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GB1570635A - 1,3,4 substituted pyrazoline derivatives - Google Patents

1,3,4 substituted pyrazoline derivatives Download PDF

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Publication number
GB1570635A
GB1570635A GB356/77A GB35677A GB1570635A GB 1570635 A GB1570635 A GB 1570635A GB 356/77 A GB356/77 A GB 356/77A GB 35677 A GB35677 A GB 35677A GB 1570635 A GB1570635 A GB 1570635A
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chlorophenyl
pyrazoline
group
phenyl
alkyl
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Koninklijke Philips NV
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Philips Gloeilampenfabrieken NV
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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 <IMAGE> 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 <IMAGE> with a compound of the formula III R1-N=C=X or with a compound of the formula <IMAGE> and, if appropriate, further reacting the resulting compound, in which R4 equals H, with an R4-halide.

Description

(54)1,3,4 SUBSTITUTED PYRAZOLINE DERIVATIVES (71) We, N.V. PHILIPS' GLOEILAMPENFABRIEKEN, a limited liability Company, organised and established under the laws of the Kingdom of the Netherlands, of Emmasingel 29, Eindhoven, the Netherlands, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- 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 name of the Applicant 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 by the formula below and which contain substituents in the 1, 3 and 4 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
in which Rl is an alkyl group, a cycloalkyl group, a phenylalkyl group 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, cycloalkyl, alkylthio, alkoxy, dialkylamino, alkylsulphonyl, acyl, acylamino, cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy and phenylalkyl radical, R, 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 dialkylamino, nitro, phenyl, halophenyl and cyano; Rl is a hydrogen atom, an alkyl group having 1-15 carbon atoms, a phenylalkyl group, a cycloalkyl group or a halomethylthio group; R, 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, diphenylamino, N,N-dialkylcarbamoyl or N,N-dialkylsulphamoyl; with the proviso that (a) when an alkyl group, phenylalkyl group, alkylthio group, alkoxy group, alkylamino group, dialkylamino group, or an alkylsulphonyl group occurs in the substituents R, to R4 then the alkyl group contains from 1 to 4 carbon atoms, (b) when the cycloalkyl group occurs in the substituents Rz to R, then the cycloalkyl group contains from 3 to 6 carbon atoms and (c) that when Rl is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R4 is a phenylalkyl, cycloalkyl or halomethylthio group, R3 may also have a meaning mentioned for R2; and X is an oxygen atom or a sulphur atom.
In one embodiment of the invention there is provided a compound of the formula given above, in which formula, Rn represents an alkyl group having from 1 to 6 carbon atoms which is substituted with an alkoxy group having from l to 4 carbon atoms, or R3 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 Rl, R2, R4 and X are as hereinbefore defined.
Structurally related 1,3,4 substituted pyrazoline derivatives are the subject matter of the United Kingdom Patent No. 1 514285. The compounds described in said Patent No. 1 514 285 also have good insecticidal properties.
Thus if an alkyl group, phenylalkyl group, alkylthio group, alkoxy group, alkyl- amino group, dialkylamino group or an alkylsulphonyl group occurs in the substituents Rl to R4, then the alkyl radical present in such group contains from 1--4 carbon atoms; and when the cycloalkyl group occurs the cycloalkyl group contains from 3-6 carbon atoms.
If an acyl group or an acylamino group occurs in R1, then the acyl part of such a group is preferably derived from an aliphatic monocarboxylic acid, for example acetic acid or propionic acid.
When R1 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 1,3,5-substituted pyrazolines, and 1,3-substituted compounds have 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 - phenylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (2 - methyl - 2 - nitro propyl) - 2 - pyrazoline, m.p. 146"C; 2) 1 (3 - trifluoromethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 methyl - 2 - nitropropyl) - 2 - pyrazoline, m.p. 1600C (decomposition); 3) 1 - (3 - nitro - 4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 (2 - methyl - 2 - nitropropyl) - 2 -pyrazoline, m.p. 1980C; 4) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methyl 2 - nitropropyl - 2 - pyrazoline, m.p. 219 C (decomposition); 5) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl - 2 pyrazoline, m.p. 135 C; 6) 1 - (4 - propylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl 2 - pyrazoline, m.p. 111 C; 7) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl 2 - pyrazoline, m.p. 117 C; 8) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - n - heptyl - 2 pyrazo line, m.p. 107 C; 9) 1 - n - butylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - n - heptyl - 2 - pyrazoline, m.p. 30 C; 10) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl 2 - pyrazoline, m.p. 115 C; 11) 1 - (3,4 - di - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl 2 - pyrazoline, m.p. 1110C; 12) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl - 2 pyrazoline, m.p. 119 C; 13) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - heptyl - 2 pyrazoline, m.p. 144 C; 14) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 1130C; 15) 1 - (4 - cyanophenylcarbamoyl) - 3 (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 114 C; 16) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 107 C; 17) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 105 C; 18) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - decyl 2 - pyrazoline, m.p. 122 C; 19) 1 - (4 - propylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 125 C; 20) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - n - decyl - 2 pyrazoline, m.p. 870C; 21) 1 - (4 - chiorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( 2 methoxy- ethyl) - 2 - pyrazoline, m.p. 87"C; 22) 1 - (4 - ethoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methoxy ethyl) - 2 - pyrazoline, m.p. 111 C; 23) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methoxy ethyl) - 2 - pyrazoline, m.p. 830C; 24) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methoxy ethyl) - 2 - pyrazoline, m.p. 159 C; 25) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (2 - methoxyethyl) - 2 pyrazoline, m.p. 104 C; 26) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (2 - piperidinoethyl) - 2 pyrazoline, m.p. 113"C; 27) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidino ethyl) - 2 - pyrazoline, m.p. 148 C; 28) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 piperidinoethyl) - 2 - pyrazoline, m.p. 113 C; 29) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidino ethyl) - 2 - pyrazoline, m.p. 111 C; 30) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidino ethyl) - 2 - pyrazoline, m.p. 134 C; 31) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline, m.p. 100 C; 32) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline; 33) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline; 34) 1 - (4 - cyanophenylcarbamoyl) - 3 - ( 4- chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline; 35) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (2 - diethylaminoethyl) 2 - pyrazoline, m.p. 87 C; 36) 1 - [N - (4 - chlorophenyl) - N - methylcarbamoylj - 3 - (4 - chlorophenyl) 4 - (2 - piperidinoethyl) - 2 - pyrazoline; 37) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenyl thioethyl) - 2 - pyrazoline, m.p. 137"C; 38) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenyl thioethyl) - 2 - pyrazoline, m.p. 1380C; 39) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenyl thioethyl) - 2 - pyrazoline, m.p. 124"C; 40) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenylthio ethyl) - 2 - pyrazoline, m.p. 122"C; 41) 1 - (4 - fluorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenylthio ethyl) - 2 - pyrazoline, m.p. 1300C; 42) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenoxy ethyl) - 2 - pyrazoline, m.p. 100"C; 43) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenoxy ethyl) - 2 - pyrazoline, m.p. 112"C; 44) 1 - (4 - benzylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl - 2 pyrazoline, m.p. 179"C; 45) 1 - (4 - phenylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl - 2 pyrazoline; m.p. 1640C; 46) 1 - (4 - phenoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl - 2 pyrazoline, m.p. 177"C; 47) 1 - [N - (4 - chlorophenyl) - N - (trichloromethylthio) - carbamoyl] - 3 (4 - chlorophenyl) - 4 - phenyl -2 - pyrazoline, m.p. 177"C; 48) 1 - [N - benzyl - N - (4 - chlorophenyl) - carbamoyl] - 3 - (4 - chlorophenyl) 4 - phenyl - 2 - pyrazoline, m.p. 116 C; 49) 1 - [N - cyclohexyl - N - (4 - chlorophenyl) - carbamoyl] - 3 - (4 - chloro phenyl) - 4 - phenyl - 2 - pyrazoline, m.p. 138 C; 50) 1 - phenylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - cyclohexylmethyl - 2 pyrazoline, m.p. 179"C; 51) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyclohexyl methyl - 2 - pyrazoline, m.p. 153 C; 52) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyclohexyl 2 - pyrazoline, m.p. 123 C; 53) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlerophenyl) - 4 - cyclohexylmethyl 2-pyrazoline, m.p. 173"C; 54) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyclohexylmethyl 2 - pyrazoline, m.p. 228 C; 55) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyclohexylmethyl 2 - pyrazoline, m.p. 131 C; 56) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - cyclohexylmethyl - 2 pyrazoline, m.p. 169 C; 57) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - methoxyphenyl) - 4 - - phenyl ethyl - 2 - pyrazoline, m.p. 143 OC; 58) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - methoxyphenyl) - 4 - - phenyl ethyl - 2 - pyrazoline, m.p. 111 C; 59) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - methoxyphenyl) - 4 phenylethyl - 2 - pyrazoline, m.p. 1100C; 60) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - methoxyphenyl) - 4 - p - phenyl- ethyl - 2 - pyrazoline, m.p. 1420C; 61) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - methoxyphenyl) - 4 - p - phenyl ethyl - 2 - pyrazoline, m.p. 1580C; 62) 1 - cyclohexylcarbamoyl - 3 - (4 - methoxyphenyl) - 4 - - phenylethyl - 2 pyrazoline, m.p. 126"C; 63) 1 - (4 - chiorophenylcarbamoyl) - 3 - (4 - isopropoxyphenyl) - 4 - p - diethyl- aminoethyl - 2 - pyrazoline; 64) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - isopropoxyphenyl) - 4 - p - diethyl- aminoethyl - 2 - pyrazoline; 65) 1 - phenylcarbamoyl - 3 - (4 - isopropoxyphenyl) - 4 - p - diethylaminoethyl 2 - pyrazoline; 66) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - isopropoxyphenyl) - 4 - (3- diethylaminoethyl - 2 - pyrazoline; 67) 1 - (4 - isopropylphenylcarbamoyl) - 3 - (4 - isopropoxyphenyl) - 4 - p- diethylaminoethyl - 2 - pyrazoline; 68) 1 - cyclohexylcarbamoyl - 3 - (4 - isopropoxyphenyl) - 4 - p - diethylamino- ethyl - 2 - pyrazoline; 69) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [ - (N - methyl piperazino) - ethyl] - 2 - pyrazoline, m.p. 159 C; 70) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [ - (N methylpiperazino) - ethyl] - 2 - pyrazoline, m.p. 173 C; 71) 1 - (4 - methylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [ - (N methylpiperazino) - ethyl] - 2 - pyrazoline, m.p. 159 C; 72) 1 - (4 - isobutylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [ - (N methylpiperazino) - ethyl] - 2 - pyrazoline, m.p. 136 C; 73) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - [ - (N - methyl piperazino) - ethyl] - 2 - pyrazoline; 74) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 145 C; 75) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 141 C; 76) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 95 C; 77) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 184 C; 78) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 1260C; 79) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - - phenyl sulfonethyl - 2 - pyrazoline, m.p. 203 C; 80) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - - phenyl sulfonethyl - 2 - pyrazoline, m.p. 181 C; 81) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - - phenylsulfonethyl 2 - pyrazoline, m.p. 194 C; 82) 1 - (4 - methylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - - phenyl sulfonethyl - 2 - pyrazoline, m.p. 210 C; 83) 1 - phenylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - - phenylsulfonethyl - 2 pyrazoline, m.p. 168 C; 84) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - - phenyl sulfonethyl - 2 - pyrazoline, m.p. 168 C; 85) 1 - (4 - isobutylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - - phenyl sulfonethyl - 2 - pyrazoline, m.p. 156 C; 86) 1 - (3 - trifluoromethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenylsulfonethyl - 2 - pyrazoline, m.p. 180 C; 87) 1 - (3 - chloro - 4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenylsulfonethyl - 2 - pyrazoline, m.p. 1200C; 88) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethoxy carbonylpropyl) - 2 - pyrazoline, m.p. 135 C; 89) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 ethoxycarbonylpropyl) - 2 - pyrazoline, m.p. 97 C; 90) 1 - (4 - methylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethoxy carbonylpropyl) - 2 - pyrazoline, m.p. 88 C; 91) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [3 - (dimethyl carbamoyl) - propyl] - 2 - pyrazoline, m.p. 136 C; 92) 1 - (4 - isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [3 - (di methylearbamoyl) - propyl] - 2 - pyrazoline, m.p. 158 C; 93) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [2 - (dimethyl carbamoyl) - propyl] - 2 - pyrazoline, m.p. 145 C; 94) 1 - (3,4 - dichlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - [3 - (di methylcarbamoyl - propyl] - 2 - pyrazoline, m.p. 169 C; 95) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - methoxy propyl) - 2 - pyrazoline, m.p. 122 C; 96) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - methoxy propyl) - 2 - pyrazoline, m.p. 127 C; 97) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 methoxypropyl) - 2 - pyrazoline, m.p. 124"C; 98) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (3 - methoxypropyl) 2 - pyrazoline, m.p. 97"C; 99) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - methoxy propyl) - 2 - pyrazoline, m.p. 190 C; 100) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - methoxy propyl) - 2 - pyrazoline, m.p. 1430iC; 101) 1 - (4 - chlorophenylcarbamoyI) - 3 - (4 - chlorophenyl) - 4 - (3 - piperidino propyl) - 2 - pyrazoline, m.p. 107 C; 102) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - piperidino propyl) - 2 - pyrazoline, m.p. 120 C; 103) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyanomethyl - 2 pyrazoline, m.p. 175 C; 104) 1 - (4 - cyonphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyanomethyl - 2 pyrazoline, m.p. 205 C; 105) 1 - (4 - isopropylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyanomethyl 2 - pyrazoline, m.p. 157 C; 106) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - cyanomethyl 2 - pyrazoline, m.p. 205 C; 107) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - cyanomethyl - 2 pyrazoline, m.p. 170 C; 108) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - ethylthio ethyl) - 2 - pyrazoline, m.p. 102 C; 109) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - ethyl thioethyl) - 2 - pyrazoline, m.p. 830C; 110) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - ethyl thioethyl) - 2 - pyrazoline, m.p. 111 C; 111) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - ethylthio ethyl) - 2 - pyrazoline, m.p. 190 C; 112) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - ( - ethylthioethyl) - 2 pyrazoline, m.p. 98 C; 113) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - dimethyl aminoethyl) - 2 - pyrazoline, m.p. 1310C; 114) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - dimethyl aminoethyl) - 2 - pyrazoline, m.p. 175 C; 115) 1 - cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - ( - dimethylaminoethyl) 2 - pyrazoline, m.p. 115 C; 116) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ((3 - di- ethylaminoethyl) - 2 - pyrazoline, m.p. 117 C; 117) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ( - dimethyl aminoethyl) - 2 - pyrazoline, m.p. 103 C; 118) l - (4 - isopropylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ((3 - di- methylaminoethyl) - 2 - pyrazoline, m.p. 157 C; 119) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxycarbonyl methyl - 2 - pyrazoline, m.p. 1140C; 120) 1 - phenylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - ethoxycarbonylmethyl - 2- pyrazoline, m.p. 98 C; 121) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxycarbonyl methyl - 2 - pyrazoline, m.p. 113 C; 122) 1 - (4 - isobutylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxycarbonyl methyl - 2 - pyrazoline, m.p. 123 C; 123) 1 - (4 isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxy carbonylmethyl - 2 - pyrazoline, m.p. 96"C; 124) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxy- carbonylmethyl - 2 - pyrazoline, m.p. 85 C; 125) 1 - (3,4 - dichlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxy carbonylmethyi - 2 - pyrazoline, m.p. 1250C; 126) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - ethoxycarbonyl methyl - 2 - pyrazoline, m.p. 159 C; 127) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethylthio propyl) - 2 - pyrazoline, m.p. 105 C; 128) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethylthio propyl) - 2 - pyrazoline, m.p. 1300C; 129) 1 - (4 - ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethylthio propyl) - 2 - pyrazoline, m.p. 870C; 130) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - ethylthio propyl) - 2 -pyrazoline, m.p. 860 C; 131) 1 - (4 - methylthiophenylcarbamoyl) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pyrazoline, m.p. 97"C; 132) 1 - (4 - chlorophenylcarbamoyl) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pvrazoline, m.p. 970 C; 133) 1 - (4 - ethoxyphenylcarbarnoy1) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pyrazoline, m.p. 1050C; 134) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pyrazoline, m.p. 1520C; 135) 1 - (4 - isobutylphenylcarbamovl) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pyrazoline, m.p. 1100C; 136) 1 - (4 - fluorophenyicarbamoyl) - 3 - (4 - trifluoromethylphenyl) - 4 - (3 methoxypropyl) - 2 - pvrazoline, m.p. 1130C; 137) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - cyano- propyl) - 2 - pyrazoline, m.p. 126"C; 138) 1 - (4 - methylthiophenylcarbamovl) - 3 - (4 - chlorophenyl) 4 - (3 - cyano propyl) - 2 - pyrazoline, m.p. 109"C; 139) 1 - phenylcarbamovl - 3 - (4 - chlorophenyl) - 4 - (3 - cyanopropyl) - 2 pyrazoline, m.p. 1480C; 140) 1 - (4 - chlorophenvlcarbamovl) - 3 - (4 - chlorophenyl) - 4 - (3 - cyano propyl )- 2 - pyrazoline, m.p. 1200C; 141) 1 - (4 - isopropylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (3 - cyano propyl) - 2 - pyrazoline, m.p. 154 C; 142) 1 - (4 - fluorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 1300C; 143) 1 - (4 - nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - benzyl - 2 pyrazoline, m.p. 1670C; 144) 1 - (4 - chlorophenylcarbamovl) - 3 - (4 - chlorophenyl) - 4 - (dimethyl carbamoylmethyl) - 2 - pyrazoline, m.p. 151 CC; 145) 1 - phenylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - dimethylcarbamoylmethyl) 2 - pyrazoline, m.p. 1450 C; 146) 1 - (4 - ethylphenylcarbamovl) - 3 - (4 - chlorophenyl) - 4 - (dimethyl carbamoylmethyl) - 2 - pyrazoline, m.p. 1550C; 147) 1 - (4 - methoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (dimethyl- carbamoylmethyl) - 2 - pyrazoline, m.p. 1510C; 148) 1 - (4 - cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (dimethyl carbamoylmethyl) - 2 - pyrazoline, m.p. 2100 C; In particular, compounds of the above mentioned general formula in which Rl, R2, R4 and X are defined as above and R3 represents an alkyl group having from 1 to 6 carbon atoms substituted with an alkoxy having from 1 to 4 carbon atoms, or wherein Rs 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 R1, R2 and R4 have the above mentioned meanings, and R, 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.
On the basis of their strong insecticidal activity the substances of the invention may be used in low dosages in controlling insects. The amount of the 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 0.05-1kg of the active substance per hectare yields good results.
For practical application, the compounds of the invention are processed to com positions. In these compositions 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 dispersions, pastes, dusting powders, wettable powders, miscible oils, granules, invert emulsions, aerosol compositions and fumigating candles.
Wettable powders, pastes and miscible oils are compositions in concentrate 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. 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 the 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) - 1,1,1trichloroethane and hexachloroepoxyoctahydro - dimethanonaphthalene; 2. carbamates, for example N - methyl - 1 - naphthyl - carbamate; 3. dinitrophenols, for example 2 - methyl - 4,6 - dinitrophenol and 2 - (2butyl) - 4,6 - dinitrophenyl) - 3,3 - dimethylacrylate; 4. organic phosphorus compounds, for example dimethyl - 2 - methoxycarbonyl - I - methylvinyl - phosphate; 0,0 - diethyl - 0 - p.nitrophenylphosphorthiate; N - monomethyl - amide of 0,0 - dimethyldithiophosphoryl acetic acid; Acaricides, for examples: 5. diphenylsulfides, for example p - chlorobenzyl - p - chlorophenylsulfide and 2,4,4',5 - tetrachlorodiphenyl - sulfide; 6. diphenylsulphonates, for example p - chlorophenyl benzene sulfonate; 7. methylcarbinols, for example 4,4 - dichloro - a - trichloromethylbenzhydrol; 8. quinoxaline compounds, for example methylquinoxaline dithiocarbonate.
Fungicides, for example: 9. organic mercury compounds, for example phenyl mercury acetate and methyl mercury cyanoguanide; 10. organic tin compounds, for example triphenyltin hydroxide and triphenyltin acetate; 11. alkylene bis - dithiocarbamates, for example, zinc ethylene bis - diethiocarbamate and manganese ethylene bis - dithiocarbamate; and 12. a - 2,4 - dinitro - 6 - (2 - octyl - phenyl - crotonate), 1 - bis - (dimethyl- amino)phosphoryl - 3 - phenyl - 5 - amino 1,2,4 - triazole, 6 - methyl - quinoxaline2,3 - dithiocarbonate, 1,4 - dithioanthraquinone - 2,3 - dicarbenitrile, N - trichloromethylthiophthalimide, N - trichloromethylthiotetrahydrophthalimide, N - (7,1,2,2tetrachloroethylthio) - tetrahydrophthalimide, N - dichlorofiuoromethylthio - Nphenyl - N' - dimethylsulphonyldiamide and tetrachloroisophthalonitrile.
As already noted above the active compounds of the invention arc novel substances which can be prepared according to methods which are known per se for the synthesis of similar substances or methods analogous thereto.
For example the substances can be prepared by reacting a compound of the general formula
wherein R2 and Ra have the above-indicated meanings, with a compound of the formula R1-N=C=X wherein R1 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 diethylether or petroleum ether.
The compounds in which R4 is not a hydrogen atom can be prepared from the pyrazolines obtained in the above-described manner, in which R4 = H according to methods which are known per se. Compounds in which R4 is an alkyl group can be obtained, for example, by reacting the compound in which R4 = H with an alkyl halide in a polar solvent in the presence of an acid binding agent.
Another method of preparing compounds in which R4 is not a hydrogen atom is the reaction of a pyrazoline derivative which is not substituted in the 1 position with an Rl, R4 disubstituted carbamoylchloride or Rl, R4 disubstituted carbamic acid ester.
The above mentioned starting material of the formula
can be prepared in various manners dependent on the meaning of the substituents B. and Ra. Inter alia, when the substituents R2 and R3 are a substituted or non-substituted pyridyl group, thienyl group or phenyl group, the said starting material can be prepared by reacting a compound of the formula
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.
The 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
being obtained. The reaction is carried out at elevated temperature for example the boiling point of the solvent used.
The above-mentioned starting material can also be obtained by reacting a compound of the formula
with dimethylamine and paraformaldehyde, a compound of the formula
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 formula
is obtained again.
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
being obtained.
The invention will now be described in greater detail with reference to the following examples.
EXAMPLES.
I. 1 - (p - chlorophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - methoxy ethyl) A2 - pyrazoline. a) 10.6 g of dimethylaminehydrochloride, 4.0 g of paraformaldehyde and 21.3 g of 4' - chloro - 4 - methoxy - butyrophenone were suspended in 30 ml of dioxan. This mixture was then refiuxed 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 - methoxy butene - 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 - chlorophenyl) - 4 - (2 - methoxyethyl) - A2 - pyrazoline were obtained. Boiling point (0.35-0.40 mm Hg): 155-1650C. c) 7.7 g of p - chlorophenyl - isocyanate were added to the solution of 12 g of 3 - (p - chiorophenyl) - 4 - (2 - methoxyethyl) - A2 - pyrazoline in 50 ml of dry ether. After stirring for 1 hour the ether was distilled off and replaced by 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; melting point 870 C.
In an analogous manner the following compounds were prepared: 1 - (p - ethoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - methoxyethyl) A2 - pyrazoline, m.p. 111"C; 1 - (p - methylthiophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - methoxy ethyl) - A2 - pyrazoline, m.p. 830C; 1 - (p - nitrophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - methoxyethyl) A2 pyrazoline, m.p. 159 C; 1 - cyclohexylcarbamoyl - 3 - (p - chlorophenyl) - 4 - (2 - methoxyethyl) - A2 pyrazoline, m.p. 1040 C; II. 1 - (p - chlorophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - piperidinoethyl) - A2 pyrazoline. a) A suspension of 26.6 g of 4' - chloro - 4 - piperidinobutyrophenone, 4 g of paraformaldehyde and 10.6 g of 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) - 4 - piperidinoburane were obtained. b) A solution of 26.7 g of the compound obtained according to a) and 10 ml of hydrazinehydrate in 35 ml of ethanol were refluxed for 7 hours and then distilled.
18.1 g of 3 - (p - chlorophenyl) - 4 - (2 - piperidinoethyl) - A2 - 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 - piperidinoethyl) - # - pyrazoline in 500 ml 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 1340C.
The following compounds were prepared in an analogous manner: 1 - cyclohexylcarbamoyl - 3 - (p - chlorophenyl) - 4 - (2 - piperidinoethyl) - #- pyrazoline, m.p. 113 C; 1 - (p - cyanophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - piperidinoethyl) # - pyrazoline, m.p. 148 C; 1 - (p - isopropoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - ( 2 - piperidino ethyl) - # - pyrazoline, m.p. 113 C; 1 - (p - ethylphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - piperidinoethyl) A' - pyrazoline, m.p. 1110.C; 1 - (p - chlorophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - diethylamino ethyl) - # - pyrazoline, m.p. 100 C; 1 - (p - ethylphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - dimethylaminoethyl) # - pyrazoline, on oil; 1 - (p - isopropoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - diethylamino ethyl) - A2 - pyrazoline, an oil; 1 - (p - cyanophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - diethylamino ethyl) - A' - pyrazoline, m.p. 700 C; 1 - cyclohexylcarbamoyl - 3 - (p - chlorophenyl) - 4 - (2 - diethylaminoethyl) - #- pyrazoline, m.p. 87"C; 1 - (p - chlorophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenylthioethyl) # - pyrazoline, m.p. 137 C; 1 - (p - isopropoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenylthio ethyl) - # - pyrazoline, m.p. 138 C; 1 - (p - methylthiophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenylthio ethyl) - # - pyrazoline, m.p. 124 C; 1 - (p - ethylphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenylthioethyl) # - pyrazoline, m.p. 122 C; 1 - (p - fluorophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenylthioethyl) 2 pyrazoline, m.p. 130"C; HI. 1 - (p - isopropoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 phenoxyethyl) - A' - pyrazoline. a) A mixture of 27.5 g of 4' - chloro - 4 - phenoxybutyrophenone, 4 g of paraformaldheyde and 10.9 g of dimethylaminehydrochloride in 40 ml of dioxan was reflexed 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 - chlorobenzoyl) - 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 ml 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) - 4 (2 - phenoxyethyl) - A2 - pyrazoline were obtained. c) 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; melting point 1000 C.
The following compounds are prepared in a similar manner: 1 - (p - methylthiophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - (2 - phenoxy-. ethyl) - A' - pyrazoline, m.p. 1120C; 1 - (p - benzylphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - phenyl - A' - pyrazo line, m.p. 179 C; 1 - (p - phenylthiophenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - phenyl - #- pyrazoline, m.p. 164 C; 1 - (p - phenoxyphenylcarbamoyl) - 3 - (p - chlorophenyl) - 4 - phenyl - A2- pyrazoline, m.p. 1770C; 1 - [N - (p - chlorophenyl) - N - (trichloromethylthio)carbamoyl] - 3 - (p - chloro phenyl) - 4 - phenyl - - pyrazoline, m.p. 1770C; 1 - [N - benzyl - N - (p - chlorophenyl) - carbamoyl] - 3 - (p - chlorophenyl) - 4 phenyl - # - pyrazoline, m.p. 116 C; 1 - [N - cyclohexyl - N - (p - chlorophenyl)carbamoyl] - 3 - (p - chlorophenyl) - 4 phenyl - # - pyrazoline, m.p. 138 C; IV. The active compounds according to the invention were dispersed in water in concentrations of 300, 100, 30, 10, 3, 1 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 than 50% mortality TABLE Bioacidal activity against larvae of Leptinotarsa decemlineata and Pieris brassicae
Bioacidal activity Compound concentration expressed in mg of active substance per litre (PPM) number according to the aforementioned list Cola L Pieris Brassicae 300 100 30 10 3 1 0,3 300 100 30 10 3 1 0,3 1 # # - 2 + + # - + + 4 + + + + # - + 5 + + + + - + + + 6 + + # - + + 7 + # - + + 10 + # - + + # 11 + + + # - 12 + # - + + 13 # - + + # 14 # # - 15 # - + 16 # - 17 # # - + # 21 + + + + + # - + + 22 + + + # # # - + 23 + + + # - + + 24 + + + # - + + TABLE (cont.) Bioacidal activity against larvae of Leptinotarsa decemlineata and Pieris brassicae
Biocidal activity Compound concentration expressed in mg of active substance per litre (PPM) number according to the aforementioned list Cola L Pieris Brassicae 300 100 30 10 3 1 0,3 300 100 30 10 3 1 0,3 27 + + # # - + + + + # 28 + + + + - + + + + + 29 + + + + + # - + + + + + # 30 + + + + # - + + + + + + 31 + + + + # - + + + + + 32 + + + + # - + + + + + 33 + + + + - + + + + # 34 + + + + - + + + + 35 + + + # - + + + # 36 + + 37 + + + # - + + 38 + + # - + 39 + + 40 + + 41 + + 42 + # - + 43 # + 51 + + + # - + + 52 + # - + + TABLE (cont.) Biocidal activity against larvae of Leptinotarsa decemlineata and Pieris brassicae
Biocidal activity Compound concentration expressed in mg of active substance per litre (PPM) number according to the aforementioned list Cola L Pieris Brassicae 300 100 30 10 3 1 0,3 300 100 30 10 3 1 0,3 55 + + 57 + + # # - + + 58 + + 59 + + + # - + + # 60 + + 61 + + 62 + + 63 + + + # - + + + + # 64 + + 65 + + 66 + + + - + + + + # 67 + + 69 + + # - + + + + 72 # # - + + + 74 + + + + # - + + + 76 + + - + + 79 + + + + # - + # 84 + + # # 88 + + + # - + + + + 89 + # # - + + + 91 + + # # - + + + + 94 + + + - + + +

Claims (37)

  1. WHAT WE CLAIM IS:1. A compound of the general formula
    wherein R1 is an alkyl group, a cycloalkyl group, a phenylalkyl group 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, cycloalkyl, alkylthio, alkoxy, dialkylamino, alkylsulphonyl, acyl, acylamino, cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy and phenylalkyl radical3 R, 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, monoalkylamino or dialkylamino, nitro, phenyl, halophenyl and cyano; R, is a hydrogen atom, an alkyl group having 1-15 carbon atoms, a phenylalkyl group, a. cycloalkyl group or a halomethylthio group; R, 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, diphenylamino, N,N - dialkylcarbamoyl or N,N - dialkylsulphamoyl; with the proviso that (a) when an alkyl group, phenylalkyl group, alkylthio group, alkoxy group, alkylamino group, dialkylamino group, or an alkvlsulphonyl group occurs in the substituents R to R4 then the alkyl group contains from 1 to 4 carbon atoms, (b) when the cvcloalkyl group occurs in the substituents R1 to R4 then the cycloalkyl group contains from 3 to 6 carbon atoms and (c) that when R1 is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R4 is a phenylalkyl group, a cycloalkyl group or a halomethylthio group, R3 may also have a meaning mentioned for R2; and X is an oxygen atom or sulphur atom.
  2. 2. A compound as claimed in Claim 1, in which R,, R2, R4 and X are defined as in Claim 1 and Ra represents an alkvl group having from 1 to 6 carbon atoms substituted with a alkoxy group having from 1 to 4 carbon atoms or R3 is an alkvl group having from 1 to 6 carbon atoms substituted with a dialkvlamino group, the alkyl radicals of which may with the nitrogen atom form a heterocyclic ring.
  3. 3. 1 - (4 - Chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methoxyethyl) - 2 - pyrazoline.
  4. 4. 1 - (4 - Ethoxyphenylcarbamoyl) -3 - (4 - chlorophenyl) - 4 - (2 - methoxy. ethyl) - 2 - pyrazoline.
  5. 5. 1 - (4 - Methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 methoxyethyl) - 2 - pyrazoline.
  6. 6. 1 - (4 - Nitrophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - methoxyethyl) - 2 - pyrazoline.
  7. 7. 1 - (4 - Cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidinoethyl) - 2 - pyrazoline.
  8. 8. 1 - (4 - Isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2piperidinoethyl) - 2 - pyrazoline.
  9. 9. 1 - (4 - Ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidino- ethyl) - 2 - pyrazoline.
  10. 10. 1 - (4 - Chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - piperidinoethyl) - 2 - pyrazoline.
  11. 11. 1 - (4 - Chlorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline.
  12. 12. 1 - (4 - Ethylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethylaminoethyl) - 2 - pyrazoline.
  13. 13. 1 - (4 - Isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2diethylaminoethyl) - 2 - pyrazoline.
  14. 14. 1 - (4 - Cyanophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - diethyl aminoethyl) - 2 - pyrazoline.
  15. 15. 1 - Cyclohexylcarbamoyl - 3 - (4 - chlorophenyl) - 4 - (2 - diethylaminoethyl) - 2 - pyrazoline.
  16. 16. 1 - (4 - Chlorophenylcerbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenylthioethyl) - 2 - pyrazoline.
  17. 17. 1 - (4 - Isopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2phenylthioethyl) -2 - pyrazoline.
  18. 18. 1 - (4 - Methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2phenylthioethyl) - 2 - pyrazoline.
  19. 19. 1 - (4 - E hylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenylthioethyl) - 2- pyrazoline.
  20. 20. 1 - (4 - Fluorophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2 - phenylthioethyl) - 2 - pyrazoline.
  21. 21. 1 - (4 - Thopropoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2phenoxyethyl) - 2 - pyrazoline.
  22. 22. 1 - (4 - Methylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - (2phenoxyethyl) - 2 - pyrazoline.
  23. 23. 1 - (4 - Benzylphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl - 2pyrazoline.
  24. 24. 1 - (4 - Phenylthiophenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl 2 - pyrazoline.
  25. 25. 1 - (4 - Phenoxyphenylcarbamoyl) - 3 - (4 - chlorophenyl) - 4 - phenyl - 2pyrazoline.
  26. 26. 1 - [N - (4 - Chlorophenylj - N - (trichloromethylthio) - carbamoyl] - 3 (4 - chlorophenyl) - 4 - phenyl -2 - pyrazoline.
  27. 27. 1 - [N - Benzyl - N - (4 - chlorophenyl) - carbamoyl] - 3 - (4 - chlorophenyl) - 4 - phenyl - 2 - pyrazoline.
  28. 28. 1 - [N - Cyclohexyl - N - (4 - chlorophenyl) - carbamoyl] - 3 - (4 - chloro phenyl) - 4 - phenyl - 2 - pyrazoline.
  29. 29. A method of preparing compounds of the general formula
    wherein Ra, B,, R3, R4 and X have the meanings stated in Claim 1, characterized in that a compound of general formula
    wherein R2 and R, have the meanings given in Claim 1, in the presence of a solvent is reacted at room temperature with a compound of the formula R,--NN-C=X wherein Rl and X have the meanings indicated in Claim 1.
  30. 30. Insecticidal composition, characterized in that the composition contains a compound of the general formula
    wherein R,, R,, R,, R4 and X have the meanings stated in Claim 1 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.
  31. 31. A composition as claimed in Claim 30, characterized in that the composition also contains a known biocidal compound and/or an artificial manure.
  32. 32. A method of preparing an insecticidal composition, characterized in that a compound of the general formula
    wherein R1, R2, R,, R4 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.
  33. 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.
  34. 34. A method of preparing a compound according to Claim 29 substantially as hereinbefore described.
  35. 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.
  36. 36. A method of preparing an insecticidal composition according to Claim 32 substantially as hereinbefore described.
  37. 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.
GB356/77A 1976-01-09 1977-01-06 1,3,4 substituted pyrazoline derivatives Expired GB1570635A (en)

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NLAANVRAGE7600178,A NL183400C (en) 1976-01-09 1976-01-09 METHOD FOR PREPARING AN INSECTICIDE PREPARATION CONTAINING A PYRAZOLINE COMPOUND AND METHOD FOR PREPARING A PYRAZOLINE COMPOUND WITH INSECTICIDE ACTION

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0065334A1 (en) * 1981-05-12 1982-11-24 Duphar International Research B.V New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal compositions on the basis of these compounds
EP0058424A3 (en) * 1981-02-17 1983-01-19 Nissan Chemical Industries Ltd. Pyrazoline derivatives
GB2166137A (en) * 1984-10-25 1986-04-30 Fmc Corp Pyrazoline insecticides
WO1993018038A1 (en) * 1992-03-02 1993-09-16 E.I. Du Pont De Nemours And Company Arthropodicidal amides

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014810A3 (en) 1979-01-18 1980-11-26 Fbc Limited Pesticidal pyrazoles, their production, compositions and uses, as well as intermediates and their preparation
ATE4593T1 (en) * 1979-07-03 1983-09-15 Duphar International Research B.V PYRAZOLINE DERIVATIVES, PROCESSES FOR THE PREPARATION OF THESE COMPOUNDS, AND INSECTICIDE COMPOSITION BASED ON THESE COMPOUNDS.
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
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
DE4217863A1 (en) * 1991-08-28 1993-03-04 Bayer Ag SUBSTITUTED PYRAZOLINE
DE4217862A1 (en) * 1991-08-28 1993-03-04 Bayer Ag SUBSTITUTED PYRAZOLINE
DE4218745A1 (en) * 1992-06-04 1993-12-09 Schering Ag 1- (4-cyanophenylcarbamoyl) pyrazoline

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Publication number Priority date Publication date Assignee Title
BE795264A (en) * 1972-02-09 1973-08-09 Philips Nv NEW PYRAZOLINE COMPOUNDS WITH INSECTICIDAL ACTIVITY
NL158178B (en) * 1974-07-12 1978-10-16 Philips Nv METHOD OF PREPARING INSECTICIDE PREPARATIONS CONTAINING A PYRAZOLINE DERIVATIVE, SO PREPARED PREPARATIONS, AND METHOD OF PREPARING PYRAZOLINE DERIVATIVES WITH INSECTICIDE ACTION.
DE2700289A1 (en) * 1977-01-05 1978-07-06 Bayer Ag SUBSTITUTED PHENYLCARBAMOYL-2-PYRAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES
DE2700288A1 (en) * 1977-01-05 1978-07-13 Bayer Ag PHENYLCARBAMOYL PYRAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0058424A3 (en) * 1981-02-17 1983-01-19 Nissan Chemical Industries Ltd. Pyrazoline derivatives
EP0065334A1 (en) * 1981-05-12 1982-11-24 Duphar International Research B.V New pyrazoline derivatives, method of preparing the new compounds, as well as insecticidal compositions on the basis of these compounds
GB2166137A (en) * 1984-10-25 1986-04-30 Fmc Corp Pyrazoline insecticides
WO1993018038A1 (en) * 1992-03-02 1993-09-16 E.I. Du Pont De Nemours And Company Arthropodicidal amides

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AU2118877A (en) 1978-07-20
IT1076002B (en) 1985-04-22
PT66039B (en) 1978-06-20
CA1111048A (en) 1981-10-20
HU180915B (en) 1983-05-30
NL7600178A (en) 1977-07-12
ES454857A1 (en) 1978-01-16
FR2337715B1 (en) 1982-02-19
NL183400C (en) 1988-10-17
PT66039A (en) 1977-02-01
SE435176B (en) 1984-09-10
JPS6213349B2 (en) 1987-03-25
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NL183400B (en) 1988-05-16
NZ183006A (en) 1979-01-11
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OA05550A (en) 1981-04-30
DK142985C (en) 1981-10-12
GR63086B (en) 1979-08-09
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BE850220A (en) 1977-07-07
CS205031B2 (en) 1981-04-30
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FR2337715A1 (en) 1977-08-05
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YU1877A (en) 1983-01-21
PL109512B1 (en) 1980-06-30
ZA7714B (en) 1978-08-30
CH631870A5 (en) 1982-09-15
DK142985B (en) 1981-03-09
SE7700067L (en) 1977-07-10
JPS5287166A (en) 1977-07-20
DD129396A5 (en) 1978-01-18
DE2700258A1 (en) 1977-07-14
PL110077B1 (en) 1980-06-30
PL195195A1 (en) 1978-08-28

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PS Patent sealed [section 19, patents act 1949]
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Effective date: 19930106