Note: Descriptions are shown in the official language in which they were submitted.
~3~
-- 1 -
1,2,4-triazol-~yl~propionitrile derivativec~
their preparation and use.
The present invention is concerned with new
1,2,4-triazol-1~yl~propionitrile derivatives, their
5 preparation and use as biocidal agenkx, esp~cially
those having a fungicidal, herbicidal, bactericidal
and growth regulating action.
Imidaæolyl-propionitrile derivatives having a
fungicidal action ~re ~lready kno~n ( see German
Offenlegungsschrift ~o. 26 04 047). These, however,
have a relatively narrow range of action, which is
unsatisfactory.
: It is an aim of the present invention to provide
new propionitrile derivatives that offer a wide
variety of possible applications t especially in the
field of plant prote~tion, and have a broad fungicidal
range of action.
The present inYention provides a compound of the
general formula
~0
R 1
R C _ C~
C~
in which
,...........
s~
R repre~ents an aryl radical ~hich i~ unsubsti~uted
or substituted by one or more of the same
or different ~ubstituent~ selected from halogen
atoms, (C~-C4)alkyl group~, (C~-C~)alkoxy group~
(Cl-C~)alkylthio groups9 trifl~oromethyl groups
and nitro groups,
and
R~ represents a (C1~C10)alkyl radical~ a (~3,C~)alkenyl
radical, a (C3-C8~alkynyl radical or a phenylalkyl
. radical which is un3ub~titute~ or substituted by
one or more of the ~ame or different ~ubstituent~
selected from halogen atoms, (C~ C4)alXyl groups,
~C~-C4)alkoxy groups, (C1-C~)alkylthi 3 groupsO
trifluoromethyl groups and nitro groups,
15 or an acid addition salt thereof with an inorganic or
oxganic acid.
The compounds according to the present invention
are, in the broadest sense, biocidally active, but are
distinguished in particular by a fungicidal action in
20 which they are ~urprisingly superior to known activ~
substance~ of analogous constitution and mode of action~
The fungicidal action ~urprisingly extends to
action against fungi which attack different systematic
positions in plants. In th~ treatment of parts of the
25 plant above 50il level the cornpounds of the present
invention can give protection agai~st wind-borne
pathGgen~. To control seed-tran~rmtted pathogens, the
- \
~s~
-- 3 --
compounds can also be used for treating seeds
them~elves. In addition, these compounds can act
systemically, that is to say they can be taken up by the
roots of the plant, for example after being app1ied to
the seed, and be tran~ported to the parts of the plant
above soil level to protect those parts against pathogens.
Further actions e~hibited by compounds of the present
invention which may be mentioned are growth-regulatory
action and bactericidal action.
Owing to the broad range of action which they have
been found to possess, the compounds are suitable not
only for the protection of crop plants but also for
the general protection of materials and for the control
of/ for example, microbes causing disease in humans
and an;m~l5, and, as a result, their possible applications
are very varied.
As may be appreciated, the f i~lds of application
in which the compounds exhibit outstanding actions can
vary in accordance with the specific meaning of the
substituents. Thus, they can be u~ed as fungicides,
plant growth regulators or bactericides.
An alkyl group present in a compound of the
invention may ~e a straight-chain or hranched-chain
alkyl group. Similarly an alkenyl or alkynyl group
present in a compound of the invention may be a straight~
chain or branched-chain alkenyl or alkynyl groupn
~ ~\
In the compounds of the general formula I
R may repre~ent, for ~xample, any of the following groups:
phenyl, 2-fluorophenyl, 3-fluorophenyl,
4~fluorophenyl, 2-chlorophenyl, 3- hlorophenyl,
4-chlorophenyl, 2-bromophenyl t 3-bromophenyl,
4 bromophenyl, 2-iodophenyl, 3 iodophenyl,
4-iodophenyl, 2,4-dichlorophenyl, 3,4 dichl~ro-
phenyl, 2,6 dichlorophenyl, 2-methylphenyl,
3 methylphenyl, 4-methylphenyl, 2-ethylphenyl,
3-ethylphenyl, ~-ethylphenyl, 2 propylphenyl,
3~propylphenyl, 4-propylphenyl, 2 isopropylphenyl,
3-isopropylphenyl/ 4-isopropylphenyl, 2-butyl-
pheny:L, 3-butylphenyl, 4-butylphenyl, 2-sec.-
butylphenyl, 3-~ec~-butylphenyl, 4-sec.-butyl-
phenyl, 2-~ert.-butylphenyl, 3-tert~-butylphenyl,
4~tert~-butylphenyl t 2-methoxyphenyl, 3-methoxy
phenyl J 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxy-
phenyl, 4-ethoxyphenyl, 2~ methylthiophenyl,
3-methylthiophenyl, 4-methylthiophenyl, 2-ethylthio~
phenyl, 3 ethylthiophenyl, 4-ethy~thiophenyl,
2-trifluoromethylphenyl, 3-~rifluorome~hylpheny
4 trifluoromethylphenyl, 2-nitrophenyl, 3-nitro-
phenyl, 4-nitrophenyl, 3-fluoro-4-methoxyphenyl;
3-chloro-5-nitrophenyl, 4-chloro-2~fluorophenyl,
3,495-trimethoxyphenyl, and 2-chloro-2-nitro-
phenyl
and
-- 5 --
R~ may repre~ent, for example, any one o~ the following
groups: (C1~C10)alkyl, for example methylg ethyl,
propyl, butyll pentyl, hexyl 9 heptyl, octyl,
nonyl, decyl, isopropyl, 2,2-dimethylprop-1-yl,
3,3-dimethylbu~2-yl, (C3-C8)alkenyl, for
ex~nple allyl, 2-buten-1-yl, 3-methyl-2 buten-
1-yl, hexenyl, heptenyl, octenyl, phenylalkyl,
for example benzyl, 2 fluorobenzyl, 3-fluoro-
benæy~, 4-fluorobenzyl~ 2-chlorokenzyl, 3-chloro~
benzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromo-
benzyl, 4-bromobenzyl, 2 3 4-dichlorobenzyl, 2,6-
dichlorobenzyl, 3,4-dichlorobenzyl, 2-methyl~enzyl~
3 methylbenzyl~ 4-methylbenzyl/ 2-nitrobenzyl,
3-nitrobenzyl, 4-nitrobenzyl, 2-trifluoro-
methylbenzyl, 3-tr.ifluoromethylbenæyl, 4-tri~
fluoromethylbenzyl, 2-metho~ybenzyl, 3~metho~y-
benzyl, 4~methoxybenzyl, 2-ethoxy~e~zyl, 3-ethoxy-
benzyl, 4-ethoxybenzyl, 2-propoxybenzyl, 3-pro-
poxybenzyl, 4-propoxybellzyl 9 2 butoxybenzyl,
3-butoxybenzyl, 4-butoxy~enæyl, 2-methylthioberlzyl,
3-methylthiobenzyl, 4-methylthiobenzyl, 2~ethyl-
thiobenzyl, 3-ethylthiobe~zyl, 4-ethylthiobenzyl~
2~butylthiobenzyl, 3-butylthiobenzyl, and 4-butyl-
thiobenzyl.
An aryl radical repre,sented by R i~s preferably a
phenyl group, especially an alkyl or halogen-
substituted phenyl group.
S9~;~
A radical represented ~y Rl is preferably a
~C~-Clo)~lkyl group or an allyl group.
I~oxganic and organic acids for the formation o
the acid addition salts of the present invention which
may be mentioned by way of example are hydrohalic acids~
such a~, for examp e, hydrochloric acid and hydrobromic
acid~ phosphoric acid, sulphuric acid, nitric acid,
especi~lly conc~ nitric acid, mono- or bi-functional
~arboxylic acid~ and hydroxycar~oxylic acids~ such as,
for example, acetic acid~ maleic acid, ~uccinic acid~
fumaric acid, tartaric acid, citxic aoid~ sàlicylic
acid, sorbîc acid~ lactic acid t and also ~ulphonic
acids, ~uch as, for example, ~ toluenesulphonic acid
and 1,5-naphthalenedisulphonic acid.
The acid addition salts of the present invention
may be obtained by the customary salt formation
proce~eQ, for example by dissolving a compound of the
gener~l formu~a I in a suitable solvent and addi~g the
desired acidr
A~ an acid addition salt of a compound of the present
invention, a hydronitrate salt is preferred.
The compounds of the prese~t in~ention that are
distinguished by an outstanding fungieidal action are
especially those compounds of the general formula I in
which the radical
R represent~ any one of the following group~-
phenyl, 7-chlorophenyl d 3 chlorophenyl, 4-chloro-
C3`~
phenyl, 2,4-dichlorophenyl, 3,4~dichlorophenylO
4-bromop~enyl, 2-~luorophenyl, 4-fluorophenyl and
2-methylphenyl
and the radical
R1 repre~ents any one of the following group~:
ethyl, allyl t propyl~ isopropyl, butyl and hexyl~
Preferably, of these compound~, there are to be
mentioned ~ho~e in which
R represent~ a phenylO 4~chlorophenyl or 2-methyl-
phenyl yroup
and
Rl repre~ents a propyl~ i~opr3pyl or butyl group.
~ ha following COmpGUndS according to the inven~ivnha~e been found to have an outst~n~ing action:
2-isopropo~y-2-phenyl-3~ c4-triazol-l yl~-propioni-
trile hydronitrate,
2-butoxy-Z-~2-methylphenyl)-3-(1,2,4-tri~zol-l yl3
propionitrile hydronitrate,
2-phenyl-2-propoxy-3-~1,204-triazol-l-yl~ propionitrile
hydronitrate,
2-butoxy-2-(4-chlorophenyl)-3-(1 t ~ o 4-triazol~l-yl~-
propionitrile hydronitrate,
2 (4-chlorophenyl)-2-propo~y~3 (1,2,4-triazol-l-yl)-
propionitrile hydronitrate,
2-i~opropoxy-2-phenyl-3-(1,2,4-triazol-l-yl)-propion-
nitrile,
5~
a -
2-butoxy~2-(2-methylphenyl~-3-~1~2,4-triazol-1-yl)-
propionitrile,
2-hexyloxy-2-phenyl 3~ 2,4-txiazol-1-yl)-propionitrile
hydronitrate,
S 2~butoxy~2~(4-ch`lorophenyl) 3~ 2~4-tria
propionitrile~
2 t4-chlorophenyl)-2-propoxy-3~ 2~4~riazo~ yl)
propionitrile,
2-~exylo~y-2-(2-methylphenyl)-3~ 2~4-triazo~ yl)
10 propionitrile hydronitrate D
2 butoxy-2-phenyl-3-~1,2,4-triazol-1-yl)~propionitrile
hydronitrate,
2-butoxy-2~(2-chlorophenyl~ 3~(t,2,4~triazol-1-yl~-
propionitrile hydronitrate,
2-ethoxy-2-phenyl-3-(1,2~4-triazol-1-yl)-propionitrile
hydronitrate,
2-allyloxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile
hydronitrat~,
2-(2-chlorophenyl)-2~propoxy~3~ 2,4-triazol-1-yl)-
propionitrile hydronitrate,2-(4-chlorophenyl)-2-hexyloxy-3-~1,2~4-triazol~l-yl)-pxopionitril~ hydronitrate,
2-hexyloxy-2 (2-methylphenyl)-3~ 2,4-triazol-1-yl)-
propionitrile,
2-butoxy-2-ph~nyl-3-~1~2,~-triazol-1-yl~ propionitrile~
2-(2 ch~orophenyl~-2-butoxy-3~ 9 4~triazol~l-yl)
propionitrileO
5~
.,
2~ethoxy-2-phenyl-3-(1,2,4-triazol-1-yt)-propionitrile,
2-allyloxy-2-phenyl-3-(1,2,4-triazol-1-yl)-propionitrile,
2-(2-chlorophenyl)-2-propoxy~3-(1,2,4 triazol-l-yl~-
propionitrile.
Th~ compounds ~ccording to the pre~ent invention
exhibitO in p~rticular, fungicidal actions but/ at the
same timP/ are distinguished by a growth-xegulatory
action in a number o~ crop plants~ Further, dep~n~;n~
on the type of plant and the application quantityO
herbicidal effects also are produoed and make possible
weed control in such c ses.
Since the compounds according to the inv~ntion can
both bring about quantitative and qualitative changes
in the plant~ and alter the metabolism o plant~ they
are to be classified as plant yrowth regulatorsO which
are di~tinguished by the following possible application~:
inhibition of the vegetati~e growth in woody and
herbaceous plant~, for example on road~ides, railway
track3? etc., to prevent l~lsh growth,
2~ growth inhibition in cereals to prevent lo~ging
or snapping off and in cotton ~o increase the yield,
illfluencing of branching of vegetative and
gen~rative organs in orn~mental and crop plants to
increase the amOUllt ~f blo~som or in tobacco and
~5 tomatoes to inhibit the formation of side sh~ots,
improvement of fruit quality, for example an increase
in the sugar content in ~ugar cane, in sugax beet ox
in fruit, and a more even maturation of the crop whieh
result~ in higher yield3,
3~
. ,
-- o --
raising of the re3istance to climatic effect~ quch
a3 cold and drought~
influenciny of the latex flow in rubber pl~nt~
Other po~sible applications areo
development of parthenocarpic fruits, pollen
sterility and sex determi~ation,
control of the germination of seeds or the pro-
duction of buds~
defolia~ion or influenciny of fruit drop to faci-
li~ate harvestinq.
Th~ compounds accordi~g to the invention are
especially suitable for influencing the growth of Beta
(~eet) cxop~ but also have desirable growth-regulatory
; effect~ in cereals, soya and cotton or also generally
in plantation crops.
It will be appreciated that not every com~ound
will have the same herbi~ida~, fungicidal and/or
regulating actions with every ~ype o plant, type o
applicationt time of application or concentration appliedO
Depending on the purpose ~f application, the
application quantities are generally in the range of from
0.05 to 5 kg of active substance/hectare, but gr~ater
applic~tion quantities may be used if appropriate. When
two or more cornpounds axe used the range of from 0.05
~o 5 kg per hectare refer3, of course~ to the total
application quantities~
The time of application varie~ in accordance with
the purpose of application and the climatic conditions~
The compounds o t~e present invention can ~e
applied to seeds, germinating ~eeds (before or after
S emergence~, roots, stalks, l~ave~, blos~om, produce or
other parts of the plant~ as desired.
Surprisingly, the action of the compounds according
to the present inYention i9 broader or stronger than
that of known products having the same direction of
actionO
In addition to the actions described above, the
compounds according to the present inventio~ al50 have
a bactericidal action which allows further pos~ible
application~. Treatment of animate, for example living
plan~s, and ; n~n;m~te ~ubstrates to pro~ect against
bacterial attack is thu~ possible.
The present invention accordingly al30 pxovide~
a biocidal preparatio~ which c~mprises at least one
compound selected rrom compounds of the general formula
I and salts thereof with inorganic and organic acids,
in admixture or ~onjunction with a suitable carrier.
The present invention further provide~ a method
of protecting a living plant against weeds and/or
phytopathogenic fungi andJor of regulating its growth,
wherein the living plant and/or the area in the vicinity
of the ~iving plant i~/are treated with a compound
sel~cted from compounds of the general formula I and
~alt~ thereof with inorganic and organic acid~
.3~
,~ ..
- 12 -
The present invention fuxther provides a method of
protecting a crop area against weeds and/or phytopath~-
genic fungi and/or of regulating the growth of plant~ in
the area, wherein the crop area is treated with a
compound selected from compounds of the general fonnula
I and salts thereof with inoryanic and organic acids.
The pre~e~t invention further provide3 a method
of dressing seeds0 wherein t~e seeds are treated with
a compound selected from compounds of the general formula
I and salts thereof with inorganic and organic acid~.
The present invention also provide~ a method of
protecting a substrate against hacteria, wherein the
su~strate i~ treated with a sompound select~d from
compounds of the general formula I and salts thereof with
inorganic and organic acidsO
The presenk invention further provides a pack
which compri~es a compound selected from compound~ of
the general formula I and salts thereof with inorganic
and organic acids, together with instructions for it5
use as a herbici~e and/or fungicide and/or bactericide
and/or for regulating the growth of a living plant~
The compounds according to the invention can be
used on their own or in admixture wit h one anothex or
with other active substances. Other plant-protective
25 agent s or pest-cont rolling agerlt s or defoliants may
opkionally be added~ depending on the desired application~
5~
13 -
The active substances of the present invention or
mixtures thereof are advantageously ap~lied in the
form of biocidal preparations, for example powder~,
strewable agent3l granule~, solutions, emulsions or
suspension~, with the addition of solid and/or liquid
carriers, and diluPnt~ and, if de~ired, wetting ayents,
adhe3ive agent~, emulsifiers and/or dispersing auxili~rie~O
Suita~le liquid carriers are, for exampleg water 9
aliphatic and aromatic hydrocarkon~, for example benzene,
lG toluenel xylene, cyclohexanone, i~ophorone, dimethyl
sulphoxide, dimethylformamide, and al~o mineral oil
fractions and vegetable oilq9
As solid carrier~ there are suitable mineral
earth~, for ex~mple Tonsil ~a trade marX~, silica gel,
talcO kaslin, attapulgite, limestone, silicic acid and
vegetable product~, for exam~le meals.
Surface~actiYe substance which may be mentioned
are, for examplel calciwm lignin sulphonate, polyoxy-
ethylene-alkylphenyl ethers, naphthalenesulphonic acids
~0 and salts there~f~ formaldehyde condensates, fatty
alco~ol sulphates and al~o substituted benzenesul.phonic
acids and salts thereof.
Where the active substances are to be u~ed fGr
dressiny seeds, they may also be admixed with colouring
substances to give the dressed seed a clearly visible
coloux.
The total amount of the active ~ub~tance or
suhstance~ in the various preparations can vary within
wide limit~ For example, the ~gents ma~y contain in
the range of from approxi~ately 10 to 9~0 by weight
active ~ubstance(s), from approximately 90 to 10
by weight liquid or solid carrier~s) and also, if
desired, up to 2~h by weight ~urface-active agent(s~.
The agent3 may be ~pplied in custom~ry manner,
for ~m~l e with water as the carrier in spray
liquor quantities of in the range of from appro~imately
~00 to 1000 litre~/hectare. It is equally possible
to use the agents in a s~-called "Low-Volume-Proce3s"
or "Ultra-Lvw-~olume-Process" and to apply them in the
fvrm of so-called microgranules.
The following constikuents~ for example, may be
used for the manufacture of a preparatio~ of the
invention:
A. Sprayable powder
a) 40 % by weight active substance
25 % by weight clay minerals
20 % by weight silicic acid
10 % by weigh~ cellulose pitch
5 % by weight surface-active substance based on a
mixture o~ the calcium salt o~
5~
~ 5 ~
l; ,~ni n~phonic acid ~d al~l~
phenolpolygl~cvl ethe~s
b) 25 % by weight active substa~e
60 % by weight kaoli~
10 5~ b;y ~-eight silicic acid
5 5~ bsr weight surface~ astive su~sta7lces based nn
the sodium ~alt of :~met~
o~ e;yltaurirle ~ ~he calcium ~alt
0~ J ~ ~i n~ulphon:ic acid
lo . c3 lo ~ by ~eight acti~e ~ubsl;~ce
60 % b~sr ~eight clay mi~eral~
:15 ~ by weight ~ilicic acid
10 ~ ~y weight oell~lo~ pit~h
5 % by weight ~ face acti~e su~3t~ces ba~ed o:~
.,he 30dium s~lt o~ ~-methyl~ oleyl~
tau~ e a~d the ~ci~m sal t o~
1 ~ ~n i n ~ l.phonic ac~id
R. Pa~e
4~ ~ by weight act~ive substance
20 5 % b~ weight sodi~L~n aluminium s~licate
15 5~ by weight cetylpol~gl~col e~he~o ~ith 8 moles o:~
ethylerLe o~:ide
2 ~; by wei~ht spindle vil
10 % ~y weight polyeth~lerleglyc~l
25 2~ part~ water
C. Emulsion concentrate
25 % by weight active sub~tance
15 % by weight cyclohexanone
55 % by weight ~ylene
5 % by weight mixture o~ nonylphenylpolyoxyethylene
or calcium dodecyl~enzene ~ulphonate~
The pre~ent invention further prQVideS a process
for the preparation of a compound of the invention, or
a salt thereof, which compri~es reacting a c~mpound
of the general formula
O~
R _ C _ CH2 - Y II
CN
in which R and Rl have th~ meaning~ given above and Y
represents a halogen atom or an alkylsulphonyloxy or
arylsulphonyloxy radical which is optionally halogenat~d
in the side chain
with a compcund o~ the formula
~ - CH
Il 11
HC N
H
or an alkali. metal derivative thereof
if desired in the pre~ence o~ a ~olvent and,
optionally, in the pre~ence of a ba~e
9~
1 7
and, if d~ired, a ~ompound of the general formula I
i~ convexted into an acid addition salt thereof with
an inorganic or organic acid and/or acid addition
salt i~ converted înto a corre~ponding free compound
of the general formula I.
As a halo~en atom represented by Y, ther~ may
be mentioned, for ~x~mrle, a chlorine, bromine and
iodine atom' as an alkylsulphonyloxy ra~ical
repre~ented by Y ther~ are suita~le, for exa~ple
a methyl,, ethyl--, propyl~ and trifluoromethyl-
sulphonyloxy group, and a~ an arylsulp~onyloxy
radical represented by ~ there may be ~entioned~ ~or
exampl~, a ben enesulphonyloxy and p-toluenesulphonyloxy
group,
The reaction may ke carried out bo~h with an
exce~s of 1,204-triazole optionally in the presence
of a ~olvent and with the addition of a strong base,
for example sodi~m hydroxide ox potassium hydroxide.
In additi~n~ a 1,2,4 triazole-alkali metal
derivative may be used instead of 1,2,4-triazoleO
Suitable solvents are those which are inert
toward~ the reactants, preferably those o~ a polar,
aprotic nature, ~uch a~ ~,N-dimethylfonmamide,
,~ ¢~ 3<~
- 18 -
dimethylacetamide, ~-methylpyrrolidone,
tetramethylurea~ hexamethylphosphoric acid triamide
and k~nzonitrile, but higher boiling point aromatic
and aliphatic hydrocar~ons, such as toluene,
5 chlorobenzene or xylene, may also be u~ed~
The reaction tempera~ure may be varied within
wide limit~O A temperature in the range of from
10~ C to 200C i~ preferred~ The reaction may be
caxried out under normal or exce~s pressure.
The 1,2,4-triazol-1-yl-propionitriles according
to the invention are, in general, almost colourless
and odourless ~olid substance~O The acid addition
- 19 ~
salts derived therefrom are also colourless ~nd
odourles~, crystalline compounds. The free base3 are
~paringly soluble in water and more or les~ readily
soluble in organic so7vents, such a~, for exa~ple,
alcohols d ethers or chlorinated hydrocarbons~ The acid
addition salts are to some extent soluble in water and
readily soluble in polar organic solvents such as
acetonitrile~ N,~-dimethylform~mide~ lower alcohols~
chloroform and methylene chloride.
The following Examp~e.~ illustrate the invention. Unless
otherwise specified 9 percentages are given hereinafter on a
- weight basis~ -
Exampl~ 1
2-Isopropoxy-2-phenyl 3~ 2~4-triazo~ yl)~propi
nitrile hydronitrate
(Compound no. 2)
0.55 mol of 1,2,4-triazole is added~ while stirring
and cooling, to sodium hydride (0.55 mol~ suspended in
50 ml of dry dimethyl formamide (DM~). O.11 mol of
2-isopropoxy-3-methylsulphonyloxy-2-phenylpropionitrile
in 50 ml of DMF i~ then added an~ the whole is maintained
at a bath temperature of 150 C for 1.5 hours. After
cooling, the mixture is extracted three times with
100 ml of ether, the com~ined ether phases are washed
twice with water and dried with ma~nesium sulphateO
MgS0~. The ether i9 concentrated by rotary evaporation
in vacuo, 50 ml of isopropanol are added to the
residue an~, while 3tirring and cooling J 6~8 ml of
~ hJ
- 20 _
concentrated nitric acid are added dropwi~e. After the
additon of 80 ml of ether, the mix~ure i9 ~tirred for a
further 1~4 hour and then suction-filtered.
Recry~talli~ation i~ effected from isopropanoln
m.~. 185-189 C (with deco~po~itlon)
Yield: 15 g = 43 % o~ the theoretlcal yield~
Example 2
2 Isopropoxy-2-phenyl-3~(1,2,4-triazol-l-yl~-pr~pi~
nitrile
(C~ d no. 3)
10 g of the hydronitxa~e of ~-isopropoxy~2-phenyl-
3-(1 t 2,4-triaæol-l-yl~-propionitrile ~btained in Example
1 are di~olved in ~ethanol and 8 ml of 32 %:-~
strength ~mmo~ia water are added~ ~he mixture is poured
into water, extracted with ethyl acet~te, dried over
magnesium ~ulphate, MgS04, the ethyl acetate i~
concentrated by rotary evaporation in VACUO, a lit~e
ethyl acetate and active carbon are added, the mixture
i~ boiled briefly, 3u~tion-filtered and again concen
tratecl by rotary evaporation. The re~ulting ~olid i~
analytically pure~
m.p. 176-177C
Yield: 6.65 g ~ 83 % of the theoretical yieldO
~ 21 -
The Xoll~win~ compounds according to the invention
can be prepared in an analogou~ r~anner tc~ that de~cribed
in Exal~ple 1 or E~ample 2. "D" under physical con3tant
indicate~3 ~decompo~;it~
3{~
~2 -
Compound no. N~me of c~mpound Physical c~n~tant
lo 2-~xyloxy-2-t2-
methylphenyl)-3~
(1,2,4~triazol-1-
ylj-prop.ionitrile
hydronitrate m.p. 159-162C (D)
4. 2-Butoxy-2 (2-
methylphenyl~-3
(102,4-triazol-l~
y7)-propionitrile m.p. 58 62~C
2-Butoxy-2-(2-
methylphenyl)-3-
~1,2,4-triazol-1-
yl) propionitrile
~5 hydronitrate m.p. 158-~61C (D)
2-Hexyloxy~2~ 20
methylphenyl3~3-
( 1 ~ 2 J 4-triazol 1-
yl)~propionitrile nD40: 1.5121
2D 7. 2-Butoxy-2~phenyl-
3-(~2,4-$riazol~-
l-yl)-propionitrile
hydr~nltrate m.p. 159~1~0C (D3
8~ 2~Butoxy~2~2-
chlorophenyl)-3
(1,2,4-triazol-1-
yl)-propionitrile
hydronitrate m.p. 142.5-i44C ~D~
_ ~3 _
Compound no. Name of compound Physical constant
9. 2-Ethoxy-2-phenyl-
3-~1,2,4-triazol-l-
yl)-propionitrile
hydronitrate mOp. 169-170~C (D)
10. 2-P~enyl-2-propoxy-
3~ 2,4-tria ol~l-
yl3-pxopionitrile
hydronitrate m.p. 178 179 C ~D)
~0 11. 2-~3~Chlorophenyl)-
2-hexyloxy-3-(1,2,4-
triazol-l-yl)~propio~
nitrile hydronitrate m.p. ~73-~75~C (D)
12~ 2-Butoxy-2-phenyl-
3-(1,2,4-triazol-
l-yl)-propionitrile m.p. 67-68C
13. 2-Pheny~-2-propoxy-
3-(1S2 t 4-triazol
l-yl)-propionitrile mvp. 107-108C
20 1~0 2-~thoxy-2-phenyl-
3 (1,2~4-triazol-
l-yl)-propionitrile m.p. 74~75~C
15 . 2--~Iexyloxy~ 2-phenyl-
3- ( 1, 2, 4-triazol~
l~yl )-propionitrile
hydrorlitrate m.pO 158~1 60C ~D~
-- 24 --
Compound no,, ~ne of compound Phy3ical con~tant
1 ~. 2~ 1ylox~r~2-
~enyl-3 r ( 1 ~ 2 ~ 4
txiazol-l-yl )-
propionitrile
hydronitrate m~p. 145-~47C (D~
1 7 . 2-Butoxy~ 2- ( 4
chlorophenyl )-3-
( 1, 2, 4 -triazol-
l-yl )~propio
nitrile hydro-
nitrate m~pO ~ 73-1 ~5C ~D)
1 8. 2-Allyloxy-2-phenyl-
3- ~ 1, 2, 4~triazol~
l~yl )-propionitrile m.p. 86-88C
19 . 2-~5ethoxy-2-phenyl
3- ~ ~, 2, 4-triazol-
l-yl )-propionitrile m.p. 77-?9C
20 . 2-~Ie~yloxy~ 2-phe~nyl-
3- ( 1 ~ 2 ~ 4-triazol-
l-yl )-propionitrile ~IIIap~ 58 SOC
21 ,. 2- ( 2-Chlorophenyl ~
2-hexyloxy 3~ ~1, 2, 4-
triazol-1-yl ~-
propionitrile hydrc)
nitrate m.p. 157--1 59C (D)
_ . I
~5~
,.,
~ ~5 --
Co~pous~d no. Narne of compound Physical constant
~2 . 2- ( 2-Chlorophenyl )-
2--p~opoxy--3--( 1, 2,
txiazol~ yl ~-pro-
pionitrile hydro-
nitrate la.p,, 138-1 39C~c (D)
2 3 7 2- ( 4-Chlorc:phenyl ) -
2-propo~-3-(1 "2,~
triazol-l-yl )-prs-
1 S~ pionitrile hydrs:
- nitra~e m.p. 155-1 7~C (D)
24 ~. 2- ~ 4-Chlorophenyl 3-
2-hexyloxy-3- ( t ~ 2, 4
triazol-~ -yl )-pro-
pionitrile hydro-
nitrate m~p. 155-1 5g C (D)
2~ . 2~ Chlorophenyl )-
2 ~propoxy- 3 ( 1, 2, 4-
triazol-l-yl ~-pro-
pionitrile m~p.115-119~
26 . 2-BIltoxy-2- ( 4-
chlorophenyl )-3~
( 1, 2, 4-triazol-l -
yl )-propionitrile m.p.54-60C
27 . 2- ( 2-Methylphenyl )-
~--oc~loxy-3-5 l, ~ ~4-
triazol l-yl ~-pro~
pionitrile hydro~
nitrate m~p . ~ 2l3 1 34~C ~D )
5~3~
26
Compound no. Name c:~f compound ~hy3ical constant
28......... 2-Decyloxy-2-
( ~-methylphenyl )
3- ( 1, 2, 4-~riazol-
l~ propionitrile
hydronitrate m.p. 116~1 20C7c ~D~
2g ,. ~- ( 2-Methylphenyl )~
2--oc~rloxy--3~ 9 4-
triaæol-l-yl ~-pro-
pionitrile nD2C). 1.~930
30. 2- ( 2-Chlorophenyl )-
2-~ut~x~ 3- ( I , ~ ~ 4-
triazol-l-yl )-pro-
pioni~ril.o n~ ~40 1 . 5273
1 5 3 ~ . 2- ( 2-Chlorophenyl )-
2-propoxy-3 ~ ~ 1, 2 t 4~
triazol~l-yl ~-pro-
pionitrile nD40 t . 5 308
3 2 . 2-Butoxy 2- ( 2, 4-
clichl~rophenyl )-
3- ( 1, 2, 4-triazol-
1-yl )-propioni~rile
hydronitrat~ ra.p. 163-1 66C
3 3 " ~ -~3utc~xy--2-- ~ 2 " ~
dichlorophenyl ~-
3- ( t 3 ;! ~ 4-triazc)l-
l-yl ~-propionitrile m.p,. 53-55C
35~
.. , ~
_ 27 ~
Compo~md no. Ncl~e of compound Physical constant
3~. 2~ lo~y 2-
(2,4-dichloro-
phenyl)~3-(1,2,4-
triazol-l~yl)-pro-
pionitri~ m~p. 104-1 07C
35. 2-(3,4~ichloro-
p~enyl)-~-propoxy-
3-~1,2,4-triazol-
l-yl)-propionitrile
hydronitr~te m.p. 1~ 155C (D~
36. 2-(3,4-Dichloro-
phenyl)-2-propoxy-
3-(1,2,~-triazol-
l-yl)-propionitrile m.p. 60-66C
37. 2-~3,4-Dichloro-
phenyl)-2~hexyloxy-
3~(1,2~4-triazol-
l-yl)-propionitrile
hydronitrate ~.p. 166-168~
38. 2-~3~4-Dichloro~-
~henyl)-2-hexyloxy~
3-(1,~,4-triazol-
1 yl)-prQpionitrile nD40 1.5240
25 390 2-~4-Fluorophenyl)-
2~pr~poxy-3-~1,2,4-
triazol~l-yl~pro-
pionîtrile hydro-
nitrate m.p~ 172-175C [D~
3~43~
~ 28 _
Compound no. ~ame of compound Phy~ical con~tant
40 n 2-(4~Fluorophenyl~-
2-propoxy-3-(1,2,4-
triazol-l-yl)-pxo-
pionitrile m.p. 98-100C
41. 2-Butoxy-2-(4-~
fluorophe~yl)-3-
(1,2,4-triazol-
l-yl)-propionitrile
hydronitrate m.p. 173-175~C (D~
42. 2-Butoxy-2-~4-
fluorophenyl)-
3-~1,2,~-triazol-
l-yl~propionitrile m.p~ 56-58~C
43. 2-(2-Fluorophenyl)-
2-propoxy-3-(1 t ~ ~ 4~
triazol-l-yl)-pro-
pionitrile hydro~
nitrat~ m~p~ 150-153~C (D)
44. 2-(2-Fluorophenyl~-
2-propoxy-3-(1,2,4-
triazol-l-yl)-pro~
pionitrile m.p. 66-69C
45. 2-Butox~-2-(2-
fluorophenyl)-3-
~1,2,4-triazol-l-
yl)-propionitrile
hydronitrate m.p~ 138-143& (D)
3~
- 29 -
Compound no~ ~me of compound Phy3ical con~t~nt
4~0 2-~utoxy-~-(2-
fluorophenyl3 3-
(1,2,4-triazol
l-yl)-propionitrile m~pO 76-79C
47~ 2 (2~Fluorophenyl) -
2-h~xyloxy 3-~1,204
triazol-l-yl)-pro-
pionitrile hydro-
nitxate m.p. 134-137 (D)
48~ 2-(2-Fluorophenyl)-
2-hexyloxy-3-(1,2,4-
triazol~l-yl)-pro~r
pionitrile m.pO 58-60~C
15 49. 2-(4-Bromophenyl~-
2-propoxy-3-(1,2,4
triazol-l~yl)-pro-
pionitrile hydro-
nitrate m.p. 150-153C (D)
20 50. ~-(4-Bromophenyl)-
2~propoxy-3-~1,2,4
triazol-l-yl)-pro-
pionitril2 m.p. 118-121~C
51. 2-~4-Bromophenyl~-
2-hexyloxy-3-(1,2,4-
triazol~l-yl)-pro-
pionitrile hydro-
nitrate m~pO 161-164~C ~D~
t,~-' 7
Q~
- 30 _
Compound noO Name of compound Physical con~k~nt
52. 2 (4 Bromophenyl~-
2-hexyloxy-3-(1,2,4-
triazol-l~yl)-pxo-
pionitrile m.p. 60-62C
53. 2-(2,4~Dichlo~o
phenyl)~2-propo~y-
3~ 2,4-triazol~
l-yl)-propionitrile
hydronitrate m.p. 166-170C (D)
54. ~-(2,4-Dichloro-
phenyl)-2-propoxy-
3~ 2,4 tria~ol~
l-yl)-propionitril~ m.p~ 61~63C
55. 2-~2-Methylphenyl~-
2~pentyl~3~(1,2,4~
triazol-l-yl)-prs-
pionitrile hydro-
nitrate m~p. ~51=~54C (D)
5~- 2 (2-Methylp~enyl)-
2-pentyl~3-~1,2,4-
triazol-l-yl)-pro-
piGnitrile ~ 4~: 1.5~1
57. 2-(4-Methylphenyl)-
2-propoxy-3~ 2~4
kriazol-l~yl)-pro-
pion.itrile hydro~
nitrate m~pO t70~171~C (D~
~9~
Compound noO Name of compound Physical con~tant
58~ 2~exyloxy-2~(4~
methylphenyl)-3-
(1,2,4-triazol~
yl)-propionitrile
hydronitrate m~p. 177-1 8~C ~D)
S9~ 2-(4-Methylphenyl)-
2-propoxy-~-(1ç2,4-
triazol-l~yl)-pro-
pionitrile m.p. 1 20 - 124&
500 2-~exyloxy-2~
methylphenyl) 3-
( 1, , 4-t~iazol~l
yl)-propionitrile n~400 1.5065
15 61. 2~But~xy-2-~4-
methylphenyl)-3-
(1,2,4-triazol-1-
yl)-propionitrile mOp~ 71-73C~
~ 32 -
The 3-aryl- and 3-alkyl-sulphonyloxypropionitrile~
of the ge~eral for~ula II in which Y repre ent3
respectively aryl~ and alkyl~3ulphonyloxy which are to
bP used as starting materials ha~e not hithexto been
5 described in the literature.
~ hey may be obtained by hydroxymethylati~gO by
methods known ~ se, phenylacetonitriles of the
_
general formula
- Rl
R C~ III
C~
in which R and R1 have the meanings given a~ove,
some of w~ich are known or can be obtained by method3
known E~ se (cfo for example Rubin et al. ! JACS 67,
192 f (19~5), Hess et a~., Ber~ dto chem. GesO 50,
394 ~1917))or by rea~ting the 3-hydroxypropionitriles
of the general formula
0 R
R ~ C~ _ O~I IV
1 2
CN
with a suitable sulphonic acid derivativel for example,
a sulphonic acid chloride, optionally with the addition
of an acid binder~ The hydroxymethyl compounds
of the general formula IV have not hitherto
3~;~
-- 33--
been k~o~ ~rom the literatu:rei
The mar~u~acture of a Btl3:rt~;, material is des-
cribed belo~
~S-Meth~rlsulphon~ 2-phen~1~2-proPo:~-Pr~ ~ionitrile
27 g (00154 mol) of 2-p~e~ propo~y-aceto~ .
~itrile are d*ssol~rea in 120 ml of p;srridi~, ~d la;,~ g
~0~,614 mol~ o~ paraformaldehyde are addea~ To ~
su~perl~ion~ 7.7 ml o~ tet;rabutylammonium h;yaro~:ide
(T~0~) are added as a 40 ~ ~tre~th sc)lu~io~ wh~l~
~0 cooling with ice and the whole is m~ ed thoroughl~ by
srigorous B'GirT~g. ~fter a fe~ hours (~1~ morLLto~i~g),
the mixture i~ poured i~ltC ice~water allG e~ctracted
wi Ith ether,, The ethe~ p~se i~ ~ashea wi~h dil~te
hydr~c~loYic acid and the:r~ with ~di~n chloride ~ol~-
5 tiorl ~d dried over ma,gDesium ~lalp~atel. ~ter re-
mo~ing ~he dryi~lg age~t by iiltrati~n a~d co~centrat-
ing by rotary evaporatio~ in vacuo, a colourles~ oil
reln~;nF~ beh~:Ld which is fou~d to be homo~eIleo~s
according t~ t~in layer chromato~ph~ a~ caD be
20 *ur~her prooes~ed Wit~lGUJt further puri~icati~e,
Yield~ 28.4 g = 90 ~ o~ the theoretical ~eld of 3
hydro~y-2 pl~exlyl-2-propo~ propio~tril~
~D D 1~ 5027
28 g ( O ~ 6 mol ) OI 3-hydro~y-2~phe~yl-2--pr~
25 po~y-propionitrile are dissolved i~ 200 ~1 of toltle~
and 19,D5 g ( 0~171 mol) of meth~e3ulpho~1 c~loride
are added~. ~t lO~C, 18,.6 g (0,,18~ mol~ OI t~ Le~h;yl
I
9~
3~,
amir~e are added dropwi~e. The mi~ure is sti~red for
30 minute~ at room temperature9 Ii~tered ~rom the
precip~tated triethylamin~ h~drorhloride and co~ce~-
tratedO ~he re~iaue i~ taken up ~n ether~ ~a~hed ~ith
5 ~?ater~ driea over magnesium sulphate arld c~rlcentrated.
~he oily re~idue i~ f~ d ts be p~re accord:Lng to th~
7 a;srer chromatograph;~O
~ielda 32~27 g - 86 ~ OI the theoretical ~ield o~ 3-
me~h;yls~alpho;~yl-2~phe2:ly?-2 propo:~y-propio-
0 nitr;l~
rlD20: 1. 5QOS)
~ he following e:~empla~ emb~dime~t~ illustratethe po~ible applicatio~s o~ the compo~d~ acco:rd~g
to the ~ventio~) in the ~orm o~ the preparatioII3
5 menti onea abov~O
~amPle
E:f ~ect OI prophylactic leaf treatme~t ~gain~t true
milde~r ~rYsiphe ~r~min;æ ~ barley irl a greenho~
~oung barle r plaD~ at the Iir3t lea~ stage were
20 ~pray~d u:llt~l drippi:~g wet with the stated concentratio~
When the spray coating~ had dried9 the treated plant~
a~d also untreated co~trol plants were inoculated
with d~ mildew spore~ by bei~g ~tr~ked ~ith in~ected
plants. The te~t pla~t~ were then cu:Lti~ted i~n a
25 greenhou~e a~ appro:~imately 20 to 22C and; a~ter
o~e ~ee ,, ~ere E1~18e~19~1l *or the RercerLt 3ge attack of
~m 3~ ~
the lea~ ~ur~aceO ~he fungicidal e~fec~ WEL8 ca:Lcu-
lated a~ ~ollow~
100 ~ttac3~ ~ treated O lO0 _ % eE~f~ct;
httack in urltrea~ed
5~he compounds ~ere us~d P9 20 ~6 ~tren~th ~ormu
lation~ .
Compow~d accord~ Er~ he ,E~r~m;n~
t~ the in~elltion ~oO ~ effe~t
5~0 ppM ILOO ppm;~
1 lOO 95
2 ~00 ~9
100 ~Oo
4 10~ 100
lOû ~5
1 5 6 lOO 94
7 lOO 100
8 l~O lO0
10~ ~
2~ 11 100 9
1~ 100 1~
1~ 100 100
14 ~OO 100
1~ 100 100
1~ 10~ 10
1~ 100 ~ 0
18 1(~
Compvu~d accord~ng :~iphe ~mi n-;
to the i~Yentio~ ~Jo~ f:e~ct
~00 ppm 10~ pp6
19 10~:) 10
101
)0 9~
~00 1~0
23 109 1~)0
2~ 100
0 ~5 100
26 1(10
~8 100 95
3C) 10~ 100
31 10~) 100
33 100 lt)O
34 1~30 10~
3~ 100 100
36 lbO 1(:~0
38 ~ 0~
41 100 1~0
~2 100 lQO
44 100 ~ ~0
~8 1(~ 95
49 100 lC)~)
~ 10
51 lûO 10~
52 100 100
s~
-- 37
Compound according:E~rvsiphe ~ram:lnis
t~ the i~er~tion NoO ~ eXfect
50û ppm 103 ppm
53 1(~0 100
0 ~0~
' 100 1~0
~7 1~0 l~û
58 100 100
5~ 100 :1 00
1 O 60 10~ 100
~1 100 100
amPle 4
~ffect of prophylactic lea~ treatme::Lt agai~L3t
Er~siphe cichoracearum in go~ -plant~ ~ a greenhou~ -
~ourd pla~Lts sprayed u~til drippi:clg ~et ~ith the
~tated concentrations ~ere ~oculatcd9 aIter the ~pray
coati~g had dri~at by being du~ted with d~ milde~
~pores o~ :E~}siphe cichoracearum a:~d i:~lcubated toge~her
~.h inoculated untreated co~trol plarlts i3~ a g~ee~-
20 hou~e at 24C. ~ter o~e ~e~k~ the ~urXace area
a:fIected by milde~ a~ a percentage OI the en~ire lea~
~urface ar~a was estirllated9 ~he fungicldal effect ~as
calculated as f ollow6:
100 100 o ~ttack i~ treated = ~, eEf~c~;
httack i~ untreaJçed
~he letter "~ the fol~ ow~ng table denote~
~s~
3~ ~
thal; th~ iungicida~ ac~ion co~d al60 be ~s~e~ed
the growth of the plant~ ( a~ter treatme~t~ ~nd wa~ .
xound to be positive~ Tha~ is to sa;sr, the act.ive
~ubst~ces ~re tran~ported s:~ste~icall~ in the addi-
5 tio~al growth ~d showed one hu~dred per ce~t aetio~
i n Rt mildew ~n that grow th al800
The compoulld~ accordirlg to the inventio~l were
used a3 20 5~ s-~rength formulati~n~0
Compou~d according ~ lph~ cichoracear~m
~o to the in~ention 15~o~ ~ effect
250 ~5 5 2.5 0.5 ppm
1~08 10~8 10~
100~ 1005 lOOs
3 10û6 100~ 06
4 100~ 1~0~ 100
10~ 1008 10~
6 1008 1~)09 100
7 ~00 100 1~0
8 . 100~ 9E~ 100
. 9 100~ 1008 100
100~ 10~ 10~
11 100~ lOOs 100
12 10~ 100
13 100~
1~ 1008 1008 100
1~ 100~ 1~0 10~
1~ lûO~ 100 99O 5
.2~
Compound accordingErv~iphe cichoracearum
the ~ent i~ eII e ct
25C) ~ 2~g45 PP~
17 ~0~ 1008 1~0
1~ 10~)~ 100
19 100~ 100 97
1006
0~' 100 9~
~2 100~ 103 1 00
0 ~7 l~)Os
2g ~.00~
32 - 1005
37 100
39 l~û~
1 ~ 40 10~8
~ lOûs
lC~
4~; 1008
47 100
~ ~6 100
~:~ampl~ 5
:E~fect ~%) of prophylactic lea~ treatment aga~n~t
Helmintho~porium teres (= P~reno~hora tere~3, net
blotch disea~e, in barley
Yo~g barle;y plant~ at the fir~t lea~ stage were
~pray~d until dripping ~et with the atated co~centra-
tion~. When the ~pray coating~3 ~ad dried, the treated
5~
.
-~ 40 ~
plant~ and untreated control pl~ta wzre ~prayed ~ith
a ~u~pensio~ o~ ~he conidio~pores of He:Lmintho~orium
teres a~d :incubated ill a moi6t chamber ~or 2 day~ at
~rcm 20 to 22CC., ~he pla~ts ~e~ç then culti~ated in
5 a gree~iholl~e at 20 to 22ar O~le ~ek a:~ter ~oculatioxl,
the percPntage attack of the les:~ sur:~ace~ wa~ no~edl,
~he f~gicidal e~ect wa~ calculated a~ ~ol:lo~o
~ttack i~l treated . 100
100 ~ ef~ect
~ttack i~ untrea~e~
~ he compound~-were used a~ 20 ~ strength :forml:Lla
ti~n~"
Compou~d according Hel "~ tho~o~ium teres
to the in~er~tion ~0~D ~ e:ffect
5G0 ppm1 00 ppm 10 ppm
100 100
2 l~0 lO0 lO0
3 lO0 ~ :)0 ~()
g5 90
l~0 lO0
6 9~
7 9~ 90
8 8
1~)0 8
2~ lO 95 g5
100 90
12 94 9C)
~1~5~
Compou~d accord-~g Helmintho~pori~m teres
to the inve~tion ~o,, ,~ effect
500 ppm lûû ppm 10 ppm
1~5 92 85
14 ~39 8~)
- 15 94 9~
16 94 80
17 89
18 100 7~)
1 0~9 9~
7~)
23 . ~35
~, 9~ go
~ 9~ 95
1 5 2~ 80
27 90
:E~am~le 6
:liifect o~ proph~ylactic leaf treatmell~ agai~st dwarf
~ Puccinia horde:~ in ba:rley in a controlled cl~mat~
20 plænt grow~h chamber
You~g barle;y p:La~t~ at the ~i~st lea~ stage were
sprayed until dripping ~et with the ~ta ted conce~tra~
tion9~ When the spra~ coati:~gs had dried" the treated
pl~nts and untrea~ed c~:~trol plants were ~culated
b~y be:ing ~troked with plan~s ai~ectea by dwar~ rust
and placed ~ a plant grow th c~m~er~ ~t ~ 5C, and in
almDst moi~turesaturated air ~or the first tw~ day~,
~5~3~
.~
~2
~he pla~s were culti~rated ~or 10 day~O ~e per-
ce~tage propor~ion OI the :Leaf ~urface attacked b;y
~ust ~ the~ :~oted~D ~h~ fu:ngic~dal effect wa~ calcu~
lated as follOW8:
Atta~k i~ treat~d ~, 101~
; e*feot
~ttaek ~n ~trea~
'~he compo~ds wer~ used a~ 20 ~ ~tre~gth ~rm~a~
t~ons~,
o Compound . according
to the invention ~o., Placcinia hordei
~ ef~ect
500 ppm 100 ppm 20 pp~
1~ 77
1 5 2 ~0 ~3
100 100 83
100 1~0 94
. 6 100 9~
2~ 7 10~ 98 E~9
8 10~ 34 94
9 80
~0 100 98 ~4
11 89
12 ~
1~ ~39
14 ~5 80
~5~
-- ~3. --
C~mpsu~d according . .
to the inventinn Ii~ ccln a hordei
5C0 ppm 100 ppm 20 p~m
~. 7~3
~7 100 100 1
~ 9~3
1~ 95
~35
21 1~) :) 7
0 22 1~0 100
23 79
~4 90 7~
9 :) gO
27 85
5 30 ~;
31 g7
~am~le 7
~ctio~ n~t Pseudomvnzs ph~3eolicola, the cause o~
halo b~ight in bean~; ~ itro
Biomalt agar ~as r~oledj after heat st~r~ ation9
t~ appro~imatel;sr 45C aIld was then poured, together
with the te~t ~ubatance~ which had been m~:ed together
i~ a~ aqueou~ preparatiorLp ir~to plast~c~ petri dishesO
Whe:~ the nutrie~t medilam had ~et, the dishe~ o:f treated
agar alld a:Ls0 di~hee cont~;nirl untreated agax a~ a
co~trol were inoculated ~ the cen~re by mean~ o~
-
-- 44 ~
inoculat:ing lo~p with a suspe~ion of the halo bli~ht
pathogen Pseudomonas ~haseolicola. ~he di~he~ were
therl incubated at ~2C. ~Xter 2~ ~eek~, the radial
E3pread o~ the colo~e~ of bacte~ia which had grG~I
5 were mea~ured. ~om the ~verage Df t~o repe~itio~s
per te~t 3ample9 the bact~ria inhibi.ti:~lg action wa~
calculated as :~OllC~7E3.,
l~adial growth in treated O lOû = ~% ~h biti~
R~ growth i~ urltreatea
The compoundæ. were uæed a~ 20 % stre~gth ~o~nula
tionse,
Compo~d according 5~ action ~ith 250 ppm
to the i~ention N o O acti~e E~lab~ta~ce co~centratio:a
12 62
73
21 64
2~ 66
20 :Example 8
Act~ y o~ su}:)stance~ ln va~?ur f O~L again~t
FIelminthos~orium teres in barley in a greenhouse~
To determine thevapo~lr acti~ity, a po~ Cont~nin~
appro~cimatel~r 20 barley seedlings ~it.h the second lea~
~5 be~ nning to appezr was placed bet~eerL ~ pots oi
barley OXI which a d:~ ~p~;y coatillg ~ad dried ~ter a
dripping wet treatmen~G. The drip~ing wet treatme~t
5 ~ ~ ~
-- 45 ~
was carried out at arl active ~ub~tance concentration
o~ 0;,~ su~pensiox~ of the co~dia o~ the net
blotc~ pathogen Eelmintho~p~rium tere~, prepa:red with
a~ aqu~ou~3 ~o~ution o~ 0.,05 5~ ~odi~m oleate alld 0.0~! ~
5 gela~ine and adJ~sted to 10091:)00 ~p~re~; per m~ ;tre9
~a~ aprayed over ~11 three p4t~ in each test ~amp3~eO
~ter spraying o~ the ~pore~, the three pots i~ ~ach
te~t ~ample were enclo~ed in a polyethylene bag ~or
three d~ya a~d kepg ~der gree~:house c~xlditic:~3 o~
appro:~:imately 20Co The bags ~ere the:l:L opened ~y
cuttin~ them at the lev81 o' the leaf tips" ~ter 13
days ~ the num~er o~ net blo~ches per pot ~aa courltedO
m thi~ the :f~gic:~dalvapour action wa~ cal~ ed
as ~ollow~:
net blotches o~ e:~:pos~d barley ~ 100 = ~ actio~L
100
~et blotche~ on u~e g:po~ed barley
~he substar~ces according to ~:he in~e~tiorl were
u~ed a~ 20 ~ ~tre~th ~ormulati3ns. ~11 vapcur e~s-
i!O posures could be tolerated by t}:Le plants.
Compound according ~ effect
to the lnventio~ ~o~.
1~0
3 10
4 99
I
_ 46 ~--
Compotand accordi~g
to the ixaventio~ No" % ~f~e~
O 1
:L~ 8
5 Com~arlson a~ent
1- (4--Chloropheno~ 3 9 3 dlm~thyl~
1-(19,2~4 tria~ol-l-yl~ bu~rlon~ 86
:Exam~l~ 9
Sy~temic e~ect OI ~oil treatme~t beiore emerge~ce
~in~t ~ugar b~et mi:Lde~ :Ervsiphe pc>l~o~ ~ a gree~
house
Pla~ pot s~rn with BUgar ~eet were ~prayed with
0~,3 kg o~ actl~e substance per hectare a~d placea be~
~ide u~trea~ed pot~ in a greenho~e a~ appro:;:imately
20C. ~fter the beet plants had emerged (12 to 14 per
po1;~ ~ a ~aitirLg period ~as observed u~til the ~ir~t
two trlle le~es had de~eloped a~d the plants were the~
in~culated b~ being dusted with the dry ~pore~ o~
true beet mildew ~ siphe Pol~onil ~hree wee~
2c~ ~ ater ~ eekæ a~ter æoil treal;merlt~ the Attack oi
the lea~e~ was a~sessed, T~e ~ungîcidal effect c~uld
ha~e been achi eved only a~ a re~ult of the substance~
be~g ab~orbed v~a the plant roots arld was calculated
a~ ~0110~30
25 . Attack ~ treated ~
eI:~ect
~ttack ~n u~.treated
I
5~
. .
~7
~ he compound~ were u~ed as 20 ~ strengt~ formula~
tion~ 11 treatments ~ere ~ou~d to be tolerable
the pla:zlt6 and res~lted ~ mo:re vigorou~ ~d more
compact gro~h in comp~iso~ wit~ the untreated co~trol~
5 Compound according
to the inventio~ ~ot. ~fe~
1~ 10
13 10
14 10
10 E~ample 10
Soya and wheat ~ere sprayed i~ pr~emerge~ce with
eml:L18iO:!18 OI the test ~ub~tance~ he q~Pntit~ applied
was appro:gimately 2 kg o~ active substarlce~hectare.
The pla:~-t8 were then cu:Lti~ated in ~ gree~ouse and
5 m~a~red ~ter th~ee week~O
~ he recorded perce~tage growth inhibi~io~ iB
given iIl the ~able~
Oompound according Gro~th inhil~i~ion 1~ %
to the ~ve~tio~ Nc~o ~o;ya Wheat
2 39 28
~2 ~3
7 17 7
g 0 17
1~ 4 ~4
25 14 17 2~,
t~
....
Compo~nd accord~ Growth inhibition
to the i~ention ~ S~a Wheat
18 13 1~
22 6~ 21
~7
2~ 35 24
26 3
Com~ariE;on com~ound
1 o 2-Chloro~th;yl~r:~neth;yl_
ammonium chlor~ de 0 17
It will be ~3ee~ t~t 2 as a rale, the ac~io:~ c:f
the compou~d~ accord~g to the i:~entiorl iB stro:z~ge2
than that o~ t~e compari son comp~nd.
5 ~amPle ~1
Rice was treated i~ pre-emerge~oe with the com;~
pounds according to the invention irL application
quantitie~ o~ 2 kg of acti~e æub~.,ance~hec~are~, ~ter
three weeks ' cultivatio~ in a greenhou~;e, the per-
20 ce~tage gro~h inhibition ~as dete~minedO
Thi~ ls sh~wn in the ~able
~ompound accordingGrowth i~hlbitio~
to the ~nvention ~oO
22 ~1
2~ 7
., I
5~
_ 49 _
Gompo~d accordi~lg
t~ the inve~tion ~o.Growth inhibitior
- 26 1
Coml~ari~on comound
5 2-Ch:Loroe~hyltrimethyl~
ammon:ium chloride O
~ he growth inhibition b;y the compounds accordi3:~g
to the in~erltion was not achieved by the comparison
compou3~d with the applicatio~ used her~.
Exam~le 12
Sugar beet ~a~ sprayed ln pre-emergence with all
appli.cation quantity of 2 k~g of active ~ub~tallce~hec;
tare0 T~e perce~tage ~ro~rth ir~ibition a~d the colour
o~ the pl~ts a:fter three ~eek~' cultivatiorl in a
5 g~e~hou~e ~ere recordedl,
~ he re~ult~ are sho~m in the following ~bleO
Compound accordi~g
to the i~ention ~og ~ro~rth inhibition ~ ~ Coîou:r
g
~ 3~ 1
7 34
8 37 0
9 25
37
1~ 22
~5~¢~
~ 50
~ompo~d acoordirlg
t~ the invention NoO Gro~th i~h~bition ir~ lour
13 41 e~
14 4~ 0
1~ 53
17 ~
:1 ~ . 22
~9 3
2~ ` ~7
1~ 2~ 6
~2 ~7
3 ~3
2~ 22
69
26 ~7 2
~omParison a~ent
2 Chlsroethyltrimethyl
ammorlium chloride O O
~ Eey to colour: O ~ - as control
1 = i~tenBe green
2 - dark g:ree~
~he oompotmds according to the invention a~fect
the gx owth of the beets whil~t the same is not achieved
bsr the comparisorl c~mpound i~ the applica'Gio~ used here~.
-- 51 --
~xam~l ~ 13
fect of propl~ actic leaf treat!nent agairL~t th0 lea~
~pot pathogen Fusarium culmorum ill Italiar~ millet
( Penni~etum .~:laucum~ ~ a greeI~ou~
~o~g millet plant~ ~appro~ ~ate~y ~0 pe~ po~
with the ~eco~ld lea:F be~;nni~f~ t~ appear were ~pra~ea
u~til drippi~ wet with the ~tated concent~atiorl~0
When 1the ~pray coa~Ging~ had dried9 the treated pl~n~G~
arld untreated co~rol pl~ts were spra sred with a s~6-
0 pensio~ l~f the conidia of ~sarium culmorum a3ld place~
damp in a greenhou~e ai; approx~ately 22C. ~ter
days, the percentage proportion of the leaf ~ ace
a l;tacked was e~timated ., ~he lungicida~ effect wa~
cal~ulated a~ f~llo~:
10~ . Attack iQ treated
dttack in uIltreated
100 ~ eff ect
The compou~d~ accorai~ to the in~e~tion wer~
used a~ 20 % strengih formu:Lation~0
;~0 Compounà accordi~g 5~ e~ect with
to the ixlve~tis:n NoO 500 ppm lOa ppm
100 100
3 91
9 80
12 90
13 10
- 52 --
Compo~a~d according5~ effec~ ~ith
to the i~entio~ ~o.500 ppm lûO ppm
14 100
16 9~
11 95
1~3 95
19 90
22 99 9
1 0 23 1()~ g9
2~ 100 97
2~ 100 9
~6 98 93
27 9~
1 5 2~ 97 90
~0 97 90
31 100 ~8
~am~le 14
~ect o~ proph;~rlactic lea~ ~reat~erLt again~t -the
2C) lea~ po~ ho~en Cercospora betico~a in su~ar beet
i~ a gxeenho-a~e
Sugar beet plants having a~ lea~t two wel:l
de~eloped trae leaveswere spra~e~ ~tîl ~ippi~g wet
with the stated concentrations . ~hen the spra;y coat-
25 ir~g~ :had dried, the treated pla~t~ and untreated c~trol pla~tfi were spr~red with a ~laspensio~ ~ th~
3~
-- ~3
conidia O:e ~ercoapora beticola and ~ncubated d~mp f or
da~ a greenhou~e at 26OC~D ~he pl~nts wer~ ~e~
clllt~vated u~der ~ormal gree~hou~e conditio~ ~o
weeks a~ter treatment9 the percentage atta~ wa~
5 a~e~s~d~
~he fungicidal e~fect wa~ calcula~d as fo:Llow~:
lûO o Attack i~ treated
100 ~ - c % effect
l~ttac~ in untreated
~he compou~d~ wer~ used as 20 % ~trength :Eorm~l
tions~
Compou~d accora~ eIfect with
to thein~e~tion 15~o;, 500 ppm 100 pp~
3 lOO lOO
ll 93
12 9~
13 lOo
1~ ~3
16 100
17 ~7
19 93
87
2~ 100 96
22 ~30 100
~3 100 lOC~
24 1~)0 100
~5~
_ 5~
Compound accord~g~ effec~ h
t~ the illvent~orL ~oO 500 ppm 10~ ppm
96 95
~6 10~ ~6
27 9~ ~8
28 100 9
~9 1~)0 9~
OO lOD
~1 100 ~00
0 E:~amp'le 15
:~fiect OI ~eed treatmeD,t ~; nF::t ~eed-borDe
He~inthos~ri~ ativllm (ca~e oi f~ot rot) in barleyO
Barleg ~eed in~ectea ~ith :EIelm~ntho~orium ~ati~m
was treated ~ith the acti~e ~u~tan~e i~ application
quantit;y of 50 m~ OI active 8ubstance per 100 ~amO
2 g o~ treated eeed and 2 g o~ untreated seed were i~
each ca~e ~ow~ i~L pot~ in t~o repet~tio~s and incl;Lbat~d
at 15C i~ ~ cl imatic chamber~. ~?rom the ~me that th~
pla~t~ emerged~ arti~icial lighti~Lg wa~ gi~er~ ~ a 12
20 hoar o;ycl~. ~fter 4 week~ l the percentage o~ plant~
~howing ioot rot wa5 determ~ledo ~ the ~ntreated
pl~nts were diseased~
-- 55 --
Compound accord~
to t~e inven~io~ No. ~ e~ect
100
99
4 lC~
9~,5
~ he compo~and~ were used a~ 20 5~ strength ~ormula~
~ion~ .
:Examp~ e 16
0 :Efîec~ o~ ~eed treatme~t ~i n.q~c ~eed~o~n~ Phoma
betae in 8uga:r bee1t.
Sugar beet seed in~ected with P~noma betae wa~
treated with 250 mg o~ active ~ub3ta~ce per lO0 gramp
25 grai~ of treated a:~d OI untreated ~eed were i:n eaoh
ca~e ~ow~ iD pot~ i~ fo~r repetition33. Whe:tl the plant~
had emerged, a:rti~icial lighti~g was give2l in a 12
holar cycle,D ~n~il t~e end oi the ~est after 7 ~e~s,,
t~e di~ea~ed plan~ were c~ ted ~eekly and removed~
~ total OI 76.,1 % e~ the emerged plant~ i~L the untreated
20 contrs~l were diseased,. The protectlve e:~fe~t o~ th~
treatment wa~ calculated as Iol:Low~:
~ttack i~ tre~ted . :L00
100 ~ e~ect
~ttack in ~treated
The compound~ accordi~lg to the i~vention were us2d
a~ 20 % ~trength ~orm~at~ on~,
56
~ompou~d according
to t:he i~entlo~ ~o, ~ e~ect
~7
$ 4 g7
109
6 8~
92
13 9
14
aompari~on a~erLts
beta~ 33iphen~1 4-~lo~y)-~
alpha~(l, l~di~ethyïe~hyl~
1, 2 9 4-triazol-1 et~anol 51
1 5 1- ( 4~Chlorophe~o~ dimethyl-
1-(1,2~4-triazol-1wyl)~ 2-b~tarLorle ~7
i
