Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
iC377~)44
The present invention is concerned with new herbicidally
active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide deri-
vatives, with a process for the manufacture of these compounds
and with their use.
1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a
herbicidal action have already been known (German Offenlegung-
sschriften Nos. 1,816,696 and 2,118,520). However, they have
only a very limited spectrum of selectivity towards crop plants.
Accordingly, the problem upon which the present
invention is based has been to make available a herbicidal agent,
which, in addition to having an outstanding action against weeds,
has a broad spectrum of selectivity towards crop plants.
This problem is solved in accordance with the present
invention by the compounds of the general formula I, as defined
below.
The present invention accordingly provides compounds
of the general formula I
~i
N N-B
¦¦ I / CH3 (I)
R-s(O)n-C /C=N-CO-N e:
in which R represents an aliphatic hydrocarbon group, B
represents a monovalent metal equivalent and n represents 0, 1 ~.
or 2.
The compounds of the present invention are distinguished
by a broad soil- and leaf-herbicidal action. They can be used for
combating mono- or di-cotyledonous weeds (including certain un-
desired plants not normally considered as weeds). h-
With the compounds of the present invention there can be
combated by the pre-emergence method and also the post-emergence r
method agricultural weeds amongst which there ~ay be mentioned,
for example, Sinapis ssp., Stellaria media, Sene\cio vulgaris,
- 1 - ~.~ , .
. .
107704~
Matricaria chamomilla, Ipomoea purpurea, Chrysanthemum se~etum,
Lam _m amplexicaule, Centaurea cyanus, Amaranthus retroflexus, E
Alopecurus myosuroides, Echinochloa crus galli, Setaria italica,
Sorghum halepense and Lolium perenne.
For combating seed weeds there are generally used
~uantities within the range of from 1 kg of active substance
per hectare to 5 kg of active substance per hectare. Thereby, the
active compounds of the present invention have been found to be
selective in commercial vegetable crops, for example bush-bean,
ground-nut, potato, pea, rice, maize, sorghum and soya crops.
When two or more compounds of the general formula I are used the
range of 1 kg to 5 kg refers of course to the total amount applied
of these compounds.
At higher rates of application the compounds are also
suitable as total nerbicides for the destruction or suspension E
of waste land flora during a period of vegetation.
The present invention accordingly also provides a
herbicidal preparation which comprises a compound of the general
formula I, in admixture or conjunction with a suitable carrier.
The preparation may of course contain one or more compounds of the ~:
general formula I.
The present invention further provides a method of
protecting a living plant against weeds, wherein the area in the
vicinity of a living plant is treated with a compound of the
general formula I.
The present invention further provides a method of pro-
tecting a crop area against weeds, wherein a crop area is treated
with a compound of the general formula I.
The present invention further provides a method of
protecting a waste land against weeds, wherein a waste land is
treated with one or more compounds of the general formula I, the
compound(s) being used in a total amount of more than 5 kg per
hectare.
-- 2
1077044
The present invention further provides a pack which
comprises a compound of the general formula I together with
instructions for its use as a selective herbicide.
The compounds of the present invention may be used
either alone, or in admixture with one another or with other
active substances. If desired, there may be added other defolia- 5
ting, plant protecting or pest combating agents depending on the
purpose desired.
When it is intended to broaden the spectrum of action,
other herbicides may also be added. For example, there are suit-
able as herbicidally active components to be added active sub-
stances of the group of triazines, aminotrizoles, anilides, dia-
zines, uracils, aliphatic carboxylic acids and halogenocarboxylic
acids, substituted benzoic acids and aryloxy-carboxylic acids,
hydrazides, amides, nitriles, esters of such carboxylic acids,
carbamic acid esters and thiocarbamic acid esters, ureas,
2,3,6-trichlorobenzyloxy-propanol and thiocyanate-containing
agents. As other additives there are also to be understood,
for example, non-phytotoxic additives, which cause a synergistic
increase in action with herbicides, for example wetting agents,
emulsifiers, solvents and oily additives.
The active compounds of the general formula I or mix- t~
tures thereof are advantageously used in the form of herbicidal
preparations, for example powders, strewable preparations, gran-
ules, solutions, emulsions or suspensions, with the addition cf
liquid and/or solid vehicles or diluents, and, if desired, of
surface-active agents, for example wetting, adherent, emulsifying
and/or dispersing agents. ~;
Suitable liquid carriers are, for example, water,
aliphatic hydrocarbons, aromatic hydrocarbons, for example benzene,
toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide
and dimethylformamide, and also mineral oil fractions.
3 -
1077044
As solid carriers there are suitable, for example,
mineral earths, for example tonsil, silica gel, talcum, kaolin,
attaclay, limestone and silicic acid, and vegetable products,
for example meals.
As surface-active agents there may be mentioned, for
example, calcium lignin sulphonate, polyoxyethylene alkylphenol
ethers, naphthalene sulphonic acids and salts thereof, phenol
sulphonic acids and salts thereof, formaldehyde condensates,
fatty alcohol sulphates and also substituted benzene sulphonic
aclds and salts thereof.
The total amount of the active compounds(s) of the
general formula I in the various herbicidal preparations may vary
within wide limits. For example, the preparations may contain
approximately 10 to 80% by weight of active compound(s), approx-
imately 90 to 20% by weight of liquid or solid carrier and, if
desired, also up to 20~ by weight of surface-active agent(s).
The active compounds may be applied in the usual manner,
for example with water as carrier in quantities of spray liquor
of about 100 to 1000 litres per hectare. It is also possible to
apply the active compounds by the so-called "low-volume" and
"ultra-low-volume" methods and it is also possible to apply them
in the form of so-called microgranules.
Among the compounds of the general formula I there may
be used in accordance with the present invention, more especially,
those in which R represents an alkyl, alkenyl or alkynyl group
containing up to 6 carbon atoms and B represents an alkall metal
atom, preferably a lithium, sodium or potassium atom.
As alkyl, alkenyl and alkynyl groups there come into
consideration for this purpose, for example, straight-chained
and branched alkyl, alkenyl and alkynyl groups, for example
methyl, ethyl, propyl, isopropyl, allyl, 2-propynyl, n-butyl,
isobutyl, sec.-butyl, tert.-butyl, 2-butenyl, 1-methyl-2-propenyl,
1077044
n-pentyl, isopentyl, neopentyl, tert.-pentyl, l-methyl-butyl,
l-ethyl-propyl, n-hexyl and isohexyl groups.
The compounds of the present invention of the general
formula I are salts, which exist ionically corresponding to the
following polar formulae
N Nl
R-S()n ~ L N-CO-N B( ) >
N - - N
R-SIO) ~ - N-CO-N ~ c
N N _ (_
R-S(O)n~ N-C-N / 3 B(+) ,
or formulated in general as
N -N (-) O
R_5(o)n ~ S N ~
For the sake of simplicity these ionic forms are not
shown by the general formula I, but it is to be understood herein
that each compound of the general formula I includes any one of
the aforesaid ionic forms.
The new compounds of the general formula I may be
prepared, for example, by the process of the present invention r
as defined below.
The present invention accordingly further provides a
process for the manufacture of a compound of the general formula
I, wherein
(a) dimethylcarbamoyl chloride of the formula II
-- 5 --
1~77044
H3C
N-CO-Cl (II) 8
H3C
is reacted in the presence of an acid-binding agent with a 1,3,4-
thiadiazolylamine of the general formula III
N - - N
R-S(O)n-C /C NH2 (III)
in which R and n have the meanings given above, to form a 2-
(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid
dimethylamino derivative of the general formula IV
CO N / C 3
- N -- N CH
~1 1 3 ,
; R-S(O)n-C C
S ~CO-N 3 (IV) ,
`CH3
in which R and n have the meanings given above, which is split
with a metal compound of the general formula V
BY (V) , k
in which B has the meaning given above and Y represents a hydrogen ~,
atom or a hydroxyl, lower alkoxy or amino group, or
(b) a 1-(1,3,4-thiadiazol-2-yl)-3,3-dimethylurea derivative of
the general formula VI
N N
CH3
\ S \ (VI)
C 3
in which R and n have the meanings given above, is reacted with
a metal compound of the general formula V
sY (V)
in which B and Y have the meanings given above.
- 6 - ~
10770~4
Each step of the process of the present invention may,
if desired, be carried out in the presence of a solvent. E
The reaction of the components is carried out at between
0 and 100C, but generally at room temperature.
For the synthesis of the compounds of the present
invention the reactants are used in approximately equimolar
amounts. As reaction media there are suitable polar organic ~ r
solvents, alone or in admixture with water. Their choice depends,
according to generally known view-points, on the metal compounds
of the general formula BY used. As solvents or suspension media
there may be mentioned amongst many, for example, acid amides, ~ -
for example dimethylformamide, acid nitriles, for example aceton- r
itrile, alcohols, for example methanol and ethanol, and ethers, for
example tetrahydrofuran. h
The isolation of the compounds of the present invention
formed is carried out finally by distilling off the solvent used
under atmospheric or a reduced pressure or by precipitation with ~'
less polar organic solvents, for example with ketones, for example
acetone, or ethers, for example diisopropyl ether.
Some specific compounds of the present invention are ~`
listed in the following Table:
-TABLE
Name of the compound Physical constant l
~
Potassium salt of 5-ethylthio-2-
(dimethylcarbamoylimino)-1,3,4-
thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-methylsulphonyl-
1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-propylthio-
1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-propylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
1C~7704~
Name of the compound Physical_constant
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-methylthio-1,3,4-thiadiazolin-
3-ide . M.p. >250C
Potassium salt of 5-ethylsulphonyl-2-
(dimethylcarbamoylimino)-1,3,4-thia-
diazolin-3-ide M.p. >250C
Sodium salt of 5-ethylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C J
Sodium salt of 2-(dimethylcarbamoylimino)-
5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-butylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 5-butylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 5-butylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 5-ethylsulphonyl-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino)
-5-methylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-
5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoylimino)-
5-methylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 230C
(decomposition)
Sodium salt of 2-(dimethylcarbamoylimino)-
5-(2-propynylthio)-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-(2-propynylthio)-1,3,4-thiadiazolin ;
-3-ide M.p. ~250C
Lithium salt of 5-ethylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoylimino)-
5-methylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-
5-isopropylthio-1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoylimino)-
5-(2-methyl-2-propenylthio)-1,3,4-thia-
diazolin-3-ide M.p. >250C
- 8 -
1(~77(~4~
Name of the com ound Physical ~onstant
_ _ P _ _ ..
Potassium salt of 2-~dimethylcarbamoyl-
imino)-5-(2-methyl-2-propenylthio)-
1,3,4-thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-hexylsulphonyl-1,3,4-thiadiazo-
lin-3-ide M.p. 213C
(decomposition) R
Sodium salt of 2-(dimethylcarbamoylimino)-
5-hexylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 236C
(decomposition)
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-hexylsulphinyl-1,3,4-thiadiazolin-
3-ide M.p. 191C
(decomposition)
Lithium salt of 2-(dimethylcarbamoylimino)-
5-hexylsulphinyl~1,3,4-thiadiazolin-3-ide M.p. 178C
(decomposition)
Lithium salt of 2-(dimethylcarbamoylimino)-
5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 193C
(decomposition)
Lithium salt of 2-(dimethylcarbamoylimino)-
5-pentylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 200C
(decomposition)
Sodium salt of 2-(dimethylcarbamoylimino)-
5-isobutylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 250C
Potassium salt of 2-(dimethylcarbamoylimino)-
5-isobutylsulphinyl-1,3,4,-thiadiazolin-3-ide M.p. 250C
Lithium salt of 2-(dimethylcarbamoylimino)- ~.
5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 248C ~r
Sodium salt of 2-(dimethylcarbamoylimino)-
5-hexylthio-1,3,4-~d~ li... -3-ide M.p. 250C
~hl`~ c zo/;n p
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-hexylthio-1,3,4-thiadiazolin-3-ide M.p. 250C
Sodium salt of 2-(dimethylcarbamoylimino)-
5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 226C
(decomposition)
Potassium salt of 2-(dimethylcarbamoylimino)-
5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 176C
(decomposition) L
Lithium salt of 2-(dimethylcarbamoylimino)-
5-pentylsulphinyl-1,3,4-thiadiazolin-3-ide M.p. 174C
(decomposition)
Sodium salt of 2-(dimethylcarbamoylimino)-
5-hexylsulphonyl-1,3,4-thiadiazolin-3-ide M.p. 216C
(decomposition)
1~77044
Name of the compound Physical constant
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-(2-methyl-2-propenylthio)-
1,3,4-thiadiazolin-3-ide M.p. 250C
(decomposition) c
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylthio-1,3,4-thiadia-
zolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphonyl-1,3,4-
thiadiazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphonyl-1,3,4-thia-
diazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphinyl-1,3,4-
thiadiazolin-3-ide M.p. 247C E
(decomposition)
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphinyl-1,3,4-thia-
diazolin-3-ide M.p. 240C h
(decomposition) ~,
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphinyl-1,3,4-thia- ~.
diazolin-3-ide M.p. 245C
(decomposition) ~
Lithium salt of 2-(dimethylcarbamoyl- ~'
imino)-5-propylsulphonyl-1,3,4-thiadia-
zolin-3-ide M.p. 250C
(decomposition)
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylsulphonyl-1,3,4-thia-
diazolin-3-ide M.p. 175C ..
(decomposition)
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-pentylthio-1,3,4-thiadiazolin-
3-ide M.p. 260C
(decomposition)
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
-- 10 --
10770~
Name of the compound Physical constant
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-propylthio-1,3,4-thiadiazolin-
3-ide M.p. 263C
(decomposition)
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-propylsulphonyl-1,3,4-thia-
diazolin-3-ide M.p. >250C
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-isopropylsulphonyl-1,3,4-
thiadiazolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylsulphonyl-1,3,4-thia-
diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-isobutylsulphonyl-1,3,4-thia-
diazolin-3-ide M.p. >250C
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-pentylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-pentylthio-1,3,4-thiadiazolin-
3-ide M.p. >250C t
Potassium salt of 2-(dimethylcarbamoyl-
imino)-5-propylsulphonyl-1,3,4-thiadia-
zolin-3-ide M.p. >250C
Sodium salt of 2-(dimethylcarbamoyl-
imino)-5-pentylsulphonyl-1,3,4-thia- - '~
diazolin-3-ide M.p. 240C r .
(decomposition) ~'
Potassium salt of 2-(dimethylcarbamoyl- ;
imino)-5-pentylsulphonyl-1,3,4-thiadia-
zolin-3-ide M.p. 230C
(decomposition)
Sodium salt of 2-(dimethylcarbamoyl- t
imino)-5-propylsulphinyl-1,3,4-thiadia-
zolin-3-ide M.p. 256C
(decomposition)
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-propylsulphinyl-1,3,4-thiadia-
zolin-3-ide M.p. 228C
(decomposition)
Lithium salt of 2-(dimethylcarbamoyl-
imino)-5-hexylsulphonyl-1,3,4-thiadia-
zolin-3-ide M.p. 158C L
(decomposition)
1(~77044
The compounds of the present invention are colourless
and odourless, crystalline bodies, which are excellently soluble
in water, readily soluble in polar organic solvents, for example
carboxylic-acid amides, for example dimethylformamide, sulphoxides,
for example dimethyl sulphoxide, and lower alcohols, for example
methanol and ethanol, are less soluble in carbonitriles, for
example acetonitrile, and are insoluble in hydrocarbons, halogen- ~-
ated hydrocarbons, ethers and ketones.
The following Examples illustrate the invention.
Examples 1 and 2 illustrate the manufacture of compounds of the
general formula I and Examples 3 to 5 illustrate the mode of
action of the compounds of the general formula I.
Example 1
Potassium salt of 5-ethylthio-2-~dimethylcarbamoylimino)-
r
1,3,4-thiadiazolin-3-ide.
To a suspension of 30.3 grams of 5-ethylthio-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethylamide
(M.p.: 91C) in 200 ml of methanol were added dropwise at room
temperature, while stirring, 6.58 grams of potassium hydroxide of ~;
85% strength, dissolved in 100 ml of methanol.
The reaction mixture, after standing overnight, was
brought to dryness in vacuo, and the residue remaining behind was
digested twice with isopropanol and dried in vacuo.
Yield: 25.2 grams (93.4~ of the theoretical yield)
M.p.: >250C
Analysis: Calculated: C 31.09~ H 4.10% N 20.72~ K 14.46
Found: C 30.89% H 4.31% N 20.43% K 14.72
Example 2
Sodium salt of 2-(dimethylcarbamoylimino)-5-methylsulphonyl-
1,3,4-thiadiazolin-3-ide.
12.5 Grams of 1,1-dimethyl-3-(5-methylsulphonyl-1,3,4-
thiadiazol-2-yl)-urea were suspended in 150 ml of methanol, and
- 12 -
1~77044
at room temperature a solution of 2 grams of sodium hydroxide in
100 ml of methanol was slowly added while stirring. æ
After standing for 2 hours, the solvent was distilled
off ln vacuo, and the residue was first washed twice with 50 ml
of isopropanol, then with diisopropyl ether and dried ln vacuo.
Yield: 12.6 grams (92.7% of the theoretical yield)
M.p.: >250C @
Analysis: Calculated: C 26.47% H 3.33% N 20.58% Na 8.44%
Found: C 26.49% H 3.38% N 20.41% Na 8.49%
Each of the other compounds of the present invention
listed in the Table above can be prepared in a manner analogous
to that described in Example 1 or 2.
Example 3
In a series of tests carried out in a greenhouse the
compounds of the present invention listed in the Table below
were each sprayed at a rate of application of 5 kg of active
substance per hectare, dissolved in 500 litres of water per
hectare, on mùstard and tomatoes as test plants by the pre- ~
and post-emergence methods. Three weeks after the treatment the ~!
results of the treatment were evaluated, the results being ~.
expressed by a numerical scale extending from 1 to 4, the value t
0 representing no action and the value 4 representing destruction
of the plants. As can be seen from the Table destruction of the ~-
test plants was generally achieved.
Compound of the present Pre-emergence Post-emergence
invention Mustard Tomato Mustard Tomato
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-propyl-
thio-1,3,4-thiadiazolin-3-
ide 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-propylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
~77044
Compound of the present Pre-emergence Post-emer~ence c
invention Mustard Tomato ~ustardTomato
E
Potassium salt of 5-ethyl-
thio-2-(dimethylcarbamoyl-
imino)-1,3,4-thiadiazolin-
3-ide 4 2 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-methylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Potassium salt of 5-ethyl-
sulphonyl-2-(dimethylcarb-
amoylimino)-1,3,4-thiadia-
zolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-methyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4
Sodium salt of 5-ethylthio-
2-(dimethylcarbamoylimino)-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-methylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 5-butylthio-2-
(dimethylcarbamoylimino)- h
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 5-ethyl- ~,
sulphonyl-2-(dimethyl-
carbamoylimino)-1,3,4-
thiadiazolin-3-ide 4 4 4 4
Potassium salt of 2-(dimethyl- i;
carbamoylimino)-5-methyl- r
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-methyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-methyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-(2-propynyl-
thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-(2-propynyl-
thio)-1,3,4-thiadiazolin-3-ide 4 4 4 4
- 14 -
1~77044
Compound of the present Pre-emergence Post-emergence
invention Mustard Tomato Mustard Tomato
Lithium salt of 5-ethyl-
thio-2-(dimethylcarbazoyl-
imino)-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoyllmino)-5-methylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
thio-1,3,4-thiadiazolin-3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-isoDropyl-
thio-1,3,4-thiadiazolin-3-ide 4 4 4 4
Potassium salt of 5-butylthio-
2-(dimethylcarbamoylimino)~
3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-(2-methyl-
2-propenylthio)-1,3,4-thia-
diazolin-3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-(2-methyl-
2-propenylthio)-1,3,4-thia-
diazolin-3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5- hexylsul-
phonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4 ~~
Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl- t
sulphinyl-1,3,4-thiadiazolin- j:
3-ide 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-hexylsulph-
inly-1,3,4-thiadiazolin-3-ide 4 - 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-hexyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 3 4 3
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
thio-1,3,4-thiadiazolin-3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-(2-methyl-
2-propenylthio)-1,3,4-thia-
diazolin-3-ide 4 4 4 4
- 15 -
1(~7704~
Compound of the present Pre-emergence Post-emergence
invention Mustard Tomato Mustard Tomato
-
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
thio-1,3,4-thiadiazolin-3-
ide 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-isobutvl- r
thio-1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-isopropynyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4 .
Lithium salt of 2-(dimethyl- ~;
carbamoylimino)-5-propyl-
sulphonyl-1,3,4-thiadiazolin- :;
3-ide 4
Lithium salt of 2-(dimethyl- ~:
carbamoylimino)-5-pentylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
thio-1,3,4-thiadiazolin-3-ide 4 4 4 4
Lithium salt of 2-(dimethyl- ~
carbamoylimino)-5-propylthio- -
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-propyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
- 16 -
~771)4~
Compound of the present Pre-emergencePost-emergence
invention Mustard TomatoMustard Tomato
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-isopropyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 a 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-pentylthio-
1,3,4-thiadiazolin-3-ide 4 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl-
thio-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-propyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide a 4 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4 "
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl- ,.
sulphonyl-1,3,4-thiadiazolin- ~;
3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-S-isobutyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl-
sulphonyl-1,3,4-thiadiazolin-
3-ide 4 ~ 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-isobutyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 L
Potassium salt of 2-(dimethyl- ,l
carbamoylimino)5-isobutyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide 4 4 4 4
- 17 -
1(~770~
Compound of the present rre-emergence Post-emergence
invention Mustard TomatoMustard Tomato
..
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-hexylthio-
1,3,4-thiadiazolin-3-ide - - 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-hexylthio-
1,3,4-thiadiazolin-3-ide - - 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-hexylthio-
1,3,4-thiadiazolin-3-ide - - 4 4
sodium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl~
sulphinyl-1,3,4-thiadiaæolin-
3-ide ~ ~ 4 4
Potassium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide ~ ~ 4 4
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-pentyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide ~ ~ 4 4
Sodium salt of 2-(dimethyl- ~.
carbamoylimino)-5-hexyl-
sulphonyl-1,3,4-thiadiazolin- S
3-ide ~ ~ 4 4
Sodium salt of 2-(dimethyl-
carbamoylimino)-5-propyl-
sulphinyl-1,3,4-thiadiazolin- i.
3-ide 4 4 4 4 '
Lithium salt of 2-(dimethyl-
carbamoylimino)-5-propyl-
sulphinyl-1,3,4-thiadiazolin-
3-ide . 4 4 4 4 n
. . .
Example 4
Q
In a series of tests carried out in a greenhouse the
plants listed in the following Table were treated before their
emergence with the listed agents being tested at the rates of
application given. For this purpose the agents were in each
case applied uniformly to the soil in the form of an aqueous r
solution using 1 kg of active substance per hectare with 500 litres
of water per hectare. The results show that the compounds of the
- 18 -
107704~
present invention, in contradistinction to the known compounds
used for comparison, have a good selectivity. The results
are expressed by a numerical scale extending from O to 10, the
value O representing destruction of the plant and the value 10
representing no damage.
F
i
-- 19 --
1077~D44
- n
o ~ I o ~ o :~ o ~ o
W--~t IJ-~S ~ 1'-~ P-
` ~ ~ ` ~ P~ O ~ ~ O ~ IJ- ~ ~0
~ n) u~ P 1'- W I ~ ~ O
r~ O 1' ~ (D IJ- ~ O 1'~ ~ O 1
o
3 ` ~ ~
p~ IJ. p~ ~< ~ ~. ~ IJ. I_ O
N O t-t N l-S l-t 1'- 0 ~ IJ- O l-h :~
o-- o ~ p.,-- p, _ n~
I O IJ ~ O Q~ I O pl I ~
O p~ I pJ I _
I ~ Ul N ~ N) N ~ p~ tD
~) ID I W 1-- 1 0 1~ 1 0 ~t 1'- ~.q
I ~t--I 1'- tD 1--0-- 1--0 ~3 (D
r~ tD O 1-- ~ I tD ~ I
~ 1'-
I l_ 0~
kg of active
substance/ha
~ o o Bush-bean
o o o o Ground-nut
o o o Potato
I ~ ~ Pea
OD O O
o J o ~ Maize
~ ~ R
c~ I o o lce
Sorghum
-- 20 --
1077044
$
;aasu~dole~ uln~ OS I I o o
e::)FIe~l eF~e~S o o o o
,~1.Ile~; sn~ eolu,~ouF~ ~ ~ o ,~
s~pFolnso~ul snln~adol~ ~ ~ o
~,
. ~
~3snx~l~o~l sntl~ue~eur~ o o O O
snueA~ ea~ne~ua;) o o o o
alne~Txa~ule umFulel o o o o
um~ s umula~ues~ o O o o
ealndlnd e~oulodI o o o o
.
ellluloule~ elle~F~ew o o o o
slle~lnA ol~uas o o o o
elpau~ eF~ella~s o o o o
I I I o ~ I
o ~ o r~ ~ o
rl s ~
~_ ~s
~J~ ~ ~ ~ O ~ ~
3 o ~ O I --O I a) ,1 1 --~ I
¦¦u) rl h ~) I h ~ I ~ ~ I
_ I ~ I ~ o ~ I
I ~ o I ~ o ~3 ~ o I ~
^ O ^ O Q O ^ O
.C ~ O N J- o N ~ h N ~ O N
O ~1 ~1 0 ~
O U~
~ ~ O ~r( O ~ rl a) ~ ~l O
O ~::
Ql a) rl ~ ` ~1:1 Q ` ~ ~ ` 10 Q `
O ~ O ~ ` O ~ ` O I ` O ~ `
C~ rt U~ U r IP~ U ~1 ~ ~ ~1 ~ U ~1
21
. . .
10~77044
w ~ ~D
P
". ".
~ ~ ~(D 0~
,t ~
.,
qO
N l_ N 1--'
N I ~ I U~
t ~
h
G I C G
~ ~ ~S O
(1~ G ~ 1 S
P) qO
I
kg of active
substance/ha
~ ~ Bush-bean
o I ~ Ground-nut
~ I I Potato
o I I Pea
Maize
o ~ I Rice
~ ~ I Sorghum
.. ~ , ...
.. . .
44
asuadole~ wn~51oc O O O
eaFIe~T elle~ac o O o
~I! ' Ille~ snl~ eo~ ouF~ O O O
saplolnso~ snlnaadol~ o O O
.~ .
snxal~ol~al sn~ueleur~ o o o
d snue~a ealne~ua~ o o o
."~ alne~ xaldule umluler o o o
~n~a~as ~n~a~ues~ o O o
ealndlnd eaoulodl o o o
~I
. elll~o~e~ e~ e I o O O
sFIe~lnA elaauac o O O
o o o
; elpa~ ellella~s .~
1.
~ rl
O
o
r~
~ ~ a~
,1 ~I h ~1 .C
O ~ I ~ I
U~ I ~ I N 4~
.,1 11') 1 11') 1 0
h ~
I O I O
~ ~I N r-l N ~ O
E~ I ta
O ~ ~1 ~-,1
U >~ o 0
h ~) ,~ ~ rl ~ ~ h
o ~) ~: a) ~ o
4~
,~ I -rl I ~ O ~J O
C~
~ I ~ I ` h
a~ r~) t~l ~ ~ ~ 11 11 11
~
~ ~ ~ I o o
~3
` ........... ` `,
..
1077044
Example S
In a series of tests carried out in a greenhouse the
plants listed in the following Table were treated after their
emergence with the listed agents being tested at a rate of
application of 1 kg of active substance/hectare. For this purpose
the agents were in each case sprayed uniformly over the plants.
Also in this case the compound of the present invention exhibited
3 weeks after the treatment a high selectivity coupled with an
excellent action against the weeds. The agent used for comparison
did not exhibit selectivity. Again, the results are expressed
by a numerical scale extending from O to 10, the value O represent-
ing destruction of the plant and the value 10 representing no
damage.
2 0 r
~ .
2 4 ~ r
i
10:7~4'~
~,
.~
o ~ o
uln~lOS ~ . ~
~ ~ o
,4
,~ . o ~ o
;~ ~zle~ ,~ ~
e~d o o
~.,
e~oS o o o
o ~ o
o~e~Od ~ ~
o ~ o
~nu-punolg ~ ~
,
N ~
I ` O ra
O ~) h o
I O h
0 ~1
U~
~1 0~ I
h Q ~1 0 u~I ~1
sl O rl hu~ I
E~ I ~i O
~1 (1~ ~ ~~I N
sQ~ ~: 8' .~
.
o ,, ~, ,,
O ~~ rl
O Ul :~ N OO ~:
rl ~ ~ ~1
g ~ ~
Q) .~ I; ~ h
~ ~ ~rlrl O r~
:~ O ~: O ~ ~:
C~ rl U~ ~ ~ ~
2~
1077~ 144
~`
e~lle~F elle~aS o o o
ealndlnd eao~uodI o o o
~un~ak,as umuall~ues~ o o o
auF~ede lunFIe~ o o o
't~ ' ,~
,~ snxal~ol~al sn~ue~eur~ o o o
snue~ ea~ne~ua I o o o
alne~l, xaldlue lunFIueq o o o
ule~:~ eFIe~FI~e~l o O O
sFIe~lnA el~auac o o o
eFpaul eF~ella~c o o o
,~ ~ :
I ~ o ~,
o r-l h I
,~ I O ~ r~
S^
O ,~ ,~
,~ ~ ~ O
(U ~ r~ N S
Ul
::~ r~ O ~r~
R r~ I ~a ~
I ~ r~ ~U~ ~ o
In 0-,~ h ~
a~ ~ I ~ I s
S ~ ~ ,~ ~ O
O R I
h ~ O, ~r
O ,~ S ~ ~ ~
1~ -1 0 h ~ ` 'C ~1 0
r~ O U~ >1 N O a) ~ ~ 'Ct
,~ S (~ E~
~ ~ E~ ,~ o
o ~ ~ a ~ ~
Q) .,~
~a ,~ ,~
o ~ o ~a s ~~ a~ h
Ur~ U~ ~ o o
26
; . - ... ..
