AP36A - Pyrazoline insecticides - Google Patents

Pyrazoline insecticides Download PDF

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Publication number
AP36A
AP36A APAP/P/1985/000014A AP8500014A AP36A AP 36 A AP36 A AP 36A AP 8500014 A AP8500014 A AP 8500014A AP 36 A AP36 A AP 36A
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hydrogen
halogen
formula
lower alkyl
compound
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APAP/P/1985/000014A
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AP8500014A0 (en
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Angelina Joy Duggan
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Fmc Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Pyrazoline Insecticides

Description

This invention pertains to the field of bioaffecting chemical compositions; more specifically, it pertains to novel pyrazoline insecticides, processes and intermediates thereto, insecticidal compositions containing the pyrazolines, and to the use of the pyrazolines for controlling insects.
Pyrazolines are five-membered heterocyclic ring compounds with the following formula and ring atom » numbering scheme:
H
It is known in the insecticide art that certain 1-carbamoyl pyrazoline derivatives are insecticides. For example, U.S. 4,174,393 discloses the insecticidal activity of 1-carbamoyl pyrazolines also carrying phenyl substituents in the 3 and 4 positions of the *
pyrazoline ring.
The present invention provides pyrazolines of the following structural formula that exhibit pronounced insecticidal activity:
N
R.
'N
-2 wherein
R. is of the formula A
in which R'^ is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkyny1oxy and 1 ower haloalkyl ; or
R'
AC
AP 0 0 0 0 3 6 in which X is a bridge of the formula wherein a is 1-3, a' is 0 or 1, a + a' is* at least 2 but no greater than 3, R'and R'Ag are independently selected from hydrogen, halogen and lower alkyl, and R'^q is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl ;
Rb is a 4- or 5-substituent of the formula
•3in which R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower haloalkyl ; or
in which Y is a bridge of the formula
4O-(CR'BAR'BB)b-°b^ wherein b is 1-3, b' is 0 or 1, b*b' is at least 2 but no greater than 3, R’^ and R'gg are independently selected from hydrogen, halogen and lower alkyl, and R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl ;
in which Rg is selected from hydrogen and lower alkyl, and Rg is selected from halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRpRg wherein Rg and Rg are independently lower alkyl, and -SOnRH wherein RH is lower alkyl and n is 0-2; or
-u-
in which 2 is a bridge of the formula
-{O-(CR
CA
CB^c^c'* where in c is 1-3, c 1 is least 2 but no greater or 1, c*c ' is than 5, R'_, and Ιλ selected from r'cb are i ndependently hydrogen, halogen, and lower alkyl, in certain compounds R’qA and R’cb SLre not both hydrogen when C is 1 and C‘ is 1, and R’cc is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and 1 owe r ha 1oa1ky1 ;
R. is hydrogen or lower alkyl; and
V and K are independently oxygen or sulfur.
The terms halo and halogen when employed herein mean fluorine, chlorine or bromine. The term lower modifying alkyl, alkoxy, alkvnyloxy, and the like implies a straight or branched hydrocarbon chain of 1-6, preferably 1-4, carbon atoms; halo coupled with another term means one or more hydrogen atoms has been replaced by halogen.
Among the aforesaid pyracol ines, those compounds in which K is oxygen are preferred for most applications, especially when R'^ is a 4 - substituent, preferably halogen, for example, chlorine or fluorine, or lower haloalkoxy, for example, difluoromethoxy.
Those pvracolines in which R_ is a - - sub s: i t tier; are generally more active than the corresponding 5-substituted pvracolines, and the compounds in which R_ is ί
BAD ORI6'NAL phenyl carrying a substituent R’g are especially attractive. In this context it is preferred that R'B be a 4-substituent, especially halogen, for example, chlorine or fluorine.
With regard to R^, the most attractive insecticides usually derive from those compounds with either a 2,3-dihydro-2,2-dimethy1benzofuran-S-y1, 2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl, 2,3-dihydro2.2.3.3- tetrafluorobenzofuran-6-yl, 2,2-difluoro-l,3benzodioxol-5-yl, or a 2,2-dimethy1 -1,3-benzodioxol3-vl group, or a 4-phenoxyphenyl group. In the latter case it is preferred that R^ be hydrogen and that
R- be a 4 - substituent, especially lower haloalkoxy.
Pyrazolines of this invention having noteworthy insecticidal activity include, for example, 3-(4-difluoromethoxyphenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-S-yl)-4-phenylpyrazoline-l-carboxamide, 3,4-bis( 4-fluorophenyl)-N-2,3-di hydro-2,2,3,3-tetrafluorobe nzofuran-5-yl)pyrazoline-l-carb ox amide, 3,4-bis(4fluorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran5-yl)pyrazoline-l-carboxamide, N-(2,3-dihydro-2,2,3,3tetrafluorobenzofuran-5-yl)-3-(4-difluoromethoxyphenyl)-4-phenylpyrazoline-l-carboxamide, N-(2,2-difluoro-1,3-benzodioxol-5-yl)-3-(4-difluoromethoxyphenyl)-S'-methyl-4-phenylpyra2oline-l-carboxamide, 3,4-bis(4-chlorophenyl)-N-(2,2-dimethyl-l,3-benzodioxol-3-yl)pyrazoline-l-carbox amide, N-(2,2-difluoro1.3- benzodioxol-3-yl)-3,4-bis(4-fluorophenyl)pyrazoline-l-carboxamide, 3-(4-chlorophenyl)-N-(2,2-difluoro-1,3-benzodioxol-5-yl)-4-(4-fluorophenyl)pyrazoline-l-carboxamide, 3-(4-difluoromethoxyphenyl)-NC 2,3-d ihydro-2,2,3,3-tetrafluorobenzofuran-3-yl)-Nmethyl-4-phenylpyrazoline-l-carboxamide, 3-(4-chlorophenyl)-N-[4-(4-difluoromethoxyphenoxy)phenyl]-4-6phenylpyrazoline-l-carboxamide, N-[4-(4-difluoromethcxyphenoxy)pheny1]- 3-(4-d i fluoromet hoxypheny1)-4-(4fluorophenyl)pyrazoline-1-carboxamide, 3-(4-difluoromethoxvpheny1)-4 - (4-f1uoropheny1)-N-(2,3-dihydro2 , 2 , 3, 3-tetrafluorobenzofuran-S-yl)pyrazoline-1-carboxamide, 3-(4-difluo romethoxyphenyl)-4-(4-fluorophenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran6-yl)pyrazoline-l-carboxamide, 4-(4-chlorophenyl)-N(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-3-pheny 1pyrazoline-l-carbox amide, 3-(4-chlorophenyl)-4-(4:luorophenyl)-N- (2,3-dihydro-2,2-dimethylbenzofuran-3yl)pyrazoline-l-carboxamide, 3-(4-difluoromethoxyphenyl)-4-(4-fluorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-S-yl)pyrazoline-l-carboxamide, and
4-(4-chloropheny1)-3-(4-di fluoromethoxypheny1)-N-(2,3di hydro-2,2-dimethy1 benzofuran-5-y1)pyrazoline-1-carboxamide .
Also within the contemplation of the instant invention are insecticidal compositions comprising an insecticidally effective amount of at least one of the aforesaid pyrazolines in admixture with an agriculturally acceptable carrier. In addition, this invenΛ tion includes the method of controlling insects which comprises applying to the locus where control is desired an insecticidally effective amount of at least one of the aforesaid pyrazolines.
Pyrazolines of this invention may be produced by coupling an appropriate aromatic isocyanate or isothiocyanate with an appropriately substituted pyrazoline, a process within the scope of this invention, namely :
AP 0 0 0 0 3 6
BAD ORIGINAL
The product can be alkylated by well known methods to produce the corresponding N-alkylated pyrazolines.
The appropriately substituted pyrazoline starting materials are generally known materials. The requisite isocyanates and isothiocyanates can be prepared from the corresponding amines. A number of the amines are available in commerce. Other amines of interest can be prepared by the methods described in the following Examples.
Example 1
5-(4-Chlorophenyl)-N-(4-(4-chlorophenoxy)phenyl)-4Dhenvlpvrazoline-1- carboxamide
Under a dry nitrogen atmosphere a stirred mixture of 10.9 g ( 0.077 mole) 4-f1uoronitrobenzene, 9.9S g (0.077 mole) 4-chlorophenol, and 11.8 g (0.085 mole) potassium carbonate in 175 mL of dimethy1sulfoxide was heated at 70°C for two days. The reaction mixture was cooled and filtered. The filtrate was diluted with water until a volume of one liter was obtained. This mixture was extracted with three 200 mL portions of
-8diethyl ether. The combined ether extract was washed with water followed by an aqueous saturated sodium chloride solution. The washed extract was dried over anhydrous sodium sulfate and filtered. Evaporation of the filtrate under reduced pressure yielded 13.5 g 4-(4-ch1orophenoxy)nitrobenzene (mp 67-70°C).
Hydrogenation of 13.5 g (0.054 mole) 4-(4-chlorophenoxy)nitrobenzene with a catalytic amount (0.15 g) of platinum oxide in 230 mL of tetrahydrofuran produced a quantative yield of 4 - ( 4-chlorophenoxy)ani1ine.
To a stirred solution of 0.73 g (0.0034 mole)
- (4-chlorophenoxy)ani1ine in 25 mL of toluene was added dropwise a solution of 0.43 mL (0.0036 mole) trichloromethylchloroformate in 20 mL of toluene.
After complete addition, the mixture was heated at 85°C for three hours. This mixture was cooled to room temperature and the solvent evaporated under reduced pressure to leave a residue. The residue was dissolved in 25 mL of diethyl ether. This solution was added dropwise to a stirred slurry of 1.0 g (0.0034 mole) of 3-(4-chlorophenyl)-4-phenylpyrazoline in diethyl ether. Three d rops of triethyl amine were added and the mixture was stirred at room temperature for two days. The solvent was evaporated from the mixture to yield 0.92 g of 3-(4-chlorophenyl)-N-(4-(4chlorophenoxy)phenyl]-4-phenylpyrazoline-l-carboxamide (mp 158-161%).
Analysis:
Calc. C.66.92; H.4.22
Found C,66.06; H,4.93.
nmr: 8.06 ppm (CDClj)
Example 2
3-(4-Chlorophenyl)-N-(2,3-dihydro - 2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-1-carboxamide
During a one hour period an ice cold mixture of 43 mL concentrated nitric acid and 50 mL of concenAP 0 0 0 0 3 6
BAD obig'nal trated sulfuric acid was added dropwise to 100.0 g (0.6 mole) 2,3-dihydro-2,2-dimethylbenzofuran while maintaining the temperature of 5°C. After complete addition the mixture was stirred at 0®C for 2.5 hours. The reaction mixture was poured into ice water and the total extracted with diethyl ether. The extract was dried over anhydrous magnesium chloride and filtered. Evaporation of the filtrate under reduced pressure produced a black oil. Purification of this oil by column chromatography on si 1 ica gel, •'/►'i eluting with toluene: n-hexane (9:1), yielded 50.0 g of 2,3-dihydro-2,2-dimethy1-5-nitrobenzofuran as a solid.
Hydrogenation of 20.0 g (0.1 mole) 2,3-dihydro2,2-dimethyl-5-nitrobenzofuran with a catalytic amount (0.2 g) of platinum oxide in 250 mL of methanol produced 16.6 g of 5-amino-2,3-dihydro-2,2-dimethy1benzofuran.
A solution of 0.43 mL (0.0036 mole) trichloromethylchloroforraate in 20 mL of toluene was added dropwise to a stirred solution of 0.56 g (0.0034 mole)
- ami no-2,3-dihydro-2,2-dimethylbenzofuran in 20 mL of toluene. Upon complete addition the mixture washeated at reflux for three hours. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure leaving a residue.
The residue was dissolved in 25 mL dry diethyl ether and the solution added dropwise to a stirred mixture of 1.0 g ( 0.0034 mole) 3 - ( 4 - chlor opher.y l) - 4 - pheny 1 pyrazoline and three drops of tri ethyl amine in 25 mL of diethyl ether. The reaction mixture was stirred at room temperature for approximately 18 hours, at which time a solid was filtered from the mixture. The filter cake was slurried in ethanol and recovered by filtration to yield 0.47 g of 3-(4 - chiorophenyl)-N (2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazo1ine-1 -carboxamide (mp 160-162°C).
Analyst s :
Calc. C,70.00; H,5.43
Found C,69.50; H,3. 36 nmr: 9.0 0 ppm (DMSO-d^,’
Other members of the series prepared by similar techniques are represented by the following additional Examples. Melting points are given in degrees Celsius. The nmr singlet corresponding to the ®NH proton, characteristic of these compounds, is also given in some cases. Unless stated otherwise, the nmr solvent is CDCl^. Elemental analyses are shown in some instances.
Example 3
5-( l,3-Benzodioxol-5-yl)-3-(4-chlorophenyl)-N-(4-p en oxypheny 1)-pyrazoline-1 -carboxamide , mp 1 2 5- 12 8. 8 . 36.ppm (CDC1 -/DMSO-d6)
Ex amp 1e 4
5-( 1,3-Benzodioxol-5-yl)-N-[4-(4-chlorophenoxy)phenylΙό-( 4 - chlorophenyl) pyra zol i ne-1 - carbox ami de , mp 174-175. 8.06 ppm
Ex ample 5
N- ( 2,3-Di hydro-2,2-dimethylbenzofuran-5-yl)-3,4-diphenylpyrazoline-1-carboxamide , mp 139-143. 7.96 ppm
Example 6
- ( 4-Di fluorome thoxyphenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl) - 4-phenylpyrazoline-1-carboxamide, mp 75-82. 7,96 ppm
Example 7 (+)-3,4-bis(4-Chloropheny1)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-1-carboxamide , mp 134-137. 7.93 ppm
AP 0 0 0 0 3 6
Example 8
3,5-bis(4-Chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-l-carboxamide, mp 175-180. 8.86 ppm (DMSO-d^)
Example 9
N-(l,4-Benzodioxan-6-yl)-3-(4-chlorophenyl )-4-phenylpyrazoline-1-carboxamide , mp 112-115. 7.96 ppm
Example 1 p
N-(l,4-Benzodioxan-6-yl)-3,4-bis(4-chlorophenyl)pyrazoline-l-carboxaraide, mp 140-145. 7.96 ppm
BAD ORIGINAL
Ex amp le 11
5-(4 -Chloropheny1)-N-(2,3-di hydro·2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-l-carbothioamide, mp 93-9;. 10.12 ppm (D‘!SO-d6)
Example 12
3,4-bis(4-Chlorophenyl)-N-(2,3-dihydro-2,2-dimethylben;oturan-5-yl)pyra;oline-l-carbothioamide, mp 149-154. 9.00 ppm (DMSO-d^
Example 13
N-( 1 ,4-3en;odioxan-6-yl )-3, 5-bis(4-chlorophenyl)pyrazoline-1 -carboxamide, mp 83- 8 5.. 9.3 3 ppm (DMSO-d^)
Example 14
N-(2,3-Dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)-3(4-difluoromethoxyphenyl)-4-phenyipyrazoline-l-carboxamlde
Into a pressure bottle was placed 15.0 g (0.086 mole) 2-chloro-4-nitrophenol, 11.9 g (0.086 mole) potassium carbonate, 1.5 g (0.02 mole) propanethiol, 33.7 g (0.13 mole) 1,2-dibromotetrafluoroethane and 115 mL of N,N-dimethylformamide. The pressure bottle was sealed and the mixture stirred at 50°C for 48 hours. The pressure bottle was cooled to room temperature, opened, and the contents poured into a separatory funnel. Approximately 200 mL of a 2N sodium hydroxide solution was added to the separatory funnel. The resultant mixture was extracted with four 300 mL portions of diethyl ether. The extracts were combined and washed with two 100 mL portions of a 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure leaving an oil. The reaction described above was repeated three additional times. The residual oils from the four experiments were combined and purified by column chromatography on silica gel, eluting with n-heptane: toluene (95:5), to yield 57.6 g of 3-chloro4-(2-bromo-l,l,2,2-tetrafluoroethoxy)nitrobenzene as an oil.
Into a pressure bottle was placed 10,0 g (0.028 mole) 3-chloro-4-(2-brorao-l,l,2,2-tetrafluoroethoxy)nitrobenzene, 9.0 g (0.14 mole) copper powder (200 mesh), 0.45 g ( 0.0028 mole) 2,2’-bipyridyl, and 40 mL of dimethylsulfoxide. The pressure bottle was sealed and the reaction mixture stirred at 190-195’C for two hours. The pressure bottle was cooled to room temperature, opened, and the contents poured into a
- 1 2separatory funnel. Approximately 200 mL of a 2N hydrochloric acid solution was added to the separatory funnel. The mixture was extracted with 'three 150 mL portions of diethyl ether. The extracts were combined and washed in succession with 200 mL of a 2N hydrochloric acid solution, 200 mL of a saturated aqueous sodium chloride solution, and 200 mL of a 2N sodium hydroxide solution. The washed extract was dried over anhydrous magnesium sulfate and filtered. The solvent was evaporated under reduced pressure leaving an oil. The reaction described above was repeated six additional times. The residual oils from the seven experiments were combined and subjected to column chromatography on silica gel, eluting with toluene, to yield a yellow oil. This oil was dissolved in 125 mL methylcyclohexane and the solution placed in a freezer for approximately 18 hours. Crystals had formed and were collected by filtration to yield 20.7 g 2,2,3,3tetrafluoro-5-nitrobenzofuran. The filtrate was evaporated under reduced pressure leaving an oil. Distillation of this oil under reduced pressure provided an additional 3.0 g of product (bp 75*C/0.2 mm Hg). Hydrogenation of 2.15 g (0.011 mole) 2,2,3,3-tetrafluoro-5-nitrobenzene with a catalytic amount (0.25- g) of platinum oxide in 150 mL of methanol produced 2.15 g of 5-amino-2,2,3,3-tetrafluorobenzofuran.
A solution of 0.75 g (0.0036 mole) 5-amino2,2,3,3-tetrafluorobenzofuran dissolved in 109 mL of toluene was added dropwise to a stirred solution of 8.0 mL 20% phosgene in toluene. After complete addition the mixture was heated at reflux for two hours.
The mixture was cooled and the· solvent removed by evaporation under reduced pressure leaving a residue. This residue was dissolved in IS mL of diethyl ether and added to a stirred solution of 1.04 g (0.0036 mole) 3-(4-difluoromethoxyphenyl)-4-phenylpyrazoline bad O’
Jr
-1 3and three drops of triethy 1 amine in 100 mL of diethyl ether. After complete addition the mixture was heated at reflux for one hour, then cooled to room temperature and stirred for approximately 18 hours. The solvent was removed from the reaction mixture by evaporation under reduced pressure leaving a solid residue. Recrystallization from ethanol provided 0.99 g of N-(2,3-d ihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)-3(4-difluoromethoxyphenyl)-4-phenylpyrazo line-1-carboxamide (mp 153-159°C).
Analysis:
nmr :
Calc.
F ound 8.16 ppm
C, 58 . 5 8; H,3.29 C,57.81; H,3.73.
Example 15
3,4-bis(4-Chlorophenyl)-N-(2,2-difluoro-l,3-benzodiox ol-S-yl)pyrazoline-l-carbox amide
A solution of 1.18 g (0.0068 mole) 5-amino-2,2-difluoro-1,3-benzodiox ole , prepared by the method described in the literature and dissolved in 80 mL of tetrahydrofuran, was added dropwise to a cold (5 to 10*C) solution of 24 mL 20% phosgene in toluene.
After complete addition the mixture was stirred at 2 °C for one hour, then at reflux for 2 hours. The Solvent was evaporated under reduced pressure to leave 1.4 g of a liquid residue. In.a clean reaction flask 0.68 g of this residue was added slowly to a stirred solution of 0.93 g ( 0.0032 mole) 3,4 - bis(4-chioropheny1)pyrazoline and three drops of triethylamine in 20 mL of diethyl ether. After complete addition the mixture was stirred at room temperature for approximately 18 hours. A small amount of solid was present in the reaction mixture and was removed by filtration. The filtrate was evaporated under reduced pressure leaving
-14a residue. Purification of this residue by column chromatography on silica gel, eluting'vith n-heptane: ethyl acetate (1:1), produced 1.3 g of 3,4-bis(4chlorophenyl)-N-(2,2-difluoro-l,3-benzodioxol-5-yl)pyrazoline-1-carboxamide, (mp 15O-1S5°C).
Analysi s :
Calc. C,56.34; H.3.08
Found C.57.16; H.2.89.
nmr: 8.10 ppm
The compound of Example 50 was similarly prepared. Example 16
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3-(4-difluoromethoxyphenyl)-4-phenvlpyra2oline-l-carboxamide, mp
135-138. 8.10 ppm _
Example 17
3-( l,3-Benzodioxol-5-yl)-N-(4-phenoxyphenyl)-4-phenylpyrazoline-l-carboxamide, mp 220-223. 8.06 ppm
Example 18
3-( 4-Chlorophenyl)-N-(2,3-dihydrobenzofuran-5-yl)-4phenylpyrazoline-l-carboxamide, mp 155-158. 7.93 ppm
Example 19
3-( 4-Difluoromethoxyphenyl)-N-(2,3-dihydrobenzofuran-5yl )-4-phenylpyrazoline-l-carboxamide. 7.93 ppm.
Example 20
3,4-bis(4-Chlorophenyl)-N-(2,3-dihydrobenzofuran-5yl)pyrazoline-l-carboxamide, mp 214-216. 7.93 ppm
Example 21
3-(4-Fluorophenyl)-N-(2,3-dihydro-<2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-l-carboxamide, mp 156- 160.
7.93 ppm
Example 22
3-(4-Methoxyphenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-3-yl) - 4-phenylpyrazo1ine-1-carboxamide , mp 164-169. 8.00 ppm
Example 23
3-( 4-Trifluorome thoxyphenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-y1)-4-phenylpyrazoline-1-carboxamide, mp 81-83. 7.98 ppm
BAD ORlG'NAL
-1 5Example 24
N-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)-4-phenyl3-[4-(2-propynyloxy)phenyl]pyrazoline-l-carboxamide, rap 175-179. 8.00 ppm
Ex amp 1e 2 5
3- (l,3-Benzodioxol-5-yl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-1-carboxamide, mp 223-227. 8.90 ppm (DMSO-d^)
Example 26
4- (4-Chlorophenyl)-N-( 2,3-dihydro-2,2-dimethylbenzofuran-5-y1) - 3-phenylpyrazo1ine- 1 -carboxamide. 8.00 ppm
Example 27
3,4-bis(4-Fluorophenyl)-N-(2,3-di hydro-2, 2-dimethylbenzofuran-5-y1)pyrazo1ine-1 -carboxamide , mp 161-166.
7.93 ppm
Example 28
3-(4-Chlorophenyl)-4-(4-fluorophenyi)-N-(2,3-dihydro2.2- dimethylbenzofuran-5-yl)pyrazoline-l-carboxamide, mp 169-171. 7.96 ppm
Example 29
3-(4-Chlorophenyl)-4-( 4-methylphenyl)-N-(2,3-di hydro2.2- dimethylbenzofuran-5-yl)pyrazoline-l-carbox amide, mp 137-139. 7.96 ppm *
Example 3Q
3- (4-Chlorophenyl)-4-(4-methoxyphenyl)-N-(2,3-dihydro2.2- dimethylbenzofuran-5-yl)pyrazoline-l-carboxamide, mp 182-186. 7.93 ppm
Example 31
4- (4-Fluorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-S-yl)-3-(4-methoxyphenyl)pyrazoline-l-carboxamide, mp 179-182. 7.93 ppm
Ex ample 3 2
4-(4-Chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-3-(4-methoxyphenyl)pyrazoline-l-carboxamide, mp 157-160. 7.96 ppm
-16Example 33
3-( 4-Difluoromethoxyphenyl)-4-(4-fluorophenyl)-N-( 2,3dihydro-2,2-dimethylbenzofuran-5-yl)pyra:oline-l-carboxamide, mp 169-172. 7.93 ppm
Example 34
- (4-Chlorophenyl)-3-(4-difluoromethoxyphenyl)-N-(2,3di hydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-1-carboxamide, mp 90-95. 7.93 ppm
Example 35
3-(4-Difluoromethoxyphenyl)-N-(2,3-di hydro-2,2,3,3tetrafluorobenzofuran-6-yl)-4-phenylpyrazoline-l-carboxamide, mp 152-137. 8.33 ppm
Ex amp 1e 36
3-(4-Difluoromethoxyphenyl)-4-(4-fluorophenyl)-N-(2,3d ihydro-2,2,3,3-tetrafluorobenzofuran-6-yl)pyrazoline1-carboxamide, mp 110-114. 8.33 ppm
Example 37
3-(4-Dif luoromethoxyphenyl)-4-( 4-fluorophenyl)-N-(2,3di hydro-2,2,3,3-tetrafluorobenzofuran-5-yl)pyrazoline1-carboxamide, mp 155-159. 8.20 ppm
Example 38
3- (4-Chlorophenyl)-N-( 2,2-dimethyl-l,3-benzodi ox ol- 5yl)-4-phenylpyrazoline-l-carboxamide, mp 182-186.
7.96 ppm '
Example 39
- (4-D i f luoromethoxyphenyl) -N-(2,2-dimethyl-l,3-benzodioxol-5-yl)-4-phenylpyrazoline-1-carboxamide , mp 148- 150.
7.93 ppm
Example 40 , 4-bi s(4-Chloropheny1) - N-( 2,2-dimethyl-l,3-benzodioxol-5-yD-pyrazoline-l-carboxamide, mp 168- 169.
7.93 ppm
Example 41
N - (l,4-Benzodioxan-5-yl)-3-( 4-difluoromethoxypheny1) 4- phenylpyrazoline-1-carboxamide. 7.93 ppm
AP 0 0 0 0 3 b BADOR'G'NAL
-17Ex amp 1 e 42
N-(2,2-Difluoro-l,3-ben zodioxol-5-yl)-3-(4-difluorome tnoxypheny1) - N -methyl - 4 -phenylpyrazol ine - 1-carboxamide , mp 110-114.
Ex ample 43
4-(1, 3-Benzodi ox ο 1 - 5-y1)-N-(4-phenoxyphenyl)-3-phenylpyrazoline-1-carboxaraide , rap 195- 197 . 8.03 ppm
Example 44
N-( 1,4-Benzodioxan-6-yl)-4-(4-chlorophenyl)-3-( 4-difluoromethoxyphenyl)pyrazoline-l-carboxamide, rap 124-128.
7.93 ppm
Example 45
3,4-bis(4-Chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-N-methylpyrazoline-1-carboxamide , rap 150-155.
Example .4(¾
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3,4-diphenylpyrazoline-1-carboxamide, rap 214-216. 8.83 ppm (CDCl3/DMSO-d6)
Example 4 7
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3,4-bis(4-fluorophenyl)pyrazoline-l-carboxamide, mp 178-180. 8.10 ppm
Example Afl
3-(4-Chlorophenyl)-N - ( 2,2-difluoro-1,3-benzodioxol-Sy1)-4 - (4 - f1uoropheny1)pyrazo1ine-1-carboxamide , mp 147-151. 8.06 ppm
Example 49 '
3-(4-Difluoromethoxyphenyl)-N-(2,3-dihydro-2,2,3,3tetrafluorobenzofuran-5-yl)-N-methyl-4 -phenylpyrazoline-l-carboxamide.
Example 50
3-(4-Chlorophenyl)-4-(4-difluoromethoxyphenyl)-N-(2,3dihydro-2,2-dimethylbenzofuran-S-yl)pyrazoline-l-carboxamide, mp 155-159. 7.96 ppm
Example 51
3- (4-Difluoromethcxyphenyl)-N-'2,3-dihydro-2,2-difluorobenzofuran-5-yl)-N-methy1-4-phenyIpyrazoline1-carboxamide.
Example 52
4- (4-Chloropheny1)-N-(2,2-dif1uoro-1,3-benzodi oxol-5yl)-3-(4-difluoromethoxyphenyl)pyra:oline-l-carboxamide. 8.06 ppm BAD ο^'θ
- i C Ex amp le 53
4-(l,3-3enzodioxol-5-yl)-5-(4-chlorophenyl)-N-[4-(4: luo romet ho xy pheno xy) phenyl jpyrazol i ne ·· 1 - c arboxami de.
Example 54
4-(l,3-Benzodioxol-5-yl)-N-[4-(4-chlcrophenoxy)phenylJ3- (4-chlorophenyl)pyrazoline-l-carboxamide.
Example 55
4- (1,3-3enzodioxol-5-yl)-3-(4-chloro p hen y 1)-,S'- (2,2-difiucro-1,3-benzodioxol-3-yl)pyrazoline-l-carboxamide.
Example 56
4-(l,3-Benzodioxol-S-yl)-3-(4-chlorophenyl)-N'-(2,3-dihyd ro-2,2,3,3-tet rafluorobenzof uran - 5 -y1)pyrazoli ne-1 carboxamide.
Example 57
4-(l,3-Benzodioxol-5-yl)-3-(4-chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzo£uran-5-yl)pyrazoline-l-carboxam i de.
Example 58
4-(1,3-Benzodioxol-5-yl)-N-[4-(4-difluoromethoxyphenoxy)phenyl]-3-(4-difluoromethoxyphenyl)pyrazoline-lcarboxami de.
Example .59
4-(l,3-Benzodioxol-3-yl)-N-[4-(4-chlorophenoxy)phenyl]3- (4 - difluoromethoxypheny1)pyrazoli ne -1 - carboxamide.
Example 60
4- (l,3-Benzodioxol-5-yl)-N-(2,2-difluoro-l,3-benzodioxol-5-yl)-3-(4-difluoromethoxyphenyl)pyrazoline-lc arboxami de.
Example 61 »
4- (1,3-Benzod i oxol- 5-y1) - 3-(4-d ifluoromethoxyphenyl)N-(2,3-dihydro-2, 2, 3, 3-tetrafluorobenzofuran-5-yl)pyrazoline-l-carboxamide.
Example 62
-(1,3-Benzod i oxol-5-y1) - 3-(4-d i fluo romethoxypheny1)N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline1 -c arboxami de.
Example 63
4-(1,3-Benzod ioxol-3-y1)-S-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)--3-phenylpyrazoline-l-carboxamide.
Example 64
4-(1,3-Benzodioxol-5-yl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-y1)-3-phenylpyrazoline-1-carboxamide.
APOOOO?
bad original
-19Example 65
4-(1,3-Ben:odioxol-5-yl)-N-(2,2-difluoro-l,3-benzodioxol-5-yl)-3-phenylpyrazoli ne-l-carboxamide.
Example 66
4-(1,3-Benzodioxol-S-yl)-N-[4-(4-difluororaethoxyphenoxy)phenyl]-3-phenylpyrazoline-l-carboxamide.
Example 67
4-(1,3-Benzodioxol-5-yl)-N-[4-(4-chlorophenoxy)pheny1]3- phenylpyrazoline-l-carboxamide.
Example 68
4- ( 2 , 2-Difluoro-l, 3-benzodioxol-5-yl) - N - [ 4-(4-difTuoro-·· methoxyphenoxv)phenyl]-3-(4-fluorophenyl)pyrazoline-lc arboxami de.
Example 69
N-(4-(4-Chlorophenoxy)pheny1)-4-(2,2-difluoro-l,3-benzodioxol- 5-yl)-.3-( 4-fluor op he nyl)pyrazoli ne-l-ca rboxami de .
Example 70
4,N-bi s(2,2-Difluoro-1,3-benzod ioxol- 5-y1) -3-(4-fluoropheny 1) pyra zol i ne-1 -carbox am i de .
Example 71
4- (2,2-Difluoro-l,3-benzodioxol-5-yl)-3-(4-fluoroΛ pheny1)-N-(2,3-di hyd ro-2,2 , 3,3-tetrafluorobenzofuran5- y1)pyra zoline-1-carboxamide .
Example 72
4-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3-(4-fluorophenv1)-N-(2,3-d ihyd ro-2,2-dimethylben:ofuran-5-y1)pyrazoline-l-carboxamide.
Example 73
4-(2,2-Difluoro-l,3-benzodioxol-5-yl)-N-[4-(4-difluoromethoxyphenoxy)pheny1)-3-phenylpyrazoline-1carbcxami de.
Example ,74
N-[4-(4-Chlorophenoxy)phenyl)-4-(2,2-difluoro-l,3benzodioxol-5-y1)-3-phenylpyrazoline-l-carboxamide.
03'°*^
-20Example 75
4,\-bis(2,2-2:iluoro-l,3-benzodioxol-3-yl)-3-phenyIpyraze line-1-carboxamide.
Example 76
4-(2, 2 -D i £ 1uoro-1,3-benzodi oxol-5-yl)-N-(2,3-di hydro 2,2,3,3-tetra£luorobenzofuran-5-yl)-3-phenylpyrazoline1 -carboxamide .
Example 77
- ( 2 , 2-Di £ luoro’-l , 3-ben:odi oxol - 5-y 1) - N- ( 2 , 3-dihydro2, 3-dimethylbenzofuran-3-yl)-3-phenylpyrazoline-lcarboxamide.
Ξχ amp 1e 78 4-(2,2-Dx£luoro-l,3-benzodioxol-5-yl)-N-[4-(4-di£luoromethoxyphenoxy)phenyl]-3-(4-difluoromethoxyphenyl)pyrazoline-l-carboxamxde.
Example 79
N- [ 4 - (4 - Chiorophenoxy)phenyl 3-4-(2,2-difluoro-1,3-benzodioxol-5-yl)-3-(4-dif1uoroaethoxyphenyl)pyrazoli ne -1 carboxamide.
Example 80
4,N-bxs(2,2-Di£luoro-l,3-benzodioxol-5-yl)-3-(4-di£luoromethoxyphenyl)pyrazoline-l-carboxamide.
Example 81.
4-(2,2-Difluoro-l,3-benzodxoxol-5-yl)-5-(4-di£luoromethoxyphenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzo£uran-5-yl)pyrazoline-l-carboxamide.
Example B2
4- (2,2-Difluoro-l,3-benzodioxol-S-vl)-3-(4-difluoromethoxyphenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran5- yl)pyra;oline-1-carboxamide.
Example 83
4-( 1,4-Ber.zodxexan - 5- y I)-3-(4-chloropher.y 1)-s-[4.(4. di£luoromethoxyphenoxy)phenyl]pyrazoline-l-carboxamide.
Example 84
4-(l,4-Benzodioxan-6-yl)-N-[4-(4-chlorophenoxy)phenyl] 3-(4 - chiorophenyl)pvrazol i ne-1-carboxamide.
AP 0 0 0 0 3 6 bad ORIGINAL
-21 Example p ς
4-(l,4-3enzodioxan-6-yl)-3-(4-chIorophenyl)-N-(2,2-difluc rο -1,3-benzodioxol-5-yl)pyrazoline-l-carboxamide.
Example 85
4-(l,4-Benzodioxan-6-yl)-3-(4-chloTophenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)pyrazoline-lcarboxamide.
Example 67
4-(1,4-Benzodioxan-6-yl)-3-(4-chlorophenyl)-N-(2,3-dihydre-2,2-dimethylben:ofuran-5-yl)pyrazoline-l-carboxami de .
Example 88
4-(l,4-3enzodioxan-6-yl)-N-[4-(4-difluoromethoxyphenoxy)phenyl]-3-(4-difluoromethoxyphenyl)pyrazoline-lcarboxamide.
Example 89
4-(1,4-Benzodioxan-6-yl)-N-[4-(4-chlorophenoxy)phenyl )3- (4 - di fluoromethoxypheny1)pyrazoline-1-carboxamide.
Example 90
4- (1,4-Benzod ioxan-6-yl)-N-(2,2-difluoro-1,3-bensodioxol-3-yl)-3-(4-d ifluoromethoxyphenyl)pyrazoline-lcarboxamide.
Example 91
4-(1,4-Benzodioxan-6-yl)-3-(4-difluoromethoxyphenyl)N-(2,3-di hydro-2,2,3,3-tetrafluorobenzofuran-5-yl)pyrazoline-l-carbox amide.
Example 52
4-(l,4-Benzodioxan-6-yl)-3-(4-difluoromethoxyphenyl)N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline1- carboxamide.
Example 93
4-( 1,4-3-.-. zodioxan- 6-y 1)-N-[4-(4-difluoromethoxyphenoxy)phenyl]-3-phenylpyrazoli ne-l-carboxamide.
Example gg
4-(1,4-Benzodioxan-6-y1)-N-[4-(4-chiorophenoxy)phenyl )3-phenylpyrazoline-1-carboxamide.
o«g'mN·
-22Example 95
4-(1,4-Benzodioxan-6-yl)-N-(2,2-difluoro-l,3-benzodioxol- 5-yl) - 3-phenylpyrazoline-1-carboxamide.
Example 95
4-(l,4-Benzodioxan-6-yl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)-3-phenylpyrazoline-1-carboxamide .
Example 97 .
4-(l,4-Benzodioxan-6-yl)-N-(2,3-di hydro-2,2-dimethylbenzofuran-5-yl)-3-phenylpyrazoline-l-carboxaraide.
Example 99
3-(1,3-Benzodioxol-5-vl)-N-[4-(4-difluoromethoxyphenoxy )phenyl]-4-(4-fluoropheny 1)- N-methy lpy razoline-1carboxamide .
Example 99
3-(1,3-Benzodioxol-5-yl)-N-[4 - (4-chlorophenoxy) phenyl ] 4 - (4-fluoropheny1)pyra zoli ne-1-carboxamide.
Example TOO
3-(1,5-Benzodioxol-S-yl)-N-(2,2-difluoro-1,3-benzodioxol-5-yl)-4-(4-fluorophenyl)pyrazoline-l-carboxamide.
Example 101
3-( 1 ,3-Benzodioxol-5-yl)-4-(4-fluorophenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-yl)pyrazoline-lcarboxamide.
Example 1Q2
3-(1,3-Benzodioxol-5-yl)-4-(4-£luoropheny1)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-1-carbox amide.
Example .103
3-(2,2-Difluoro-1,3-benzodioxol-S-yl)-N-[4-(4-difluoromethoxyphenoxy)phenyl]-4 - (4-fluoropheny1)pyrazoli ne -1 carboxamide.
Example JQ4
N-[4 - (4-Chiorophenoxy)phenyl ]-3-(2,2-di£luoro-l,3-benzodioxol-5-yl)-4-(4-fluorophenyl)-N-methylpyrazoline-lcarboxamide.
£ 0 0 0 0 dV
BAD ORIGINAL
-23Example 105
3,N-bis(2,2-Di£luoro-l,3-benzodioxol-$-yl)-4-(4-fluoropher.yl)pyra zol ine-1 - carboxamide.
Example 106
3-(2,2-Difluoro-l,3-benzodioxol-5-yl)-4-(4-fluoropheny1)-N-(2,3-di hydro-2,2,3,3-tetrafluorobenzofuran5-yl)pvrazoline-1-carboxamide.
Example JQ7
3-(2,2-Difluoro-l,3-benzodioxol-5-yl)-4-(4-fluorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-1-carboxamide.
Example 108
3-(1,4-Benzodioxan-6-yl)-N-[4-(4-difluoromethoxyphenox v)phenyl]-4-phenylpyrazoline-1-carboxamide.
Example 109
3- (l,4-Benzodioxan-6-yl)-N-[4-(4-chlorophenoxy)pheny1 ) 4- phenylpyrazoline-l-carboxamide.
Example 110
3-(1,4-Benzodioxan-6-yl)-N-(2,2-difluoro-l,3-benzodioxol-5-yl)-N-methyl-4-phenylpyrazoline-l-carboxamide.
Example ]11
3-(1,4-Benzodioxan-6-yl)-N-(2,3-dihydro-2,2,3,3-tetrafluo robenzof uran -5-y1)-4-phenylpvrazoline-1-carboxami de.
Example 112
-(1,4-Benzodioxan-6-y1)-N-(2,3-dihydro-2,2-dimethy1 ben:ofuran-5-yl)-4-phenylpyrazoline-l-carboxamide.
Example 113
N-1 4-(4-Difluoromethoxyphenoxy)pheny1]-3-(2,3-dihydro2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-l-carboxamide.
Example 114
N-(4-(4-Chlorophenoxy)phenyi]-3-(2,3-dihydro-2,2-dimethy lbenzofuran-5-yl)-4-phenylpyrazoline-l-carboxamide.
BAO 0«®NN-2<iEx amp 1 e 115
N - (2, L-Difluoro-1,3-benzodioxol-5-yl)-3-(2,3-dihydro2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-lcarboxamide.
Example 116
N- (2,3-Di hydro-2,2,3,3-tetrafluorobenzofuran-5-yl)-3(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-N-methy1-4phenylpyra:oline-l-carboxamide.
Example 117 , N-b i s(2,3-Di hyd ro-2,2-dimethylbenzofuran-5-yl)-4phenylpyrazoline-l-carboxamide.
Example 118
N - (2,2-Difluoro-l , 3-benzodioxol-5-y1)-4-(4-fluorophenyl)-3-(4-methylphenyl)pyra2oline-l-carboxamide.
Example 119
4-(4-rluorophenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluoroben:ofuran-5-yl)-3-(4-methylphenyl)pyrazoline-l-carboxamide.
Example 1 20
4-(4-Fluorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-N-methy1-3-(4-me thyIpheny1)pyrazoli ne-1 carboxamide.
Example 121
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-4-(3-fluoropheny 1 )-3-(4-methyIpheny1jpyrazoline-1-carboxamide..
Example 122
- (3 - Fluorophenyl)-N-(2,3-di hydro-2,2,3,3-tetrafluorobenzof uran -5-yl )-3 -(4- methyIpheny Dpyrazolinepl-carboxami de.
Example 123
4-(3-Fluoropheny1)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-3-(4-methylphenyl)pyrazoline-l-carboxamide. Example 124 ·
N- (2,2-Difluoro-l , 3-benzodioxol-5-yl)-4-(2-fluorophenyl)-3-(4-methylphenyl)pyrazoline-l-carboxamide.
Example 125
4-( 2-Fluorophenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran-5-y1)-3-(4-methyIphenyl)pyrazoline-l-carbox ami de.
Example 126
4-(2-Fluorophenv1)-N-(2,3-dihydro-2,2-dimethyl benzofuran-5-yl)-3-( 4-me thy Ipheny l)pyrazol ine-1-carbox am ide.
Example 127
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3-(3-fluoropheny l-4-(4-fl uorophenyl)-N-methylpyrazoline-l-carboxamide. BAD ORIGINAL
AP 0 0 0 0 3 6
-25Example 1 28 ?-(3-rIuorozhenyl)-4-(4-fluorophenyl)-N-(2,3-dihydro2,2, 5, 3 -te: ra£luo robenzof uran- 5-y1)pyrazol i ne -1 - car boxami de.
Example 1 25
3- (3-F1uoropheny1)-4 - (4 - f 1 uoropheny1)-N-(2,3-dihydro2.2- dimethylbenzofuran-5-yl)pyrazoline.-l-carboxamide.
Example 130
N-(2,2-Di£luoro-l , 3-benzodioxol-5-yl)-3-(2-fluorophenyl)-4-(4-fluorophenyl)pyrazoline-l-carboxamide.
Example 131
3-(2-Fluoropheny 1)-4-(4-fluoropheny1)-N-(2,3-dihyd ro2,2,3,3-tetrafluorobenzofuran-5-yl)-N-methylpyrazoline-l-carboxamide.
Example 132
3- (2-Fluorophenyl)-4-(4-fluorophenyi)-N-(2,3-dihydro2.2- dimethylbenzofuran-5-yl)pyrazoline-1-carboxamide.
Example 1 33
3.4- bis(4-Fluorophenyl)-N-(2,3-dihydro-2,2,3,3,7-penta£luorobenzofuran-5-yl)pyrazoline-1-carboxamide.
Example 134
4- (4-Chlorophenyl)-N-(2,3-dihydro-2,2,3,3, 7-pentafluorobenzofuran-5-yl)-3-(4-methylphenyl)pyrazoline1 - c arboxamide.
Example 735
N-(2,3-Dihydro-2,2,3,3,7-pentafluorobenzofuran-S-yl)3.4- diphenylpyrazoline-l-carboxamide.
Example 136
3-(4-Difluoromethoxyphenyl)-N-(2,3-di hyd ro-2,2,3,3,7pentafluorobenzofuran-5-yl)-4-phenylpyrazoline-lcarboxami de.
Example 137
3- (4-Chlorophenyl)-N-(2,3-dihydro-2,2,3,3,7-pentafluorobenzofuran-5-yl)-4-phenylpyrazoline-1-carboxami de .
Example 138
3.4- b i s ( 4 -F1uo rophenyl) -N - ( 2, 2,6-trimethyl-l,3-benzodioxol-5-yl)pyrazoline-l-carboxamide.
Example 139
4- (4-Chlorophenyl)-N-(2,2,6-trimethyl-1,3-benzodioxol 5- y1) - 3 - ( 4-me thylphenyl)pyrazoline-1-carboxami de.
Ex ample 1 4Π
N-(2,2,6-Trimethyl-l,3-benzodioxol-5-yl)-3,4-diphenylpyrazol;ne-l-carboxamide.
Example 141
- (4 -D iFluoronethoxyphenyl)-N-(2,2,6-1 r ime t hy1-1,3benzodioxol- 5 -y1)-4-phenylpyrazoli n e-1-carboxami de.
Example 142
3-(4 - Chioropheny1)-N - (2,2,6-trimethyl-1,3-benzodioxol3- yl)-4-phenylpyrazoline-l-carboxamide.
Example 143
3.4- bis(4-Fluorophenyl)-N-(7-methoxy-2,2-dimethyl-l,3benzodioxol-5-yl)pyrazoline-l-carboxamide.
Example 144
4- (Chloropheny1)-N-(7-met hoxy-2,2-dimethy1-1,3-benzodiox ol-S-yl)-3-(4-me thy Ipheny l)pyrazoline-l-carbox amide.
Example 145
N-(7-Methoxy-2,2-dimethyl-l,3-ben:odioxol-5-yl)-3,4diphenylpyrazoline-l-carboxamide.
Example 146
3-(4-Difluoromethoxypheny1) -N-(7-methoxy-2,2-dimethyl1, 3-benzodioxol-5-yl)-4-phenylpyrazoline-l-carboxamide.
Example 147
3- (4-Chlorophenyl)-N-(7-methoxy-2,2-diraethyl-l,3-benzodioxol-5-yl)-4-phenylpyrazoli ne-1-carboxamide.
Example 148
3.4- bi s(4-Fluorophenyl)-N-[2,2-dimethyl-7-(l-methylethy1)-1,3-benzodioxol-5-yl]pyrazoline-l-carboxamide.
Example 149
4- (4-Chlorophenyl)-N-[2,2-dimethy1-7-(1-methylethyl) 1.3- benzodioxol-5-yl]-3-(4-methylpheny1)pyrazoline-1- .
carboxami de.
Example 150
N-l2,2-Dimethyl-7-(l-methylethyl)-l,3-benzodioxol-5yl]-3,4-diphenylpyrazoline-l-carboxamide.
Example 151
3-(4-Di£luoromethoxyphenyl)-N-[2,2-dimethyl-7-(lmethylethy1)-1,3-benzodioxol-5-ylJ-4-phenylpyrazoline-l-carboxamide.
Example 152
3-(4-Chlorophenyl )-N-[2,2-dimethyl-7-(l-methylethyl)1.3- benzodioxol-5-yl]-4-phenylpyrazoline-l-carboxamide.
AP 0 0 0 0 3 6 BADOFUG'NAL S
-27Example 155
3.4- bis(4-Fluorophenyl)-N-(2,3-dihydro-7-ethyl-2,2,3,3tetrafluorobenzofuran-5-yl)pyra:oline-l-carboxamide.
Example 154
4-(4-Chlorophenyl)-N-(2,3-dihydro-7-ethyl-2,2,3,3tetraf luorobenzofuran-5-yl)-3-(4-methy Ipheny Dpyrazoline-l-carboxamide.
Example 155
N-(2 ,3-Dihydro-7-ethyl-2,2 ,3,3-tetrafluorobenzofuran-Sy1)-3,4-diphenylpyra:oline-l-carboxamide.
Example ..) 5^
- ( 4-Di: luorome thoxypheny1)-N-(2,3-di hydro-7-ethy1 2,2,3,3-tetrafluoroben:ofuran-3-yl)-4-phenylpyrazo1:ne-l-carboxamide.
Example .1 57
3- (4-Chlorophenyl)-N-(2,3-di hydro- 7-ethv1-2,2,3,3tet rafluorobenzofuran-5-y1)-4-phenylpyrazoli ne-lcarboxamide.
Example .158
3.4- bi 5(4-FIuoropheny1)-N-(2,3-dihydro-7-dif1uoromethcxv-2,2-dimethylbenzofuran-5-yl)pyrazol ine-l - carboxamide . '
Example 159
4- (4 -Chlorophenyl)-N- (2,3-dihydro-7-difluoromethoxy2 , 2 - di me thy Iber.zof uran - 5 -y 1) - 3 - ( 4 -me thy Ipheny 1 )py razoline-1-carboxamide.
Example 16 C
N-(2,3-Dihydro-7-difluoromethoxy-2,2-dimethylbenzofuran-3-y1)-3,4-diphenylpyrazoline-l-carboxamide.
Example 151
- ( 4 - D i f 1 u 0 r 0 m e t h 0 x y p n e n y 1 ' - N - ' 2, 3 - d i h ··. :ro--d:fl'Joromethoxy-2,2-dimethylben:ofuran-5-yl;-4-phenylpyra:oline-1-carboxamide.
Example 162
3-(4 -Chlorophenyl)-N-(2,3-dihydro-7-difluorooethoxy2, 2-dimethylben:ofuran-5-yl)-4-phenylpyrazoline-1carboxamide.
Example 163
N-(7-Chloromethyl-2,2-dimethyl-l,3-benzodioxol-5-yl)3.4- bis(4-fluorophenyl)pyrazoline-l-carboxamide.
Example 164
N - ( 7-Chloromethyl-2, 2-dfmethyl-l, 3-benzodioxol-S-yl)4 - ( 4-chiorophenyl)-3-(4-me thylphenyl)pyrazoline-lcarboxamide.
Example 165
N-(7-Chloromethyl-2,2-dimethyl-l,3-benzodioxol-5-yl)3.4- diphenylpyrazoline-l-carboxamide.
Example 166
N- (7-Chloromethy1 - 2,2-dimethyl-1,3-benzod i oxol- 5-y1 ίο - ( 4 -d i £ luo rome thoxypheny 1) - 4 -pheny lpv razol i ne -1 carboxamide.
Example 167
N-(7-Chloromethyl-2,2-dimethyl-l,3-benzodioxol-5-yl)3-(4-chlorophenyl)-4-phenylpyra:oline-l-carboxamide.
Example 168
N-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)-3-[7-(lmethylethy1)-2,2-dimethyl-l,3-ben:odioxol-3-y1] - 4 phenylpvrazoline-l-carboxamide.
Example 169
N-(2,3-Dihydro-2,2-dimethylben:ofuran-5-yl)-3-(7methoxy- 2,2-dimethyl-l,3-benzodioxol-5-yl)-4-phenylpyrazoline-l-carboxamide.
Example 170
N-(2,3-Dihydro-2,2-dimethylbenrofuran-S-yl)-3-(7£ 1uoro- 2,2-d ime thyl-1,3-benzod i oxol- 5-yl) -4-pheny1 pyracoline-l-carboxamide.
£ 0 0 0 0 dV badorig'nW- S
-29Example 171
N-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)-3-(7-difluoromethoxy-2,2-dimethyl-l,3-benzodioxol-5-yl)-4phenylpyrazoline-l-carboxamide.
Example 172
S-(2,2-Difluoro-l,J-benzodioxol-5-yl)-3-(4-fluorophenyl)-4-(2,3-di hydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-l-carbox amide.
Example 173
N-(2,2-Difluoro-l,3-benzodioxol-5-yl)-3-(4-fluoropheny1) - 4 - (2,3-d ihydro-2,2,3,3-tet rafluorobenzofuran-5 y1)pyrazoli ne-1-carboxami de.
Fxample 174 '
3-(7-Chloromethyl-2,2-dimethyl-l)5-benzodioxol-5-yl)4,N-bis(4-fluorophenyl)pyrazoline-1-carboxamide.
Example 175
N - ( 2 , 3-Dihydro-2,2-dimethylbenzofuran-5-yl)-4-(7-(lmethylethy1)-2,2-dimethy1-1,3-ben:odioxo’-5-yiJ-5phenylpyrazoline-l-carboxamide.
Example 175
N - { 2 , 3-Di hydro - 2 , 2 - di methylbenzof uran - 5 - v 1' - 4 - f ’-me t h cxy- 2,2-d imethy 1 -1 , 3-ben:odi oxol-3-y Γ; -5-phenyipyrazo· 11ne-1-carboxamide.
-30Examp le 177
N- (2,3-Di hydro-2,2-dimethylbenzofuran-5-yl)-4-(7fluoro-2,2-dimethyl-l,3-benzodioxol-5-yl)- 3-pheny 1 pyrazoline-l-carboxamide.
Example 178
N-(2,3-Dihydro-2 ,2-d imethy1 benzofuran-5-y1)-4-(7-difluoromethoxy-2,2-dimethyl-l,3-benzodioxol-5-yl)-3phenylpyrazoline-l-carboxamide.
Example 179
4-(7-Chlororoethyl-2,2-dimethyl-l,3-benzodioxol-5-yl)3,N-bis(4-fluorophenvl)pyrazoline-l-carboxamide.
In the normal use of the insecticidal pyrazolines of the present invention, the pyrazolines usually will not be employed free from admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an insecticidally effective amount of pyrazoline. The pyrazolines of this invention, like most pesticidal agents, may be blended with the agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of an insecticide may affect the activity of the material. The present pyrazolines may be applied, for example, as sprays, dusts, or granules to the area where pest control is desired, the type of application varying of course with the pest and the environment. Thus, the pyrazolines of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concent rates, as solutions, and the like.
Granules may comprise porous or nonporous particles, such as attapulgite clay or sand, for example, which serve as carriers for the pyrazolines. The granule particles are relatively large, u diameter of
AP 0 0 0 0 3 6
BAD ORIGINAL £
-31 about 400-2300 microns typically. The particles are either impregnated with the pyrazoline from solution or coated with the pyrazoline, adhesive sometimes being employed. Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient as the insecticidally effective amount.
Dusts are admixtures of the pyrazolines with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyl1ite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as carriers for the insecticide. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful for controlling insects contains 1 part of pyrazoline, such as 3-( 4-chlorophenyl)-N-[4-(4-chlorophenoxy)phenyl]-4-phenylpyrazoline-l - carboxamide, and 99 parts of talc.
The pyrazolines of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids and into solid concentrates by admixture with talc, clays, and other known solid carriers used in the pesticide art. The concentrates are compositions containing, as an insecticidally effective amount, about 5-50% pyrazoline, such as 3-(4-chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-l-carboxamide, and 95-50% inert material, which includes surface-actιve dispersing, emulsifying, and wetting agents, but even higher concentrations of active ingredient may be employed experimentally. The concentrates are diluted with water or other liquids for practical application as sprays, or with additional solid carrier for use as dusts.
-32Typ ical carriers for solid concentrates (also called wettable powders) include fuller’s earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents. A solid concentrate formulation useful for controlling insects contains l.S parts each of sodium 1ignosulfonate and sodium laurylsulfate as wetting agents, 25 parts of 3-(4-chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)4 - (4-chiorophenyl)pyrazoline-1 -carboxamide, and 72 parts of attapulgite clay.
Manufacturing concentrates are useful for shipping low melting products of this invention. Such concentrates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on cooling to the freezing point of the pure product or below.
Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water or other liquid carriers. They may consist entirely of the pyrazoline with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively nonvolatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated.
Typical surface-active wetting, dispersing, and emulsifying agents used in pesticidal formulations include, f'or example, the alkyl and alkylarv] sulfonates and sulfates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated
APO 0 0 0 3 6
BAD origin- &
-3 3petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition products of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises about 1-15% by weight of the insecticidal composition.
Other useful formulations include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone or other organic solvents.
An insecticidal 1y effective amount of pyrazoline in an insecticidal composition diluted for application is normally in the range of about 0.001¾ to about 8¾ by weight. Many variations of spraying and dusting compositions known in the art may be used by substituting the pyrazolines of this invention into compositions known or apparent in the art.
The insecticidal compositions of this invention nay be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc. In using the compositions to control insects, it is only necessary that an insecticida 11y effective amount of pyrazoline be applied to the locus where control is desired. Such locus may, e.g., be the insects themselves, plants upon which the insects feed, or the insect habitat. When the locus is soil, e.g., soil in which agricultural crops are or will be planted, the active compound may be applied to and optionally incorporated into the soil. For most applications, an insecticidallv effective amount will be about ~5 to 4000 g per hectare, preferaoly 150 g to 3000 g per hectare.
-34The insecticidal activity of the pyrazolines whose preparation is described above was evaluated as f ollows;
The compounds were tested in foliar applications at various concentrations in aqueous solutions containing 101 acetone and 0.251 octyl phenoxypolyethoxy ethanol. Pinto bean plants were placed on a revolving turntable in a hood, and the test solutions were applied with a sprayer. The test solutions were applied to the upper and lower surfaces of the plant leaves to runoff. The plants were then allowed to dry and were severed at the base of the stem. Each stem was inserted through a paper cup into water. Ten individuals of the appropriate insect species were placed in each cup and the cup covered.· The evaluation used southern armyworm (Spodoptera eridania). Mexican bean beetle ( Epilachna vari vesti s), beet armyworm (Spodoptera ex igua), and cabbage looper (Trichoplusia ni). After 4 days at 26°C and 501 RH mortality was read. The results of the tests appear in Table 1. Insect mortality was generally less if the tests were read much earlier.
A number of the pyrazolines were also active against southern corn root worm larvae (Di abrot i ca undecimpunctata howardi Barber) when applied to the soil, and those tested were also very effective on Colorado potato beetle (Lept i nota ra decemlineata Say).
£ 0 0 0 0 dV bad original Q
-35Table 1
Foliar Evaluation
Rate
Insects (¾ Kill)
pound (ppm) MBB BAW CL
1 500 100 100
2 500 100 100
3 500 100 100
4 500 100 100
5 2 50 1 00 87 100
6 500 70 6 5 90
/ 500 100 50 90
δ SOC 100 85
G 500 90 70
10 500 100 35
11 500 85 15
12 500 100 100
1 3 500 93 50 90
14 500 100 100
1 3 500 100 90
16 500 100
1 ~ SOC 100 3 5
18 500 90 * » 5 5
19 500 100 100
20 50 2 8 0 4 C
21 50C 70 15
? 2 500 100 100
Table 1 (Continued)
Foliar Evaluation
Rate
Compound (ppm)
Insects ( % Kill)
MBB SAW BAW CD
500
30
24 250 95 100
25 500 30 75
26 500 80 6 5
5 00 75 93
28 500 95 90
29 500 10 90
30 300 5 64 60
31 500 5 6 5 70
32 500 100 50
33 500 100 80
34 500 10 75
3 5 500 100 100
36 8 100 98 4 3 90
3^ 52 98 98 s* 1 00
38 500 95 80
39 500 100 23
40 500 100 100
41 128 95 70
4 2 1 2 S 93 10C
-37Rate
Compound (ppm)
43 500
44 500
4 5 - 32
46 500
4 ‘ 500
48 8
49 500
50 500
SI 100
52 500
53 500
5 4 500
5 5 500
5 6 500
5 7 250
58 500
5 9 500
60 200
61 32
6 2 500
6 3 500
64 500
Table 1 (Continued)
Foliar Evaluation
Insects
ΗΈΈ-57W
100 100
100 100
100 100
30 40
5 10
100 100
100 100
100 100
40 60
100 95
100 10
100 83
100 80
100 100
100 1 00
100 40
100 1 00
100 60
45 100
9 5 9 5
100 95
100 100
(¾ Kill)
-ΕΆΕ—
100
00
ET
100
-33Table 1 (Continued)
Foliar Evaluation
Rate Insects_(I Kill)
Compound (ppm) MBB SAW
6 5 500 100 100
66 500 100 100
67 500 85 95
68 500 100 0
69 8 1 00 60
70 500 100 100
71 200 60 10
72 200 100 30
73 500 1 00 90
74 500 100 80
75 200 100 4 5
76 200 95 100
' / 500 80
200 0 95
Ί 500 90 5 5
79 200 95 60
SO 500 1 00 100
81 250 100 100
82 128 100 90
83 250 85 100
84 1 00 100 90
S 5 200 100 100
CL
100
AP 0 0 0 0 3 6
Table 1 (Continued)
Foliar Evaluation
Rate Insects (% Kill)
Compound (ppm) MBB BAW CL
86 16 95 95 40 100
87 500 100 100
88 100 100 25 10 85
89 200 100 100
90 1 6 100 1 00 100 90
91 32 100 100 100 100
92 500 100 100
93 500 100 100 -
94 500 100 100'
93 200 100 90
96 32 100 100 85 95
5 8 100 100 83
9S 16 100 40 5 3 80
9 9 16 100 100 90 83
100 32 100 1 00 10C 100
1 01 1000 100 100
1 0 2 128 100 100
103 16 90 95 15 100
105 · 16 100 100
1 0 6 236 100 '0
10' 1000 43 0
10S 1000 100 7 5
-40Table 1 (Continued) Foliar Evaluation
Rate Insects (I Kill)
Compound (ppm) MBB SAW %AW
109 1000 0 0
no 1000 70 0
111 1000 0 0
112 1000 100 90
11 3 1000 100 10
114 1000 100 50
113 1000 100 13
11 6 500 100 100
11 7 500 55 0
118 500 100 1 100
119 500 100 95
120 300 100 100
1 21 500 93 100
122 64 100 100
123 64 15 0
124 64 100 100
1 25 64 100 100
MB3 = SAW = BAW = r T = Mexican bean beetle southern armyworm beet armyworm cabbage looper
AP 0 0 0 0 3 6

Claims (9)

Claims:
1. An insecticidal pyrazoline characterized by the formula wherein
R, is of the formula A in which R' A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or is of the fozcrila in which X is a bridge of the formula 10CR'AAR'AB’a' wherein a is 1-3, a' is 0 or 1, a + a' is at least 2 but no greater than 3. R' AA and R’Ag are independently selected from hydrogen, halogen and lower alkyl, and R
AC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
-42R_ is a 4- or
S-substituent of the f o rmula
-\^ (hi) R B in which R'^ is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower haloalkyl ; or Rg is of the formula in which Y is a bridge of the formula <°-<CR' BAR’ BB’b-S·1 wherein b is 1-3, b' is 0 or 1, b+b' is at least 2 but no greater than 3, R'an^
R'gg are independently selected from hydrogen, halogen and lower alkyl, and R/gC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
is of the formula
AP 0 0 0 0 3 6 in which R^ is selected from hydrogen and lower alkyl; Rg is selected from lower alkyl.hydrogen, halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRpR^ wherein
-43Rg and R^ are independently lower alkyl, and is lower alkyl and n is
SO R.. wherein R„ η Η H
0or Ec is ol
~.e fo:
CC (VI) in which Z is a bridge of the formula '0-'CR' CAR' Cb’c-°C ' 1 wherein c is 1-3, c' is 0 or 1, c + c' is at least 2 but no greater than 3, R'and R'gg are independently selected from hydrogen, halogen and lower alkyl, with the proviso that R'and R'are not both hydrogen when c is 1 and c' is 1, and R' is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl ; provided that when R^ is a compound of group I and Rg is e compound of group III, R^ is not a compound of group V;
R^ is hydrogen or lower alkyl; and
V and W are independently oxygen or sulfur.
2 5. 5-(4-Difluoromethoxypheny1)-4-(4 -fluorophenyl )-N-(2,3-dihydro-2,2-dimethylbenzofuran-S-yl)pyrazoline -1-carboxamide, a compound of claim 1.
24. 4-(4-Chlorophenyl)-3-(4-difluoromethoxypheny1)-N-(2,3-dihydro-2,2-dimethylbenzo£uran-5-yl)pyrazoline-1-carboxamide, a compound of claim 1.
BA0 owe»·”-
-46?5. An insecticidal composition characterized by having in admixture with an agriculturally acceptable carrier an insecticida 1ly effective amount of at least one insecticidal pyrazoline of the formula wherein
R. is of the formula A
R* (I) in which R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or R^ is of the fomula
AP 0 0 0 0 3 6 in which X is a bridge of the formula
AB a wherein a is 1-3, a' is 0 or 1. a+a' is at least 2 but no greater than 3. R AA and R’Ag are independently selectee from hydrogen, halogen and lower al<· ?., and R'
BAD ORIG,nAL
-ύ,Ίis selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
Rd is a 4- or 5-substituent of the formula
D
R' (m) in which R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower haloalkyl; or is of the formula
BC (n) in which Y is a bridge of the formula [O-(CR’BAR’BB)b-Ob,] wherein b is 1-3, b' is 0 or 1, b + b' is at least 2 but no greater than 3, R'ba and R'BB are independently selected from hydrogen, halogen and lower alkyl, and R is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
Rq is of the formula
BC
E.
(V)
V
-48in which is selected from hydrogen and lower alkyl; Rp is selected from lower a 1 ky 1 , hydros®.''., halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRpR^ wherein Rp and Rr are independently lower alkyl, and b
-SO R.. wherein Ru is lower alkyl and n is η π π in which Z is a bridge of the formula (O-(CR'caR
Ce’c'h wherein c is 1-3, c' is 0 or 1, c + c' is at least 2 but no greater than 3, R'^ and R'cg are independently selected from hydrogen, halogen and lower alkyl, with the proviso that R'qa and R’^g are not both hydrogen when c is 1 and c’ is 1, and R'^is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl; provided that when R^ is e compound of group I end Rg is a compound ->f group III,
Rq is not a compound ?f group V:
R^ is hydrogen or lower alkyl; and
V and W are independently oxygen or sulfur.
AP 0 0 0 0 3 6
26. A composition of claim 27 characterized i n that W is oxygen. 2 7. A composition of claim 27 characterized in that R ' & is halogen or lower haloalkoxy. 28. A composition of claim 27 characterized i n that rb is a 4-substituent. 25. A method of controlling insects which charac- te r i zed bv applying to the locus where control is desi red
an insecticidally effective amount of pyrazoline of the formula B // where i n
R, is of the formula A in which R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower haloalkyl; or R^ is of the form :1a in which X is a bridge of the formula ί0-(CR'A.R’ e) -0 AA AB a a wherein a is 1-3, a' is 0 or 1, a+a' is at least 2 but no greater than 3, R' AA and R’Ag are independently selected from hydrogen, halogen and lower alkyl, and R' is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
Rn is a 4- or 5-substituent of the formula
D in which R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower haloalkyl; or Rg is of the formula in which Y is a bridge of the formula (O-(CR
BAR' BB-’b
AP 0 0 0 0 3 6 wherein b is 1-3, b' isO or 1, b+b' is at least 2 but no greater than 3, R'and R'gg are independently selected from hydrogen, halogen and lower alkyl, and R'fi is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
R(. is of the formula in which R^ is selected from hydrogen and lower alkyl; Rg is selected from lower alkyl, hydro halogen, lower alkoxy, lower haloalkoxy, lowe r haloalkyl, cyano, nitro, -NR,_RG wherein
-ΞΙ Rp and
-SO R n
Rg are independently lower alkyl, and wherein R^ is lower alkyl and n is
0- 2 ; or the formula R *
CC (7-) in which Z is a bridge of the formula [0-(CR ' R' ) -0 CA CB c c wherein c is 1-3, c' is 0 or 1, c+c' is at least 2 but no greater than 3, R'and R'£B are independently selected from hydrogen, halogen and lower alkyl, with the provi so that R' CA and R'eg are not both hydrogen when c is 1 and c' is 1, and R'^-q is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl; provided that when is a compound of group I and R^ is a compound of group III,
Rq is not a compound of group V;
R^ is hydrogen or lower alkyl; and V and W are independently oxygen or sulfur.
32. A process for producing an insecticidal pyrazoline characterized by reacting a compound of the formula
RC-N=C=W with a compound of the formula
B bad origin^ and optionally alkylating the product to produce an insecticidal pyrazoline of the formula whe re i n
R. is of the formula A
W in which R'A is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower
AC (Π) in which X is a bridge of the formula [o-(cr'aar'
AB^a’°a
AP O 0 0 0 3 6 wherein a is 1-3, a' is 0 or 1, a+a' is at least 2 but no greater than 3, R' AA and R'ab are independently selected from hydrogen, halogen and lower alkyl, and R'A(~ is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
bad original
-53RB is a 4 - or
2 1. 4-(4-Chlorophenyl)-N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)-3-phenylpyrazoline-l-carboxamide, a compound of claim 1.
22. 3-(4-Chlorophenyl)-4-(4-fluorophenyl)-N-(2,3dihydro-2,2-dimethylbenzofuran-5-yl)pyrazoline-l-carboxamide, a compound of claim 1.
2 0. 3-(4-Difluoromethoxyphenyl)-4-(4-fluoro-, phenyl)-N-(2,3-dihydro-2,2,3,3-tetrafluorobenzofuran6- yl)pyrazoline-l-carboxamide, a compound of claim 1.
2,2-dimethylbenzofuran-5-yl)-4-phenylpyrazoline-lcarboxamide, a compound of claim 1.
11. 3,4-bis(4-Fluorophenyl)-N-(2,3-dihydro2, 2,3,3-tetrafluorobenzofuran-5-yl)pyrazoline-l-carboxamide, a compound of claim 1.
12. 3,4-bis(4-Fluorophenyl)-N-(2,3-dihydro-2,2dimethy.lbenzofuran-5-yl)pyrazoline-l-carboxamide, a compound of claim 1.
13. N-(2,3-Dihydro-2,2,3,3-tetrafiJoroben:ofuran5 - y 1)-3-(4-difluoromethoxyphenyl)-4-phpnvlpyrazoline-lcarboxamide, a compound of claim 1.
14. N - ( 2, 2-Difluoro-l, 3- benzodiox·; · -S-yl)-3-(4-dif luoromethoxyphenyl)-N-methyl-4-phenyIp <razo 1ine-1-carboxamide, a compound of claim 1.
2.2- dif1uoro - 1,
2. A compound of claim 1 characterized i n that W i s oxygen. 3. A compound of claim 1 character!zed i n that R ' A is halogen or lower haloalkoxy. 4. A compound of claim 1 charac te r i zed i n that rb is a 4-substituent. S. A compound of claim 1 characterized i n that is of the formula
o:
3-benzodioxo 1 - 5-y 1, and 2,2-dimethy11.3- benzodioxol-5-yl.
4-Difluoromethoxyphenyl)-N-(2,3-dihydroΛ
5-substituent of the formula (:n) in which R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower
BC (Γ7) in which Y is a bridge of the formula 1°-(CR'BAR'BB)b-°b'! wherein b is 1-3, b' is 0 or 1, b+b' is at least 2 but no greater than 3, R'gA and R’gg are independently selected from hydrogen, halogen and lower alkyl, and B'g^ is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl ;
Rg is of the formula in which Rg is selected from hydrogen and lower alkyl; Rg is selected from lower a 1 kyl, by'5 halogen, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRgRg wherein
-5ώR are independently lower alkyl, and G wherein Ru is lower alkyl and n is Π
Rp and
-SO Ru η H
0- 2 ; or • (H) in which Z is a bridge of the formula (0-(CR'caR
CB^c •o . 1 wherein c is 1-3, c' is 0 or 1, c + c’ is at least 2 but no greater than 3, R'^^ and R'cg are independently selected from hydrogen, halogen and lower alkyl, with the proviso that and R'^g are not both hydrogen when c is 1 and c' is 1, and R'cc is selected from hydrogen,' halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl ; provided that when R^ is e comp?and of group I and Bj is a compound of group III, RCis noa conPound of group V;
R^ is hydrogen or lower alkyl; and
V and b are independently oxygen or sulfur.
AP 0 0 0 0 3 6
BAD ORIGINAL £
ANNEX
Abstract :
Pyrazoline Insecticides
Pyrazolines of the following formula are insecticides:
where i n
R^ is of the formula in which R'a is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower alkynyloxy and lower formula
AC (rz) in which X is a bridge of the formula [0(CR' R’ ) -0 AA AB a a wherein a is 1-3, a’ is 0 or 1, a>a' is at least 2 but no greater than 3, R'AA and R’Ag are independently selected from hydrogen, halogen and lower alkyl, and R'Aq
in which is selected from hydrogen and lower alkyl, and R^ is selected from '·.·-<r?go halogen, lower alkyl, lower alkoxy, lower haloalkoxy, lower haloalkyl, cyano, nitro, -NRpR^ wherein Rp and R^. are independently lower alkyl, and -SO Ru wherein R„ is lower in which 2 is a bridge of the formula 1 °-' CR ' CAR ’ CB’c-°C ·
6. A compound of claim 5 characterized in that is halogen.
of» ,0»^
7. A compound of claim 1 characterized in that Rc is of the formula or is selected from 2,3-dihydro-2,2-dimethylbenzofuran-5-yl, 2, 3-d ihydro-2,2,3,3-tetrafluorobenzofuran5-yl, 2,3-d i hyd ro-2,2,3,3-te t rafluorobenzof uran-6-y1,
8^3 owe»’1*''- &
-4515. 3,4-bi s(4-Chlorophenyl)-N-(2,2-di me thy1-1,3benzodioxol-5-yl)pyrazoline-l-carboxamide, a compound of claim 1.
16. N-(2,2-Difluoro-1,3-benzodioxol-5-yl)-3,4-bi s(4-f1uorophenyl)pyrazoline-1-carboxamide, a compound of claim 1.
17. 3-(4-Chlorophenyl)-N-(2,2-d i fluoro- 1,3-benzodioxol-5-y 1) - 4- (4-fluorophenyl)py ra zoline-1-carboxamide, a compound of claim 1.
18. 3-(4-Difluoromethoxypheny1)-N-(2,3-dihydro2,2,3,3-tet rafluorobenzof uran-5-yl)-N-methyl-4-phenylpyrazoline-1-carboxamide , a compound of claim 1.
19 . 3-(4-Difluoromethoxyphenyl)-4-(4-fluorophenyl)-N-(2,3-di hydro-2,2,3,3-tetrafluorobenzofuran5- y1)pyrazoline -1 -carboxamide, a compound of claim 1.
8. A compound of claim 1 characterized in that is of the formula
H
AP 0 0 0 0 3 6
9. A compound of claim 8 characterized in that Rg is lower haloalkoxy.
10. 3-(
9 £ 0 0 0 0 dV wherein c is 1-3, c’ is 0 or 1, c + c' is at least 2 but no greater than 3, R'CA and R'are independently selected from hydrogen, halogen and lower alkyl, and R1 is selected from hydrogen, halogen, lowe.r alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl; provided that when 3. is a co-.rcur.d
f.
lTJ’i? I snl Rgis a oompoO-.h of g~o;? {[I, ~ £ of group V;
R^. is hydrogen or lower alkyl; and
V and W are independently oxygen or sulfur.
BAD OBK3|NAU
1603Y30097V09jd is selected from hydrogen, alkyl, lower alkoxy, lower lower haloalkyl;
is a 4- or 5 - substituent of ha 1 ogen, 1 owe r haloalkoxy, and the formula (ii in which R'g is selected from hydrogen, halogen, lower alkyl, lower alkoxy, and lower haloalkyl; or Rg io o~ l·;
in which Y is a bridge of the formula t0-tCR’BAR‘BB’b-°b' 1 wherein b is 1-5, b' is 0 or 1, b+b' is at least 2 but no greater than 3, R' and R'gg are independently selected from hydrogen, halogen and lower alkyl, and R’
BC is selected from hydrogen, halogen, lower alkyl, lower alkoxy, lower haloalkoxy, and lower haloalkyl;
R,- is of the formula
APAP/P/1985/000014A 1984-10-25 1985-10-23 Pyrazoline insecticides AP36A (en)

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US66467484A 1984-10-25 1984-10-25
US70962685A 1985-03-08 1985-03-08
US77972185A 1985-09-24 1985-09-24

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AU (1) AU556949B2 (en)
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CS (1) CS252497B2 (en)
DE (1) DE3537884A1 (en)
DK (1) DK487885A (en)
EG (1) EG17848A (en)
ES (1) ES8701757A1 (en)
FR (1) FR2572400A1 (en)
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DE3545786A1 (en) * 1985-12-21 1987-06-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides
EP0300692A1 (en) * 1987-07-17 1989-01-25 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines
AU1993988A (en) * 1987-07-17 1989-02-13 E.I. Du Pont De Nemours And Company Insecticidal pyrazolines
JPH04501108A (en) * 1988-09-22 1992-02-27 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー Substituted indazole arthropodicides
JPH05112556A (en) * 1991-10-18 1993-05-07 Nippon Bayeragrochem Kk Insecticidal pyrazolines
US5684041A (en) * 1996-02-01 1997-11-04 The Procter & Gamble Company Dihydrobenzofuran and related compounds useful as anti-inflammatory agents
CN116265457B (en) * 2021-12-17 2024-09-03 湖南化工研究院有限公司 N-oxa condensed ring amide compound and preparation method and application thereof

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US4174393A (en) * 1975-07-09 1979-11-13 Duphar International Research B.V. 1,3,4-Substituted pyrazoline derivatives
CA1075242A (en) * 1974-07-12 1980-04-08 N.V. Philips Gloeilampenfabrieken 1,3,4-substituted-.delta.2-pyrazoline compounds
CA1111048A (en) * 1976-01-09 1981-10-20 Jan J. Van Daalen 1,3,4 substituted pyrazoline derivatives
US4407813A (en) * 1981-02-17 1983-10-04 Nissan Chemical Industries Ltd. Insecticidal pyrazoline derivatives and composition

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BE795264A (en) * 1972-02-09 1973-08-09 Philips Nv NEW PYRAZOLINE COMPOUNDS WITH INSECTICIDAL ACTIVITY
DE3064749D1 (en) * 1979-07-03 1983-10-13 Duphar Int Res New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal composition on the basis of these new compounds
GB2093836B (en) * 1981-02-17 1984-09-05 Nissan Chemical Ind Ltd Insecticidal pyrazoline derivatives
EP0113213B1 (en) * 1982-12-30 1988-04-06 Schering Agrochemicals Limited Pyrazoline insecticides

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CA1075242A (en) * 1974-07-12 1980-04-08 N.V. Philips Gloeilampenfabrieken 1,3,4-substituted-.delta.2-pyrazoline compounds
US4174393A (en) * 1975-07-09 1979-11-13 Duphar International Research B.V. 1,3,4-Substituted pyrazoline derivatives
CA1111048A (en) * 1976-01-09 1981-10-20 Jan J. Van Daalen 1,3,4 substituted pyrazoline derivatives
US4407813A (en) * 1981-02-17 1983-10-04 Nissan Chemical Industries Ltd. Insecticidal pyrazoline derivatives and composition

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GB2166137A (en) 1986-04-30
AU556949B2 (en) 1986-11-27
IT1203596B (en) 1989-02-15
CN1004272B (en) 1989-05-24
RO92966A (en) 1987-11-30
OA08127A (en) 1987-03-31
DK487885A (en) 1986-04-26
PL150265B1 (en) 1990-05-31
CA1265145A (en) 1990-01-30
KR880001568B1 (en) 1988-08-23
HU199808B (en) 1990-03-28
SE8505026L (en) 1986-04-26
PL255938A1 (en) 1987-11-02
YU45287B (en) 1992-05-28
CA1265145C (en) 1990-01-30
CS252497B2 (en) 1987-09-17
DK487885D0 (en) 1985-10-24
BR8505326A (en) 1986-08-05
NL8502913A (en) 1986-05-16
IN166473B (en) 1990-05-19
KR860003228A (en) 1986-05-21
MY102602A (en) 1992-08-17
RO92966B (en) 1987-12-01
HUT39073A (en) 1986-08-28
AU4859885A (en) 1986-05-01
CS761585A2 (en) 1987-01-15
GR852585B (en) 1986-02-26
IL76771A0 (en) 1986-02-28
CN85107882A (en) 1986-06-10
FR2572400A1 (en) 1986-05-02
ATA306085A (en) 1993-09-15
EG17848A (en) 1991-03-30
GB8526175D0 (en) 1985-11-27
ES8701757A1 (en) 1986-12-01
GB2166137B (en) 1988-05-11
AP8500014A0 (en) 1985-08-01
LU86134A1 (en) 1986-06-11
NZ213953A (en) 1988-09-29
DE3537884A1 (en) 1986-04-30
IT8522601A0 (en) 1985-10-24
ES548170A0 (en) 1986-12-01
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CH666029A5 (en) 1988-06-30

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