Note: Descriptions are shown in the official language in which they were submitted.
- `
11)42892 ~
This invention provides new hydroxy quinoline carbamates of
the general formula I ~
~R2 ~ -;
R4 ~ ~
--~ N ~--R
wherein one of the radicals Rl and R3 represents a group of formula II ~
Il / 5 . .
- O - C - N
R6 .
."`'''""'
and the other represents hydrogen, (Cl - C6) alkyl, or (Cl - C4) alkoxy ~: '
carbonyl; R2 represents hydrogen, (Cl - C6) alkyl, (Cl - C3) alkyl-carbonyl, ` : ~.
(Cl - C6) alkoxy carbonyl, or nitro, or Rl and R2 taken together represent a .
tetramethylene group, R4 represents a-tetramethylene group or a radical ~
-CH=CH-CH=CH- completing the tetrahydroquinoline or quinoline nucleus, :
respectively, and which may optionally be substituted by halogen, (Cl - C18)
alkyl, (Cl - C3) alkoxy, (Cl - C3) alkylthio, halogen (Cl - C2) alkoxy, ~
trifluoromethyl, (C5 - C7) cycloaIkyl, phenoxy, -NH2, di-(Cl - C4) alkylamino, ~
-N02, (Cl - C3) alkyl carbonyl, or (Cl - C6) alkoxy-carbonyl; or R4 represents
a radlcal chosen from -CH=CH-N=CH-; / .
o R H
O
-~ - 2 -
:"~
1~34289Z
R5 and R6 represent CH3 or C2H5, and
X represents oxygen or sulphur.
Among the aforesaid radicals the following are preferred:
X = O
R5 and R6 = GH3 li / 5
m e group - O - C - N (II) is preferably in R3-position.
R6
If Rl or R3 are not a group of formula II, they preferably are
hydrogen (Cl - C3) alkyl, (Cl - C4) alkoxymethyl; especially preferred is
~ = hydrogen or (Cl - C3) alkyl, and R2 = hydrogen, F, COCH3 or GOOGH3; R4
represents a tetram~thylene radical or the radical of the formula -CH=CH-CH=GH-.In the latter case derivatives of quinoline are obtained which themselves are
either - preferably - non-substituted in the benzene nucleus or substituted by `~
F, Cl, (Cl - C18) alkyl, preferably, tCl - C4) alkyl, (Cl - C3) alkoxy, `
(Cl - C3) alkylthio, CN or methylenedioxy. In case R4 and R5 together form a
(C3 - C5) alkylene radical, derivatives of tetrahydroquinoline are obtained;
in these compounds the partially hydrated nucleus is also preferably non-
substituted or substituted by one of the radicals specified for quinoline
derivatlves, furthermore by CF3 or di(Cl - C2) alkylamino.
me compounds described by form~la I can be prepared from
compounds of forn~la IIIa or IIIb, wherein either Rl or R3 is hydroxy:
OH R3
IIIb
The compounds of formulae IIIa and IIIb may be present in the
tautomeric quinolinone form:
~r~ _ 3 _
~-~ ` .'; ' .
'.',.~,
IIIa 1~42892 IIIa'
OH O
~1;/2
IIIb H ~.
IIIb'
In both cases so-called "ambident" anions areformed by the action of bases~
~ 2
which react with aIkylating or acylating agents, either at the 0- or N-atom. ~.
By applying suitable reaction conditions, the reaction can be directed so as .
to produce the preferably or exclusively O~substituted products of formula I.
1) In a preferred embodiment of the process according to the invention the
compounds of form~lae IIIa or IIIb are reacted with at least stoichiometric
quantities of carbamoyl halides or thiocarbamoyl halides of formula IV
~11 / R5
Hal - C - N \ IV ~ ~ :
R6
wherein Hal represents a halogen atom, especially chlorine or bromine.
It is especially preferable to use an excess of from 10 -
- 4 -
1~)4Z892
100% of the halide of formula IV. The reaction is carried out by dissolving
or suspending the compounds of formulae IIIa or IIIb in an anhydrous inert
solvent or diluent such as chloroform, an aliphatic ketone, acetonitrile or
dimethyl form mide and adding an organic base such as triethylamine, pyridine, -
quinoline or an inorganic basic compound, e.g. sodium carbonate, potassium
carbonate or calcium carbonate in at least stoichiometric quantities; sub-
sequently, the N, N-dialkylcarbamoyl halide is added at temperatures between
about 0 and 80C.
So as to achieve the intended 0-acylation of the ambident anions
being formed upon addition of the base, polar solvents are used and the reac-
tion temperature is advantageously kept as low as possible. mough reaction
temperatures above 30C increase the reaction rate, in some cases the portion
of N-acylated product increases with increasing temperature to the detriment
of 0-acylated products.
Reaction time varies depending on the base used and on the type
of the substituents Rl to R3 and in R4, but the reaction usually requires 4 -
to 12 hours.
2) In another preferred embodiment of the process the compounds of formula
IIIa and IIIb are reacted with phosgene, thiophosgene or chloroformic acld
(thion) esters and the intermediate products thus obtained are further reacted
with secondary amines of the formula
/ 5
H - N
R6
most conveniently in the presence of a solvent or of a suitable base.
m e reaction conditions applied in this variation of the -~
process are generally known from similar reactions and are more extensively
described in the Examples.
3) Compounds of formula I wherein Rl forms a substituted or unsubstituted
- 5 -
: ~: . '
. :
-
1~4Z892
saturated alkylene chain, may be prepared from the corresponding unsaturated
compounds by hydrogenation in known m nner.
4) If compounds of formula I are desired wherein R4 is substituted by an amino
group, these compounds may be prepared from the corresponding nitro compounds
by means of catalytic hydrogenation.
The compounds of form~la I are isolated from the reaction
mixture according to processes (1) and (2) in known manner by filtering off
the precipitated amine hydrohalides, alkali metal halides or alk~li earth
metal halides formed as by-products in the reaction and by concentrating
the filtrate containing the reaction product. If a catalytic reduction is ~`
carried out according to processes (3) and (4), the catalyst is also elimin- ~
ated by filtration. ~ -
For further purification the crude products may be distilled in
vacuo if necessary, or they may be recrystallized from an organic solvent.
The compounds of formula I represent colorless to slightly
yellowish crystalline solids or highly viscous liquids. They are well soluble -in most of the organic solvents but only slightly soluble in water. The
aqueous solutions are slightly basic.
The compounds of formula III which are used as initial compounds
for the processes according to (1) and (2) can be prepared by processes known
from literature or they may be prepared according to analogous processes.
The preparation of such initial compounds is described, for
example, in the following publications:
United Kingdom Patent No. 1,147,760; German Offenlegungsschrift
(~OS) No. 2,058,002; (DOS) No. 1,620,066; (DOS) No. 2,103,728; Monatshefte
fùr Chemie 100, 132 - 135 (1969).
me compounds of formula I according to the invention have a -
highly selective insecticidal activity which is directed almost exclusively
a B t aphids, and furthermore possess excellent systemic properties. They
show the same efficiency, whether absorbed via the plant foliage or via the
root system. Iherefore, aphids living hidden inside galls and other parts
. . . .. .... ~ .. . . . . . . . ....
1()4Z892
of the plants that are difficult to reach can also be combated with good
results. They are furthermore active against aphids which have become re-
sistant to phosphoric acid esters.
Examples of aphids which can be combated successfully by the
new compounds are Brevicoryne brassicae; Myzaphis rosarium, Aphis schneideri;
Eriosomatidae such as Eriosoma lanigerwm; gall-forming aphids such as
Pemphigus spec. as well as Myzodes persicae.
On the other hand, useful coleopters (such as lady bugs),
butterflies, orthopterae, dipterae, hymenopterae (such as ichneumon flies),
and predatory mites feeding on insect pests are not or only slightly affected
even by high concentrations of the active ingredients. The action on aquatic
organisms is insignificant; the compounds having an action on fish only at
high concentrations.
,'
~- ~ ,
.
1~4Z89Z
The compounds of the present invention or the preparations
containing them may be applied in widely varied manners. They
may be applied to the foliage and/or affected parts of it or,
on the other hand, to the earth surrounding the plant.
Marketable compositions containing these compounds may
consist of dusting formulations, powders or granules, wherein
the active ingredient is present as an admixture to ~olid
extenders or carrier materials such as inert substances in
powder or granular form. Generally, these compositions con-
tain from 3 - 75% of these compounds. Suitable solid ex-
tend~rs or carrier materials are, for example, kaolin,
bentonite, diatomaceous earth, dolomite~ calcium carbonate,
talcum, ground magnesia (chalk)~ fuller~s earth~ plaster
or agrillaceous earth. The compositions may also be used as
wettable powders which contain - in addition to the active
ingredient - known wetting agents and/or dispersing agents
and optionally fillers and/or emulsifiers as further additives.
For application in the field these formulations are
further diluted with suitable solvents, preferably with water.
me concentration of active ingredient in such ready-to-use
formulations may vary within wide limits depending on the
mode of application (foliar or root), the type of aphid
being combatted etc. Generally, the concentration may be
between about 0.0002 and 1% active substance.
The compositionsmay also be present as liquid prepa-
rations as concentrated emulsions for spray liquors which
normally contain the active ingredient together with one or
several wetting agents, dispersing auxiliaries or emulsifiers. ~ ~ -
For liquid preparations organic solvents may also be used.
-8-
~, .. . , . , - - - :. - . . - . . -
1042892
The wettable, dispersing and emulsifying agents may be of
either one of the cationic, anionic or non-ionic type.
The compounds of formula I may also be used as active
ingredients in fumigants.
The following examples illustrate the invention in detail
without - at that - limiting the range of the invention:
EXAMPLES OF PREPARATION
EXAMPLE 1:
OU~I (CH3)2
2-methyl-4-dimethylaminocarbonyloxyquinoline
a) To a suspension of 75 g (0.47 mole) of 2-methyl-4-hydroxy-
quinoline in approximately one liter of acetonitrile
130 g of anhydrous potassium carbonate were added at room
temperature. The mixture was heated to reflux temperature
(~80&) while stirring vigorously for about two hours.
After cooling to room temperature, 76.7 g (0.71 mole) of ;
dimethylcarbamic acid chloride were added and the
reaction mixture was stirr~d~l vigorously at room temperature
for about 8 hours. After cooling, it was being suction-
filtered, the filter cake was washed additionally with
some acetonitrile. The filtrates were combined and the
acetonitrile was eliminated by water jet vacuum.
The residual oil was submitted to fractionation in
vacuo. At a temperature from 158 - 161 C (0.05 mm) `
the distillation yielded 100 g of a colorless highly
:~ '
''~ ' ':"
: :-
_g_ . ,:
:.-,. .:
~, .
1~)42892
viscous liquid, the elementary analysis values of which cor-
responded to those obtained for 2-methyl-4-(dimethylaminocarbonyl-
oxy) quinoline; when submitting this liquid to thin-layer ;
chromatography and to NMR spectrum, it proved to be uniform,
Besides the results of the NMR spectrum, the presence of a
carbamate was further confirmed by IR spectroscopy.
b) 24 g (0.15 mole) of 2-methyl-4-hydroxyquinoline were dis-
solved in 200 ml of dimethylformamide (anhydrous and free
from amine), 23 g (0.22 mole) of triethylamine were added
and~ subsequently, 24 g (0.22 mole) of dimethylcarbamic
acid chloride added dropwise.
The reaction mixture was heated to 60 C (for about
8 hours) until thin-layer chromatography sHowe~the absence
of starting material.
Separated aminohydrochloride was suctioned off, the
reaction mixture was cooled to 0 to 10 C. The filter cake
was washed with a minor quantity of cold dimethyl-formamide,
the filtrates were combined and the solvent was eliminated
in vacuo. The oily residue was submitted to fractional
distillation.
At 145 C (0.01 mm) 21 g of a colorless and highly
viscous liquid were obtained.
EXAMPLE 2
OICON (CH3)2
3 ;~-
--10--
1~)4Z89Z
2-methyl-4-dimethylaminocarbonyloxy-5, ~ 7, 8-tetra-
hydroquinoline
a) 287 g (1.76 mole) of 2-methyl-4-hydroxy-5, 6, 7, 8-tetra-
hydro-quinoline were dissolved in 1650 ml of chloroform
(anhydrous and free from alcohol); to this solution 267 g
(2.64 mole) of triethylamine and 284.5 g (2.63 mole) of
dimethylcarbamic acid chloride were added successively.
The mixture is then heated at an interior temperature
of 50 C until after approximately 6 hours thin-layer
chromatography did not shown any initial compound.
After cooling to room temperature, about one liter of
ice water was added dropwise to the reaction mixture while
stirring, until the aminohydrochloride formed in the
reaction was dissolved and two liquid phases were obtained.
The organic phase was separated, washed with a minor
quantity of water, dried and concentrated. At a bath
temperature of 100& and approximately 2 - 3 mm of pressure
some ml of an oily by-product distilled off. The remaining
oily residue was dissolved in boiling n-hexane.
347 g of colorless product having a melting point
from 89 - 90 C cryst~llized out of the cooled solution. ~ ~ -
On thin-layer chromatography this product proved to be
uniform and elementary analysis yielded the expected
values for 2-methyl-4-dimethylaminocarbonyloxy-5~ 6, 7~ 8- ~ ~
tetrahydroquinoline. IR spectrographic and NMR spectro- ~ -
graphic data confirmed the formation of the expected
O-acylation product. ~
b) 16.3 g (0.1 mole) of 2-methyl-4-hydroxy-5, 6, 7, 8-tetra- ;;
hydroquinoline were dissolved in 150 ml of chloroform
--11-- - ~ .
: ''.:'-
lQ4289Z
(anhydrous and free from alcohol) and this solution was
added dropwise to a previously prepared solution of
approximately 20 g (0.2 mole) of phosgene in 100 ml of
chloroform at a maximum temperature of +10 C. After a
period of two hours at +10 C3 the reaction was completed
at room temperature for another hour. Non-reacted phos-
gene was then blown out of the solution by means of a dry
nitrogen current and the solvent was eliminated in vacuo
at room temperature. The semi-solid residue was again
dissolved in dry chloroform free from alcohol, the
solution was cooled to +10 C and an excess quantity of
dimethylamine was introduced at this temperature.
After standing for two days at room temperature, chloroform
and excess amine was eliminated by distillation in vacuo.
me residue was digested with ice water, separated from
water and dissolved in toluene. After drying and
evaporating the toluene a residue of 7 g was obtained
which crystallized thoroughly when being submitted to
trituration with n-hexane. Recrystalli~ation from
n-hexane yielded 4 g of a uniformly crystalline product
having a melting point of from 88 - 89 C. This pr0d~ct
proved to be identical with the product obtained according -
to example (2a).
c) 5 g of a nickel catalyst consisting of, 50 percent by
weight of finely distributed nickel on diatomaceous earth
were added to a solution of 20 g of the substance
according to example (1) in 1 ~iter of toluene and the
whole was heated at 100 C in a 2 1 steel autoclave with
hydrogen at a pressure of 100 atmospheres.
-12-
. - - ~ - - - - - ., - ~ - ... . . . .. .. . .. .
1C~4Z892
After 20 hours the batch was cooled, the catalyst filtered off~
washed with toluene and the filtrates were concentrated. The residue was
distilled, 11 g of a product (b.p.o 1 130 - 142C) were obtained. On
crystallization this product proved to be identical with the product obtained
according to example (2a).
E X A M P L E 3:
(Comparative Example)
OCON(CH3)2
CH3 3
. :
': ' .
2,6-dimethyl-4-dimethylaminocarbonyloxy-pyridine
30,8 g (0,25 mole) of 2,6-dimethyl-4-hydroxypyridine were sus-
pended in 500 ml of acetonitrile, 69 g (0,5 mole) of potassium carbonate
were added and the mixture was heated to reflux temperature for 2 hours.
Subsequently 47 g (0,44 mole) of dimethylcarbamic acid chloride were added
at an interior temperature of approximately 60 - 70 C and the mixture was
m~intained for 2 hours at about 80C.
After cooling the liquid phase was suctioned off, the residue
was washed with acetonitrile and the combined solutions were concentrated
(finally in vacuo). The viscous residue was dissolved in hot n-hexane. On -
cooling 37 g of colorless, uniform (DC) 2,6-dimethyl-4-dimethylaminocarbonyl-
oxypyridine having a melting point of from 75 - 76C were obtained. Chemical
structure as well as composition were confirmed by elementary analysis, IR
and NMR spectrography.
me following table shows a number of additional compounds pre-
pared according to example 1.
- 13 _
r~ -
-.~, ~,
104289Z
C~ I
Q~ O ~ C~ d o c~ d C~ _
~ d b~ _ 1:3 o ~ _~ X ~1 _ cs~ ~ o ~1
O ~1 0 ~1 ~ ~ I ~ ~ ~ ~ O
r~ ~ C`l OI '~ ~ O I
~1 ~rl o rl ~ c~ ~1 0 ~ d ~1 0 cs~ d ~1 o
o~o~ _ __ _ _
~ ~ : ~
U~
~ ~ o C`l O~ o ~ O ~
d C~ d 5~ co co co co :
~ ~ ":`
' ~
,.,
z ~ z ~ æ ~ z;
C~ ~ ~o~
o yC~ :CyC~ :~ yC~ 3 yC~ ~ ,:
.,
.~ '
. ~ c~ ~ c`l . .
v v vx~x~ vc`l x : ~
l ~ lg~
~o
1!~)4Z892
_
bO d ~ C~ d ~ _
,d ~, p ,~ ~ X ~1o o~ X o~ X
~1 ~ri O ~ rl ~ ~ ~ ~ I ~ I ~
o ~ o o ~ I c~o ,I d ~ d
_ ~1 _ ~ _ o~ _
~ .
'~:
h :::
U~ ~ ~ ~ O 1~ O el ':
d oC:~ d o c~ ~ e~ ~ oo oo
h ~ _ , `.: .
~ ~ _~) ~ O ~ O C.)~
~3~1 t~ C~ X ~ X ~
,D ~q . "'
. _ "~ ' "
~Z ~ .~ ~ x~ ~ .':, ~ .
~ C ~ ~ ~
~ ~ ~''''~''''''"
' :'~ ' """
'`:,...,'", ,:
oo o~ ~ ~1 ,~
,:
'
16)42892
D :I D U~ ~ ,1 D ~j ¦ oO ~ ¦ D ~ ¦
rl ~ ~ O O I~ X ~ ~1 X :
,I d ~ ~I d ~ I~ o ~ `D d ~
_ _ ,:
O ~ O `O O ~
O `D
D oO b ~ I ~ I I
~
o ~ O~" 0~ Y O~ ~ Y ~
~1 ~ ~ ~ ~ ~ ~ ~
l æ ~3 ~~ ~ ~
tll lo~
~: ' ,' ''
~1 ~ ~1
~ ~ '
1 6--
- . - ., - .- - ,,.. .... . . .- ~. .. . ~ . . .. ... .. . . . ~ , , .
1~4Z89Z
~ C~ ~ ~
.d ,~ ;~j ~ ~ d o c~ ~: `D ~ o ~3d ;
o~ ; I o~ ~ ~o I o ~o ~ ~
.
El ~ ~ ~ -- ~I -- d _ o~ d
_ ' :
'' "
oo ~ COO~ oo~ oo~
_ ~ ,:
'
a~ P ~ ~ 0~ æ 0~ z 0~ æ
:C e~ ~ ~ ~) :; ;
~ _ _ I .;.
~,:.,.
il ~o ~
C~ C~ ' -'-
_1'7-
. . .
1~4Z89Z
ô~
~0~ 0~_ O~ ~ oC~ ~ 1~J o~ ~
X ~ X ~ X o~ ~ , ~C
o ~ ~ ~ ~ ~ c~ ~ o a~
o~ ~ ~o o~
o
o~ '.'
3-3~ ~ o~ o ~ o ~
, .
_ O ~ C~ :C~
. , .~
_ ~r n _ ' ~
.
18 -
lQ4Z892
o _ Oo ~ e~ ~ ¦ _ ~ o o K ~ ~
;
7~
0~ ~ ~ c~ 3eN ~F~ C`~ ~
~ ~ r f~
~ 0~ ~ ~
= : ~ R ~ ~
7 7 ~ ~
1~4Z89Z
~ ~ oD O ~ _ I O ~j ~ u~
_ ~ _ ~ X ~ ~ ~ ~ ~1 ~
d ~I d :~ I ~1 I ~ :s I ~ ~ ~ ~1
1 0 ~ rl O O ~ 5: ~1 oo ~ ~1 ~ I o
0~ ~ ~o o~ ~ _ ~o ~ o ~I d ~I d ~
_ - _
h ~
c~ ~ _
d _ d ~ O oo oo ~ oo ~ O
~ Z~ Z ,~
~ O C~ ~ o~,) Z Y ~ _
~ ~ 8 8~ 8~
~ \/
.- ::
.. , ~:
7 ~ c~ c`~ c~ c~ :
- :~:
- 2(~
""
-
1)4Z892
O ~ O ~ O ~j D O ~
X c~ oc~ O d
bO ~ ~ oo
~q o o ~ I ~ ~1 _ X ~ ~
_ ,D ~ _ _ ~I O _ ._
~.
~ ~ ' ," .',
~.,1 .,.
u~
doC) ~ ~ o o o ~ o ~ o t~
,~ o ~ ~1 oo ~o oo ~
h L~ :; .
~ ~; 1~ o~ Z; O~ C~ Z ..
.Q ~q ~ c~
_ ~ n n
~ ~ u~ ~ ,
"'':' ' .
~ h c~ ~ ~ ~ : .
X ~ . '~
-- 21 --
1~428~2
oV ~ oV ~oVV ~ h r~l
C~ ~ bD V o~ o X rl
C~ ~ ~ ,~ ~ ~ Ov O
o~ l U~,~ I o l C~ ~ O o
Q I I `D ~ `O
, oo ~ ~ O ~)_ ~ ~r _
._
~ ~ h O . .
~oC~ ~ ~I~ oc) ~00 C~ ~ ~
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' ','
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- 22 -
104Z892 ~
Q~ ~ ~ _ ',. .
~o ~ ~o o~, ~ ~ ~ o~ X ~_ ..
X c~ ~1 ~1 ~ ~ ~ ,~ O ~
~ ~ o ~4 ~c~ d s~ ~ ~ C~
13 h
~_ ~ U~ o ~ O ~ ..
C~o~ o~ CO oo ~ U~ ~
.
,:,
~ C~ ~ 0~ ~ ~ ~
,n ~ ~ c~ ~ ~ ~ v ~3 .. '"'.
~ ~ =~ =~ ~
1 ~ ~
O qO~ O~ ~ ~/Z~
.- ... ~.~ .
- ~
-- 23 --
1~42892
d c~ o e ~ ~ ~ c ¦ o ~ ¦ oc' ~ c
~1 o ~ ~ o I ~ ~ ~ ~ I ~ ~
,o,O~ ~ e~ ~
dO d O O ~1 O oo O ~ O c~
0_,0~ _~_ ~ . ~
~ P --U~ ~1~ o~ Z o~ Z oC~ ~; ::
~1 =e~eO OyNo~ yel o?
~ cc~ z e?
~1 ~! lSC~ 1~ lo~ I ~g I ~ ~
I ~el I Ie~ ~ ~
. ~ '
~e
- 24 -
1~4Z89Z
- ov C~ . ,.
~ ~ o~ â) â~ :- ''
.~ ~ ~1 0 ~ ~ O ~ N ^
U~ ~3 IS~ _~ (r) S: O S: ~
~ ~ ,; ~ o~ ~_ ~ ~ ~ _, : .
1~ v 1~ o ~ ~ o ~D
~ ~`_ V ~ ~ o~ Z . . ~
~0 . ~ ''':,
^~'7 ~ ~
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-
~ ` - 25 -
1(~4Z892
bOO~ O
.,, ~ P ,, ~ ~ C~ X C~ ~, ~ C~ X ~, ~ e~ ~C
~ O ~ a o~ c~ ~ ,1 ~ 8 ~1 ~
a) o ~q o o ~ ~1 1 0 O ~ I~ I ~ .~ ~
a P~ ~_ ~ ~ _ _ ~ o
oo O o O ~0
co C~ C`l ~ N C`~
_ : .
Z ~ ,',
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.Q cq ~ C C~ ~0~ O~ Z .,
': '''
. :
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o ~
:~ ~ :
'c
a~ _~ c~ ~ ~ .: .
~ h u~ u~ u~ u~
~ ' .'
-- 26 _ . . -
-
1~4Z89Z
.
,~ ~o .~ ~ C~ -': ' ''
~ ~ ~ ~ . .`
~ ~;
~ . , .
~ - 27 - ~ ~
892
' .~
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,~o ,~ ~ U~ s ~ o~ ~ ~ ~
g~_~
~ A~ /a ~
"'. '
~G - 28 ~
1~)4Z89Z
00 `D C~ O_
~1 ~r( O ~ rl ~ l _I l ~ . .
~cq o ~ O~ ~ ~0 , '
CoC^,,g ~ ~V~ ~ ~ o ~ ~ ~ .~'
. . ': ':
~ ~ ,, o~ o~
~ _, ~ ~ ~ ~ ~ ~ ~ . ...
o b ~ :~ ~ y ~
~ ~o~ 'o'l~ ~
'æ~
~ ~ Cl~ ~o~
:: ''
~ . . .. . .. .. .. . . . . . .
1~4Z892 -
~0~ ~ bO" ~ ~ ~ I
oo ~ o C~
;~, ~, _-_ ~,
.,, ''
.~,^~ o,i o~ o,1 ~.~
~= o~ ~ o~ ~ o~ ~ ~ .
. . .. ''`-':.
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', ' '
S. U ~ ~ ~ ~ ~ '
' ..
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, :
-- -30-- :: i
.. . ... -- .. .... . , .. , . . .... . . . --.. . . . . . . . . . - . - . . .. .. .
104Z892
In the same way the follcwing com~ounds can be prepared: : :
OCON(CH3)2 OCON(CH3)2
6 5 3 ~
OCON(CH3)2 OCON(CH3)2 - :
~ a CCH
3..
OCON(CH3)2 ` 3 2
OCON(CH3)2 OCON(CH3)2 :
(cH3)2N-cHs~ f ~ ~
1 . ' ~', ~ ":
- 31 - .
~; ' ' ' '
. . .. . .
104Z89Z , ~ ,
OCON(CH3)2 ICF3 t 3)2
~ ~ ( 3)2 ~ ~ :
NC OCON(CH3)2 0 - C - N(CH3)2
N J H3C 1 N 1 N .
OCON(CH3)2 CH3 - C - N(CH3)2
N ~ 6H3 3
OCON(CH )2
3)2 ~ 1 3
CH~C6H3 N Cl
CN(CH3)2
CF3
_ 32 ~
~ ~" . ~ .
1~4Z89Z
CCON(CH3)2 ( 3)2 . :
CC13
\ , .
CH30COCH20 ~ CN3)2 ~ (C 332
OCON(CH3)2 laCON(CH3)2
~(CH3)2 ~C6H5
" ~:
~ o '.''.
S ~ OlCON(CH3)2 11
O-C-N(CH3)2
~ ''- :,.''''',.
- 33 -
... . . . ... .. . . ...
11~342892
FORMULATION EXAMPLES
E X A M P L E A:
A wettable powder easily dispersable in water is obtained bygrinding to- -
gether
12 g of 2-methyl-4-~dimethylaminocarbonyloxy)-quinoline as
active ingredient and
3 g of Silcasil(R) (highly dispersed synthetic silicic acid),
and blending this with
45-43 g of a pre-mix consisting of
10 g of cellulose pitch (potassium salt of ligninsulfonic acid)
49 g of Ca-Mg-Al-silicate
11.5 g of highly dispersed synthetic silicic acid
3.5 g of polypropylene glycol (m.w. 750)
1 g of Na-oleylmethyltauride
:
75 g of preliminary blend
That means that
60 g of this wettable powder contain
20 weight % of active ingredient - -
49 weight % of Ca-Mg-Al-silicate
16.5 wt. % of highly dispersed synthetic silicic acid
3.5 wto % of polypropylene glycol (m.w. 750)
1 weight % of Na-oleylmethyltauride
10 weight % of cellulose pitch
E X A M P L E B.
An emulsifiable concentrate consists of: ~
1.5 g (15 %) of 2-methyl-4-dimethylaminocarbonyloxy-5,5,7,8- ~ -
tetrahydroquinoline
605 g (65 %) of cyclohexane as solvent and
2.0 g (20 %) of ethoxylated nonylphenol (nonyl (ethoxy)l0
pheno~ as emulsifier.
) (R)=Registered Trade Mar~
- 34 -
1~)4;~89Z
BIOLOGICAL EXAMPLES
E X AM P L E I:
Potted horse beans (Vicia faba) were infested with 200 specimens
each of bean aphids (Doralis fabae) and, after stabilization of the popula-
tion, sprayed to the drip-off with decreasing concentrations of an aqueous
dilution of the emulsion concentrate containing the compound described in
example (1) as active ingredient 3 days late~.the percentage of killed
aphids was determined by counting the numbers of surviving and dead insects.
The following table shows the mortality rate depending on the
concentration of active substance (AS) in the aqueous dilution, as compared
to the efficiency of two compounds having s;milar structures or comparable
degrees of efficiency.
:.
- 35 - -
1~42892
T A B L E
. . _ .
Structural Concentration of% of Mortality
formula AS in the spray
liquor in %
.. _ . . _ ,
'.
Compound of Example (1) 0,00019 100
(according to the invention 0,000095 98
o,oooo48 80
0,000024 50
,0035 ~ 168
0,0006 20
OCONtCH3)2 ;
~.,
Dutch Offenlegungschrift
No. 6.606.695 (comp. agent I)
.,"'~
ICH(CH3)2 '. '~ :
(CH3)2N - C - O ~ o,oo255 96
CH3 0,0012 60
H o,ooo6 20
Isolan (comp. agent II)
,, '," '''",
.' .' :", '
Similar or identical results were obtained with the compounds
of examples 2, 3, 4, 5, 8, 9, 10, 11, 12, 14, 20, 21, 25, 28, 40, 46, 48 and
55.
E X A M P L E II:
Potted horse beans (Vicia faba), the root system of which was
wrapped in sheet plastic, were infested with bean aphids (Doralis fabae) and
treated with gradually decreasing concentrations of the product of example (1)
in such a way that an aqueous dilution of an emulsion concentrate was uniformly ~ ;
distributed in the root area by means of a glass funnel. 8 ~ays later the
~. ..... ~ ,
percentage of killed aphids was determinded by -~ -
~ - 36 -
''~ ' '
1~)4Z892
counting the numbers of surviving and dead insects.
mg of AS per
root system ¦ o.5 0.25 0.125 ¦ o.o6 0-03
of mortality ¦ 100 100 ¦ 94 ¦ 81 40
Similar or identical data were obtained with the rest of the
compounds specified in example (I).
E X A M P L ~
The stem of a horse bean plant about 25 cms high was wrapped in -
cotton (wadding) and covered with cellophane.* By means of an injection
syringe 2 ml of an aqueous suspension of wettable powder of the compound of
example (1) having the specified concentration of active substance was ~
uniformly distributed in the cotton pad. At the accordingly administered ~ `
quantities of active substance bean aphids living on the leaves of the plant
were destroyed as follows after 3 days:
concentration 0.25 0.125 o.o6 0.03 0.015
of As in the
spray liquor _
% of mortality 100 100 86 ~ 7 < 20
This test shows the capacity of the active substance to penetrate
into planttissue and to circulate within the plant. This same capacity is
also characteristic for the other compounds specified in example I.
X A M P L E IV:
.. ..
The compounds according to the present claims in the gaseous phase
were also efficient against aphids (Doralis fabae).
When a potted plant infested with bean aphids was placed under a
glass bell having a volume of 23 1 and a filter paper of 133 cm surface and
containing a given quantity of active substance was suspended in the air-
filled volume, the aphids on the test plant were destroyed after 2 days. A
test carried out with the compound of example (3), gave the following results:
*l`rade Mark
- 37 -
1~4289Z
mg of AS on
the filter 0.25 0.125 o.o6 o.o3 o.ol5
% of mortality 100 100 100 97 84
The other compositions specified in example Igave similar or
identical results.
E X A M P L E V:
Useful insects such as ichneumon flies (Coccygomimus turionellae
(L.)) are not affected by concentrations effective against aphids. This is
shown in the following experiment:
Rectangular-shaped filter p~pers (150 cm ) are sprinkled uniformly
by means of a pipet with acetone solutions of active substance in decreasing
concentrations. After drying the filter paper is put inside a glass tube in
such a way that its total interior w~ll surface is covered by the filter
paper- Subsequently, 10 females of ichneumon flies are inserted in each of
the glass tubes thus prepared and after closing the tubes with a pierced cork,
a constant flow of air (10 1 of air per hour) is passed through (suppressing
a possible gaseous phase, imitation of natural flow of air outdoors). The
following mortality rates are found after 24 hours for the use of the com~
pound of example (1).
mg of AS on% of
the filtermortality
'~ ,~
: ~ '
Compound of example (1) 0.012 100
o.oo6 ~0
(as per the invention) 0-003 0
0.0012 0
o.ooo6 o
o.ooo6 loo
0.0003 100
Carbaryl o.ooolS 40 --
(compar. agent III) 0.000075 0
Isolan 0.003 100
(compar. agent II) 0.0012 80
o.ooo6 o
. ,
- 38 - ~--
1~4Z892
The compositions mentioned in example I gave results similarly or
equally favorable as those of example (1).
E X A M P L E VI: ~:
No action was observed on lady bugs (Coccinellidae) essentially
feeding on aphids when the same concentration rates were used as those for
combating aphids~ The following example confirms this with respect to
Imagines of the species Coccinella septempunctata:
On Petri dishes lined with filter paper 10 insects each of the
above mentioned species were placed and then sprayed with decreasing con-
centrations of an aqueous dilution of the emulsion concentrate of the com-
pound of example (1) (corresponding to 600 l/ha). The following mortality
rates were found after 24 hours:
mg of AS on ~ of
the filter mortality
, .
0.003 lo
o.ools o
o.ooo~ o .:
o oD003 O
o.oools o
-- 39 --
