal efflcacy. The results produced by the compounds in the representative tests reported below are exemplary of the activity of the compounds.
Compound application rates are expressed in kilo-grams of the compound per hectare of land (kg./ha.) through-out this document.
Blank spaces in the tables below indicate that the compound was not tested agalnst the named species. In the tests below, plants were rated on a 1-5 scale, on which 1 indicates normal plants and 5 indicates dead plants or no emergence. The compounds are identified by their example numbers.
Test 1 ; broad spectrum greenhouse test ; Square~plastic pots were filled with a sandy sterilized greenhoùse soil and were planted to seeds of tomato, large crabgrass and pigweed. Each pot was indiv- ;
idually fertilized. ~ -Test~compounds were applied postemergence to some pots and preemergence to others. Postemergence applications of the compounds were sprayed over the emerged plants about 12 days after the seeds were planted. Preemergence appli-X-4223A ~ ~ -20-: . .

~06~9ff7 cations were sprayed on the soil the day after the seedswere planted.
Each test compound was dissolved in 1:1 acetone:
ethanol at the rate of 2 g. per 100 ml. The solution also contained about 2 g. per 100 ml. of an anionic-nonionic surfactant blend. One ml. of the solution was diluted to 4 ml. with deionized water, and 1-1/2 ml. of the resulting solution was applied to each pot, resulting in an appli-cation rate of 16.8 kg./ha. of test compound.
After the compounds were applied, the pots were moved to the greenhouse, watered as necessary, and observed and rated about 10-13 days after application of the com-pounds. Untreated control plants were used as standards in every test.
The table below reports results of testing typical compounds of formula ~I).
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~OG790'7 Te s t multi-spec es greenhouse test The test was conducted in general like the test above. The seeds were planted in flat metal trays, rather than in pots. The compounds were formulated according to the procedure above, except that about 6 g./100 ml. of the compound was dissolved in the surfactant-containing solvent, and the organic solution was diluted with appropriate amounts of water before application to the trays. The compounds were applied at various rates which are indicated in the table below and the results of testing against the species -named below are as follows. Where more than one replicate was run, the results were averaged.

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Test 3 resistant weed tests _ Typical compounds were evaluated in a test system which determined their ability to reduce the vigor of weeds which are resistant to many herbicides. The compbunds were formulated and dispersed, and the dispersions were applied, as described in Test 1 above. The application rate was 9.0 kg /ha. in all Of the tests reported h~re.

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The broad spectrum activity of the compounds of formula (I) is illustrated ~y the above examples. The test results point up the efficacy of the compounds against annual grasses, the relatively easily-controlled broadleaves such as pigweed, and the more resistant broadleaves such as nightshades. Plant scientists will recognize that the exemplified activity of the compounds shows that they are broadly effective against unwanted herbaceous plants, which will be referred to as weeds, for the sake of brevity.
As the above test results demonstrate, the com~
pounds are used to reduce the vigor of weeds by contacting them with an herbicidally-effective amount of one of the compounds. The term "reduce the vigor of" is used to refer to both killing and injuring the weed which is contacted with a compound. In some instances, as is clear from the test results, the whole population of the contacted weed is killed. In other instances, part of the weeds are killed and part of them are injured, and in still other instances, ~none of the weeds are killed but are merely injured by application of the compound. It will be understood that reducing the vigor of the weed population by injuring part of them is beneficial, even though part of the population survives application of the compound. The weeds, the vigor of which has been reduced/ are unusually susceptible to the stresses which normally afflict plants, such as disease, drought, lack of nutrients and so forth.
Thusj the treated weeds are likely to expire due to stress of the environment, even though they survive application of the compound. Further, if the treated weeds are growing in cropland, the crop, as it grows normally, .: .

~06'790'~

tends to shade out the treated weeds of reduced vigor.
Therefore, the crop has a great advantage over the treated - weeds in the competition for nutrients and sunlight. Still further, when the treated weeds are growing in fallow land, or industrial property which is desired to be bare, the reduction in their vigor necessarily tends to minimize the treated weeds' consumption of water and nutrients, and also minimizes the fire ha~ard and nuisance which the weeds present.
The compounds are herbicidally effective when applied both preemergence and postemergence. Thus, they can be used both by direct contact of the compounds with emerged weeds, and by applying the compounds to the soil, where they come in~to contact with germinating and emerging weeds.
Preemergence appllcation of the compounds, wherein the ger-minating and emerging weeds are contacted with the compound through soil application, is preferred.
Accordingly, an important embodiment of this invention is a method of reduclng the vigor of weeds which -comprises contacting the weeds with an herbicidally-effective .
amount of a compound of formula ~I). The term herbicidally-effective amount refers to an amount which will reduce the vigor of the treated weed. In the context of this invention, weed seeds, which are contacted with the compounds by appli-cation of the compounds to the soil, are regarded as weeds.
Amounts of herbicides are measured in terms of the weight of herbicide applied per unit area, usually called the application rate. The best application rate of a given , compound of formula (I) for the-control of a given weed ;~ 30 ~ varies, of course, depending upon the climate, soil texture, X-4223A ~ -35-~ .

lQti~7~0~

water and organic matter contents of the soil and other factors known to those skilled in plant science. It will be ~ound, however, that the optimum application rate is usual-ly in the range from about 0.5 to about 20 kg./ha.
It is not implied, of course, that all compounds of formula (I~ are effective against all weeds at all rates.
Some compounds are more effective against some types of weeds, other compounds are more effective against other types.
All of the compounds, however, are effective against at least some weeds. It is within the ordinary skill of a plant sci-entist to ascertain the weeds which are most advantageously controlled with the various compounds, and the best applica-tion rate for the particular use.
The compounds are applied to the soil or to emerged weeds in the manners usual in agriculture. It is best to apply the compounds in the form of the herbicidal compositions which are important embodiments of the pxesent invention. They may be applied to the soil in the form of ~ither water-dispersed or granular compositions, t~e preparation of which will be dis-cussed below. Vsually, water-dispersed compositions will be ; used for the application of the compounds to emerged weeds.
The compositions are applied with any o the many types of sprayer~s and granular applicators which are in wide use for the distribution of agricultural chemi~als over soil or stand-ing vegetation. In general, the compositions are formulated in the manners usual in~agr~lcultural chemistry.
Very often, the compounds are formulated as concen-~rated compositions which are appiied either to the soil orthe foliage in the form;of water dispersions or emulsions 30 ~

.
"., ~ , .. .

~06t7907 containing in the range of from about 0.1 percent to about 5 percent of the compound. Water-dispersible or emulsifiable compositions are either solids usually known as wettable powders, or liquids usually known as emulsifiable concen-trates. Wettable powders compr:ise an intimate, finely-divided mixture of the compound, an inert carrier, and surfactants. The concentration of the compound is usually from about 10 percent to about 90 percent. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the kaolin clays, the diato-maceous earths and the purified silicates. Effective surfactants, comprising from about 0.5 percent to about 10 percent of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalene-sulfonates, the alkylbenzenesulfonates, the alkyl sulfates and nonionic surfactants such as ethylene oxide adducts of ;~
phenol.
:
Typical emulsifiable concentrates of the new .
compounds comprise a convenient concentration of the com-- 20 pound, such as fxom ahout 100 to about 500 g. per llter of liquid, dissolved ln an inert carrier which is a mixture of water-immiscible solvent and emulsifiers. Useful organic solvents include the aromaticsj especially the xylenesj and ~ ~ the petroleum fractions, especially the high-boiling naph-; ~ ~thalenlc and~olefinic portions of~petroleum. Many other organic solvents may also be used such as the terpenic solvents, and the complex alcohols such as 2-ethoxyethanol.
Suitable emulsifiers for emulsifiable concentrates are ;chosen from the~same types~of surfactants used for wettable powders.

X-4223A~ -37 ,:

~0~7~13'7 When a compound is to be applied to the soil, as for a preemergence application of the compound, it is con-venient to use a granular formulation. Such a fonnulation typically comprises the compound dispersed on a granular inert carrier such as coarsely ground clay. The particle size of granules usually ranges from about 0.1 to about 3 mm. Th~ usual formulation process for granules comprises dissolving the compound in an inexpensive solvent and applying the solution to the carrier in an appropriate solids mixer. Somewhat less economically, the compound may be dispersed in a dough composed of damp clay or other inert carrier, which is then dried and coarsely ground to produce the desired granular product.
It has become custo~ary in agricultural chemistry to apply two or even more agricultural chemicals simultaneously in order to control weeds of many different types, or weeds and other pests, with a single application of chemicals.

.
The compounds of formula ~I) lend themselves well to com-bination with other~agricultural chemicals and may usefully be combined with insecticides, fungicides, nematicides and other herbicides as may b desirable.

. ~ , :

.

.
', ~ . , , :' .

. ' ' :
'

Claims (8)

The embodiments of the invention for which an exclusive property or privilege is claimed are defined as follows:
1. A compound of the general formula (I) wherein R is C1-C3 alkyl;
R1 and R2 independently are hydrogen, chloro, fluoro, bromo, methyl or trifluoromethyl, provided that R1 and R2 do not simultaneously represent hydrogen;
and provided that R1 may not be bromo or chloro in the 4-position.
2. A compound of Claim 1 wherein R is C1-C2 alkyl;
R1 is hydrogen, chloro, or fluoro; and provided that R1 may not be chloro in the 4-position; and R2 is trifluoromethyl.
3. Any one of the following compounds of Claim 1:
2-methyl-1-phenyl-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-ethyl-1-phenyl-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-methyl-1-(4-fluorophenyl)-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-methyl-1-(3-chlorophenyl)-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-methyl-1-(2-chlorophenyl)-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-ethyl-1-(3-chlorophenyl)-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 1-(3-bromophenyl)-2-ethyl-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 2-ethyl-1-(4-fluorophenyl)-4-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)-3-pyrazolin-5-one 1,4-bis(3-chlorophenyl)-2-ethyl-3-pyrazolin-5-one.
4. A process for preparing a compound of the general formula (I) wherein the various symbols are defined as in Claim 1, which comprises reacting a compound of the general formula (II) wherein the various symbols are defined as in Claim 1, with an alkylating agent in the presence of a base.
5. A method of reducing the vigor of weeds which comprises contacting the weeds with an herbicidally-effective amount of a compound of Claim 1.
6. A method of reducing the vigor of weeds which comprises contacting the weeds of an herbicidally-effective amount of a compound of Claim 2.
7. A method of Claim 6 wherein the amount of the compound is from about 0.5 to about 20 kg./ha.
8. The method of Claim 7 wherein the compound is any one of the compounds of Claim 3.
CA264,490A 1975-12-11 1976-10-29 Herbicidal 1,4-diphenyl-3-pyrazolin-5-ones Expired CA1067907A (en)

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US8252817B2 (en) 2005-04-28 2012-08-28 Bayer Intellectual Property Gmbh Dipyridyl-dihydropyrazolones and their use
US8524699B2 (en) 2006-10-26 2013-09-03 Bayer Intellectual Property Gmbh Substituted dihydropyrazolones and use thereof as HIF-prolyl-4-hydroxylase inhibitors
US8609698B2 (en) 2006-10-26 2013-12-17 Bayer Intellectual Property Gmbh Substituted dipyridyl-dihydropyrazolones and use thereof
US8653074B2 (en) 2010-11-18 2014-02-18 Bayer Intellectual Property Gmbh Substituted sodium 1H-pyrazol-5-olate
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DK529378A (en) * 1978-01-09 1979-07-10 Shell Int Research anilide
NZ213630A (en) * 1984-10-19 1990-02-26 Ici Plc Acrylic acid derivatives and fungicidal compositions
DE3527157A1 (en) 1985-07-30 1987-02-12 Bayer Ag 1-heteroaryl-4-aryl-pyrazole derivatives
DE102007044032A1 (en) 2007-09-14 2009-03-19 Bayer Healthcare Ag New substituted heteroaryl compounds are hypoxia-inducible factor prolyl-4-hydroxylase inhibitors useful to treat and/or prevent e.g. circulatory heart diseases, heart failure, anemia, chronic kidney diseases and renal failure
DE102007048447A1 (en) 2007-10-10 2009-04-16 Bayer Healthcare Ag New substituted dihydropyrazole-3-thione compounds are hypoxia inducible factor-prolyl-4-hydroxylase inhibitor, useful for preparing medicament to treat and/or prevent e.g. cardiovascular diseases, wound healing and anemia
DE102008020113A1 (en) 2008-04-23 2009-10-29 Bayer Schering Pharma Aktiengesellschaft Substituted dihydropyrazolones and their use

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Publication number Priority date Publication date Assignee Title
US8252817B2 (en) 2005-04-28 2012-08-28 Bayer Intellectual Property Gmbh Dipyridyl-dihydropyrazolones and their use
US9085572B2 (en) 2005-04-28 2015-07-21 Bayer Intellectual Property Gmbh 4-(pyridin-3-yl)-2(pyridin-2yl)-1,2-dihydro-3H-pyrazol-3-one derivatives as specific HIF-pyrolyl-4-hydroxylase inhibitors for treating cardiovascular and haematological diseases
US8524699B2 (en) 2006-10-26 2013-09-03 Bayer Intellectual Property Gmbh Substituted dihydropyrazolones and use thereof as HIF-prolyl-4-hydroxylase inhibitors
US8609698B2 (en) 2006-10-26 2013-12-17 Bayer Intellectual Property Gmbh Substituted dipyridyl-dihydropyrazolones and use thereof
US8987261B2 (en) 2006-10-26 2015-03-24 Bayer Intellectual Property Gmbh Substituted dihydropyrazolones for treating cardiovascular and hematological diseases
US8653074B2 (en) 2010-11-18 2014-02-18 Bayer Intellectual Property Gmbh Substituted sodium 1H-pyrazol-5-olate
US9533972B2 (en) 2010-11-18 2017-01-03 Bayer Intellectual Property Gmbh Substituted sodium-1H-pyrazole-5-olate

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AR218861A1 (en) 1980-07-15
PH13076A (en) 1979-11-23
PT65890B (en) 1978-05-18
DK550876A (en) 1977-06-12
GR63123B (en) 1979-09-11
CS186746B2 (en) 1978-12-29
FR2334674A1 (en) 1977-07-08
SE7613239A (en) 1977-06-12
IL50792D0 (en) 1976-12-31
CH622784A5 (en) 1981-04-30
RO72400B (en) 1983-04-30
NZ182530A (en) 1978-06-20
CA1067907A1 (en)
DD129326A5 (en) 1978-01-11
FR2334674B1 (en) 1980-11-07
NL7613810A (en) 1977-06-14
ATA911876A (en) 1979-06-15
IE43807B1 (en) 1981-06-03
PT65890A (en) 1976-12-01
AU507882B2 (en) 1980-02-28
GB1570623A (en) 1980-07-02
AT354434B (en) 1979-01-10
PL106071B1 (en) 1979-11-30
BG27547A3 (en) 1979-11-12
SU643083A3 (en) 1979-01-15
SE430413B (en) 1983-11-14
DE2651008A1 (en) 1977-06-23
IL50792A (en) 1979-05-31
IT1123686B (en) 1986-04-30
AU2043676A (en) 1978-06-15
RO72400A (en) 1983-04-29
JPS5273868A (en) 1977-06-21
JPS6033112B2 (en) 1985-08-01
ES454061A1 (en) 1978-03-01
IE43807L (en) 1977-06-11
ZA7606561B (en) 1978-06-28
MX3832E (en) 1981-08-04

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