Note: Descriptions are shown in the official language in which they were submitted.
1~90350
The present invention is concerned with new herbicidally
active 2-dimethylcarbamoylimino-1,3,4-thiadiazolin-3-ide salts,
with a process for the manufacture of these compounds and also
with their use.
` 1-(1,3,4-Thiadiazol-2-yl)-urea derivatives having a her-
bicidal action have already been known (German Offenlegungsschrif-
ten Nos. 1,816,696, 1,901,672 and 2,118,520). However, they have
insufficient action against undesired plant growth in crop planta-
tions.
The present invention provides a herbicidal agent which
has an excellent action against weeds and also a wide spectrum of
selectivity towards crop plants.
The present invention accordingly provides compounds of
the general formula I
N - -N-B
11 1 / CH3 (I)
R-C C=N-CO-N
S CH3
in which R represents a tertiary butyl group and B represents a
~20 lithium sodium or potassium atom.
The compounds of the present invention are distinguished
~` by their broad soil-herbicidal and leaf-herbicidal action. They
can be used for combating mono- and di-cotyledonous weeds.
~.
,
.'
. i .
;30
~ -- 2 -- ~A;
,
0350
With the compounds of the present invention there are
combated by pre-emergence and also by post-emergence methods
agricultural weeds, for example Sinapis ssp., Stellaria media,
Senecio vulgaris, Matricaria chamomilla, Ipomoea purpurea,
Chrysanthemum segetum, Lamium amplexicaule, Centaurea cyanus,
Amaranthus retroflexus, Alopecurus myosuroides, Echinochloa
crus galli, Setaria italica, Sorghum halepense, Lolium perenne
and Galium aparine.
For combating seed weeds there are generally used rates
of application of 0.5 kg of active substance per hectare to 5 kg
of active substance per hectare. When two or more compounds of
the general formula I are used the range of 0.5 to 5 kg refers
of course to the total amount applied of these compounds. There-
; by, the active compounds of the general formula I have proved
to be selective in crops of useful plants, for example bush bean,
ground-nut, potato, pea, maize, rice, sorghum and soya crops.
At higher rates of application the active compounds are
also suitable as total herbicides for the destruction or
suppression 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.
'
lt~90350
The present invention further provides a method of
protecting 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. -
The present invention further provides a pack which
comprises a compound of the general formula I together with
instructions for its use as a herbicide.
The compounds of the present invention may be used
,.
`~ either alone, orin admixture with one another or with other active
substances.
Depending on the purpose desired, there may be mentioned
-~ in this connection, for example, the following herbicidally
- active substances which may, if desired, be added to the
'.~ compounds of the invention only immediately before use:
i substituted anilines,
-, 20 substituted aryloxycarboxylic acids and also salts, esters and
amides thereof,
substituted ethers,
substituted arsonic acids and also salts, esters and amides thereof,
substituted benzimidazoles,
substituted benzisothiazoles,
~ substituted benzthiadiazinone dioxides,;.
substituted benzoxazines,
substituted benzoxazinones,
substituted benzthiazoles,.,
- 30
~"
10~)350
: substituted benzthiadiazoles,
~ substituted biurets,
`. substituted quinolines,
: substituted carbamates,
substituted aliphatic carboxylic acids and also salts, esters
and amides thereof,
substituted aromatic carboxylic acids and also salts, esters
and amides thereof,
- substituted carbamoylalkyl-thio- or dithio-phosphates,
substituted quinazolines,
: substituted cycloalkylamido-carbonthiolic acids and also
; salts, esters and amides thereof,
. substituted cycloalkylcarbonamido-thiazoles,
substituted dicarboxylic acids and also salts, esters and
amides thereof,
substituted dihydrobenzofuranyl sulphonates,
substituted disulphides, ~:
substituted dipyridylium salts,
~ . .
' substituted dithiocarbamates,
~: 20 substituted'dithiophosphoric acids and also salts, esters and
. - amides thereof,
substituted ureas,
~ substituted hexahydro-lH-carbothioates,
-: substituted hydantoins,
substituted hydrazides, :~
- substituted hydrazonium salts,
.: .
.-` substituted isoxazole-pyrimidones,
substituted imidazoles,
substituted isothiazole-pyrimidones,
:
'
~t~90350
substituted ketones,
substituted naphthoquinones,
substituted aliphatic nitriles,
substituted aromatic nitriles,
substituted oxadiazoles,
substituted oxadiazinones,
substituted oxadiazolidinediones,
- substituted oxadiazinediones,
substituted phenols and also salts and esters thereof,
substituted phosphonic acids and also salts, esters and amides
;,` thereof,
substituted phosphonium chlorides, .
;~, substituted phosphonalkyl-glycines,
i. substituted phosphites,
substituted phosphoric acids and also salts, esters and amides
thereof,
substituted piperidines,
substituted pyrazoles,
. substituted pyrazolalkyl-carboxylic acids and also salts,
r 20 esters and amides thereof,
substituted pyrazolium salts,
substituted pyrazolium alkyl sulphates,
substituted pyridazines,
substituted pyrimidines,
substituted pyrrolidones,
` substituted pyridazones,
; substituted pyridine carboxylic acids and also salts, esters
and amides thereof,
--6--
''.
1(~90350
substituted pyridines,
substituted pyridine carboxylates,
substituted pyridinones,
substituted pyrimidones,
substituted pyrrolidine carboxylic acids and also salts,
: esters and amides thereof,
substituted pyrrolidines,
substituted aryl sulphonic acids and also salts, esters and
amides thereof,
substituted styrenes, -
substituted tetrahydro-oxadiazine-diones,
substituted tetrahydromethanoindenes, :.
.,
, substituted tetrahydro-diazole-thiones, -~
` substituted tetrahydro-thiadiazine-thiones, ~-
substituted tetrahydro-thiadiazolediones,
: substituted thiadiazoles,
substituted aromatic thiocarboxylic acid amides,
substituted thiocarboxylic acids and also salts, esters and
amides thereof,
substituted thiolcarbamates, -
substituted thiophosphoric acids and also salts, esters and
amides thereof,
substituted triazines,
substituted triazoles,
substituted tetrahydro-oxadiazole-diones,
substituted thioureas,
substituted uracils and ~-
substituted uretidine-diones.
:
~;
.
1(!~()350
Furthermore, there may also be used other additives, for
example non-phytotoxic additives which produce with herbicides
- a synergistic increase in action, for example wetting agents,
emulsifiers, solvents and oily additives.
Advantageously, the active compounds of the general
formula I or mixtures containina them are used in the form of
herbicidal preparations, for example powders, strewable
preparations, granules, solutions, emulsions or suspensions,
~' with the addition of liquid and/or solid vehicles or diluents,
` 10 and, if desired, of surface-active agents, for example wetting,
adherent, emulsifying and/or dispersing assistants.
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.
.` 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.
. 20 As surface-active agents there may be mentioned, for
example, calcium lignin sulphonate, polyoxyethylene alkylphenyl
ethers, naphthalene sulphonic acids and salts thereof, phenol
sulphonic acids and salts thereof, formaldehyde condensates,
fatty alcohol sulphates and also substituted benzene sulphonic
- acids and salts thereof.
The total amount of the active substance or substances -~
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), approximately 90 to
~, .
: `' l(~9~J350
20% by weight of liquid or solid carrier and also, if desired, up
to 20% by weight of surface-active agent(s).
The application of the active compounds may be carried
out in the usual manner, for example, with water as carrier in
quantities of spray liquors from approximately 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
also to apply them in the form of so-called microgranules.
The compounds of the present invention are salts which
; 10 exist ionically corresponding to the following polar limiting
formulae
: 30
A~ g
.
1(~9()350
. ~, .
N N I(--)
R ~ / N CO N f ( ) ~ >
\5
.,
< B (+) < >
CH3
N
R ~ ~ ~(~) CH
S ~ '
or formulated in general as
-- N~
I `I /CH3
R ~ ~ CH
--1 0--
1(~90350
For the sake of simplicity these limiting formulae 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 hitherto unknown compounds of the general formula
I may be prepared, for example, by the process of the present
invention, as defined below.
The present invention accordingly further provides a
process for the manufact~re of a compound of the general formula
I, wherein
(a) dimethylcarbamoyl chloride of the formula II ~.
3 \
N-CO-Cl II :~
- H3C
is reacted in the presence of an acid-binding agent with a
1,3,4-thiadiazol-2-amine of the general formula III
: R-~ C-NH2 III, .
\ S /
., .
. in which R has the meaning given above, to form a 2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-carboxylic acid dimethyl-
amide derivative of the general formula IV
. ~ - - . - . .
: .
,
--11--
.
- ' , . :-
. . ~
.
~ 0350
po-~
C0-N /
. ~
in which R has the meaning given above, which is split with a
metal compound of the general formula V
' 10
B( )Y( ) (V),
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-dimethyl-urea derivative
of the general'formula VI
R-~ ~ ~C-~H-C0-~ < ~VI)
, . .
20 in which R has the meaning given above, is reacted with a metal
- compound of the general formula V
,
B( )Y( ) (V~
in which B and Y have the meanings given above.
~, Each step of the process of the present invention may,
if desired, be carried out in the presence of a solvent.
. . .
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
- 30 invention the reactants are used in approximately equimolar
~1
quantities.
:
-12-
--~ lQ90350
.~
As reaction media there are suitable polar organic solvents,
alone or in admixture with water. Their choice depends on
generally known considerations regarding the use of the metal
- compounds of the general formula B( )Y( ). As solvents or
suspension media there may be mentioned amongst many, for
: example, acid amides, for example dimethylformamide, acid nitriles,
for example acetonitrile, alcohols, for example methanol or
ethanol, and ethers, for example tetrahydrofuran.
For synthesizing the compounds of the general formula
IV there may be used as the acid-binding agents all the usual acid-
binding agents, for example organic bases, advantageously tertiary
amines, for example triethylamine or N,N-dimethylaniline, pyridine
derivatives, or inorganic bases, for example oxides, hydroxides,
carbonates and alkanoic acid salts of alkali metals or alkaline
earth metals; liquid acid-binding agents may serve simultaneously
as solvents.
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
weakly polar organic solvents, for example with ketones, for
example acetone, or ethers, for example diisopropyl ether.
The compounds of the present invention are colourless
and odourless crystalline solids, which are excellently soluble
~` in water, readily soluble in polar organic solvents, for example
carboxylic acid amides, for example dimethylformamide, sulphox-
ides, for example dimethyl sulphoxide, and lower alcohols, for
example methanol and ethanol, sparingly soluble in carbonitriles,
for example acetonitrile, and insoluble in hydrocarbons, halo-
genated hydrocarbons, ethers and ketones.
',
-13-
~ .
`- 109()350
:`
The foilowing Examples illustrate the invention. Examples
`;; 3 to 5 illustrate the mode of action of the compounds of the gen-
` eral formula I.
Example 1
; 27.1 Grams of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-
thiadiazolin-3-carboxylic acid dimethylamide melting at 100C
were suspended in 150 ml of methanol. There was added dropwise,
while stirring, a solution of 4 grams of sodium hydroxide in 100
ml of methanol at room temperature. After 3 hours there was
obtained a clear solution, from which the methanol was then dis-
tilled off in vacuo. The residue that remained was digested with
acetonitrile, filtered with suction to remove the washing agent ~-
and dried ln vacuo at 80C.
Yield: 15.5 grams (69.8% of the theoretical yield~ of the sodium
salt of 5-ethyl-2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-
ide having a melting point of >250C.
C7HllN4NaOS M.W.: 222.26
Analysis
Calculated: C 37.83% H 4.99% N 25.21% Na 10.34~
Found: C 37.70% H 5.05% N 24.95% Na 10.76%
Example 2
, .
8.1 Grams of 1-(5-tert.-butyl-1,3,4-thiadiazol-2-yl)-
3,3-dimethyl-urea melting at 121C were dissolved together with
0.853 gram of lithium hydroxide in 70 ml of methanol. The solu-
tion was then concentrated in vacuo, and the residue
. . .
- 14 -
0350
was triturated with a mixture of diisopropyl ether and isopropanol,
filtered off with suction and washed with diethyl ether. By
drying in vacuo at 120C there were obtained 7.8 grams (93.8%
of the theoretical yield) of the lithium salt of 5-tert.-butyl-
2-(dimethylcarbamoylimino)-1,3,4-thiadiazolin-3-ide having a
` melting point of >250C.
CgH15LiN4OS M.W.: 234.26
Analysis
Calculated: C 46.15% H 6.45% N 23.92% Li 2.96%
Found: C 46.04% H 6.33% N 23.73% Li 2.68%
Each of the other compounds of the present invention
listed in the following Table may be prepared in a manner
analogous to that described in Example 1 or 2.
~; ." '
.," ~
,,~ : . -.
I 20
'?
~' ~
': . .
:
.,'
~t~$'03SO
Name of the compound Physical constant
Sodium salt of 2-(dimethylcarbamoylimino)- M.p.: 288C
5-isopropyl-1,3,4-thiadiazolin-3-ide (with decomposition)
Sodium salt of 5-tert.-butyl-2-(dimethyl- M.p.: 306C -
carbamoylimino)-1,3,4-thiadiazolin-3-ide (with decomposition)
Potassium salt of 5-ethyl-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250 DC
.;: Lithium salt of 5-ethyl-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
:~ Sodium salt of 2-(dimethylcarbamoylimino)-
: 5-propyl-1,3,4-thiadiazolin-3-ide M.p.: >250~C
Sodium salt of 5-isobutyl-2-(dimethyl-
carbamoylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250C
Lithium salt of 2-(dimethylcarbamoylimino)-
5-isopropyl-1,3,4-thiadiazolin-3~ide M.p.: >250C
Sodium salt of 2-~dimethylcarbamoylimino)-
5-methyl-1,3,4-thiadiazolin-3-ide M.p.: >250C
; Lithium salt of 5-(1,1-dimethylbutyl)-2-
. (dimethylcarbamoylimino)-1,3,4-thiadiazolin-
3-ide M.p.: >250C
Sodium salt of 5-butyl-2-(dimethylcarbam-
.'r oylimino)-1,3,4-thiadiazolin-3-ide M.p.: ~250~C
~ Lithium salt of 5-butyl-2-(dimethylcarba-
. 20 moylimino)-1,3,4-thiadiazolin-3-ide M.p.: >250C
: Example 3
,.
In a series of tests carried out in a greenhouse the
compounds of the present invention mentioned 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 to Sinapis sp. and Solanum sp. as test plants by
the pre- and post-emergence methods. Three weeks after the
:
- 30
1(~903SO
treatment the results thereof were evaluated, the results being
- expressed by a numerical scale extending from 0 to 4, the value
0 representing no action and the value 4 representing destruction
of the plant. As Will be seen from the Table destruction of the
; test plants was generally achieved.
.
~- ~
. -
.'
.
-.
-
'
~,
~'
~. -17-
105~0350
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.. ' ~'o'
U~
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a
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.. - ~ ~ ~ ~ ~r ~r ~ ~r
.. o ~
.~ p~ rl
., U~
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. -~
. .,
.,
. .
.' ~
t ~ O
Q
a~
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,. ~1 ,
O 1 1. 0 0
1 1 S~
., ~1 ~ rlO ~1 ''
~. ~ o ~ e o
o ~ 1 o
I Q ~1 0~1 1 o u-
I ~ ~ ~ O I
~ O ~ ~
Q
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~ ~ O
o ~ ~ ~ o a~ ~
~ Q
Q ~~ ~ ~E~ Q ~ S.l
h II ri E3 `-- ~ ~1 -- rd
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,S: N Q ,1~ a)~ ~
Q) Ei ~1 ~ N :~ IO I .~ I E~ I Q I rl I
~N I U~ ~rl11') ~1 0 ~1 ~ N ~1 11'1 ~1 ~1
'' a) ~r .C O 0 ~1 0 0 0 ~1 0
.. ` ~ ~1 ~ 1 ~) ~I N ~ N O N ~I N 4~ N O N
O t~7 0 1 0 1~ O (O O
o ~1 1
e ~ ~ ~ e
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o ~ o ~ o ~e o ~ o ~ 1 ~ o ~ o ~
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-18-
lt35~03S()
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a~ o
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J~ ,1
O
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I In
a) ~1
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3 -
l . . .
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o ~ o o
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h 1 1 ~1
t~
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a~
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I ~~ ~ ~rl~ Q,
~ ~ ua) ~ ~ --
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O ~-rl~ ~ ~-rl>l-rl ~
h N E~ J ~ I$) I O
~-rl ra I `~-rl ~ I R I
: S~~ ra -- F I ~R ~ I
rl C~l ~1 0U) ~1 ~1 0 ~
4~ ~ O~ ~ O~ O ~1 U
~:O ~ ~ NO ~ q~ N O N ~
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O ~ rl ~ O ~rl ra O ~
-19-
1~)90350
Example 4
In a series of tests carried out in a greenhouse the
plants mentioned in the following Table were treated before
their emergence with the listed agents being tested at a rate of
application of 1 kg of active substance per hectare. For this
purpose the agents were in each case applied uniformly to the
soil in the form of an aqueous solution using 500 litres of
water per hectare. The results show that the compounds of the
present invention have a better action than the known compound
used for comparison. The results are expressed by a numerical
scale extending from 0 to 10, the value 0 representing
destruction of the plant and the value 10 representing no damage.
'
` 20
.~
-20-
lO9V350
. ' F eFI~aS o o ~ I I o
d ~aulOdI o o o o o o o o
,~ s umula~l~ues~u;~ o o o o o o o o
e UmF11~9 ~1 o I I r~
snu,~u~leur~ o o o o o o o o
.
ealne~ua;) o o t~ N I O ~ ~
. . _
~ e umFulel o o o o o o o ~
- _ _ O O
' 11:) ~FI~:'Fl~ o o o o o o
.. a) -.
'A OF~)auaS O O O O o O o o tJ~
~11
Ul ~F~a~s o o o o o o ~ In ~
S I I 1 o I o ~ o ~ -
~ ~ ~,
a~ F~ I ~ I ~ I o o
azF~ oo I ~ o 1~ 0 0 0 o
.
,- ~aa I I co ~ oo c~ o ~
o~oa O l O O O O O O
~ ~ ~ ~ ~ ~ ~ .
:.~nu-puno~g o oo o o o o o o - -
. ~ ~ ~ . ~ ~ ~ ~
;ueaq ~sn~ I I I I 1~ , ~ ~ .
a;)u~sqns
aAF~ F ~ 1 ~ ~ ~ ~ ~ ~ ,1 ~ P~ ~
.'. I I ~` a~ O . ,
Is ,~ o
.: ,1 ~ ~ I v a) s,~ ~ ~ s I ~ ^ ~ v
~ ''I ~''I ~) ~ ~~''1 ~1 ~~) ~~I N
O N~ ~ S IO ~ (I~ ~rl a)
O E~ 1 S I ~ ~ ~ ~k rl ~ ~1~ ~D~1 1
I O ~ ~ '~ O ~
,~~ N ~D r ~ N ~ ~~ ~) ~
S~ rlh ~ --~~ o N
t~ S ~ I ~--O V.,
. . ~ ~ ~~ ~-- o ~ la I N~1 ~1 1
~1 ~ I1~ I N~1 r lCN la ~ 0~1 rl~-1 N
5~ ~ R ~ ~ ~ ~SI -rl S N~S ~ 111
IO Z ~)
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u~ r~1 ` S ~l I ` ~ S~1 d O `V ~ ~1
a) ~ IO ~ ~ s In r~ s
h 'I~ ` ~ ~ ` I I--S
~,'. ~ ~ r o ~ n I~ S
'' a) .o~ v
~ IH ~ ~ O ~ ~ ~ OO ~ ~ `~ O a
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~ O~ a ~ I h
a) o ~-,~
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,, S.~ ~ ~ a) s ~ o
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~1 rl ~ QS ~ -1 Ql~ QQ ~1 Ir) a) 11
a) k ~ ~ ~ ~
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P~ O ca ~ V cn E~ ~ v~ V
:.
--21--
,
,, .
` 1090350
Example 5
. .
In a series of tests carried out in a greenhouse the
plants mentioned 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 per hectare. For this
purpose the agents were in each case sprayed uniformly over the
plants in the for~ of an aqueous solution using 500 litres of
water per hectare. Also in this case, three weeks after the
treatment, the compounds of the present invention exhibited
a high selectivity coupled with an excellent action against
the weeds. The agent used for comparison did not exhibit a
good action. Again, the results are expressed by a numerical
scale extending from 0 to 10, the value 0 representing
destruction of the plant and the value 10 representing no damage.
.. .
~ 20
. .
;.
~,
~~ -22-
:`
so
~ - - -
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:` _I
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- e umFIe3 o o o o ~ ~ ~ o o o
I Sn~ueleU}~ o o o o o o o o o ~
-
:~ ealne~ua~
O O I O I N O O O 00
. .
e umlu~e~ o o ~I ~ o o o o o
~ -
u,:) eF~e~FI~e~ o o ~ ~ o o ~r o o co
'A OF )auaS o o o o o o o o o ~r
- u~ ellella~
lOS ~ I I O Q)
.,a;~l~r ~ :
.. . I I o 1~ o o 1~ 1 1 o
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aZFe~ I ~ o CD o a~ c~ I I o O
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o~e~a I r 1` 1 1- 1 , , , O ~'
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aoue~sqns
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