Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~L213~
The present invention relates to a process Eor
combatting fungi by applica-tion of new diamine derivatives,
and to fungicide compositions containing such derivatives
as active ingredients.
It has been disclosed that N-trichloromethylthio-
tetrahydrophthalimide can be used as a fungicide (Chemical
Week, June 21st, 1972, page 46).
It has now been found that diamine derivatives of
the Eormula
R~ R4
~ A~-A l0-R5 I,
R n
wherein R' is chlorine, bromine, Cl-C8-alkyl, cyclohexyl,
benzyl, methoxy, ethoxy or acetyl, n is 0, 1 or 2, R2 is
C1-C4-alkyl, C3-C4-alkenyl, C1-C3-alkoxy, A is -tCH2)2-,
- CH3 CH3
(CH2)3-, -CIH-CH2-, -CH2-CH-, -CH-CH2-CH2-, R is methyl,
CH
ethyl, n-butyl, or unsubstituted benzyl, R4 and R5 independ-
ently of one another are methyl, ethyl, propyl, butenyl or
propargyl, or R4 and R5, together with the nitrogen, are an
unsubsti-tuted or rnethyl-substituted pyrrolidine, piperidine
or morpholine ring, R6 is C1-C5-alkyl, allyl, but-2-en-1-yl,
4-chlorobut-2-en-1-yl, propargyl, naphth-1-ylmethyl, naphth-2-
y~.methyl, unsubstituted benzyl, benzyl substituted by fluorine,
chlorine, iodine, C1-C5-alkyl, methoxy, trifluoromethyl,
cyano or nitro, R is Eurther 1-phenoxyethyl, 1-phenoxy-
propyl or 1-phenoxybutyl, each of which is unsubstituted or
subs-tituted by halogen, Cl-C4-alkyl, methoxy or trifluoro-
mothyl, or R6 is 4-(C1-C8-alkyl)-phenyl-(2-methyl--1-propyl),
~7
~1
~LZ~3~
-- 2
and Z is an anion of a non-phytotoxic acid to act on the
areas, material, pl~nts or seeds threatened by a fungus
attack.
The present invention therefore proposes a
fungicidal composition comprising such a diamine derivative
as active ingredient, and a process for combatting fungi
such or diamine derivative.
In accordance with a preferred embodiment of the
invention, the diamine of formula (I) as defined above is
such that R1 is chlorine, brornine, C1-C8-alkyl, cyclohexyl,
benzyl, methoxy, ethoxy or ace-tyl, n is 0, 1 or 2, R2 is
Cl-C4-alkyl, C3-C4-alkenyl, Cl-C3-alkoxy, A is -(CH2)2-,
1 3 CIH3
-(CH2)3-, -CIH-CH2-, -CH2-CH-, -CH-CH2-CH2-, R3 is methyl,
CH3
ethyl, n-butyl, or unsubstituted benzyl R4 and R5 inde-
pendently of one another are methyl, ethyl, propyl, butenyl
or propargyl, or R4 and R5, together with the nitrogen, are
an unsubstituted or methyl-subs-tituted pyrrolidine, piperidine
or morpholine ring, R6 is C1-C5-alkyl, allyl, but-2-en-1-yl,
~-chlorobut-2-en-1-yl, propargyl, naphth-l-ylmethyl,
naphth-2-ylmethyl, unsubstituted benzyl, benzyl substituted
by fluorine, chlorine, iodine, C1-C5-alkyl, methoxy, trifuoro-
methyl, cyano or nitro, R6 is further 1-phenoxyethyl, 1-phe-
noxypropyl or 1-phenoxybutyl, each of which is unsubstituted
or substituted by halogen, C1-C4-alkyl, methoxy or trigluoro-
methyl, or R6 is 4-(C1-C8-alkyI)-phenyl-(2-methyl-1-propyl),
and Z is an anion of a non-phytotoxic acid.
Rl is, for example, hydrogen, fluorine, chlorine,
bromine, C1-C8-alkyl, eg. methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, tert.-butyl, n-pentyl, tert.-arnyl,
.
. . .
. .
. _
,a
- 2a ~
,
1,1-dimethylbutyl, l,l~dimethylpentyl, l,l-dimethylhexyl,
l,l-diethylpropyl or l,1,2-trimethylpropyl, halo-Cl-C4-alkyl,
eg. 2-chloro-1,1-dimethylethyl or trifluoromethyl, cyclohexyl,
phenyl, halophenyl, eg. 4-chlorophenyl, benzyl, halobenzyl,
eg. 4-chlorobenzyl, phenylethyl, Cl or C2 alkoxy, eg. methoxy
or ethoxy, or Cl- or C2-alkylcarbonyl, eg. acetyl, propionyl or
benzoyl.
R~ is, for example, methyl, ethyl, propyl, butyl,
allyl or crotyl.
CIH3
A is, for example, -CH2)2-, -(CH2)3, -CH-CH2-,
CH3
or -CH-CH2CH2-, preferably 1,2-, 1,3- or 1,4-cyclohexylene
( ~ , ~ or ~ ).
R is, for example, methyl or ethyl.
R4 and R5 are each, for example, methyl, ethyl,
pr~ ~ ~
..';
- 3 - O.Z.~050/35932
4-fluorobenzyl, 4-chlorobenzyl, 3-chlorobenzyl, 4-bromo-
benzyL, 3,4~d;chlorobenzyl or Z,4-dichlorobenzyl, or 3-
tr;fluorometnylbenzyl, 4-trifluoromethylbenzyl, 4-methyl-
benzyl, 4-(tert.-butyl)-benzyl, 4~methoxybenzyl, 4-cyano-
benzyl or 4-n;trobenzyl.
Preferred compounds of the formula I are those in
wh;ch R3 and R4, together ~;th A and the two nitrogen
atoms, form a p;perazine or perhydrod;azepine ring, or
those ;n which R4 and RS, together w;th N, form an
unsubst;tuted or methyl-subst;tuted pyrrol;d;ne, p;per;-
d;ne or morphol;ne r;ng.
R6 ;s, for example, methyl, ethyl, propyl, butyl,
;sobutyl, pentyl, allyl, but-2-en-1-yl, 4-chlorobut-2-en-
1-yl, propargyl, naphth-1-ylmethyl, naphth~2-ylmethyl,
unsubst;tuted or subst;tuted benzyl, eg. Z-fluorobenzyl,
4-fluorobenzyl, Z-chlorobenzyl, 3-chlorobenzyl, 4-chloro-
benzyl, 3-bromobenzyl, 4-bromobenzyl, 3-tr;fluoromethyl-
benzyl, 4-tr;fluoromethylbenzyl, 3-methylbenzyl, 4-methyl-
benzyl, 4-tert.-butylbenzyl, 4-cyanobenzyl, 4-nitroben.yl,
2,4-dichlorobenzyl, 3,4-d;chlorobenzyl, 2,4-d;methylbenzyl,
4-methoxybenzyl or 2,3,6-trichlorobenzyl, or 1-t4-tert.-
butylphenyl~-2-methylprop-3-yl, 1-phenoxyeth-2-yl, 1-
phenoxyprop-3-yl, 1-t3-chlorophenoxy)-eth-2-yl, 1-~4u
chlorophenoxy)-eth-2-yl, 1-~4-methylphenoxy)~eth-2-yl,
1-~4-methoxyphenoxy)-eth-Z-yl, 1-~4-ni-trophenoxy)-prop-3-
yl, 1-t4-trifluoromethylphenoxy)-eth-Z-yl or 1-phenoxy-
but-4-yl. Z is, for example, methylsul~onate, p-dodecyl-
benzenesulfonate, sulfate, methosulfate, ni~r~te, phos-
phate, iodide, or in p3rticular chloride or brornide.
- 4 - O~Z.OQ50/35932
The novel d;am;ne der;vat;ves of the formula I
possess a chiral carbon atom attached to the ligand R2, and,
depend;ng on the nature of R1, R3, R4, R5~ R6 and A, may
possess further ch;ral centers in these radicals. The
optically pure enantiomers or the d;astereomers can be
obtained by a conventional method. The present invention
also embrace~3 these compounds in pure form and in the form
of m;xtures. ~oth the pure enant;omers or the d;as-
tereomer pa;rs and the m;xtures obta;ned ;n the synthesis
are active as fung;cides.
The d;am;ne der;vat;ves of the formula I are
obtained, for example, by a process wherein a compound of
the formula
R3 R4
II,
Rln R
where A, R1, R2, R3, R4, ~5 and n have the above
meanings, is reacted w;th a compound R6Z,where R6 and Z
have the above mean;ngs.
The react;on ;s carr;ed out in the presence or
absence of a solvent or d;luent, at from 20 to 150C,
preferably from 30 to 140C. The reaction ;s advanta-
geously carr;ed out us;ny equ;molar amounts of the start;ngmater;al of the formula II and the compound R6Z.
Examples of preferred solvents or d;luents which
are inert to the reactants are aliphatic or aromatic
hydrocarbons or aliphatic or aromatic halohydrocarbons,
such as pentane, cyclohexane, benzene, toluene, xylenes
- 5 - O.Z.0050J35932
and chlorobenzene, aliphat;c ketones, such as acetone,
methyl ethyl ketone, diethyl ketone and cyclopentanone,
ethers, such as diethyl ether, dimethoxyethane, methyl
tert.-butyl ether, tetrahydrofuran and dioxane, esters,
such as ethyl acetate, nitriles, such as acetonitrile,
amides, such as dimethylformamide, dimethylacetamide and
N-methylpyrrolidone, and m;xtures of these solvents.
The preparat;on of the starting compounds o~ the
formula II by a convent;onal process ;s described
together w;th the synthesis of the novel compounds of the
formula I.
Examples of su;table quatern;zing agents o~ the
formula R6Z, in addition to the alkyl, alkenyl, alkynyl,
benzyl and aralkyl haLides, are dimethyl-sul ate, diethyl
sulfate and sulfonates of the formula R-S03-R6~ where R~
is C1-C7-alkyl or is aralkyl or phenyl which ;s sub-
st;tuted by halogen or alkyl.
The ~xamples wh;ch follow illustrate the prepara-
t;on of the compounds of the formula I.
EXAMPL~ 1
a) 274 g of trans-1,2-diam;nocyclohexane and 134.4 g
of 3-~4-tert~-butylphenyl)-Z-methylpropyl chloride
(German Laid-Open Applica-tion DOS 2,752,096) were stirred
for 10 hours at 140C and then cooled to +10C ;n an ice
bath, and 200 ml of a 50% strength by weight sodium
hydroxide solution were added slowly, followed by the
addition of 200 ml of ether. The organic phase was
separated off, dried over potassium hydroxide and dis-
tilled to give 151 g of ~-(3-~4-tert.-butylphenyl)-2-
~23~3~;;9.8
- 6 - O.Z.0050/35932
methylpropyl)-trans-1,2-diaminocyclohexane of boil;ng
point 175-180C/0.3 mbar. Yield: 83.3~. of theory~
Using the above method, 274 9 of a mixture of 70%
of trans-1,2-diaminocyclohexane and 30~ of cis-1,2-
diaminocyclohexane gave 154.1 9 of N-t3-(4-tert~-butyl-
phenyl)-2-methylpropyl)-1,2-d;aminocyclohexane as a cis/
trans m;xture of boil;ng point 175-185C/0.3 mbar.
Y;eld: 85% of theory.
b) 151 9 of N-t3-~4-tert.-butylphenyl)-2-methyl-
propyl)-trans-1,2-d;am;nocyclohexane were added dropw;se
;n the course of 30 minutes to a mixture of 260 ml of 98%
strength formic ac;d and 400 ml of 40% strength aqueous
formaldehyde solution, at from 50 to 80C~ The mixture
was stirred for 10 hours at from 90 to 95C and then
cooled to +10C~ 234 ml of 36~ strength hydrochloric acid
were added carefully, and the mixture was then evaporated
down under reduced pressure. The res;due was stirred
with 940 ml of 30;' strength sodium hydroxide solution,
and the mixture was extracted by shaking with three t;mes
150 ml of ether. The ether extract was dried over
potassium hydroxide and distilled to g;ve 132 9 of
N',N",N"-trimethyl-N'-~3-~4-tert.-butylphenyl)-Z-methyl-
propyl)-1,2-d;am;nocyclohexane of bo;ling point 180-190C/
0.3 mbar and n25 = 1.5097. ~ield: 76.5% of theory.
c) 9.2 9 of 4-tert.-butylbenzyl chloride were added
to a solution of 10.5 9 of N',N",N"-trimethyl-N'-(3-t4-
tert.-butylphenyl)-2-methylpropyl)-1,2-diaminocyclohexane
in 10 ml of dioxane and 45 ml of acetonitrile, and the
mixture was stirred for 16 hours at 80C and then
-- ~z~
- 7 - O~Z.0050/35932
evaporated down under reduced pressure. The resldue was
washed with three times 2Q ml of ether and was dried for
3 hours at 80C under a pressure of 0.2 mbar. 11 9 of
Nl-~N"-(3-(4-tert.-butylphenyl)-2-methylpropyl)-N"-methyl-
aminocyclohexyl]-N',~ dimethyl-N'-(4-tert.-butylbenzyl)-
ammonium chloride were obtained as a pale yellow resin
(compound 1). Yield: o8.7% of theory.
IR spectrum tfilm): 3,0Z2, 2,964, 2,866, 1,512, 1,476,
1,463, 1,364, 1,270, 1,110, 1,030, 843 and 563 cm 1.
EXAMPLE 2
a) 57 9 of trans-1,2-diaminocyclohexane, 208 9 of
3-(4-tert.-butylphenyl)-2-methylpropanal and 3 ml of
acetic acid in 300 ml of toluene were refluxed for 5 hours
until 18 ml of an azeotropic mixture of ~ater and toluene
had distilled off. The toluene was then distilled off
under reduced pressure, and the residua ~as directly
reacted further to give 223 9 of the Schiff base
CH3 CH3
CH3--C--< ~/~--CU CH--~=~--~\ ~\
O
CH3
CIH3 CH3
CH3-C-~\ O ~-CH CH-CH_`~
`~;eld: 91.7~ of ~heory.
b) 200 9 of the Schiff base were dissolved in 500 ml
of methanol, 38 9 of sod;urn borohydr;de were added, a
l;ttle at a t;me, at 0C, and the m;xture was st;rred for
12 hours at 20C. Thereafter, the methanol was dist;l!ed
off, the res;due was d;ssolved ;n 500 ml of methylene
chlor;de, the solut;on was st;rred for 1 hour w1th 300 ml
~2~
- 8 - O.Z.0050/35932
of 25-~ strength potassium hydroxide solution, the organic
phase was separated off, washed with twice ZCû ml of
water and dr;ed over sodium sulfate, and the methylene
chloride was distilled off under reduced pressure. The
residue comprised 195 9 of N',N"-b;s-~3-(4-tert.-butyl-
phenyl)-2-methylpropyl~-1,2-d;aminocyclohexane in the
form of a pale brown resin. Yield: 97.5% of theory.
c~ 200 g of Nt,N"-b;s-C3-t4-tert.-butylphenyl)-2-
methylpropyl~-1,Z-diaminocyclohexane were added~ a little
at a t;me, to a mixture of 134 ml of a 40% strength
aqueous formaldehyde solut;on and 86.6 ml of 98~ strength
formic acid, at from 50 to ôOC. The mixture was stirred
for 10 hours at 95C and then cooled to +10C, Z34 ml
of 36% strength hydrochloric acid were added carefully and
the mixture was then evaporated down under reduced
pressure. The residue was stirred with 9~0 ml of 3û%
strength sodiurn hydroxide solution and extracted by
shaking with four times 150 ml of ether. The ether
extract was washed wi-th twice 100 ml of water, dr;ed over
potassium hyciroxide and thenconcentrated for 3 hours at 100C
under a pressure of 0.2 mbar. 185.4 g of N',N"-dimethyl-
N',~"-bis-C3-(4-tert.-rJutylphenyl)-2-methylpropyl]-1~2-
diaminocyclohexane were obtained in the form of a pale
brown resin. Yield: 87.7'~ of theory.
d) 7.2 g of ~enzyl bromide were added to a solution
of 1û.9 9 of N',N"-bis-C3-t4-tert.-butylphenyl)-2-methyl-
propyl~-1,2-diaminocyclohexane in 20 rnl of dio~ane and
30 ml of acetonitrile, and the mix~ure uas s-t;rred for
3 days at 70~C and then evaporated down under reduced
- 9 - O.Z.~050/35932
pressure. The res;due was washed three times w;th
petroleum ether and finally dried for 4 hours at 100C
under a pressure of 0.2 mbar. 6.6 9 of N'-Crl"-methyl-
N"-t3-(4-tert.-butylphenyl)-2-methylpropyl)-aminocyclo-
hexyl]-N'-methyl-~l'-benzyl-~'-(3-~4-tert.-butylphenyl)-
2-methylpropyl)-ammon;um brom;de were obta;ned ;n the form
of a pale brown res;n ~compound 2). Yield: 4s.6æ of
theory.
I~ spectrum ~f;lm): 3,030, 2,962, 2,866, 1,515, 1,460,
10 1,393, 1,364, 1,269, 1~204, 1,109, 853 and 706 cm 1.
EXAMPLE 3
a) 533 g of 3-~4-tert.-butylphenyl)-2-methylpropyl
chloride and 714 g of 4-methylp;perazine were stirred for
7 hours at 140C and then cooled to +10C in an ;ce
bath, and 4ûO ml of 50% strength sodium hydroxide solution
were added slowly, followed by the addition of 500 ml of
ether. The organ;c phase was separated of T, dr;ed over
sod;um hydro~ide and distilled to give 640 9 of 1-methyl-
4-C3-~4-tert.-butylphenyl)-Z-methylpropyl]-piperaz;ne of
bo;l;ng point 135-140C/0.3 mbar.
Z0 b) A solution of 14.4 9 of 1-methyl-~-C3-~4-tert.-
butylphenyl)-Z-methylpropyl]-piperazine and 10~3 g of
benzyl bromide in 200 ml of ethyl acetate was refluxed
for 6 hours, af-ter which the mi~ture was evaporated down
to 80 ml and then cooled to ~5C. The precipitated pro-
duct was ~;ltered off under suction, washed w;th ether
and dried. 18.4 9 of 1-methyl-l-benzyl-4-~3-~4-tert.-
butylphenyl)-2-methylpropyl~-pipera~;nium bromide were
obtained in the form of colorless crystals of melt;ng
~2~3~
- 10 - I O.z~0050/35932
point 216C ~compound 3).
The compounds below were prepared by a simi lar
procedure .
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- 18 - O.Z. 0050/35932
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- 19 - 0. Z. 0050/35932
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- 20 - o. z . 0050/35932
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- 21 -
The diamine derivative used as active ingredlents
in the process and compositions according to the invention
have a s-trong action on microorganisms. They are especially
suitable for preventing and curing plant diseases caused by
fungi, e.g., Botrytis cinerea in grapes and strawberries,
Monilia fructigena in apples, Phytophtora infestans in
potatoes and tomatoes, Plasmopara viticola in grapes, and
Alternaria solani in tomatoes.
The fungicidal or bactericidal agents contain from
0.1 to 95, and prererably from 0.5 to 90, wt~ of active
ingredient. Depending on the type of effect desired, the
application rates are from 0.1 to 5 kg of active ingredient
per hectare.
The imidazolium salts according to the invention
are also suitable for industrial purposes, e.g., as wood
preservatives. The compounds have also been found to have
not only a fungicidal action, but also a bac-tericidal action -
they are also suitable as such for use in crop protection and
as industrial microbicides. For instance the following micro-
organisms may be combated:Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae,
Citrobacter freundii, Proteus vulgatis, Pseu domonas aeruginosa,
Pseudomonas luorescens, Xanthomonas vesicatoria, Xanthomonas
malvaccarum, Erwinia carotovora, Erwinia amylovora,
Desulfovibrio desu~furicans, Streptoverticillium rubrire-ticuli,
Aspergillus niger, Aspergillus versicolor, Penicillium
funiculosum, Paecilomyces variotii, Trichoderma viride,
Chaetomium globosum, Candida albicans, Geotrichum candidans,
Monilia sitophila, Scen0desmus ~uadricauda, Chlorella
vulgaris and Nostoc rnuscorum.
__
3 5 ~ ~
- 22 - O.Z. 0050~35932
The usual use concentrations are from 0.01 to 1% Oe actlve
ingredient, based on the weight of the material to be protected;
when the active lngredients are used ~or water treatment in oil
production, ln swimmlng baths, cooling towers, air humidifylng
unlts, flower preservatives or in the paper industry, amounts of
from 5 to 100 ppm are sufficlent to suppress microorganism develop-
ment.
The agents according to the in~ention may al~o be mixed and
applied wlth other actlve lngredlents, e.g., herbicldes, insec-
ticldes, growth regulators, fungicides and fertillzers. When mi~ed
with other funglcldes, the spectrum of fungicidal action is in
many cases increased; with a number of these funglcidal composl
tions, synergistic effects also occur; i.e., the funglcidal action
of the combination product i5 greater than the e~fect of the indi-
vidual components added together.
~ xamples of ~ungicides which may be combined wlth the com-
pounds according to the invention are: sulfur, dithiocarbamat,es
and their derivatives, e.g. iron(III) dimethyldithlocarbamate,
zinc dimethyldlthlocarbamate, manganese zinc N,N-ethylenediamine-
-bls-dithlocarbamate, zinc N,N-ethglene-bis-dithiocarbamate, tetra-
methylthiuram disulflde, the ammonia comple~ of zlnc N,N-ethylene-
-bls--dlthiocarbamate and N,N'-polyethylene-bls-(thlocarbamoyl)-
-di3ulfide, zlnc N,N'-propylene-bis-dlthiocarbamate, and the
ammonia complex of zlnc N,Nt-propylene-bls-dithlocarbamate and
N-N'-polypropylene-bis-(thiocarbamoyl)-disulfide; nltro derlv-
atlves, e.g. dinitro-(l-methylheptyl)-phenyl crotonate, 2-sec.-
.
.
LB
- 23 - O~Z~ 0050/35932
-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate and 2-sec.-butyl-
-4,6-dinitrophenyl isopropyl carbonate; heterocyclic compounds,
e.g. N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimlde, N-tri-
chloromethylthio-phthalimide, 2-heptadecyl-2-imidazoline acetate,
2,4-dichloro-6-(o-chloroanilino)-s-triazine, 0,O~diethyl phthal-
imidophosphonothloate, 5-amlno-1-(bls-(dimethylamino)~phosphinyl)-
-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,~-dlthlaanthraquinone, 2-
-thio-1,3-dithio~ ,5-b)-qulnoxaline, methyl 1-(butylcarbamoyl)-2-
-benzimidazole-carbamate, 4-(2-chlorophenylhydrazono)-3-methyl-5-
-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its
copper salt, 2,3-dihydro-5-carboxanllldo-6-methyl-1,4-oxathilne-
-4,4-dio~ide, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,
2-fur-2-yl-benzimidaæole, piperazine-1,4-diyl-bis-(1-(2,2,2-tri-
chloroethyl)-formamlde), 2-thiazol-4-yl-benzim~dazole, 5-butyl-2-
-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chlorophenyl)-
-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-
-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene and
various fungicides, e.g. dodecylguanidine acetate, 3-(2~(3~5-di-
methyl-2-hydroxycyclohexyl)-2-hydroxyethyl)-~lutarimide, hexa-
chlorobenzene, N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-
-sulfuric acid diamide, 2,5-dimethyl-furan-3-carboxylic acid
anilide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid
anllide, l-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloro-
ethane, 2,6-dlmethyl-N-tridecyl-morpholine and its salts, 2,6-di-
methyl-N-cyclododecyl-morpholine and its salts, D,L-methyl-N-(2.,6-
-dlmethylphenyl)-M-furoyl(2)-alanate, methyl D,L-N-(2,6-dimethyl-
phenyl)-N-(2'-methoxyacetyl)-alanate, diisopropyl 5-nitroisoph-
~2~ 8
- 24 - O.Z. 0050/35932
thalate, l-(1',2',4'-triazolyl-1')-[1~ chlorophenoxy)]-3,3-di-
methylbutan-2-one, 1-(1',2',l1'-triazolyl-1')~~1-(4'-chloropnen-
oxy)]-3,3-dimethylbutan-2-ol, N-(2,6-dinlethylphenyl)-N-chloro-
acetyl-D,L-2-aminobutyrolactone, N-(n-propyl)-N-(2,4,6-trichloro-
phenoxyethyl)-N'-imidazolylurea, N-cyclohexyl-N-metho~y-2,5-di-
methyl-furan-3-carboxamide, 2,4,5-trimethyl-furan-3-carboxanilide,
5-methyl-~-vlnyl-3~(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolldine,
5~methoxymethyl-5-methyl-3-(3,5-dichlorophengl)-2,4-dioxo-1,3-oxa-
zolidine, N-C3-(p-t~rt.-butylphenyl)-2-methyl-propyl]-cis-2,6-di-
methylmorpholine, ~I-formyl-N-morpholine-2,2,2-trichloroethyl-
acetal, l-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dloxolan-2-yl-
-methyl]-lH-1,2,4-triazole, and 1-~2-(2,4-dichlorophenyl)-4-n-
-propyl-1,3-dioxolan-2 yl-methyl]-lH-1,2,4-triazole.
The active ingredients are applied for instance in the form
of directly sprayable solutions, powders, suspensions (including
high-percentage aqueous, oily or other suspensions), dispersions,
emulsions, oil dispersions, pastes, dusts, broadcasting agents, or
granules by spraying, atomizing, dusting, broadcastlng or
watering. The forms of application depend entirely on the purpose
for which the agent~l are being used, but they must ensure as fine a
dlstribution of the novel active ingredients as pos~ible.
~ or the preparation of solutions, emulsions, pastes and oil
dispersions to be sprayed direct, mineral oil fractions of medium
to high boiling point, such as kerosene or diesel oil, ~urther
coal-tar olls, and oila of vegetable or animal orlgin, aliphatlc,
cyclic and aromatic hydrocarbons such as benzene, toluene, xylene,
paraffln, tetrahydronaphthalene, alkylated naphthalenes and their
- 25 - O~Z. 0050/35932
derivatives such as methanol) ethanol, propanol, butanol, chloro-
form, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-
benzene, lsophorone, etc., and strongly polar solvents such as
dimethylformamide, dimethyl sulfoxlde, N-~ethylpyrrolidone, water,
etc. are suitable.
Aqueous formulations may be prepared from emulsion concen-
trates, pastes, oil dispersions or wettable powders by adding
water. ~o prepare emulsions, pastes an~ oil disperslons the ingre-
dients as auch or dissolved ln an oil or solvent may be homoge-
nized in water ~y means of wettlng or disperslng agenks, adherentsor emulsiflers. Concentrates whlch are suitable for dllution with
water may be prepared ~rom active ingredlent, wettlng agent, ad-
herent, emulsi~ying or dispersing agent and possibly solvent or
oil.
E~amples of surfactants are: alkali metal, alkaline earth
metal and ammonlum salts of llgninsulfonic acid, naphthalenesul-
fonlc acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl
sulfates, and alkyl sulfonates, alkali metal and alkallne earth
metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-
fate, fatty alcohol sulfates, alkali metal and alkaline earthmetal salts of fatty acids, salts of sulfated hexadecanols, hepta-
decanols, and octadecanols, salts of sulfated fatty alcohol glycol
ethers, condensation products of sulfonated naphthalene and
naphthalene lerivatives with formaldehyde, condensation product3
of naphthalene or naphthalenesulfonlc aclds with phenol and form-
aldehyde, polyoxyethylene octylphanol ethers, ethoxylated isooctyl-
phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-
3~
- 26 - O.Z. 0050/35932
phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkyl-
aryl polyether alcohols, isotridecyl alcohol, fatty alcohol
ethylene oxide condensates, ethoxylated castor oil, polyo~y-
ethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl
alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite
waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by
mixlng or grlnding the active ingredients with a solld carrier.
Granules, e.g., coated, impregnated or homogeneous granules,
may be prepared by bonding the active ingredients to solid car-
rlers. Examples of F~olid carriers are mineral earths such as
silicic acid, sllica gels, silicates, talc, kaolin, Attaclay,
limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous
earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground
plastics, fertilizers such as ammonium sulfate, ammonium
phosphate, anLmonium nitrate, and ureas, and vegetable products
such a~ grain flouræ, bark meal, wood meai, and nutshell meal,
cellulosic powders, etc.
Examples o~ such formulations are given below.
I. 90 parts by welght of compound 14 ls mixed with 10 parts bD
weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which
ls suitable for application in the form of very fine drops.
II. 20 parts by weight of compound 15 is dissolved ln a mixture
consi~ting of 80 parts by weight of xylene, 10 parts by weight of
the adduct of 8 to 10 moles o~ ethylene oxide and 1 mole o~ oleic
acid-N-monoethanolamide, 5 parts by weight of the calcium salt of
dodecylbenzeneslllforLic acid, and 5 parts by weight of the adduct
3 ~ ~ ~
- 27 - O.Z. 0050/35932
of 40 moles of ethylene oxide and 1 mole of castor oll. By pourin~
the solution into water and uniformly distributing it therein, an
aqueous dispersion is obtained.
III. 20 parts by we~ght of compound 56 is dissolved ln a mi~ture
conslsting of 40 parts by weight of cyclohexanone, 30 parts by
weight of isobutanol, 20 parts by weight of the adduct of 7 moles
of ethylene oclde and 1 mole of isooctylphenol, and 10 parts by
weight of the adduct of 40 moles of ethylene oxide and 1 mole of
castor oll. Bg pouring the solution into water and finely distri-
butlng it therein, an aqueous dlsperslon is obtained.~t. 20 parts by weight of compound 57 ls dlssolved ln a mixture
consisting of 25 parts by weight of cyclohexanol, 65 parts by
weight of a mineral oil fraction having a boillng polnt between
210 and 280C, and 10 parts by T~elght of the adduct of 40 moles
of ethylene oxide and 1 mole of castor oil. By pourlng t'ne solu-
tion lnto water and uniformly distributing lt therein, an aqueous
dlsperslon is obtained.
V. 80 parts by weight of compound 63 is well mixed with 3 parts
by welght of the sodium salt of di~sobutylnaphthalene-alpha-sul-
fonlc acid, 10 parts by welght of the sodium salt of a llgnin-sul-
fonlc acid obtalned from a sulflte waste llquor, and 7 parts by
weight of powdered slllca gel, and trlturated in a hammer mill. By
unlformly distributing the mi:cture in water, a spray liquor is
obtained.
VI. 5 parts by welght of compound 68 is lntlmately mixecl with
95 parks by welght of particulate kaolin. A dust ls obtained con-
taining 5% by weight of the active ingredient.
3 ~ ~ ~
- 28 - O.Z. 0050/35932
VII. 30 parts by weight of compound 69 ls intlmately mixed with a
mixture consistinO Of 92 parts by weight of powdered sillca gel
and 8 parts by weignt of para.ffin oil which has been sprayed onto
the surface of this sllica gel. A formulation of the active ingre-
dient is obtained having good adherence.
VIII. 40 parts by ~eight of compound 73 ls intimately mixed with
10 parts of the sod~um salt of a phenolsulfonic acid-urea-form-
aldehyde condensate, 2 parts of sllica gel and 48 parts of water
to give a stable aqueous dispersion.
IX. 20 parts of compound 76 is intimately mixed with 2 parts of
the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a
fatty alcohol polyglycol ether, 2 parts of the sodium salt of a
phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a
parafflnic mineral oil. A stable oily dispersion is obtained.
The following experiments demonstrate the biological action
of the novel compounds. The prior art agent used for comparlson
purposes was N-trichloromethylthiotetrahydrophthalimide (A).
Experiment 1
Action on Botrytis cinerea
Pimiento seedlings of the "Neusiedler Ideal Elite" variety
were sprayed, after 4 to 5 leaves were well developed, to runoff
with aqueous suspensions containing (dry basis) 80~ of active
ingredient and 20% of emulsifier. After the sprayed-on layer had
dried, the plants were sprinkled wlth a conidial suspenslon of the
fungus Botrytis cinerea, and placed at 22 to 24C in a chamber of
hlgh humidity. After 5 days, the disease had spread to such a great
extent on the untreated plants that the necroses covered the ma~or
portion of the leaves.
5 ~ ~
- 29 - O.Z. 0050/35932
The results of this experiment show that ~or example active
ingredients nos. 1, 2, 9, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22,
23, 24, 25, 26, 2i', 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 40,
46, 50, 58, 63, 64, 65, 65, 68, 69, 70, 75, 78 and 97 applied as
0.05% spray liquors, had a better action (e.g., 100%) than pr~or
art compound A (e.g., 70%).
Experiment 2
Action of Phytophthora lnfestans
Leaves of potted tomatoes of the "Gro~e Fleischtornate"
variety were spra~ed with aqueous liquors containing (dry basis)
80% of active ingredient and 20% of emulsifier. After the sprayed-
-on layer had dried, the leaves were infected with a zoospore sus-
pension of Phytophthora infestans. The plants were then placed for
5 days in a steam-saturated chamber kept at 16 to 18C. After
this period, the disease had spread on the untreated control
plants to such an extent that the fungicidal action of the com-
pounds was able to be assessed.
The results of the experiment show that for example actlve
ingredients nos. 2, 31, 33, 34, 35, 40, 46, 57, 59, 60, 63, 65,
66, 68, 69, 73, 75 and 78, applied as 0.025% spray liquors, had a
better action (e.g., 97%) than compound A (e.g., 60%).
Experiment 3
Action on Plasmopara viticola
-
Leaves of potted vines of the ~ller-Thurgau varlety were
sprayed with aqueous suspensions containing ~dry basis) 80% of
active ingredient and 20% of emulsifier. To assess the duratlon of
action, the plants were set up, after the spra~ed-on layer had
- 30 - O.Z. 0050/35932
dried, for 10 days in the greenhouse. Then the leaves were
infected with a zoospore suspension of Plas~opara viticola. The
plants were first placed for 16 hours in a steam-saturated (moist)
chamber at 24C, and then in a greenhouse for 8 days at from 20
to 30C. To accelerate and intensify the sporangiophore discharge,
the plants were then again placed in the moist chamber for
16 hours. ~he extent of fungus attack was then assessed on the
undersides of the leaves.
The results of this experiment revealed that for instance
active ingredients nos. 40, 46, 59, 60, 63, 68, 69, 75 and 73.
applied as 0.25% spray liquors, had a good fungicidal action
(e.g., 90%)-
Experiment 4 -
Action on Aspergillus niger
To determine the action on fungi, the active ingredients are
added, in amounts of 100, 50, 25 and 10 parts per million parts of
solution, to a nutrient solution ideally suited for promoting the
growth of the fungus Aspergillus niger. 20 ml of the mixture of
nutrient solution and active ingredient was introduced into lO0 ml
test tubes and inoGulated with 0.3 mg of Aspergillus spores. After
the flasks had been incubated at 36C for 120 hours, the extent of
fungus spread (predominantly on the surface of the nutrient solu-
tion) was assessed.
The results of this experiment show that for instance acti~e
ingredients nos. 1, 1ll, 15, 22~ 28, 82 and 83, applled for example
in amounts of 100, 50, 25 and 10 parts per million parts of
nutrient solution, had a good action (e.g., 100%).
~Z~
31 O~Z D 0050/35932
E~periment 5
Action on Staphylococcus aureus
__ _ _ _ _ ~
To determine the action of the novel compounds on bacteria,
5 ml of increasing dilutlons of the active ingredients was added
to 5 ml of doubly concentrated nutrient brot'n in sterile test
tubes, and mixed. The tubes were then inoculated by addlng one
dropl of a 16-hour old broth culture (diluted 1:10) of the
bacterla specle~ Staphylococcus aureus, and incubated for 24 hours
at 37C. After thls time, sample~ were transferred from the tubes
to bacteria nutrient media which were then also incubated for
24 hours at 37C.
These results show that for instance actlve ingredients
nos. 14, 15, 22, 25, 28, 32, 33, 34, 40, 41, 58, 59, 60, 63, 64,
66, 67, 70, 74, 77, 79, 81, 82, 83 and 97, applied at a dilution
rate of 1:10,000 (100 ppm), had a good action (e.g., 100~).
