Note: Descriptions are shown in the official language in which they were submitted.
.,
BAYER AKTIENGI:SELLSCHAFT 51368 Leverkusen
Konzernverwaltung RP
Patente Konzern RT/li-359w
Substituted benzimidazoles
The invention relates to new substituted benzimidazoles, to a number of
processes for
their preparation and their use as agents for combating pests.
It is known that certain phosphoric acid esters or carbamates, such as, for
example, the
compound O,S-dimethyl-thiolo-phosphoric acid amide or the compound N-methyl-O-
(2
isopropoxyphenyl)-carbamate possess insecticidal properties (cf. e.g. DE-12 10
835 or
DE 11 08 202).
However, the extent and/or duration of the action of these previously known
compounds, especially on certain insects or at low application concentrations,
is not
completely satisfactory in all areas of application.
New substituted benzi;midazolea of the general formula (I)
X
a
X. N
yRs ~I)
Xs ~ N
C H-R2
X y
R
have now been found,
in which
Le A 29 089-PCT
~~~~~1~
R1 represents hydrogen, alkyl or optionally substituted aryl,
RZ represents hydroxyl, cyano, alkoxy or optionally substituted amino,
R3 represents perhalol;enoalkyl, and
Xt, X2, X3 a~ld X4, iindependently of one another, in each case represent
hydrogen, halogen., nitro or optionally substituted aryloxy, but with at least
one of the substituents X1, X2, X3 or X4 being different from hydrogen,
with the exception of t:he compound 1-cyanomethyl-2-trifluoromethyl-5,6-
dichlorbenzimidazole.
The compounds of the formula (I) may if appropriate, depending on the nature
and
number of the substitvuents, be; present as geometric and/or optical isomers
or regio-
isomers, or their isomer mixtures in varying composition. Both the pure
isomers and
the isomer mixtures a~-e claicne;d according to the invention.
It has also been found that the new substituted benzimidazoles of the general
formula
(I)
X
z
X. w N
3 ~ / ~~ R3
X ~N
X CH-R
R
l5 in which
R~ represents hydrogen, alkyl or optionally substituted aryl,
R2 represents hydroxyl, cyano, alkoxy or optionally substituted amino,
Le A 29 089-PCT - 2 -
~~~~~~3
R3 represents perhalo~;enoalkyl, and
X~, X2, X3 at~d X4, independently of one another, in each case represent
hydrogen, halogen, nitro or optionally substituted aryloxy, but with at least
one of the substitu~ents Xt, X2, X3 or X4 being different from hydrogen,
with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-
dichlorbenzimidazole,
are obtained if 1 H-benzimidazoles of the formula (II)
X
r 2
N
y Rs
X3 ~ N
H
X
(II)
in which
l0 R3, X~, X'', X3 and X4 have the meaning given above,
are reacted with compounds of the formula (III)
R
A-CH z (III)
R
in which
A represents a suitable leaving group,
R~ has the meaning given above and
Le A 29 089-PCT - 3 -
R2 has the meaning given above
optionally in the presence of a diluent and optionally in the presence of a
reaction
auxiliary.
Finally, it has been found that the new substituted benzimidazoles of the
general
formula (I) possess a l;ood actiivity against pests.
Surprisingly, the substiituted be:nzimidazoles of the general formula (I)
according to the
invention exhibit a considerably improved insecticidal activity in comparison
to the
phosphoric acid esters or carbtunates known from the prior art, such as, for
example,
the compound O,S-dimethyl-thiolo-phosphoric acid amide or the compound N-
methyl-
l.0 O-(2-isopropoxyphenyl)-carbarnate, which are closely related compounds in
terms of
their action.
A general definition of the substituted benzimidazoles according to the
invention is
given by the formula (;I). Preferred compounds of the formula (I) are those in
which
R~ represents hydrogen, slxaight-chain or branched alkyl having 1 to 8 carbon
1'a 5 atoms or phenyl which is optionally substituted once or more than once
by
identical or different substituents, possible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,
alkylthio, alkylsulphinyl or alkylsulphonyl having in each case I to 6 carbon
atoms, in each case straiight-chain or branched halogenoalkyl, haIogenoalkoxy,
:?0 halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having
in
each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen
atoms,
in each case sl:raight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl,
alkoxycarbonyl or alko;~iminoalkyl having in each case 1 to 6 carbon atoms in
the individual alkyl moieties, divalent dioxyalkylene having I to 5 carbon
atoms
:?5 which is optionally substituted once or more than once by identical or
different
substituents comprising halogen and/or straight-chain or branched alkyl having
1 to 6 carbon atoms and/or straight-chain or branched halogenoalkyl having 1
Le A 29 089-PCT - 4 -
V ~ ~. 4-~ ~ :~
to 6 carbon atoms and 1 to 13 identical or different halogen atoms, or phenyl
which is optionally substituted once or more than once by identical or
different
substituents comprising halogen and/or straight-chain or branched alkyl having
1 to 6 carbon atoms and/or straight-chain or branched halogenoalkyl having 1
to 6 carbon atoms and 1 to 13 identical or different halogen atoms,
R2 represents hydroxyl, cyano, alkoxy having 1 to 8 carbon atoms or amino
which
is optionally substituted once or twice by identical or different
substituents,
possible substi~:uents being:
straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or
l0 branched alkenyl having 2 to 8 carbon atoms, cycloalkyl having 3 to 8
carbon
atoms, alkoxyc:arbonyl., alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-
thiocarbonyl having in each case 1 to 8 carbon atoms in the individual
straight-
chain or branched alkyl. moieties, a divalent closed alkanediyloxycarbonyl
ring
having 2 to 6 carbon atoms in the alkanediyl moiety, or arylalkyl or aryl
having
t 5 in each case 6 to 10 carbon atoms in the aryl moiety and optionally 1 to 6
carbon atoms in the straight-chain or branched alkyl moiety, each of which is
optionally substituted once or more than once by identical or different
substit-
uents, possible substituents of aryl in each case being those mentioned for
R1,
R3 represents straight-chain or branched perhalogenoalkyl having 1 to 8 carbon
:?0 atoms and 1 to 17 identical or different halogen atoms, and
Xl, X2, X3 and X4, independently of one another, in each case represent
hydrogen,
fluorine, chlorine, bromine, iodine, nitro or aryloxy having 6 to 10 carbon
atoms in the aryl moiety which is optionally substituted in the aryl moiety
once
or more than once by identical or different substituents, possible possible
25 substituents of aryl being those mentioned for R1, but with at least one of
the
substituents X~, X2, X3 or X4 being different from hydrogen, and
with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-
dichlorobenzimidazole.
Le A 29 089-PCT - S -
~14~~~3
Particularly preferred compowlds of the formula (I) are those in which
Ri represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon
atoms or phenyl which is optionally substituted once to three times by
identical
or different suhstituents, possible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,
alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 4 carbon
atoms, in each case straight-chain or branched halogenoalkyl, halogenoalkoxy,
halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in
each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
in each case' straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl,
alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 4 carbon atoms in
the individual ~31ky1 moities, divalent dioxyalkylene having 1 to 4 carbon
atoms
which is optionally substituted once to six times by identical or different
substituents comprising. halogen and/or straight-chain or branched alkyl
having
1 to 4 carbon ;atoms and/or straight-chain or branched halogenoalkyl having 1
to 4 carbon atoms and 1 to 9 identical or different halogen atoms, or phenyl
which is optionally substituted once to five times by identical or different
substituents comprising halogen and/or straight-chain or branched alkyl having
I to 4 carbon ,atoms and/or straight-chain or branched halogenoalkyl having I
to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
R2 represents hydroxyl, cyano, alkoxy having 1 to 6 carbon atoms or amino
which
is optionally substituted once or twice by identical or different
substituents,
possible substi tuents being:
straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or
branched alkenyl having 2 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon
atoms, alkoxy~~arbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-
thiocarbonyl h;iving in each case 1 to 6 carbon atoms in the individual
straight-
chain or branched alkyl moieties, a divalent closed alkanediyloxycarbonyl ring
having 2 to 5 carbon atoms in the alkanediyl moiety, or arylalkyl or aryl
having
Le A 29 089-PCT - 6 -
~~~.~6~3
in each case E~ or 10 carbon atoms in the aryl moiety and optionally 1 to 6
carbon atoms iin the straight-chain or branched alkyl moiety, each of which is
optionally substituted once to five times by identical or different
substituents,
possible substituents of aryl being those mentioned for R~,
R3 represents straight-chain or branched perhalogenoalkyl having 1 to 6 carbon
atoms and 1 to 13 identical or different halogen atoms, and
X~, X2, X3 and X4, independently of one another, in each case represent
hydrogen,
fluorine, chlorine, bromine, iodine, nitro or aryloxy having 6 or 10 carbon
atoms in the aryl moiety, which is optionally substituted once to five times
by
identical or tii:fferent substituents, possible possible substituents of aryl
being
those mentioned for R~, but with at least one of the substituents X1, X2, X3
or
X4 being different from hydrogen,
with the exception of tlhe compound 1-(cyanomethyl-2-trifluoromethyl-5,6-
dichlorobenzimidazole. Prefewed aryl radicals which can be mentioned are
phenyl and
naphthyl.
Compounds of the formula (I) which are very particularly preferred are those
in which
Rt represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon
atoms or phenyl which is optionally substituted once or twice by identical or
different substiituents, I>ossible substituents being:
halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,
alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 3 carbon
atoms, in each case straight-chain or brmched halogenoalkyl, halogenoalkoxy,
halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in
each case 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms,
in each case straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl,
alkoxycarbonyl or alkoximinoalkyl having in each case 1 to 3 carbon atoms in
the individual alkyl moiieties, divalent dioxyalkylene having 1 to 3 carbon
atoms
Le A 29 089-PCT - 7 -
which is optionally sulbstituted once to four times by identical or different
substituents comprising halogen and/or straight-chain or branched alkyl having
1 to 3 carbon ~~toms and/or straight-chain or branched halogenoalkyl having 1
to 3 carbon atoms and 1 to 7 identical or different halogen atoms, or phenyl
S which is optionally substituted once to tluee times by identical or
different
substituents comprising halogen and/or straight-chain or branched alkyl having
1 to 3 carbon atoms and/or straight-chain or branched halogenoalkyl having 1
to 3 carbon atoms and 1 to 7 identical or different halogen atoms,
R2 represents hydroxyl, cymo, alkoxy having 1 to 6 carbon atoms or amino which
is optionally substituted once or twice by identical or different
substituents,
possible substituents being:
straight-chain or branched alkyl having I to 4 carbon atoms, straight-chain or
branched alken,yl having; 2 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon
atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-
thiocarbonyl having in each case 1 to 4 carbon atoms in the individual
straight-
chain or branched alkyl moieties, a divalent closed alkanediyloxycarbonyl ring
having 2 to 4 carbon atoms in the alkanediyl moiety, or phenylalkyl or phenyl
having optionalily 1 to :3 carbon atoms in the straight-chain or branched
alkyl
moiety, each of which is optionally substituted once or twice by identical or
a0 different substctuents, possible substituents of phenyl in each case being
those
mentioned for lfZl,
R3 represents straight-chain or branched perhalogenoalkyl having 1 to 4 carbon
atoms and 1 to 9 identical or different halogen atoms, or cyano, and
X~, X2, X3 and X4, independently of one another, in each case represent
hydrogen,
chlorine, bromiine, nitro or phenyloxy which is optionally substituted in the
phenyl moiety up to three times by identical or different substituents,
possible
substituents of phenyl being those mentioned for R~, but with at least one of
the
substituents X~., X2, X3 or X4 being different from hydrogen,
Le A 29 089-PCT - 8 -
~.~~3~~3
with the exception of the compound 1-cyanomethyl-2-trifluoromethyl-5,6-
dichlorobenzimidazole.
Apart from the compounds mentioned in the Preparation Examples, the following
individual substituted benzimidazoles of the general formula (I) may be
mentioned:
Le A 29 089-PCT - 9 -
~~4~~~
x
2
x..~ ~, N
s~l , \~R3
~N
\C H-R2
X
R
X1 X2 X3 X4 R1 R2 R3
Br H CI H H i zHs CF3
N
~COOCZHS
Br H Br H H i zHs CF3
N
~COOCZHs
Br H NO2 H H CzHs CF3
N
~COOCZHs
CI H Ca H H i zHs CF3
N
~COOCZHS
CI H Br H H i zHs CF3
/N
~COOCZHS
H H N02 H H i zHs CF3
N
~COOCzHs
Le A 29 089-PCT - 10 -
X1 X2 X3 X4 R1 R2 R3
Br H CE;H50 H H CZHS CF3
N
~ ~COOCZHS
C1 H c~ H H C2H5 CF3
cy ~ o- N
C ~ ~
c~ COOCZHs
Cl H c~
H H CI.~HS CF3
cy~o- N
C~ ~ ~
COOCZHS
Br H ~Cl H H CI.~Hs CZFS
/N
~COOC~HS
Br H Br H H C~..~Hf C2F5
/N
~COOCzHs
H CI ' Cl H H i~Hs C2F5
/N
~COOC~HS
Cl H c' H H -O-C2H5 CF3
cy ~ o-
C1 H c' H H -O-C2H5 CF3
r=''~
cy~o-
Le A 29 089-PCT - 11
X1 X2 X3 X4 R1 R2 R3
Br H CI H H CZHS C2F5
N
~COOC2H5
Br H E3r H H i NHS C2F5
N
~ ~COOC,HS
H CI ~ (:1 H H i ZHs C2F5
N
~ ~COOC=HS
Br H rd02 H H CZHS C2F5
N
~COOCzHt
CI H CI H H CIZHS C2F5
N
~COOCZHS
Cl H lBr H H i ?Hs C2F5
.
/N
~COOCZHs
H H N02 H H i NHS C2F5
/N
~COOC2H5
Le A 29 089-PCT - 12 -
~~.48~~~
X1 X2 X3 X4 R1 R2 R3
Br H C6H50 H H i ZHS C2F5
N
~COOCZHS
Cl H c' H H CzHs C2F5
cy/ o~ N
ct '/ \COOCzHs
E
Cl H c' H H i ?Hs C F
2 5
~~\ /~°- N
~COOCZHS
Br H (:1 H H -0-C2H5 C2F5
Br H Etr H H -O-C2H5 C2F5
H Cl (:l H H -O-C2H5 C2F5
Br H NOZ H H -0-CZHS C2F5
C( H C:1 H H -O-C2H5 C2F5
CI H Ear H H -O-C2H5 C2F5
H H N02 H H -O-C2H5 C2F5
Br H C6H50 H H -O-C2H5 C2F5
Cl H c' H H
_ 0 C2H5 C2H5
c'-~_ / o-
c'
Cl H c' H H
0 C2H5 C2F5
ct-~_~o-
Le A 29 089-PCT - 13 -
X1 X2 X3 X4 R1 R2 R3
Br H C! H H i ZHs n-C3F~
N
~COOCZHS
Br H Br H H i zHs n-C3F7
N
~~COOCzHs
i
H C! ~C! ~~ H i NHS n-C3F7
N
~~COOCzHs
Br H N02 H H CzHs n-C3F7
N
~ COOCZHS
Cl H C:l H H i zHs n-C3F7
N
~ ~ COOCZHS
Cl H Br H H i ZHS n-C3F7
N
~COOCZHS
Le A 29 089-PCT - 14 -
~~~~~~3
X1 X2 X3 X4 R1 R2 R3
H H N02 H H i zHs n-C3F2
N
~COOCzHs
Br H CE;H50 H H j ZHS n-C3F~
/N
~COOCZHS
i
CI H ~ H H i zHs n-C3F~
ct~ ~ o- N
ci ~ \COOCzHs
CI H c' H H i ZH5 n-C3F7
cy~o- N
~COOC~HS
Br H CI H H -O-CZHS n-C3F~
Br H 13r H H -O-CZHS n-C3F~
H C1 CI H H -O-C2H5 n-C3F~
Br H N02 H H -O-C2H5 n-C3F~
Cl H CI H H -O-C2H5 n-C3F~
Cl H Br H H -O-C2H5 n-C3F~
H H N02 H H -O-C2H5 n-C3F~
Br H C67H50 H H -O-C2H5 n-C3F2
Cl H c~ H H -O-C2H5 n-C3F~
cy 1 0-
c~
Le A 29 089-PCT - 15 -
,. L
X1 X2 X3 X4 Rl R2 R3
C1 H c~ H H -O-C2H5 n-C3F~
ci ~~o-
CI H " H H -O-C2H5 CF3
F,C-~-
Cl
C1 H " H H -O-C2H5 C2F5
F,C~-~ O-
'
CI
CI H " H H -O-C2H5 n-C3F~
F,C-
-
C1
CI H _ H H CZHS CF3
F,C ~
~ O
- N
c~ / \COOC2H5
CI H " H H C~HS C2F5
i ~
F,'- /N \
-
c~ COOC2H5
CI H " H H CZHS n-C3F~
F,c ~ ~ o-
/ \
c~ COOC~HS
Le A 29 089-PCT - 16 -
x1 XZ :K3 X4 R1 R2 R3
C1 H CI H H -O-C2H5 n-C7H15
H Cl C1 H H -O-C2H5 n-C7H15
CI H CI H H i ZHS n-C7H15
N
~COOC~ HS
H CI CI H H ~CZHS n-C7H15
N
~ ~COOCzHs
i
CI H '" H H CZHs n-C7H 15
F~c- / \ o-
N
ci ~ ~COOCzHs
Using, for example, 5,6-dichl.oro-2-trifluoromethyl-benzimidazole and
chloromethyl
ethyl ether as starting compownds, the course of the reaction of the process
according
to the invention can be represented by the following formula scheme:
CI
~~-C F3 + C I-C HZ O-C 2H5
CI
H
- HCI CI ~ N
Base ~ ~ ~ \' CF3
CI
CH2 O-CzHs
general definition of the 1 H-benzimidazoles required as starting substances
for
carrying out the process accordling to the invention is given by the formula
(II). In this
formula (II), R.3, X~, X2, X.3 .and X4 preferably represent those radicals
which have
already been mentioned as preferred for these substituents in connection with
the
description of the compounds ~of the formula (I) according to the invention.
Le A 29 089-PCT - 17 -
The 1 H-benzimidazoles of the; formula (1I) are known or can be obtained by
analogy
with known processes (cf. e.g. J. Amer. Chem. Soc. 75, 1292 [1953]; US
3,576,818).
A general definition .of the compounds additionally required as starting
materials for
carrying out the process according to the invention is given by the formula
(III). In this
formula (III), R~ and R2 preferably represent those radicals which have
already been
mentioned as preferred for these substituents in connection with the
description of the
substances of the formula (I) according to the invention.
A preferably represents a leaviing radical which is usual in alkylating
agents, preferably
halogen and in particular chlorine, bromine or iodine, or represents in each
case
optionally substituteid ,alkylsulphonyloxy, alkoxysulphonyloxy or
arylsulphonyloxy, such
as, in particular, methanesulphonyloxy, trifluoromethanesulphonyloxy,
methoxysulphonyloxy, ethoxysulphonyloxy or p-toluenesulphonyloxy.
In addition, A also represents, an alcohol, alkanoyloxy or alkoxy group, such
as, for
example, a hydroxyl, acetoxy or methoxy group if the intention is to use the
process
1 S according to the invention to prepare compounds of the formula (I) in
which RI is
different from hydrogen.
The compounds of the formula (III) are known or can be obtained by analogy
with
known processes (c~ e.g. DE 20 40 175; DE 21 19 518; Synthesis 1973, 703).
Suitable diluents for carrying; out the process according to the invention are
inert
organic solvents. These include, in particular, aliphatic, alicyclic or
aromatic, optionally
halogenated, hydrocarbons such as, for example, benzine, benzene, toluene,
xylene,
chlorobenzene, dic;hlorobenzene, petroleum ether, hexane, cyclohexane,
dichloromethane, chloroform or carbon tetrachloride; ethers such as diethyl
ether,
diisopropyl ether, dioaane, tetrahydrofuran or ethylene glycol dimethyl or
diethyl ether;
ketones such as accaone, butanone or methyl isobutyl ketone; nitrites such as
acetonitrile, propionit~rile or benzonitrile; amides such as N,N-
dimethylformamide, N,N-
dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or
hexamethylphosphori~~ triamid,e; esters such as methyl acetate or ethyl
acetate, or bases
Le A 29 089-I'CT - 18 -
such as pyridine, or organic acids such as formic acid or acetic acid.
The process according; to the invention is preferably carried out in the
presence of a
suitable reaction auxiliary. Suitable such auxiliaries are all conventional
inorganic or
organic bases. 'they include, for example, alkaline earth metal or alkali
metal hydrides,
hydroxides, amides, a'.~~coholatea, acetates, carbonates or hydrogen
carbonates, such as,
for example, sodium hydride, sodium amide, lithium diethylamide, sodium
methylate,
sodium ethylate, potassium tert-butylate, sodium hydroxide, potassium
hydroxide,
ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate,
ammonium
acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate,
sodium
hydrogen carbonate or ammonium carbonate, organolithium compounds such as n-
butyllithium, and tei'ti;~cy amines such as trimethylamine, triethylamine,
tributylamine,
di-isopropyl-ethylamine, tetramethylguanidine, N,N-dimethylaniline, pyridine,
piperidine, N-methylpiperidi:ne, N,N-dimethylaminopyridine, diazobicyclooctane
(DABCO), diazobicyclononenf: (DBN) or diazabicycloundecene (DBU).
In cases where the int~:ntion is to use the process according to the invention
to prepare
compounds of the forrnula (L) in which Rl is different from hydrogen, suitable
reaction
auxiliaries also include; organic or inorganic acids, such as, for example,
sulphuric acid,
hydrochloric acid, p-toluenesulphonic acid and perfluorobutanesulphonic acid,
or
strongly acidic ion exchangers.
:20 The process according to the invention can optionally also be carried out
in a two-phase
system such as, for example, water/toluene or water/dichloromethame,
optionally in the
presence of a suitable phase-transfer catalyst. Examples which may be
mentioned of
such catalysts are: tetrabutylammonium iodide, tetrabutylaunmonium bromide,
tetrabutylammonium chloride, tributyl-methylphosphonium bromide, trimethyl-C ~
3/C I s-
:25 alkylammonium chloride, trimethyl-C~3/C~5-alkylammonium bromide, dibenzyl-
dimethyl-ammonium methyl sulphate, dimethyl-C ~ 2/ C 14-alkyl-benzylammonium
chloride, dimethyl-C~2/C~4-al'~kyl-benzylammonium bromide, tetrabutylammonium
hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride,
trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris-[2-(2-
30 methoxyethoxy)-ethyl:-amine.
Le A 29 089-PCT - 19 -
~.~~-8~~ 3
When carrying out the process according to the invention, the reaction
temperatures can
be varied over a relatively wide range. It is in general carried out at
temperatures of
between -70°C and +;!00°C, preferably at temperatures of between
0°C and 130°C.
The process according to the invention is usually carried out under
atmospheric
pressure. However, it is also possible to work under increased or reduced
pressure.
Carrying out the process according to the invention requires the use, per mole
of 1 H-
benzimidazole of the formula (II), of in general from 1.0 to 5.0 mol,
preferably from
1.0 to 2.5 mol, of compound of the formula (III) and optionally from 0.01 to
5.0 mol,
preferably from 1.0 to 3.0 mol, of reaction auxiliary.
In a particular embodiment it is also possible first of all, in a prior
reaction step, to
silylate the 1H-benzimidazoles of the formula (II) using conventional
silylation
processes, for example, with hexamethyldisila~zane or trimethylsilyl chloride,
optionally
in the presence of a suitable cai:alyst such as, for example, sulphuric acid,
trifluoroacetic
acid, ammonium sulphate, imiidazole or saccharin, at temperatures of between -
20°C
and +150°C, and in a subsequent, second step to react the 1-tri-
methylsilylbenzimidaz;oles, which are obtainable in this way, with alkylating
agents of
the formula (II) in accordance with the process according to the invention. In
this case
it is of advantage to add tin tE;trachloride as a catalyst for the alkylation
reaction (cf.
e.g. Chem. Heterocycl'~,. Comp. USSR 24, 514 [1988]).
The implementation o~f the reaction, the working-up and the isolation of the
reaction
products are carried out by IUnown methods (cf. also in this respect the
Preparation
Examples).
The purification of the: end products of the formula (I) is carried out using
conventional
methods, for example by column chromatography or by recrystallization.
Characterization is carried out on the basis of the melting point or, in the
case of non-
crystallizing compounds - especially in the case of regioisomer mixtures -
using proton
nuclear magnetic resonance spectroscopy (1H-NMR).
Le A 29 089-PCT - 20 -
The active substances are suitable for combating animal pests, preferably
arthropods
and nematodes, in pau-ticular insects and arachnids, which are encountered in
agri-
culture, in forests, in 'the protection of stored goods and materials, and in
the hygiene
sector. They are effective against normally sensitive and resistant species
and against
all, or individual, dev~~lopmemtal stages.
The abovementioned bests include:
From the order of the: Isopoda, for example, Oniscus asellus, Armadillidium
vulgare
and Porcellio scaber;
from the order of the Diplopoda, for example, Blaniulus guttulatus;
from the order of the Chilopoda, for example, Geophilus carpophagus and
Scutigera
spec.; '
from the order of the Symphyla, for example, Scutigerella immaculate;
from the order of the Thysanura, for example, Lepisma saccharine;
from the order of the Collembola, for example, Onychiurus armatus;
from the order of the Orthoptera, for example, Blatta orientalis, Periplaneta
americana,
Leucophaea maderae, :Blattella germanica, Acheta domesticus, Gryllotalpa spp.,
Locusta
migratoria migratorioides, Mel.anoplus differentialis and Schistocerca
gregaria;
from the order of the Dermapl:era, for example, Forficula auricularia;
from the order of the Isoptera, .for example, Reticulitermes spp.;
:20 from the order of the Anoplura, for example, Phylloxera vastatrix,
Pemphigus spp.,
Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.;
from the order of the lVlallophaga, for example, Trichodectes spp. and
Damalinea spp.;
from the order of the Thysanoptera, for example, Hercinothrips femoralis and
Thrips
tabaci;
from the order of the Heteropte:ra, for example, Eurigaster spp., Dysdercus
intermedius,
Piesma quadrate, Cirr~ex lectularius, Rhodnius prolixus and Triatoma spp.;
from the
order of the Homoptera, for ex~~nple, Aleurodes brassicae, Bemisia tabaci,
Trialeurodes
vaporariorum, Aphis g;ossypii, Brevicoryne brassicae, Cryptomyzus ribis,
Doralis fabae,
Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae,
Myzus
spp., Phorodon humuli, Rho;palosiphum padi, Empoasca spp., Euscelis bilobatus,
Nephotettix cincticef~s, Lecanium corm, Saissetia oleae, Laodelphax
striatellus,
Nilaparvata lugens, ~,onidiell;~ aurantii, Aspidiotus hederae, Pseudococcus
spp. and
Le A 29 089-PCT - 21 -
Psylla spp.;
from the order of th~~ Lepidoptera, for example, Pectinophora gossypielta,
Bupalus
piniarius, Cheimatobia brurnata, Lithocolletis blancardella, Hyponomeuta
padella,
Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria
spp.
Bucculatrix thurberielta, Phylllocnistis citrella, Agrotis spp., Euxoa spp.,
Feltia spp.,
Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis
flammea, Prodenia titura, Spodoptera spp., Trichoplusia ni, Caprocapsa
pomonella,
Pieris spp., Chilo spp., Pyrausta nubitalis, Ephestia kuehnietta, Galleria
mellonella,
Tineola bissellietla, Ti:nea peltionetta, Hofmannophila pseudospretella,
Cacoecia podana,
Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona
magnanima
and Tortrix viridana;
from the order of 'the Coleoptera, for example, Anobium punctatum,
lZhizopertha
dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus,
Agelastica
atni, Leptinotarsa decemlinea~ta, Phaedon cochleariae, Diabrotica spp.,
Psylliodes
chrysocephata, Epilaclma varivestis, Atomaria spp., Oryzaephilus surinamensis,
Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites
sordidus,
Ceuthorrhynchus assiimilis, l~ypera postica, Dermestes spp., Trogoderma spp.,
Anthrenus spp., Atta~,enus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,
Niptus
hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio motitor, Agriotes
spp.,
:20 Conoderus spp., Melolontha metotontha, Amphimallon sotstitialis and
Costelytra
zealandica;
from the order of the: Hymenoptera, for example, Diprion spp., Hoplocampa
spp.,
Lasius spp., Monomorium pharaonis and Vespa spp.;
from the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex
spp.,
:25 Drosophila melanogaster, Musca spp., Fannia spp., Calliphora
erythrocephata, Lucilia
spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,
Stomoxys
spp., Oestrus spp., Hypoderrr~a spp., Tabanus spp., Tannia spp., Bibio
hortulanus,
Oscinetta frit, Phorbia spp., Pc:gomyia hyoscyami, Ceratitis capitata, Dacus
oleae and
Tipula paludosa;
:30 from the order of the Siphonaptera, for example, Xenopsylla cheopis and
Ceratophyllus
spP~
from the order of the Araclmida, for example, Scorpio maurus and Latrodectus
mactans;
Le A 29 089-PCT - 22 -
.
from the order of the ~~carina, l;or example, Acarus Biro, Argas spp.,
Ornithodoros spp.,
Dermanyssus gallinae, Eriopllyes ribis, Phyllocoptruta oleivora, Boophilus
spp.,
Rhipicephalus spp., Amblyomzna spp., Hyalomma spp., Ixodes spp., Psoroptes
spp.,
Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
Panonychus spp.
and Tetranychus spp.
The phytoparasitic pematodEa include Pratylenchus spp., Radopholus similis,
Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne
spp.,
Aphelenchoides spp., :Longidorus spp, Xiphinema spp. and Trichodorus spp..
The active substances according to the invention are active not only against
pests in
plants, hygiene and's~tored goods, but also, in the veterinary sector, against
animal
parasites (ectoparasites and endoparasites) such as ixodic ticks, argasid
ticks, scab
mites, trombiculid mitEa, flies (piercing and lapping), parasitizing fly
larvae, lice, biting
lice, feather lice, fleas and wo~:-ms which live as endoparasites.
They are effective against normally sensitive and resistant species and
strains, and
l5 against all parasitizin;; and non-parasitizing developmental stages of the
ecto- and
endoparasites.
The active substances according to the invention are notable for a high degree
of
insecticidal activity.
They can be employed with particularly good success for combating
phytopathogenic
:Z0 insects, as, for example, against the larvae of the mustard beetle
(Phaedon cochleariae)
or against the caterpillars of the cabbage moth (Plutella maculipennis) or
against the
tobacco budworm (Heliothis virescens), and for combating phytopathogenic
mites, as,
for example, against the red spider mite (Tetranychus urticae) or for
combating
phytopathogenic nematodes, as, for example, against the nematode species
Globodera
:ZS rostochiensis.
In addition, the active substances according to the invention can also be
employed for
combating pests in hygiene and stored goods, as, for example, against the
house-fly
Le A 29 089-PCT - 23 -
~~48~I3
(Musca domestics) or against cockroach species, such as, for example,
Periplaneta
americana.
Moreover, the active; substances according to the invention can be employed
with
particularly good success for combating pests which live as parasites of warm-
blooded
creatures, as, for example, against scab mites (Psoroptes ovis).
In addition, the active substances according to the invention also possess a
fungicidal
activity in vitro.
Depending on their particular iphysical and/or chemical properties, the active
substances
can be converted 'into the customary formulations, such as solutions,
emulsions,
suspensions, powders,, foams, pastes, granules, aerosols, natural and
synthetic materials
impregnated with aeti~,ve substance, very fine capsules in polymeric
substances and in
coating compositions for seed, and furthermore in formulations used with
burning
equipment, such as fumigating cartridges, fumigating cans, fumigating coils
and ~ the
like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in a known manner, for example by mixing the
active
substances with extenders, that is, liquid solvents, liquefied gases under
pressure, and/or
solid carriers, optionally with the use of surface-active agents, that is,
emulsifying
agents and/or dispersing agents, and/or foam-forming agents. In the case of
the use of
water as an extender, organic; solvents can, for example, also be used as
auxiliary
solvents. As liquid solvents, there are suitable in the main: aromatics, such
as xylene,
toluene or alkylnaphrhalenes, chlorinated aromatics or chlorinated aliphatic
hydro-
carbons, such as chlorobenzc.nes, chloroethylenes or methylene chloride,
aliphatic
hydrocarbons, such as cyclohexane or paraffins, for example mineral oil
fractions,
alcohols, such as butanol or glycol as well as their ethers and esters,
ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,
strongly polar
solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water;
by
liquefied gaseous extenders or carriers are meant liquids which are gaseous at
ambient
temperature and under atmospheric pressure, for example aerosol propellants,
such as
halogenated hydrocarbons as well as butane, propane, nitrogen and carbon
dioxide; as
Le A 29 089-PCT - 24 -
~14~~~~
solid carriers there are suitable: for example ground natural minerals, such
as kaolins,
clays, talc, chalk, quartz, at~tapulgite, montmorillonite or diatomaceous
earth, and
ground synthetic minerals, such as highly disperse silica, alumina and
silicates; as solid
carriers for granules there are: suitable: for example crushed and
fractionated natural
rocks such as calcite, marble:, pumice, sepiolite and dolomite, as well as
synthetic
granules of inorganic: and organic meals, and granules of organic material
such as
sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or
foam-
forming agents there are suitable: for example non-ionic and anionic
emulsifiers, such
as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,
for example
alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates as well
as albumen hydrolysis products; as dispersing agents there are suitable: for
example
lignin-sulphite wash liquors and methylcellulose.
Adhesives such as carboxymeahylcellulose and natural and synthetic polymers in
the
form of powders, granules or latices, such as gum arabic, polyvinyl alcohol
and
polyvinyl acetate, as well as natural phospholipids, such as cephalins and
lecithins, and
synthetic phospholipids, can bf: used in the formulations. Other additives can
be mineral
and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron
oxide,
titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin
dyestuffs, azo
dyestuffs and metal plzthalocy;mine dye-stuffs, and trace nutrients such as
salts of iron,
manganese, boron, copper, cobalt, molybdenum and tin.
The formulations in general contain between 0.1 and 95 per cent by weight of
active
substance, preferably between 0.5 and 90%.
The active substances according to the invention can be present in their
commercially
available formulations and in the use forms prepared from these formulations,
as a
mixture with other active substances such as insecticides, attractants,
sterilizers,
aca.ricides, nematicide~s, fungicides, growth-regulating substances or
herbicides. The
insecticides include, for example, phosphoric acid esters, carbamates,
carboxylic acid
esters, chlorinated hydrocarbons, phenylureas, substances produced by
Le A 29 089-PCT - 25 -
microorganisms, etc.
Furthermore, the acti~re substances according to the invention can be present
in their
commercially availal;~le formulations and in the use forms prepared from these
formulations as a miraure with synergists. Synergists are compounds which
raise the
activity of the active substances without the synergist which is added
necessarily being
active itself.
The active substance,content oiFthe use forms prepared from the commercially
available
formulations can vary within wide ranges. The active substance concentration
of the use
forms can be from 0.00000(11 up to 95 per cent by weight of active substance,
preferably between U.~D001 and 1 per cent by weight.
Application is effected in a customary manner appropriate to the use forms.
When used against pests in hygiene and stored goods, the active substances are
notable
for an outstanding residual action on wood and clay and for a good alkali
stability on
limed substrates.
The active substances which can be used in accordance with the invention are
also
suitable for combating insects, mites, ticks etc. in the sector of animal
husbandry and
cattle rearing, the combating of the pests enabling better results to be
achieved, e.g.
higher milk yields, greater weiight, more attractive coats, longer lifespan
etc.
In this sector, the application of the active substances which can be used in
accordance
:20 with the invention is c,~rried out in a known manner, for example by oral
administration
in the form of tablela, capsules, drinking formulations or granules, by dermal
or
external application in the forms of, for example, dipping, spraying, pouring
on (pour-on
or spot-on) and powdering, and by parenteral administration in the form, for
example,
of injection, and, furthermore, by the feed-through method. In addition,
application as
:25 a shaped article (collar, ear-tal;) is also possible.
The preparation and the use .of the active substances according to the
invention is
evident from the following examples.
Le A 29 089-PCT - 26 -
..
Preparation Exam~~s:
Example 1:
CI~ ~ N
~~ ~~--CF3
CI~ '~ N
v
CH2 O-C2H5
A solution of 14.1 g (0.15 mol) of chloromethyl ethyl ether in 40 ml of ethyl
acetate
is added dropwise to ;a mixture of 36 g (0.12 mol) of 5,6-dichloro-2-
trifluoromethyl-
I H-benzimidazole, 33 g (0.24 mol) of powdered potassium carbonate and 300 ml
of
ethyl acetate at room t~cmperah~re, and, after addition is complete, the
mixture is heated
for a further 4 hours .at boiling temperature. For working up, the reaction
mixture is
cooled and washed twice with 150 ml of water each time, dried over sodium
sulphate
and concentrated in vacuo. The residue is purified by chromatography on silica
gel
(eluent: dichloromethane).
32.4 g(83%oftheory)of5,6-dichloro-1-ethoxymethyl-2-trifluoromethyl-
benzimidazole
are obtained with a melting point of 89-92°C.
In a corresponding manner and in accordance with the general instructions for
the
preparation, the following substituted benzimidazoles of the general formula
(I) are
'L 5 obtained:
i
X
2
X. ~ N
3 ~ / ~~ R3
X _' N
\C H-RZ
X
R
Le A 29 089-PCT - 27
. . ~ (~
Ex. X1 X2 X 3 X4 R~ R2 R3 physical
No. properties
2 H CI CI H 1(-3 CHj CF3 m.p.120-121°C
I
N
~ ~COOCH3
3 H CI Cl H H CH3 CF3 m.p. 9S-97°C
N
~ ~COOC~HS
4 H CI CI H H j ZHS CF3 m.p. 104-106°C
/N
~COOCzHs
S H CI CI H H i ?Hs CF3 m.p. 88-89°C
/N
~COOCH3
6 H Cl CI H H n-C~,H~ CF3 m.p.102-103°C
N
'~ ~COOCH3
7 CI H CI H H -O-C2HS CF3 m~P~ 57-61°C
(H) (CI) (H) (CI) (87:13)
8 CI H CI H Hf CH3 CF3 m.p. 95-100°C
(H) (C1) (H) (CI) I (92:8)
/N
~COOCH3
9 H Cl H H H -O-CH(CH3)2 CF3 1 H_~ *):
(H) (~'() 5.63; S.6S; 7.35;
' 7.40; 7.57; 7.78 ;
7.63; 7.85
Le A 29 089-PCT - 28 -
Ex. X1 X2 ~i'3 X4 Rl R2 R3 physical
No. properties
H CI I-f H H CN CF3 IH-NMR*):
5.15; 5.18; 7.45;
(H) (CI) 7.55; 7.83; 7.90
I 1 H CI H H H -0-C2H5 CF3 I H-NMR*):
(H) (C11) 5.43; 5.48; 7.28-
8.01
12 H CI 'H H H -O-C2H5 CF3 m.p.75°C
13 H H Cl H H -O-C2H5 CF3 m.p.73°C
14 H CI Hi H H CH3 CF3 1H-NMR*):
5.88; 5.92; 7.35;
(H) (C1) ~N~COOCzHs 7.67; 7.92
I S H CI H H H i ZHS CF3 1H-NMR*):
(H) (C1) N 5.88; 5.90; 7.41;
~COOCzHs 7.79; 7.81
16 H CI H H H n-C3H, CF3 1H-NMR*):
5.89; 5.96; 7.37;
~N~COOC2H5 7.78; 7.78; 7.81
17 H Cl H: H H OH CF3
18 H N02 H H H -O-C2H5 CF3 IH-NMR*)
(H) ~~~2)
7.79-8.78;
A: 5.73
B: 5.74
19 H N02 H: H H -O-C2H5 CF3 m.p.:48C
Le A 29 089-PCT - 29 -
~~.4~~~
Ex. X1 X2 I~'3 X4 Rl R2 R3 physical
No. properties
~0 H H N02 H H -O-CZHS CF3 m.p. ; 90°C
2l H N02 H Ei I-I -O-n-C3H~ CF; 1H-NMR*)
7.so-s.7o;
(H) (N02) A:5.80
B: 5.85
22 H N02 H H H CH3 CF3 1H-~*).
7.95-8.80; .
~~02) /N~ A: 5.96
COOCZHS
B: 5.99
23 H N02 H H H CZHs CF3 1H-NMR*):
7.90-8.75;
(H) (Td02) /N~ A:5.97
COOC2H5
B: 5:38
24 H N02 H H H n~3H~ CF3 1H-NMR*)-
7.91-8.80; .
(H) (h(O2) /Ny A:5.97
COOCZHS
B: 5.99
25 H N02 H H H OH CF3 1H-NMR~~
7.85-8.9;
(H) (I~f02) A:5.85
B: 5.89
26 H F H H H -O-C2H5 CF3 1H-NMRfi):
(H) (F) A: 5.63; 7.10-7.90
B: 5.69
Le A 29 089-PCT - 30 -
~~ 4~~~ 3
Ex. X1 X2 X 3 X4 Rl R2 R3 physical
No. properties
27 H c~ H H: H -O-C2Hg CF3 1H-NMR*):
cF,- ~~~ o-- 5.61; 5.68; 6.91-
7.85
ci
(H) cF~~ o_
ci
28 H c~ , H H H -O-n-C3H7 CF3 1H-NMR*):
cF, ~-~ o__ c~ 5.63; 5.79;
o_ 6.82-7.86
H ct ~- c~
( )
29 H c~ H H H ~H, CF3 1H-NMR*):
CF, ~-~ O- c1 N 5.84; $.86;
~ ~COOCzH, 6.86-7.90
cl ~ --(j''_
(H) ct
3 0 H c~ H H H ~H, CF3 1 H-NMR*):
CF,- ~-~ O-- c1 N 5.80; $.84;
~ ~c~~Hs 6.88-7.89
a
(~ c'
31 H c~ H H H n-pH, CF3 1H-NMR*):
CF, ~-~ O-- ~~ N 5.78 (S),
-~( ~ ~cooc,x, 5.88 (s),
c~ ~a~~o._
(H) ci 6.88-7.95
(m)
32 H c~ H H H CN CF3 1H-NMR*):
cF, ~-~ o-- c~ 5.11; 6.95; 7.04;
_ 7.74 ; 7.93
ci
(H)
Le A 29 089-PCT - 31 -
Ex. X~ X2 X3 X4 R~ Rz R3 physical
No, properties
33 Br Cl C:1 H H ~~H~ CF3 m.p.100-103°C
-N
COOCzH,
The ~H-NM:EZ spectra were recorded in deuterochloroform (CDCl3) or
hexadeutero-dimethyl sulphoxide (DMSO-d6) using tetramethylsilane (TMS) as the
internal standard. The value given is the chemical shift as d in ppm.
Le A 29 089-PCT - 32 -
~~.4~~~3
Preparation of the sta~-tin~ compound:
Example II-1:
CI ~ ,N
~~-CFa
CI ~ N
H
35.4 g (0.2 mol) of 4,5-dichlorophenylene-diamine are heated with 150 ml of
trifluoroacetic acid for 3 hours at reflux temperature. For working up, excess
trifluoro-
S acetic acid is distilled off and the residue is partitioned between 100 ml
of water and
300 ml of ethyl acetate. The organic phase is separated off and washed
successively
with in each case 100 ml of aqueous sodium hydrogen carbonate solution and
water,
dried over sodium s~~lphate and concentrated in vacuo. The residue is purified
by
chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:1 ).
42.1 g (81% of theory) of 5,6-dichloro-2-trifluoromethyl-1H-benzimidazole are
obtained with a melting point of 225-230°C.
In a corresponding manner, the following 1 H-benzimidazoles of the formula
(II) are
obtained:
X
2
X. ~ N
yR3 (i1)
X3 N
a H
X
Le A 29 089-PCT - 33 -
Ex. No. X~ X1 X3 X4 R3 physical
properties
II-2 H ~I H H CF3 m.p.227°C
CF~~~U-
~~CI ~' /-\
(H) ci
II-3 H F H H CF3 m.p.213C
(F)
II-4 H N02 H H CF3 m.p.151C
(N02)
II-5 H CI H H CF3 m.p.193C
(H) (CI)
II-6 Cl ' H Cl H CF3 m.p.165-170C
(~ (CI) (~ (C1)
II-7 Br (CI) CI H CF3 m.p.195-149C
*> The ~H-NMR spectra were recorded in deuterochloroform (CDC13) or hexade
utero-dimethyl sulphoxide (DlvISO-d6) using tetramethylsilane (TMS) as the
internal
standard. The value given is the chemical shift as d in ppm.
Chloro-(2-halogeno-l~~fluoromethyl-ethoxy)-urethanes of the formula
/CHzX
CI--CHz-O-O-C\H
CH2F
in which
X represents fluorine or chlorine
[the individual compounds concerned are chloro-(2-fluoro-1-fluoromethyl-
ethoxy)
methane (formula (I), X = fluorine) and chloro-(2-chloro-1-fluoromethyl-
ethoxy)
methane (formula (I), X = chlorine)]
are obtainable by reacting halogenated isopropanols of the formula
Le A 29 089-PCT - 34 -
~CHZX
HO--Cue/ H
\CF-i1F
in which
X represents fluorine or chlorine
at -20 to +20°C with :formalde:hyde and hydrogen chloride.
They are used for tl'se preparation of substituted benzimidazoles of the
formula
X
z
X ~ N
X/ ~ / N~--C F3 C H2X
4
X CHZ-O-C/\ H
\C H2F
S in which
X represents fluorine or chlorine and
Xt, X2, X3 and X4, independently of one another, in each case represent
hydrogen,
halogen, cyano, nitro, iin each case optionally substituted alkyl, alkoxy,
alkyl-
thio, alkylsulphinyl, alk:ylsulphonyl or cycloalkyl, optionally substituted,
fused-
on dioxyalkylene, or represent hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl,
cycloalkoxycarbonyl, in each case optionally substituted amino or
aminocarbonyl or in each case optionally substituted aryl, aryloxy, arylthio,
arylsulphinyl, ;~rylsulpl-~onyl, arylsulphonyloxy, arylcarbonyl,
aryloxycarbonyl,
arylazo or arylo:hiomethylsulphonyl, but with at least one of the substituents
X~,
1 S X2, X3 or x:4 representing a halogenoalkyl with the exception of the
chlorometh~~l radical, halogenoalkoxy, halogenoalkylthio,
Le A 29 089-PCT - 35 -
~14~6~
halogenoalkylsulphinyl., halogenoalkylsulphonyl, alkylsulphonyl, optionally
substituted fused-on dioxyalkylene, hydroxycarbonyl, alkylcarbom~l,
alkoxycarbonyl, cycloa.lkoxycarbonyl, in each case optionally substituted
amino
or aminocarbonyl or in each case optionally substituted aryl, arylthio,
arylsulphinyl, arylsulplhonyl, arylsulphonyloxy, arylcarbonyl, aryloxycarbonU,
arylazo or ary:lthiomethylsulphonyl,
from benzimidazoles of the formula
X
z
X ~ N
X3 ~ / N>--C F3
4
X H
Example
192 g of 1,3-difluoro-2-propanol were admixed with 66 g of paraformaldehyde
(finely
powdered). Then, at -10°C, a vigorous stream of hydrogen chloride gas
was passed in
with stirring until a cllear 2-phase mixture had been formed. Subsequently the
organic
phase was separated off, dried with calcium chloride and subjected to
fractional
distillation in vacuo. 183 g (6f% of theory) of chloro-(2-fluoro-1-
fluoromethyl-etho~~-)-
methane were obtained with a boiling point of 50 to 54°C at 20 mbar.
The cha.rac-
teristic absorptions in the NMR spectra were as follows:
IH-NMR: 5.6 ppm arid 4.55 ppm.
~9F-NMR: -233 ppm.
Fluorinated 1,3-benzo-dioxoles of the formula
Le A 29 089-PCT - 36 -
R
z
R. 4 ~ p z C F3
5I \
R3' s ~ 0 CHXCF3
4
R
in which
X represents hydrogen, fluorine, chlorine or bromine, and
R1 and R4 may be idc;ntical to or different from one another and in each case
denote
hydrogen, halogen, C~-C6-alkyl, C~-C6-alkoxy, halogeno-C~-C6-alkyl, C6-Clo-
aryl, COOH,'' C:N, NCC), COO-CI-C6-alkyl, NH-C~-C6-alkyl, N(C~-C6-alkyl)2,
and
R2 and R3 represent I'd02 or NH2,
are obtainable by reacting 1,2-~dihydroxybenzenes
,
R
z
R ~ OH
R3 \ OH
4
R
in which
R~ to R4 have the meaning given above, but R1 to R3 do not represent OH, COCI
or
S02C1,
in the presence of a base and a diluent at -20 to +200°C with a
hexafluorobutene of the
formula
2
C F3 X
X C F3
cis-trans
Le A 29 089-PCT - 37 -
~.~4~~~3
in which
X ~ represents hydrogen or halogen and
X2 represents halogen,
or by reacting 1,2-dihydroxybe:nzenes which are provided with a protective
group and
are of the formula
R
z 5
R ~ OR
R3 \ OH
4
R
in which
R~ to R4 have the me~ming given above and
RS represents a protective group or
R5, together with R:~, represents a -C(CH3)2-O- radical
first with a hexafluorobutene of the formula
z
C F3 X
X C F3
cis-trans
in which
X ~ represents hydrogen or halogen and
Le A 29 089-PC'T - 38 -
X2 represents halogen,
to obtain an intermediiate of the formula
R
2 5
F~, ~ OR
CF
F~ ~ 4 O-C
R
CF3
in which
XI and R~ to RS have: the meaning given above,
S then eliminating the protective; group RS from the intermediate of the above
formula,
and then reacting the OH compound thus obtainable with a base, to obtain 1,3-
benzo-
dioxoles of the above formula.
1,3-Benzo-dioxoles which contain two adjacent amino groups can be converted
with
trifluoroacetic acid into the corresponding benzimidazole, e.g. of the
following formula
R
F C-~N / ~ ~~~CF3
O C HXC F3
4
H R
in which
R~, R4 and X have the meaning given above.
From these compounds it is possible to obtain, by alkylation, benzimidazole
derivatives
Le A 29 089-PCT - 39 -
9
/R
CH
0
which are substituted on the nitrogen atom with a R radical.
Le A 29 089-PCT - 40 -
2.~4~~~3
Examples
Example 1 a
2-(2,2,2-Trifluoroethy l)-2-trifleroromethyl-1,3-benzodioxole
11 g of pyrocatechol vvere dissolved in 200 ml of dimethylfomamide, and 18 g
of 45%
S strength by weight aqueous sodium hydroxide solution were added. 20 g of 2-
chloro-
1,1,1,4,4,4-hexafluoro-2-butene were added dropwise at 75°C to the
mixture. Stirring
was continued at 75°C for 30 minutes. The mixture was then poured into
500 ml of
ice-water and extracte~3 with diethyl ether. The organic phase was washed with
water,
dried with magnesium sulphate and concentrated. Finally, the product was
distilled
l0 under a high vacuum. The yielLd was 1 S g (= 56%) and the boiling point was
60°C at
mbar. The NMR spectra showed the following characteristic absorptions: ~ 9F-
NMR:
-59.0 and -84.6 ppm; ~ H-NMR: 3.02 ppm.
Example 2 a
2-( 1-Chloro-2,2,2-triflvuoroethyl)-2-trifluoromethyl-1,3-benzodioxo1e
l5 110 g of pyrocatechol were dissolved in 1,500 ml of acetonitrile, and 200 g
of
triethylamine were added. 235 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-
butene were
added dropwise at 75"C to thf: mixture. Stirring was continued at 75°C
for 2 hours.
1,200 ml of the solvent were then distilled off in vacuo and the residue was
taken up
in 1,500 ml of water. The product was extracted with diethyl ether and the
organic
:?0 phase was washed twice with 10% strength by weight aqueous sodium
hydroxide
solution and once with water. After drying with magnesium sulphate the product
was
concentrated and subjected to :fractional distillation in vacuo. The yield was
258 g (_
84% of theory). The broiling point was 63°C at 12 mbar. The NMR spectra
showed the
following characteristic abso~ptions: 19P-NMR: -66.8 and -79.7 ppm; 1H-NMR:
~'.5 4.71 ppm.
Le A 29 089-PCT - 41 -
~~_~8~~~
Examples 3a
2-( 1,1,1,4,4,4-Hexafluoro-2-butenoxy)-methoxybenzene
260 g of 2-methoxyyhenol were dissolved in 1 I of dimethylformamide (technical
grade), and 220 g of 45% sodium hydroxide solution were added. Then 400 g of 2-
chloro-1,1,1,4,4,4-hex~afluoro-2-butene were added dropwise with stirring at
22°C.
Stirring was continued at 22°C' for 2 hours. Then 1.5 1 of ice-water
was added and the
mixture was extracted with me;thylene chloride.
The combined organic phases were washed twice with 10% strength sodium
hydroxide
solution and once with saturated NaCI solution, dried with MgS04 and
distilled. The
yield was 329 g (58% of theory) and the boiling point was 68-70°C at 12
mbar. The
NMR spectra showed the following chau~acteristic absorptions: ~9F-NMR: -57.6
and
-67.9 ppm; 1 H-NMR: 5.92 ppm.
Example 4a
2-( 1,1,1,4,4,4-hexafluoro-2-bul:enoxy)-phenal
IS 286.1 g of 2-(1,1,1,4,4,4-hexa~fluoro-2-butenoxy)-methoxybenzene from
Example 3a
were dissolved in a mixture of 500 ml of glacial acetic acid and 500 ml of 48%
strength hydrobromic acid, and 5 g of triethylbenzylammonium chloride were
added.
The mixture was stirred at a. bath temperature of 150°C until,
according to gas-
chromatographic monitoring, complete reaction had been achieved. The mixture
was
:~0 then allowed to cool, and 2 kg of ice-water were added. The aqueous phase
was
extracted thoroughly vVith Cl-12C:12. After drying with MgS04 the solvent was
stripped
off and the residue was distilled in vacuo. The yield was 200 g (50% of
theory) and the
boiling point was 81)°C at 16 mbar. The NMR spectra showed the
following
characteristic absorptions: ~9F-NMR: -59.6 and -69.6 ppm; ~H-NMR: 6.1 ppm.
Le A 29 089-PCT - 42 -
~a.4~~~~
Example Sa
2-(2,2,2-Trifluoroethyl )-2-trifluoromethyl-1,3-benzodioxole
200 g of 2-(1,1,1,4,4,4-hexafluo~ro-2-butenoxy)-phenol from Example 4a were
dissolved
in 400 ml of acetonitril~e, and 5 g of triethylamine were added. The mixture
was stirred
at 70°C for 4 h. Distillation wa.s then carried out in vacuo. The yield
was 162 g (81
of theory) and the boiling point was 60°C at 10 mbar. The NMR spectra
showed the
following characteristic absorptions: 19F-NMR: -59.0 and -84.6 ppm; ~H-NMR:
3.02 ppm.
Example 6a
2-(2-Chloro-1,1,1,4,4,4~-hexaflu.oro-2-butenoxy)-1-benzyloxybenzene
g of 2-benzyloxyphenol were dissolved in 100 ml of dimethylformamide, and 9 g
of 45% strength sodium hydroxide solution were added. 23 g of 2,3-dichloro-
1,1,1,4,4,4-hexafluoro-2-butene: were then added dropwise at room temperature.
After
the exothermic reaction had sulbsided the mixture was stirred at room
temperature for
15 a further 1 hour and then added to water and extracted with tert-butyl
methyl ether. The
mixture was dried with MgSO,t and the solvent was then stripped off. The yield
was
29 g (74% of theor~r). The NMR spectra showed the following characteristic
absorptions: ~ 9F-NMR: -59.5, -60.5, -61.7 and -62.8 ppm.
Example 7a
20 2-(2-Chloro-1,1,1,4,4,4E-hexaflu.oro-2-butenoxy)-phenol
24.4 g of 2-(2-chloro-1,1,1,4,,4,4-hexafluoro-2-butenoxy)-1-benzyloxybenzene
from
Example 6a were dissolved in 150 ml of tetrahydrofuran and treated at room
temperature for 4 hours with 3 bar of hydrogen in the presence of 2 g of Pd/C
( 10%).
The mixture was then filtered and the filtrate concentrated and distilled in
vacuo. The
5 yield was 13.2 g (69°/ of theory) and the boiling point was
56°C at 0.15 mbar.
Le A 29 089-PCT - 43
21~~~~~
Example 8a
2-( 1-Chloro-2,2,2-trif luoroeth:yl)-2-trifluoromethyl-1,3-benzodioxole
11.7 g of 2-(2-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy)-phenol from Example
7a were
dissolved in 40 ml of tert-butyl methyl ether, and 40 ml of 1 N sodium
hydroxide
solution were added. After stirring at room temperature for 30 minutes, the
organic
phase was separated off, dried with MgS04 and distilled. The yield was 10 g
(88% of
theory) and the boiling point was 63°C at 12 mbar. The NMR spectra
showed the
following characteristic abscrrptions: ~9F-NMR: -66.8 and -79.7 ppm; IH-NMR:
4.71 ppm.
Example 9a
2,2-Dimethyl-4-(1,1,1,4,4,4-he;xafluoro-2-butenoxy)-1,3-benzodioxole (formula
V, RS
together with R1 = -C',(CH3)2-O- radical)
46 g of 2,2-dimethyl-4-hydro~;y-1,3-benzodioxole (formula IV, RS together with
R3 =
-C(CH3)2-O- radical) were dissolved in 200 ml of N-methylpyrrolidone, and 31 g
of
40% strength by weight aqueous sodium hydroxide solution were added. 54.8 g of
2-
chloro-1,1,1,4,4,4-hex.afluoro-2-butene were then added dropwise while
stirring at room
temperature. After stirring further for 1 hour, the batch was poured into
water and
extracted with tert-butyl methyl ether. The organic phase was washed with 10%
strength by weight aqueous sodium hydroxide solution and dried with magnesium
sulphate, and the readily volatiile fractions were removed on a rotary
evaporator. There
remained 73.8 g (= 80% of theory) of a product which was 95% pure according to
gas
chromatography. The characteristic absorptions in the NMR spectra were: ~9F-
NMR:
-58.1 and -68.5 ppm; ~H-NMR: 6.73, 6.55, 6.03 and 1.70 ppm.
Le A 29 089-PCT - 44
.a
Example 10a
1,2-Dihydroxy-3-( 1,1,1,4,4,4-hexafluoro-2-butenoxy)-benzene
65 g of the product from Example 9a were heated to boiling, at reflux, with
200 ml of
concentrated aqueous hydrochloric acid for 4 hours, while stirring. The
mixture was
S then diluted with 300 ml of water and extracted with methylene chloride.
After drying
the extract with magnesium sulphate, the solvent was stripped off from the
organic
phase to give 54 g of a 90% pure product. Recrystallization from cyclohexane
gave
colourless crystals with a melting point of 105°C. The characteristic
absorptions in the
NMR spectra were as~ follows: t9F-NMR: -57.7 and -67.7 ppm; 1H-NMR: 6.77,
6.50,
6.21 and 5.42 ppm.'
Example 11 a
2-(2,2,2-Trifluoroethyl)-2-(trifluoromethyl)-4-hydroxy-1,3-benzodioxole
(formula (I),
R~ = OH, X = H, X == CI-I, R2 and R3 = H).
43.5 g of the product from Example 10a were dissolved in 300 ml of
acetonitrile, and
1.5 g of triethylamine was added at room temperature. After stirring at room
temperature for 2 hours, the solvent was stripped off and the residue
distilled in vacuo.
The yield was 17 g (-= 39% of theory), the boiling point was 85°C at
0.1 S mbar, and
the melting point was 65°C. T:he characteristic absorptions in the NMR
spectra were as
follows: ~9F-NMR: -~~9.0 and -84.5 ppm; ~H-NMR: 6.80, 6.55, 6.2 and 3.01 ppm.
Example 12a
2,2-Dimethyl-4-(3-chloro-1,1, :l ,4,4,4-hexafluoro-2-butenoxy)-1,3-
benzodioxol~formula
(V), R~ and RS together are -C(CH3)Z-O-, X~ = C1, R2 + R3 = H, A = CH).
33.2 g of 2,2-dimethyl-4-hydroxy-1,3-benzodioxole were reacted in analogy to
Example
9a with 47 g of 2,3-dic;hloro-1,1,1,4,4,4-hexafluoro-2-butene. The product
obtained was
distilled in vacuo, and a 1:1 molar mixture of cis/trans isomers was obtained.
The yield
Le A 29 089-PC'r - 45 -
was 51 g (= 70% of '.theory) amd the boiling point was 70°C at 0.15
mbar. The charac-
teristic absorptions in the NM:R spectra were as follows: 19F-NMR: -60.0, -
61.6, -62.2
and -63.4 ppm; ~ H-I'f MR: 6. i'9, 6.65 to 6.48 and 1.7 ppm.
Example 13a
1,2-Dihydroxy-3-(3-r.hloro-1,1,1,4,4,4-hexafluoro-2-butenoxy)-benzene(formula(
V ),R ~
=OH, R2+R3=H, A=C'H:, RS=H, Xt =Cl)
18 g of the product from Ex~unple 12a were reacted in analogy to Example 10a
with
SO ml of concentrated hydroclhloric acid. 15.7 g of a 97% pure product were
obtained.
The product was ~ 1:1 molar mixture of the cis/trans isomers. The
characteristic
absorptions in the NIVIR specara were, as follows: t9F-NMR: -60.2, -61.3, -
62.2 and
-63.3 ppm; 1H-NMR: 6.80, 6.45 and 6.25 ppm.
Example 14a
2-( 1-Chloro-2,2,2-trifluoroeth;yl)-2-trifluoromethyl-4-hydroxy-1,3-
benzodioxole
g of the product from Example 13a were dissolved in 50 ml of acetonitrile, and
15 1 ml of triethylamine was added. After stirring for 15 minutes, the solvent
was stripped
off and the residue w~~s distilled in vacuo. For purification the product was
taken up in
diethyl ether and filtered through silica. After stripping off the diethyl
ether there
remained 10.5 g of the product (= 70% of theory). The melting point was 139 to
141 °C. The characteristic absorptions in the NMR spectra were as
follows: ~ 9F-NMR:
-66.6 and -79.3 ppm; tH-NM:R.: 8.4, 6.76, 6.60, 6.50 and 4.70 ppm.
Example 15a
5-Nitro-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole
A solution of 54.4 g of 2-(2,:Z,2-trifluoroethyl)-2-trifluoromethyl-1,3-
benzodioxole in
75 ml of methylene chloride was added dropwise at 10°C to a mixture of
40 ml of
Le A 29 089-f CT' - 46 -
~~~8~~~
65% strength by weight nitric acid and 40 ml of concentrated sulphuric acid.
The
mixture was stirred at room temperature for a further I hour and then poured
into ice-
water, the organic phase was then separated off and the aqueous phase was
extracted
with methylene chloride. The combined organic phases were washed with water,
dried,
and freed from readily volatil'~e constituents. There remained 95 g of the
product (_
86% of theory) with a melting point of 87 to 88°C.
The NMR spectra showed the i:ollowing characteristic absorptions: ~9F-NMR: -
59.0 and
-69.4 ppm; ~ H-NMR: 3.10 pp:m.
Example 16a
5-Nitro-2-(1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole
613 g of 2-(1-chloro-2,2,2-l:rifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole
from
Example 2a were dissolved in 1.2 1 of methylene chloride, and the solution was
added
dropwise at 0 to 10°C' to a mixture of 400 ml of 65% strength nitric
acid and 400 ml
of concentrated sulphuric acid. The mixture was stirred at room temperature
for a
further 2 hours. It w;as then .added carefully to 2 1 of ice-water and
extracted with
methylene chloride. The combined organic phases were washed 2 times with
water,
dried and concentrated. The yield was 652 g (93% of theory). The NMR spectra
showed the following characteristic absorptions: 19F-NMR: -66.4 and -79.2 ppm;
1 H-
NMR: 4.81 ppm.
Example 17a
5,6-Dinitro-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole
A mixture of 250 ml of 100% strength by weight nitric acid and 350 ml of
concentrated sulphuric; acid w;as added dropwise to an initial charge of 317 g
of the
product from Example; I Sa. The mixture was stirred at 55°C for 2
hours. The mixture
was then cooled and poured into ice-water. The product was extracted with
methylene
chloride, washed until neutral with sodium hydrogen carbonate solution, dried,
and
Le A 29 089-PC'T - 47 -
freed on a rotary evaporator from readily volatile constituents. The yield was
339 g (_
94% of theory) and t:he melting point was 101 to 103°C.
The NMR spectra showed the following characteristic absorptions: t9F-NMR: -
60.9 and
-86.5 ppm; 1 H-NMR: 3.18 pp~m.
Example 18a
5,6-Dinitro-2-( I -chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-
benzodioxole
A mixture of 250 rnl of 100% strength by weight nitric acid and 350 ml of
concentrated sulphuric acid eras added to an initial charge of 352 g of S-
nitro-2-( 1-
chloro-2,2,2-trifluorocahyl)-2-trifluoromethyl-1,3-benzodioxole from Example
16a. The
mixture was stirred at 60°C for 2 hours. It was cooled, poured into ice-
water and
extracted with methyl~ene chloride. After washing the mixture with sodium
hydrogen
carbonate solution, and drying, it was concentrated on a rotary evaporator.
The yield
was 392 g (91% of theory) and the melting point was 125°C. The NMR
spectra
showed the following characteristic absorptions: I9F-NMR: -68.5 and -81.0 ppm;
1H
NMR: 4.86 ppm.
Example 19a
5-Amino-2-(2,2,2-trifl,uoroethyl)-2-trifluoromethyl-1,3-benzodioxole
57.4 g of the product from E~;:ample 15a were dissolved in 400 ml of
tetrahydrofuran
and hydrogenated with hydrogen in the presence of 4 g of catalyst (palladium
on
carbon, 10% by weight) at 3'0°C for 5 hours and at 50 bar. The mixture
was then
filtered, the solvent removed, and the remaining filtrate distilled under a
high vacuum.
37 g of product (= 63% of theory) were obtained with a boiling point of
83°C at
0.07 mbar. '9F-NMR: -59.0 and -84.6 ppm; ~H-NMR: 2.98 ppm.
Le A 29 089-PCT - 48
Example 20a
5-Amino-2-( I -chloro-2,2,2-tri fluoroethyl)-2-trifluoromethyl-1,3-
benzodioxole
72 g of 5-nitro-2-1;1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-
benzodioxole
from Example 16a were dissolved in 500 ml of tetrahydrofuran, and hydrogenated
on
5 g of palladium on carbon (5%) at room temperature for 5 hours with 15 to 20
bar of
hydrogen. The mixture was then filtered and the solvent stripped off in vacuo.
The
yield was 60 g (93% of theory) and the boiling point was 80 to 82°C at
0.1 mbar. The
NMR spectra showed the folllowing characteristic absorptions: 19F-NMR: -66.5
and
-79.4 ppm; ~ H-NMR: 4.68 ppm.
Example 21 a
5,6-Diamino-2-(2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-benzodioxole
339 g of the product from Ex~unple 17a were dissolved in 2,000 ml of
tetrahydrofuran,
and 20 g of catalyst (palladiwm on carbon, 5% by weight) were added.
Hydrogenation
was carried out with hydrogen at 25 to 30 bar and at room temperature for 13
hours.
The mixture was then filtered and the solvent stripped off in vacuo. A solid
remained.
The yield was 274 g (= 96%. of theory). 19F-NMR: -61.2 and -86.6 ppm; ~H-NMR:
3.02 ppm.
Example 22a
2-(2,2,2-Trifluoroeth~rl)-2-trifluoromethyl-1,3-benzodioxole
306.5 g of 2-(1-chloro-2,2,2-trifluoroethyl)-2-trifluoromethyl-1,3-
benzodioxole from
Example 2a were dissolved in 500 ml of THF, and 101 g of triethylamine and 30
g of
palladium on carbon (5% by weight) were added. Hydrogenation was then carried
out
with 100 bar of hydrogen at 110°C for 48 h. The mixture was then
filtered, the solvent
stripped off in vacuo and the residue subjected to fractional distillation in
vacuo. The
yield was 126 g (46°/. of theory) and the boiling point was 60°C
at 10 mbar. The NMR
Le A 29 089-PCT - 49
__
spectra showed the following .characteristic absorption: ~9F-NMR: -59.0 and -
84.6 ppm;
~ H-NMR: 3.02 ppm.
o-Phenylenediamines containiing fluoroalkyl(ene) groups and of the formula
R 3
NHR
Rz NH2
in which
S R1 represents C',F3, OCF3., SCF3, S02-Ct-C6-alkyl, which can be straight-
chain or
branched and may be substituted wholly or partially by fluorine, N(CF3)2, a
phenyl or phc~.noxy radical with CF3 or CN in the 4 position and optionally
further substituents, 1,1,2,3,3,3-hexafluoropropoxy, 1,1,2-trifluoro-2-chloro-
ethoxy, 1,1,2,2-tetr;afluoroethoxy, 1,1,2-trifluoro-2-chloro-ethylthio or
1,1,2,3,3,3-heatafluorolpropylthio, and, independently thereof,
R2 represents F, Cl, Br, C;N, CH3, OCF3, S02-Ct-C6-alkyl which can be straight-
chain or branched and may be substituted wholly or partially by fluorine, COO-
C~-C6-alkyl, COC>C6H5, 1,1,2,2-tetrafluoroethoxy, 1,1,2,3,3,3-
hexafluoropropoxy or 1,1,2-trifluoro-2-chloro-ethoxy, and
R3 represents hydrogen, C:OCH3 or COCF3, where
R~ and R2 can together represent a -O-CFCI-CFCI-O- radical,
with the exception of the compounds described in EP-A 251 013 and EP-A 487
286,
are obtainable by dinitrating a benzene derivative of the formula
D
i
D
Le A 29 089-PCT - 50 -
.. ~~l~~~l~
in which
D~ represents CF;;O, CF3;i, CHF2CFz0, CHFCI-CF20, CF3CHFCF20, CF3CF20,
CF3CF2CF20, CF3CF,,S or CF3CHFCF20, and
D2 represents CF:~O, CF3S, CHF2CF20, CHFCI-CF20, CF3CHF-CF20, CF3CF20,
S CF3CF2CF20, CF3CF; S or CF3CHFCF20, fluorine, chlorine, bromine, C1-C6-
alkyl or C~-C~~-alkoxy.,
and subsequently reducing the; nitro groups to obtain compounds in which R1
and R2
are in the 4 and S po:~itions with respect to the amino groups and have the
meaning of
D ~ and D2. '
If it is intended to prepare compounds in which Rl has the meaning given above
and
is in the 4 position with respect to the amino groups, and R2 represents Cl or
Br and
is in the 5 position with respect to the amino groups, then, for example, a
nitrobenzene
derivative of the forrrrula
N02
CI or B ~ Hal
in which
R~ has the meaning given and
Hal represents fluorine, chllorine or bromine,
can be reacted with ammonia, the Hal group thus being exchanged for an amino
group,
and the resulting nitroaniline can be reduced.
If it is intended to prepare compounds in which R~ has the meaning given above
and
is in the 4 position with respeca to the amina groups, R2 represents chlorine
or bromine
and is in the 6 position with respect to the amino groups and R3 denotes
hydrogen,
then, for example, a nitroaniline of the formula
Le A 29 089-PCT - 51
~1~~~~3
R ~ N02
NH2
in which
R~ has the meaning given. above
can be reacted with a chlorinating or brominating agent, a chlorine or bromine
atom
thus being introduced into the position meta to the vitro group, and the vitro
group can
subsequently be reduced.
If it is intended to prepare compounds in which R1 represents a donor group in
the 4
position with respect to the two amino groups, R2 represents an acceptor
group, e.g.
COO-C~-C6-alkyl, C1~1, CF.3 or S02-C~-C6-alkyl, and R3 is not hydrogen, a
benzene
derivative of the formula
,
D
i
A
in which
D I has the meaining given above and
A represents CF_s, S02-C1-C6-alkyl which is straight-chain or branched and may
be substituted wholly or partially by fluorine, COO-C~-C6-alkyl or CN,
for example, can then be manonitrated (introduction of the N02 group into the
position
para to D 1 ), the N02 group c,an be reduced to the NH2 group, the NH2 group
can be
acylated with, for example, acetic acid or trifluoroacetic acid, the product
cam again be
mononitrated (introduction of this N02 group into the position ortho to the
NHCOR
group where R = e.g. CH3 or (:F3), this NOZ group can be reduced to the NH2
group
and, optionally, if it is desiredl to prepare a compound of the above formula
where R3
= hydrogen, the acyl group cam be eliminated by hydrolysis.
Le A 29 089-PCT - 52 -
2~4~~~3
The o-phenylenediamines containing fluoroalkyl(ene) groups, in which R3
denotes
hydrogen, can initially be reacted with trifluoroacetic acid to give 2-
trifluoro-
methylbenzimidazoles, of the formula
i
R
N
~~.-CF3
~N
2 ~
R H
and then further reacted with compounds of the formula
R
A-C H
Ra
5 where R~ and RZ adopt the above scope of meaning,
R4 represents hydrogen, alkyl, alkoxy or optionally substituted aryl,
RS represents hydlroxyl, cyano or in each case optionally substituted alkyl,
alkenyl,
alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, amino, aminocarbonyl,
alkylcarbonyl. alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphonyl,
(hetero)ary l, (he;tero)arylcarbonyl, (hetero)aryloxycarbonyl,
(hetero)arylcarbonylox:y or (hetero)arylaminocarbonylaminocarbonyloxy, and
A denotes a suitable leaving group.
Leaving groups are known to those skilled in the art and are, for example,
halogen,
alkyl(alkoxy, aryl)sulphonyloxy, hydroxyl or alkoxy.
Le A 29 089-PCT - 53 -
Examples
Examples 1 to 6 b (Dinitration and reduction)
Example 1 b
320 g of 1,2-bis-(2-chloro-1,1,;?-trifluoroethoxy)-benzene were added dropwise
to 500 g
of a mixed acid containing 3a% by weight of HN03 and 67% by weight of H2S04.
After one hour at 40°C, 250 ml of 20% strength by weight oleum
were added
dropwise. The mixture was thf;n heated to 80°C and stirred for 15
hours. Subsequently
a further 120 ml of 20% strength by weight oleum and 250 g of the
abovementioned
mixed acid were adfied dropwise. After 6 hours at 80 to 82°C, the
mixture was cooled
and poured onto ice. The organic phase was separated off and washed with
water. After
azeotropic drying ~Nith 1,;Z-dichloroethane, 350 g of 96% by weight pure
1,2-dinitro-4,5-bis-(2-chloro-1,1,2-trifluoroethoxy)-benzene were obtained
(oil, nDO:
1.4832, GC 99.1 %).
350 g of this dinitro c:ompoun.d were added dropwise to a mixture of 1.5 1 of
ethanol,
1 S 50 ml of water, 30 ml of concentrated aqueous hydrochloric acid and 470 g
of iron
filings, and heated tn boiling; at reflux for a total of 15 hours. The
solution was
subsequently cooled and then filtered, the filtrate concentrated, and the
residue
recrystallized from cyclohe:xane. 216 g of 1,2-diamino-4,5-bis-(2-chloro-1,1,2-
trifluoroethoxy)-benzene having a melting point of 58 to 60°C were
obtained.
Example 2 b
In analogy to Example l, the: corresponding 4,5-dinitro compound (oil, no :
1.4852)
and the corresponding; 4,5-diamino compound (oil, 87% by weight pure) were
prepared
from 1,2-bis-(1,1,2,3.3,3-hexaifluoropropoxy)-benzene.
Example 3 b
In analogy to Example 1, the corresponding 4,5-dinitro compound (melting point
56 to
Le A 29 089-PCT - 54 -
2~.~~~~3
57°C) and the corresponding 4,5-diamino compound (melting point 67 to
68°C) were
prepared from 1-( 1,1,:Z-trifluoro-2-chloroethoxy)-2-chlorobenzene.
ExamQle 4 b
In analogy to Example 1, the corresponding 4,5-dinitro compound (melting point
73 to
S 75°C) and the corresponding 4,5-diamino compound (oil, 98% by weight
pure, npo:
1.5485) were prepared from 1-trifluoromethoxy-2-bromobenzene.
Example 5 b
In analogy to Exam~l~e 1, the corresponding 4,5-dinitro compound (melting
point 55 to
56°C) and the corresponding 4,5-diamino compound (melting point 56 -
57°C) were
prepared from 1-trifluorometh.oxy-2-chlorobenzene.
Example 6 b
The corresponding 4,5-dinitro compound (oil) and the corresponding 4,5-diamino
compound (oil) were prepared from 1-(1,1,2,3,3,3-hexafluoropropoxy)-2-chloro-
benzene.
Examples 7 to 12 b
Pressurization with ammonia and reduction
Example 7 b
260 g of 3-nitro- 2,5-dichlorobenzotrifluoride, 130 ml of water and 10 g of
tetraethylammonium chloride were initially introduced into an autoclave, and
120 ml
of liquid ammonia w~:re injecl;ed. The mixture was then heated to 130°C
and stirred for
10 hours at this tennperaturc:. The mixture was cooled and then filtered, and
the
precipitate which was separated off was washed with water and dried. 194 g of
2-
amino-3-nitro-5-chlo~ro-benzotrifluoride with a melting point of 67°C
resulted.
Le A 29 089-PCT - 55 -
~~4~~~~
134 g of the nitroaniline obtained as described above were dissolved in 800 ml
of
ethanol, and then 20 ml of wate:r, 10 ml of concentrated aqueous hydrochloric
acid and
160 g of iron filings were added. The mixture was heated for 15 hours to
boiling at
reflux, then cooled and filtered with suction and the filter residue washed
with
S dichloromethane; the organic phases were subsequently freed from the solvent
under
reduced pressure. 171 g of :S-chloro-3-trifluoromethyl-1,2-diaminobenzene with
a
melting point of 53°C resulted.
Example 8 b
In analogy to Example 7, first 3-nitro-4-amino-6-chloro-
difluorochloromethoxybenzene
(melting point 73°e) and from this 3,4-diamino-6-chloro-
difluorochloromethoxy-
benzene (oil) were obl:ained from 3-nitro-4,6-dichloro-
difluorochloromethoxybenzene.
Example 9 b
In analogy to Example 7, first ?.-bromo-S-nitro-6-amino-benzotrifluoride
(melting point
80 to 82°C) and from this 3-b:romo-5,6-diamino-benzotrifluoride
(melting point 52 to
I S 54°C) were prepared from 3-bromo-5-nitro-6-
chlorobenzotrifluoride.
Example 10 b
In analogy to Example; 7, first 3-cyano-4-amino-5-nitro-benzotrifluoride
(melting point
99 to 100°C) and from this 3-cyano-4,5-diamino-benzotrifluoride were
prepared from
3-cyano-4-chloro-5-nitro-benzotrifluoride.
Example 11 b
In analogy to Example: 7, first :3-chloro-5-nitro-6-amino-benzotrifluoride
(melting point
53 to 54°C) and from this 3-c;hloro-5,6-diamino-benzotrifluoride were
prepared from
3,6-dichloro-5-nitro-b~~nzotriflnoride.
Le A 29 089-PCT - 56 -
~14~~1~
Example 12 b
First 2-bromo-4-amino-5-nitro-( 1,1,2-trifluoro-2-chloro-ethoxy)-benzene
(melting point
90°C) and from this 2-bromo-4,5-diamino-(1,1,2-trifluoro-2-chloro)-
ethoxybenzene
were prepared from 2-'bromo-4-fluoro-5-nitro-( I,1,2-trifluoro-2-chloro)-
ethoxybenzene.
Example 13 b
(Halogenation of a nitroaniline and reduction)
24 g of finely powdered 2-nitro-4-trifluoromethylmercaptoaniline were
dissolved in
50 ml of trifluoroaCetic acid, and 18 g of bromine were metered in at
20°C. The
mixture was then stirred at 20"C for 3 hours and at 40°C for a further
30 minutes. The
mixture was added to water and the product was taken up in dichloromethane.
Following removal of the solvent, 31 g of 6-bromo-2-nitro-4-trifluoromethyl-
mercapto-
aniline resulted.
155 g of the nitroanil:ine thus ;prepared were heated to boiling at reflux for
1 S hours in
700 ml of ethanol tngether with 15 ml of water, 10 ml of concentrated aqueous
hydrochloric acid an<i 70 g of iron filings; the mixture was then filtered,
the filtrate
freed from solvent under reduced pressure, and the crude solid product
recrystallized
from cyclohexane. 11.2 g of fi-bromo-4-trifluoromethyl-mercapto-1,2-
diaminobenzene
with a melting point of 60 to 61 °C were obtained.
Example 14 b
In analogy to Example 13, 27 g of 2-nitro-4-trifluoromethyl-sulphonylaniline
in 100 ml
of acetic acid were brominated with 18 g of bromine.
After work-up, 32 g of 2-nit:ro-6-bromo-4-trifluoro-methylsulphonyl-aniline
resulted:
melting point 147°C.
32 g of the nitroamine thus prepared were reduced with iron filings in alcohol
and
Le A 29 089-PCT - 57 -
~1~.~~13
aqueous hydrochloric acid. 24 g of 3-bromo-5-trifluoromethylsulphonyl-
phenylene-1,2-
diamine resulted; melting point 155 - 157°C.
Example 15 b
In analogy to Example 14, 27 g of 2-nitro-4-trifluoromethylsulphonyl-aniline
in 100 ml
of acetic acid were chlorinated with 10 g of chlorine. 29 g of 2-nitro-4-
trifluoromethylsulphonyl-6-ch.loro-aniline resulted; melting point 138 -
139°C.
13 g of 3-chloro-5-trifluoromethylsulphonyl-1,2-phenylenediamine (melting
point:
143 - 145°C) were obtained by reduction.
Example 16 to 20 b
(Nitration and reduction in 2 stages)
Example 16 b
263 g of 4-(2,6-dichloro-4-trifluoromethyl)-phenoxy-acetanilide were dissolved
in
1,100 ml of dichloromethane, and taken as initial charge at 10°C. 88 g
of 98% strength
by weight nitric acid were then added dropwise at this temperature. The
mixture was
subsequently stirred at 10°C for 1 hour and at 30°C for 2
further hours. After the
addition of 300 ml 01~ water, the phases were separated and the organic phase
was freed
from dichloromethane under reduced pressure. There remained 253 g of 2-nitro-4-
(2,6-
dichloro-4-trifluoroir~ethyl-phenoxy)acetanilide with a melting point of 138 -
140°C.
91 g of the acetaniliide thus prepared were dissolved in 800 ml of dioxane, 10
g of
Raney nickel were added, and hydrogenation was carried out at 25 to
45°C in a hydro-
genation apparatus with a maximum of 50 bar hydrogen pressure. The apparatus
was
let down, the mixture was filtered, and the dioxane was distilled off under a
slight
vacuum. There remained 65 ~; of 2-amino-4-(2,6-dichloro-4-trifluoromethyl-
phenoxy)-
acetanilide with a melting point of 222 - 223°C.
Le A 29 089-PCT - 58 -
~~4-813
Example 17 b
In analogy to Example 16.. first 3-trifluoromethyl-4-methoxy-6-nitro-
acetanilide
(melting point 143 - 144°C) and from this 3-trifluoromethyl-4-methoxy-6-
amino-
acetanilide (melting point 164 - 165°C) were prepared from 3-
trifluoromethyl-4-
methoxy-acetanilide.
Example 18 b
In analogy to Example 16, first 3-trifluoromethyl-4-fluoro-6-nitro
trifluoromethylacetanilide (meslting point 78°C) and from this 3-
trifluoromethyl-4
fluoro-6-amino-trifluoromethy'.lacetanilide (melting point 92 - 93°C)
were prepared from
3-trifluoromethyl-4-fluoro-trifluoromethyl-acetanilide.
Example 19 b
In analogy to Example 16, first 3-trifluoromethyl-4-bromo-6-nitro-
trifluoromethylacetanilide (me:lting point I 10 - 112°C) and from this
3-trifluoromethyl-
4-bromo-6-amino-trifluoromethylacetanilide (melting point 63 - 65°C)
were prepared
from 3-trifluoromethyl-4-bromo-trifluoromethylacetanilide.
Example 20 b
In analogy to Example; 16, first 3-trifluoromethylthio-4-chloro-6-nitro-
trifluoromethylacetaniilide (melting point 99 - 100°C) and from this 3-
trifluoro-
methylthio-4-chloro-6.-amino-t:rifluoromethylacetanilide (melting point 88 -
90°C) were
prepared from 3-trifluorometh.ylthio-4-chloro-trifluoromethylacetanilide.
Example 21 b
0.2 mol of 3-bromo-_'>-trifluoromethyl-phenylene-diamine were heated with 150
ml of
trifluoroacetic acid ;at reflua; temperature for 3 hours. For working up,
excess
trifluoroacetic acid w:as distilled off and the residue was partitioned
between 100 ml of
Le A 29 089-PCT - 59
water and 300 ml of ethyl acetate. The organic phase was separated off, washed
successively with in each case 100 ml of aqueous sodium hydrogen carbonate
solution
and water, dried over sodium sulphate, and concentrated in vacuo. The residue
was
purified by chromatol;raphy on silica gel (eluent: cyclohexane/ethyl acetate
1:1).
S 4-Bromo-6-trifluorom.ethyl-2-l:rifluoromethyl-1 H-benzimidazole with a
melting point of
149 - 1 S 1 °C was obtained.
Example 22 b
0.03 mol of 4-bromo-6-trifluoromethyl-2-trifluoromethyl-1H-benzimidazole and
0.06 mot of powdered potassium carbonate were heated in 70 ml of ethyl acetate
at
reflux temperature for 15 minutes; 3.9 g (0.04 mol) of chloromethyl methyl
thioether
in 20 ml of ethyl acetate were: then added, and the mixture was heated with
stirring at
reflux temperature for a further 4 hours. For working up, the reaction mixture
was
cooled and then washed twice with in each case 40 ml of water, dried over
sodium
sulphate and concentrated in vacuo, and the residue was purified by
chromatography on
silica gel (eluent: dic:hloromet:hane).
1-Methylthiomethyl-4-bromo-6-trifluoromethyl-2-trifluoromethyl-benzimidazole
with a
melting point of 56 - 60°C was obtained.
Use Examples:
In the Use Examples which follow, the compounds listed below were employed as
comparison substancca:
O
ii
0-C-NH-CH3
C
0-i-C3H~
N-Methyl-O-(2-isopropoxyphenyl)-carbamate (cf. e.g. DE 11 08 202)
Le A 29 089-PCT - 60
O
I I
C H30-P-NH2
SCH3
O,S-Dimethyl-thiolo-phosphoric acid amide (c~ e.g. DE 12 10 835)
Le A 29 089-PCT - 61 -
Example A:
Phaedon larvae test:
Solvent: 7 harts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active substance, 1 part by weight of
active
substance is mixed with the stated amount of solvent and the stated amount of
emulsi-
fier, and the concentrate is dilluted with water to the desired concentration.
Cabbage leaves (Br~ssica oleracea) are treated by being dipped into the
preparation of
the active substance of the desired concentration and are infested with
mustard beetle
larvae (Phaedon cochleariae), as long as the leaves are still moist.
After the desired time, the destruction in per cent is determined. 100% means
that all
the beetle larvae have been kiilled; 0% means that none of the beetle larvae
has been
killed.
In this test the following compound, for example, from the Preparation
Examples
exhibits superior activity over the prior art: 7.
Le A 29 089-PCT - 62 -
Table A:
Phaedon larvae test
Active substances Concentration Degree of
of active destruction
substance in % after
in % 3 days
O (A) 0.1 I 00
II 0.01 70
O-C--NH-CH3
\ 0.001 0
O-i~:3H~
(known)
CI (7) 0.1 100
0.01 100
\ N ~ 0.001 100
\~--CF3
C1 / N
CHI-OC21-i~
C1 N
\ -CF3
/ N
Cl Cf~-OC2Hs
Le A 29 089-PCT - 63
~~ 4-8~~.~
Example B
Plutella test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active substance, 1 part by weight of
active
substance is mixed with the stated amount of solvent and the stated amount of
emulsi-
Pier, and the concentrate is diluted with water to the desired concentration.
Cabbage leaves (Bra;aica oleracea) are treated by being dipped into the
preparation of
active substance of t:he desired concentration and are infested with
caterpillars of the
diamond-back moth yPlutella maculipennis) while the leaves are still moist.
After the specified periods o:f time, the destruction in % is determined. 100%
means
that all the caterpillars have been killed; 0% means that none of the
caterpillars has
been killed.
In this test the following compound, for example, from the Preparation
Examples
exhibits superior activity over the prior art: 1 and 7.
Le A 29 089-PCT - 64 -
Table B:
Plutella test
Active substances Concentration Degree of
of active destruction
substance in % after
in % 3 days
O (A) 0.1 100
0.01 100
O-C-NFi-CH, 0.001 10
O-i-C, H~
(known)
C ~ N (1) 0.1 100
\~CF3 0.01 100
0_001 100
C1 ~
CH2 O--C;ZHS
Cl (7) 0.1 100
0.01 100
N 0.001 100
\~-_CF3
CI / N
Cl~-OCzHs
CI N
\ -CF3
N
Cl Cl
Le A 29 089-PCT - 65 -
Example C:
Heliothis virescens test
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
S To produce a suitable preparation of active substance, I part by weight of
active
substance is mixed with the stated amount of solvent and the stated amount of
emulsi-
fier, and the concentrate is diluted with water to the desired concentration.
Soya shoots (Glycirie max) are treated by being dipped into the preparation of
active
substance of the desired concentration and are infested with the tobacco bud
worm
(Heliothis virescens) while the; leaves are still moist.
After the desired time;, the de:>truction in per cent is determined. 100%
means that all
the caterpillars have been killed; 0% means that none of the caterpillars has
been killed.
In this test the following compounds, for example, from the Preparation
Examples
exhibit superior activity over the prior art: 1, 2, 6, 7, 9, 18, 22 and 27.
Le A 29 089-PCT - 66 -
. , ~148~~~
Table C:
Heliothis virescens test
Active substances Concentration Degree of
of active destruction
S substance in % after
in % 3 days
O (A) 0.1 10
i1
O-C-~-1~H3
O-_;.~3 H~
(knownl)
C ~ N ~ (1) 0.1 100
~~---CF3
C1
\CHZ O--CZHs
Cl ~ N (2) 0.1 100
~~--CF3
C1 / N
C;H3
CH2-N
~C--OCH3
y
O
CI ~ N (6) 0.1 100
~~---CF3
C1
,n-C3H~
CH2 __N
\C--OCI~
O
Le A 29 089-PCT - ('7
Table C: yContinued)
Heliothis virescens test
Active substances Concentration Degree of
of active destruction
substance in % after
in % 3 days
C1 (7) 0.1 100
\ N
\~--CF3
Cl ~ N
C> h-OC2lHs
CI N
j,--CF3
N
Cl C~~-OC~ Hs
N (9) 0.1 100
\~--CF3
Cl / N
v
CIA, -O-i-C:~ H~
C1 N
\ -CF3
N
CH2 ~'1-~.3~
Le A 29 089-PCT _ bg _
-
Table C: (Continued)
Heliothis virescens test
Active substances Concentration Degree of
of active destruction
substance in % after
in % 3 days
---CF3
CHz--OCZHS
,N (18) 0.1 100
\~--.CF3
'N
OzN
CH2--OC2H5
OZN ~ ' ,N
~N
N (22) 0.1 100
~~-CF3
N
02N v ; C~
(:Hz-N
\C-OCzHs
OzN ~ N y
\~CF:3
N
~CH3
CHz-N
\C-OC21-i~
O
Le A 29 089-PCT - 69 -
~.
Table C: (Continued)
Heliothis virescens tf~st
Active substances Concentration Degree of
of active destruction
substance in % after
in % 3 days
CI (27) 0.1 100
\ O w. N
~>--CF3
F3C ~(.I
CFii-OC2H5
F3C / C;1 ~' N
\ ~ ~ /~ ~~~3
\,/ N
Cl CF'Zz-OC21'is
Le A 29 089-PCT - 70 -
Example D
Tetranychus test (OlP-resistant)
Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active substance, I part by weight of
active
substance is mixed with the stated amount of solvent and the stated amount of
emulsi-
fier, and the concenorate is diluted with emulsifier-containing water to the
desired
concentrations.
Bean plants (Phaseolus vulg~~ris) which are heavily infested with all
developmental
stages of the red spider mite (Tetranychus urticae) are dipped in a
preparation of the
active substance of the desired concentration.
After the desired time, the destruction in per cent is determined. 100% means
that all
the spider mites ham: been killed; 0% means that none of the spider mites has
been
killed.
1 S In this test the following compounds, for example, from the Preparation
Examples
exhibit superior activity over the prior art: 8, 21, 22, 23, 24 and 25.
Le A 29 089-PCT - 71 -
Table D:
Tetranychus test (OP-resistant)
Active substances Concentration Degree of
of active destruction
substance in % after
in % 7 days
O (B) 0.01 60
CH30- i ~-NHZ
S~~H3
(known)
Cl . (8) 0.01 100
N
~~~--CF3
/ /
Cl N ,CH3
CE-~-N
\C;-OCR
O
Cl
N
~>---CF3,
N
CH3
CI f'~ N
\C-OCH3
O
Le A 29 089-PCT - 72 -
2~4.~~~~
Table D: (Continued)
Tetranychus test (OP-resistant)
Active substances Concentration Degree of
of active destruction
substance in % after
in % 7 days
,N (21) 0.01 98
\ -CF3
'N
02N
~z-_O-n-~~
OZN ~ ; ,N
\/ CF3
/ 'N
CHi--O-n-C3I-h
(22) 0.01 100
\~Cl' 3
02N / td
CIA-rf
C-OC2H5
OzN .~ lV Cp
~~--CF3
~CI-T3
v
C-OC21-i~
O
Le A 29 089-PCT - 73 -
~~.~~~~3
Table D: (Continued
Tetranychus test (OI'-resistant)
Active substances Concentration Degree of
of active destruction
substance in % after
in % 7 days
(23 ) 0.01 100
\~Cl'3
r~
OZN \ /CZHs
CHz--N
~C--OCzHs
OzN ~ 1~T
\~-CIF
1~1
\ /C2H5
CHZ-td
\C-OC2H5
O
(24) 0.01 100
\~---CF3
OZN ~ 1V /n-C3~
C~-_rJ
\C-OC2Hs
OzN \ N (),,
\~--_C,F3
N
\ /n_C3H.r
CHZ--lV
~C--OCZHS
O
Le A 29 089-PCT _ ~4 _
Table D: (Continued
Tetranychus test (OlP-resistant)
Active substances Concentration Degree of
of active destruction
substance in % after
in % 7 days
(25) 0.01 98
\~_ C,.F3
lV
OzN ~
CHz-OH
OzN ~ N
\~--C;F3
N
CI-~w-OH
Le A 29 089-PCT - 75 -
~.. ~~~.$~~~
Example E
Nematodes: Critical concentration test
Test nematode: Globodera ros,tochiensis
Solvent: 31 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active substance, 1 part by weight of
active
substance is mixed with the stated amount of solvent, the stated amount of
emulsifier
is added and the concentrate is diluted with water to the desired
concentration.
The preparation of active substance is intimately mixed with the soil which is
heavily
contaminated with thc: test nematodes. The concentration of the active
substance in the
preparation is of practically no importance here, only the amount by weight of
active
substance per unit volume of soil, which is given in ppm (= mg/1), being
decisive. The
treated soil is transferred into pots, potatoes are planted in it, and the
pots are
maintained at a greenhouse temperature of 20°C.
After six weeks the potato roots are examined for cysts and the degree of
effectiveness
of the active substance is determined in %. The degree of effectiveness is
100% if
infestation has been 'totally avoided, and is 0% if infestation is just as
high as in the
control plants in soil which is untreated but contaminated in the same way.
In this test the folle~wing compound, for example, from the Preparation
Examples
exhibits superior activity over the prior art: I and 7.
Le A 29 089-PCT - 76 -
Table E:
Nematodes test (Glolbodera rostochiensis)
Active substances Degree of destruction in
at an active substance
concentration of 20 ppm
O (B) 0
CH30-P--NHZ
SCFi3
(known)
C ~ N (1) 100
~~--CF3
CI
O--CzHs
Cl (7) 100
\ N
~~--CF3
Cl / N
1
C~ _.O~~zHs
CI N
N
1CH2=-OC2H5
Cl
Le A 29 089-PCT - '7'7
..
Example F:
Psoroptes ovis test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 parts by weight of nonylphenol polyglycol ether
To produce a suitable preparation of active substance, 3 parts by weight of
active
substance are mixed v~rith 7 parts of the solventlemulsifier mixture indicated
above, and
the emulsion concentrate thus obtained is diluted with water to the desired
concentra-
tion.
1 ml of this active substance preparation is pipetted into suitably sized PP
blister packs.
About 25 mites are then transferred into the active substance preparation.
After 24 hours the effectiveness of the active substance preparation is
determined in %.
100% means that all i:he mites have been killed; 0% means that none of the
mites has
been killed.
In this test, the following compounds, for example, of the Preparation
Examples display
superior action comp~ued to the prior art: 3, 4, 5 and 18.
Le A 29 089-PCT - 78 -
Table F:
Psoroptes ovis test
Active substances Concentration Degree of
of active destruction
S substance in in
ppm of a.i.
C ~ N (3) 10 100
\~CF3
Cl / ~N~ /CHf3
CHfz N
\COOCZHs
~~--CF,
'CHZ O___Cz~~S
C ~ N (4) 10 100
\~---CF3
Cl / N~' /CzHs
CFi2 N~
COC~zHs
C ~ N (5) 10 100
\~---CF3
Cl / N~ /C;~HS
CI~Z N~
COOCH3
N (18) l0 loo
\>-CF3
OzN / N
\~CH2 O--CzHS
OzN ~ N
/ N
Le A 29 089-PCT - 79 -
Example G:
Periplaneta americana test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 parts by weight of nonylphenol polyglycol ether
To produce a suitable preparation of active substance, 3 parts by weight of
active
substance are mixed with 7 pans of the abovementioned solvent/emulsifier
mixture, and
the resulting emulsion concentrate is diluted with water to the desired
concentration.
2 ml of this active substance preparation are pipetted onto filter paper discs
(diameter:
9.5 cm) which are located in suitably sized Petri dishes. After drying the
filter discs,
five cockroaches (Periplaneta ~unericana) are transferred to the Petri dishes
and covered.
After 3 days the effectiveness of the active substance preparation is
determined in %.
100% means that all the cockroaches have been killed; 0% means that none of
the
cockroaches has been killed.
In this test the follo~Ning compounds, for example, from the Preparation
Examples
exhibit superior activity over the prior art: 7, 8, 18, 19, 20 and 25.
Le A 29 089-PCT - 80 -
.-
Table G:
Periplaneta americana test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
CI (7) 1000 100
100 100
N
~~---CF3
C1 / N
\CHZ O--CZHs
C ~ N
~~----CF3
N
C1 \Ciii O-C ZHs
C1 (8) 1000 100
100 100
N
~~--CF3
Cl / ~N\ %
CF(i N
\COUCH3
C ~ N
~~--CF3
N\ ~CH3
Cl C~;~ N\
COOCH3
Le A 29 089-PCT - 81 -
~. ~.8 ~ ~.~
Table G: (Continued)
Periplaneta americana test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
OzN ~ N (18) 1000 l00
~~-CF3
/ N
\~CHZ O--CzHs
N
~~,--CFA
/ /
OzN N\
~CHZ O--CzHs
OzN .~ N (19) 1000 100
~>-CF3
/ N
'CHZ O--CzHs
N (20) 1000 100
~~~--CFi
OzN Nv
\Cli2 O--CzHs
Le A 29 089-PCT - 82 -
Table G: (Continued)
Periplaneta americana test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
OZN ~ N (25) 1000 100
\~..Ch3
/ 'N
\CHZ -OH
~ ~N
\~---.-CF3
OzN / . _N
\CHZ -OH
Le A 29 089-PCT - 83 -
~~4~~~3
Example H_
Musca domestica test:
Solvent: 35 parts by weight of ethylene glycol monomethyl ether
Emulsifier: 35 part: by weight of nonylphenol polyglycol ether
To produce a suitable preparation of active substance, 3 parts by weight of
active
substance are mixed with 7 parts of the abovementioned solvent/emulsifier
mixture, and
the resulting emulsion. concentrate is diluted with water to the desired
concentration.
2 ml of this active substance preparation are pipetted onto filter paper discs
(diameter:
9.5 cm) which are located in suitably sized Petri dishes. After drying the
filter discs, 25
test organisms (Musca domestica; strain WHO [N]) are transferred to the Petri
dishes
and covered.
After 3 days the effectiveness of the active substance preparation is
determined in %.
100% means that all the flies have been killed; 0% means that none of the
flies has
been killed.
In this test the following compounds, for example, from the Preparation
Examples
exhibit superior activity over the prior art: 7, I1, 18, 19, 20 and 25.
Le A 29 089-PCT - 84 -
Table H:
Musca domestica test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
C1 (7) 1000 100
100 >50
N
~~--CF3
CI ~ N
\CH.t O--CzHs
C ~ N
~~--CF3
N
Cl \CHZ O-C'.ZHs
C1 ~ N (11) 1000 100
~~--CF3
N
CH2 OCZHs
~ ,N
~~---CF3
C1 ~ N
\C:Hz OCZl3s
Le A 29 089-PCT - 85 -
~~.~.8~13
Table H: (Continued)
Musca domestica test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
02N ~ N (18) 1000 100
\~,-CF; 100 >50
N
~CHZ O--CZHs
N
~~---CF3
OzN ~ N
\~CH2 O.-CzHs
OZN ~ N ( I 9) 1000 I 00
\~-CFA 100 100
N
y
~CHz 0--CZHs
N (20) 1000 100
\~~-CF 100 >5O
3
OzN ~ Nv
\CHZ O--CzHs
Le A 29 089-PCT - 86 -
Z~ 4.~61~
Table H: (Continued)
Musca domestica test
Active substances Concentration Degree of
of active destruction
substance in in
ppm of a.i.
OZN ~ tJ (25) 1000 100
/ 1J
\CHz ~OH
~ N
OzN / , N
\CHZ ~OH
Le A 29 089-PCT - 87 -
