Note: Descriptions are shown in the official language in which they were submitted.
` 2~3~3~
O.Z. 0050/41504
N-(3-Phenyl-2-methyl~ropyl and -methylProp~2-enyl~-
zaheterocycles
The present invention relat~s to novel N-(3-
phenyl-2-methylpropyl and -methylprop-2-enyl)-azahetero-
S cycle~ of the formula I
R I ~CH--..C--CH 2--Het
CH3
where the dotted bond is a possible additional bond and
R1 is tert-butoxy or a radical
R -o-ctcH3~2-
in which R% is hydrogen or Cl-C4-alkyl, and
Het is a 5 membered to 7-mem~ered azaheteroaliphatic ring
whose N a~om i~ bonded to the remaining molecular moiety
of I and the ring may also contain, as a further hetero
atom, an oxygen or ~ulfur atom which i~ no~ adjacent to
the nitrogen and/or may furthermore carry one or two of
the following sub~tituent~: Cl-C4-alkyl groups or radi-
cal~ R3-o-(CH2) n~ ~ in which
R3 is hydrogen, Cl-C4-alkyl or C~- or C2-alkoxycarbonyl and
n i~ 0, 1 or 2,
with ~he provi~o that R3-o~ i8 not ~ to the nitrogen of
the heterocycle,
an~ the N-oxide~ and the plant-tolerated acid addition
~alts and quaternary salt~ of I.
The pre~ent invention furthermore relates to a
process for tha preparation of the~e compound~, their use
a~ fungicides and ungicides which contain these com-
pound~ a~ ackive 3ubstance~.
Th~ pre~ant invention also relate~ to 3-phenyl-
2-mathylpropanal~ and 3-phenyl-2-methylprop-2-enal6 o
the formula II
.
R 1 ~3CH--..f--CHO
CH3 II
in which Rl i~ tert-butoxy or ~O-C(CH3)2-,
and 3-phenyl-2-methylpropanols of the formula III
.
.
. . .
3 1
- 2 - o.z. 0050/41504
Ql ~ OH IXI
as intermediates.
The literature discloses various fungicidal
compounds of the type I which, instead of the radical Rl,
contain tert~butyl (DE-A-26 56 747, DE-A-27 52 135,
EP-A-O 333 and EP-A-243 940), tert-butyl which may be
substituted by chlorine or alkyl (EP-A-174 565~,
isopropyl (EP-A-6 992), C4-Cl2-alkyl, phenyl, cycloalkyl,
cycloalkylalkyl or aralkyl (DE-A-27 52 096) or unsub-
stituted or substituted phenoxy (EP-A-252 8703.
However, the abovementioned compounds are satis-
factory only to a limited extent with regard to tolera-
tion by plants as well as to their fungicidal action and
the duration of action, particularly in the case of low
application rates and concentrations.
It is an object of the present invention to
provide novel fungicidal substance~.
We have found that this object is achieved by the
N-~3-phenyli~obutyl)-azaheterocycles of the formula I
which were defined at the outset.
Tha substituents in the no~el compounds I have
the following speciic meanings:
R1 is tert-butoxy or R2-O-C(CH3) 2 in which
R2 is hydrogen or Cl-C4-alkyl, such as methyl, ethyl,
isopropyl or tert-butyl,
preferably tert-butoxy or l-methoxy-l-methylethyl, and
Het is a 5-membered to 7-membered a~aheteroaliphatic ring
whose N atom is bonded to the remsining molecular moiety
I and the ring may also contain, as a hetero atom, an
oxygen or sulfur atom which is not adjacent to the
nitrogen atom and~or may carry one or two of the follow-
ing substituents:
branched or ~traight-chain Cl-C4-alkyl, æuch as methyl,
ethyl, isopropyl or tert-butyl, preferably methyl or
ethyl, and
R3-o-CH2- and R3-o-CHz-CH2- or R3-o-, which is not ~ to the
- 3 _ o.z. 0050/41504
nitrogen atom of the heterocycle and in which
R3 is hydrogen,
Cl-C4-alkyl, such as methyl, ethyl, isopropyl or ter~-
butyl, preferably methyl, or
methoxycarbonyl or ethoxycarbonyl,
in particulax pyrrolidin-l-yl, piperidin-l-yl, azepan-1-
yl, morpholin-4-yl, thiomorpholin-4-yl, 2-methyl-
pyrrolidin-l-yl, 3-methylpiperidin-1 yl, 4-tert-butyl-
piperidin-l-yl,3,4-dimethylpiperidin-1-yl,3,5-dimethyl-
piperidin-l-yl, 2,6-dLmethylpiperidin-l-yl, 3-methyl-4-
ethylpiperidin-l-yl, 3-ethyl-4-methylpiperidin-1-yl, 2-
methylazepan-l-yl, 3-methylazepan-1 yl, 2,5-dimethyl-
morpholin-4-yl, cis-2,6-dimethylmorpholin~4-yl, 2,6-
dimethylmorpholin-4-yl (cis-/tran~-mixture), 3-hydroxy-
piperidin-1-yl, 4-hydroxypiperidin-1-yl, 4-methoxy-
piperidin-1-yl~3-hydroxymethylpiperidin-1-yl,4-hydroxy-
methylpiperidin-l-yl, 3-methoxymethylpiperdin-1-yl, 4-
methoxymethylpiperidin-l-yl, 3-ethoxymethylpiperidin-1
yl, 3-propoxymethylpiperidin-1-yl, 3-acetoxymethyl-
piperidin-l-yl, 3-propionoxymethylpiperidin-1-yl, 4-
methoxyethylplperidin-l-yl and 3-acetoxyethylpiperidin
l-yl .
Particularly suitable compound~ I are those in
which R1 i text-butoxy or l-methoxy-l-methylethyl and
Het is piperidin-l-yl, azepan-1-yl, mo~pholin-4-yl, 2,6-
dimethylpiperidin-1-ylor Ci8 ~-2,b-dimethylmorpholin-4-yl.
Tho Example~ describe preferred compounds I.
The N-(3-phenyl-2-methylpropyl and -methylprop
2-enyl)-azeheterocycles are obtainable in various ways,
preferably by the following methodss
1) Reduction of an aldehyde II in the presence of an
azaheterocyclic rinq H-Het
la) Catalytic reduction with hydrogPn
R 1 J~ ~ H 2 ,~H e t
II I
The hydrogenation is advantageously carried out
2~g~
- ~ - O.Z. 0050/~1504
in an autoclave at a hydrogen pressure of +;rom 2 to 100,
preferably from 90 to 100, bar. A~ a rule, it i8 carried
out in the ab~ence of a ~olvent or in an inert solvent or
diluent, such aR benzene, toluene, tetrahydrofuran,
dioxane or methanol, at a reaction temperature of from 0
to 180C, prefera~ly from 30 to 110C.
Advantageou~ly, the aldehyde II and the aza-
heterocycle H-Het are used in a stoichiome~ric ratio,
al~hough an excess of one component or the other, for
example no~ more than 10~, may al~o be advisable in some
ca~es .
Depending on the type of ca~aly~t used, compound~
I having a 2-methylpropylene or a 2-methylprop-2-enylene
group a~ a bridge member may be obtained. Catalysts
which lead to compounds I having a ~atura~ed bridge
msmber are preferred.
Noble metals, such as rhodium and especially
palladium, preferably in the form of supported catalysts
containing silicate~, such as aluminum silicates and
magnesium silicates, and in particular aluminum oxide,
titanium dioxide or carbon a~ carrier~ are suitable as
catalysts for the hydrogenation.
As a rule, the amount o~ catalyst is from 1 to
50~, preferably from 2 to 10%, based on the amount of
aldehyde II used.
In a particularly 3uitable procecs for the
preparation of the co~pound~ I having a 2-methylpropylene
group as a bridg3 member, an aldehyde Rl-phenyl-4-C~O is
reacted with propionaldehyde and an azaheterocycle H-Het
3Q under hydrogenating condition~, as described in DE-A-
31 05 446.
lb) Catalytic reduction with a metal hydride
~ + H Het - -~ ~ Het
Rl II Metal hydride R1
The reduction i8 advantageously carried out in an
,
.' : ' .
- . .
.
3 ~
- S - O.Z. 0050/4150~
inert solvent or diluenk, ~or example an alcohol, such as
methanol or ethanol.
Example~ of suitable metal hydrides are alkali
metal or alkaline earth metal hydrides or the alkali
metal salts of boron hydrides or aluminum hydrides.
Sodium cyanoborohydride to which not more than 0.5 mole
equivalent of a cocatalyst, such a~ zinc(II) chloride,
may also be added, is particularly suitable.
As a rule, from 2 to 4 equivalents, based on the
amount of aldehyde II used, of reducing agent are
sufficient.
The aldehyde II and azaheterocycle H-Het ar~
usually used in a stoichiometric ratio, although an
excess of one component or the other, for e~ample not
more than 10%, may also be advisable in some cases.
The reaction is usually carried ou~ at atmos
pheric pressure or under the autogenou~ pres~ure of the
particular solvent.
The reaction tempera~ure is in general from 0 to
80C.
lc) Reduction with organic reducing agent~
A particularly suitable organic reducing agent is
formic acid.
Regarding the solvent~, the stoichiometric
amounts and the pressure, the data given for method lb)
are applicable.
In the case of liquid reducing agent~, the
raaction can al50 be carried out in tha absence of a
solvent, in a large exce3~ of the reducing agent, for
example not more than 10~, based on the amount of
aldehyde II.
The reaction temperature i8 in general from 80 to
180C, preferably from 120 to 160C.
The reaction i~ u~ually carried out at atmos-
pheric pres~ure.
2) Nucleophilic substitution by an azaheterocycle
3 8 ~
- 6 - O.Z. 0050/41504
~L 3~se ~ ~Het
R~ + H-Het
IV
L is a nucleophilically ~3ubstitutable leaving
group, in particular a halogen atom, such as chlorine,
bromine or iodine, sulfonyl, such as methanesulfonyl, p-
toluenesulfonyl or p-bromosulfonyl, or methylsulfate.
The reaction is advantageously carried out in a
solvent or diluent, such as methanol, ethanol, aceto-
nitrile, dime~hylformamide or dimethyl sulfoxide, or in
a excess of the azaheterocycle.
Examples of suitable bases are alkali metal
carbonates, such as sodi~m carbonate and potassium
carbonate, bicarbonates, such as sodium bicarbonate and
potassium bicarbonate, pyridine, 4-dimethylaminopyridine
and triethylamine, or H-Het itself, in not less than a
~3toichiometric amoun~, ba~ed on the amoun~ of I~I, for
complete conversion.
Advantageously, all starting compound~ are used
in a roughly stoichiometric ratio, although an excess of
one componen~ or the o~her, for example not more than
lO~, may also be advisable in some cases.
If the a~aheterocycle i~ used as a solvent and/or
as a base, H-Xet is pre~ent in a larger excess.
The reaction usually takes place at a suff icient
rate at aboYe 30C. In general, the temperature is from
40 to 160C, preferably from 50 to 130C.
Since the reaction i~ not pre~sure-dependen~, it
is advantageously carried out at atmospheric pres4ure.
3) Etherlfication of hydroxy compounds I [R1 =
R2-O-C(C~I3)2-]
~~~r~~~~~Het I) Base ~'~~~~~Het
(CH3)2c ~ 2~ ~CI-C4- (CH3)2c ~
OH I Alkyl)-L O-(CI-C4-)All~yl
I
The reaction iB advantageously carried out in an
inert solvent, such as dimethylformamide.
As a rule, the alcohol i~ converted into its
.
.
3 ~
- 7 - ~.Z. OOS0/41504
alcoholate by reaction with a strong base, for example
sodium hydride or methylmagne~ium bromide, at about 0-
~OC .
The subsequent substitution of the leaving group
L by the alcoholate ion usually takes place at a suffi-
cient ra~e at above 0C.
In general, the temperature is from 20 to 100C.
Advantageou~ly, the s~arting compounds are used
in a stoichiometric ratio, although an excess of one
component or the othex, for example no~ more than 10%,
may b~ advisable in ~ome ca~es.
Since the reaction is not pre~sure dependent, it
is prefera~ly carried out at atmospheric pressure.
Examples of the pxeparation ofcompounds of type I
which carry a hydroxyl, hydroxyalkyl or alkoxyalkyl group
on the azaheterocycle are de~cribed in ~P-A 174 565.
The starting compounds II are obtainable by
conventional methods of alcohol conden~ation reactions of
para-substituted aromatic aldehydes with propionaldehyde
and, if de~ired, ~ubqequent partial hydrogenation:
RI~CHO ~ 01~3 ,~ C~t. Rl~--
II II
The saturated alde~ydes II can also be reduced by
conventional methods to alcohol~ III, which can be
reacted with a mineral acid or w1th a reactive compound
HL in a conventional manner to give the in~ermediateR IV:
~0 H 2 ~OH HL ~L
Rl~ Cat. Rl Rl
II (saturated) III IV
The aldehydes II which are novel comprise
3-t4~ hydroxy-1-mQthylethyl)phenyl]-2~methylpropenal,
3-~4-tl-hydroxy-1-methylethyl)phenyl]-2 ~methylpropanal,
3- [ 4-tert-butoxyphenyl ] -2-methylpropellal and
3-[4-~ert-butoxyphenyl~-2-methylpropanal.
.
~3~
~ 8 - O.Z. 0050/4150~
In the preparation of compounds I having a double
bond in the isobutyl moiety, the E-isomers are predomin-
antly formed as well as a small amount of the Z-isomers.
The two isomers can, if desired, be separated from one
another in a conventional manner.
The N-oxide can be prepared by conventional
methods from the compounds I, for example by reacting
them with an organic peracid, such as metachloroper-
benzoic acid.
Suitable acid addition salts are the salts of
acids which do not adversely affect the fungicidal action
of I, for example the salts of hydrochloric acid, hydro-
bromic acid, sulfuric acid, nitric acid, phosphoric acid,
boric acid, formic acid, acetic acid~ propionic acid,
lauric acid, palmitic acid, stearic acid, oxalic acid,
malic acid, malonic acid, benzoic acid, methanesulfonic
acid, dodecylbenzene ulfonic acid and saccharinic acid.
Other suitable salts are the N-alkylated, in particular
methylated and ethylated, and the N-benzylated deriva-
tives of the compounds I.
The novel compounds I having a saturated bridgemember contain a center of asymmetry. Furthermore, all
acid addition salts, quaternary salts and N-oxides may
contain one c0nter of asymmetry at the nitrogen atom of
the heterocycle. All optically active compounds act as
racemates, the form in which they are obtained in most
preparation proce~ses, but can, if desired, al~o be
separated inko the pure isomers by the conven~ional
methods, for axample by chromatography ovex an optically
active adsorbent.
The compounds I are suitable a fungicides.
Preparation Examples
. .
,
3'L
g - O.Z. 0050/~150
E~AMPLE 3
4-[3-(4-tert-Butoxyphenyl)-2-methylpropyl]-cis-2,6-
dlmethylmorpholine
CH3
CH3 ~ N 0
CH3-C~
I CH3
c~3
A mixture of 25 g (0.1 mol) of 3-(4-tert-butoxy-
phenyl)-2-methylpropyl p-toluenesulfonate, 25 g (0022
mol) of cis-2,6-dimethylmorpholine and 100 ml of toluene
was refluxed for 4 hours and then washed with 10%
strength by weiqht aqueous potassium hydroxide solution~
The organic phase was then worked up in a conventional
manner to give the product. Yield: 60% of theory;
bp. 120C/0.1 mbar.
Intermediate A
3-(4-tert-Butoxyphenyl)-2-methylpropan-1-ol
C~f OH
CH3--f
c~3
10 g (0.58 mol) of p-tert-butoxybenzaldehyde were
added to a solution of 600 ml of methanol and 13.3 g of
50~ strength aqueous sodium hydroxide solution in the
course of about 10 minutes, a gentle stream of nitrogen
being passed through the solution. The mixture was
heated to about 40C, after which 36.4 g (0.62 mol) of
propionaldehyde were added dropwise in ~he course of 1
hour. Aft~r:stirring had been carried out for a further
30 minutes, the pH was brought to 7.5-8 with 10% strength
aqueous sulfuric acid, and the sodium ~ulfate fonmed was
filtered off. The resulting 3-(4-tert-buto~yphenyl)-2-
methylpropenal wa~ hydrog~nated using 15 g (0.26 mol) of
Raney nickel as a catalyst in the course of 3 hours at a
hydrogen pre sure of 100 bar and at 60C. After the
pressure had been let down and the autoclave cooled, the
.
,
~<~ 3 ~
- 10 - O.Z. 0050/41504
content of the autoclave was worked up in a conventional
manner to give the product. Yield: 66%; bp.: 133C/0~5
mbar.
Intermediate B
3-(4-tert-Butoxyphenyl)-2 methylpropyl p-toluenesulfonate
SO 2~3CH 3
o6 g (0.34 mol) of p-toluenesulfonyl chloride
were added to a mixture of 77 g (0.34 mol) of 3-(4-tert-
butoxyphenyl)-2-methylpropan-l~ol in 150 ml of pyridine
at about 20C. Stirring was carried out for 2 hours,
10after which about 250 ml of toluene and 250 ml of water
were added, ~he organic ph~e was ~eparated off and the
solvent was removed under reduced pressure. The crude
product was reacted, without further purification, with
the azaheterocycle to give the end product.
15EXAMPLE 8
4-{3-~4~ Methoxy-l-methylethyl)-phenyl]-2-methylprop~
2-en-l-yl}-cis-2,6-dimethylmorpholine
CH3
CH3 1 ~ N ~
C~3 c~3
A mix~ure of 10.0 g (46 mmol) of 3-~4-(l-methoxy-
1-methylethyl)-phenyl]-2-methylpropenal [prepared simi-
larly to Example 3, Intermediate A, without ~he hydro-
genation (yield 87% of theory, bp. ~20C/0.2 mbar)], 5.6
g (48.6 mmol) of cis-2,6-dimathylmorpholine, 3.7 g (27
mmol) of zinc chloride, 3.4 g (54 mmol) of ~odium cyano-
borohydride and 100 ml of ab~olute methanol wa~ stirred
for 48 hours at about 20C under a protective nitrogen
atmosphere. The solvent was then removed under reduced
pressure. The re~idue was taken up in about 150 ml of
methyl tert-butyl ether and 40 ml of dilllte sodium
3 ~
- 11 - O.~. 0050/4150~
hydroxide solution, the phase~ were ~eparated and the
organic portion was worked up in a conventional manner to
give thP product. Yield. 54% of theory; bp. 150C/0.3
mbar.
EXAMPLE 9
4-{3-[4-(1-Methoxy-l-me~hyl2thyl)-phPnyl]-2-methylprop-
C H 3
yl}-cis-2,6 dimethylmorpholine ~
CH 3~ N ()
CH3--I CH3
CH3
The compound was prepared similarly to Example 8
from 10 g (45 mmol) of 3-[4-tl~methoxy-1-methylethyl)-
phenyl]-2-methylpropanal and 6.7 g (58 mmol) of cis-2,6-
dimethylmorpholine, u ing 3.7 g (27 mmol) of zinc chlo-
ride and 3 . 4 g (54 mmol) of sodium cyanoborohydride.
Yield: 76~ o~ theory; bp. 145C/0.4 mbar.
Intermediate C
3-[4-(1-Methoxy~1-methylethyl)-phenyl]-2-methylpropanal
CH3-o ~ CHO
CH3
100 g (0.46 mol~ of 3-[4-~1-methoxy-1-methyl-
ethyl)-phenyl]-2-methylpropenal (prepared similarly to
Example 3, Intermediate A, wi~hout carrying out the
hydrogenation (bp. 120C/0.2 mbar)] in 50 g of methanol
were hydrogenated for 12 hours at 80C and at a hydrogen
pres~ure of 50 bar over a metal cataly t. This consisted
of palladium (O.5~) on alumina. After cooling had been
carried out and the pressure let down, the mixture wa~
worked up in a conventional manner ~o obtain the product.
Yield: 62~ of theory; bp. 90-94C/0.2 mbar.
Table 1 shows further compound~ I, which were
obtained, or are obtainable, similarly to the Example
compound~.
'.' , .
.
~ ~J ~
- - 12 - O. Z . 0050/~1504
_
L
._ 3 _ ~'1 ~ ~ ~ ~ 3
O O O O O O C:~ O O O
o o ~ r o ~ o o
_ _ _ _ _
e c ~
_ .__ ._ ._ ._ = ~ ._
~ C _ _ C C _ '
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~-- ~ O c ~ O ~ c ~ ~ c ( ~ ~. _ :~
,_~9 ~~ ,_ ~D ~ 3 ~ ~ ~ --o 'O- ~ L ~ ~
OL ~`I L "I O S_~I ~ L S_ ~ ~ _ C ~ ~:7 ~ _ ~ ~ --
~_~ I 'V ~ L VI I ~ O ~ V :-~ J
3. ~ v ~ ~: ^ ~ v ~ L e cc s s ~ ~ 1 ~ ~ ~ ~S
-
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v
-
c c s; c c c c ~ c ~ ~ c ~ ~ c s: c c o ~
o
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-
~ x -- ~ -- -- x xo o o o o ~
~_ L ~ I_ L ~ ~ _ _ ~ V
L U U U U ~J ~J U ~ ~
_l
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.~ ` , , . ., ' .
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~3~
- 13 - O. Z . 0050/~1504
-
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o
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-- -- -- V . _ _ . _ , _ _ ,_
_ ~-- C L ~
-- :~ V C.J ~ Vl C C~
C ~ -- L ::~ -- C -- ~-- -- -- -- -- -- ._~
-- V (~1 '` V ~J I ^ -- -- V C ~ .--
.-- C I -- CL
O C :~ -- C _ ~ -- _ -- C ~
~ X o X _ ~ X X ~ X X X X ~ X ~ ~-- J
X O ~-- O :~ 5 0 0 ~ O O O O ~C O -- V ~
-- ~' ~ ~ ~:1 v ~ ",, ~, ., -- ~ -- -- E~
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llJ .: CL S ~ n ~ S ~J ~ ~ I LI C 'D ~ 1J
'Oo
O O O O O O O O O O O O O O O O O O
a~ c c ~ ~: c ~: c 1:: ~ c c c c c c c ~_ ~
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~ 3.,L
- 14 - O.Z. 0050/~1504
The N-(3-phenyl-2-methylp~opyl and -methylprop-
2-enyl)-azaheterocycle~ I have excellent activity against
a broad spectrum of phytopathogenic fungi, in particular
from the cla~ consisting of the AscomycetQs and Basidio-
mycetes. Some of them have systemic activity and can be
used as foliage and soil fungicides.
They are particularly important for controlling
a large number of fungi of various crops, such as wheat,
rye, barlPy, oats, rice, corn, gras~, cotton, soybean,
coffee, sugar cane, wine, fruit tree~ and ornamentals and
vegetable plants, such as cucumbers, beans and
cucurbitaceae, as well as on the seeds of these plant.~.
Th~y are particularly suitable for controlling
the following plan~ di~ea~e~:
Erysiphe graminis (powdery mildew3 in cereals,
Ery~iphe cichoracearum and Sphaerotheca fuliginea on
cucurbitaceae,
Podosphaera leucotricha on apple~,
Uncinula necator on grapevines,
Puccinia specie~ on cereals,
Rhizoctonia species on co~ton and lawn~,
Ustilago species on cereals and 3ugar cane,
Venturia inaequalis ~cab) on apples,
Helmintho~porium species on cereal~,
Septoria nodorum on wheat,
Bo~rytis cinerea (gray mold) on strawberriee and grape
vines,
Cercospora arachidlcola on peanut~,
Pseudocercosporella herpotrichoides on wheat and barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoe~,
~u~arium and verticillium ~pecies on various plan~s,
Pla~mopara viticola on grapevine~ and
Alternaria specie~ on vegetables and fruit.
The compounds I ars ve~y par~icularly well suited
to controlling Pyricularia oryzae on rice.
The compound~ are applied by spraying or du~ing
~, ~3 ~ 3
- 15 - O.Z. 0050/41504
the plants with the active ingredients or treating the
seeds of the plants with the acti~e ingredienk3.
Application is effected before or after infecti on of the
plants or seeds with the fungi.
They can be converted into the conventional
formulations, such as solutions, emulsions, suspensions,
dusts, powders, pastes and granules. The application
forms depend on the intended use~; they ~hould in any
case ensure fine and uniform distribution of the N-(3-
phenyl-2-methylpropyl and -methylprop-2-enyl~-aæahetero-
cycle. The formulations are prepared in a known manner,
for example by extending the active ingredient with
solvents and~or carriers, if required with the use of
emulsifiers and dispersants; where wa~er i~ used as a
diluent, other organic solvents may also be employed as
auxiliary solvents. Suitable assistants for this purpose
are essentially solvents, such a~ aromatics (eg. xylene),
chlorinated aromatics (eg. chlorobenzenes), paraffins
(egO mineral oil fractions), alcohol~ (eg. methanol or
butanol), ketones (eg. cyclohexanone), amines (eg.
ethanolamine or dLmethylformamide) and water; carriers,
such as ground natural minerals (eg. kaolins, clays, talc
or chalk) and ground synthetic minerals (eg. finely
divided silica or silicates); emulsifiers such aR non-
ionic and anionic emulsifiers (eg. polyoxyethylene fatty
alcohol ethers, alkyl ulfonates and arylsulfonates) and
disper~an~s, such a~ lignin3ulfite waste liquors and
methylcellulose.
The fungicides contain in general from 0.1 to 95,
preferably from 0.5 to 90, % by weight of active
ingredien~.
The application rate are from 0.02 to 3 kg of
active ingredient per ha, depending on the type of effect
desired. The novel compounds can also be used in mater--
ial protection (timber protection), for example against
Paecilomyces variotii.
The quantity of active ingredient required for
A.
- 16 - O.Z. 0050/41504
seed treatment is in general from 0.001 to 50 g, prefer-
ably 0.01 to 10 g, per kilogram of sesd.
The agents or the ready-to-use formulations
prepared therefrom, such as solutions, emulsions, suspen-
S sions, powders, dusts, pastes or granules, are applied in
a known manner, for example by spraying, atomizing,
dusting, broadcasting, dressing or pouring.
Exampl~s of such formulations are:
I. A solution of 90 parts by weight of compound No. 3
and lO parts by weigh~ of N-methyl-~-pyrrolidone,
which is suitable for use in the form of very small
drops;
II. A mixture of 20 parts by weight of compound No. 4,
80 parts by welght of xylene, 10 parts by weight of
the adduct of from 8 to 10 moles of ethylene oxide
with 1 mole of oleic acid N-monoethanolamide, 5
parts by weight of the calcium salt of dodecyl-
benzenesulfonic acid, 5 partq by weight of the
adduct of 40 moles of ethylene oxide with 1 mole
of castor oil; a dispersion is obtained by finely
dis~ributing the solution in water;
III. An aqueous dispersion of 20 parts by weight of
compound No. 5, 40 parts by weight of cyclohexan-
one~ 30 parts by weight of isobutanol and 20 parts
by weight of the adduct of 40 moles of ~thylene
oxide with 1 mole of castor oil;
IV. An aqueou~ di~persion of ~0 parts by weight o
compound No. 8, 25 part~ by weight of cyclohexanol,
65 parts by weight of a mineral oil fraction
boiling within a range from 210 to 280C and 10
part~ by weight of the adduct o~ 4 mole of
ethylene oxid~ and l mole of castor oil;
V. A mixture, milled in a hammer mill, of 80 parts by
weight of compound No. 9, 3 parts by weight of th~
~odium salt of diisobutylnaphthalene-~-sulfonic
acid, 10 parts by weight of the ~odium salt of a
ligninAulfonic acLd obtained from a sulfite waste
- 1.7 - o.z. 0050/41504
liquor and 7 parts by weLghk of silica gel powder;
a spray liquor is obtained by finely distributing
the mixture in water;
VI. An intLmate mixture of 3 parts by weight of com-
pound No. 10 and 97 partR by weight of finely
divided kaolin; this dusting agent contains 3% by
weight of active ingredient;
VII. An intimate mixture of 30 parts by weight of
compound No. 11, 92 parts by weight of silica gel
powder and 8 parts by weight of liquid paraffin,
which has been sprayed onto the surface of this
silica gel; this formulation Lmparts good adhesion
to the active ingredient;
VIII. A stable aqueous dispersion of 40 parts by weight
of compound No. 12, 10 parts by weight of the
sodium salt of a phenylsulfonic acid/ure~formalde-
hyde condensate, 2 parts by weight of silica gel
and 48 part~ by weight of water, which can be
further diluted;
IX. A stable oily dispersion of 20 parts by weight of
compound No. 13, 2 parts by weight of the calcium
salt of dodecylbenzenesulfonic acid, 8 parts by
weight of a fatty alcohol polyglycol ether, 20
parts by weight of the sodium salt of a phenol-
sulfonic acid/urea/formaldehyda condensate and 68
parts by weight of a paraffinic mineral oil.
In these application forms, the novel agents may
also be present to~ether with other active ingredients,
for example with herbicide~, insecticides, growth regula-
tors, fungicides or fertilizer~. In many ca3e~ the
fungicidal action spectrum is increased on mixing with
fungicides .
Use Example~
The comparison substance u ed was
CH3
C H 3
~ 7~
- 18 ~ O.Z. 0050/41504
which is disclosed in EP-A 262 870 (compound No. 7).
EXAMPLE 1
Activity against brown rust on wheat
Leaves of pot-grown wheat seedlings of the
S Kanzler variety were dusted with spores of brown ru~t
(Puccinia recondita). The pots were then placed for 24
hours at from 20 to 22C in a chamber at from 90 to 95%
relative humidity. During this tLme, the spores germina-
ted and the germ tubes penetrated into the leaf tissue.
The infected plant~ were sprayed to run-off with 0.025~
strength aqueous spray liquor which contained 80~ of
active ingredient and 20~ of emulsifier, the p rcentages
being based on dry substance, and, after the spray
coating had been dried on, were placed in a greenhouse at
from 20 to 2~C and from 65 to 70% relative humidity.
After 8 days, the extent of development of rust funguR on
the leaves was evaluated.
The result show~ that, when used as a 0.025
strength by weight spray liquor, active ingredients 9,
10, 11 and 13 have a better fungicidal action (95%) than
the known comparative substance (30~).
EXAMPLE 2
Activity against wheat mildew
Leaves of pot-grown wheat seedlings of the
Fruhgold va~iety were sprayed with a 0.025~ strength
aqueous spray liquor which contained 80% of active
ingredient and 20% of emulsifier, the percen~ages being
based on dry material, and, 24 hours after the spray
coating had dried on, were dusted with spores of wheat
mildew (Erysiphe graminis var. tritici). The test plants
were then placed in a greenhouse at from 20 to 22C and
from 75 to 80% relative humidity. After 7 days~ ~he
extent of development of mildew wa~ evaluated.
The re~ult show~ that, when u~ed as a 0.025%
strength by weight spray liquor, active ingredients 3, 4,
5, 9, 10, ll and 13 have a better fungicidal action (98%~
than the known comparative substance (50~).
