Note: Descriptions are shown in the official language in which they were submitted.
1.060~ZZ
l-THIADIAzoLyL-5-AcyLIMID~zoLIDINoNEs
.. ..
Specification
This invention relates to new compositions of matter
and more specifically relates to new chemical compounds of
the formula
Il 3 . :
O - C - R
N N
~ f H --CH
R - C C - N
~ / \C I - R2
11
O (I)
.
., ' ..... .
wherein R is selected from the group consisting of alkyl, ~ :
. cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkyl- : .
i, sulfonyl and alkylsulfinyl; R2 is selected from the group
~ consisting of alkyl, alkenyl, haloalkyl and
. ~ . - . .:
R4 ~ .
- I - C~- CH :
R
wherein R4 and R5 are each selected from the group consisting ;
of hydrogen and alkyl; and R3 is selected from the group con~
t, ~ .
:~ sisting of alkyl, alkenyl, haloalkyl, alkynyl, alkoxyalkyl, :~:
cycloalkyl and --: -
wherein X is selected from the group consisting of alkyl,
alkoxy, halogen, haloalkyl, alkylthio, nitro and cyano; n
i8 an integer from 0 to 3; and m is the integer 0 or 1.
,,
. cb/
~0600ZZ
The compoundq of the present invention arc un-
expectedly useful as herbicides.
In a preferred embodiment of this invention Rl is
selected from the group consisting of lower alkyl, cycloalkyl
of from 3 to 7 carbon atoms, lower alkenyl, lower chloroalkyl,
lower bromoalkyl, trifluoromethyl, lower alkoxy, lower alkyl-
thio, lower alkylsuIfonyl and lower alkylsulfinyl; R2 is select-
ed from the group consisting of lower alkyl, lower alkenyl,
lower haloalkyl and
R4 : ;
- C - C CH
wherein R and R5 are hydrogen or alkyl of up to 3 carbon
atoms; and R is selected from the group consisting of lower
.
. alkyl, lower alkenyl, lower haloalkyl, lower alkynyl, lower
alkoXyalkyl, cycloalkyl of from 3 to 7 carbon atoms and
H(5-n)
_ ~CN2~m ~
. :
'' ' - -.
wherein X is selected from the group consisting of lower alkyl,
lower alkoxy, halogen, lower haloalkyl, nitro, cyano and lower -
alkylthio; n is. an integer from 0 to 3; and m is the integer
0 or 1.
The term "lower" as used herein designates a
straight or branched carbon chain of up to six carbon atoms. :~
.: .,
. The compounds of the present invention can be
~1 30 prepared by reacting a compound of the formula
.,:
.~,
cb/ - 2 -
-, .
. : .
.~ , . . . j . .. .
10600ZZ
OH
N~ f H --CH2
\ /Ç \C ~ - R
O ~II)
wherein Rl and R2 are as heretofore described, with an acid
anhydride of the formula
R3 - ~ - O - ~ - R3 ~III)
wherein R3 is as heretofore described, in the presence of a
catalytic amount of _-toluenesulfonic acid. This reaction
can be effected by combining the reactants and the catalyst
at room temperature in an inert organic reaction medium and ~-
: .
then heating the reaction mixture on a steam bath with stirring -
for a period of from 1/2 to 4 hours. After this time the
.. , . .. ~
reaction mixture can be cooled and the desired product can be
~' recovered by filtration if formed as a precipitate or upon
~1 evaporation of the organic reaction medium if soluble therein.
;` In some $nstances the acid anhydride can be used as a solvent
for a compound of formula II, obviating the use of an inert
,
i solvent as the reaction medium. When lower alkanoic anhydrides
~ J'~
are used, water can be added to the reaction mixture to pre-
cipitate the desired product upon completion of the reaction.
' The product can then be purified by conventional means such as
f recrystallization and the like. In some instances the fore-
~ ~ .
going reaction results in the formation of a mixture of products
consisting of the desired compound of this invention and de-
~3~ hydrated starting material of the formula
' ' , ' ' .
. f'~
C2~ 3- ~
:, ' , ` '
, :: ~
106002Z
N ~I CH _ CH
\ S f C N - R2
ll ` ~`:
~IV)
wherein Rl and R2 are as described. In these instances the
desired product can be isolated by fractional precipitation.
j The compounds of this invention c~ also be prepared `~
~. .
by reacting a compound of formula II with an acid halide of
the formula
: O
Cl - 11 - R3 ~V ) ~ ` :
wherein R3 is as heretofore described,in the presence of an
acid acceptor such as a tertiary amine. This preparational
method can be utilized when the desired anhydride of formula
4, III is not available. This reaction can be effected by slowly
7 ~adding the acid chloride of formula V with stirring to a solu- -
tion of an about equimolar amount of a compound of formula II ~;
in an inert organic solvent, in the presence of an acid acceptor,.
~; at a temperature of ahout 10 to 30~C. After the addition is
completed, the react;on mixture can be heated at a temperature
ranging up to the reflux temperature of the mixture to ensure
completion of the reaction. The desired product can then be
recovered by first filtering the reaction mixture to remove
acid àcceptor chloride, followed by stripping off the solvent
if the product is soluble therein, or, if formed as a precipi-
tate, by filtration and subsequent washing and purification.
~ The compouDds of formula II can be readily prepared
.~1 28 by heating a compound of the formula ;~
, 1 ~ . ~ , ' .
~ cb/ - 4
.,
~ ,~ . ..
" 1060022
~ OCH3
R _ C C _ N ~ C _ N _ C112 _CH
S H O R ol H3 (VI)
wherein Rl and R2 are as heretofore described, in a dilute,
aqueous, acidic reaction medium for a period of about 10 to
about 60 minutes. Temperatures of from about 70C to the
reflux temperature of the reaction mixture can be utilized.
The reaction medium can comprise a dilute aqueous inorganic
acid such as hydrochloric acid at a concentration of from
a~out 0.5 to about 5 percent. Upon completion of the reaction
the desired product can be recovered as a precipitate by cool-
ing the reaction mixture. This product can be used as such
or can be furt~er purified by conventional means such as
recrystallization and the like.
The compounds of formula VI can be prepared by
reacting a molar amount of an isocyanate dimer of the formula
~ r
¦ S
2 (VII)
~; wherein Rl is as heretofore described, with about two molar
J~ amounts of dimethyl acetal of the formula
~, OCH3
H - N - CH - CH
2 1CH 3 (VIII)
! wherein R2 is as heretofore described. This reaction can be
, effected by heating a mixture of the isocyanate dimer and the
acetal in an inert organic reaction medium such as benzene at :
, 30 the reflux temperature of the reaction mixture. Heating at
. reflux can be continued for a period of from about 2 to about
30 minutes to ensure completion of the reaction. A~ter this
.. . :
-, cb/ ~
~ . ., . . . . . . . . ~ . .
~0600ZZ
time the desired product can be recov~red upon evaporation of
the reaction medium and can be used as such or can be further
purified by standard techniques in the art.
The isocyanate dimer of formula VII can be prepared
hy reacting a thiadiazole of the formula
Rl - C~ ~ - Nl:2
S (IX)
wherein Rl is as heretofore described, with phosgene. This
reaction-can be effected by adding a slurry or solution of the
thiadiazole, in a suitable organic solvent such as ethyl ace-
tate, to a saturated solution of phosgene in an organic solvent
such as ethyl acetate. The resulting mixture can be stirred
at ambient temperatures for a period of from about 4 to
about 24 hours. The reaction mixture can then be purged with
nitrogen gas to remo~e unreacted phosgene. The desired product
can then be recovered by filtration, if formed as a precipitate,
or upon evaporation of the organic solvent used if soluble
f therein. This product can be used as such or can be further
purified as desired.
Exemplary thiadiazoles of formula IX useful for
,~ preparing the compounds of the present invention are 5-methyl-
2-amino-1,3,4-thiadiazole, 5-ethyl-2-amino-1,3,4-thiadiazole,
S-propyl-2-amino-1,3,4-thiadiazole, 5-t-butyl-2-amino-1,3,4-
thiadiazole, 5-allyl-2-amino-1,3,4-thiadiazole, S-pent-3-enyl-
f~ 2-amino-1,3,4-thiadiazole, 5-chloromethyl-2-amino-1,3,4-
thiadiazole, 5-~-chloroethyl-2-amino-1,3,4-thiadiazole, 5-~
f chloropropyl-2-amino-1,3,4-thiadiazole, 5-trichloromethyl-2-; amino-1,3,4-thiadiazole, 5-trifluoromethyl-2-amino-1,3,4-
thiadiazole, 5-methoxy-2-amino-1,3,4-thiadiazole, 5-ethoxy-2- -
amino-1,3,4-thiadiazole, S-propoxy-2-amino-1,3,4-thiadiazole,
S-butyloxy-2-amino-1,3,4-thiadiazole, 5-hexyloxy-2-amino-1,
.
cb/ - - 6 -
1060~ZZ
3,4-thiadiazole, 5-mcthylthio-2-amino-1,3,4-thiadiazol~, 5-
ethylthio-2-amino-1,3,4-thiadiazole, 5-propylthio-2-amino-1,
3,4-thiadiazole, 5-butylthio-2-amino-1,3,4-thiadiazole, 5-methyl-
sulfonyl-2-amino-1,3,4-thiadiazole, 5-ethylsulfonyl-2-amino-1,
3,4-thiadiazole, 5-butylsulfonyl-2-amino-1,3,4-thiadia201e, 5-
methylsulfinyl-2-amino-1,3,4-thiadiazole, 5-ethylsulfinyl-2-
amino-1,3,4-thiadiazole, 5-propylsulfinyl-2-amino-1,3,4-thia-
diazole, 5-butylsulfinyl-2-amino-1,3,4-thiadiazole and the
like.
Exemplary suitable acetals of formula VIII for pre-
paring the compounds of this invention are the dimethyl acetal
of 2-methylaminoacetaldehyde, the dimethyl acetal of 2-ethyl-
aminoacetaldehyde, the dimethyl acetal of 2-propylamino-
acetaldehyde, the dimethyl acetal of 2-butylaminoacetaldehyde,
the dimethyl acetal of 2-pentylaminoacetaldehyde and the di-
methyl acetal of 2-hexylaminoacetaldehyde.
Exemplary suitable acid anhydrides of formula III
are acetic anhydride, propionic anhydride, butanoic anhydride,
pentanoic anhydride, hexanoic anhydride, acrylic anhydride,
butenoic anhydride, pentenoic anhydride, chloroacetic anhydride,
, bromoacetic anhydride, ~-chlorobutanoic anhydride, cyclohexyl-
,
carboxylic anhydride, benzoic anhydride, toluic anhydride, ~-~
4-chlorobenzoic anhydride, 3-bromobenzoic anhydride, 4-fluoro-
benzoic anhydride, 4-methoxybenzoic anhydride, 4-ethoxybenzoic
i .: ,
anhydride, 4-chloromethylbenzoic anhydride, 4-trifluoromethyl- -
benzoic anhydride, 3,4,5-trichlorobenzoic anhydride, 3-methyl-
thiobenzoic anhydride, 3-ethylthiobenzoic anhydride, 4-butyl-
thiobenzoic anhydride, phenylacetic anhydride, 4-methylphenyl-
` acetic anhydride, propynoic anhydride, butynoic anhydride,
.
methoxyacetic anhydride, ~-methoxypropionic anhydride, ~-
ethoxybutanoic anhydride and the like.
Exemplary suitable acid chlorides of formula V
cb/ _ 7
.
.,
- . .. ..... .
1~60022
useful for preparing the compounds of the present invention
are the acid halides of the samc acids as set forth above
in the examples of acid anhydrides.
The manner in which the compounds of the present
- invention can be prepared is more specifically illustrated in
the following examples.
Example 1
Preparation of 5-t-Butyl-1,3,4-
thiadiazol-2-yl Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
~100 ml) was charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry of 5-t-butyl-2-amino-1,
3,4-thiadiazole ~10 grams~ in ethyl acetate (300 ml) was added
to the reaction vessel and the resulting mixture was stirred
~or a period of about 16 hours resulting in the formation of
a precipitate. The reaction mixture was then purged with
nitrogen gas to remove unreacted phosgene. The purged mix-
ture was then filtered to recover the desiréd product 5-t-
hutyl-1,3,4-thiadiazol-2-yl isocyanate as a solid having a
melting point of 261 to 263C.
Example 2
' Preparation of the Dimethyl Acetal of 2-~1-Methyl-3-
~5-~-butyl-1,3-,4-thiadiazol-2-yl)ureido]acetaldehyde
A mixture of 5-t-butyl-1,3,4-thiadiazol-2-yl iso-
- cyanate dimer (6 grams), the dimethyl acetal of 2-methylamino-
acetaldehyde ~3.9 grams) and benzene (50 ml) was charged into
a glass reaction flask equipped with a mechanicf~ stirrer and
reflux condenser. The reaction mixture was heated at reflux,
~,~ with stirring for a period of about 5 minutes. After this -
~ ~time the reaction mixture was stripped of benzene to yield an
` oil which solidified upon standing. The resulting solid was
then recrystallized from pentane to yield the desired product
the dimethyl acetal of 2-El-methyl-3-(5-t-butyl-1,3,4-thiadiazol-
2-yl)ureido]-acetaldehyde having a melting point o~ 80-82C.
cb/ - 8 - -
11~600Z2
Example 3
Preparation of 1-(5-t-Butyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-methyl-3-~5 t-butyl-l,
3,4~thiadiazol-2-yl)ureido]acetaldehyde (16 grams), concentrated
hydrochloric acid ~10 ml) and water (500 ml) were charged into
a glass reaction vessel equipped with a mechanical stirrer,
thermometer and reflux conden~er. The reaction mixture was
heated at reflux for a period of about 15 minutes. The reaction
mixture was filtered while hot and the filtrate was then cooled,
resulting in the formation of a precipitate. The precipitate
was recovered by filtration, dried and was recrystallized from
a benzene-hexane mixture to yield the desired product 1-(5-t-
butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-
2-one having a melting point of 133 to 134C.
Example 4
Preparation of 1-~5-t-Butyl-1,3,4-thiadiazol-
~ - 2-yl)-3-methyl-5-acetyloxy-1,3-imidazolidin-2-one
j l-~5-_-Butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-
~ 20 hydroxy-1,3-imidazolidin-2-one ~70 gramsj, acetic anhydride
-~ (56 grams) and a catalytic amount of toluenesulfonic acid
were charged into a glass reactionvessel equipped with a
mechanical stirrer and thermometer. The reaction mixture was
heated on a steam bath with continued stirring for a period
of about 2 hours. After this time water ~500 ml) was added
to the reaction mixture resulting in the formation of a preci-
i1 pitate. The precipitate was recovered by filtration and was
dried in an oven at 60C. The dried product was then re-
~, ~ crystallized from methanol to yield the desired product 1-(5-
, 30 t-butyl-1,3,4-thiadiazol-2-yl~-3-methyl-5-acetyloxy-1,3-
imidazolidin-2-oné having a melting point of 141C.
,: :
cb/ ~ 9 ~
, . :
, ~:
1060l);~
Example 5
Preparation of 5-Trifluoromethyl-
1,3,4-thiadiazol-2-yl Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
ll~0 ml) was charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry of 5-trifluoromethyl-2-
amino-1,3,4-thiadiazole (45 grams) in ethyl acetate ~300 ml)
was added to the reaction vessel and the resulting mixture
was stirred for a period of about 16 hours resulting in the
formation of a precipitate. The reaction mixture was then
pur~ed with nitrogen gas to remove unreacted phosgene. The
pur~ed mixture was filtered to recover 48 grams of a white
solid. This solid was recrystallized from dimethyl formamide
to yield the desired product 5-trif ~ romethyl-1,3,4-thiadiazol-
-I 2-yl isocyanate dimer.
Example 6
Preparation of the Dimethyl Acetal of 2-[1-Methyl-3-(5-
trifluoromethyl-1,3,4-thiadiazol-2-yl)ureido]acetaldehyde -
A mixture of 5-trifluoromethyl-1,3,4-thiadiazol-2-yl
-~ 20 isocyanate dimer ~9.5 grams), the dimethyl acetal of 2-methyl-
aminoacetaldehyde ~5.8 grams) and benzene ~60 ml) are char~ed
into a glass reaction vessel equipped with a mechanical stirrer
and reflux condenser. The reaction mixture is heated at reflux
for a period of about 15 minutes. After this time the mixture ;~
is stripped of benzene under reduced pressure to yield a solid -
product as the residue. This product is recrystallized from
~ heptane to yield the desired product the dimethyl acetal of
-~ 2~ methyl-3-~5-trifluoromethyl-1,3,4-thiadiazol-2-yl)ureido)-
I acetaldehyde having a melting point of 101 to 102~C.
`!
Example 7
` Pxeparation of 1-~5-Trifluoromethyl-1,3,4-thiadiazol- -
2-vl3-3-methYl-5-hvdroxY-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-methyl-3-(5-trifluoro-
meth~l-1,3,4-thiadiazoI-2-yl)ureido3acetaldehyde ~15 grams),
."~ .
cb/ - 10 -
4 ~ !
~06002Z
water ~400 ml) and hydrochloric acid t4 ml) were charged
into a glass reaction vessel equipped with a mechanical
stirrer, thermometer and reflux condenser. The reaction
mixture was heated at reflux for a period of about 15 minutes.
The reaction mixture was then filtered while hot and the fil-
trate was cooled resulting in the formation of a precipitate.
The precipitate was recovered by filtration, was dried and
was recrystallized from an ethyl acetate-hexane mixture to
yield the desired product 1-(5-trifluoromethyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one having a melt-
ing point of 136 to 138C.
Example 8
Preparation of 1-~5-Trifluoromethyl-1,3,4-thiadiazol-
2--y1)-3-methyl-5-acetyloxy-1,3-imidazolidin-2-one
1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-hydroxy-1,3-imidazolidin-2-one (0.05 mole), acetic
anhydride (6 ml), acetic acid (20 ml) and toluenesulfonic acid
~0.1 gram) are charged into a glass reaction vessel equipped -
with a mechanical stirrer and thermometer. The reaction mix-
ture is stirred at room temperature for a period of about 24
hours. After this time water ~200 ml) is added to the reaction
mixture. The resulting mixture is then extracted with ether.
.
The ether extract is washed with aqueous sodium carbonate
and is dried over anhydrous magnesium sulfate. The dried
solution is then filtered and stripped of solvent under
reduced pressure to yield a solid residue. This solid residue
is recrystallized from a water-methanol mixture to yield the
desired product 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-acetyloxy-1,3-imidazolidin-2-one as a crystalline
..
1 30 solid having a melting point o 72 to 74C.
;i` Additional compounds of the present invention which i~-
, can be prepared by the procedures of the foregoing examples
are l-t5-hexyl-1,3,4-thiadiazol-2-yl)-3-ethyl-5-acetyloxy-1,3-
.. . .
cb/ - 11 -
,
: - :
` 106002Z
imidazolidin-2-one, 1-~5-t-butyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-propionyloxy-1,3-imidazolidin-2-one, 1-(5-trifluoro-
methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-butanoyloxy-1,3-
imidazolidin-2-one, 1-(5-pentyl-1,3,4-thiadiazol-2-yl)-3-ethyl-
5-acryloyloxy-1,3-imidazolidin-2-one, 1 (5-_-butyl-1,3,4-
thiadiazol-2-yl)-3-propyl-5-chloroacetyloxy-1 ! 3-imidazolidin-
2-one, 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-allyl-5-cyc].o-
hexylcarbonyloxy-1,3-imidazolidin-2-one, 1-(5-trifluoromethyl-1,
3,4-thiadiazol-2-yl)-3-chloromethyl-5-acetyloxy-1,3-imidazo-
lidin-2-one, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3- ~ :
propargyl-5-(3-methylbenzoyloxy)-1,3-imidazolidin-2-one, 1-(5-tri~
fluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-chlorobenzoyl-
oxy)-1,3-imidazclidin-2-one, 1-(5-_-butyl-1,3,~-thiadiazol-2-yl)-
3-(1,1-dimethylprop-2-ynyl)-5-(4-methoxybenzoyloxy)-1,3-imidazo-
lidin-2-one, 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5- ~ :
(4-trifluoromethylbenzoyloxy)-1,3-imidazolidin-2-one, 1-(5- : -
trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-methyl- ~ -
thiobenzoyloxy)-1,3-imidazolidin-2-one, 1-(5-trifluoromethyl-
1,3,4-thiadiazol-2-yl)-3-ethyl-5-acetyloxy-1,3-imidazolidin-2-
one, 1-~5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-ethyl-5-
- methoxyacetyloxy-1,3-imidazolidin-2-one, 1-(5-t-butyl-1,3,4-
thiadiazol-2-yl).-3-methyl-5-(3-methylphenyl-acetyloxy-1,3-
imidazolidin-2-one, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-
yl)-3-methyl-5-propynoyloxy-1,3-imidazolidin-2-one, 1-(5-
trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-propyl-5-(3-cyano- .~:
benzoyloxy)--1,3-imidazolidin-2-one, 1-(5-sec-butyl-1,3,4-
thiadiazol-2-yll-3-propyl-5-(4-nitrobenzoyloxy)-1,3-imidazo-
lidin-2-one, 1-~5-t-butyl-1,3,4-thiadiazol-2-yl~-3-propyl-
5-~enzoyloxy-1,3-imidazolidin-2-one, 1-(5-trifluoromethyl-1,
3,4-thiadiazol-2-yl)-3-propyl-S-benzoyloxy-1,3-imidazolidin-
one, 1-(5-ethyl-1,3,4-thiadiazol-2-yl)-3-ethyl-S-acetyloxy-l, :
3-imidazolidin-2-one, 1-(5-propyl-1,3,4-thiadiazol-2-yl)-3-
propyl-S-propanoyloxy-1,3-imidazolidin-2-one, 1-(5-butyl-1,3,
4-thiadiazol-2-yl)-3-butyl-5-butanoyloxy-1,3-imidazolidin-2-
cb/ - 12 -
.. . ... . . : :. .. .
1C~60022
one, l-(5-pentyl-1,3,4-thiadiazol-2-yl)-3-pentyl-S-pentanoyl-
oxy-1,3-imidazolidin-2-one, 1-(5-hexyl-1,3,4-thiadiazol-2-yl)-
3-hexyl-5-hexanoyloxy-1,3-imidazolidin-2-one, 1-(5-cycloheptyl-
1,3,4-thiadiazol-2-yl)-3-but-3-enyl-5-pent-4-enoyloxy-1,3-
imidazolidin-2-one, 1-(5-but-2-enyl-1,3,4-thiadiazol-2-yl)-3-
pent-4-enyl-5-hex-4-enoyloxy-1,3-imidazolidin-2-one, 1-(5- :'
pent-3-enyl-1,3,4-thiadiazol-2-yl)-3-hex-5-enyl-5-~-chloro- ;:
acetyloxy-1,3-imidazolidin-2-one, 1-(5-hex-4-enyl-1,3,4-thia-
diazol-2-yl)-3-~-chloroethyl-5-~-bromobutanoyloxy-1,3-imi-
dazolidin-2-one, 1-(.5-~-chloroethyl-1,3,4-thiadiazol-2-yl)-
3-iodomethyl-5-~-chloropentanoyloxy-1,3-imidazolidin-2-one,
5-~-chloropropyl-1,3,4-thiadiazol-2-yl)-3-trifluoromethyl-
5-~-chlorohexanoyloxy-1,3-imidazolidin-2-one, 1-(5-bromomethyl-
1,3,4-thiadiazol-2-yl)-3-~-chloroethyl-5-~-iodoacetyloxy-1,3-
imidazolidin-2-one, 1-~5-~-bromoethyl-1,3,4-thiadiazol-2-yl)-
3-~-bromopropyl-5-cyclopropylcarbonyloxy-1,3-imidazolidin-2~
one, 1-(5-trichloromethyl-1,3,4-thiadiazol-2-yl)-3-~-bromohexyl- ; -'
5-cyclobutylcarbonyloxy-1,3-imidazolidin-2-one, 1-(5-~-chloro-
hexyl-1,3,4-thiadiazol-2-yl)-3-~-chlorohexyl-5-cyclopentyl-
carbonyloxy-1,3-imidazolidin-2-one, 1-~5-ethoxy-1,3,4-thia-
diazol-2-yl)-3-(1,1-diethylprop-2-ynyl)-5-cycloheptylcarbonyl-
oxy-1,3-imidazolidin-2-one, 1-(5-butoxy-1,3,4-thiadiazol-2-yl)-
3-(1,1-dipropylprop-2-ynyl)-5-~2-ethylbenzoyloxy)-1,3-,-imidazo-
lidin-2-one, 1-(5-hexyloxy-1,3,4-thiadiazol..2-yl)-3-methyl-5-
(3-propylbenzoyloxy~.-1,3-imidazolidin-2-one, 1-(5-ethylthio-1,
3,4-thiadiazol-2-yl~-3-methyl-5-~4-hexylbenzoyloxy)-1,3-imidazo-
lidin-2-one, 1-~5-propylthio-1,3,4'-thiadiazol-2-yl)-3-methyl-
5-~.3-ethoxybenzoyloxy)-1,3-imidazolidin-2-one, 1-(5-pentylthio-
1,3,4-thiadiazol-2-yl~-3-methyl-5-(4 butoxybenzoyloxy)-1,3-
'imidazolidin-2-one, 1-(5-hexylthio-1,3,4-thiadiazol-2-yl)-3-
methyl-S-t4-hexyloxybenzoyloxy)-1,3-imidazolidin-2-one, 1-(5-
ethylsulfonyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-~4-bromo-
.
cb/ - 13 -
.,. , . ,i .. . ,
10600ZZ
benzoyloxy)-1,3-imidazolidin-2-one, 1-(5-propylsulfonyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-(4-iodobenzoyloxy)-1,3-imidazo-
lidin-2-one, 1-(5-pentylsulfonyl-1,3,4-thiadiazol-2-yl)-3- ~
methyl-5-(4-flu~robenzoyloxy)-1,3-imidazolidin-2-one, 1-(5- - :
hexylsul~onyl-1,3,4-thiadiazol-2-yl)-3-methyl-S-(2,4-dichloro~
benzoyloxy)-1,3-imidazolidin-2-one, 1-(5-ethylsulfinyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-(2,4,6-trichlorobenzoyloxy)-1,3-
imidazolidin-2-one, 1-(5-propylsulfinyl-1,3,4-thiadiazol-2-
yl)-3-methyl-5-(3,4-dibromobenzoyloxy)-1,3-imidazolidin-?-one,
1-~5-~utylsulfinyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-tri-
fluoromethylbenzoyloxy~-1,3-imidazolidin-2-one, 1-(5-hexylsulfinyl- :
1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-chloromethylbenzoyloxy)-
1,3-imidazolidin-2-one, 1-(5-isopropyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-alkylthiobenzoyloxy-1,3-imidazolidin-2-one, 1-t5~
isopropyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-propylthiobenzoyl-
oxy-1,3-imidazolidin-2-one, 1-~5-isopropyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-pentylthiobenzoyloxy-1~3-imidazolidin-2-one~
1-~5-isopropyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hexylthio-
benzoyloxy-1,3-imidazolidin-2-one, 1-(5-methyl-1,3,4-thia- . :
diazol-2-yl)-3-methyl-5-butynoyloxy-1,3-imidazolidin-2-one, :-
1-(5-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-pent-4-ynyloxy-
1,3-imidazolidin--2-one, 1-~5-methyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-hex-4-ynyloxy-1,3-imidazolidin-2-one, 1-(5-methyl-1,
3,4-thiadiazol-2-yl)-3-methyl-5-~-methoxypropionyloxy-1,3-
midazolidin-2-one, 1-(5-methyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-~-methoxybutanoyloxy-1,3-imidazolidin-2-one, 1-(5- -
methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-3-methoxypentanoyloxy-
1,3-imidazolidin-2-one, 1-(5-methyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-~-ethoxypropionyloxy-1,3-imidazolidin-2-one, 1-t5-
methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-propoxyacetyloxy-1,3-
imidazolidin-2-one, 1-(5-methyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-butoxyacetyloxy-1,3-imidazolidin-2-one, 1-~5- methyl-1,
3,4-thiadiazol-2-yl)-3-methyl-5-hexyloxyacetyloxy-1,3-imidazo-
lidin-2-one, 1-~5-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-
- 14 - :
~6002~
(3,4-dichlorophenylacetyloxy)-1,3-imidazolidin-2-one, 1-(5-
methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-trifluoromethyl-
phenylacetyloxy)-1,3-imidazolidin-2-one, 1-(5-methyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-~2-methyl-4-chlorophenylacetyloxy)-
1,3-imidazolidin-2-one, 1-(5-methyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-(-3-methylthiophenylacetyloxy)-1,3-imidazolidin-2-one,
1- ~-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(2-methoxyphenyl-
acetyloxy)-1,3-imidazolidin-2-one and the like.
For practical use as herbicides the compounds of
lQ this invention are generally incorporated into herbicidal com-
positions which comprise an inert carrier and a herbicidally
toxic amount of such a compound. Such herbicidal compositions,
which can also be called formulations, enable the active com-
pound to be applied conveniently to the site of the weed
infestation in any desired quantity. These compositions
can be solids such as dusts, granules, or wettable powders;
or they can be liquids such as solutions, aerosols, or emulsi-
fiable concentrates.
For example, dusts can be prepared by grinding and
blending the active compound with a solid inert carrier such
as the talcs, clays, silicas, pyrophyllite, and the like.
Granular formulations can be prepared by impregnating the com-
pound, usually dissolved in a suitable solvent, onto and into
granulated carriers such as the attapulgites or the vermi-
culites, usually of a particle size range of from about 0.3
to 1.5 mm. Wettable powders, which can be dispersed in
~ater or oil to any desired concentration of the active com-
pound, can be prepared by incorporating wett~ing agents into
concentrated dust compositions.
j 30 In some cases the active compounds are sufficiently
soluble in common organic solvents such as kerosene or xylene
so that they can be used directly as solutions in these solvents.
~b/ - 15 -
1~600;~2
Frequently, solutions of herbicides can be dispersed under
superatmospheric pressure as aerosols. However, preferred
liquid herbicidal compositions are emulsifiable concentrates,
which comprise an active compound according to this invention
and as the inert carrier, a solvent and an emulsifier. Such
emulsifiable concentrates can be extended with water and/or
oil to any desired concentration of active compound for appli-
cation as sprays to the site of the weed infestation. The
emulsifiers most commonly used in these concentrates are
nonionic or mixtures of nonionic wlth anionic surface-active
agents. With the use of some emulsifier systems an inverted
emulsion (water in oil) can be prepared for direct application
, to weed infestations.
A typical herbicidal composition according to this
invention is illustrated by the following example, in which
the quantities are in parts by weight.
~ . .... .
, EXAMPLE 9
Preparation of a Dust
, Product of Example 4 10
1 20 Powdered Talc go
-, The above ingredients are mixed in a mechanical
grinder-blender and are ground until a homogeneous, free-
flowing dust of the desired particle size is obtained.
~j
ThiS dust is suitable for direct application to the site of
the weed infestation.
The compounds of this invention can be applied as
herbicides in any manner recognized by the art. One method
~i for the control of weeds comprises contacting the locus of
said weeds with a herbicidal composition comprising an inert
carrier and as an essential active ingredient, in a quantity
which is herbicidally toxic to said weeds, a compound of the
. :, .
~ cb/ ~ - 16 -
'; . , ."~ ~,':
600ZZ
present invention. The concentration of the new compoun~ of
this invention in the herbicidal compositions will vary greatly
with the type of formulation and the purpose for which it is
designed, but generally the herbicidal compositions will com-
prise from about 0.05 to about g5 percent by weight of the active
compounds of this invention. In a preferred embodiment of
this invention, the herbicidal compositions will comprise
from about 5 to about 75 percent by weight of the active com- -
pound. The compositions can also comprise such additional
substances as other pesticides, such as insecticides, nema-
tocides, fungicides, and the like; stabilizers, spreaders,
deactivators, adhesives, stickers, fertIlizers, activators,
synergists, and the like.
The compounds of the present invention are also
useful when combined with other herbicid~s and/or defoliants,
dessicants, growth inhibitors, and the like in the herbicidal
compositions heretofore described. These other materials can
comprise from about 5% to about 95% of the active ingredients
~n the herbicidal compositions. Use of combinations of these
other herbicides and/or defoliants, dessicants, etc. with the
compounds of the present invention provide herbicidal composi-
tions which are more effective in controlling weeds and often
provide results unattainable with separate compositions of
the individual herbicides.
Weeds are undesirable plants growing where they are ~-
not wanted, having no economic value, and interfering with
~he production of cultivated crops, with the growing of orna-
mental plants, or with the welfare of livestock. Many types
of weeds are known, including annuals such as pigweed, lambs-
3~ quarters, foxtail, crabgrass, wild mustard, field pennycress,
ryegrass, goose grass, chickweed, wild oats, velvetleaf, purs-
lane, barnyardgrass, smartweed, knotweed, cocklebur, wild
-
cb/ - 17 -
,
0600zz
buckwheat, kochia, medic, corn cockle, ragweed, sowthistle,
coffeeweed, croton, cuphea, dodder, fumitory, groundsel, hemp
nettle, knawel, spurge, spurry, emex, jungle rice, pondweed,
dog fennel, carpetweed, moringglory, bedstraw, ducksalad,
naiad, cheatgrass, fall panicum, jimsonweed, witchgrass,
: switchgrass, watergrass, teaweed, wild turnip and sprangle-
top; biennials such as wild carrot, matricaria, wild barley,
campion, chamomile, burdock, mullein, roundleaved mallow, bull
thistle, houndstongue, moth mullein and purple star thistle; -
or perennials such as white cockle, perennial ryegrass, quack-
grass,Johns~ongrass, Canada thistle, hedge bindweed, Bermuda ...... .
grass, sheep sorrel, curly dock, nutgrass, field chickweed,
dandelion, campanula, field bindweed, Russian knapweed,
mesquite, toad~lax, yarrow, aster, gromwell, horsetail,
, . . . .
ironweed, sesbania, bulrush, cattail, winter-cress, horse-
.. nettle, nutsedge, milkweed and sicklepod.
. Similarly, such weeds can be classified as broad-
.leaf or grassy weeds. It is economically desirable to control
the growth of such weeds without damaging beneficial plants
or livestock.
. The new compounds of this invention are particularly
.~ valuable for weed control because they are toxic to many speci~s .
and groups of weeds while they are relatively non-toxic to ...
many beneficial plants. The exact amount of compound required
will depend on a variety of factors, including the hardiness .
of the particular weed species, weather, type of soil, method ;
of application, the kind of beneficial plants in the same
area and the like. Thus, while the application of up to only
. ~ .
about one or-two ounces of active compound per acre may be
. 30 sufficient for good control of a light infestation of weeds ~:. :
.l growing under adverse conditions, the application of ten ..
- pounds or more of an active compound per acre may be required
. . ~.
. cb/ - 18 - . ::
. ~
;. . , - .
~0600ZZ
for good control o a dense infestation of hardy perennial
weeds growing under favorable conditions.
The herbicidal toxicity of the new compounds of
this invention can be illustrated by many of the established
testing techniques known to the art, such as pre- and post-
emergence testing.
The her~icidal activity of the compounds of this
invention was demonstrated by experiments carried out for the
pre-emergence control of a variety of weeds. In these experi-
ments small plastic greenhouse pots filled with dry soil were
seeded with the various weed seeds. Twenty-four hours or less
after seeding the pots were sprayed with water until the soil
was wet and the test compound formulated as an aqueous emulsion
of an acetone solution containing emulsifiers was sprayed at
the indicated concentrations on the surface of the soil.
After spraying, tne soil containers were placed in
the greenhouse and provided with supplementary heat as required
and daily or more frequent watering. The plants were maintained
under these conditions for a period of from 15 to 21 days, at -
which time the condition of the plants and the degree of injury
to the plants was rated on a scale of from 0 to 10, as follows:
0 = no injury, 1,2 = slight injury, 3,4 = moderate injury, -
5,6 = moderately severe injury, 7,8,9 = severe injury and
lO = death. The effectiveness of the compounds is demonstrated
by the following data:
. ~ '
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.
.. ' '
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.. . .
`` ~0600ZZ
T~BLE I
INJURY RATING
Product of Example 4
Concentration
~Pounds per Acre)
.. .... .. .
Weed Species 4 1 1/4
Yellow Nutsedge 10 8 5
Wild Oats 10 10 9
Jimsonweed 9 9 8
Velvetleaf 10 10 9
~ Johnsongrass 10 10 10
"' Pi~weed 10 10 10
Mustard 10 10 10
Yellow Foxtail 10 10 10
Barnyardgrass 10 10 10
,l Crabgrass 10 10 10
'
~ Cheatgrass 10 10 lO
i~ Morningglory 10 10 lO
. ';: .
The herbicidal activity of the compounds of this ~ -
, 20 in~ention was also demonstrated by experiments carried out
.
7~ for the post-emergence control of a variety of weeds. In
these experiments the compound to be tested was formuiated
a~ an aqueous emulsion and sprayed at the indicated dosage
,.
on the foliage of the weeds that had attained a prescribed
ize. After spraying, the plants were placed in a green-
houSe and watered daily or more frequently. Water was not ~ -
~ applied to the foliage of the trea-ted plants. The severity
,i of the injury was determined 10 to 15 days after treatment
and was rated on the scale of from 0 to 10 heretofore described. ~-~
_ .. . ~ . . . . . .
~1 ~ 30 The effectiveness of the compounds is demonstrated by the -
:7~ ~ following data:
',
1 20 -
.. .
.~, . .
~060022
TABLE II
INJURY RATING
Product of Example 4
Concentration
(Pounds per Acre)
Weed Species 4 1 1
Yellow Nutsedge 10 10 4
Wild Oats 10 10 10
Jimsonweed 10 10 10
Pigweed 10 10 10
Johnsongrass 10 10 10
'i, Bindweed 10 9 10
Mustard 10 10 10
Yellow Foxtail 10 10 10
Barnyardgrass 10 10 10
Crabgrass 10 10 10
Mornin~glory 10 10 10
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it ~ ,
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.
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