Note: Descriptions are shown in the official language in which they were submitted.
iO75248
This inventi.on relates to a compound having fungicidal
activity, and to processes for controlling or eradicating
fungi using this compound.
Accordingly we provide the compound S-methyl 3-
S furfurylidene-2-met~lyl-dithiocarbazate.
The compound may be made by any of the following
methods:
Me SO
2 3 2 ` H2N-N-CSSK 2 4~ H2N-N-CSSCH3 -
CH3 CHq
~/-- ~LCH=N-N-CSSCH3 ~ CHO
. Il B- 1~2N-N~-CH3+CS2+KOH ~ H2N-N-CSSK
CH 3
--CII=N-N-CSSK ~ 4 ) ~--CH=N-N-CSSCH3
. ~ Ir~ ~1 Cs2-l-KOH
C. ~ ~ CHO~H2N-NH ~ ~ ~ CH--N-NH
CH 3
~1-CH=N-N-CSSR 2S4~ ~LCEI--N-N
. CH3 CSSCH3
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D. ~ ~ + (Ctl3)254 ~ ~ CH3
E. ~ CH3 ~ ~ ~ CH=N-NNa 2
CH=N-N-CS.SNa i ~ CH=N-N-CSSCH3
3 H=N-N-cSScH3
G. O ~Na+CSC12 ~ ~ CH=N-N-CS-Cl
~ CH=N-N-CSSCH3
. . .
H. ~ CH=N-NH + C53(CH~ ~ CH3
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~n a further embodiment of our invention we provide
a process of era(licating undesired fungi which process
comprisinE t~cating media infested with fungi with com-
positions containing S-methyl 3-furfurylidene-2-methyl-
dithiocarbazate.
It is to be understood that the fungicidally active
compositions of this invention may comprise, in addition to
the active ingredient described hereinabove~ one or more
other compounds having fungicidal activity.
The compound and compositions of the invention
; may be used as foliar sprays for the control of fungi on
plants but we have found that they are particularly useful
' as seed dressings.
Accordingly in yet a further embodiment of our
invention we provide a process of treating seeds~ which
process comprises treating seeds prior to sowing with a
composition containing fungicidally effecti~e amount of S-methyl
3-furfurylidene-2-methyl-dithiocarbazate.
: ! - In particular the present invention relates to a
process of treating seeds to control or eradicate the incidence
of fungi of the families Tilletia and Ustila~o thereon or
therein.
l The fungi Til~etia and Ustila~o are diseases which may
`,1 cause heavy damage to grain crops such as wheat and barley.
~ 25 It is known in the art that these diseases may be controlled
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by thc applic.l~ion of seed dressing compositions comprising
an efective amount of a suitable fungicidal organo-mercury
compound. ~lowcver toxicity and environmental studies have
sho~n that tl~e use bf thcse compol~nds i.s highly undesirable~
and in addition some species of the fungi Tilletia exhibit
resistance to them.
We have now found a compound which is highly effective
against bunt and smut and which do not suffer the disadvantages
of the prior art active ingredient compounds, and which in
addition are highly effective against the resistant species of
the fungi ?illetia.
The seed dressings of this invention may comprise, in
addition to the S-methyl~3-furfurylidene-2-methyl-dithiocarbazate,
one or more other compounds having fungicidal activity especially
compounds active against cereal pathogens other than bunt. Such
other compounds indicate for example fungicides such as, e.g.,
Mancozeb~ Thiram~ 8-hydroxy quinoline and insecticides such
as, e.g., Lindane, Malathion.
I Especially useful compositions for use as seed dressing
i 20 compositions comprise from 1 to 90% w/w preferably from 2.5%w/w to 75% w/w of the S-methyl 3-furfurylidene-2-methyl
dithiocarbazate.
Our compositions may be formulated in the form of
dusting powders or granules wherein the active ingredient is
mixed with a solid inert carrier. Suitable solid inert
1075248
carricrs may be, for example, kaolin, powdered chalk, talcs,
kieselg~hr, dolomite, calci~ carbonate, powdered magnesia,
Fullerls earth, gypsum~ ~le~ittls earth~ diatomaceous earth~
china clay, bentonite, and other colloidal clays.
Alternatively the seed dressing composit~ons may be
in the form of dispersible powder orgranulescomprising~ in
addition to the active ingredient an inert carrier comprising
a wetting agent to facilitate the dispersion of the powder or
~anulesin liquids. Such powders or granules may include fillers,
suspending agents and the like. The preferred dispersible
powders comprise the active ingredient mixed with a finely
ground colloidal clay together with a dispersing agent.
Suitable dispersing agents are known from the prior art
and may be of the cationic~ anionic or non-ionic type. Suit-
able agents of the cationic type include for example quaternary
ammonium compounds such as cetyltrimethylammonium bromide.
Suitable agents of the anionic type include for example soaps~
salts of aliphatic monoesters of sulphuric acid, for example
sodium lauryl sulphate~ salts of sulphonated aromatic compounds~
for example sodium dodecyl-benzene sulphonate~ sodiwm, calcium,
or ammonium lignosulphonate~ butylnaphthalene sulphonate and
a mixture of the sodium salts of di~isopropyl and tri-
isopropylnaphthalene sulphonic acids. Suitable agents of the
non-anionic type include for example the condensation products
of an alkykene oxide such as ethylene oxide or propylene oxide
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Wit}l fatty alcohols such as oleyl alcohol or cetyl alcohol~
or with alkylphcll~ls such as octyl-phenol~ nonyl-phenol and
octyl-cresol. Otller non-ionic agents are the partial esters
derived from ,ong chain fatty acids and hexitol anhydrides~
the condensation products of the said partial esters with
an alkylene oxide such as ethylene oxide or propylene oxide
and the lecithins.
Suitable suspending agents are for example, hydrophilic
colloids, for example polyvinyl pyrrolidone and sodium carboxy-
methyl cellulose~ and the vegetable gums~ for example gumacacia and gum tragacanth.
We have found that deposition of a seed dressing
composition containing S-methyl 3-furfurylidene-2-methyl-
dithiocarbazate in an amount of from 50 to 1500 ppm effectively
controls or prevent fungal growth to some extent at least.
For economic control of Tilletia ~. we prefer that
seeds are treated so that they contain on their surface
from 250 to 1500 ppm of the S-methyl 3-furfurylidene-2-methyl
dithiocarbazate based on the weight of the seed.
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~075Z48
Our invcntion is illustrated by, but no way limited to,
the following examples.
Example 1
This example describes the preparation of S-methyl 3-
furfurylidene-2-methyl-dithiocarbazate according to the
equation i.e.
~'CHO + H2N - N - C - S - CH3
CH3 S
CH = N - N - C - S - CH3
CH3 S
Acetic acid (5 mls) was added to 50 ml of ethanol, this
solution was warmed, and 2.7 g of S-methyl-2-methyl-dithiocarbazate
.
was added with stirring. Furfuraldehyde (1.9 g) was added and
a crystalline precipitate was obtained which was re-crystallized
from ethanol yielding 3.3 g of S-methyl 3-furfurylidene-2-
methyl-dithiocarbazate melting at 98C. The identity of the
product was confirmed by mass spectrometry. On further
recrystallization from ethanol and charcoal the melting point
increased to 104 C.
Example 2
This example describes the fungicidal action of
compositions according to the present invention in vitro.
To a 1 ml volume of toluene was added 0.004 g of S-methyl
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_ 9 _
3-furfuryliden~-2-methyl-dithiocarbazate and 0.02 g of a
1:1 mixture by weight of ~IAlkanate~l CS (~Alkanate~ CS is a
Registered Tradc Mark of ICI Australia Ltd for a proprietary
anionic surface activc composition) and "Teric" 200 ("Teric"
is a Registercd Trade Mark of ICI Australia Ltd for nonionic
surface active compositions comprising alkylphenol/alkylene
oxide condensates).
This solution was thcn further diluted with water and
mixed with molten agarto give weight per volume concentrations
of active ingredient compound of 0.4, 2 and 10 ppm in the
final product.
- The prepared agar mixtures were poured into petri
dishes, allowed to solidify, and were then inoculated with
; spores of Tilletia foetida. A petri dish containing an agar
composition comprising no active ingredient was prepared in a
' similar manner.
I In addition petri dishes containing agar compositions
1 comprising as active ingredient "Vitavax" (IlVitavaxll is a
; Registered Trade Mark of Uniroyal Inc for fungicidal
compositions comprising as active ingredient 5, 6-dihydro-2-
methyl-l~ 4-oxathiin-3-carbox-anilide) were prepared and
inoculated substantially in the manner described above. After
incubation of the inoculated slides at 10 to 18C for 7 days
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of spores was observed. The control obtained is shown in
Table l below.
TABLE l
Active Ingredient % Inllibition of Spores
Compound (Rating*)-Concentration
of Active Ingredient
(ppm).
0 2 -- 0.4
, - _
¦ ~ ~ C1 '~ C113¦ 3 ¦ 3 ¦ 2
'1Vitavax" 3 l 0
Control - No ~ctive 1ngredien~ 0 U 0
* Rating 3 = 90 - 100% Inhibition of spores
2 = 60 - 90% Inhibition of spores
l = 30 - 60% Inhibition of spores
0 - 0 - 30% Inhibition of spores
Example~3
This example describes the fungicidal action of a
composition according to the present invention against the fungi
- Tilletia foetida (B.H.C. susceptible) and
; Tilletia foetida (B.H.C. resistant) under field
conditions.
Samples of wheat seed (c.v. Olympic)were inoculated
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~ith spores of each of the fungal species Tilletia foetida
(B.H.C susceptible) and Tilletia foetida (B H.C resistantl
in the following manner. Spores of each fungus were admixed
with wheat seed at a rate of 0 4 g of spores per 99 6 g. of
seed and the mixtures were blended by rotation in sealed
containers on the rollers of a ball mill for twenty minutes.
The samples of inoculated seed were then dressed
with a fungicidal composition according to the present
invention and comprising 50% w/w of S-methyl 3-furfurylidene-
2-methyl-dithiocarbazate, 3% w/w of ethylene glycol, 5% w/w
of "Celite" 298, and 42% w/w of china clay, by application
of the said fungioidal composition at a rate of 1 g per kg
of inoculated seed and blending by rotation in a sealed con-
tainer on the rollers of a ball mill for twenty minutes to
produce uniform products containing 500 ppm by weight of
active ingredient compound. "Celite" is a trade mark for a
diatomaceous silica product,
Each sample of dressed seed was then sown through a
. ~
seed drill in 4 single row plots each 22 yards in length. The
seed was then allowed to germinate and the wheat plants were
allowed to mature. At harvest the seed heads were collected
and the control of disease assessed. The percentage of
diseased heads is presented in Table 11 below
For purposes of comparison the sowing procedure
described above was substantially repeated except that the
dressed seed was replaced by samples of seed inoculated with
each of the fungi
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- 12 -
describcd above but not treated with a f-mgicidal composition.
Thc pcrc~ntage of diseased heads obtained in these
comparative tests is also presented in Table 11 below.
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1075Z48
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Examp]e 4
This cx.lmple dcscribcs the fungicidal activity of
compositions of the present invcntion against Puccinia
coronata (oat rust).
Two hundred millilitres of all aqueous composition
comprising 0.05% w/v of S-methyl 3-furfurylidene-2-methyl
dithiocarbazate was sprayed onto a pot of 30 5" tall oat
plants. Twenty four hours after spraying the plants were
inoculated with Puccinia coronata (oat rust) by dusting them
with a concentrated spore suspension taken from infected
plant material. After inoculation the oats were placed in a
high humidity cabinet for 24 hours and then returned to the
glass house. The plants were assessed eight days after
inoculation and found to be substantially free of disease.
Examples 5 and 6
This example describes the control of the fungi
Rhizoctonia solani (early blight of tomatoes), C~ratocYstis
poradoxa (pineapple disease of sugar cane) and Venturia
ine~ualis (black spot or apple scab).
~l 20 Small quantities of an aqueous ball milled suspension
of S-methyl 3-furfurylidene-2-methyl-dithiocarbazate were
; mixed with 20 millilitre volumes of an aqueous composition
comprising 0.5~ w/w of potato dextrose agar and 0.5% w/w of
water agar and the mixtures were then poured into petri dishes
~ 25 and allowed to set. Sufficient of the a~ueous suspension was
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included to proYit3e agar c~inpositions having active
ingredicnt concentrations of 10 ppm by weight and 25 ppm
by weight in the final agar compositions.
A one centimetre cu~e of agar infected with Rhizoctonia
S _lani~ Ceratocystis ~ or Venturia inequalis was then
placed in each petri dish and the growtll of the fungi was
assessed four days later. The results are presented in
Table III below.
TABLE III
.... _ . _ ,
% Inhibition of Spores (rating)*
Fungal Species Concentration of Active Ingredient
~. ' . - ....
Rhizoctonia solani~ 3 3
Ceratoc~stis oradoxa 3 3
Venturia _neaual,is _ 3
. ............... , ............ ...
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* As for Example 2
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Example 7
Analogues of S-methyl 3-furfurylidene-2-methyl-
dithiocarbazate as shown in Table IV below were prepared by
reaction of a carbonyl compound (A) wlth various dithio-
carbazates (B) according to the method of Example 1.
TABLE IV
..
Structure A B m.p.
ll I Me Me ll 1I Me S
0~ c ~ ~ O ~ O ~ H2N-N-C-S-Me ~ 89
; ~LCH=N-Y ~ LHo ~ H2N-N-C S-B1 ~ 93
CH=N NH O --CHO N2N-NH-C-S-Me ~ 150
_~ ~ ~--CHO ~ H2N-NH-C-S-EC
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Examplc ~
This exlmplc de.scribes the fun~icidal action of the
analo~lles pr~parcd ill Example 7 in tlle field nnder natural
conditions.
Wheat secd (c.v. Olympic)~ was inoculated with a
mixture of equal amounts of Tilletia foeti~a spores HCB
rcsistant and IICB susceptible and Tilletia caries by
admixin~ 1 g o~ the mixed spores with each lb of seed and then
tumble mixing the mixture for 20 minutes. Separate samples
of inoculated seed was then dressed with a composition by
comprlsing 50% w/w of china clay and 50% w/w of each of the
compounds listcd in Table V at rates of 0.01 g per 20 g of
inoculated seed, 0.01 g per 13.3 g of inoculated seed and 0.01 g
per 10 g of inoculated seed, and tumble mixing the mix~tures w~til
uniform products containing 250 ppm, 375 ppm and 500 ppm com-
pound respective]y were obtained.
For each Pungicidal composition and at each application
rate~ dressed seed was then sown through a seed drill in 6
single row plots each 10 feet in length. The seed was then
allowed to germinate and the wheat plants allowed to mature.
, The trials of each treatment rate were carried out in a
different part of Victoria.
For purposes of comparison the sowing procedurc cles-
cribed above was substantially repeated except that the
dressed seed was replaced by untreated ino~lated seed.
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At harvest the seed heads were collected and the
control of thc disease assessed. The percenta~e of diseased
heads is SllO~l in Table V below.
TABLE V
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. ~ disease
Compound 500 375 250
, ppm ppm ppm _
CH = N - - C - S - Me ~ 0.18 ~ 0.70 ~ 2.27
h 11 Me Me S
J -C - N - N - C - S - Me 25.79 4.73 25.79
C S _ Et 4-67 6.2
CH = N - NH - C - S - Me ~ 15.7710.70 ~ 11.21 ~
¦ I ~_CH = N - H - C - S - Et 15.30 17.10 14.93 ¦
Control (no treatment) 32.06 60.03 24.20
S The results obtained demonstrate tha~ the oompounds of
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Exalllple 7 l~a~-e activity against Tilletia foetida and
Ti]]ctia ~ari(~s. Ilowevcr this activity is much less than
the activity of the colllp()und of tlle present invention.
Examl)]c 9
11.8 g of potassillm hydroxide werc dissolvcd in 80 ml
of ethanol. After the reaction mixture was cooled to 10,
9.2 g of methylhydrazine was added and the ~ixture stirred
for 5 minutes.
14.5 g of carbon disulphide were added dropwise
keeping the temperature between 10-15. The reaction mixture
was stirred at room temperature for 2 hours. 120 ml of water
was added~ then 27.8 g of dimcthyl sulphate was added dropwise
keeping the temperature below 20. After stirring for 2
hours at room temperature, 18 g of furfuraldehyde was added
dropwise and with vigorous stirring~ then the reaction mixture
was stirred for 1/2 hour at room temperature. 200 ml of water
was added, then the mixture was cooled below 10, then the
precipitate was filtered off, washed with water, and dried at
60 in vacuum. Yield of S-methyl-3-furfurylidene-2-methyl-
dithiocarbazate -- 36.5 g mp = 100 (90%).
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5.9 g of potassium hydroxide were dissolved in 40 ml of
ethanol and the solution cooled to room temperature, then 4.6 g
of methylhydrazine was added. After cooling to 10~ 7.25 g
of carbon disulphide was added dropwise with stirring~ keeping
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the temperaturc below 15. After stirring or 2 hours at
room tcmperaturc, 9 g of furfural was added dropwise with
stirring. Potassium 3-(2-furfurylidene)-2-methyl-
dithiocarbazate was formed during stirring for 2 hours at
room temperaturc. 100 ml of ether was added~ the suspension
was cooled below 10 and the product was filtered off, washed
with chilled ether and dried. 12 g of this product was sus-
pended in 150 ml of methanol and 19 g of dimethyl sulphate
- was added and the mixture was stirred for 5 hours at rGom
temperature. Water was then added to 500 ml and after
stirring for 15 minutes and cooling below 10, the product
was filtered off and washed with water. The product had a
m.p. of 103 and was identified as being S-methyl-3-furfurylidene~
2-methyl-dithiocarbazate.
,~, 15 Example 11
9.8 g methyl hydrazine was stirred with 70 mls
absolute ethanol. 19.2 g furfural was added dropwise to the
reaction mixture~ and stirred at room temperature for 12 hours.
10.8 g potassium hydroxide (dissolved in 40 mls ethanol)
I 20 was added all at once~ and then 15.2 g carbon disulphide
`i added dropwise (15C).
The reaction mixture was stirred at room temperature
for 16 hours, cooled to 10C for 12 hours and filtered. A
¦ product with mp 237 was obtained and this was identified
by spectroscopic means to be potassium 3~(~-furfurylidene)-2-
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mct;hyl-dit~lioc.lrbazate .
~--CI~0 + l~2NN~IC~13 ~ ~ CH=NN~ICH
Q CH--NNCS.K
Cll
4.8 g of this salt was dissolved in 50 ml of 50% aqueous ethanol
then 2.52 g of dimethyl sulphate was added dropwise over 1 hour
and further stirred for 2 hours. After cooling below 10 the
product was filtered off~ washed in the chilled ethanol and
dried. It was identified by spectroscopic means to be S-methyl
3-furfurylidene-2-methyl-dithiocarbazate.
; Exa ~
1 g of 2-(2-furyl)-4-methyl-1~3,4-thidiazolidine-5-
thione was dissolved in 50 ml of warm ethanol~ and after
cooling to room temperature 1.26 g of dimethyl sulphate was
added. After stirring for 2.5 hours at 50~ o.69 g potassium
was added~ the mixture was heated for 1.5 hours at 50~ then
allowed to ~tand overnight. The reaction mixture was filtered
and the filtrate was evaporated to dryness. The residue was
re~rystallised from ethanol and pure S-methyl 3-furfurylidene-
1 2-methyl-dithiocarbazate (mp = 103) was obtained.
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