FUNGICIDAL PREPARATIONS

PREPARATIONS FONGICIDES

English Abstract

2079998 9115120 PCTABS00007
The use of certain well known very long chain quaternary
n-Alkyltrimethyl ammonium salts (ATAX), alkylbenzyl-dimethyl ammonium
salts (AKX) and dialkyldimethyl ammonium salts (DADAX) of general
formulae (I ATAX, II AKX, and III DADAX), respectively, wherein R
is straight chained or branched alkyl or alkylene with more than
17 carbon atoms, R' is straight or branched alkyl or alkylene with
more than 11 carbon atoms, and X is a halogen, acetate, sulfate,
or phosphate anion, of low phytotoxicity in plant protection for
controlling and combating fungi, fungicidal compositions
comprising such compounds either alone or in combination with other
fungicidally active agents, and methods for controlling or combating
fungi in plants by applying said compositions to the plants, and
the use of such compounds as additives to fungicidal compositions
are described.

Claims

WO 91/15120 PCT/DK91/00096
18
PATENT CLAIMS
1. A fungicidal composition comprising at least one n-
Alkyl(ene)trimethyl ammonium salts, alkyl(ene)benzyl-dimethyl
ammonium salts and/or dialkyl(ene)dimethyl ammonium salts
(DADAX) of the general formulae I, II, and III, respectively
<IMG> , X ATAX (I)
<IMG> , X AKX (II)
<IMG> , X DADAX (III)
wherein R is straight chained or branched alkyl or alkylene
with more than 17 carbon atoms, R' and R" which are the same
or different, are straight or branched alkyl or alkylene with
more than 11 carbon atoms, and X is a halogen, acetate,
sulfate, or phosphate anion.
2. The composition of claim 1, wherein R is n-C18H37
(stearyl), n-C20H41 (eicosyl), or n-C22H45 (behenyl), R'=R"are n-
C12H25 (lauryl), n-C14H29(myristyl), n=C16H33(cetyl), n-C18H37
(stearyl), n-C20H41 (eicosyl) or n-C22H45 (behenyl), and X is
B=Br, C=Cl, Ac=acetate, S=sulfate, or P=phosphate.
3. The composition of claim 1 or 2, wherein R is stearyl
and/or behenyl.
4. The composition of any of claims 1 to 3, comprising a
mixture of compounds wherein R is eicosyl and behenyl.

WO 91/15120 PCT/DK91/00096
19
5. The composition of any of claims 1 to 4, comprising a
further fungicidally active agent.
6. The composition of claim 5, wherein said further
fungicidally active agent is chosen from the group comprising
residual fungicidal dithiocarbamates, systemic fungicidal
carbamates, metal ethyl phosphonates, and acylalanines, or
mixtures thereof.
7. The composition of claim 6, wherein said dithiocarba-
mate(s) are chosen from maneb and mancozeb.
8. The composition of claim 6, wherein said carbamate(s)
is propamocarb.
9. The composition of claim 6, wherein said acylalanine(s)
is metalaxyl.
10. The composition of any of the claims 1 to 9, wherein
said salt(s) is present in an amount of from 0.001% by weight
to above 1.0% by weight, preferably from 0.01% by weight to
0.5% by weight.
11. A concentrate or primary composition of any of claims
1 to 9, wherein said salt(s) is present in an amount of from 1%
to 100% by weight, preferably from 5% to 30% by weight.
12. The composition of any of claims 5 to 10, wherein said
further fungicidally active agent is present in an amount of
from 0.001% to 30% by weight.
13. The concentrate of claim 11, wherein a further
fungicidally active agent is present in an amount of from 5% to
80% by weight.

WO 91/15120 PCT/DK91/00096
14. A method of controlling plant pathogenic fungi
including yeast in plants, wherein a fungicidally active amount
of a composition as claimed in any of claims 1 to 13 is applied
to said plants.
15. The method of claim 14, wherein the fungi to be
controlled belong to the Mastiqomycotina.
16. The method of claim 15, wherein the fungi to be
controlled belong to the Oomycetes.
17. The method of claim 16, wherein the fungus to be
controlled is a Phytophthora or Pythium.
18. The method of any of claims 14 to 17, wherein the
plants whereto said composition is applied belong to the
dicotyledons.
19. The method of claim 18, wherein said plant is chosen
from the group comprising sun flower, tomato, cucumber, and
potato.
20. The method of claim 19, wherein said plant is potato.
21. The method of any of claims 14 to 20, wherein said
composition is applied to said plants prior to, at the outset,
or after establishment and detection of an attack by fungi by
spraying or dusting, preferably by foliar spraying.
22. The method of any of claims 14 to 20, wherein said
composition is applied to the roots of said plants prior to or
during planting by dipping said roots into a liquid composition
of any of the claims 1 to 13.
23. The method of any of the claims 14 to 22, wherein said
composition is applied in an amount of from 0.01 kg/ha to 10
kg/ha, preferably in an amount of from 0.05 kg/ha to 5 kg/ha.

WO 91/15120 PCT/DK91/00096
21
24. Use of at least one compound as defined by one of the
formulae I, II, and III in any of claims 1 to 4 as an additive
to a fungicidally active composition or compound.
25. Use of stearyl trimethyl ammonium chloride as an
additive to a fungicidally active composition or compound.
26. Use of behenyl trimethyl ammonium chloride as additive
to a fungicidally active composition.
27. Use of a mixture of eicosyl and behenyl trimethyl
ammonium chloride as an additive to a fungicidally active
composition or compound.

Description

WO91/15120 PCT/DK91/0~96
~ 3 ~ ~
Title: Fungicidal Preparations
Field of the invention:
The present invention relates to the use of certain very long
chain quaternary ammonium compounds of low phytotoxicity in
plant protection for controlling and combating fungi. It
relates to fungicidal compositions comprising such compounds
either alone or in combination with other fungicidally active
agents, methods for controlling or combating fungi in plants by
applying said compositions to the plants, and the use of such
compounds as additives to fungicidal compositions.
lS BACRGROUND OF THE INVENTION.
n-Alkyltrimethyl ammonium salts (ATAX), alkylbenzyl-dimethyl
ammonium salts (AKX) and dialkyldimethyl ammonium salts (DADAX)
of the general formulae I, II, and III, respectively, are well
known compounds.
fH3
R - N~ - CH3, X ATAX (I)
CH3
R - N+ - CH ~ ,X AKX (II)
CH3
fH3
R' - N' - R", X~ DADAX (III)
CH3
For the purpose of this invention the expression very long
chain quaternary ammonium compound (VLCQAC) will be used as
collective term for compounds in the ATAX (formula I), AKX

WO91/15120 PCT/DK91/00096
~. ;..,..,.j,
(formula II), and DADAX (formula III) series. In formulae I,
II, and III above R is straight chained or branched alkyl or
alkylene with more than 17 carbon atoms, R' and R" that may be
the same or different are straight or branched alkyl or
alkylene with more than ll carbon atoms, and X is a halogen,
acetate, sulfate, or phosphate anion.
Quaternary ammonium compounds ~QACs) with shorter chain lenyths
than VLCQACs are widely used as disinfectants and as pharma-
ceutical preservative~.
A vast literature on the antimicrobial activity of QACs e~istsand only a few representative papers are discussed here.
The antimicrobial activity of some alkyltrimethyl-ammonium
bromides (the ATAX-type) with n-alkyl chain lengths between
Cs and C22 has been described by Gilbert & Al-Taae [Letters in
Applied Microbiology 1, 101-104 (1985)]. It is concluded that
the antimicrobial activity maximizes for n-alkyl substituent
chain lengths of between 14 and 16 with bacterial strains being
most sensitive towards the C14-compound and the fungi toward the
C16-compound.
Similarly, the effect of the n-alkyl chain length on the
antimicrobial activity of AKCs with a n-alkyl chain length
betwe~n C1 and C18 has been described by Daoud, Dickinson and
Gilbert [Microbios 37, 73-85 (1983)]. They conclude that fungi
were most sensitive towards C12, Gram-positive bacteria towards
- C14, and the Gram-negative bacteria towards C16.
In a large comparative study of the bacteriostatic, fungista-
tic, and algistatic activity of fatty nitrogen compounds,
Hueck, Adema, and Wiegmann [Applied Microbiology 14(3), 308-
319 (1966)] conclude that for the C12, C14, C16, and C18 compounds
in the alkyltrimethyl ammonium chloride series, the highest
biostatic activity is found for the C14 compound. In the
dialkyl-dimethyl-ammoniumchloride series with n-alkyl ranging
from C8 to C18, the best fungistatic effect is apparently reached

WO91/15120 PCT/DK91/00096
~r~ r~ ~3
for the di-Clo compound.
Despite their excellent fungicidal and fungistatic properties,
QACs of the above types have found little use as agricultural
fungicides. A recent monograph of pesticide chemistry [Ma-
tolcsy, Nadasy, and Andriska, eds. : Studies in Environmental
Science 32, Pesticide Chemistry, Elsevier (1988)] only mentions
didecyldimethyl ammonium bromide (DDDAB) as a compound having
a protective and curative effect against apple scab (Venturia
inaloualis).
The reasons is probably to be found ln the phytotoxicity of
the QACs. In investigations of the eradication of overwin-
tering apple powdery mildew (Podosphaera leucotricha (Ell. &
Ev.) Salm), benzalkonium chloride, which is a mixture of C12,
C14 and C16 n-alkyl benzyl dimethyl ammonium chlorides completely
eradicated mildew but was very phytotoxic [Hislop & Clifford:
Annals of Applied Biology 82, 557-568 (1976); Hislop, Clifford,
Holgate, and Gendle: Pesticide Science 9, 12-21 (1978)].
Didecyl-dimethyl ammonium bromide was also phytotoxic in this
study, where no other QACs were investigated.
The phytotoxicity of QACs has also been noted in an investi-
gation of the toxicity of a number of different bactericides
to Clavibacter michiaanense and to the tomato plant, Lvcoper-
sicon esculentum [Thompson: Journal of Applied Bacteriology
61, 427-436 (1986)]. Cetyltrimethyl ammonium bromide (CTAB),
benzalkonium chloride and N-cetylpyrinidium chloride were very
efficient bactericides but were phytotoxic even in a concen-
tration of 2-20 ug/ml. As above this study was limited to the
compounds mentioned.
The phytotoxic effect of QACs on tomato plants has also been
observed by Edgington in a study of the effect of chain length
of QACs upon their use as systemic fungicides [Edgington:
Phytopathology 56, 23-25 (1966)]. He concludes that as the
alkyl group of n-alkyl QACs is lengthened from ethyl to dodecyl
in the alkyl trimethyl ammonium bromide series (using the six

WO91/15120 PCT/DK91/00096
compounds of an even number of C-atoms in the n-alkyl chain),
the compounds become more fungito~ic, but slight necrosis of
the stem is seen with the C12-compound. Edgington furthermore
observes that the use of QACs, with more than 8 carbon atoms in
the n-alkyl chain, as systemic fungicides, is limited by their
adsorption to sand, roots, and xylem.
The use of QACs, and especially cetyltrimethyl ammonium bro-
mide (CTAB), in combination with an 8-hydroxy-chinoline deri-
vative and a thiabenzazol in a fungicide of low phytotoxicitywhen applied to seed, grain, or fruits has been described in
Offenlegungsschrift DE 2342005. However, only the use of CTAB
for seed, grain, and fruits is exemplified.
Furthermore, the use of dicocodimethyl ammonium chloride (coco
being a mixture of C8 to C18-alkyl) for combating Podos~haera
leucotricha on overwintering apple buds has been exemplified in
Offenlegungsschrift 2408662. The Phytotoxicity of a 5% aqueous
solution of didecyl dimethyl ammonium bromide (DDDAB) has been
noted in this work too. No other compounds were exemplified in
this study.
DESC~IPTION OE T~E INVENTION.
- 25
From the publications summarized above it appears that the use
of QACs in plant protection despite their fungicidal effects,
is limited by their phytotoxicity. Furthermore, the use of
VLCQACs as biocidal agents has been limited.
The present invention reports for the first time the use of
VLCQACs as fungicides obtaining improved disease control in
plants. It has here been demonstrated that a synergistic effect
of VLCQACs and another fungicidally active compound or compo-
sition is often obtained. This synergistic effect allowsapplication of the other fungicide in considerably lower
dosages than the ones usually applied while still retaining the
same or improved control effect of the fungal pathogen.

U()91~1;12() ~CT/DK91/OnO96
Examples of other fungicides which can be combined with the
VLCQACs of the invention include the residual fungicidal di-
thiocarbamates (e.g. maneb (BAS~-maneb 80, BAsF) and mancozeb
S (dithane M45/LF, Kemisk Vzrk K~ge, Denmark)), and the systemic
fungicidal carbamates (e.g. propamocarb (Previcur@ N,
Schering), metal ethyl phosphonates (Fosetyl-aluminium,
Rhone-Poulenc), and acylalanines (metalaxyl, Ridomil~ 5b
(metalaxyl and mancozeb in combination = RidomilX MZ).
The diluent or carrier in the compositions of the invention
can be a solid or a liquid optionally in association with an
other surface-active ingredient, for example a dispersing
agent, emulsifying agent or wetting agent. Suitable surface-
active include nonionic agents as condensation products offatty acid esters of polyhydric alcohol ethers, e.q. sorbitan
fatty acid esters, condensation products of such esters with
ethylene oxide e.q. polyoxyethylene sorbitan fatty acid esters,
block copolymers of ethylene oxide and propylene oxide, ace-
tylenic glycols such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol,
or ethoxylated acetylenic glycols.
The concentration of the VLCQACs in the compositions of the
present invention when used alone or in combination with a
conventional fungicide, as applied to plants is preferably
within a range of 0,OOl to above l,0 per cent by weight,
especially 0,Ol to 0,5 per cent by weight.
In a primary composition or concentrate that usually should be
diluted prior to application the amount of VLCQACs can vary
widely and can be, for example, in the range from about 1% to
about 100% by weight, preferably from about 5~ to 30~ by weight
i of the composition.
The concentration of the other fungicidally active ingredient
in the mixed composition of the present invention, as applied
to plants is preferably within the range of 0,OOl to lO per
cent by weight , especially 0,Ol to 5 per cent by weight. In

w~ 91/1~120 ,~ 3~, ~ PCT/DK91/00~96
a primary composition the amount of active ingredient can vary
widely and can be, for example, from 5 to 80 per cent by weight
of the composition.
The active VLCQAC preparation or the compositions of the
invention can be applied directly to the plant by, for examp-
le, spraying or dusting either at a time when an attack of the
fungus has been established and determined on the plant for
combating the fungus or fungi or before the appearance of
fungus as a protective measure. In both such cases the prefer-
red mode of application is by foliar spraying. It is generally
important to obtain good control of fungi in the early stages
of plant growth as this is the time when the plant can be most
severely damaged. The spray or dust can conveniently contain
a pre- or post-emergence herbicide if this is thought
necessary.
Sometimes, it is practicable to treat the roots of a plant
before or during planting, for example, by dipping the roots
in a suitable liquid or solid composition. When the active
VLCQAC preparation of the invention is applied directly to the
plant a suitable rate of application is from O.Ol to lO kg per
hectare, preferably from 0.05 to 5 kg per hectare.
In the following Table I the VLCQACs used in the Examples of
this specification is listed. For the compound names the
following abbreviations are used: L=n-C1zH2s (lauryl), M=n-C~4H29
(mYristyl)~ C=n-C16H33 (cetyl), S=n-C~8H37 (stearyl), Ei=n-C20H41
(eicosyl), Be=n-C22H4s (behenyl), DD=(n-C~OH2~) 2 (didecyl)~ DL=(n-
c12H25)2 (dilauryl), DM=(n-C14H29)2 (dimyristyl), DS=(n-C18H37)2
(distearyl), T=(CH3)3 (trimethyl), D=(CH3)2 (dimethyl), K=C6H5-
CH2N~ (benzyldimethylammonium), and A=N~ (ammonium), and the
anions B=Br , C=Cl .

WO9~ 120 PCT/DK91/0009~
2~ 3r ~
TABLE I: QACs used in the experiments.
r IC~i3
R N~ R X
CH3
COMPOUND R1 R2 X
LTAC n_C12H2s CH3 Cl
MTAC n C14Hz9 CH3 Cl
CTAC n_Cl6H33 CH3 Cl
STAC n ClBH37 CH3 Cl
20/22TAC n-C20H4l and
1:3 mixture of n CzH4s CH3 Cl
BeTAC n_C22H45 CH3 Cl
n ClzH25 CH3 Br
n C~4H2s CH3 Br
n_C16H33 CH3 Br
n Cl8H37 CH3 Br
n C12H25 C6H5 CH2 Cl
n C~4Hzs C6Hs-CH2 Cl
n C16H33 C6Hs~CH Cl
n C~8H37 C6Hs-CH Cl
EiKC n C20H41 C6Hs~CH Cl
LKB n C12H25 C6H5 CH2 Br
n C14H29 C6H5 CH2 Br
n C16H33 C6H5 CH2 Br
n C18H37 C6H5 CH2 Br
-~ 30 n-C1 H CH3 S04
n-C16H33 CH3 P4
n C16H33 CH3 CH3CO2
n_C1sH37 CH3 S04
n C18H37 CH3 P4
n-C18H37 CH3 CH3CO2
DDAC n C10H21 n C10H21 Cl
DLDAB n C12HZ5 n c1ZH25 Br
DMDAB n Cl4H29 n Cl4Hzg Br
DSDAC n Cl8H37 n-C18H37 Cl

WO91/15120 ~ c~ PCT/DK91/00096
The inVentiQn is illustrated in the following examples:
Example 1.
LTAC, MTAC and CTAC were prepared by quaternisation of alkyldi-
methylamine with methyl chloride at a pressure of 3 kg/cm3 in
water. A 25% aqueous solution was used.
STAC, 20/22TAC and BeTAC were prepared by quaternisation of
alkyldimethylamine with methyl chloride at a pressure of 3
kg/cm3 in acetone followed by crystallization.
LKB was prepared by reaction of alkyldimethyl-amine in water
with benzyl bromide. A 25% aqueous solution was used.
EiKC was prepared by reaction of alkyl-dimethylamine with
benzyl ~hloride in refluxing acetone followed by
crystallization.
The commercial product from Lonza, Bardac 22, which is a 50%
solution of DDDAC in water/isopropanol mixture was used.
DLDAB and DMDAB were prepared by reaction of alkyldime-
; 25 thy~amine with alkylbromide.
DSDAC was Querton from Berol-Nobel.
The identity and purity of the compounds were determined by
HPLC and 13C-NMR as well as with conventional titration
techniques.
The HPLC method was a modified version of the one published by
Helboe [Journal of Chromatography 261, 1983, 117-122] based on
chromatography of ion pairs of the QAC with an W absorbing
counterion. By using a Nucleosil CN column with methanol:water
(70:30) containing 5 mM p-toluene sulphonic acid as the eluent
compounds in the ATAX and the AKC series with from 12 to 22

wos~ 20 PCT/~K91/00096
9 ~ 3~
carbons in the long alkyl chain can easily be separated.
13C-NMR was performed on a 500 MHz spectrometer at a frequency
of 125.97 MHz with simultaneous broad band decoupling. Samples
were run in 10 mm tubes using CDCl3 as solvent and as deuterium
lock. The shifts obtained were in agreement with those reported
by Fairchild [Journal of the American Oil Chemist Society,
59(7), 1982, 305-309] except for an absorption at 25 ppm, which
was not observed by Fairchild.
E~ample 2
Phytophthora infestans on pota~o.
Potato plants (Variety: Sava ecology, grown 14 days in 7 cm
plastic pots. 1 plant/pot) were sprayed with aqueous solutions
of the compounds shown in the following Table II, the
concentration of active substance being listed in the Table.
The solutions furthermore contained 0.1% Tween~ 20 and 5%
ethanol.
After spraying with the solutions the plants were incubated at
18-20C for 24 hours after which they were inoculated with an
aqueous suspension of Phytophthora infestans sporangia.
Following inoculation, the potato plants were incubated in
humid chambers. The dark/light interval during the incubation
period was 6 hrs/18 hrs. The degree of control and phytotoxici-
ty was assessed 6 days after the inoculation.
The score of control is expressed on a scale from 0 to 9 with
9 being complete control. The phytotoxicity is evaluated on a
scale from P0 (no phytotoxicity) to P4 (complete collapse or
extinction). The results will thus be given in the form X-Py
where X is the degree of control and Py is the phytotoxicity.
The results are shown in the following Table II:

WOslJIsl20 PCT/DK91/00096
- J ~
TABLE II
Concentration 0.3% 0.1% 0.033%
Compounds
LTAC a--p4 6 b_p3 2--P2
5MTAC a--p4 8--gb-P3 9 Pl-2
CTAC a-p3 2b-P23 7-P
STAC 8-P2 8-P1 7-P
20/22-TAC 8-9-Po 9~ Po 8-Po
DDDAC P23 P2 7~
Untreated control : g-P0
Reference : 9-P0 (6 ml Dithane/l)
Inoculated control : 2-Po
15 a~ Impossible to evaluate due to the phytotoxicity.
b) Uncertain evaluation due to the phytotoxicity.
The results clearly show the remarkable effects of the VLCQACs
STAC and especially 20/22-TAC, the latter being able to give
control of PhytoPhthora infestans without causing phytotoxic
effects.
Example 3
Phvtophthora infe~tan~ on potato plants.
.~
Potato plants were tested as in Example 2. However, Surfynol
TGE (0,05%) was used as dispersing agent. The results are shown
in the following Table III:

W(~91/15l20 PCT/DK91/00096
1 1 2 . , ~3 ~
TABLE III
Concentration. 0.3% 0.1~ 0.033
Compound
STAC a _ P2 3 Pz 5 ~ P1
52 0/ 2 2 -TAC 7 - pO 7 - pO 5 _ pO
DLDAB ~ Pl 7 - Pl 7 - PO
DMDAB 5 ~ PO 4 ~ PO 2 ~ PO
DSDAC 7 - PO 7 - PO 5 - PO
- EiKC 7 - pO 5 _ p 5 _ p
Untreated control: 9 - P0
Reference : 9 - P0
Inoculated contr.: 2 - PO
15 a) See footnote in Example 2.
The present results demonstrate that inhibition of a fungal
'~ attack can be obtained without phytotoxic effects for VLCQACs
both in ATAX, AKX, and the DADMX-series. The use of Surfynol~
instead of Tween~ 20, however, seems to decrease the effect of
VLCQACs a little.
Example 4
In ~itro effect of OACC.
QACs's inhibitory effect on specified stages of the life cycle
of several species of Oomycetes was tested on microtiter
plates. The QACs were dissolved in a dilute salts solution and
the minimal inhibitory concentration (MIC) was determined.
Concentrations tested were 333, 66, 13.2, 2.6, 0.5, and 0.0
~g/ml DS (= dilute salts solution [Dill and Fuller:
Arch.Microbiol. 87, 92-98, 1971]). The results are shown in the
following table IV:

WOgl/l5l20 PCT/DK91/00096
12
TABLE IV
20/22
Species\ \Compound LTAC MTAC CTAC STAC -TAC DDDAC
Allomyces
gametogenesis 333 66 13.2 333 66 13.2
Gamete stability 13.2 2.6 0.5 66 13.2 0.5
Zoosporogenesis 333 66 66 333 333 66
Zoospore 66 13.2 13.2 66 66 2.6
stability
lO Hyphal growth 66 13.2 13.2 ~333 66 13.2
Pythium sP. 207-86
Hyphal growth 333 66 13.2 66 13.2 13.2
(3 days)
15 Zoospore release 333 13.2 2.6 66 2.6 13.2
(2 days)
Zoospore 13.2 13.2 <0.5 <0.5 2.6 <0.5
stability
Cyst-hyphae 2.6 13.2 2.6 0.513.2 2.6
formation (1 day)
PYthium ultimum
Hyphal growth 333 66 2.6 66 13.2 2.6
(3 days)
25 Oospore 333 66 66 333 66 13.2
germination (1 day)
:, Oospore 66 13.2 2.6 66 13.2 0.5
formation (3 days)
30 Phytophthora ~arasitica
hyphal growth 6666 2.6 66 66 2.6
(3 days)
Zoosporangium 13.2 13.2 2.6 66 66 2.6
oospore formation (3 days)

WO91/15120 PCT/DK9i/00096
13 2C ~.'~
TABLE IV Continued
20/22
Species\ \Compound LTAC MTAC CTAC STAC -TAC DDDAC
PhYtophthora s~. 360-86
hyphal growth 333 13.2 2.6 66 13.2 2.6
(3 days)
Oospore formation 333 2.6 2.6 66 13.2 2.6
(4 days)
: l0 Phvtophthora infe~tzn~
sporangium 333 66 2.6 66 <0.5 2.6
germination and hyphal growth (2 days)
Table IV shows that CTAC and DDDAC generally have the best
score of MIC values in this test system where there are no
problems with phytotoxicity. However, it is interesting to note
that 20/22-TAC has the lowest MIC value for Phytophthora
infestans.
` 20
Example 5
Plasmopara hastedii on Sunflower.
Small Sunflower plants were sprayed with aqueous solutions or
suspensions of QACs approximately 24 hours before inoculation
with a spore suspension of P. halstedii. The results were
evaluated after 7 days, and are indicated in Table V below.

WO91/1~120 PCT/D~91/00096
--f ~3
14
TABLE V
Concentration 0.3~ 0.1% 0.033%
Compound
LTAC a _ p - P4 7 - P3
5MTAC a _ p a _ p a _ p
CTAC - p4 9 _ p3~ 9 _ p3C
STAC 9 - P3' 9 ~ P3 9 ~ P3
20/22-TAC 9 - Pz 6 - P0 9 - P0
EiKC 9 - P0 8 - P0 5 ~ Po
lODDDAC 9 - Pz 9 - P1 9 ~ P
DLDAB a _ p4 9 _ p 9 _ p
DMDAB 9 - P3 9 ~ Po 9 ~ Po
DSDAC g - P~ 5 - P0 5 - P0
~) and b) as in Example 2. " Stunted growth.
From Table V it is apparent that VLCQACs are very efficient
fungicides in this test system too. Also, it is seen that the
phytotoxicity apparently poses a problem to the QACs of short
chain length.
Example 6
pseudoDerenospora cubensis on Cucu~ber.
:
Leaves of cucumber were sprayed with aqueous solutions/
suspensions of QACs approximately 24 hours before inoculation
- with a spore suspension of P. cubensis. The results were
evaluated after 7 days, and are shown in Table VI below.

WO91/15120 PCT/DK91/~096
2~
TABLE VI
Concentration0.3~ 0.1% 0.033%
Compound
LTAC a _ p a _ p 2 - P1
5MTAC a _ p 2 - P2 ~ P3
CTAC a _ p 8 ~ P2 ~ P
STAC 7 - P1 9 ~ Po 5-6 - P0
2 0/ 2 2 -TAC 7 - P0 4 - P0 2 - PO
EiXC 5 ~ P3 5 ~ P 4 ~ P
lODDDAC a _ p a _ p~
DLDAB a _ p4 0 _ p3 5 - P
DMDAB 6 - P0 6 - P1
DSDAB 8 Pl 5 ~ PO 5 - P0
15 a) As in Example 2.
The effect of VLCQACs against Pseudoperonospora cubensis on
Cucumber is evident, but the optimal effect is seen with the
STAC in this example.
ExamDle 7
- 8ynergistic effe~t of BeTAC and Dithane~.
25 Potato plants were sprayed with solutions containing Dithane0,
BeTAC (dissolved in 5% aqueous ethanol) and 0.1% Tween0 20.
After l day, the plants were inoculated with sporangia suspen-
sion of Phytophthora infestans and incubated 6 days at 18~C/
18 hrs light - 13C/6 hrs dark and a relative humidity of 80%.
Evaluation of the results gave following Table VII:

U'O91/1~120 PCT/DK91/00096
2- ,~3.
16
TABLE VII
Concentration
of DithaneX mi/l o 0.006 0.06 6
Concentration
of BeTAC%
0 1 - P 1 - P 2 - P~ 9 P0
O. 001 1 - P 1 - P 1 - P
0.01 2 - P0 3 ~ Po 4 ~ Po
Notation as in Example 2.
An untreated control scored 9 - P0
This example shows clearly the synergistic effect between the
VLCQAC BeTAC and the conventional fungicide Dithane~.
Example 8
~; sYnergictic effect of BeTAC and Ridomil~ MZ.
;~
Potato plants were sprayed with a solution containing BeTAC
and/or the fungicide Ridomil~ MZ and 0.1% W/W Tween9 20. BeTAC
. was dissolved in 5% ethanol. Ridomil~ MZ was diluted to a
concentration of 0.005 mg/ml (1:1000 of normal dose). The
conditions were as in Example 7.
. 25
TABLE VIII
- Concentration of
Ridomil~ MZ mg/ml 0 0.0005 0.005
Concentration
30 of BeTAC in%
0 1 ~ Pu 3 ~ Po 7
0.01 2 - P0 6 - P0 8 - P0
0 05 3 - P0 8 - P0 9 - P0
The results show that the VLCQAC BeTAC exhibits a synergistic
effect in combination with Ridomil~ MZ.

WOsl/l5120 PCT/DK91/00096
, , ~3"~
17
Example 9
o~Cs phytotoxicitY on mono- and di-cotYledons
Aqueous solutions of QACs containing 0,1% Tween 20 were sprayed
on small plants until "run off". The evaluation of phytotoxi-
city after 72 hrs is listed in Table IX.
TABLE IX
Plants Barley Maize Sunflower Potato Tomato
Age of plants 1 week 3 weeks 3 weeks 4 weeks 4 weeks
Compounds and
conc. in %
0,5 % Po Po P1 Pol P1
20STAC O,l % Po Po Po Po Po
MTAC 0,3 % P1 p1 p3 P~ P2 .
0,5 % P3 P~ P3 P3 P3
LKB 0,1 % P1 Po Po1 P1 Po-
P0 = Non Phy~otoxic.
P4 = Total extinction.
As seen in the Table the VLCQAC STAC (C18-chaln) was
less phytotoxic than LKB (C12-chain) and MTAC (C~4-chain).

Representative Drawing