CA1111048A - 1,3,4 substituted pyrazoline derivatives - Google Patents
1,3,4 substituted pyrazoline derivativesInfo
- Publication number
- CA1111048A CA1111048A CA269,399A CA269399A CA1111048A CA 1111048 A CA1111048 A CA 1111048A CA 269399 A CA269399 A CA 269399A CA 1111048 A CA1111048 A CA 1111048A
- Authority
- CA
- Canada
- Prior art keywords
- group
- pyrazoline
- chlorophenyl
- alkyl
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
ABSTRACT OF THE DISCLOSURE
The invention relates to novel 1-carbamoyl and 1-thio-carbamoyl-.DELTA.2-pyrazolines of the formula:
The invention relates to novel 1-carbamoyl and 1-thio-carbamoyl-.DELTA.2-pyrazolines of the formula:
Description
It is known from German Offenlegungsschrift 2,304,584 in the name of Applicants that pyrazoline compounds which are substituted in the 1,3- or 1,3,5-positions of the pyrazoline ring exert a biocidal activity with respect to arthropods, for example, mites and insects.
It has now been found that new pyrazoline compounds which satisfy the formula below a:nd which, as may be read from the formula, contain substituents in the 1, 3 and 4-positions of the pyrazoline ring, have a very strong insecticidal activity.
10The compounds according to the present invention may be represented by the formula R ~ J R3 N
N
X = C - N - R
in which Rl is an alkyl group, a cyclo alkyl group, a phenyl alkyl group of which the phenyl nucleus may be substituted with halogen, alkyl or nitro, a pyridyl or pyrimidyl group which 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 to 2 substituents selected from the group consisting of halogen, alkyl, halogenalkyl, cycloalkyl, alkyl-thio, alkoxy, dialkylamino, alkylsulphonyl, acyl, acylamino,cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy, and phenylalkyl radi.cal, R2 is an alkyl group, a cycloalkyl group, a phenyl group or a phenyl group substituted with 1 to 2 sub-stituents select.ed from the group consisting of halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, mono- or dialkylamino, nitro, phenyl, halophenyl and cyano, R4 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 unsubstituted alkyl group having 5 - 10 carbon atoms; or R3 is an alkyl group having l to 6 carbon atoms which is substituted by one or more of the following substituents:
a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a halogen atom, a cyano group, an alkoxycarbonyl group, a phenyl group optionally substituted by nitro, halogen or alkyl, a phenoxy group, a phenylthio group, a phenylsulphinyl group, a phenylsulphonyl group, a : dialkylamino group the two alkyl radicals of which may form together with the nitrogen atom to which they are bound a piperidine or pipera~ine group, w~ich groups may be substituted by alkyl having l - 4 carbon atoms, an alkylphenyl- or diphenylamino group, an N,N-dialkylcarbamoyl g~oup, and an N,N-dialkylsulphamoyl group; on the understanding that when Rl is a phenyl group substituted by phenylthio, phenoxy or phenyl-alkyl and/or R4 is a phenylalkyl, cycloalkyl, P~IN.8275 7-l~.76 or halogenmethylthio group, only in such a case R3 may also have a meaning mentioned for R2;
and X is an oxygen atom or a sulphur atom.
- Structurally related 1,3,4-substituted pyrazoline derivatives are the subject Inatter of - the non-published Netherlands Patent Application 74. o~433 ~ The compounds described in said Applica-tion also have good insecticidal properties.
If an alkyl group, phenylalkyl group, ; 10 alkyl-thio group, alkoxy group, alkylamino group, dialkylamino group or an alkylsulphenyl group occurs in the substituents R1-R4, then the aLkyl radical present in such group contains 1-4 carbon atoms; and in the case where as cyclo-alkyl group occurs the cycloalkyl group represented by R1 to Rl contains 3-6 carbon atoms.
If an acylgroup or an acylamino group occurs in R1, then the acyl part of such a group is preferab-Ly derived from an aliphatic monocarboxylic acid, ; - for example acetic acid or propionic acid.
when R1 represents a heterocyclic ring which contains 1 to 2 nitrogen atoms, -this is preferably a pyridine or pyrimidine ring.
;~ It has been found by biological evaluation exami~nation that the compounds according -to the invention have a good insecticidal activity and, already at low dosages, they are capable of controlling, for example, beetles, larvae of beetles, larvae of mosquitoes as well as caterpillars.
,. . : . . : . .
~ ~ `
It has surprisingly been found that the insecticidal - activity of the compounds according to the invention is consid-erably better than that of the known 1,3- and 1,3,5-substituted pyrazolines. It has been found that in many cases the substances according to 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. For compounds from the known series of 1,3,5-substituted pyrazolines and 1,3-substituted compounds, there is often found, apart from 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.
Many of the active substances according to the invention show, for example, an optimal activity in a concen-tration of 0.3 - 3 ppm show against the larvae of the Colorado beetle, and in a concentration of 0.3 - 30 ppm show a maximum activity against the caterpillar and furthermore in a concen-tration of 0.03 - 0.3 ppm show a maximum activity against larvae of the yellow-fever mosquito. The following active substances are particularly suitable:
1) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-(2-methyl-2-nitro-propyl)-2-pyrazoline, m.p. 146C;
It has now been found that new pyrazoline compounds which satisfy the formula below a:nd which, as may be read from the formula, contain substituents in the 1, 3 and 4-positions of the pyrazoline ring, have a very strong insecticidal activity.
10The compounds according to the present invention may be represented by the formula R ~ J R3 N
N
X = C - N - R
in which Rl is an alkyl group, a cyclo alkyl group, a phenyl alkyl group of which the phenyl nucleus may be substituted with halogen, alkyl or nitro, a pyridyl or pyrimidyl group which 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 to 2 substituents selected from the group consisting of halogen, alkyl, halogenalkyl, cycloalkyl, alkyl-thio, alkoxy, dialkylamino, alkylsulphonyl, acyl, acylamino,cyano, nitro, phenyl, halophenyl, phenylthio, phenoxy, and phenylalkyl radi.cal, R2 is an alkyl group, a cycloalkyl group, a phenyl group or a phenyl group substituted with 1 to 2 sub-stituents select.ed from the group consisting of halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, mono- or dialkylamino, nitro, phenyl, halophenyl and cyano, R4 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 unsubstituted alkyl group having 5 - 10 carbon atoms; or R3 is an alkyl group having l to 6 carbon atoms which is substituted by one or more of the following substituents:
a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a halogen atom, a cyano group, an alkoxycarbonyl group, a phenyl group optionally substituted by nitro, halogen or alkyl, a phenoxy group, a phenylthio group, a phenylsulphinyl group, a phenylsulphonyl group, a : dialkylamino group the two alkyl radicals of which may form together with the nitrogen atom to which they are bound a piperidine or pipera~ine group, w~ich groups may be substituted by alkyl having l - 4 carbon atoms, an alkylphenyl- or diphenylamino group, an N,N-dialkylcarbamoyl g~oup, and an N,N-dialkylsulphamoyl group; on the understanding that when Rl is a phenyl group substituted by phenylthio, phenoxy or phenyl-alkyl and/or R4 is a phenylalkyl, cycloalkyl, P~IN.8275 7-l~.76 or halogenmethylthio group, only in such a case R3 may also have a meaning mentioned for R2;
and X is an oxygen atom or a sulphur atom.
- Structurally related 1,3,4-substituted pyrazoline derivatives are the subject Inatter of - the non-published Netherlands Patent Application 74. o~433 ~ The compounds described in said Applica-tion also have good insecticidal properties.
If an alkyl group, phenylalkyl group, ; 10 alkyl-thio group, alkoxy group, alkylamino group, dialkylamino group or an alkylsulphenyl group occurs in the substituents R1-R4, then the aLkyl radical present in such group contains 1-4 carbon atoms; and in the case where as cyclo-alkyl group occurs the cycloalkyl group represented by R1 to Rl contains 3-6 carbon atoms.
If an acylgroup or an acylamino group occurs in R1, then the acyl part of such a group is preferab-Ly derived from an aliphatic monocarboxylic acid, ; - for example acetic acid or propionic acid.
when R1 represents a heterocyclic ring which contains 1 to 2 nitrogen atoms, -this is preferably a pyridine or pyrimidine ring.
;~ It has been found by biological evaluation exami~nation that the compounds according -to the invention have a good insecticidal activity and, already at low dosages, they are capable of controlling, for example, beetles, larvae of beetles, larvae of mosquitoes as well as caterpillars.
,. . : . . : . .
~ ~ `
It has surprisingly been found that the insecticidal - activity of the compounds according to the invention is consid-erably better than that of the known 1,3- and 1,3,5-substituted pyrazolines. It has been found that in many cases the substances according to 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. For compounds from the known series of 1,3,5-substituted pyrazolines and 1,3-substituted compounds, there is often found, apart from 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.
Many of the active substances according to the invention show, for example, an optimal activity in a concen-tration of 0.3 - 3 ppm show against the larvae of the Colorado beetle, and in a concentration of 0.3 - 30 ppm show a maximum activity against the caterpillar and furthermore in a concen-tration of 0.03 - 0.3 ppm show a maximum activity against larvae of the yellow-fever mosquito. The following active substances are particularly suitable:
1) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-(2-methyl-2-nitro-propyl)-2-pyrazoline, m.p. 146C;
2) 1-(3-trifluoromethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methyl-2-nitropropyl)-2-pyrazoline, m.p. 160C
(decomposition);
' ~. ' . .
PI~N.~275 7.12.76
(decomposition);
' ~. ' . .
PI~N.~275 7.12.76
3) 1-(3-nitro-4-methoxyphenylcarbamoyl)-3-(~l-chlorophenyl)
-4-(2-methyl-2-nitropropyl)-2-pyrazoline~ m.p. 198C;
4) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-~2-methyl-2-nitropropyl)-2-pyrazoline, m.p. 219C
(deeomposition);
4) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-~2-methyl-2-nitropropyl)-2-pyrazoline, m.p. 219C
(deeomposition);
5) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 135C;
6) 1-(4-n-propylphenylcarbamoyl)-3-(4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 111C;
7) 1~(4-methoxyphenylcarbamoyl)-3-(~l-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 117C;
8) I-cyelohexylcarbamoyl-3-(4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 107C;
9) 1-n-bu-tylcarbamoyl-3-(4-ehlorophenyl)-4-n-hep-tyl-2-pyrazoline, m.p. 30C;
10)1-(4-methylthiophenylcarbamoyl)-3-t4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 115C;
11)1-(3,4-di-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 111C;
12)1-(4-nitrophenylcarbamoyl)-3-(4-ehlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 11~C;
13)1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-n-heptyl-2-pyrazoline, m.p. 144C;
14)1-(4-ehlorophenylearbamoyl)-3-(4-ehlorophenyl)-4-n-decyl-2-pyrazoline, m.p. 113C;
15)1-(4-eyanophenylcarbamoyl)-3-(4-chlorophenyl-4-n-deeyl-2-pyrazoline, m.p. 114C;
16)1-(4-nitrophenylearbamoyl)-3-(4-ehlorophenyl)-4-n-deeyl-2-pyrazoline, m.p- 107C;
Pl~.8275 7.12.76
Pl~.8275 7.12.76
17) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-n-decyl-2-pyrazoline, m.p. 105C;
1~) 1-(4-methylt}liophenylcarbamoyl)-3-(4-chlorophenyl)-4-n-decyl-2-pyrazoline, m.p. 122C;
19) 1-(4-n-propylpheny]carbamoyl)-3-(4-chlorophenyl )-Ll -n-decyl-2-pyrazoline, m.p. 125C;
20) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-n-decyl-2-pyrazoline. m.p. 870C;
21~) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)~
~ 10 (2-methoxyethyl)-2-pyrazoline, m.p. 870C;
- 22) 1-(4-ethoxyphenylcarbamoyl)-3-(ll-chlorophenyl)-/l-(2-methoxyethyl)-2-pyrazoline, m.p. 111C;
23) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2pyrazoline, m.p. 830C;
24) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2-pyrazoline, m.p. 159C;
25) 1-;cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(2-meth ethyl)-2-pyrazoline, m.p. 104C;
26) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline, m.p. 113C;
27) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-piperidinoethyl)-2-pyrazoline, m.p. 148C;
; 2~ (4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-l~-(2-piperidinoethyl)-2-pyrazoline, m.p. 113C;
29) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-lpiperidinoethyl)-2-pyrazoline, m.p. 111C;
30) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4 (2-piperidinoethyl)-2-pyrazoline, m.p. 134C;
P~IN.8275 7-12.76 31) 1 -(4-chlorophenylcarl)amoyl )-3~ (4-chloropl1enyl )-4-(2-diethylaminoethyl ) -2-pyrazoline, m .p . 'I 00 C;
32) 1 - (4-ethylphenylcarbamoyl ) -3- (~-chlorophenyl )-4-' (2-die-thylaminoethyl )-2-pyrazoline;
33) 1- (ll-isopropoxyp1lenylcarbamoyl )-3- (4 chlorophenyl )-Il-(2-diethylaminoethyl ~-2-pyrazoline;
- 34) 1 - (4-cyanophenylcarbamoyl )-3- (4-chlorophenyl )-4-(2-diethylaminoethyl )-2-pyrazoline;
35) 1 -cyclohexylcarbamoyl-3- (4-chlorophenyl )-4-(2-diethylamonoethyl)-2-pyrazoline, m.p. 87C;
36) 1-[N-(4-chlorophenyl)-N-methylcarbamoyl~l-3-(4-chloro-B ~on~-l ) -4- (2-piperidinoethyl )-2-pyrazoline;
37) 1- (4-clllorophenylcarbamoyl )-3- (4-chlorophenyl )-4-(2-phenylthioethyl ) -2-pyrazoline, m . p . 137 C ) 15 38) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-phenylthioethyl)-2pyrazoline, m.p. 138C;
39) 1- (4-methylthiophenylcarbamoyl )-3- (4-chlorophenyl)-!~-(2-phenylthioethyl)2-pyrazoline, m. p . 124C;
l~o) 1-(4-ethylphenylcarbamoyl)-3-(~-chlorophenyl)-1~-(2-phenylthioe-thyl ) -2-pyrazoline, m . p . 122 C;
4-,1) 1- (4-:~luorophenylcarbamoyl ) -3- (4-chlorophenyl )-4-(2-phenylthioethyl)-2-pyrazoline, m.p. 130C;
42) 1- (4-isopropoxyphenylcarbamoyl )-4- (!1-chlorophenyl )-4-(2-phenoxyethyl)-2-pyrazoline, m.p. 100C;
43) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-phenoxyethyl ) -2-pyrazoline, m . p . 112 C;
44 ) 1- (Ij -benzylphenylcarbamoyl ) -3- (4-chlorophenyl ) -4-phenyl-2-pyrazoline, m.p. 'I79C;
P~IN.8275 7.12.76 ,. . .
45) 1- (4-phenylthiophenylcarbamoyl)-3- (4-chlorophenyl)-4-phenyl-2-pyra~oline, m.p. 164C;
46) 1-(4-phenoxyphenylcarbamoyl) -3- (4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p. 1770C;
47) 1-[N-(1-chlorophenyl)-N-(trichloromethylthio)-carbamoyl~ -3-(4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p~ 177C;
48) 1-LN-benyl-N-(4-chlorophenyl)-carbamoy~ -3-(4-chloro-phenyl)-4-phenyl-2-pyrazoline, m.p. 116C;
49) 1-LN-cyclohexyl-N-(4-chlorophenyl)-carbamoy ~-3-(4-chlorophenyl)-4-phenyl-2-pyrazoline~:m.p. 138C;
50) 1-phenylcarbamoy~3-(4-chlorophenyl)-4-cyclohexyl-methyl-2-pyrazoline, m p. 179C;
`. - 51) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 153C;
` 15 52) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 123C;
- ~53) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 173C;
54) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4 cyclohexylmethyl-2-pyrazoline, m.p. 228C;
55) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-, cyclohexylmethyl-2-pyrazoline, m.p. 131C;
~ 56) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-; cyclohexylmethyl-2-pyrazoline, m.p. 169C;
57) 1-~4-chlorophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~-phenylethyl-2-pyrazoline, m.p. 143C;
58) 1-~4-ethylphenylcarbamoyl)-3-(4-methoxyphenyl)-4-p-phenylethyl-2-pyrazoline~ m.p. 111C;
_g_ - , ~ . .
~ 8 7.12.76 ,' .
59) 1~ -isopropoxyphenylcarbamoyl)-3-(4-me-thoxyphenyl)-Ll-p-phenylethyl-2-pyrazoline, m.p. 110C;
- 60) 1-(4-cyanophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~phenylethyl-2-pyrazoline, m.p. 1L12C;
61) 1-(nitrophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~-phenylethyl-2-pyrazoline, m.p. 1580C;
. C y~/o .
D 62) 1-~*~hexylcarbamoyl-3-(4-methoxyphenyl)-4--phenylethyl-2-pyrazoline, m.p. 126C;
63) 1-(4-chlorophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-p-diethylaminoethyl-2-pyrazoline;
64) 1-(4-nitrophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-~diethylaminoethyl-2-pyrazoline;
65) 1-phenylcarbamoyl-3-(4-isopropoxyphenyl)-4-~-diethylaminoethyl-2-pyrazoline;
66) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-~iethylaminoethyl-2-pyrazoline;
67) 1-(4-isopropylphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4--diethylaminoethyl-2-pyrazoline;
68) 1-cyclohexylcarbamoyl-3-(4-isopropoxyphenyl)-4-~-diethylaminoethyl-2-pyrazoline;
69) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-_ l ~-(N-methylpiperazino)-ethyl~-2-pyrazoline, m.p.l59C;
70) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-(N-methylpiperazino)-ethyl -2-pyrazoline, m.p. 173C;
71) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-r~- (N-methylplperazino)-ethyl~-2-pyrazoline, m.p. 159G;
72) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-r~- (N-methylpiperazino)-ethyl~-2-pyrazoline, m.p.136C;
p~.8275 7.12~76 73) 1-cyclohexylcarbamoyl-3-(ll-chlorophenyl)-4-[~-(N-methylpiperazino)-ethyl~-2-pyrazoline;
74) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 145C;
75) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 141C;
76) 1-(4-ethylphenylcarbamoyl)-3-(LI-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 95C;
, 77) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-'~ 10 benzyl-2-pyrazoline, m.p. 184C;
78) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline. m.p. 126C;
79) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorphenyl)-4-~-phenylsulfonethyl-2-pyrazoline, m.p. 203C;
80) -1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-phenylsulfonethyl-2-pyrazoline, m.p. 181C;
81) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-frphenyl-sulfonethyl-2-pyrazoline, m.p. 194C;
82) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsulfonethyl-2-pyrazoline, m.p. 210C;
i 83) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-~ phenylsulfon-ethyl-2-pyrazoline, m.p. 168C;
84) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 168C;
85) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 156C;
86) 1-(3-trifluoromethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-phenylsul~onethyl-2-pyrazoline, m.p. 180C;
~, P~IN.8275 7.12.76 4~
- 87) 1-(3-chloro-4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 120C;
88) 1-(4-chlorophenylcarbamoyl)-3-(4-Chlorophenyl)-4-(3-carbethoxypropyl)-2-pyrazoline, m.p. 135C;
589) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-LI-(3-carbethoxypropyl)-2-pyrazoline, m.p. 97C;
90) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-carbethoxypropyl)-2-pyrazoline, m.p. 88C;
91) 1-(4-chlorophenylcarbamoyl)-3-~4-chlQrophenyl)-4-10~3-(dimethylcarbamoyl)-propyl~-2-pyrazQline, m.p. 1360C;
92) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-` ~3=(dimethylcarbamoyl)-propyl~ -2-pyrazoline, m.p.158C;
93) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-C3~dimethylcarbamoyl)-propyl~-2-pyrazoline~ m.p.145C;
1594) 1-(3,4-dichlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-; [3-(dimethylcarbamoyl)-propyl~-2-pyrazoline, m.p. 169C;
- 95) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p~ 122C;
96) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-20(3-methoxypropyl)-2-pyrazoline, m.p. 127C;
97) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 124C;
98) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(3-methoxy-propyl)-2-pyrazoline, m.p. 97C;
2599) 1-(4-cyanophenylcarbamoyl)-3-(4-chlQrophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 190C;
100) 1-(4-nitrophenylcarbamoyl)-3-(4--chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline. m.p. 1430C;
P~ .82~5 ~ 7.12.76 101) 1-(4-chlorophenylcarbamoyl)-3-(1l-chlorophenyl)-4-3-piperidinopropyl)-2-pyrazoline, m.p. 107C;
102) 1-(4-cyanophenylcarbamoyl)-3-(4-chlarophenyl)-4-(3-piperidinopropyl)-2-pyrazoline, m.p. 120C;
5 103) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 175C;
104) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 205C;
105) I-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-10cyanomethyl-2-pyrazoline, m.p. 157C;
106) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 205C;
107) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 170C;
108) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 102C;
109) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 830C;
110) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-20(~-ethylthioethyl)-2-pyrazoline, m.p. 111C;
111) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 190C;
112) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-ll-(~-ethylthioethyl)-2-pyrazoline, m.p. 98C;
25113) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoethyl~-2-pyrazoline, m.p. 131C;
114) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoe-thyl)-2 pyrazoline9 m.p. 175C;
~ PIIN 8275 - 1~5) 1-cyclohexylcarbamoyl-3-(LI-chlorophenyl)-4-(/S-dimethylaminoethyl)-2-pyrazoline, m.p. 115C;
116) 1-(4-methylthiopenylcarbamoyl)-3-(4-chlorophenyl)-II-(,~-dimethylaminoethyl)-2-pyrazoli~e, m.p. 117C;
5 117) 1-(4-methoxyphenylcarbamoyl)-3-~4-chlorophenyl)-4-~-dimethylaminoethyl)-2-pyrazoline, m.p. l03C;
118) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoethyl)-2-pyrazoline, m-p. 157C;
119) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-10carbethoxymethyl-2-pyrazoline, m.p. 114C;
120) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-carbethoxy-methyl-2-pyrazoline, m.p. 980C;
121) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 113C;
15122) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 123C;
123) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxlrmethyl-2-pyrazoline, m.p. 960C;
124) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-20carbethoxymethyl- 2-pyrazoline, m.p. 85C;
125) 1-~3,4-dichlorophenylcarbamoyl)-3-(4-chlorophènyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 125C;
126) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 159C;
25127) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophcnyl)-4-3-ethylthiopropyl)-2-pyrazoline, m.p. 105C;
128) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-ethylthiopropyl)-2-pyrazoline, m.p. 130C;
,' ' ~ '' .
P~-IN.8275 7.12.76 129) 1-(4-ethylphenylcarbamoyl)-3-(chlorophenyl)-4-; 3-ethyl-thiopropyl)-2-pyrazoline, m.p. 870C;
` 130) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-` (3-ethylthiopropyl)-2-pyrazoline, m.p. 860C;
131) 1-(4-methyl-thiophenylcarbamoyl)-3-(4-trifluoromethyl-phenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97C;
132) 1-(4-chlorophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97C;
133) 1-(4-ethoxyphenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 105C;
134) 1-(4-cyanophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-- 4-(3-methoxypropyl)-2-pyrazoline, m.p. 152C;
135) 1-(4-isobutylphenylcarbamoyl)-3-(4-trifluoromethyl-phenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 110C;
136) 1-(4-fluo-^ophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 113C;
- 137) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-cyanopropyl)-2-pyrazoline, m.p. 126C;
138) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-,;
(3-cyanopropyl)-2-pyrazoline, m.p. 109C;
139) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-(3-cyanopropyl)-Z-pyrazoline, m.p. 148C;
140) 1-(4-chlorophenylcarbamoyl)-3-(chlorophenyl)-4-(3-cyanopropyl~-2-pyrazoline, m.p. 120C;
141) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-cyanopropyl)-2-pyrazoline, m.p. 154C;
142) 1-(4-fluorophenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 130C;
PilN.8275 ~ 7.12.76 11~3) 1-(4-nitropllenylcarbamoyl)-3-(L~-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 167C;
1l~l~) 1-(ll-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 151C, 145) 1-phenylcarbamoyl-3-~4-chlorophenyl)-4-(dimethyl-carbamoylmethyl)-2-pyrazoline, m.p. 1 Ll 5~C;
146) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 155C;
147) 1-(4-me-thoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 151C;
148) 1-(4-cyanophenylcarbamoyl)-3-(L~-chlorophenyl)-L~-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 210C;
In particular the compounds of the above general formula, in which R3 is an alkyl radical having 1 to 6 carbon atoms~hich is substituted with an alkoxy - group having 1 to L~ carbon atoms or a dialkylamino group of which the alkyl radicals together with the ni-trogen atom to which they are bound can form a heterocyclic ring, show , very strong insecticidal properties.
In addition to the strong insecticidal activity it has been found that the compounds of the above general formula, in which R1, R2 and RL~ have the above meanings, and R3 i~; an alkyl group having 1 to 6 carbon a-toms which is substituted with a cyano group or a dialkylamino group, which two alkyl radicals can form - with the nitrogen atom to which they are bound - a possibly alkylated heterocyclic ring which may comprise a second hetero atom, also show fungicidal properties.
PI-~.8275 ~ 4~ 7.12.76 .
. . .
On the basis of their strong insecticidal activity the substances according to the invention may be used in low dosages in controlling insects. The amoùnt 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 insec-ts, 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 according to the invention are processed to compositions.
~n these compositions the active substance is mixed with solid carrier material or dissolved or dispersed in;a liquid carrier material, if desired combined with auxi-liary substances, for example surface-active substances and stabilizers.
, 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 concentratedform which are diluted with water prior to or during use.
- The invert emulsions are mainly used in a:ir applications, namely when large areas are treated with a comparatively small quantity of composition. -, PHN.8275 7.12.76 ~. .
The invert emulsions can be prepared shortly before or even during the spraying in the spraying apparatus by emulsi~ying water in an oily solution or an oily dispersion of the active substance. Some types o~
compositions ~ill be described in greater detail hereina~ter by way of example.
Granular compositions are prepared, for example, by taking up the active substance in a solvent and impregnating theresulting solution, optionally in the presence o~ a binder, on granular carrier material, for example porous granules (for example pumice and attaclay), mineral non-porous- granules (sand or ground marl), organic granules (~or example dried coffee grounds and cut tobacco stems).
A granular composition can also be prepared by compressing the active substance together with pol~dered minerals in the presence o~ lubricating agents and binders and to disintegrate and sieve the compressed product to the desired grain size.
Dusting powders can be obtained by intimately mixing the active substance with an inert solid carrier material, *or example in a concentration of 1 to 50 ~
by weight. As examples o~ suitable solid carrier materials may be mentioned talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chal~, bentonite, attapulgite and colloidal SiO2 or mixtures of these and similar sub-stances. Organic carrier materials, ~or example, ground sheels of walnuts may also be used.
1~) 1-(4-methylt}liophenylcarbamoyl)-3-(4-chlorophenyl)-4-n-decyl-2-pyrazoline, m.p. 122C;
19) 1-(4-n-propylpheny]carbamoyl)-3-(4-chlorophenyl )-Ll -n-decyl-2-pyrazoline, m.p. 125C;
20) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-n-decyl-2-pyrazoline. m.p. 870C;
21~) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)~
~ 10 (2-methoxyethyl)-2-pyrazoline, m.p. 870C;
- 22) 1-(4-ethoxyphenylcarbamoyl)-3-(ll-chlorophenyl)-/l-(2-methoxyethyl)-2-pyrazoline, m.p. 111C;
23) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2pyrazoline, m.p. 830C;
24) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2-pyrazoline, m.p. 159C;
25) 1-;cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(2-meth ethyl)-2-pyrazoline, m.p. 104C;
26) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline, m.p. 113C;
27) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-piperidinoethyl)-2-pyrazoline, m.p. 148C;
; 2~ (4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-l~-(2-piperidinoethyl)-2-pyrazoline, m.p. 113C;
29) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-lpiperidinoethyl)-2-pyrazoline, m.p. 111C;
30) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4 (2-piperidinoethyl)-2-pyrazoline, m.p. 134C;
P~IN.8275 7-12.76 31) 1 -(4-chlorophenylcarl)amoyl )-3~ (4-chloropl1enyl )-4-(2-diethylaminoethyl ) -2-pyrazoline, m .p . 'I 00 C;
32) 1 - (4-ethylphenylcarbamoyl ) -3- (~-chlorophenyl )-4-' (2-die-thylaminoethyl )-2-pyrazoline;
33) 1- (ll-isopropoxyp1lenylcarbamoyl )-3- (4 chlorophenyl )-Il-(2-diethylaminoethyl ~-2-pyrazoline;
- 34) 1 - (4-cyanophenylcarbamoyl )-3- (4-chlorophenyl )-4-(2-diethylaminoethyl )-2-pyrazoline;
35) 1 -cyclohexylcarbamoyl-3- (4-chlorophenyl )-4-(2-diethylamonoethyl)-2-pyrazoline, m.p. 87C;
36) 1-[N-(4-chlorophenyl)-N-methylcarbamoyl~l-3-(4-chloro-B ~on~-l ) -4- (2-piperidinoethyl )-2-pyrazoline;
37) 1- (4-clllorophenylcarbamoyl )-3- (4-chlorophenyl )-4-(2-phenylthioethyl ) -2-pyrazoline, m . p . 137 C ) 15 38) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-phenylthioethyl)-2pyrazoline, m.p. 138C;
39) 1- (4-methylthiophenylcarbamoyl )-3- (4-chlorophenyl)-!~-(2-phenylthioethyl)2-pyrazoline, m. p . 124C;
l~o) 1-(4-ethylphenylcarbamoyl)-3-(~-chlorophenyl)-1~-(2-phenylthioe-thyl ) -2-pyrazoline, m . p . 122 C;
4-,1) 1- (4-:~luorophenylcarbamoyl ) -3- (4-chlorophenyl )-4-(2-phenylthioethyl)-2-pyrazoline, m.p. 130C;
42) 1- (4-isopropoxyphenylcarbamoyl )-4- (!1-chlorophenyl )-4-(2-phenoxyethyl)-2-pyrazoline, m.p. 100C;
43) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-phenoxyethyl ) -2-pyrazoline, m . p . 112 C;
44 ) 1- (Ij -benzylphenylcarbamoyl ) -3- (4-chlorophenyl ) -4-phenyl-2-pyrazoline, m.p. 'I79C;
P~IN.8275 7.12.76 ,. . .
45) 1- (4-phenylthiophenylcarbamoyl)-3- (4-chlorophenyl)-4-phenyl-2-pyra~oline, m.p. 164C;
46) 1-(4-phenoxyphenylcarbamoyl) -3- (4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p. 1770C;
47) 1-[N-(1-chlorophenyl)-N-(trichloromethylthio)-carbamoyl~ -3-(4-chlorophenyl)-4-phenyl-2-pyrazoline, m.p~ 177C;
48) 1-LN-benyl-N-(4-chlorophenyl)-carbamoy~ -3-(4-chloro-phenyl)-4-phenyl-2-pyrazoline, m.p. 116C;
49) 1-LN-cyclohexyl-N-(4-chlorophenyl)-carbamoy ~-3-(4-chlorophenyl)-4-phenyl-2-pyrazoline~:m.p. 138C;
50) 1-phenylcarbamoy~3-(4-chlorophenyl)-4-cyclohexyl-methyl-2-pyrazoline, m p. 179C;
`. - 51) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 153C;
` 15 52) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 123C;
- ~53) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyclohexylmethyl-2-pyrazoline, m.p. 173C;
54) 1-(4-nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4 cyclohexylmethyl-2-pyrazoline, m.p. 228C;
55) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-, cyclohexylmethyl-2-pyrazoline, m.p. 131C;
~ 56) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-; cyclohexylmethyl-2-pyrazoline, m.p. 169C;
57) 1-~4-chlorophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~-phenylethyl-2-pyrazoline, m.p. 143C;
58) 1-~4-ethylphenylcarbamoyl)-3-(4-methoxyphenyl)-4-p-phenylethyl-2-pyrazoline~ m.p. 111C;
_g_ - , ~ . .
~ 8 7.12.76 ,' .
59) 1~ -isopropoxyphenylcarbamoyl)-3-(4-me-thoxyphenyl)-Ll-p-phenylethyl-2-pyrazoline, m.p. 110C;
- 60) 1-(4-cyanophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~phenylethyl-2-pyrazoline, m.p. 1L12C;
61) 1-(nitrophenylcarbamoyl)-3-(4-methoxyphenyl)-4-~-phenylethyl-2-pyrazoline, m.p. 1580C;
. C y~/o .
D 62) 1-~*~hexylcarbamoyl-3-(4-methoxyphenyl)-4--phenylethyl-2-pyrazoline, m.p. 126C;
63) 1-(4-chlorophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-p-diethylaminoethyl-2-pyrazoline;
64) 1-(4-nitrophenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-~diethylaminoethyl-2-pyrazoline;
65) 1-phenylcarbamoyl-3-(4-isopropoxyphenyl)-4-~-diethylaminoethyl-2-pyrazoline;
66) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4-~iethylaminoethyl-2-pyrazoline;
67) 1-(4-isopropylphenylcarbamoyl)-3-(4-isopropoxyphenyl)-4--diethylaminoethyl-2-pyrazoline;
68) 1-cyclohexylcarbamoyl-3-(4-isopropoxyphenyl)-4-~-diethylaminoethyl-2-pyrazoline;
69) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-_ l ~-(N-methylpiperazino)-ethyl~-2-pyrazoline, m.p.l59C;
70) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-(N-methylpiperazino)-ethyl -2-pyrazoline, m.p. 173C;
71) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-r~- (N-methylplperazino)-ethyl~-2-pyrazoline, m.p. 159G;
72) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-r~- (N-methylpiperazino)-ethyl~-2-pyrazoline, m.p.136C;
p~.8275 7.12~76 73) 1-cyclohexylcarbamoyl-3-(ll-chlorophenyl)-4-[~-(N-methylpiperazino)-ethyl~-2-pyrazoline;
74) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 145C;
75) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 141C;
76) 1-(4-ethylphenylcarbamoyl)-3-(LI-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 95C;
, 77) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-'~ 10 benzyl-2-pyrazoline, m.p. 184C;
78) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline. m.p. 126C;
79) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorphenyl)-4-~-phenylsulfonethyl-2-pyrazoline, m.p. 203C;
80) -1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-phenylsulfonethyl-2-pyrazoline, m.p. 181C;
81) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-frphenyl-sulfonethyl-2-pyrazoline, m.p. 194C;
82) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsulfonethyl-2-pyrazoline, m.p. 210C;
i 83) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-~ phenylsulfon-ethyl-2-pyrazoline, m.p. 168C;
84) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 168C;
85) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 156C;
86) 1-(3-trifluoromethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-phenylsul~onethyl-2-pyrazoline, m.p. 180C;
~, P~IN.8275 7.12.76 4~
- 87) 1-(3-chloro-4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-~-phenylsul~onethyl-2-pyrazoline, m.p. 120C;
88) 1-(4-chlorophenylcarbamoyl)-3-(4-Chlorophenyl)-4-(3-carbethoxypropyl)-2-pyrazoline, m.p. 135C;
589) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-LI-(3-carbethoxypropyl)-2-pyrazoline, m.p. 97C;
90) 1-(4-methylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-carbethoxypropyl)-2-pyrazoline, m.p. 88C;
91) 1-(4-chlorophenylcarbamoyl)-3-~4-chlQrophenyl)-4-10~3-(dimethylcarbamoyl)-propyl~-2-pyrazQline, m.p. 1360C;
92) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-` ~3=(dimethylcarbamoyl)-propyl~ -2-pyrazoline, m.p.158C;
93) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-C3~dimethylcarbamoyl)-propyl~-2-pyrazoline~ m.p.145C;
1594) 1-(3,4-dichlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-; [3-(dimethylcarbamoyl)-propyl~-2-pyrazoline, m.p. 169C;
- 95) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p~ 122C;
96) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-20(3-methoxypropyl)-2-pyrazoline, m.p. 127C;
97) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 124C;
98) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(3-methoxy-propyl)-2-pyrazoline, m.p. 97C;
2599) 1-(4-cyanophenylcarbamoyl)-3-(4-chlQrophenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 190C;
100) 1-(4-nitrophenylcarbamoyl)-3-(4--chlorophenyl)-4-(3-methoxypropyl)-2-pyrazoline. m.p. 1430C;
P~ .82~5 ~ 7.12.76 101) 1-(4-chlorophenylcarbamoyl)-3-(1l-chlorophenyl)-4-3-piperidinopropyl)-2-pyrazoline, m.p. 107C;
102) 1-(4-cyanophenylcarbamoyl)-3-(4-chlarophenyl)-4-(3-piperidinopropyl)-2-pyrazoline, m.p. 120C;
5 103) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 175C;
104) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 205C;
105) I-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-10cyanomethyl-2-pyrazoline, m.p. 157C;
106) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 205C;
107) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-cyanomethyl-2-pyrazoline, m.p. 170C;
108) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 102C;
109) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 830C;
110) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-20(~-ethylthioethyl)-2-pyrazoline, m.p. 111C;
111) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-ethylthioethyl)-2-pyrazoline, m.p. 190C;
112) 1-cyclohexylcarbamoyl-3-(4-chlorophenyl)-ll-(~-ethylthioethyl)-2-pyrazoline, m.p. 98C;
25113) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoethyl~-2-pyrazoline, m.p. 131C;
114) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoe-thyl)-2 pyrazoline9 m.p. 175C;
~ PIIN 8275 - 1~5) 1-cyclohexylcarbamoyl-3-(LI-chlorophenyl)-4-(/S-dimethylaminoethyl)-2-pyrazoline, m.p. 115C;
116) 1-(4-methylthiopenylcarbamoyl)-3-(4-chlorophenyl)-II-(,~-dimethylaminoethyl)-2-pyrazoli~e, m.p. 117C;
5 117) 1-(4-methoxyphenylcarbamoyl)-3-~4-chlorophenyl)-4-~-dimethylaminoethyl)-2-pyrazoline, m.p. l03C;
118) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(~-dimethylaminoethyl)-2-pyrazoline, m-p. 157C;
119) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-10carbethoxymethyl-2-pyrazoline, m.p. 114C;
120) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-carbethoxy-methyl-2-pyrazoline, m.p. 980C;
121) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 113C;
15122) 1-(4-isobutylphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 123C;
123) 1-(4-isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxlrmethyl-2-pyrazoline, m.p. 960C;
124) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-20carbethoxymethyl- 2-pyrazoline, m.p. 85C;
125) 1-~3,4-dichlorophenylcarbamoyl)-3-(4-chlorophènyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 125C;
126) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-carbethoxymethyl-2-pyrazoline, m.p. 159C;
25127) 1-(4-chlorophenylcarbamoyl)-3-(4-chlorophcnyl)-4-3-ethylthiopropyl)-2-pyrazoline, m.p. 105C;
128) 1-(4-cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-ethylthiopropyl)-2-pyrazoline, m.p. 130C;
,' ' ~ '' .
P~-IN.8275 7.12.76 129) 1-(4-ethylphenylcarbamoyl)-3-(chlorophenyl)-4-; 3-ethyl-thiopropyl)-2-pyrazoline, m.p. 870C;
` 130) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-` (3-ethylthiopropyl)-2-pyrazoline, m.p. 860C;
131) 1-(4-methyl-thiophenylcarbamoyl)-3-(4-trifluoromethyl-phenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97C;
132) 1-(4-chlorophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 97C;
133) 1-(4-ethoxyphenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 105C;
134) 1-(4-cyanophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-- 4-(3-methoxypropyl)-2-pyrazoline, m.p. 152C;
135) 1-(4-isobutylphenylcarbamoyl)-3-(4-trifluoromethyl-phenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 110C;
136) 1-(4-fluo-^ophenylcarbamoyl)-3-(4-trifluoromethylphenyl)-4-(3-methoxypropyl)-2-pyrazoline, m.p. 113C;
- 137) 1-(4-methoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-cyanopropyl)-2-pyrazoline, m.p. 126C;
138) 1-(4-methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-,;
(3-cyanopropyl)-2-pyrazoline, m.p. 109C;
139) 1-phenylcarbamoyl-3-(4-chlorophenyl)-4-(3-cyanopropyl)-Z-pyrazoline, m.p. 148C;
140) 1-(4-chlorophenylcarbamoyl)-3-(chlorophenyl)-4-(3-cyanopropyl~-2-pyrazoline, m.p. 120C;
141) 1-(4-isopropylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(3-cyanopropyl)-2-pyrazoline, m.p. 154C;
142) 1-(4-fluorophenylcarbamoyl)-3-(4-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 130C;
PilN.8275 ~ 7.12.76 11~3) 1-(4-nitropllenylcarbamoyl)-3-(L~-chlorophenyl)-4-benzyl-2-pyrazoline, m.p. 167C;
1l~l~) 1-(ll-chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 151C, 145) 1-phenylcarbamoyl-3-~4-chlorophenyl)-4-(dimethyl-carbamoylmethyl)-2-pyrazoline, m.p. 1 Ll 5~C;
146) 1-(4-ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 155C;
147) 1-(4-me-thoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 151C;
148) 1-(4-cyanophenylcarbamoyl)-3-(L~-chlorophenyl)-L~-(dimethylcarbamoylmethyl)-2-pyrazoline, m.p. 210C;
In particular the compounds of the above general formula, in which R3 is an alkyl radical having 1 to 6 carbon atoms~hich is substituted with an alkoxy - group having 1 to L~ carbon atoms or a dialkylamino group of which the alkyl radicals together with the ni-trogen atom to which they are bound can form a heterocyclic ring, show , very strong insecticidal properties.
In addition to the strong insecticidal activity it has been found that the compounds of the above general formula, in which R1, R2 and RL~ have the above meanings, and R3 i~; an alkyl group having 1 to 6 carbon a-toms which is substituted with a cyano group or a dialkylamino group, which two alkyl radicals can form - with the nitrogen atom to which they are bound - a possibly alkylated heterocyclic ring which may comprise a second hetero atom, also show fungicidal properties.
PI-~.8275 ~ 4~ 7.12.76 .
. . .
On the basis of their strong insecticidal activity the substances according to the invention may be used in low dosages in controlling insects. The amoùnt 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 insec-ts, 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 according to the invention are processed to compositions.
~n these compositions the active substance is mixed with solid carrier material or dissolved or dispersed in;a liquid carrier material, if desired combined with auxi-liary substances, for example surface-active substances and stabilizers.
, 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 concentratedform which are diluted with water prior to or during use.
- The invert emulsions are mainly used in a:ir applications, namely when large areas are treated with a comparatively small quantity of composition. -, PHN.8275 7.12.76 ~. .
The invert emulsions can be prepared shortly before or even during the spraying in the spraying apparatus by emulsi~ying water in an oily solution or an oily dispersion of the active substance. Some types o~
compositions ~ill be described in greater detail hereina~ter by way of example.
Granular compositions are prepared, for example, by taking up the active substance in a solvent and impregnating theresulting solution, optionally in the presence o~ a binder, on granular carrier material, for example porous granules (for example pumice and attaclay), mineral non-porous- granules (sand or ground marl), organic granules (~or example dried coffee grounds and cut tobacco stems).
A granular composition can also be prepared by compressing the active substance together with pol~dered minerals in the presence o~ lubricating agents and binders and to disintegrate and sieve the compressed product to the desired grain size.
Dusting powders can be obtained by intimately mixing the active substance with an inert solid carrier material, *or example in a concentration of 1 to 50 ~
by weight. As examples o~ suitable solid carrier materials may be mentioned talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chal~, bentonite, attapulgite and colloidal SiO2 or mixtures of these and similar sub-stances. Organic carrier materials, ~or example, ground sheels of walnuts may also be used.
-18-.
PHN.8275 ~ 7.~2.76 Wsttable po~-~ders are prepared by mixing 1 to 80 parts by weight ~f a solid inert carrier, for example the above-mentioned carrier materials, with 10 to 80 par-ts by weight of the active substance, 1 to 5 parts by weigh-t 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 setting agen-t, for example, sulphates of aliphatic alcohol, alkylarylsulphonates or fatty acid condensation products.
~or the preparation of miscible oils the active compound ls 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 distillates which are rich in aromatices, for exampIe, solvent natphtha, distilled tar oil and mixtures of these liquids. As emulsifiers may be u,ed 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 50 % 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 subs-tance in a readily water-miscible liquid, for example acetone, to ~hich solution _~9_ - PHN.8275 ~ 7.12.76 '~ ' .
a dispersion agent and possibly a wetting agent have been added. An aqueous dispersion of the ac-tive substance is obtained upon diluting with water shortly before or during spraying.
An aerosol composition according to the invention is obtained in the usual manner by incor-porating 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.
~ gating 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 - 15 contain, ~or 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 c combustion, for example, kaolin, bentonite and/or colloidal -~ 20 silica.
In addition to the above-mentioned ingrédients, the compositions according to the invention may also - contain other substances kno~Yn for application in this kind of compositions.
~or 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, .
.
' . . ~- .
- ,: .
- P}IN.8275 7. 1 1 .7G
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 according to the invention. As a result of this the activity spectrum of the compositions is broadened and synergism may occur.
The follo~ing known insecticidal, fungicidal and acariridal compounds are suitable for use in such combination compositions:
Insecticides such as:
1. chlorinatecl hydrocarbons, for example, 2,2-bis-(p-chlorophenyl)-1,1,1-trichloroethane and hexachloro-epoxyoctahydro-dimethanonaphthalene;
2. carbamates, for example, N-methyl-1-naphthyl-carbamate;
3. dinitrophenols, forexample 2-methyl-4,6-dinitrophenol and 2-(2-butyl)-4,6-dinitrophenyl)-3 9 3-dimethylacrylate;
Z 4. organic phosphorus compounds, for example dimethyl-2-methoxy-carbonyl-2-methylvinyl-phosphate; 0,0-die-thyl-0-p.nitrophenyl-phosphorthioate; N-monomethylamide of 0,0-dimethyldithiophosphoryl acetic acid;
; Acaricides, for example:
5. diphenylsulfides, for example p-chlorobenzyl-p-chloro-phenylsulfide and 2,4,4',5-tetrachlorodiphenylsulfide;
6. diphenylsulphonates, for example p-chlorophenyl benzene sulphonates;
, P~IN.8275 ~ 7.11.76 7. methylcarbinols, for example 11,4-d:ichlo:ro-a-trichloro-methy]benzhydrol;
8~ quinoxaline compounds for example methylquinoxaline dithiocarbonate.
Fun~icides~ for example:
9. organic mercury compounds, for example phenyl mercury acetic and methyl mercury cyanoguanide;
10.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 12.2,4-dinitro-6-(2-octyl-phenyl-crotonate), 1-bis-(dlmethylamino)phosphoryl-3-phenyl-5-amino-1,2,4-triazol-6-methyl-quinoxaline-2,3-dithiocarbonate, 1,4-dithioanthraquinone-2,3-dicarbonitrile, N-trichloro-methylthiophthalimide, N-trichloro-methylthiotetra-hydrophthalimide, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-dichloro-fluoromethylthio-N-phenyl-N'-dimethylsulphonyldiamide and tetrachloro-isophthalonitrile.
As already noted above the active compounds according to the present invention are novel substances which can be prepared according to methods which are known per se for the synthesis of similar substances or methods analogous thereto.
. ' ` ' ~ PHN.8275 ~ 8 7.12.76 .
` .
For ~xample the substances can be prepared by reacting a compound of the formula R2 ~ JR3 \ N ~ -. ~
.
wherein R2 and R3 have the above-indicated meanings, I 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 ~esence 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 substi-tu-ted in the 1 position with an R1, R4 disubstituted cabamoylchloride or R , R disubstituted carbamic acid ester.
1~
.; .
. , .
PIIN.8275 7-12.76 , The above-men-tioned starting material of the formula 2 1 I r 3 ' ~
can be prepared in various manners dependent on the meaning of the substituents R2 and R3. 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 R2 ~ ~ ~ CH2 - R3 with formaldehyde in acid medium and in the presence of a sol~ent and a catalyst, so that a compound of the formula 2 ~ 3 3 . ` O H2 1j is obtained.
The reaction is carried out at elevated temperature, for example a-t the boiling point o~ the solvent used. Suitable solven-ts are, for example, alcohols, for example methanol. A useful catalyst is, for example pipericline.
- 2 4 _ ~ .
.
.
PIIN.8275 ~ 4 ~ 7-12.76 The resulting product is then reacted with hydra~ine in the presence of a solvent, for example an alcohol, for example propanol, a compound of the formula 2 ~ T 3 " N
Nl /
H
;~ 5 being obta~ned. 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 R2 ~ C - CH2 - R3 :, . ' ~ .
with dimethylamine and paraformaldehyde, a compound of the formula R2 ~ I - CH - CH2 - N(CH3)2 being formed. The reaction is carried out at eleva-ted tempera-ture 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 R2 ~ ~ - R3 is obtained again.
' ~ PHN.~275 ~ 8 7-l2.76 The resulting products are then reac-ted with hydrazine at elevated temperature and in the presence of a solvent, for example e-thanol, a compound of the formula R ~ r R
-: 5 N~
: - H
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-methoxyethyl)~ -pyrazoline.
a) lo.6 g of dimethylaminohydrochloride, 4,0 g of para~
formaldehyde and ?1 .3 g of 4'chloro-~-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. 1~ater and e-ther were added to the ¦ residue, the ether layer was separated, washed with water and dried with sodium sulpha-te and evaporated.
Yield 21.2 g of 2-(p-chlorobenzoyl)-4-methoxybutane-1.
b~ A solution of 21.1 g of 2-(p-chloroben~oyl)-4-methoxy-butene-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-methoxye-thyl)- ~ -pyrazoline were obtained. Boiling point (0.35 ~ o.l~o mm Hg~:
;. 155-1~5C.
.
PHN.8275 ~ /.12.76 c) 7.7. g of p-chloropheIlyl~isocyana-te ~ere added to the solution of 12 g of 3-(p-chlorophenyl)-l~-(2-methoxy-ethyl)- ~ -pyrazoline in 50 ml of dry ether.
After stirring for 1 hour the ether was distilled off and replaced by 50 ml of petroleum e-ther. 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. 870C.
- In an analogous manner the following compounds were prepared:
1-(p-ethoxyphen~ylcarbamoyl)-3-(p-chlorophenyl)-4-(2-methoxy-ethyl)-~ -pyrazoline, m.p. 111C;
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)~4-(2-methoxyethyl)-~ -pyrazoline, m.p. 830C;
1-(p-nitrophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-methoxyethyl)-~ -pyrazoline, m.p. 159C;
; 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-methoxy-ethyl)-Q -pyrazoline, m.p. 104C;
II. 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-piperidinoethyl)-~ -pyrazoline.
a) A suspension of 26.6 g of 4~-chloro-ll-piperidino-butyrophenone, 4 g of paraformaldehyde and 10.6 gof dimet;hylamlne-hydrochloride in 40 ml of dioxan was refluxed for 24 hours. After evaporation, water was addedl and the reaction mixture was rendered alkaline with 50% sodium hydroxide solution. After extracting with ether, washing with water, drying and evaporating P~IN.8275 7-12.76 .
26.7 g of 1-(dimethylamino)-2-(p-chlorobenzoyl)-4-piperidinobutane were obtained.
b) A solution of 26.7 g of the compound obtained ' according to a) and 10 ml of hydrazinehydrate in 35 ml o~ ethanol were re~luxed for 7 hours and then distilled. '18.1 g o~ 3-(p-chlorophenyl)-4-(2-piperidino-ethyl)-~ -pyrazoline were obtained. Boiling point (0.4 -0.5 mm Hg): 200-2080C;
c) 15.4 g of p-chlorophenylisocyanate were added to a , tO solution of 29.2 g of 3-(p-chlorophenyl)-4-(2-piperidino-ethyl)- ~ -pyrazoline in 5COml 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 , - preamble was obtained; melting point 134C.
`~ ~5 The following compounds were prepared in an analogous manner:
~ 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)_l~_(2-piperidino-'' ethyl)-~ -pyrazoline, m.p. 113C;
; 1-(p-cyanophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-piperidino-' ethyl- ~ -pyraY.oline, m.p. 148C;
;~ 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-' (2-piperidinoethyl)-~ -pyrazoline, m.p. 113C;
1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4-' (2-pipe:ridinoethyl)- ~ -pyrazoline, m.p. 111C;, 25 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-diethylaminoethyl)- ~ 2-pyrazoline, m.p. 100C;
1-(p-e-thylphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-diethylaminoethyl)- ~ -pyrazoline, .1 .
' '' ' ' -PIIN.8275 7.12.76 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-cliethylaminoethyl)- ~ -pyrazoline, 1-(p-cyanophenylcarbamoyl)-3-(p-chlQropheny})-4-(2-diethylaminoethyl)- ~ -pyrazoline~
1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-die-thyl-; aminoethyl)- ~ -pyrazoline, m.p. 87C;
1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)-~ -pyrazoline, m.p. 137C;
1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 138C;
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 124C;
1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2~phenylthioethyl)- ~2-pyrazoline, m.p. 122C;
1-(p-fluorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 130QC;
III. 1(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenoxyethyl)- ~ -pyrazoline.
i a) A mixture of 27.5 g of 4'-chloro-4-phenoxybutyrophenone, ¦ 20 4 g of paraformaldehyde and 10.9 g of dimethylamino-hydrochloride in 40 ml of dioxan was refluxed for 40 hours. After cooling, adcling water and extracting wi-t;h 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.
1.
l'XN.8275 7.12.7G
; b) A solution of 28.5 ~ 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)-ll-(2-phenoxyethyl)- ~ -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 ` 10 the reaction mixture was sucked off. In this manner 2.2 g of the compound mentioned in the ti-tle was ' obtained; m.p. 100C.
The following compounds are prepared in a similar manner:
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenoxyethyl)-~ -pyrazoline, m.p. 112C;
1-(p-benzylphenylcarbamoyl)-3-(p-chlorophenyl)-4-phenyl--pyrazoline, m.p. 179C;
1-(p-phenylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-' 2 `! 20 phenyl-~ -pyrazoline, m.p. 164C;
1-(p-phenoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-phenyl~ pyrazoline, m.p. 177C;
1- CN_ (p-ehlorophenyl)-N-(trichloromethylthio)carbamoyl~-3-(p-ehlorophenyl)-4-phenyl- ~ 2-pyrazoline, m.p. 177C;
1- LN-benzyl-N-(p-chlorophenyl)-earbamoyl1 -3-(p-chloro-phenyl)- L; -phenyl- ~ -pyrazoline, m.p. 116C;
1- LN-cyelohe~yl-N-(p-ehlorophenyl)carbamoyl~ -3-(p-chloro-phenyl)-4-phenyl- ~ -pyrazoline, m.p. 138C;
I
... .. . . : . . : .
PllN.8275 7.12.7~
..~4~
IV.The active compounds according -to the inven-tion are dispersed in water, and that in concentrations of 300; 100; 30; 10; 3~ 1 and 0.3 mg o:f the active compound per litre of aqueous dispersion.
The insecticidal activities of these dispersions were determined in the usual manner against Leptinotarsa decemlineata (Colorado beetle) and Pieris brassicae (cabbage worm).
The r~sults of these tests are recorded in the following table. The meanings of the characters used in the table are as follows:
+ = 90 to 100% mortality ~ = 50 to ~30~ mortality - = ~ 50~ mortality .
. - . : , :
~3L ~L~4~3 P ~lN . 8 2 7 5 -~. I2.7~
. _ _. . _. _ ~ . _ ___._ __ _____ ___.. __ _ ____ ~. ~: 0~ . . .~
_, .~
I I -~J
o ~ _ _._. _~___ ._ ... _ ,.~._ _~ __ ~ .~ __.. _ __._.. ~. _.. .. ~ ____ .... _______ . U~ ~ ~ +l + +
h h _~
. ~ ~ ~ I I I + ~ -~
h ~ o _ . . ___ . .
~ ~ ~1 O
+~ ~ I +l I I +l I +l I I 1 1 + + +
~1 td .__ -------------~
m oo +I++++ ++ I +l+i-~++++
+~ rl h . . . ____ __.~.__ _ t~ +' o O
~ o ~1 O
~ l~ ~ I + + + + + + I + + I + I + + + + + + + +
E ~ q-~ ---- ~ ~
O ~1 bD O . I
;' E . ... ... ~
'' td 1~ ~ ~ ~ +1 +1 +1 .~ ~ _ .. . _______._ _ _.. _.. _.____ _ ..... __ .
. ~ ~ ~ ~ +1 1 1 + +1 1 1 1 1 +., O ~ U~ ____ ___ ___._~_. .__._._. _.. _~_. .~ _ ,1 o h ~ O ~
+~ . ~ ~ ~ I + + I +l + +l +l +l +l + +
~ ~ C)- o _~ __ .,........ _._~_~__ ~ O C~ I +I+ ~ +l I l+ I ' I l+ + + + +I+ +
~) ~ _I _ _______ ~_ _.__.. ~_ _._ ..... ____ h g :' h ~ ~ +l + + + + +l +l + +l ¦ -11 ¦ I +l + + + + + + +
'o . ....................... _. .... _____ a O~ ~ . ~
1 ~
+~
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,.~ +~
+0,~
' O O ~ ~
- ' m ~ ~ ~ .
OO g . .
o ~1 ~ o r` O ~ N ~ ~ I~ CO C~\ .
o +. .- .- .- .- .- .- .- .-h ~
h .
.~1~.
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::.?' ~ , r -~
PllN . 82'75 4~3 i . 12 . 7G
. ,_ _ ~
a~ o ~ , . _ . _ __ __ __ . ____ ___.___ ,1 ~ + I I I
. ~
h ~ + + + +¦
1~ O .. ____ ___ , a) o ~ + + + + + +l ~ U~ _ , ... , ... , .. .
~ U~ o u~ h ~ + + + + + + ~ 1 1 1 +J
.'' ~
.~ O
h + + I I -~ + + +
~o P~ O
_ , ....
,1 ~0 .` ~ ~ ~
. o ,~ O
~d . __ .. _. ....
~ ~ ~ i I I
~ ~q .~
o ~ ~ +l +l +l , . r~ X t~ O ._ ~
m ~ ,, ~ + + + + + +l +l I . - +J +l +l O _ ._ .. . .. ~
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PHN.8275 ~ 7.~2.76 Wsttable po~-~ders are prepared by mixing 1 to 80 parts by weight ~f a solid inert carrier, for example the above-mentioned carrier materials, with 10 to 80 par-ts by weight of the active substance, 1 to 5 parts by weigh-t 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 setting agen-t, for example, sulphates of aliphatic alcohol, alkylarylsulphonates or fatty acid condensation products.
~or the preparation of miscible oils the active compound ls 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 distillates which are rich in aromatices, for exampIe, solvent natphtha, distilled tar oil and mixtures of these liquids. As emulsifiers may be u,ed 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 50 % 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 subs-tance in a readily water-miscible liquid, for example acetone, to ~hich solution _~9_ - PHN.8275 ~ 7.12.76 '~ ' .
a dispersion agent and possibly a wetting agent have been added. An aqueous dispersion of the ac-tive substance is obtained upon diluting with water shortly before or during spraying.
An aerosol composition according to the invention is obtained in the usual manner by incor-porating 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.
~ gating 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 - 15 contain, ~or 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 c combustion, for example, kaolin, bentonite and/or colloidal -~ 20 silica.
In addition to the above-mentioned ingrédients, the compositions according to the invention may also - contain other substances kno~Yn for application in this kind of compositions.
~or 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, .
.
' . . ~- .
- ,: .
- P}IN.8275 7. 1 1 .7G
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 according to the invention. As a result of this the activity spectrum of the compositions is broadened and synergism may occur.
The follo~ing known insecticidal, fungicidal and acariridal compounds are suitable for use in such combination compositions:
Insecticides such as:
1. chlorinatecl hydrocarbons, for example, 2,2-bis-(p-chlorophenyl)-1,1,1-trichloroethane and hexachloro-epoxyoctahydro-dimethanonaphthalene;
2. carbamates, for example, N-methyl-1-naphthyl-carbamate;
3. dinitrophenols, forexample 2-methyl-4,6-dinitrophenol and 2-(2-butyl)-4,6-dinitrophenyl)-3 9 3-dimethylacrylate;
Z 4. organic phosphorus compounds, for example dimethyl-2-methoxy-carbonyl-2-methylvinyl-phosphate; 0,0-die-thyl-0-p.nitrophenyl-phosphorthioate; N-monomethylamide of 0,0-dimethyldithiophosphoryl acetic acid;
; Acaricides, for example:
5. diphenylsulfides, for example p-chlorobenzyl-p-chloro-phenylsulfide and 2,4,4',5-tetrachlorodiphenylsulfide;
6. diphenylsulphonates, for example p-chlorophenyl benzene sulphonates;
, P~IN.8275 ~ 7.11.76 7. methylcarbinols, for example 11,4-d:ichlo:ro-a-trichloro-methy]benzhydrol;
8~ quinoxaline compounds for example methylquinoxaline dithiocarbonate.
Fun~icides~ for example:
9. organic mercury compounds, for example phenyl mercury acetic and methyl mercury cyanoguanide;
10.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 12.2,4-dinitro-6-(2-octyl-phenyl-crotonate), 1-bis-(dlmethylamino)phosphoryl-3-phenyl-5-amino-1,2,4-triazol-6-methyl-quinoxaline-2,3-dithiocarbonate, 1,4-dithioanthraquinone-2,3-dicarbonitrile, N-trichloro-methylthiophthalimide, N-trichloro-methylthiotetra-hydrophthalimide, N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, N-dichloro-fluoromethylthio-N-phenyl-N'-dimethylsulphonyldiamide and tetrachloro-isophthalonitrile.
As already noted above the active compounds according to the present invention are novel substances which can be prepared according to methods which are known per se for the synthesis of similar substances or methods analogous thereto.
. ' ` ' ~ PHN.8275 ~ 8 7.12.76 .
` .
For ~xample the substances can be prepared by reacting a compound of the formula R2 ~ JR3 \ N ~ -. ~
.
wherein R2 and R3 have the above-indicated meanings, I 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 ~esence 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 substi-tu-ted in the 1 position with an R1, R4 disubstituted cabamoylchloride or R , R disubstituted carbamic acid ester.
1~
.; .
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PIIN.8275 7-12.76 , The above-men-tioned starting material of the formula 2 1 I r 3 ' ~
can be prepared in various manners dependent on the meaning of the substituents R2 and R3. 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 R2 ~ ~ ~ CH2 - R3 with formaldehyde in acid medium and in the presence of a sol~ent and a catalyst, so that a compound of the formula 2 ~ 3 3 . ` O H2 1j is obtained.
The reaction is carried out at elevated temperature, for example a-t the boiling point o~ the solvent used. Suitable solven-ts are, for example, alcohols, for example methanol. A useful catalyst is, for example pipericline.
- 2 4 _ ~ .
.
.
PIIN.8275 ~ 4 ~ 7-12.76 The resulting product is then reacted with hydra~ine in the presence of a solvent, for example an alcohol, for example propanol, a compound of the formula 2 ~ T 3 " N
Nl /
H
;~ 5 being obta~ned. 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 R2 ~ C - CH2 - R3 :, . ' ~ .
with dimethylamine and paraformaldehyde, a compound of the formula R2 ~ I - CH - CH2 - N(CH3)2 being formed. The reaction is carried out at eleva-ted tempera-ture 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 R2 ~ ~ - R3 is obtained again.
' ~ PHN.~275 ~ 8 7-l2.76 The resulting products are then reac-ted with hydrazine at elevated temperature and in the presence of a solvent, for example e-thanol, a compound of the formula R ~ r R
-: 5 N~
: - H
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-methoxyethyl)~ -pyrazoline.
a) lo.6 g of dimethylaminohydrochloride, 4,0 g of para~
formaldehyde and ?1 .3 g of 4'chloro-~-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. 1~ater and e-ther were added to the ¦ residue, the ether layer was separated, washed with water and dried with sodium sulpha-te and evaporated.
Yield 21.2 g of 2-(p-chlorobenzoyl)-4-methoxybutane-1.
b~ A solution of 21.1 g of 2-(p-chloroben~oyl)-4-methoxy-butene-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-methoxye-thyl)- ~ -pyrazoline were obtained. Boiling point (0.35 ~ o.l~o mm Hg~:
;. 155-1~5C.
.
PHN.8275 ~ /.12.76 c) 7.7. g of p-chloropheIlyl~isocyana-te ~ere added to the solution of 12 g of 3-(p-chlorophenyl)-l~-(2-methoxy-ethyl)- ~ -pyrazoline in 50 ml of dry ether.
After stirring for 1 hour the ether was distilled off and replaced by 50 ml of petroleum e-ther. 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. 870C.
- In an analogous manner the following compounds were prepared:
1-(p-ethoxyphen~ylcarbamoyl)-3-(p-chlorophenyl)-4-(2-methoxy-ethyl)-~ -pyrazoline, m.p. 111C;
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)~4-(2-methoxyethyl)-~ -pyrazoline, m.p. 830C;
1-(p-nitrophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-methoxyethyl)-~ -pyrazoline, m.p. 159C;
; 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-methoxy-ethyl)-Q -pyrazoline, m.p. 104C;
II. 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-piperidinoethyl)-~ -pyrazoline.
a) A suspension of 26.6 g of 4~-chloro-ll-piperidino-butyrophenone, 4 g of paraformaldehyde and 10.6 gof dimet;hylamlne-hydrochloride in 40 ml of dioxan was refluxed for 24 hours. After evaporation, water was addedl and the reaction mixture was rendered alkaline with 50% sodium hydroxide solution. After extracting with ether, washing with water, drying and evaporating P~IN.8275 7-12.76 .
26.7 g of 1-(dimethylamino)-2-(p-chlorobenzoyl)-4-piperidinobutane were obtained.
b) A solution of 26.7 g of the compound obtained ' according to a) and 10 ml of hydrazinehydrate in 35 ml o~ ethanol were re~luxed for 7 hours and then distilled. '18.1 g o~ 3-(p-chlorophenyl)-4-(2-piperidino-ethyl)-~ -pyrazoline were obtained. Boiling point (0.4 -0.5 mm Hg): 200-2080C;
c) 15.4 g of p-chlorophenylisocyanate were added to a , tO solution of 29.2 g of 3-(p-chlorophenyl)-4-(2-piperidino-ethyl)- ~ -pyrazoline in 5COml 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 , - preamble was obtained; melting point 134C.
`~ ~5 The following compounds were prepared in an analogous manner:
~ 1-cyclohexylcarbamoyl-3-(p-chlorophenyl)_l~_(2-piperidino-'' ethyl)-~ -pyrazoline, m.p. 113C;
; 1-(p-cyanophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-piperidino-' ethyl- ~ -pyraY.oline, m.p. 148C;
;~ 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-' (2-piperidinoethyl)-~ -pyrazoline, m.p. 113C;
1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4-' (2-pipe:ridinoethyl)- ~ -pyrazoline, m.p. 111C;, 25 1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-diethylaminoethyl)- ~ 2-pyrazoline, m.p. 100C;
1-(p-e-thylphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-diethylaminoethyl)- ~ -pyrazoline, .1 .
' '' ' ' -PIIN.8275 7.12.76 1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-cliethylaminoethyl)- ~ -pyrazoline, 1-(p-cyanophenylcarbamoyl)-3-(p-chlQropheny})-4-(2-diethylaminoethyl)- ~ -pyrazoline~
1-cyclohexylcarbamoyl-3-(p-chlorophenyl)-4-(2-die-thyl-; aminoethyl)- ~ -pyrazoline, m.p. 87C;
1-(p-chlorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)-~ -pyrazoline, m.p. 137C;
1-(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 138C;
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 124C;
1-(p-ethylphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2~phenylthioethyl)- ~2-pyrazoline, m.p. 122C;
1-(p-fluorophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenylthioethyl)- ~ -pyrazoline, m.p. 130QC;
III. 1(p-isopropoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenoxyethyl)- ~ -pyrazoline.
i a) A mixture of 27.5 g of 4'-chloro-4-phenoxybutyrophenone, ¦ 20 4 g of paraformaldehyde and 10.9 g of dimethylamino-hydrochloride in 40 ml of dioxan was refluxed for 40 hours. After cooling, adcling water and extracting wi-t;h 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.
1.
l'XN.8275 7.12.7G
; b) A solution of 28.5 ~ 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)-ll-(2-phenoxyethyl)- ~ -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 ` 10 the reaction mixture was sucked off. In this manner 2.2 g of the compound mentioned in the ti-tle was ' obtained; m.p. 100C.
The following compounds are prepared in a similar manner:
1-(p-methylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-(2-phenoxyethyl)-~ -pyrazoline, m.p. 112C;
1-(p-benzylphenylcarbamoyl)-3-(p-chlorophenyl)-4-phenyl--pyrazoline, m.p. 179C;
1-(p-phenylthiophenylcarbamoyl)-3-(p-chlorophenyl)-4-' 2 `! 20 phenyl-~ -pyrazoline, m.p. 164C;
1-(p-phenoxyphenylcarbamoyl)-3-(p-chlorophenyl)-4-phenyl~ pyrazoline, m.p. 177C;
1- CN_ (p-ehlorophenyl)-N-(trichloromethylthio)carbamoyl~-3-(p-ehlorophenyl)-4-phenyl- ~ 2-pyrazoline, m.p. 177C;
1- LN-benzyl-N-(p-chlorophenyl)-earbamoyl1 -3-(p-chloro-phenyl)- L; -phenyl- ~ -pyrazoline, m.p. 116C;
1- LN-cyelohe~yl-N-(p-ehlorophenyl)carbamoyl~ -3-(p-chloro-phenyl)-4-phenyl- ~ -pyrazoline, m.p. 138C;
I
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PllN.8275 7.12.7~
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IV.The active compounds according -to the inven-tion are dispersed in water, and that in concentrations of 300; 100; 30; 10; 3~ 1 and 0.3 mg o:f the active compound per litre of aqueous dispersion.
The insecticidal activities of these dispersions were determined in the usual manner against Leptinotarsa decemlineata (Colorado beetle) and Pieris brassicae (cabbage worm).
The r~sults of these tests are recorded in the following table. The meanings of the characters used in the table are as follows:
+ = 90 to 100% mortality ~ = 50 to ~30~ mortality - = ~ 50~ mortality .
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Claims (17)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compound of the 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 pyridyl or pyrimidyl group which 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 to 2 substituents selected from the group con-sisting of halogen, alkyl, haloalkyl, cycloalkyl, alkylthio, alkoxy, dialkylamino, alkylsulphonyl, acyl, acylamino, cyano, nitro, phenyl, halo-phenyl, phenylthio, phenoxy and phenylalkyl radical, R2 is an alkyl group, a cycloalkyl group, a phenyl group or a phenyl group substituted with 1 to 2 substituents selected from the group consisting of halogen, alkyl, halo-alkyl, cycloalkyl, alkylthio, alkoxy, monoalkylamino or dialkylamino, nitro, phenyl, halophenyl and cyano; R4 is a hydrogen atom, an alkyl group having 1 - 15 carbon atoms, a phenylalkyl group, a cycloalkyl group or a halomethyl-thio group; R3 is an unsubstituted alkyl group having 5 - 10 carbon atoms or R3 is an alkyl group having 1 to 6 carbon atoms which is substituted by one or more of the following substituents:
a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a halogen atom, a cyano group, an alkoxycarbonyl group, a phenyl group optionally substituted by nitro, halogen or alkyl, a phenoxy group, a phenyl-thio group, a phenylsulphinyl group, a phenylsulphonyl group, a dialkylamino group the two alkyl radicals of which may form together with the nitrogen atom to which they are bound a piperidine or piperazine group, which groups may be substituted by alkyl having 1 - 4 carbon atoms, an alkylphenyl- or di-phenylamino group, an N,N-dialkylcarbamoyl group, and an N,N-dialkyl-sulphamoyl group; on the understanding that when R1 is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R4 is a phenyl-alkyl 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.
a cycloalkyl group, an alkoxy group, an alkylthio group, a nitro group, a halogen atom, a cyano group, an alkoxycarbonyl group, a phenyl group optionally substituted by nitro, halogen or alkyl, a phenoxy group, a phenyl-thio group, a phenylsulphinyl group, a phenylsulphonyl group, a dialkylamino group the two alkyl radicals of which may form together with the nitrogen atom to which they are bound a piperidine or piperazine group, which groups may be substituted by alkyl having 1 - 4 carbon atoms, an alkylphenyl- or di-phenylamino group, an N,N-dialkylcarbamoyl group, and an N,N-dialkyl-sulphamoyl group; on the understanding that when R1 is a phenyl group substituted by phenylthio, phenoxy or phenylalkyl and/or R4 is a phenyl-alkyl 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. A compound as claimed in claim 1, in which R3 is an alkyl radical having 1 to 6 carbon atoms which is substituted with an alkoxy group having 1 to 4 carbon atoms or a dialkylamino group of which the two alkyl radicals together with the nitrogen atom to which they are bound may form a piperidine or piperazine ring.
3. 1-(4-Chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-)2-methoxyethyl)-2-pyrazoline.
4. 1-(4-Ethoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2-pyrazoline.
5. 1-(4-Methylthiophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxy-ethyl)-2-pyrazoline.
6. 1-(4-Nitrophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-methoxyethyl)-2-pyrazoline.
7. 1-(4-Cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline.
8. 1-(4-Isopropoxyphenylcarbamoyl)-3-t4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline.
9. 1-(4-Ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline.
10, 1-(4-Chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-piperidino-ethyl)-2-pyrazoline.
11. 1-(4-Chlorophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-diethylamino-ethyl)-2-pyrazoline.
12. 1-(4-Ethylphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-diethylamino-ethyl)-2-pyrazoline.
13. 1-(4-Isopropoxyphenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-diethyl-aminoethyl)-2-pyrazoline.
14. 1-(4-Cyanophenylcarbamoyl)-3-(4-chlorophenyl)-4-(2-diethylamino-ethyl)-2-pyrazoline.
15. 1-Cyclohexylcarbamoyl-3-(4-chlorophenyl)-4-(2-diethylaminoethyl)-2-pyrazoline.
16. A method of preparing compounds of the formula wherein R1, R2, R3, R4 and X have the meanings stated in Claim 1, characterized in that the compounds are prepared by reacting a compound of formula wherein R2 and R3 have the meanings given in Claim 1, in the presence of a solvent with a compound of the formula R1 - N = C = X
wherein R1 and X have the meanings indicated in Claim 1.
wherein R1 and X have the meanings indicated in Claim 1.
17. A method of controlling insects in agriculture and horticulture, characterized in that the infected areas are treated with a composition containing as the active ingredient a compound as defined in Claim 1, 2 or 3 in a dosage correspond-ing to 0.05 to 1 kg of active substance per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| NL7600178 | 1976-01-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111048A true CA1111048A (en) | 1981-10-20 |
Family
ID=19825416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA269,399A Expired CA1111048A (en) | 1976-01-09 | 1977-01-10 | 1,3,4 substituted pyrazoline derivatives |
Country Status (28)
| Country | Link |
|---|---|
| JP (1) | JPS5287166A (en) |
| AT (1) | AT353260B (en) |
| AU (1) | AU510358B2 (en) |
| BE (1) | BE850220A (en) |
| BR (1) | BR7700133A (en) |
| CA (1) | CA1111048A (en) |
| CH (1) | CH631870A5 (en) |
| CS (1) | CS205031B2 (en) |
| DD (1) | DD129396A5 (en) |
| DE (1) | DE2700258A1 (en) |
| DK (1) | DK142985C (en) |
| EG (1) | EG13910A (en) |
| ES (1) | ES454857A1 (en) |
| FR (1) | FR2337715A1 (en) |
| GB (1) | GB1570635A (en) |
| GR (1) | GR63086B (en) |
| HU (1) | HU180915B (en) |
| IE (1) | IE45012B1 (en) |
| IL (1) | IL51225A (en) |
| IT (1) | IT1076002B (en) |
| NL (1) | NL183400C (en) |
| NZ (1) | NZ183006A (en) |
| OA (1) | OA05550A (en) |
| PL (2) | PL110077B1 (en) |
| PT (1) | PT66039B (en) |
| SE (1) | SE435176B (en) |
| YU (1) | YU1877A (en) |
| ZA (1) | ZA7714B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP36A (en) * | 1984-10-25 | 1988-12-06 | Fmc Corp | Pyrazoline insecticides |
| AP82A (en) * | 1986-11-11 | 1990-05-30 | Schering Ag | Insecticidal 3-substitute 4-fluorophenyl-1-(fluoroalkoxyphenyl-carbomonyl)-pyrazolines. |
Families Citing this family (13)
| 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 |
| 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. |
| 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 |
| 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 |
Family Cites Families (4)
| 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. |
| DE2700288A1 (en) * | 1977-01-05 | 1978-07-13 | Bayer Ag | PHENYLCARBAMOYL PYRAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES |
| DE2700289A1 (en) * | 1977-01-05 | 1978-07-06 | Bayer Ag | SUBSTITUTED PHENYLCARBAMOYL-2-PYRAZOLINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES |
-
1976
- 1976-01-09 NL NLAANVRAGE7600178,A patent/NL183400C/en not_active IP Right Cessation
-
1977
- 1977-01-03 ZA ZA00770014A patent/ZA7714B/en unknown
- 1977-01-04 SE SE7700067A patent/SE435176B/en unknown
- 1977-01-05 IT IT19085/77A patent/IT1076002B/en active
- 1977-01-05 DE DE19772700258 patent/DE2700258A1/en not_active Ceased
- 1977-01-06 DD DD7700196841A patent/DD129396A5/en unknown
- 1977-01-06 DK DK5377A patent/DK142985C/en active
- 1977-01-06 GB GB356/77A patent/GB1570635A/en not_active Expired
- 1977-01-06 IL IL51225A patent/IL51225A/en unknown
- 1977-01-06 NZ NZ183006A patent/NZ183006A/en unknown
- 1977-01-06 CH CH12977A patent/CH631870A5/en not_active IP Right Cessation
- 1977-01-06 IE IE24/77A patent/IE45012B1/en unknown
- 1977-01-06 HU HU77PI557A patent/HU180915B/en not_active IP Right Cessation
- 1977-01-06 YU YU00018/77A patent/YU1877A/en unknown
- 1977-01-07 CS CS77116A patent/CS205031B2/en unknown
- 1977-01-07 BE BE173949A patent/BE850220A/en unknown
- 1977-01-07 PT PT66039A patent/PT66039B/en unknown
- 1977-01-07 FR FR7700371A patent/FR2337715A1/en active Granted
- 1977-01-07 AT AT5177A patent/AT353260B/en not_active IP Right Cessation
- 1977-01-07 ES ES454857A patent/ES454857A1/en not_active Expired
- 1977-01-07 PL PL1977195195A patent/PL110077B1/en unknown
- 1977-01-07 PL PL1977212934A patent/PL109512B1/en unknown
- 1977-01-07 GR GR52531A patent/GR63086B/en unknown
- 1977-01-08 JP JP110777A patent/JPS5287166A/en active Granted
- 1977-01-09 EG EG15/77A patent/EG13910A/en active
- 1977-01-10 AU AU21188/77A patent/AU510358B2/en not_active Expired
- 1977-01-10 CA CA269,399A patent/CA1111048A/en not_active Expired
- 1977-01-10 BR BR7700133A patent/BR7700133A/en unknown
- 1977-01-21 OA OA56052A patent/OA05550A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP36A (en) * | 1984-10-25 | 1988-12-06 | Fmc Corp | Pyrazoline insecticides |
| AP82A (en) * | 1986-11-11 | 1990-05-30 | Schering Ag | Insecticidal 3-substitute 4-fluorophenyl-1-(fluoroalkoxyphenyl-carbomonyl)-pyrazolines. |
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