Note: Descriptions are shown in the official language in which they were submitted.
Z~
- 1 - 21489-6810D
I~his is a divisional application of application
Serial No. 492,846 filed October 11, 1985.
The parent application relates to novel 3-phenyl-
pyrrole derivatives, to processes for producing them, to
compositions containing them as active ingredients for controlling
phytopathogenic microorganisms and to the use of these active
ingredients. This application relates to intermediates for
producing the novel 3-phenylpyrrole derivatives~
The 3-phenylpyrrole derivatives according to the
lnvention correspond to the formula I
Rn ~ N3 ~I)
: l2
:
wherein R is cyano, trifluoromethyl or Cl-C4-alkoxycarbonyl, R2
is vinyl or a group -CH2-CH2-X, in which X is chlorine, bromine,
cyano, Cl-C4-alkoxycarbonyl, phenylsulfonyl, 4-bromophenylsulfonyl
or 4-methylphenylsulfonyl, R is halogen, Cl-C4-alkyl or Cl-C4-
haloalkyl, and n is zero, one or two.
N-substituted pyrrole compounds have already been
~26~ 3
described in the l.iterature for various application
purposes. Compounds of this type are known from the
G.B. Patent Specification No. 2,078,761 as stabilisers
for plastics, or from the German Offenlegungsschrift No.
2,028,363 as polymerisation catalysts. N-Sulfenylated
3-phenylpyrrole compounds have recen~ly been put forward
as microbicides in for example the published European
Patent Application No. EP-A 96,142.
Within the scope of the present invention, the term
'alkoxycarbonyl' denotes methoxycarbonyl, ethoxycarbonyl,
i-propyloxycarbonyl and n-propyloxycarbonyl, as well as
the ~our isomeric butyloxycarbonyl groups. Methoxy-
or ethoxycarbonyl is preferred. The same definition
and preference apply with respect to the term 'alkoxy-
ca~bonylethyl', which is represented by the symbol R2.
The preferred forms here are methoxycarbonylethyl and
ethoxycarbonylethyl. Halogen is fluorine, chlorine, bromine
or iodine, preferably chlorine. By alkyl is meant:
methyl, ethyL, i-propyl and n-propyl, as well as the four
isomeric butyl groups. Examples o~ haloalkyl are:
fluoromethyl, difluoromethyl, tri~luoromethyl, chloromethyl,
trichloromethyl, 2,2,2-trifluoroethyl, 3,3,3-trichloroethyl,
2-chloroethyl, perfluoroethyl, 2-fluoroethyl and 1,1-
dichloro-2,2,2-trifluoroethyl.
Preferred compounds of the formula I according to the
invention are those wherein:
a) the phenyl group is substituted in the 2- and 3-position
by two chlorine atoms; or
b) R is cyano or trifluoromethyl; or
c) R is ethoxycarbonylethyl or 2-cyanoethyl.
:~6~ 3
More particularly preEerred Ls a group of active
substances of the formula I in which the phenyl group
is substituted in the 2- and 3-position by chlorine atoms,
Rl is trifluoromethyl or cyano, and R2 is ethoxycarbonyl-
ethyl or 2-cyanoethyl.
To be mentioned as preferred individual compounds are:
l-ethoxycarbonylethyl-3-(2,3-dichlorophenyL)-4-
trifluoromethylpyrrole, and
l-ethoxycarbonylethyl-4-cyano-3-(2,3-dichlorophenyl~-
pyrrole.
The novel compounds of the formula I are produced
according to the invention by treating a formylglycine
derivative of the formula II
CHO
, R -N (II),
CH;~-COOH
wherein R has the meaning defined under the forrnula I,
in the presence of a condensation agent, with a phenyl-
acetylene derivative of the formula III
~ c C-Rl (III)
j~
n
wherein Rl, R and n have the meanings defined under the
formula I.
Suitable in a particular manner as a condensation agent
is acetic anhydride. There can also be used however
:1~62~3
reagents such as dicyclohexylcarbodiimide, diisopropyl-
carbodiimide, trifluoroacetic anhydride or propionic
anhydride~ The process is performed either in an inert
organic solvent, such as toluene, xylene or mesitylene,
or without solvent in an excess of the condensation agent.
The reaction temperature is in general the boiling
temperature of the reaction mixture. Depending on the
solvent, the reaction is performed at a temperature of
between 90 and 150C, preferably between 110 and 140C~
The formylglycine deriva~lves of the formula II are
novel, and have been developed and produced ~pecially for
the syn~hesis of the compounds of the ~ormula I. They
thus likewise form subject matter of the present invention.
These compounds are obtained, in a known manner,
advantageously by formylation of a glycine ester of the
formula
R -NH-CH2-COOT,
wherein R2 has the meanings defined under the formula I,
and T is Cl-C4-alkyl, with formic acid~ or by formylation
o the corresponding glycine hydrochloride with an alkali
formiate and subsequent saponification of the ester group.
The compounds of the ~ormula III in which Rl is cyano
or Cl-C4-alkoxycarbonyl are known, or they can be obtained,
by processes analogous to known processes, by the addition
of bromine and subsequent double elimination of hydrogen
bromide from the corresponding derivatives of cinnamic acid.
Novel however are those compound~ o the formula III
in which Rl is trifluorome~hyl, and n is the number one
or two. The synthesis of these compounds has been specially
developed for the production of the compounds o~ the
formula Il The novel compounds of the ormula IIIa
~ "
:~;26
-- 5 --
// ~
c ~ C-CF
/ ~ 3 (IIIa),
/ -o
n
wherein R is trifluoromethyl, and n is the number one
or two, and also the production process involving the use
of these intermediates and further novel intermediates
form therefore further subject matter oE the present
invention.
By a process according to the invention, there are
obtained the 3-phenylpyrrole derivatives of the formula I,
in which Rl is trifluoromethyl, by cleaving off hydrogen
chloride from a styrene derivative of the formula IV
._~
~:: ~ ~
~ CH=CCl-CF3 (IV),
/ ~-~
R
n
wherein R and n have the meanings defined under the
: formula I, in the presence of a base, and reacting the
formed ~ri~luoromethyl-phenylacetylene derivative of
ths ~ormula lIla
111--G
// ~
~-C~ CF3 (IIIa3,
=-
Rn
wherein R and n have the meanings de:Eined under theformula I, in the presence oE a condensation a~ent, with
a formylglycine derivative of the formula II
c~lo
R -N~ (II)
CH ~COO~I
wherein R has the meaning defined under the formula I.
The reaction conditions in the ~irst step of the
above process (IV ~ IIIa, cleavage of hydrogen chloride)
correspond to those of customary procedures: there can
thus be used a large number of bases 7 such as inorganic
hydroxides, oxides, hydrogen carbonates or carbonates
of alkali metals and alkaline-earth metals, or or~anic
bases, such as tertiary amines, and the reaction can be
performed in an inert polar, protic or aprotic solvent.
Some typical reaction conditions for elimination reactions
of this type are distinguished by the following reagent
combinations: for example potassium hydroxide in methanol,
ethanol or isopropanol; sodium methylate in methanol;
potassium tert-butylate in tert-butanol; potassium tert-
butylate in ethanol; sodium amide in liquid ammonia;
potassium hydroxide in ethylene glycol dimethyL ether;
sodium hydroxide in water; or sodium hydroxide in dimethyl
sulfoxide~ The reaction mixtures are advantageously
heated or refluxed in carr~ing out the elimination
reactions. The second reaction step is performed according
~o the reaction conditions for the reaction (II
already described in the foregoing.
The starting products of the formula IV are likewise
novel. They can be obtained for example by reactions
according to the following reaction scheme 1:
~ 6 2
Scheme 1:
l ) Zn/DMF D
. j-CIlO * C13 32) HCl/H20 )( / oH
Rrl V I Rn V I I
( C~3~CO) 2 //
VII ~ ~-CH-CCl2-CF3
p~ridine X / I
/ _D o VIII
10-CH3
Zn/CH3CO~H R
¦ VIII ~ -CH-CCl-CF3
Rn
The intermediates of the formulae VII and VIII
wherein R and n have the meanings defined under the
formula I, which stages are passed through according to
scheme 1, have not hitherto been described in the
literature. They likewise form sub;lect matter of the
present invention.
.: ~
~ 2 ~
The novel pyrrole derivatives o~ the formula I
according to the inven~ion cons~itute a valuable enlargement
of the prior art, for it has been established ~hat the
novel pyrroles of the ormula I surprisingly exhibit a
microbicidal spectrum against phytopathogenic fungi and
bacteria which is very favourable for agricultural
requirements. They not only can be used in arable farming
or in similar fields of application for con~rolling harmful
microorganisms on cultivated plants, but can be additionally
used, in the protection of stocks, for preserving perishable
goods. Compounds of the formula I have very advantageous
curative, systemic and in particular preventive properties,
and can be used ~or the protection of numerous, especially
arable, crops. The microorganisms occurring on plants or on
parts of plants (fruit, blossom, foliage, stalks, tubers
or roots) o~ various cultivated crops can be inhibited or
destroyed with the active substances of the formula I, and
also parts of plants subsequently growing remain preserved
from such microorganisms.
The active substances are effective for example against
the phytopathogenic fungi belonging to the following
classes: Ascomycetes, for example Erysiphe, Sclerotinia,
Fusarium, Monilinia and H~lminthospori.um; Basidiomycetes,
~or example Puccinia, Ti.lletia and Rhizoctonia; and also
against the Oomycetes belonging to the Phycomycetes class,
such as Phytophthora. As plant protective agents, the
compounds of the formula I can be applied with a particularly
high degree o success against important harmful fungi from
the Fungi imperfecti family, for example against Cercospora or
Piricularia, and especially against Botrytis. Botrytis spp.
(B. cinera, B. allii) constitute with botrytis disease
on grapevines, strawberries, apples, onions and other fruit
1262~3
and vegetable varieties a significant economic loss
factor. Furthermore, some compounds of the formula I
can be successfully used for protecting perishable goods
of vegetable or animal origin. They combat mould fungi,
such as Penicillium, Aspergillus, Rhizopus, Fusarium,
Helminthosporium, Nigrospora and Alternaria, as well as
bacteria, such as butyric acid bacteria, and yeasts,
such as Candida.
As plant protective agents, the compounds of the
formula I exhibit, for practical application in
agriculture, a very favourable spectrum of activity for
protecting cultivated plants, without disadvantageously
affecting these by undesirable side effects.
The compounds can also be used as dressing agents for
the treatment of seed (fruits, tubers or grain), and of
plant cuttings to protect them from fungus infections,
and also against phytopathogenic fungi occurring in the soil.
The invention thus relates also to microbicidal
compositions, and to the use of the compounds of the
formula I for controlling phytopathogenic microorganisms,
especially fungi which damage plants~ and for preventing
an infestation on plants and on provisions of vegetable
or animal origin.
In addition, the present invention embraces also the
production of (agro)chemical compositions, whereby the
active ingredient is intimately mixed with one or more
substances or groups of substances described herein. Also
included is a process for treating plants or stored
provisions, which process comprises the application of the
compounds of the formula I, or of the novel compositions,
to the plants or parts of plants, or to the locus or the
substrate thereof.
~2~
- ~o -
Within the scope oE this invention, target crops ~or
plant protection are for example tlle ollowing varieties
of plants: cereals (wheat, `barley, rye, oats, rice,
sorghum and related cereals); beet ~sugar beet and fodder
beet); pomaceous fruit, stone fruit and sof~ fruit
(apples, pears, plums, peaches~ almonds, cherries,
strawberries, raspberries and blackberries); legumes
(beans, lentils, peas and soya-beans); oil plants (rape,
mustard, poppy, olives~ sunflowers, coco, castor-oil plants,
cocoa and groundnuts~; Curcurbitacea (pumpkins, cucumbers
and melons); fibre plants (cotton, flax, hemp and jute);
citrus frl1its (oranges, lemons, grapefruit and mandarins);
varieties of vegetables (spinach, lettuce, asparagus,
varieties of cabbage, carrots, onions, tomatoes, potatoes
and paprika); laurel plants (avocada, cinnamon and
camphor); or plants such as maize, tobacco, nuts, coffee,
sugar cane, tea, grapevines, hops, bananas and natural
rubber plants; and also ornamental plants (composites).
As protective agents for stored products, the compounds
of the formula I are used either in an unmodified form
or preferably together with auxiliaries customarily
employed in formulation practice, and are thus processed,
in a known manner, for example into the form of emulsion
concentrates, brushable pastes, directly sprayable or
dilutable solutions, diluted emulsions, wettable powders,
soluble powders, dusts or granulates, and also encapsu-
lations in for example polymeric substances. The application
processes, such as spraying, scattering, brushing or
pouring, and likewise the type o~ COmpoSitiQn~ are selected
to suit the objectives to be. achieved and the prevailing
conditions. Favourable applied amounts are in general
O.Ol to at most 2 kg o active ingredient per 100 kg of
~2~;Z3L43
- 11 -
substrate ta be protectecl; the amounts depend however
quite considerably on the nature (extent of surface area,
consistency, and moisture content) of the substrate and on
environmental influences thereon.
Within the scope of the present invention, stored
stocks and provisions are vegetable and/or animal na~ural
materials and products from further processing, for example
the plants which are listed in the following and which
have been taken out from thè natural life cycle, and parts
of ~hese plants (stalks, leaves, ~ubers, seeds, fruits and
grains) 5 the materials being in the freshly harvested
conditions or in the form resulting from further processing
(pre-dried, moistened, crushed, ground or roasted). The
following productive materials may be given as examples,
which however have no limiting character with respect to the
scope of this invention: cereals (such as wheat~ barley,
rye, oats, rice, sorghum and related cereals); beet (such
as carrots 9 sugar beet and odder beet); pomaceous fruit,
stone fruit and soft fruit (such as apples, pears, plums,
almonds and cherries); legumes (such as beans, lentils,
peas and soya-bean); oil plants (such as rape, mustard,
poppy, sunflowers, coco, castor-oil plants, cocoa and
groundnuts); Cucurbitacea (such as pumpkins, cucumbers and
melons); fibre pLants (such as cotton, ~lax, hemp, jute
and net~les); citrus fruits; varieties of vege~ables (such
as varietiçs of cabbage, onions, tomatoes, potatoes and
paprika); laurel plants (such as avocada, cinnamon and
camphor~; or plants such as maize, tobacco, nuts, coffee,
sugar cane, tea, chestnuts, hops, bananas, grass and hay.
Natural products of animal origin which may be mentioned
are in particular dried processed meat and fish products,
such as dried meat7 dried fish, meat concentrates, bone
~6~3
- 12 -
meal, fish meal and dried animal ~eed.
By treatment with compounds oE the formula 1, the
treated stored products are lastingly protected against
infestation by mould fungi and other undesirable micro-
organisms. Consequently9 the formation of toxic and
in part carcinogenic mould ungi or metabolic products
thereof, such as aflatoxines and ochratoxines, is prevented~
the material is kept from decomposing, and the quality
thereof is maintained high for a prolonged period of tima.
The process according to the invention can be applied to
all dry and moist provisions and stored goods which are
susceptible to microorganisms, such as yeasts, bacteria
and especially mould fungi.
A preferred process ~or applying the active substance
comprises spraying or wetting the substrate with a liquid
preparation, or mixing the substrate with a solid
preparation of the active substance. The described
conservation process forms a part of the present invention.
Active substances of the formu~a I are customarily
used in the form of ~ompositions, and can be applied,
simultaneously or successively, with further active
substances to the area, plants or substrate to be treated~
These further active substances can be fertilisers, trace-
element agents or other preparations in~luencing plant
growth. They can however also be selective herbicides,
insecticides, fungicides, bactericides, nematicides or
molluscicides, or mixtures of several of these prep-
arations, optionally together with carriers commonly
used in ~ormulation practice, tensides or other
additives facilitating application.
Suitable carriers and additives can be solid or liquid
and they corresponcl to the substances customarily employed
in ~ormulatioll prac~ice, ~or exalnplc: n~ural or re~eneraLe~
mineral substances, solvents, dispersin~ agents, wettlng
agents, adhesives, ~hickeners, binclers or ~ertilisers.
A preferred method of applying an active substance
o the formula I, or an (agro)chemical composition
containing at least one of these active substances,
is application to the foliage (leaf application). The
number o~ applications and the amounts applied are
governed by the extent of infestation with respect to
the pathogen (fungus genus) concerned. The active
substances of the formula I can however be ~ed into the
plant through the soil and then by way of the root system
(systemic action), this being achieved by the locus of the
plant being soaked with a liquid preparation, or by the
substances being introduced in solid form into the soil,
for example in the form of a granulate (soil application).
The compounds of the formula I can also be applied to the
seed grains (coating), the grains being for this purpose
either soaked with a liquid preparation of the active
substance or coated with a solid preparation. Further
forms of application are possible in special cases, for
example the specific treatment of the stalks or buds
of the plants.
The compounds of the formula I are used either in an
unmodified form or preferably together with auxiliaries
customarily employed in formulation practice, and are
thus processed, in a known manner, for example lnto the form
of emulsion concentrates, brushable pastes, directly
sprayable or dilutable solutions, diluted emulsions,
wettable powders, soluble powders, dusts or granulates,
and also encapsulations in for example polymeric sub-
:~26~3
- 14 -
stances. The application processes, such as spraying,
atomising, dusting, scattering, brushing or pouring,
and likewise the type of composition, are selected ~o
suit the objectives to be achieved and the given condi~Lon~.
Favourable applied amounts are in general between 50 g
and 5 kg of active substance (AS) per hectare, preferably
between 100 g and 2 kg of AS per hectare, and in particular
between 200 g and 600 g of AS per hectare.
The formulations, that is to say, the compositions
or preparations containing the active substance of the
formula I and optionally a solid or liquid additive, are
produced in a known manner, for example by t~e intimate
mixing and/or grinding of the active ingredient wi~h
extenders, such as with solvents, solid carriers and
optionally surface-active compounds (tensides).
Suitable solvents are: aromatic hydrocarbons, prefer-
ably the fractions C8 to C12, such as xylene mixtures or
substituted naphthalenes, phthalic esters, such as dibutyl-
or dioctylphthalate, aliphatic hydrocarbons, such as
cyclohexane or paraffins, alcohols and glycols, as well as
ethers and esters thereof, such as ethanol, ethylene glycol,
ethylene glycol monomethyl or -ethyl ethers, ketones
such as cyclohexanone, strongly polar solvents, such
as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl-
formamide, as well as optionally epoxidised vegetable
oils, such as epoxidised coconut oil, sunflower oil or
soybean oil; or water.
The solid carriers used, for example for dusts and
dispersible powders, are as a rule natural mineral illers,
such as calcite, talcum, kaolin, montmorillonite or
attapulgîte. In order to improve ~he physical properties,
.~ 2~ 3
- 15 -
it is possible to also add highly dispersed 5ilicic acid or
highly dispersed absorbent polymers. Suitable granulated
adsorptive carriers are porous types, for example pumice,
ground brick, sepiolite or bentonite; and suitable
nonsorbent carriers are materials such as calcite or sand.
There can also be used a great number of pre-granulated
materials o inorganic or organic nature, such as in
particular dolomite or ground plant residues, for example
cork powder or sawdust.
Particularly advantageous additives facilitating
application and rendering possible a marked reduction in
the amount of active substance applied are moreover
natural (animal or vegetable) or synthetic phospholipides
from the class comprising the cephalins and lecithins,
for example: phosphatidylethanolamine, phosphatidylserine,
phosphatidylcholine, sphingomyelin, phospha~idylinosite
phosphatidyl glycerol, lysolecithin, plasmalogenes or
cardiolipin, which can be obtained for example from animal
or plant cells, especially from the brain, heart, liver,
egg yokes or soya beans. Applicable commercial mixtures
are for example phosphatidylcholine mixtures. Synthetic
phospholipides are for example dioctanoylphosphatidyl-
choline and dipalmitoylphosphatidylcholine.
Depending on the nature of the active ingredient o~
the formula I to be formulated, suitable surface-active
compounds are nonionic, cationic and/or anionic tensides
having good emulsifying, dispersing and wetting properties.
By 'tensides' are also meant mixtures of tensides~
Suitable anionic tensides are both so-called water-
soluble soaps as well as water-soluble, synthetic
surface-active compounds.
Soaps which are applicable are for example the alkali
~26~3
- ~6 -
metal, alkaline-eart~ metal or optionally substituted
ar~monium salts oE higher fatty acids (C10-C~2), for example
the Na or K salts o oleic or stearic acid, or of natural
fat~y acid mixtures~ whlch can be obtained for example Erom
coconut oil or tallow oil. Also to be mentioned are the
fatty acid-methyl-laurine salts.
So-called synthetic tensides are however more
frequently used, particularly fatty sulfonates, fatty
sulfates, sulfonated benzimidazole derivatives or
alkylarylsulfonates. The fatty sulfonates or sulfates
are as a rule in the form of alkali metal, alkaline-earth
metal or optionally substituted ammonium salts, and
contain an alkyl group having 8 to 22 C atoms, 'alkyl'
including also the alkyl moiety of acyl groups, for
example the Na or Ca salt of ligninsulfonic acid, cf
dodecylsulfuric acid ester or of a fatty alcohol sulfate
mixture produced from natural fatty acids. Included among
these are also the salts of sulfuric acid esters and
sulfonic acids of fatty alcohol ethylene oxide adducts.
The sulfonated benæimidazole derivatives preferably con~ain
2 sulfonic acid groups and a fatty acid group ha~ing
8 - 22 C atoms. Alkylarylsulfonates are for example the
Na~ Ca or triethanolamine salts of dodecylbenzeneæulfonic
acid7 of dibu~ylnaphthalene~ulfonic acid or of a
naphthal~nesulfonic acld-formaldehyd2 condensation product.
Also suitable are correspondin~ phosphates, for example
salts of the phosphoric ester of a p-nonylphenol-(4~14)-
ethylene oxide adduct,
Suitable nonionic tensides are in particular polyglycol
ether derivatives of aliphatic or cycloaliphatic alcohols,
satura~ed or unsatura~ed fatty acids and alkylphenols,
which can contain 3 to 30 glycol ether groups and 8 to 20
~L~623l~3
carbon atoms in the (aliphatic) hydrocarbon radical and
6 to 18 carbon atoms in the alkyl moiety of the alkyl-
phenols.
Further suitable nonionic tensides are the water-
soluble polyethylene oxide adducts, which contain 20 to
250 ethylene glycol ether groups and 10 to 100 propylene
glycol ether groups, with polypropylene glycol, ethylene-
diaminopolypropylene glycol and alkylpolypropylene glycol
having 1 to 10 carbon atoms in the alkyl chain. The
compounds mentioned usually contain 1 to 5 ethylene
glycol units per propylene glycol unit. Examples of
nonionic tensides which may be mentioned are: nonylphenol-
polyethoxyethanol, castor oil polyglycol ethers,
polypropylene/polyethyleneoxy adducts, tributylphenoxy~
polyethoxyethanol, polyethylene glycol and octylphenoxy-
polyethoxyethanol. Suitable also are fatty acid esters
of polyoxyethylenesorbitan, such as polyoxyethylene-
sorbitan-trioleate.
In the case of the cationic tensides, they are in
particular quaternary ammonium salts which contain as
N-substituents at least one alkyl group having 8 to 22
carbon atoms and, as fur~er subs~ituents, lower,
optionally halogenated alkyl, bPnzyl or lower hydroxyalkyl
groups~ The salts are preferably in the form of halides,
methyl sulfates or ethyl sulfates, for example stearyl-
trimethylàmmonium chloride or ben2yldi~2-chloroethyl)-
ethylammonium bromide. In the field covering stored
provisions, the additives which are preferred are those
that are safe for human and animal foodstuffs.
The tensides customarily used in formulation practice
are described, inter alia, in the following publications:
~621~3
~ 21489-6810D
"Mc Cutcheon's Detergents and Emulsifiers Annual"
MC Publishing Corp., Ridgewood, Wew Jersey, 1981:
H. Stache, "Tensid-Taschenbuch" (Tenside Handbook,
2nd Edition, C. Hanser Verlag, Munich/Vienna, 1981, and
M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III,
Chemical Publishing Co., New York, 1980-1981.
The agroehemical preparations contain as a rule 0.1 to
99%, particularly 0.1 to 95~, of active ingredient of the formula
I, 99.9 to 1~, especially 99.8 to 5%, of a solid or liquid addi-
tive, and 0 to 25%, in particular 0.1 to 25%, of a tenside.
Whereas commereial products are preferably in the form
of concentrated compositions, the preparations employed by the
end-user are as a rule diluted.
The compositions ean contain further ad~itives, such as
stabilisers, anti~oaming agents, viscosity regulators, binders and
adhesives, as well as fertilisers or other aetive ingredients for
obtaining special effeets.
(Agro)chemieal eompositions of the types deseribed herein
likewise form part of the present invention.
The ~o~lowing Examples serve to further illustrate ~he
invention of this divisional applieation and of the parent
applieation witheut limiting the seope thereof. Pereentage values
and 'parts' relate to weight. There are also used the following
symbols: h = hour; RT = room temperature; abs. = absolutely
anhydrous; DMF = dimethylformamide; and pressure ~alues are in
millibar (mb) or bar (b).
1~62
- 19 -
Production Examples
Example Pl: N-EthoxYcarbonylethYl N-formy~L~l~cine
115.5 g of N-et~oxycarbonylethyl~N-formylglycine
ethyl ester are dissolved in 150 ml of ethanol, and the
solution is cooled to 0C. To it is then added dropwise
a mixture of 28.0 g of potassium hydroxide, 60 ml of
wa~er and 120 ml oE ethanol. The reaction mixture is
stirred for 18 h at RT, and is subsequently concentrated
by evaporation under reduced pressure. After the addition
of a small amount of water, the mixture is acidified with
concentrated hydrochloric acid to pH 1. By extraction
wlth chlorofonn, drying, and concentration of the organic
phase by evaporation, there is obtained N-ethoxycarbonyl-
ethyl-N-formylglycine in the form of a yellowish oil
(compound No. 1.3).
Example P2: N-(2-Cyanoethyl~-N-formYl~lycine
A mixture of 21.0 g of N-(2-cyanoethyl)-glycine
ethyl ester and 18.3 g of formic acid is refluxed for
2 h. After concentration of this mixture under reduced
pressure, the residue is taken up in 50 ml of ethanol,
and cooled to 0C; there is then added dropwise a solution
of 25.5 g of potassium hydroxide and 40 ml of water in
80 ml of ethanol. After the reaction solution has warmed
up to room temperature, the solvent is evaporated off, and
the residue is acidified to pH 1 with conc. hydrochloric
acid. The mixture is saturated with sodium chloride and
subsequently extracted with ethyl acetate. The combined
organic extracts are concentrated by evaporation to thus
obtain N-(2-cyanoethyl)-~-formylglycine, m.p. 112-114C
(compound No. 1.1).
~2~;Z3L~
- 20 -
x~æ~ (2-Chloro-3,3,3-trifluoropropen-l-y1)-2,3-
dichlorobenzene
a) (2,2-DlchLoro-3l3,3-trifluoro-l-hydroxypropyl2-2~3
dichlorobenzene
A suspension of 35.0 g of 2~3-dichlorobenzaldehyde,
41.2 g of l,l,l-trichloro-2,2,2-trifluoroethane and l6.4 g
of zinc powder in 360 ml of DMF is stirred for 66 h at RT,
and subsequently taken up in a mixture of 600 ml of 10%
hydrochloric acid and 600 g of ice. By extraction with
ether, drying, and concentration of the organic extracts
by evaporation3 there is obtained (2,2-dichloro-3,3,3-
trifluoro-l-hydroxypropyl~-2,3-dichlorobenzene in the form
of a yellow oil (compound No. 5.lO).
b) (l-Acetoxy-2~2-dichloro-3,3,3-trifluoropropy~)-2,3-
dichlorobenzene
33.0 g of pyridine are added to a mixture of 57.0 g
of ~2,2-dichloro-3,3,3-trifluoro-l-hydropropyl)-2,3-
dichlorobenzene and 39.1 g of acetic anhydride, and the
whole is stirred for 4 h at RT. The mixture is poured
into ice-water, acidified with 10% hydrochloric acid,
extracted with ether and dried; the ethereal extracts are
subsequently concentrated by evaporation to thus obtain
(l-acetoxy-2,2-dichloro-3,~,3-trifluoropropyl~-2,3-
dichlorobenzene, m.p. 92-95C from ethanol
(compound No. 6.10).
c) A solution of 59.0 g of (1-acetoxy-2,2-dichloro-3,3,3-
trifluoropropyl)-2,3-dichlorobenzene in 350 ml o acetic
acid is heated to 40C, and 13.0 g of zinc powder are added
portionwise. To effect completion of the reaction, the
reaction mixture is heated at 90C for 3 hours. In further
processing, the reaction mixture is taken up in ice-water,
'6~ 3
- 21 -
and extracted with ether. The combined organic phases
are washed with water, sodium hydrogen carbonate solution
and sodium chloride solution; they are then dried over
magnesium sulfa~e, and concentrated by evaporation to thus
obtain (2-chloro-3,3,3-trifluoropropen-l-yl)-2,3-dichloro-
benzene in the form of yellow oil (compound No~ 4.10).
Example P4: 1-EthoxycarbonYlethyl-3-(2 ? 3-dichl~phenyl~-4
trif uoromethylpyrrole
a~ 2~3-Dichloro~ 3,3-trifluoropro~y~-1-Yl)-benzene
To a solution of 31.7 g of ~2-chloro-3,3,3-trifluoro-
propen-l-yl)-2,3-dichlorobenzene in 50 ml of tert-butanol,
there is added dropwise at RT a solution of 14.1 g of
potassium tert-butylate in 750 ml of tert-butanol in such
a manner that the temperature of the reaction solution
does not exceed 30C. After continued stirring at RT for
18 h, the mixture is taken up in ice-water and extracted
with ether~ The organic phases are combined, washed with
water and sodium chloride solution, and conce~trated by
evaporation. There is thus obtained~ after distillation
in vacuo, 2,3-dichloro-(3,3,3-tri~luoropropyn-1-yl)-benzene
in the form of colourless oil, b.p. 92-98C at 22 mb
(compound ~o. 2.27).
b) 23.9 g of 2,3-dichloro-(3,3,3-trifluoropropyn-1-yl)-
benæene and 20.3 g of N-e~hoxycarbonylethyl-N-ormyl-
glycine are dissolved in 100 ml of acetic anhydride, and
the solution is refluxed for 24 h. The mixture is
concentrated by evaporation under reduced pressure; the
residue is subsequen~ly taken up in toluene, and puriEied
by chromatography through silica gel. The solvent is
evaporated off, and from the eluate i5 thus obtained
1~621~3
- 22 -
1 ethoxycarbonylethyl-3-(2,3-dichLorophenyl)-4-trifluoro-
methylpyrrole in the form oE a colourless oil
(compound No. 3.117).
Example P5: 4-Ethoxycarbonyl-1-(2-cyanoethyl)-3-pheny
~Q~
17.4 g of phenylacetylenecarboxylic acid ethyl ester
and 15.6 g of N-(2-cyanoethyl)-N-~ormylglycine are
dissolved in lOO ml of acetic anhydride, and the solution
is refluxed for 24 h. The mixture is concentrated by
evaporation under reduced pressure; the residue is then
i taken up in toluene, and purified by chromatography through
silica gel. The solvent is evaporated off, and from the
eluate is obtained 4-ethoxycarbonyl-1-(2-cyanoethyl)~3-
phenylpyrrole in the form of a yellow oil (compound No. 3.3).
Example P6: l-(2-Cyanoethyl)-3-(2,3-dichlorophenyl)-4
tr~fluoromethylpyrrole
23.9 g of 2,3-dichloro-(3,3,3-trifluoropropyn-1-yl~-
benzene and 15.6 g of N-(2-cyanoethyl)-N-formylglycine
are dissolved in 100 ml of acetic anhydride, and the
solution is refluxed for 24 h. The mixture is concentrated
by avaporation under reduced pressure, the residue is then
taken up in toluene, and purified by chromatography through
silica gel. The solvent is evaporated off, and from the
eluate is obtained l-(2-cyanoe~hyl)-3-~2~3-dichlorophenyl)-
4-trifluoromethylpyrrole, m.p. 83-R5C from etherl~exane
(compound No. 3.28~.
There are obtained in an analogous manner the
in~ermediates and final products listed in the following
Tables.
~ .
- 23 -
T ab l e 1: /c~lo
R - N
CH2-cooH
C omp O No . R2
1.1 -cH2-cH2-cN
1.2 2 H2 COOCH3
1.3 2 2 COOC2H5
1.4 -cH2-cH2-cooc3~7-i
1.5 2 2 OC3117 n
1,6 ~c~2-cH2-cooc4H9-n
1.7 -CH=CH2
1.8 2 CH2 Cl
D ~
1.9 -CH2-CH2-So2~ CH3
: 1.10 -cH2-c~2-so2-~ Br
1.11 -CH2-CH -SO -C H
1.12 ~cH2-cH2~Br
~2~3
-- 2~ --
Table 2: .
F - C-- C - Rl
Comp .No ~ ~1
.. _ ... . ~ .... _ ._ ~ .. . .. .. _
2.1 C6H5- CF3
2.2 C6H5 COOCH3
2.. 3 C6~15 COOC2H
2.4 C6H5 CN
2.5 2-Cl-C 11 - CF3
2.6 2-cl-c6H4- COOC2H
2.7 2-Cl-C H - CN
2.8 2-Cl-C H - 3H
2.9 3-Cl-C H - 3
2.10 3-Cl-C6H4- CN
2.11 3-Cl-C H - COOC2H
2.12 3-Cl-C H - 4~
2.13 2-CF3-C6H ~ COOCH3
2.14 2-CF3-C ~l - COOC2H
2.15 2-CF3-C H - CF3
2.16 2-CF3-C H - CN
2.17 4-Cl-C H - COOCH3
2.18 4-Cl~C H - CF3
2.19 4-Cl-C H - CN
2.20 2-cF3-4-cl-c H - CN
2.21 2-CF3-4-Cl-C H - CN
2.22 2_cF3_4_cl_c6H3~ COOCH3
2.23 2-Cl-4-Cl-C6H3_ CN
21~3
- 25 ~
Table 2 (continuation)
_ . .
Comp .No . E Rl
__ - . ~ _ ~ ..
2 . 24 2-C1-4-CI-C H ~ CF3
2 . 25 2-cl-4-cl-c6H3- 2 5
2 . 26 2-cl-3-cl-c6~l3- CN
2 . 27 2-Cl -3-Cl-C6H3- CF3
2 . 28 2-C1-3-cl-c6H3_COOCH3
2 . 29 2-cl-3-cl-c6H3-COOC2H5
2 . 30 2-cl-3-cl-c6H3-CC3H7~i
2 . 31 2-cl-3-cl-c6H3- 3H7 n
2 . 32 2-Cl -3-Cl-C6H3-C54H9-n
2 . 33 2-cl-3-cl-c6H3- 4H9 s
2 ~ 34 2-Cl -3-Cl -C6H3- OC4~9
2 . 35 2-Cl -3-Cl -C6H3- 3
2 . 36 2-cl-4-cF3-c6H3- CN
2 . 37 2-cl-4-cF3-c6~3-- COOCH3
2 . 38 2-Cl -4-CF3-C6H3- COOC2H5
2 . 39 4-CH -C H 3
2 . 40 4-CH -C H - CN
2 ~ 41 4-CR3-C H ~ COOC113
2 . 42 2-F-C6H4- CF3
2 .43 2-F-C6H4- CN
2 . 44 2-F-C6H4- COOCH3
~LZ~ 3
- 26 -
Table 3:
F~ R
Il 11
;/-
R2
Cc~p.No. E ¦ Rl R2
.. ~ . . . , . _ . .
3.1 C6H5- CF3 -CH2-CH2-CN
3.2 C6H5- COOCH3 -CH2-CH2-CN
3.3 C6H5- COOG2H5 -cH2-cH2-cN
3.4 C6H5- CN -cH2-cH2-cN
3.5 2-Cl-C H - CF3 -cH2-cH2-cN
3.6 2_cl c6H4_CUOC2H5 -cH2-cH2-cN
3.7 2-Cl-C H - CN ~cH2-cH2-cN
3.8 2-Cl-C H - COOCH3 -cH2-cH2-cN
3.9 2-Cl-C H ~ 3H7 i -cH2-cH2-cN
3.10 3-Cl-C H ~ CF3 -cH2-cH2-cN
3.11 3-Cl-~6~14- CN -cll2-cl~2-cN
3.12 3-cl-c6H4- COOC2H5 -cH2-cH2-cN
3.13 3-Cl-C H ~ 4H9 n -cH2-cH2-cN
3.14 2-F.C6H4- CF3 -cH2-cH2-cN
3.15 6H4 CN -cH2-cH2-cN
3.16 2-F-C6H4- COOCH3 -cH2-cH2-cN
3.17 2-CF ~C H ~2H5 -cH2-cH2-cN
3.18 2-CF3-C6H4-COOCH3 -cH2-cH2-cN
- 27 -
Table 3 (continuation)
Comp . No . E 1 R2
~_ .. ~ . . ._ ._ ~ ~
3.19 2-CF -C H - CF3 -cH2-cH2-cN
3 . 20 2-CF -C H - CN -c}l2-cH2-cN
3. 21 4-cl-c6H4- COOCH3 -cH2-cH2-cN
3. 22 4-cl-c6H4- CF3 -cEl2-cH2-cN
3 . 23 4-Cl -C H - CN
6 4 -cH2-cH2-cN
3 . 24 2-cl-4-cl-c6H3- CF3 -cH2-cH2-cN
3 . 25 2-Cl-4-Cl -C6H3_ CN -cH2-cH2-cN
3 . 26 2-cl-4-cl-c6H3- COOCH3 -cH2-cH2-cN
3 . 27 2-cl-3-cl-c6H3- CN -cH2-cH2-cN
3 . 28 2-C1-3-Cl-C6H3- CF3 -cH2-cH2-cN
3. 29 2-cl-3-cl-c6N3- COOCH3 -cH2-cH2-cN
3, 30 2-cl-3-cl-c6H3- COOC2H5 -cH2-cH2-cN
3 . 31 2-cl-3-cl-c6H3- COOC -H -i -cH2-cH2-cN
3 . 32 2-cl-3-cl-c6H3- 3H7 n -cl~2-cH2-cN
3, 33 2-cl-3-cl-c6H3- 4H9 n -c~l~-cH2-cN
3 . 34 2-cl-3-cl-c6H3- C4~9 5 -cH2-cH2-cN
3 . 3S 2 -C1-3 -Cl -C6 K3- 4H9 i -CH2~CH2-CN
3.36 2-cl-4-cF3-c6H3- CF3 -cH2-C}l2- CN
3. 37 2-cl-4-cF3-c6H3- CN . -cH2-cH2-cN
3 . 38 2-C1-4-CF3-C6H3-COOCH3 -cH2-cH2-cN
3 . 39 4-CH -C H - CF
3 6 4 3 -cH2-cH2-cN
3, 40 4-CH3-C H ~ CN -C~l2-cH2-cN
3.41 4-CH3~C H ~ ¦COOCH3 l -C~l2~CH -CN
~2~3
- 28 -
~ (continuation)
Comp . No . E 1 R2
__ . . . _ .. ~
3.42 2-cF3~ cl-c6~3- CN -cH2-cH2-cN
3,43 2-cF3-4-cl-c6H3-CF3-cH2-cH2-cN
3.44 2-cF3-4-cl-c H _ COOCH3 -cH2-cH2-cN
3.45 2-cl-3-cl-c6H3- CN2 2 COOCH3
3.46 2-cl-3-cl-c6H3- ~F3-2 2 OOCH3
3.47 2-cl-3-cl-c6H3-COOCH32 H2 COOC113
3.48 2-cl-3-Cl-c6H3-COOC2H5-c~l2-c~2-coocH3
3.49 2-Cl-3-Cl C6H3-3H7 i 2H2 COOCH3
3.50 2-cl-3-cl-c6H3-3H7 n 22 OOCH3
3~51 2-cl-3-cl-c6~l3-4Hg n 2H2 COOCH3
3.52 2-cl-3-cl-c6H3-4H9 5 22 OOCH3
3.53 2-cl-3-cl-c6H3-COOC4Hg-i 22 COOCH3
3.54 2-C1 4-cF3-c6H3- CF3 -c~2-cH2-coocH3
3~5 2-cl-4-cF3-c6H3-CN2 2 OOCH3
3.56 2-cl-4-cF3-c6H3-COOCH3CH2 CH2 COOCH3
3.57 4-CH -C H ~ CF32 2 OOCH3
3.58 4-CH3-C H ~ CN-CH2-CH2-COOCH3
3,59 4-CH3-C H - COOCH32 2 OOCH3
3.60 2-CF3-4-Cl-C H -CN2 2 COOCH3
3.61 2-cF3-4-cl-c H -CF32 2 OOCH3
3.62 2-cF-4-cl-c6H3-COOCH3-CH2-CH -COOCH
3.63 C6H5- CF3-CH2-CH2-COOCH3
3.64 ¦C6ils- ¦ COOCH3f -CH2-CH2-COOcH3
3.65 C6H5- COOC2115¦ -cH2-cH2-coocH3
J~Z~ 3
29
Table 3 (con~inu~tion)
Comp.No. E 1 ; R2
_ _ _ ._ . _ .
3.66 C6H5- CN 2 2COOCH3
3.67 2_Cl_C6H4_CF3 2 2OOCH3
3.68 2-Cl-C H - COOC2H5 2 2 COOCH3
3.69 2-Cl-C H - CN 2 2 COOCH3
3.70 2-Cl-C H - COOCH3- 2 2 CoocH3
3.71 2-Cl-C H - 3H7 i 2 2OOCH3
3.72 3-Cl-C6H4- CF3 2 2OOCH3
3.73 3-cl-c6H4- CN 2 2COOCH3
3.74 3-Cl-C 11 -COOC2H5 2 2COOCH3
3.75 3-Cl-C H - 4Hg n 2 2CoocH3
3.76 2-F-C6H4- CF3 2 2OCH3
3.77 2-F-C6H4- CN 2 2COOCH3
3.78 2-F C 11 -COOCH3 ` 2 2CoocH3
3~7g 2-CF3-C H - COOC2H5 2 GH2 COOCH3
3.80 2-C~3-C H - COOCH3 2 2 OOCH3
3.81 2-CF3-C H - CF3 H2 CH2 COOCH3
3 . 82 2-CF -C H - CN 2 2 H3
3.83 4-Cl-c6H4- COOCH3 2 2COOCH3
3.84 4-Cl-C6H~- CF3 2 2COOCH3
3.85 4-Cl-C H CN 2 2COOCH3
3.86 2-cl-4-cl-c6H3-CF3 2 2COOCH3
3.87 2-cl-4-cl-c6H3- CN ~2 COOCH3
3.88 2-cl-4-cl-c6H3-COOCH3 2CH2 COOCH3
3.89 2-Br-c6H4- 2 200CH3
~2~ L3
- 30 -
Table 3 (con~inuation)
Comp . No . E 1 R2
.. .. . .. ~ .. _ .. _ ~ _. _
3.90 C6~5- CF3 2 2 COOC2H5
3.91 C6H5- COOCH3 -C112-CH -COOC H
3.92 C6H5- COOC2H5 2 2 OOC2H
3.93 C6H5- CN 2 H2 COOC2H5
3.94 2_cl_c6H4 3 2 2 OC2H
3.95 2-Cl-C ll - COOC2H5 -CH2-CH -COOC H
3.96 2-Cl-C H - CN -CH2-CH -COOC H
3.97 2-Cl-C H - COOCH3 2 2 COOC2H
3.98 2-Cl-C H - 3H7 i 2 2 COOC2H
3.99 3-Cl-C6H~- CF3 -CH2-CH -COOC H
3.100 3-Cl-C6H4- CN 2 2 COOC2H
3.101 3-Cl-C6H4- COOC2H5 2 2 0oc2H
3.102 3-Cl-C6H4- 4 9 n -CH2-CH2-COOC H
3.103 2-F-C6H4- CF3 2 2 COOC2H
3,104 2-F-C6H4- CN -C1l2-cH2-coo2H5
3.105 2-F-C6H4- COOCH3 2 2 OC2H
3.106 2-CF -C H - COOC2~15 2 H2 COOC2H5
3.107 2-CF3-C H - COOCH3 2 H2 COOC2H
3.108 2 c~3_c6H4_ CF3 2 2 COOC2H
3.109 2-CF -C H - CN -CH2-CH -COOC H
3.110 4-Cl-C6H4- COOCH3 2 2 OOC2H
3.111 4-Cl-C6H4_ F3 -C1l2-cH2-cooc H
3.112 ¦4_C1_C6H4_ ¦ CN ¦ 2 H2 COOC2H
3.113 ¦2-CI-4-C1-C6H3-¦CF3 1 -C1l2-cH2-cooc H
Z~4L3
- 31 -
able 3 tContinuation)
Comp.No.¦ E 1 : R2
~__ __ . _ _ .. ... .. --_
3.114 2-cl-4~cl-c6~l3- CN -CH2-CH -COOC H
3.115 2-C1-4-Cl-C 11 ~COOC,13 -C1~2 C112-COOC ~I
3.116 2-cl-3-cl-c6H3- CN -CH2-CH -COOC H
3.117 2-cl-3-cl-c6~l3- CF3 2 2 COOC2H5
3.118 2-C1-3 Cl-c6H3-COOCH3 -CH2-CH -COOC ~l
3.119 2-cl-3-cl-c6H3~COOC2H5 -CH2-CH -COOC H
3.120 2-cl-3-cl-c6H3- C3H7 i 2 2 Cooc2H5
3.121 2-C1-3-Cl-c6H3_ 3H7 n -CH2-CH -COoC ~
3~122 2-cl-3-cl-c6H3- 4~g n ~2 Cooc2H5
3.123 2-cl-3-cl-c6H3- 4Hg s 22 COOC2H5
3.124 2-cl-3-cl-c6H3-Cooc4ll9-i 2H2 COOC2H5
3.125 2-cl-4-cF3-c6H3- CF3 22 COOC2H5
3.126 2-cl-4-cF3-c6H3- CN 22 COOC2H5
3.127 2-cl-4-cF3-c6H3- COOCH3 2H2 COOC2H5
3.123 4-CH3-C ~ ~ CF3 22 COOC2H5
3.129 4-~H3-C6~1 ~ CN -CH2-CH -COOC H
3.130 4-CH -C H - COOCH3 2 2 COOC2H5
3.131 2-CF3-4-Cl-C U - CN 2 2 COOC2H5
3.132 2-cF3_4_cl_c6H3_ CF3 2 2 COOC2H5
3.133 2-cF3-4-cl-c H - COOCH3 2 2 COOC2H5
3.134 2-cl-3-cl-c6~l3- CN ~cH2-cH2-cooc3H7-n
3~135 2-Cl-3-Cl-C 11 CF3 -CH2-C~12-coOc H
3.136 ¦2-C1-3-Cl-C6~13- ¦COOCH3 ¦ -CH2-CH2-COOC H -n
3.137 ¦2-C1-3-C1-C6~13- ¦COOC2~5 ¦ -C~l2-CH2-COOC ~1 -n
i2
- 32 -
Table 3 tcontinuation)
Comp. No. E Rl R2
~_ _ _ _ .. . _ . _
3.138 2-cl-3-cl-c6H3-C3H7 i -CH2-CH -COOC H -n
3.139 2-cl-3-cl-c6H3- 3 7 n -C~l2-cH2-cooc H -n
3.140 2-cl-3-cl-c6H3- 4H9 n -cH2-cH2-cooc3H7-n
3.141 2-cl-3-cl-c6H3- 4 9 8 -CH2-CH -COOC H -n
3.142 2-cl-3-cl-c6H3~ 4 9 i -CH2-CH -COOC H -n
3.143 2-cl-4-cF3-c6H3- CF3 -CH2-CH2-COOC H -n
3.14~ 2-cl-4-cF3-c6H3- CN -cH2-cH2-cooc3H7-n
3.145 2-cl-4-cF3-c6H3- COOCH3 ~cH2-cH2-cooc3H7-n
3.146 4-CII -C H - CF3 -CH2-CH -COOC H -n
3.147 4-CH -C H - CN -CH2-C~ -COOC H -n
3.148 4-CII -C H - COOCH3 ~cH2-cH2-cooc3H7-n
3.149 2-cF3-4-cl-c6H3- CN ~cH2-cH2-cooc3H7-n
3.150 2-CF3-4-Cl-C H _ CF3 -CH2-CH -COOC H -n
3.151 2-CF3-4-Cl-C H - COOCH3 -CH2-CH2-COOC H -n
3.152 C6H5- CF3 -CH2-CH -COOC H -n
3.153 C6H5- COOCH3 -C~2-C~ -COOC H -~
3.154 C6H5- COOC2H5 ~cH2-c~2-cooc3~7-n
3.155 C6H5- CN -CH2-CH -COOC 11 -n
3.156 2-Cl-C H - CF3 -CH2-CH -COOC H -n
3.157 2-Cl-C H - COOC2H5 -cH2-cH2-cooc3H7-n
3.158 2-cl-c6H4- CN -CH2-CH -COOC H -n
3.159 2-Cl-C H COOCH3 -CH~-cH2-cooc3~l7-~
3.160 ¦2-C1-C H - ¦ 3H7 i ¦ -CH2-CH -COOC H -n
- 33 -
Table 3 (continuation)
Comp . No E Rl : R2
~ ~ , _ _, _ _ _
3.161 3-cl-c6~1~- CF3 ~c}l2-cH2-cooc3~l7-n
3.162 3-cl-c6H4- CN -CH2-CH -COOC H -n
3.163 3-cl-c6H4- COOC2H5 ~cH2-cH2~cooc3~7-n
3.164 3-cl-c6H4- 4~l9 n ~cll2-c~l2-cooc3}l7-n
3.165 2 F~C6H4 CF3 -CH -CH -COOC H -n
3.166 2-F-c6~l4- CN ~C112-C}12-COOC31l7-n
3.167 2-F-C6H4- COOCH3 -CH2-CH -COOC H -n
3.168 2-CF -C H - COOC2H5 -CH2-CH -COOC 11 -n
3.169 2-CF3-C H ~COOCH3 2 H2 COOC3H7 n
3.170 2-CF -C H - CF3 -CH2-CH -COOC H -n
3.171 2-CF3-C ~1 ~ CN ~cH2_cH2_cooc3H7-n
3.172 4-Cl-C6H4- COOCH3 -CH2-CH -COOC H -n
3.173 4-Cl-C6H4- 3 -CH2-CH -COOC H -n
3.174 4-Cl-C6H4- CN -CH2-CH -COOC H -n
3.175 2-cl-4-cl-c6H3- 3 ` -CH2-CH -COOC H -n
3.176 2-C1-4-Cl-C6H - CN ~cH2-cH2-cooc3H7-n
3.177 2-cl-4-cl-c6H3-COOCH3 ~cHz-cH2-cooc3H7-n
3.17B 2-C1-3-Cl-C6~3_CN -CH-CH
3.179 2-cl-3-cl-c6H3- CF3 -CH-CH
3 .180 2-cl-3-cl-c6H3- CN -cH2cH
3.181 2-cl-3-cl-c6H3 ~ CF3 -c~2-cH
//
3.182 2-cl-3-cl-c6H3 ~ CF3 CH2-C112-52- ; ~-CII
3.183 2-cl-3-cl-c6H3- CN 2 CH2 S02 ; j -CH3
--o
43
- 34 -
Table 4
E - CH = CCl - CF3
Comp. No. E
. 1 C6~15-
4 . 2 2-Cl-C H -
4 . 3 3-C 1 -C6H4-
4 ~ 4 4-Cl -C6H4-
4 . 5 2-F-C6H4-
4 . 6 2-Br-C6H4-
4 . 7 2-CF3-C H -
4 . 8 2 . CF-4-cl-c6H3-
4 . 9 2-Cl-4-Cl -C 11 -
4 .10 2-cl-3-cl-c6H3-
4 .11 2-Cl-4 -CF3-C6H3-
4 .12 4-~ ~13-C6H4-
2:~3
- 35 -
Table 5
E - CH - CC12 ~ CF3
OH
Comp. No. E
. _ . ..
5.1 C6H5-
5 o 2 2-Cl-C6H4-
5 . 3 3-Cl-C6H4-
S . 4 4-Cl -C~H4-
5, 5 2-F-C6 H4-
5 . 6 2-~r-C61~4-
5, 7 2-CF3-C H -
5 . ~ 2_CF3_4_Cl_C6H3_
5 . ~ 2-cl-4-cl-c6H3-
5. 10 2 Cl-3-Cl-C6~3-
5 .11 ~-cl-~-cF3-c6H3
5 . 12 4-CH3-C H
~;~6~L43
- 36 -
Table 6
E - CH - CC12 - CF3
O-COC~3
Comp. No. E
_ _ _
6.1 C6H5-
6.2 2-Cl-C6H4
6.3 3-Cl-C6H4-
6.4 4-Cl-C6H4-
6.5 Z-F-C6H4-
6.6 2-~r-C6H4-
6.7 2-CF -C6H -
6.8 2-CF3-4-Cl-C H -
6.9 2-Cl-4-Cl-C6~3-
6.10 2-Cl-3-Cl-c6H3-
6.11 2-Cl-4-CF3-C6H3-
6.12 4-CH3-C6H4-
1~2~3
- 37 -
Formulation Examples for liquid active in~redients of
the formula I ~% - per cent b~ wei~ht)
Fl Emulsion concentrates a) b) c)
_
active ingredient from Table 3 25% 40% 50%
calcium dodecylbenzenesulfonate 5% 8% 6%
castor oil-polyethylene glycol 5% - -
ether (36 mols of ethylene oxide)
tributylphenol-polyethylene glycol 12% 4%
ether (30 mols of ethylene oxide)
cyclohexanone - 15% 20%
xylene mixture 65% 25% 20%
Emulsions of any required concentration can be produced
frDm concentrates of this type by dilution with water.
F2. Solutions a) b) c~ d)
active ingredient from Table 3 ~0% 10% 5% 95%
ethylene glycol-monomethyl ether 20% - - -
polyethylene glycol (M.W. 400) - 70%
N-methyl-2-pyrrolidone - ?0%
epoxidised coconut oil - - l~/o 5%
ligroin ~boiling limits 160-l90~C) - - 94%
~M.W. = molecu~ar weight)
The solutions are suitable for application in the form
of very fine drops.
F3. Granulates a) b)
-
active ingredient from Table 3 5% 10%
kaolin 94%
highly dispersed silicic acid 1%
a~tapulgite ~ 90%
The active in~redient i5 dissolved in methylene
chloride, the solution is sprayed onto the carrier, and
the solvent is subsequently evaporated oEf in vacuo.
~lZ6~3
- 38 -
F4. Dusts a) b)
active ingredient ~rom Table 3 2% 5%
highly dispersed silicic acid 1% 5%
talcum 97%
kaolin ~ 90%
Ready-for-use dusts are obtained by the intimate
mixing ~ogether of the carriers with the active ingredient.
Formulation Examples for solid active in~redients of the
formula I (% - per_cent by wei~ht)
~ LI~L~_~ey~ a) b) c)
active ingredient from Table 3 25% 50% 75%
sodium lignîn sulfonate 5% 5%
sodium lauryl sulfate 3% - 5%
sodium diisobutylnaphthalene sul.fonate - 6% 10%
octylphenolpolyethylene glycol ether - 2%
(7-8 mols of ethylene oxide)
highly dispersed silicic acid 5% 10% 10%
kaolin 62% 27%
The active ingredient is well mixed with the additives,
and the mixture is thoroughly ground in a suitable mill.
Wettable powders which can be diluted with wa~er to ~ive
suspensions o the required concentration are obtained.
F6. Emulsion concentrate
... . _
active ingredient from Table 3 10%
octylphenol polyethylene glycol ether 3%
(4-5 mols of ethylene oxide)
calcium dodecylbenzenesulfonate 3%
castor oil polyglycoL ether 4%
(35 mols of ethylene oxide)
cyclohexanone 30%
xylene mixture 50%
i~;Z3~3
- 3~ -
Emulsions of the required concentration can be obtained
from this concentrate by dllution with water.
F7. Dusts a) b)
active ingredient from Table 3 5% 8%
talcum 95%
kaolin - 92%
Dusts ready for use are obtained by mixing the active
ingredient with the carriers and grinding the mixture
in a suitable mill.
F8. Extruder granulate
active ingredient from Table 310%
sodium lignin sulfonate 2%
carboxymethylcellulose 1%
kaolin 87%
The active ingredient is mixed and ground with the
additives, and the mixture is moistened with water. This
mixture is extruded and subsequently dried in a stream
of air.
F9. Coated ~ranulate
active i~gredient ~rom Table 33%
polyethylene glycol (M.W. 200)3v/o
kaolin 94%
(M.W. = molecular weight~
The finely ground active ingredient is evenly applied
in a mixer to the kaolin moistened with polyethylene
glycol. Dustfree coated granules are obtained in this
manner.
~ ` \ ~ ~
iZ~43
- 40 -
F.lQ. Suspension cOncentL^ate
active ingredient from Table 3 40%
ethylene glycol 10%
nonylphenolpolyethylene glycol ether 6%
(15 mols of ethylene oxide)
sodium lignin sulfonate 10%
carboxymethylcellulose 1%
37% aqueous ~ormaldehyde solution 0.2%
silicone oil in the iorm of a 0.8V/o
75% aqueous emulsion
water 32%
The finely ground active ingredient is intimately
mixed with the additives. There is thus obtained a
suspension concentrate from which can be produced, by
dilution with water, suspensions of the concentration
required.
Biolo~ical E_amples
Example Bl. Action a~ainst Botr~tis cinerea on beans
Residual~protective action
Bean plants about lO cm in height are sprayed with
a spray liyuor prepared from wettable powder of the active
ingredient (0.02% of active lngredient). The plants are
infested after 48 hours with a conidiospore suspension of
the fungus~ The extent of fungus infection is assessed
ater incubation of the infested plants for 3 days at
21~C with 95-L00% relative humidity.
The compounds fro~ Table 3 greatly reduce fungus
infection not only in the above model test but also in
the ~ield test. At a concentration o~ 0.02%~ compounds
from ~or example Table 3 prova fully ef~ective
(infection O to 5%). Infection on untreated but infested
bean plants is 100%.
~1~6Z~43
Exam~le B2: Action against Botry_is cinerea on a~ples
Artificially damaged apples are treated by applying
drops of spray liquor, prepared from wettable powder of
the active substance, to the damaged areas on the apples.
The treated fruit is then inoculated with a spore suspension
of Botrytis cinerea, and is incubated for one week at
about 20C with high relative humidity.
For an assessment of the results, the decayed areas
of damage are counted, and from the number is deduced
the fungicidal action of the test substance. Amongst
other effective compounds tested, the compounds from
Table 3 completely prevent fungus infection, whereas the
level of infection on untreated control fruit is 100%.
