Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The present invention relates to 1,1-diphenyl-2-nitro-
propane and -bu~ane deriva~ives, tO processes for
their preparation and to ~heir use in pest control.
The said 1,1-diphenyl-2~nitropropane and -butane
derivatives have the formula
1 (I) ; ;;
' ~2 -
wherein
,~ ~
Rl represents Cl-C3-alkyl,
R2 represents p-(Cl-C3)-alkoxyphenyl,
p-(Cl-C3)-alkylmercaptophenyl or
3,4-methylenedioxyphenyl, and
Z represents 02N-CH-CH3 or 02N-CH-C2H5.
The alkyl, alkoxy or alkylmercapto groups denoted
by Rl to R3 can be branched-chain or straight-chain.
These groups are: methyl, methoxy, methylmercapto,
ethyl, ethoxy, et~ylmercapto, propyl, propoxy, propyl-
mercapto, isopropyl, isopropoxy and isopropylmercapto.
Compounds of formula I preferred on account of
their action are those wherein
Rl represents Cl-C3-alkyl, ~ ;
R2 represents p-(Cl-C3)-alkoxyphenyl or ~-
p-(Cl-C3)-alkylmercaptophenyl, and
~. :
? z represents 02N-CH-CH3 or 02N C~H C2H5-
~ - 2 -
:" ,~ . '
:, .
.:~ :, , , . , : . ,: ,
.~3~ 7~
Particularly preferred compounds of formula I
are those wherei.n p
R represents Cl-C3-alkyl,
R2 represents p-(Cl-C3)-alkoxyphenyl, and ~
Z represents 02N-CH-CH3 or 02N-CH-C2H5. ~ -
The compounds of formula I can be prepared, for
~;~ exampleg analogously to the following known methods:
~ .
~, a) X~
.~ . . condensation agent
~ . -H20
~' ~ ~
b) R2_1H_z + ~ R~ ~:
OH ; :~
.
condensation agent
. . . ~ .
:`,i~ ' ~ . - ' ", .,
~ ' ~
, .
' " ~ '
G ~ ~
~ - 3 -
:,
.'.~ ' ; ,
.' :
.
~ A . ' '` : ' . . . .. '.. ` . . _ . . ........ ._ __ . , .. . , _ _.. ~, . ... _, ._ ,_ _ . _ ,,, .,. . _ _ .. ,, ., ., .. , .. ,, ,.
. ~,~"_____,
.
',"' '
~ i7~
; Applicable condensation agents are inorganic acids
such as sulphuric acid; organic acids such as acetic
acid; Lewis acids such as aluminium chloride or
boron trifluoride in the form of complexes with
inorganic or organic acids, such as phosphoric acid,
acetic acid, etc..
The reaction is performed under normal pressure,
, at a temperature of between -30 and 100C, preferably
between 0 and 40C, and optionally in solvents such --
as, e.g. acetic acid, nitroalkanes or methylene
chloride.
~' The starting materials of formula II are in part
known, or can be prepared by methods analogous to
known methods, e.g. analogous to those described in
the US Patent Specification No. 2,516,186.
, ~ .
The compounds of formula I have a broad biocidal ;
action, and can be used for the control of various
plant and animal pests. ~ ;
`- Compared with analogous compounds, the compounds of formula I have a surprisingly better insecticidal action,
.. : .
` particularly against stored-food pests and mosquitoes,
. ~ - .
a toxicity level suitable for application and better
s decomposability.
- The action of the compounds according to the invention
l 25 extends moreover to all development stages, such as eggs,
" :
.' ~ 4 ~
.~
larvae, nymphs, pupae and adults of insects of the
families: Acrididae, ~lattidae, Gr~llidae, Gryllo~al-
L ~r~S oC oric~ae~
pidae, Tettigoniidae, Cimicidae, ~ ,
Reduviidae, Aphididae~ Delphacidae, Diaspididae,
Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae,
Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae~
Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae,
Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Culicidae, -
Trypetidae and Pulicidae, as well as acarids of the
families: Ixodidae, Argasidae and Dermanyssidae. `~
'- . ' , .' -
! The insecticidal or acaricidal action can be ~ ; ~. .. ~
.. . ,~ . . :
appreciably widened and adapted to suit given circumstances
~^l by the addition of other insecticides and/or acaricides. -
.,j . .
Suitable additives are, e.g. the following active substances: ;~
organic phosphorus compounds,
;;.................. ..
nitrophenols and their derivatives,
formamidines, ureas, carbamates and
.~,i
-3 chlorinated hydrocarbons.
'"~ . .
q The compounds of formula I are combined with particular
~ 20 advantage with substances having a synergistic or
~.~
. intensifying effect. Examples of such compounds are
pyrethrin synergists such as piperonyl butoxide or
Z-(3,4-methylenedioxyphenoxy)-3,6,9-trioxa-undecane
(Sesoxane).
;"J, .~ ~
, ~ ~
.~ ,
.
, ~ _ S
''~ ' :. '
:.'', ~ ` .
~: ,
::
i ~ ' ' .
The compounds of formula I can be used on their own
or together with suitable carriers and/or additives. Suit-
able carriers and additives may be solid or liquid, and
they correspond to the substances common in formulation
practice, such as, e.g. natural and regenerated substances,~
solvents, dispersing agents, wetting agents, adhesives,
i thickeners, binders and/or fertilisers.
For application, the compounds of formula I can
be processed into the form of dusts, emulsion concentrates,
~ lO granulates, dispersions, sprays, or s~olutions, the form-
- ulation of these prep~rations being effected in a manner
commonly known in practice. ,~41so to be mentioned are
cattle dips and spray races, in which aqueous preparations
are used.
- : :
"~ The agents according to the inventivn are pro-
duced in a manner known per se by the intimate mixing and~'
- or grinding of active substances of formula I with
. , .suitable carriers, optionally with the addition of dis-
~ persing agents or solvents which are inert to the active
:? 20 substances. The active substances can be obtained and
used in the following forms:
solid preparations: dusts, scattering agents, granulates,
.! , :
coated granulates, impregnated gran-
ulates and homogeneous granulates;
liquid preparations~
: :
a) water dispersible active~substance concentrates: ~- -
wettable powders, pastes, emulsions;
b) solutions.
.' , :
- 6 -
.
The content of active substance in the described
agents is between 0~1 and 95%; it is to be mentioned in
this connection that in the case of application from an ;~
, aeroplane, or by means of other suitable devices,
concentrations of up to 99.5% can be employed, or
even the pure active substance.
:: ~
The active substances of formula I can be pre~
pared~ for example, as follows: ~
Dusts ~-
The following substances are used in the prepara~
tion of a3 a 5% dust, and b) a 2% dust: ;
~ a)5 parts of active substance,
-l 95 parts of talcum;
~ b)2 parts of active substance,
':1
1 part of highly dispersed silicic acidg
97 parts of talcum.
: .`i
The active substances are mixed and ground with
the carriers.
.~,
:.
:~
;........................................................................ ~` .
:.' ~ .
i
`, ;: ~.,.
- 7 -
, .
~ , ! .
~ ~7~
Granulate:
` The following substances are used to produce a
5% granulate:
5 parts of active substance, ~ -
0.25 parts of epichlorhydrin~
0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorhydrin
and dissolved with 6 parts of acetone; the polyethylene
, . . . . .
glycol and cetyl polyglycol ether are then added. The
solution thus obtained is sprayed on to kaolin, and -
l the acetone subsequently evaporated off in ~acuo.
.j
~ Wettable powder:
j The following constituents are used for the prepar-
ation of a) a 40%, b) and c) a 25%, and d) a 10% wettable
powder:
a) 40 ~ parts of ac-tive substance,
5 parts of sodium lignin sulphonate, ;~
1 part of sodium dibutyl-naphthalene sulphonate,
54 parts of SlliClC acid~
; b)25 parts of active substance,
'~ 4.5 parts of calcium lignin sulphonate
1.9 parts of Champagne chalk/hydroxyethyl cellulose
mixture (1~
1.5 pa~ts of sodium dibutyl naphthalene sulphonate, -
s 19.5 parts of silicic aeid, -`~
. 8
. .. .
~, . . : ,. . . , : . .
J~
19.5 parts of Champagne chalk,
28.1 parts of kaolin. ~;
;~ c) 25 parts of active substance, -~
;~ 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol ~ -
1.7 parts of Champagne chalk/hydroxyethyl
`~ cellulose mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselguhr,
46 parts of kaolin~
` 10 d) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulphates,
parts of naphthalenesulphonic acid/formaldehyde
:
.~
condensate,
~2 parts of kaolin.
The active substances are intimately mixed, in -
`~ suitable mixers~ with the additives~ the mixture being then
ground in the appropriate mills and rollers. Wettable
;i~ powders are obtained which can be diluted with water to give ;~
suspensions of an~ desired concentration. ~ -
Emulsifiable concent_ates:
The following substances are used to produce
a) a 10% and b) a 25% emulsifiable concentrate:
J
a) 10 parts of active substance,
3.4 parts of epoxidised vegetable oil,
,...................................................................... ~ .,
_ 9 _
,i
~)
' ,-'' , ' '
. ' '' . ' ; ' ~ ' .. : '
3.4 parts of a combination emulsifier consisting of
fatty alcohol polyglycol ether and alkylaryl-
sulphonate calcium salt,
parts of dimthylformamide,
43.2 parts of xylene.
b) 25 parts of active substance,
2.5 parts of epoxidised vegetable oil,
parts of an alkylarylsulphonate/fatty alcohol-
polyglycol ether mixture
5 parts of dimethylformamide,
57.5 parts of xylene.
From these concentrates it is possible to produce,
by dilution with water, emulsions of any desired concentration.
~pray:
~ The following constituents are used to prepare a
`~i 5% spray:
. ~
parts of active substance, -
1 part of epichlorhydrin,
94 parts of ligroin (boiling limits 160 -190C).
.. . .
, . .
.:~.....
s
-
,
:
- 10 -
.~ . .
~m~ :
A) Preparation of ]-p-e~hoxyphenyl-l-p~olyl-2
nitro-propane
19.5 g of 1-p-tolyl-2-nitro-1-propanol and 14 6 g
of ethoxybenæene are dissolved in 80 ml of methylene
. ~ .
chloride, and the solution added dropwise at 0C,
` with vigorous stirring, to 90 g of conc. sulphuric
acid and 10 ml of water. The mixture is stirred for
two hours at room temperature, and then poured into ~ ~;
` 400 ml of ice water.
.,~ . .
The product is taken up in methyl chloride, and
washed with saturated sodium bicarbonate solution. ~fter
the solvent has been evaporated off, the oil remaining
~! behind is dried in high vacuum at 60C for 2 hours to
obtain 27.2 g (= 91% of theory) of l-p-ethoxyphenyl-l- ;~
p-tolyl-2-nitropropane in the form of a viscous, ~ ;
; dark yellow oil havin~ a refractive index of nD9 = 1.5571.
.,j . :
i ~ :
-:
'`-;
..
:: - , . . .
B) ~E~arat~on of_l-p-ethylmerca~tophe~ p ~ A~
_
2-nitropropane
19.5 g of 1 p-tolyl-2-nitro-1-propanol and 16.2 g of
; ethylmercaptobenzene are dissolved in 80 ml of
methylene chloride, and the solution added dropwise
at 0C ~o 90 g of conc. sulphuric acid and 10 ml of
water. The mixture is stirred for 2 hours at room
temperature, then poured into ice water, and the
product extracted with methylene chloride.
~ 10 The solvent is evaporated off and the oil remaining
`.,7~ behind dried at 60C in high vacuum for 4 hours: the
-. ~7
~ yield is 29 g of 1-p-ethylmercapto-phenyl-1-p-tolyl-2-
j nitropropane in the form of viscous, dark yellow oil
~, having a refractive index of nl9 - 1.5629. -;
. 15 The following compounds are prepared in an
`,~ analogous manner: ``t`~
`, '' ~: :
i \~H/ 2
, y . ' ', ~ '
,j ,
:.: .
~ - 12 - ~ ~
,', ,
.,
.: . .
.. ,.. . . , ,,,, :
. -;.......................................... ... .
_ _ . . Physical data ~ -
-CH3 CH30- H ~ :
-CH3( ) 3 7 H n~ = 1,5503
-CH3( ) 3 7 H n~[~ = 1,5434
. -CH3C2H5S- H n~ = 1,5811
-CH3 3 H nD = 1,597
. -CH3 (n) 3 7S H nL = 1,5741 : .
-CH3 ~ ) 3 7 H nl~ = 1,5740
-C2H5 3 H n~ = 1,5626 :
-C2H5 2 5 H n~ = 1,5554
, ~ 3 7( ) CH30- H M.P. 87 - 88 C ~:
-a3H.~(n) 2 5 H n~ = 175488
1 3 7 (i )CH30- H M. P. 115 - 117 C
Z 3 7( ) C2H5- H nD = 1,5529 :
3 7( ) ( ~ 3 7 H nL = 1,5431
. : 3 7( ) ( ) 3 7 H nl~ = 1,5450 ~ :
3 7( ) ( ) 3 7 H ~ = 1,5685
3 7( ) ( ) 3 7 H nL = 1~,5640
. .
Z CH3 -0-CH2-0- n20 = 1,5792
-C2115 1 --C~2-o- 1nD=I 5498
~'
- ~'
- 13-
., : .
.
2 5\ / 2
CH
CH
R / ~ \ X
Y
.~
Rl ~_ _ _ P~lysLcal data : : :
_ _ _ .
-CH3 3 H nD = 1,553
-CH3 C2H5 H M. P.: 88-90 C :
-CH3 (n) 3 7 H M.P.: 53-55C . :
-CH3 ~ ) 3 7 H nD = 1~548
-CH3 3 H M~P.: 78-82 C ~ ~
-CH3 C2H5S- H M.P.: 76-80 C ; - -
-CH3 (n) 3 7 H nD = 1,5633
-CH3 (i)C3H7S- H n20 = 1,5698
2 5 3 H nD = 1 ~5568
-C2H5 2 5 H nl9 = 1,5509
3 7( ) 3 H nD = 1,5514
~C3H7(n) C2H5- H nD = 1,5413
C3 7( ) CH30- H nD = 1~5536
3 7( ) C2H5- H nD= 1,5470 ~ ~;
3 7( ) (n) 3 7 H nD = 1,5418 ; :
3 7( ) (i) 3 7 H nD = 1,5413
( ) (n) 3 7 H nD = 1~5554 ~:
3 7( ) (i)C3H7S- H nD = 1,5633
.,` . __ . __ .
. 2 5 -0-CH2-0- nD = 1,5476
-CH3 2 nD = 1,5638
,, _ _. _ _ ____. l
-- 14
., .
,., . . , , . . , , ,;
~ 7
Example 2
A) Insecticidal stomach poison action
Cotton and potato plan~s were sprayed with a 0.1%
aqueous active-substance emulsion (obtained from a 10%
emulsifiable concentrate).
After the drying of the resulting coating, Spodoptera
littoralis or Heliothis virescens larvae L3 were placed
on the cotton plants, and Colorada beetle larvae
` (Leptinotarsa decemlineata) on the potato plants. The
test was carried o~t at 24C with 60% relative humidity. -
The compounds according to Example 1 exhibited in the
:j :
above test a good insecticidal stomach poison action
~ against Spodop~eralittoralis, Heliothis virescens and ~;
3' - ~-
Leptinotarsa decemlineata larvae.
B) Contact action a~ainst stored-food pests
, 15 and house pests
Five parts by weight of an active substance and five
parts by weight of talcum are mixed together and finely
ground. ~ further 90 parts by weight of talcum are mixed
in to obtain a 5% dust; this can be used as a starting 20 mixture for l:l-dilutions for graduated tests of the
active substances with respect to their action against
stored-food pests and house pests.
~i The test insects, German cockroach
(Phyllodromia germanica)
American cockroach
(Periplaneta americana)
- 15 -
~ ,
.
7#~
Russian cockroach
(Blatta orientalis),
yellow mealworm imago
(Tenebrio molitor) larvae, `
larder beetle imago
(Dermestes frischii) larvae~
pelt bee~le larvae
~Attagenus pellio~,
European house cricket `~
(Acheta domesticus), and ~ -
grain weevil
(Sitophilus granarius),
are placed on filter paper in glass dishes, the filter
paper having been treated with 2 g of the 5% formulation. ~ ~ ;
The amount of active substance is 100 mg of AS/m2. The
applied l:l-dilutions then givc 2.5%, 1.25%, 0.6%, 0.31%
and 0.16% active-substance formulations, which correspond
to active-substance amounts of 50, 25, 12.5, 6.2 and 3.1 mg -
of AS/m2 when 2 g of the respective dust formulation is
used for each glass dish.
Compounds according to Example 1 exhibited in the
above test contact action against Phyllodromia germanica,
Periplaneta americana, Blatta orientalis, Tenebrio molitor,
Dermestes frischii, Attagenus pellio, Acheta domesticus
and Sitophilus granarius.
' . - . '.
':
- 16 -
.
C) Contact action ~ st adults of A'edes aezypti
With use of an acetone solution, amounts of 1, 0.1,
` 0.01 and 0.001 mg of active substance per Petri dish were
applied. Each test was performed twice with 10 mosquitoes
.
for each concentration. Both the rate of action and
j the applied amount for a 100% mortality were taken into
account in effecting an evaluation.
Compounds according to Example 1 exhibited in the
above test a favourable action against adults of
Aedes aegypti.
., .
Example 3
Action against Chilo suppressalis
~`j Rice plants of the variety Caloro were planted,
`~ 6 plants per pot, in plastic pots having a top diameter
of 17 cm, and grown to a height of ca. 60 cm. Infestation
i 15 with Chilo suppressalis larvae (Ll; 3-4 mm long) was
- carried out 2 days after application of the active
^~ substance in granular form (amount applied = 8 kg of
active substance per hectare) to the paddy water. The
, evaluation of the insecticidal action was made 10 days `~
`'`t 20 after application of the granules.
,
Compounds according to Example 1 were effective
against Chilo suppressalis in the above test.
. . ,
;: ~:
'~
. , `
Example 4
Action a~ainst ticks
A) ~ ce~halus bursa
, ~ .
In each case~ 5 adult ticks or 50 tic~ larvae were
placed in~o a small glass test tube; the test tubes
were then immersed for 1 to 2 minu~es in 2 ml of an
aqueous emulsion from a di]ution series of 100, I0,
1 and 0.1 ppm of test substance. The tubes were then
sealed with a standardised cotton plug, and inverted so
that the active-substance emulsion could be absorbed
by the cotton wool.
An evaluation in the case of the adults was made
after 2 weeks, and in the case of the larvae after 2 -
days. There were two repeats for each test.
B) Amblyomma hebraeum
With a solution series analogous to that in Test A,
' tests were carried out using in each case 20 larvae.
Compounds according to Example 1 were effective in
these tests against adults and larvae of Rhipicephalus
bursa and against larvae of Amblyomma hebraeum.
,`~''' ` ~
,. . .
';
- 18 -
,~ ' .
.
