Note: Descriptions are shown in the official language in which they were submitted.
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
R4
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,
-3-
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.
-4-
,. . : . . : . .
~ ~ `
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
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);
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;
--6--
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;
--10--
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;
~,
--1 1--
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;
-12-
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;
-13-
~ 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;
-14-
,' ' ~ ''
.
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.
-16-
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. -
,
-17-
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,
-20-
.
.
' . . ~- .
- ,: .
- 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;
-21-
,
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.
-22-
. ' ` '
~ 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~
-23
.; .
. , .
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
R3
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.
'
-25-
~ 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.
-26-
.
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
-27-
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,
-28-
.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
-31-
.
. - . : , :
~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 ~
+~
. ~
,.~ +~
+0,~
' O O ~ ~
- ' m ~ ~ ~ .
OO g . .
o ~1 ~ o r` O ~ N ~ ~ I~ CO C~\ .
o +. .- .- .- .- .- .- .- .-
h ~
h .
.~1~.
--32--
~_ i J.
::.?' ~ , 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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