IE45012B1 - 1,3,4 substituted syrazoline derivatives - Google Patents

1,3,4 substituted syrazoline derivatives

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Publication number
IE45012B1
IE45012B1 IE24/77A IE2477A IE45012B1 IE 45012 B1 IE45012 B1 IE 45012B1 IE 24/77 A IE24/77 A IE 24/77A IE 2477 A IE2477 A IE 2477A IE 45012 B1 IE45012 B1 IE 45012B1
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Ireland
Prior art keywords
chlorophenyl
pyrazoline
group
phenyl
carbamoyl
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IE24/77A
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IE45012L (en
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Duphar Int Res
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Publication of IE45012B1 publication Critical patent/IE45012B1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/98—Nitrogen atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Compounds of the formula I in which R1, R2, R3, R4 and X have the meaning defined in Patent Claim 1, are potent insecticides. They form the active substances of the novel insecticide preparations. They are prepared by reacting a compound of the formula II with a compound of the formula III R1-N=C=X or with a compound of the formula and, if appropriate, further reacting the resulting compound, in which R4 equals H, with an R4-halide.

Description

This invention relates to 1,3,4 substituted pyrazoline derivatives and to insecticidal compositions which contain the derivative as an active ingredient.
It is known from German Offenlegungsschrift 2,304,584 in the 5 name of the Application that pyrazoline compounds which in the 1,3 or 1,3,5 positions of the pyrazoline ring are provided with a substituent, exert a biocidal activity with respect to arthropods, for example mites and insects.
It has now been found that new pyrazoline compounds as defined 10 by the formula below and which contain substituents in the 1,3 and positions of the pyrazoline ring, have a very strong insecticidal activity.
The compounds according to the present invention may be represented by the general formula X = C — N — Rin which R-j is an alkyl group, a cycloalkyl group, a phenylalkyl group in which the phenyl nucleus may be' substituted with halogen, alkyl or nitro, a heterocyclic ring which contains 1 or 2 nitrogen atoms and may be substituted with halogen, alkyl or nitro, a ' 4 S 01S phenyl group or a phenyl group which is substituted in the 2,3 or 4 positions with 1 or 2 substituents selected from halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, dlalkylamino, alkylsulphonyl, acyl, acylamino, cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy and phenylalkyl radical, R2 is an alkyl group, a cycloalkyl group, a pyridyl group or a thienyl group which may be substituted with halogen, alkyl or nitro, a phenyl group or a phenyl group substituted with 1 or 2 substituents selected from halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, mono- or aialkylaraino, nitro, phenyl, halophenyl and cyano, R,i is a hydrogen atom, an alkyl group having 1-15 carbon atoms, a phenylalkyl group, a cycloalkyl group or a halomethylthio group; R3 is an alkyl group having 5-10 carbon atoms or an alkyl group having 1 to 6 carbon atoms which is substituted by cycloalkyl, alkoxy, alkylthio, nitro, halogen, cyano, alkoxycarbonyl, phenyl optionally substituted by nitro, halogen or alkyl, phenoxy, phenylthio, phenylsulphinyl, phenylsulphonyl, dialkylamino the alkyl groups of which may form together with the nitrogen atom to which they are bound a saturated or an unsaturated, optionally substituted heterocyclic ring which may contain a second hetero atom, alkylphenyl, di phenyl ami no, Ν,Ν-dialkylcarbanrayl or O-dialkylsulphamoy!; with the proviso that fa) when an alkyl group, phenylalkyl group, alkylthio 9'foup, alkoxy group, aikylammo group, dialkylamino group, or an alkyl sul phonyl group occurs in the substituents R-j to R^ then the alkyl group contains from 1 to 4 carbon atoms, (b) when the cycloalkyl group occurs in the substituents R^ to R^ then the cycloalkyl group contains from 3 to 5 carbon atoms and (c) that when R.| is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R^ is a phenylalkyl, cycloalkyl cr halomethylthio group, R3 may also have a meaning mentioned for R2; and X is an oxygen atom or a sulphur atom. • 45012 In one embodiment of the invention there is provided a compound of the formula given above, in which formula, Rg represents an alkyl group having from 1 to 6 carbon atoms which is substituted with an alkoxy group having from 1 to 4 carbon atoms, or Rg is an alkyl group having from 1 to 6 carbon atoms substituted with a dialkylamino group in which the alkyl radicals may form a heterocyclic ring with the nitrogen atom and Rp Rg, and X are as hereinbefore defined.
Structurally related 1,3,4 substituted pyrazoline derivatives are the subject matter of Patent Specification No. 41836. The compounds described in said Patent No. 41836 also have good insecticidal properties.
Thus if an alkyl group, phenylalkyl group, alkylthio group, alkoxy group, alkylamino group, dialkylamino group or an alkylsulphonyl group occurs in the substituents R^ to R^, then the alley! radical present in such group contains from 1-4 carbon atoms; and when the cyeloalkyl group occurs the cyeloalkyl group contains from 3-6 carbon atoms.
If an acyl group or an acylamino group occurs in Rj, then the acyl part of such a group is preferably derived from an aliphatic monocarboxylic acid, for example acetic acid or propionic acid.
When R^ represents a heterocyclic ring which contains 1 or 2 nitrogen atoms, this is preferably either a pyridine or pyrimidine ring.
It has been found by biological evaluation examination that the compounds of the invention have a good insecticidal activity and, in particular at low dosages, they are capable of controlling, for example, beetles, larvae of beetles, larvae of mosquitoes and caterpillars.
It has surprisingly been found that the insecticidal activity of the compounds of'the invention is considerably better than that of the known 1,3- and 1,3,5-substituted pyrazolines. It has been found that in many cases the compounds of the invention also have a good activity against the yellow fever mosquito in addition to an excellent activity against both the Colorado beetle and the caterpillar. Compounds from the known series of l, 3,5-substituted pyrazolines, and 1,3-substituted compoundshave a good activity against larvae of the Colorado beetle, a less strong activity against the caterpillar (larvae of the Cabbage White butterfly) and, in general no or substantially no activity against larvae of the yellow-fever mosquito.
The active compounds of the invention show, for example an optimal activity, in a concentration of 0.3-3 ppm against the larvae of the Colorado beetle, and in a concentration of 1.3-30 ppm show a maximum activity against the caterpillar and furthermore, in a concentration of 0.03-0.3 ppm show a maximum activity against larvae of the yellow-fever mosquito. The following active compounds are particularly suitable. 1) 1 - phenyl carbamoyl -3-(4- chlorophenyl) -4-(2- methyl - 2 - nitropropyl) - 2 - pyrazoline, m.p. 145°C: 2) 1-(3- tri fl uoromethyl phenyl carbamoyl) -3-(4- chlorophenyl) -4-(2- methyl - 2 - nitropropyl) - 2 - pyrazoline, m. p. 160°C (decomposition); 3) 1-(3-nitro-4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl) -4-(2-methyl-2-nitropropyl)-2-pyrazollne, m.p. 198°C; 4) 1-(4-chlorophonylcarbamoyl)-3-(4-chlorophenyl)-4(2-methyl-2-nitropropyl)-2-pyrazoline, m.p. 219 °C (decomposition); ; ) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4i)-heptyl-2-pyrazollne, m.p. 135°C; 6) 1-(4-n-propylphenylcarbamoyl)-3-(4-chlorophenyl)-4n-heptyl-2-pyrazoline, m.p. 111°C; 7) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4n-heptyl-2-pyrazoline, m.p. 117°C; 8) 1-cyclohexylcarbamoy1-3-(4-chlorophenyl)-1|-n-heptyl2-pyrazoline, m.p. 107°C; 9) 1-n-butylcarbamoyl-3-(4-chJ or ophenyl )-1;-n-heptyl2-pyrazoline, m.p. 30°C; ) 1-(ll -me thylthj ophenylcarbamoyl)-3-(4-chloropbenyl)-4n-heptyl-2-pyrazoline, m.p. 115°C; 11) 1~(3> 4-di-chlorophenylcarbamoyl)-3-(4-chloropheftyl)-4rt-heptyl-2-pyrazoline, m.p. 111°C; 12) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4n-heptyl-2-pyrazoline, m.p. 119°C; 13) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4n-heptyl-2-pyrazoline, m.p. 144°C; 14) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4n-decyl-2-pyrazoline, m.p. 113°C; ) 1-(4-cyanophenylcarbamoyl)-3-(h-ohlorophenyl-4n-decyl-2-pyrazoline, m.p. 114°C; 16) 1-(4-rtitrophenylcarbamoyl)-3-(4-chlorophenyl)-4n-decyl-2-pyrazoline, m.p- 107°C; -643012 17) 1-(4 -methoxyphonylcarbamoyl)-3-(4-chlorophenyl)-4n-decyl-2-pyrazoline, m.p. 105°C; 18) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4n-decyl-2-pyrazoline, m.p. 122°C; I?) 1-(4~n~propylphenylcarbamoyl)-3-(4-chlorophenyl)~4n-decyl-S-pyrazoline, m.p. 125°G; ) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-n-decyl2-pyrazoline. m.p. 87°C5 21) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-410 (2-methoxyethyl)-2-pyrazoline, m.p. 87°C; 22) 1-(4-ethoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(2-methoxyethyl)-2-pyrazoline, m.p. 111°C; 23) 1-(4 -methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-methoxyethyl)-2pyrazoline, m.p. 83°C; 24) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-methoxyethyl)-2-pyrazoline, m.p. 159°C> ) 1-,cyclohoxylcarbamoyl-3-(4-chlorophenyl)-4-(2-methoxy ethyl)~2-pyrazoline, m.p. 104ο0; 26) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-420 (2-piperidino-ethyl)-2-pyrazoIine, m.p. 113°C; 27) 1-(4-cyanophenylcarhamoyl)-3-(4-chlorophenyl)-4(2-piperidinoethyl)-2-pyrazoline, m.p. 148°C5 2β) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(2-piperidinoethyl)-2-pyrazoline, m.p. 113°Cj 29) 1-(4~ethylphenylcarbamoyl)-3~(4-chlorophenyl)-4(2-piperidinoethyl)-2-pyrazoline, m.p. 111°C; ) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-piperidinoethyl)-2-pyrazoline, m.p. 134°C; -7· 31) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-diothylaminoethyl)-2-pyrazoline, m.p. 100°C; 32) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4(2-diethylaminoethyl)-2-pyrazoline; 33) 1-(4 -isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(2-diethylaminoethyl)-2-pyrazoline; 34) , 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-diethylaminoethyl)-2-pyrazoline; .).1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4(2-diethylamonoethyl)-2-pyrazoline, m.p. 87°C; 36) 1-^N-(4-ehlorophenyl)-N-mothylcarbamoylJ-3-(4-chloropyenyl)-4-(2-piperidinoethyl)-2-pyrazoline; 37) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-phenylthioethyl)-2-pyrazoline, m.p. 137°Cf 38) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(2-phenylthioethyl)-2-pyrazoline, m.p. 138°C; 39) T-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-phenyltiiioethyl)2-pyrazoline, m.p. 124°C; 4θ) 1-(4-6 thylphe nylcarbamoyl)-3-(4-chlorophenyl)-4(2-phenylthioethyl)-2-pyrazoline, m.p. 122°C; 44) 1-(4-f’luorophenylcarbamoyl)-3-(4-chlorophenyl)-4(2-phenylthioethyl)-2-pyrazoline, m.p. 130°C; 42) 1-(4-isopropoxyphenyloarbamoyl)-3-(4-chlorophenyl)-4(2-phenoxyethyl)-2-pyrazoline, m.p. 100°C; 3) 1-(4-me thylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4•(2-phenoxyethyl)-2-pyrazoline, m.p. 112aC; 44) 1-(4-benzylphenylcarbamoyl)-3-(4-chlorophenyl)-4phenyl-2-pyrazoline, m.p. 179°C; 45) 46) 47) 48) 4?) 50) 51) 52) 53) 54) 55) 56) 57) 58) 1-(4-phenylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4phenyl-2-pyrazoline, m.p. 164°C; 1-(4-phenoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4phenyl-2-pyrazoline, m.p. 17790; 1-1 N-(4-chlorophenyl)-N-(trichloromethylthio)-carbamoyl 3-(4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p·. 177°C; 1-^N-benzyl-N- (4-chlorophenyl)-carbamoylj-3-(4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p. 116°C; 1-^N-cyclohexyl-N-(4-chlorophenyl)-carbamoyl^-3(4-chlGrophenyl)-4-phenyl-2-pyrazoline, m.p. 138°C; 1-phenylcarbamoyl-3"(4-chiorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m p. 179°C; 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 153°C> 1—(4—iaopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 123°C; 1-( 4-- cyanophenyl carbamoyl)-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 173οθΐ 1-(4-ni trophenylcarbamoyl)-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 228°Cj 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 131°0; 1~cyclohexylcarbamoyl-3-(4-chlorophenyl)-4cyclohexylmethyl-2-pyrazoline, m.p. 109°C; 1-(4-chlorophenylcarbamoyl)-3-(4-methoxyphenyl)-4jS-phenylethyl-2-pyrazoline, m.p. l43°Cj 1-(4-ethylphenylcarbamoyl)-3-(4-methoxyphenyl)-4^-phenylethyl-2-pyrazoline, m.p. 111 °C; -945012 i 59) 1-(4 -isopropoxyphcnylcarbamoyl)-3-(4-methoxyphenyl)-4g •-•phenylethyl-2-pyrazoline, m.p. 110°C; 6θ) 1-(4-cyanophenylcarbamoyl)-3-(4-methoxyphenyl)-4g-phenylethyl-2-pyrazoline, m.p. l42°C; 61) i-(4^ni trophenyl carbamoyl) -3-(4-methoxyphenyi )-4g-phenylethyl-2-pyrazoline, m.p. 158°C; 62) 1- cyolOhexylcarbamoyl-3-(4-methoxyphenyl)-4g-phenylethyl-2-pyrazoline, m.p. 126°C; 63) 1-(4-chlorophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4g-diethylaminoethyl-2-pyrazoline; 64) 1-(4-nitrophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4g-die thylamino e thyl-2-pyrazoline ; 65) 1-phony1carbamoyl-3-(4-iHopropoxyphonyl)-4g-d! ethylaminootliyl-2-pyrazoJ ine; 66) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4 g~diethylaniinoethyl-2~pyrazoline; 67) 1-(4-isopropylphenylearbamoyl)-3-(4-isopropoxyphenyl)-4(5 -diethylaminoethyl-2-pyrazoline; 68) 1-cyclohexylcarbamoyl-3-(4-isopropoxyphenyl)-4p-diethylaminoethyl-2-pyrazoline; 69) 1-(4-chiorophenylcarbamoyl)-3-(4-chlorophenyl)-4|^g-(N-methylpiperazino)-ethylJ-2-pyrazoline, m.p.159 °θ! 70) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4|jj-(N-methylpiperazino)-ethylJ-2-pyrazoline, m.p. 173°C; 71) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4£(5-(N-methylpiperazlno)-ethylJ-2-pyrazoline, m.p. 159°C$ 72) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4|fS.-(N-methylpiperazino)-ethylJ-2-pyrazoline, m.p. 13^°0; •104301a 73) 1-cyelohexylcarbamoyl-3-(4-chlorophenyl)-4[β-(Ν -mothylpiperazino)-ethy.l"J~2-pyrazoline; 74) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4benzyl-2-pyrazoline, m.p. 145°C} 75) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4benzyl-2-pyrazoline, m.p. l4l°C; 76) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4benzyl-2-pyrazoline, m.p. 95°Cj 77) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-410 taenzyl-2-pyrazoline, m.p. 184°C; 78) 1-cyclohexylcarbamoyl-3(4-chlorophenyl)-4-benzyl-2pyrazoline. m.p. 126°C; 79) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorphenyl)-4S-phenylsulfonethyl-2-pyrazolins, m.p. 203°C; 80) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4?-phenylsulfonethyl-2-pyrazoline, m.p. 181 °C: 81) l-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-S-phenylsulfonethyl-2-pyrazoline, m.p. 194°Cj 82) 1-(4-methylphenyIcarbamoyl)-3-(4-chlorophenyl)-420 g-phenylsulfonethyl-2-pyrazolino, m.p. 210°C; 83) 1-phenylcarbamoyl-3- (4-chlorophenyl )-4-{!»· phenyl sulfonethyl-2-pyrazoline, m.p. ΐ68βΟ; 84) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4g-phenylsulfonethyl-2-pyrazolinej m.p. 168°C; 85) 1-(4-isobutylphenyloarbamoyl)-3-(4-chlorophenyl)-4g-phenylsulfonethyl-2-pyrazoline, m.p. 150°Cj 86) 1-(3-trifluoromethylphenyIcarbamoyl)-3-(4-chlorophenyl)-4B-phenylsulfonethyl-2-pyrazoline, m.p. 180°C; 87) 1-(3-chloro-4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl) 4-^9-phenylsulfonethyl-2-pyrazoline, m.p. 120°C; 88) 1-(4-chlorophenylcarbamoyl )-3-(4-chlorophenyl)-4(3—eth0xycarbony1propy1)-2-pyrazoiine, m.p. 135°C; 89) 1-(4-is0propoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(3-ethoxycarbonylpropyl)'2-pyrazoiine, m.p. 97eC; 90) 1-(4-methylphenylcarbamQyl)-3-(4-chlorophenyl)-4(3- ethoxycarbonylpropyl)-2-pyrazoiine, m.p. 88°C; 91) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4I 3-(dimethylcarbamoyl)-propylI-2-pyrazoline, m.p. 136°C; 92) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-43-(dimethylcarbamoyl)-propylj-2-pyrazoline, m.p.158°C; 93) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4imethylcarbamoyl)-propyl -2-pyrazoline, m.p.145°C; 94) 1-(3,4-diohlorophenylcarbamoylj-3-(4-chiorophenyl)-4^3-(dimethylcarbamoyl)-propyl^|-2-pyrazoline, m.p. 169°C; 95) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(3-raethoxypropyl)-2-pyrazoline, m.p. 122SC; 96) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4(3-methoxypropyl)-2-pyrazoline, m.p. 12?°C; 97) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophonyl)-4(3-m°thoxypropyl)-2-pyrazoline, m.p. 124°C; 98) l-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4(3-methoxy-propyl)-2-pyrazoline, m.p. 97°C5 99) 1-(4-cyanophenylcarhamoyl)-3-(4-chlorophenyl)-4(3-mothoxypropyl)-2-pyrazoline, m.p. 190°C; 100) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4(3-methoxypropyl)-2-pyrazoline. m.p. 143°C; -124301 10Ί ) 1- (4—chloro'pheny lcarbamoyl )-3-(4-chlorophenyl)-43-piporidinopropyl)-2-pyrazoline, m.p. 107°C; 102) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4(3-pipei’idinopropyl)-2-pyrazoline, m.p. 120°C; 103) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4cyanomethyl-2-pyrazoline, m.p. 175°C; 104) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4cyanomethyl-2-pyrazoline, m.p. 205°C; 105) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4cyanomethyl-2-pyrazoline, m.p. 157°C; 106) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-5cyanomethyl-2-pyrazoline( m.p. 205°C; 107) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4cyanomethyl-2-pyrazoline, m.p. 170°C; 108) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4{$-ethylthioeihyl)-2-pyrazoline, m.p. 102°C; 109) 1-(4-methoxyphenylcarbamoyl)-3-(4~chlorophenyl)-4(g-ethylthioethyl)-2-pyrazoline, m.p. 83®Cj 110) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4 (Jg-ethylthioethyl)~2-pyrazoline , m.p. 111°C; 111) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4~ (g-ethylthioethyl)-2-pyrazoline, m.p. 190°C; 112) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4(6-ethylthioethyl)-2-pyrazoline, m.p. 98®C; 113) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4(g-dimethylaminoethyl)-2-pyrazoline, m.p. 131®θΐ 114) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4(6-dimethylaminoethyl)-2-pyrazoline, m.p. 175°C> -13115) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4(S-dimethylaminoethyl)-2-pyrazoline, m.p. 115°C; ' i ! t 116) .1 -(4-methylthiopenylcarbamoyl)-3-(4-chlorophenyl)-4(β-dimethylaminoethyl)-2-pyrazolinie, m.p. 117°C; 117) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(β-dimethylaminoethyl)-2-pyrazoline, m.p. 103°C; 118) 1-(/. -is opropyIphenylcarbamoyl)-3-(4-chlorophenyl)-(t(g-dimethylaminoethyl)-2-pyrazoline, m-p. 157°C; 119) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-410 ethoxycarbonylmethy! -2-pyrazoline, m.p. 114°C; 120) 1-phenylcarbamoyl-3-(4-chlorophenyl )-4-ethoXycarbonylmethyl-2-pyrazoline, m.p. 98ξ0; 121) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4ethoxycarbonylmethyl-2-pyrazoline, m.p. 113°C; 122) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4ethoxyearbonylmethyl-2-pyrazoline, m.p. 123*0; 123) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4 ethoxycarbonylmethyl-2-pyr'azoline, m.p. 96°C; .124) 1-'(4-methoxyphenylcarbamoyl)-3-(4-ohlorophenyl)-420 ethoxycarbonylmethyl - 2-pyrazoline, m.p. 85°C; 125) 1-(3,4-dichlorophenylcarbamoyl)-3-(4-chlorophenyl)-4 ethoxycarbonylmethyl-2-pyrazoline, m.p. 125°C; 126) 1-(4-cyanophenylcarbamoyl)-3-(4Ichlorophenyl)-4ethoxycarbonylmethyl-2-pyra2oline, m.p. 159°C; 127) 1-(4-ch.lorophonylcarbamoyl)-3-(4-chlorophenyl)-43-ethylthiopropyl)-2-pyrazoline, m.p. 105°C; 128) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophehyl)-4(3-ethylthiopropyl)-2-pyrazoline, m.p. 130°C; -14129) 1-(4-ethylphenylcarbamoyl)-3-(chlorophenyl )-43- ethylthiopropyl)-2-pyrazoline, m.p. 87°C; 130) 1-(4 -methoxyphonylcarbanioyl)-3-(^-oblorophenyl)-4(3-etftylthiopropyl)-2-pyrazoline, m.p. 86°C; 131) 1-(4-methylthiophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97°Cj 132) 1-(4-chlorophenylcarbamoyl)-3-(^-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97°θΐ 133) 1-(4-ethoxyphenylcarbamoyl)-3-(4-trifluoromethylphenyl)4- (3-methoxypropyl)-2-pyrazoline, m.p. 105°C; 13^) 1-(4-cyanophenylcarbamoyl)-3-(4-trifluoromethylphenyl)4~(3-mcthoxypropyl)-2-pyrazoline, m.p. 152°Cj 135) 1-(4-isobutylphenylcarbamoyl)-3-(4-trifluoromethylphenyl )-4- (3-methoxypropyl )-2-pyrazoline , m.p. 110°Ci 136) 1-(4-fluorophenylcarbamoyl)-3-(4-trifluoromethylphenyl)4-(3-methoxypropyl)-2-pyrazoline, m.p. 113°Cj 137) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4(3"byanopropyl)-2-pyrazoline, m.p. 126°C; 138) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4(3-cyanopropyl)-2-pyrazoline, m.p. 109oCj 139) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-(3-cyanopropyl)2-pyrazoline, m.p. 148°C; ΐ4θ) 1-(4-chlorophenylcarbamoyl)-3-(chlorophenyl)-4(3-cyanopropyl)-2-pyrazoline, m.p. 120°C; 141) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4(3-oyanopropyl)-2-pyrazoline, m.p. 154°C; 142) 1-(4-fluorophenylcarbamoyl)-3-(4-chlorophenyl)-4benzyl-2-pyrazoline, m.p. 130°Cj -15· 012 143) 1-(4- ni tropheny! carbamoyl) -3-(4- chlorophenyl) 4 - benzyl - 2 - pyrazoline, m.p. 167°C; 144) 1-(4- chlorophenylcarbamoyl -3-(4- chlorophenyl) 4 - (dimethylcarbemoylmethyl) - 2 - pyrazoline, m.p. 151°C; 145) 1 - phenylcarbamoyl -3-(4- chlorophenyl) - 4 dimethyl carbamoylmethyl) - 2 - pyrazoline, m.p. 145°C; 146) 1-(4- ethyl phenyl carbamoyl) - 3 - (4 * chlorophenyl) 4 - (dimethylcarbamoylmethyl) - 2 - pyrazoline, m.p. 155°C; 147) 1-(4- methoxyphehyicarbawoyi) - 3-(4- chlorophenyl) - 4 - (dimethylcarbamoylmethyl) - 2 - pyrazoline, m.p. 151°C; 148) 1-(4- cyanophenylcarbamoyl) -3-(4- chlorophenyl) 4 - (dimethylcarbamoylmethyl) - 2 - pyrazoline, m.p. 210°C; In particular, compounds of the above mentioned general formula in which Rp Rg, R^ and X are defined as above and Rg represents an alkyl group having from 1 to 6 carbon atoms substituted with an alkoxy having from T to 4 carbon atoms, or wherein Rg is an alkyl group having from 1 to 6 carbon atoms substituted with a dialkylamino, the alkyl radicals of which may form together with the nitrogen atom to which they are bound a heterocyclic ring, have strong insecticidal properties. Further to the insecticidal activity, it has been found that compounds having the above mentioned general formula wherein Rp Rg and R^ have the above mentioned meanings, and Rg represents an alkyl group having 1 to 6 carbon atoms which is substituted by a cyano or dialkylamino group, the alkyl groups of which may together form an optionally alkyl substituted heterocyclic ring, which may contain a second hetero atom, have a fungicidal activity. 45013 On the basis of their strong insecticidal activity the substances of the invention way be used in low dosages in controlling insects. The amount of tho dosage depends on a variety of factors, for example, the substance used, the kind of insect, the formulation used, the state of the crop infected with insects, and the prevailing weather conditions. In general, for the control of insects in agriculture and horticulture a dosage corresponding to 0.05 ~ 1 kg of the active substance per hectare yields good results.
For practical application, the compounds of the invention are processed to compositions.
In these composicions the active substance is mixed with solid carrier material or dissolved or dispersed in a liquid carrier material, if desired, combined with auxiliary substances, for example surface-active substances and stabilizers. In one embodiment a composition according to the invention also contains a biocidal compound and/or an artificial manure.
Examples of compositions according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersion?, pastes, dusting powders, wettable powders, miscible oils, granules, invert emulsions, aerosol compositions and fumigating candles.
Wettable powders, pastes and miscible oils are compositions in concentrated form which are diluted with water prior to or during use.
The invert emulsions are mainly used in air applications, namely when large areas are treated with a comparatively small quantity of composition. -1745013 The invert emulsions can be prepared shortly before or even during the spraying in the spraying apparatus by emulsifying water in an oily solution or an oily dispersion of the active substance. Some types of 5 compositions will be described in greater detail hereinafter by way of example..
Granular compositions are prepared, for example, by taking up the active substance in a solvent and impregnating the resulting solution, optionally in the presence of a hinder, on granular carrier material, for example porous granules (for example pumice and attaclay), mineral non-porous- granules (sand or ground marl), organic granules (for example dried coffee grounds and cut tobacco stems)« A granular composition can also be prepared by compressing the active substance together with powdered , minerals in the.presence of lubricating agents and binders and to disintegrate and sieve the compressed product to the desired grain size.
Dusting powders can he obtained by intimately mixing the active substance with an inert solid carrier material, for example in a concentration of 1 to 50 $ by weight. As examples of suitable solid carrier materials may be mentioned talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and colloidal SiOg or mixtures of these and similar substances . Organic carrier materials, for example, ground shells of walnuts may also he used. -18«SOI 3 Vottablo powders nru prepared by mixing 1 to 80 parts by weight of a solid inert carrier, for example the above-mentioned carrier materials, with 10 te 80 parts by weight of the active substance, to 5 parts by weight of a dispersion agent, for example the lignine sulphonates or alkylnaphthalene sulphonates known for this purpose, and preferably also 0.5 to 5 parts by weight of a wetting agent, for example, sulphates of aliphatic alcohol, alkylarylsulphonates or fatty acid condensation products.
For the preparation of5miscible oils the active compound is dissolved or finely divided in a suitable solvent which preferably is poorly water-miscible and an emulsifier is added to this solution. Suitable solvents are, for example, xylene, toluene, petroleum ι I distillates which are rich in .aromatics, for example, solvent naphtha, distilled tar oil and mixtures of these liquids. As emulsifiers may be used for example, alkylphenoxy polyglycol ethers, polyoxyethylene sorbitan esters of fatty acids or polyoxyethylene sorbitol esters of fatty acids. The concentration of the active compound in these miscible oils is not restricted to narrow limits and may vary, for example, between 2 and 5θ by weight.
In addition to a miscible oil may also be mentioned as a liquid and highly concentrated primary composition a solution of the active substance in a readily watermiscible liquid, for example acetone, to which solution -192 a dispersion agent and possibly a wetting agent have been added. An aqueous dispersion of the active substance i ' is obtained upon diluting with water shortly before or £ during spraying.
An aerosol composition Of the invention is obtained in the usual manner by incorporating the active substance, optionally in a solvent, in a volatile liquid to be used as a propellant, for example a mixture of chloro-fluoro-derivatives of methane and. ethane.
FUmigating candles or fumigating powders, that is compositions which can generate a pesticidal smoke while burning, are obtained by taking up the active substance in a combustible mixture which may v' contain, for example, as a fuel, a sugar or wood, preferably in a groundform, a substance to maintain the combustion, for example, ammonium nitrate or potassium chlorate, and in addition a substance to delay the combustion, for example, kaolin, bentonite and/or colloidal silica.
In addition to the above-mentioned ingredients the compositions of the invention may also contain other substances known for application .in this kind of Compositions .
For example, a lubricant such as calcium stearate or magnesium stearate, may be added to a wettable powder or a mixture to be granulated. Adhesives for example, -20s S 0 l 2 polyvinyl alcohol and cellylose derivatives or other colloidal materials,, such as casein, may also be added to improve the adhesion of the pesticidal composition to the surface to be protected.
Known pesticidal compounds may also be incorporated in the compositions of tha invention. As a result of this the activity spectrum of the compositions is broadened and synergism may occur.
The following known insecticidal, fungicidal and acaricidal compounds are suitable for use in such combination compositions: Insecticides such as: 1. chlorinated hydrocarbons, for example, 2,2-bis-(p~ chlorophenyl)-1,1,1-trichloroethane and hexachloroepoxyoctahydro-dimethanonaphthalenei 2. carbamates, for example, ft-methyl-1-naphthyl-earbamate; 3· dinitrophenols, forexample 2-methyl~4,o-dinitrophenol and 2-(2-butyl)-4,6-dinitrophenyl)-3, 3-dimethylacrylate; 4. organic phosphorus compounds, for example dimethy1-2methoxy-carbonyl-2~methylvinyl-phosphate; 0,0-diethyl0-p.nitrophenyl-phosphorthioate 5 N-monomethyl-aitlide of 0,0-dimethyldithiophosphoryl acetic acid; Acaricides-, for example; . diphenylsulfides, for example p-chlorobenzyl-p-chlorophenylsulfide and 2,4,41,5-tetrachlorodiphenylsulfide; 6. diphenylsulphonates, for example p-chlorophenyl benzene sulphonate; . -21»5> v 7. methylcarbinols, for example 4,4-dichloro-a-triehloromethylhenzhydrol; 8. quinoxaline compounds for example methylquinoxaline dithiocarbonate . ’ Fungicides, for example:9. organic mercury compounds, for example phenyl mercury acetic and methyl mercury cyanoguanide;. .organic tin compounds, for example triphenyltin hydroxide and triphenyltin acetate; 11.alkylene bis-dithiocarbamates, for example, zinc ethylene bis- dithiocarbamate and manganese ethylene bis-dithiocarbamate; and 12. ai;2t4-dinitro-6-(2-ocfyl-phenyl-crotonate), 1-bis(dimethylamino)phosphoryl-3-phenyl-5-amino-1,2,4triazol-6-methyl-quinoxaline-2,3-dithiocarbonate, 1,4-dithioanthraquinone-2,3-dicarbonitrile, N-trichloromethylthiophthalimide, N-trichloro-methylthiotetrahydrophthalimide, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophtlialimide, N-diohloro-fluoromethylthio20 N-phenyl-N’-dimethylsulphonyldiamide and tetraohloroisophthalonitrile.
• As already noted above the active .· compounds of the invention are novel substances which can be prepared according to methods which are known 25 per se for the synthesis of similar substances or methods analogous thereto. -22•2501s For Example the substances can be prepared by reacting a compound of the general formula R„ wherein R^ and R^, Lave the above-indicated meanings, with a compound of the formula R, - N = C = X wherein R^ and X also has the above-mentioned meaning.
The reaction is carried out at room temperature and in the presence of a solvent, for example an ether for example diethylethor or petroleum ether.
The compounds in which R^ is not a hydrogen atom can be prepared from the pyrazolines obtained in the above-described manner, in which = H according to methods which are known per se . Compounds in which R^ is an alkyl group can ba obtained, for example, by reacting tho compound in which R, = H with an alkyl halide in a 4 polar solvent in the pesence of an acid binding agent.
Another method of preparing compounds in which R^ is not a hydrogen atom is the reaction of a pyrazoline derivative which is not substituted in the position with an R^, R^ disubstituted Carbamoylchloride or ίί , K disubstituted carbamic acid ester. 4 -234 5 012 The above-mentioned starting material of the formula can be prepared in various manners dependent on the meaning of the substituents Rg-and R^ . Inter alia, when the substituents R^ and R^ are a substituted or nonsubstituted pyridyl group, thienyl group or phenyl group, the said starting material can be prepared by reacting a compound of the formula R - C - OH - R_ 2 6 2 3 with formaldehyde in acid medium and in the presence of a solvent and a catalyst, so that a compound of the formula is obtained.
The reaction is carried out at elevated temperature, for example at the boiling point of the solvent used. Suitable solvents are, for example, alcohols, for example methanol. A useful catalyst is, for example piperidine . -24The resulting product is then reacted with hydrazine in the presence of a solvent, for example an alcohol, for example propanol, a compound of the formula H being obtained. The reaction is carried out at elevated tomperaturo for example tho boiling point of the solvent used.
The above-mentioned starting material can also be obtained by reacting a compound of the formula R2 - p CH2 S3 with dimethylamine and paraformaldehyde, a compound of the formula E - C - CH - CH- - N(CH-) 2 il ! 2 3 o e3 being formed. The reaction is carried out at elevated temperature in the presence of a solvent, for example ethanol. Upon prolonged heating, dimethylamine is usually split off again so that a compound of the formula is obtained again. -253013 The resulting products are then reacted with hydrazine at elevated temperature and in the presence of a solvent, for example ethanol, a compound of the formula H being obtained.
The invention will now be described in greater detail with reference to the following examples.
EXAMPLES i I. 1-(p-chlorophenylcarbamoyl)~3-(p-chlorophenyl)-4(2-methoxyethyl)Δ 2-pyrazoline. a) 10.6 g of diinethylaminohydrochloride, 4,0 g of paraformaldehyde and 21.3 g of 4'chloro-4-methoxybutyrophenone were suspended in 30 ml of dioxan. This mixture was then refluxed for 30 hours after which it was cooled.
Dioxan was then evaporated for the greater part under reduced pressure. Water and ether were added to the • residue, the ether layer was separated, washed with water and dried with sodium sulphate and evaporated.
Yield 21.2 g of 2-(p-chlorobenzoyl)-4-methoxybutene-1. b) A solution of 21.1 g of 2-(p-chlorobenzoyl)-4-methoxybutene-1 and 10 ml of hydrazinehydrate in 50 ml of ethanol was boiled for 5 hours. After distillation, 12.3 g of 3-(p-chiorophenyl)-4-(2-methoxyethyl)-/\ 25 pyrazoline were obtained. Boiling point (0-35 — 0.40 mm Hg) 155-165°C. -26· 3 0 1 g ο) 7·7· g of p-chlorophenyl-isocyanate were added to the solution of 12 g of 3-(p-chlorophenyl)-4-(2-methoxyethyl)-£, -pyrazoline in 50 ml of dry ether.
After stirring for 1 hour the ether was distilled off and replaced hy 50 ml of petroleum ether. Stirring was continued for another 5 hours and the petroleum ether was sucked off. Yield 17.4 g of the compound mentioned in the title; m.p. 87°C.
In an- analogous manner the following compounds were prepared: 1-(p-ethoxyphenylcarbamoyl)-3-(p-chiorophenyl)-4-(2-methoxy ethyl)-/, -pyrazoline, m.p. 111 °C; 1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)T4(2~methoxyethyl)-A 2-pyrazoIine, m.p. 83°C; 1-(p-nitrophenylcarbamoyl)-3-(p-chlorophenyl)-4(2-methoxyethyl)--pyrazoline, m.p. 159°O; 1-cyclohexylcarbamoyl~3-(p-chlorophenyl)-4-(2-methoxyethyl)-A -pyrazoline, m.p. 104°C; II. 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-42 (2-piperidinoethyl)-Δ -pyrazoline. a) A suspension of 26.6 g of 4’-chloro-4-piperidinobutyrophsnone, 4 g of paraformaldehyde and 10.6 gof dimethylamine-hydrochloride in 40 ml of dioxan was refluxed for 24 hours. After evaporation, water was added and the reaction mixture was rendered alkaline with 50$ sodium hydroxide solution. After extracting with ether, washing with water, drying and evaporating 26.7 g of 1-(dimethylamino)-2-(p-chlorobenzoyl)-4piperidinobutane were obtained. b) A solution of 26.7 g of the compound obtained according to a) and TO ml of hydrazinehydrate in ml of ethanol were refluxed for 7 hours and then distilled. 18.1 g of 3-(p-chlorophenyl)-4-(2-piperidinoethyl)-^ -pyrazoline were obtained. Boiling point (0.4 -0.5 mm Hg): 200-208°C; c) 15.4 g of p-chlorophenylisocyanate were added, to a solution of 29.2 g of 3- (p-chlorophenyl)-4-(2-pi.peridino2 ethyl)-Δ -pyrazoline in 500ml of petroleum ether.
The mixture was stirred for 12 hours and then sucked off. In this manner 36.4 g of the compound mentioned in the title was obtained; melting point 13^°C.
The following compounds were prepared in an analogous manner: 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-piperidinoethyl)-A -pyrazoline, m.p. 113°C; 1-(p-cyanophen3rloarbamoyl)-3-(p-chlorophenyl)-4-(2-piperidino 2 ethy1)-^ -pyrazoline, m.p. 148°C; 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4(2-piperidinoethyl)-£, -pyrazoline, m.p. 113°C; 1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4(2-piperidinoethyl)-Zs2-pyrazoline, m.p. 111°C; 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4(2-diethylaminoethyl)-&^-pyrazoline, m.p. 100°C; 1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-42 (2-diethylaminoethyl)-A. -pyrazoline, an oil; -284 5 012 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophcnyl)-4(2-diothylaminoethyl)-A -pyrazoline, an Oil; 1-(p-cyanophenylcarbamoyl)-3-(p-chlQropheny|)-4(2-diethylaminoethyl)- A. -pyrazoline, m.p. 70 C; 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-diethylaminoethyl )- A ^-pyrazoline , m.p. 87°Cj 1- (p-chlorophenylcai'bamoyl)-3-(p-chlorophenyl)-4(2-phenylthioethyl)-b?-pyrazoline, m.p. 137°C; 1~(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4(2-phenylthioethyl)-/i^-pyrazoline, m.p. 13θ°0; 1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4(2-phenylthioethyl)-Δ-pyrazoline, m.p. 124°C; 1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4( 2-r phenyl thioethyl)-Λ 2-pyrazoline, m.p. 122°C; 1-(p-fluorophenylcarbamoyl)-3-(p-ehlorophenyl)-4(2-phenylthioethyl)- A2-pyrazoline, m.p. 130°C; III. 1(p-isopropoxyphenylcarbainoyl)-3"(p-chlorophenyl)" 4-(2-phenoxyethyl)- A ‘-pyrazoline . a) A mixture of 27·5 S 41-chloro-4-phenoxybutyrophenone 2θ 4 g of paraformaldehyde and 10.9 g of dimethylaminohydrochloride in 4o ml of dioxan was refluxed for 40 hours. After cooling, adding water and extracting with ether, the ether layer was separated, washed with water, dried and evaporated. In this manner 28,5 g of 2-(p-chloro-benzoyl )-4-phenoxybutene-1 were obtained. b) A solution of 28.5 g of the compound obtained according to a) and 10 ml of hydrazinehydrate in 50 ini of ethanol was refluxed for 5 hours. The reaction mixture was then cooled and sucked off.
In this manner- 19 g of 3-(p-chlorophenyl)-42 (2-phenoxyethyl)- & -pyrazoline were obtained. b) 1.8 g of isopropoxyphenylisocyanate were added to a solution of 3 g of the compound obtained according to b) in 15 ml of ether. After stirring for 3 hours the reaction mixture was sucked off. In this manner 2.2 g of the compound mentioned in the title was obtained; m.p. 100°C.
The following compounds are prepared in a similar manner: 1-(p-methylthiophenylcarbamoyl)-3-(p-uhlorophenyl)-4(2-phenoxyethy1)-Δ -pyrazoline, m.p. 112°C; 1-(p-benzylphenylcarbamoyl)-3-(p-chlorophenyl)-4-phenyl2 Δ -pyrazoline, m.p. 179°C5 1-(p-phenylthi ophenylcarbamoyl)-3-(p-chlorophenyl)-42 phenyl-A -pyrazoline, m.p. 164°C; 1-(p-phenoxyphenylcarbamoyl)-3-(p-chlorophenyl)-42 phenyl-Δ -pyrazoline, m.p. 177°C; 1- Qf-(p-chlorophenyl)-N-(trichloromethylthio Jcarbamoylj-3 (p-chlorophenyl)-4-phenyl-/i1 2"Pyrazoline, m.p. 177°C; 1- JjN-benzyl-N-(p-chlorophenyl)-earbamoyl'j -3-(p-chloro2 phenyl)-4-phenyl-Δ -pyrazoline, m.p. 1l6°C; 1- jji-cyclohexyl -N-(p -chlorophenyl)carbaraoyl^j -3"(p-chloro 2 phenyl)-4-phenyl- Δ -pyrazoline, m.p. 138°C; -30isoia IV. The active compounds according to the invention were dispersed in water in concentrations of 300, TOO, 30, 10, 3, and 0.3 mg of active substance per litre of aqueous dispersion.
According to standard test procedures the insecticidal activity of these dispersions was evaluated with Leptinotarsa decemlineata (Colorado Potato beetle), and Pieris brassicae (Large Cabbage White) as insects. The results of these tests are given in the following Table. The meanings of the symbols used in this Table are: += from 90 to 100% mortality + = from 50 to 90% mortality - = less then 50% mortality.
TABLE -32. 0) Jq σΑ O i d so i a P> •ri H t" + III fl Φ OS + + + +1 1 1 ft Φ 0 Φ tf 0 •ri O + + + + + +i 1 C tf •P co A 3 CO 0 *> Pieris Brass o cn + + + + + + 1 1 1 1 +1 100 + + + + + + + 1 | + + + + •ri +> 0 tf j ooC + + + + + + + + + + + + + + + + + + + + + =H o •P •ri •ri jo 0 tf H tf td a •ri in o* Ti Φ to T" I 1 i •ri 0 0 w Φ fl ft h) cn +1 +1 +1 I 1 1 1 1 1 . 1 ri « H 0) tf H 0 Ό ’ " + + + + + +1 +1 1 +1 +1 +1 R 0 •ri •P tf fl •P fl 0 0 fl 0 X} y O Cn + + + + + + +1 1 + 1 +1 + ! too + + + + + + + +| + +1 + + o © -ΓΛ + + + + + + + + + + + + + .+1+ + + + + + + Φ Λ -P •d § 0 £ 0 •P *0 R •ri aforementioned list 0 © fl 0 0 0 tf fl Φ 1 3 a o m *- CM cn cn cn cn «fl* cn tn cn vo cn Ο cn CO OS © tcn cn -fl· -=r cm cn τ- cm tn ^t· -fl· >n in m £*- CO >n tn cs o in vo ac fcivity 33· Biocidal activity < concentration expressed in mg of active substance per litre (PPM) Φ rt? U •r* tn tfi nJ S- CQ V) *£ QJ a. 4 SO iPg o r~ 1 1 co +1 +1 1 11 o + 4- 4-11 + 1 + I O CO + 4- + + +!· 4- + + + o • o r~ + + + + + + +1 + + + + 300 + + + + + + +.+ + + + + + + + + Cola L CO o r— 1 1 . co ι +| +| ι ι ι o +| ι ι + + +f +| ι +| ι © co + + +| ι + i + +| + +| +| + o o + + ++| + + + + + +|+ + O o co + + + + + + + + +1+ + + + + + + + Compound Number according to the acorementioned list r-MfQ'tin^iscniN'ikocn'icocrii-gr WlO-«NlSNP*C0 00 C0ai©

Claims (34)

1. A compound of tha general formula ftl * X~C—Π-R, wherein Rj is an alkyl group, a cycloalkyl group, a phenylalkyl group 5 of which the phenyl nucleus may be substituted with halogen, alkyl or nitro, a heterocyclic ring which contains 1 or
2. Nitrogen atoms and may be substituted with halogen, alkyl or nitro, a phenyl group or a phenyl group which is substituted in the 2, 3 or 4 positions with 1 or 2 substituents selected from halogen, alkyl, haloalkyl, 10 cycloalkyl, alkylthio, alkoxy, dialkylamino, alkyl sulphonyl, acyl, acylamino, cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy and phenylalkyl radical, / 1S an a ^yl group, a cycloalkyl group, a pyridyl group or a thienyl group which may be substituted with halogen, alkyl or nitro, a phenyl group or a 15 phenyl group substituted with 1 or 2 substituents selected from halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, monoalkyl ami no or dialkylamino, nitro, phenyl, halophenyl and cyano; R 4 is a hydrogen atom, an alkyl group having 1-15 carbon atoms, a phenylalkyl group, a cycloalkyl group or a halomethylthio group; R 3 is an alkyl group having 5-10 carbon atoms or an alkyl group having 1 to 6 carbon atoms which is substituted by cycloalkyl, alkoxy, alkylthio, nitro, halogen, cyano, alkqxycarbonyl, phenyloptionally substituted by nitro, halogen or alkyl, phenoxy, 5 phenylthio, phenylsulphinyl, phenylsulphony!, dialkylamino the alkyl groups of which may form together with the nitrogen atom to which they are bound a saturated or an unsaturated, optionally substituted heterocyclic ring which may contain a second hetero atom, alkyl phenyl, di phenyl amino, N,N - di alkyl carbamoyl or 10 N,N - dialkylsulphamoyl; with the proviso that (a) when an alkyl group, phenylalkyl group, alkylthio group, alkoxy group, alkylamino group, dialkylamino group, or an alkylsulphony! group occurs in the substituents R·] to R^ then the alkyl group contains from 1 to 4 carbon atoms, (b) when the cycloalkyl group occurs in the 15 substituents to then the cycloalkyl group contains from 3 to 6 carbon atoms and (c) that when R-j is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R^ is a phenylalkyl group a cycloalkyl group or a halomethylthio group, Rg may also have a meaning mentioned for R 2 ; and X· is an oxygen atom or sulphur atom. 20 2. A compound as claimed in Claim 1, in which Rp Rg, R^ and X are defined as in Claim 1 and R 3 represents an alkyl group having from 1 to 5 carbon atoms substituted with an alkoxy group having from 1 to 4 carbon atoms or R 3 is an alkyl group having from 1 to 6 carbon atoms substituted with a dialkylanrino group, the alkyl radicals 25 of which may with the nitrogen atom form a heterocyclic ring. 450ΐ 3
3. 1-(4- Ch 1 orophenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - methoxyethyl) - 2 - pyrazoline.
4. 1-(4- Ethoxyphenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - methoxyethyl) - 2 - pyrazoline.
5. 1-(4- Methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 (2 - methoxyethyl) - 2 - pyrazoline. S. 1-(4- Nitrophenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - methoxyethyl) - 2 - pyrazoline.
6. 7. 1-(4- Cyanophenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - pi peridinoethyl) - 2 - pyrazoline.
7. 8. 1-(4- Isopropoxyphenyl carbamoyl) -3-(4- chlorophenyl) 4-(2- pi peri di noethyl) - 2 - pyrazoline.
8. 9. 1-(4- Ethyl phenyl carbamoyl) - 3 - (.4 - chlorophenyl) - 4 (2 - piperi di noethyl) - 2 - pyrazoline.
9. 10. 1-(4- Chi orophenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - pi peri di noethyl) - 2 - pyrazoline.
10. 11. 1-(4- Chlorophanylcarbamoyl) -3-(4- chlorophenyl) - 4 (2 - di ethyl ami noethyl) -2.- pyrazoline.
11. 12. 1-(4- Ethyl phenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - diethylaminoethyl) - 2 - pyrazoline.
12. 13. 1-(4- Isopropoxyphenylcarbamoyl) -3-(4- chlorophenyl) 4-(2- di ethy lami noethyl) - 2 - pyrazoline.
13. 14. 1-(4- Cyanophenyl carbamoyl) - 3 - (4 - chlorophenyl) - 4 (2 - diethyl aminoethyl) - 2 - pyrazoline.
14. 15. 1 - Cycl ohexyl carbamoyl -3-(4- chlorophenyl) -4-(2diethyl aminoethyl) - 2 - pyrazoline.
15. 16. 1-(4- Chi orophenyl carbamoyl) -3-(4- chlorophenyl) - 4 (2 - phenyl thioethyl) - 2 - pyrazoline.
16. 17. 1-(4- Isopropoxyphenylcarbamoyl) -3-(4- chlorophenyl) 4-(2- phenyl thioethyl) - 2 - pyrazoline. .
17. 18. 1-(4- Methyl thi opheny! carbamoyl) -3-(4- chlorophenyl) 4-(2- phenyl thioethyl) - 2 - pyrazoline. 5
18. 19. 1-(4- Ethyl pheny Icarbamoyl) - ’3 - (4 - chlorophenyl) - 4 (2 - phenylthioethyl) - 2 - pyrazoline.
19. 20. 1-(4- Fl uoropheny! carbamoyl) -3-(4- chlorophenyl) - 4 (2 - pheny1thioethyl) - 2 - pyrazoline.
20. 21. 1-(4- Isopropoxyphenyl carbamoyl) -3-(4- chlorophenyl) - 4 10 (2 - phenoxyethyl) - 2 - pyrazoline.
21. 22. 1-(4- Methylthiophenylcarbamoyl) -3-(4- chlorophenyl) - 4 (2 - phenoxyethyl) - 2 - pyrazoline.
22. 23. 1-(4- Benzyl phenyl carbamoyl) -3-(4- chlorophenyl) - 4 phenyl - 2 - pyrazoline. 15
23. 24. 1 -(4 - Phenylthiophenylcarbamoyl) -3-(4 - chlorophenyl) - 4 phenyl - 2 - pyrazoline.
24. 25. 1-(4- Phenoxyphenylcarbamoyl) -3-(4- chlorophenyl) - 4 phenyl - 2 - pyrazoline. 25. 1 - Γν - (4 - chlorophenyl) - N - (trichloromethylthio) 20 carbamoyl]] -3-(4- chlorophenyl )-4-phenyl - 2 - pyrazoline.
25. 27. 1 - [jl - Benzyl - N - (4 - chlorophenyl) - carbamoyl] - 3 (4 - chlorophenyl) - 4 - phenyl - 2 - pyrazoline.
26. 28. 1 - [N - Cyclohexyl - N - (4 - chlorophenyl) - carbamoyl] - 3 (4 - chlorophenyl) - 4 - phenyl - 2 - pyrazoline.
27. 29. A method of preparing compounds of the general formula \Z X= C—N-R, wherein R^, Rg, Rg, and X have the meanings stated in Claim 1, characterized in that a compound of general formula \.Z wherein Rg and Rg have the meanings given in Claim 1, in the presence of a solvent is reacted at room temperature with a compound of the formula Rp N -C = X wherein R-j and X have the meanings indicated in Claim 1. ϊ* ι _ it.
28. 30. Insecticidal compositions, characterised in that the composition contains a compound of the general formula N χ == C — N — R ] R 4 wherein Rp Rg, Rg, R^ and X have the meanings stated in Claim 1 5 mixed with a solid carrier material, or dissolved or dispersed in a liquid carrier material, if desired with a surface active agent and/or a stabilizing agent.
29. 31. A composition as claimed in Claim 30, characterized in that the composition also contains a known biocidal compound and/or an artificial 10 manure.
30. 32. A method of preparing an insecticidal composition, characterized in that a compound of the general formula 4S012 wherein Rp R 2 , R 3 , R^ and X have the meanings indicated in Claim 1, is mixed with solid or liquid inert carrier materials, optionally with the addition of surface-active substances, lubricants, stabilizers or other known biocidal compounds or artificial manures.
31. 33. A method of controlling insects in agriculture and horticulture, characterized in that the infected areas are treated with a composition as claimed in Claim 30 or Claim 31 in a dosage corresponding to 0.05 - 1 kg of active substance per hectare.
32. 34. A method of preparing a compound according to Claim 29 substant ially as hereinbefore described.
33. 35. A composition containing a compound as claimed in Claim 1 mixed with or dissolved in an inert, solid or liquid carrier material substantially as hereinbefore described. 35. A method of preparing in insecticidal composition according to Claim 32 substantially as hereinbefore described.
34. 37. A method of controlling insects in agriculture or horticulture using a composition according to any one of Claims 30, 31 or 35 substantially as hereinbefore described.
IE24/77A 1976-01-09 1977-01-06 1,3,4 substituted syrazoline derivatives IE45012B1 (en)

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EP0014810A3 (en) 1979-01-18 1980-11-26 Fbc Limited Pesticidal pyrazoles, their production, compositions and uses, as well as intermediates and their preparation
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
JPS57209275A (en) * 1981-06-19 1982-12-22 Nissan Chem Ind Ltd Novel pyrazoline derivative, its preparation, and vermin-controlling agent containing said derivative as active component
ATE14309T1 (en) * 1981-05-12 1985-08-15 Duphar Int Res PYRAZOLINE DERIVATIVES, PROCESS FOR THEIR MANUFACTURE AND INSECTICIDE PREPARATIONS CONTAINING THEM.
AU556949B2 (en) * 1984-10-25 1986-11-27 Fmc Corporation Pyrozoline insecticides
ZA858002B (en) * 1984-10-25 1987-04-29 Fmc Corp Pyrazoline insecticides
EP0182746A3 (en) * 1984-11-16 1988-10-12 Ciba-Geigy Ag Pyrazoline derivatives
DE3545786A1 (en) * 1985-12-21 1987-06-25 Schering Ag Pyrazoline derivatives, their preparation, and their use as insecticides
DE3638631A1 (en) * 1986-11-11 1988-05-26 Schering Ag PYRAZOLINE, THEIR PRODUCTION AND USE AS A MEDICINE WITH INSECTICIDAL AND ACARICIDAL EFFECT
DE4032089A1 (en) * 1990-01-24 1991-07-25 Bayer Ag SUBSTITUTED PYRAZOLINE DERIVATIVES
DE4217862A1 (en) * 1991-08-28 1993-03-04 Bayer Ag SUBSTITUTED PYRAZOLINE
DE4217863A1 (en) * 1991-08-28 1993-03-04 Bayer Ag SUBSTITUTED PYRAZOLINE
WO1993018038A1 (en) * 1992-03-02 1993-09-16 E.I. Du Pont De Nemours And Company Arthropodicidal amides
DE4218745A1 (en) * 1992-06-04 1993-12-09 Schering Ag 1- (4-cyanophenylcarbamoyl) pyrazoline

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BE795264A (en) * 1972-02-09 1973-08-09 Philips Nv NEW PYRAZOLINE COMPOUNDS WITH INSECTICIDAL ACTIVITY
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DE2700288A1 (en) * 1977-01-05 1978-07-13 Bayer Ag PHENYLCARBAMOYL PYRAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES
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SE435176B (en) 1984-09-10
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FR2337715B1 (en) 1982-02-19
PT66039A (en) 1977-02-01
CH631870A5 (en) 1982-09-15
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