Note: Descriptions are shown in the official language in which they were submitted.
`~- 10783gl ~
1 - THIAZOLYL IMIDAZOLIDINONES
This invention relates to new compositions of
matter ar.d more specifically relates to new chemical
compounds of the formula
Q
CH---CH 2 ~ '
H --C-N ~ ¦ I 1:
C - N N - R~
/ \/ :''
X - C - S C
(I)
wherein X is selected from the group consisting of halogen
and alkylsulfonyl; R' is selected from the group consisting
of alkyl, alkenyl, haloalkyl and
R4
- C - C _ CH
1~5 : '
", 10 wherein R4 and R~ are each selected from the group consist-
ing of hydrogen and alkyl; Q is selected from the group
I consisting of OH, I and
- N - R3 - O - C - R6; R2 and R3
are each selected from the group consisting of hydrogen, ~:
alkyl, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl,
cycloalkyl and
H(5-m)
- (CNz)p ~
Y;
.
R6 is selected from the group consisting of alkyl, alkenyl,
haloalkyl, alkynyl, alkoxyalkyl, cycloalkyl and
- 1 - ~ .
bm: -
1078391
,
1(5-m)
-(CH2)P - ~
\==~\ - '' :
Ym; ' ~ ~'
p is the integer O or l; Y is selected from the
group consisting of alkyl, alkoxy, alkylthio, halogen,
haloakyl, nitro and cyano; and m is an integer from o to 3.
.; .~
The compounds of the present invention are useful i
as herbicides. ;~
In a preferred embodiment of the present
invention X is selected from the group consisting of
' chlorine, bromine, and lower alkylsulfonyl; R' is selected
from the group consisting of lower alkyl, lower alkenyl, ~-
, lower haloalkyl and
I
:a ~<5
q wherein R~ and R' are each selected from the group consist-
1 ing of hydrogen and alkyl of up to 3 carbon atoms; and R2
: and R~ are each selected from the group consisting of
hydrogen, lower alkyl, lower alkenyl, lower haloalkylr
lower hydroxyalkyl, lower alkoxyalkyl, cycloalkyl of from
3 to 7 carbon atoms and
(5-m)
-~CH2)P ~
~ , ~'
Ym; :~
R6 is selected from the group consisting of lower alkyl,
bm:
- 1078391
lower alkenyl, lower haloalkyl, lower hydroxyalkyl,
lower alkoxyalkyl, cycloalkyl of from 3 to 7 carbon atoms
and .
1(5-m)
-~C~12)p~
~ . .
' 1, . ,`.
p is the integer 0 or 1; Y is selected from the group
consisting of lower alkyl, lower alkoxy, lower alkylthio,
halogen, lower chloroalkyl, lower bromoalkyl, trifluoro-
methyl, nitro and cyanoi and m is an integer from 0 to 3.
The term "lower" as used herein designates a
straight or branched carbon chain of up to 6 carbon atoms.
The compounds of the present invention wherein
~:¦ R 2 ~
Q is - N - R9 can be prepared by reacting a compound of
the formula - .
OH :
~ H - C -- N IH - fH2
j ~ C - N N - Rl :
X - I ' 5 / ~ / ;.
11 ',
:.'. '. ,
(II)
wherein X, n and Rl are as heretofore described, with
.. . . . .
an amine of the formula
~1 R2
H - ~ - R9 (III)
wherein R2 and R~ are as heretofore described. This
reaction can be effected by combining the compound of ::
formula II with an about equimolar amount or excess molar
~ _ 3 -
bm:
--" 107839~
amount of the amine of formula II in an inert reaction
medium, such as heptane or toluene, and then heating
the reaction mixture, with stirring, at its reflux
temperature and azeotropically removing the water of
reaction. 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 evaporation
of the organic reaction medium if soluble therein. The
product can then be purified by conventional means such
as recrystallization and the like.
The compounds of the present invention wherein
R
~ is - O - C - R can be prepared by reacting the compound
of formula II with an acid chloride of the formula
Cl - - R~ (VIII)
wherein R2 is as heretofore described, in the presence of
an acid acceptor such as a tertiary amine. This reaction
can be effected by slowly adding the acid chloride of
formula VIII with stirring to a solution of an about
equimolar amount of the compound of formula II in an
inert organic solvent, in the presence of the acid acceptor,
at a temperature of about 10 to 30C. After the addition
is completed, the reaction 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 acceptor chloride, followed
by stripping off the solvent if the product is soluble
therein, or~ if formed as a precipitate, by filtration
and subsequent washing and purification.
bm:
`-` 1078391
The compounds of this invention can also be - '
prepared by reacting a compound of formula II with an acid
anhydride of the formula
R2 _ ~ _ o - ~ - R2 (IX)
wherein R2 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 fQr a period of from ~ 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 evaporation of the organic reaction
medium if soluble therein. In some instances the acid
anhydride can be used as a solvent for the compound of
formula IIr obviating the use of an inert solvent as the
reaction medium. When lower alkanoic anhydrides are used,
water can be added to the reaction mixture to precipitate
- .
the desired product upon completion of the reaction~ The
product can then be purified by conventional means such
as recrystallization and the like, In some instances the
foregoing reaction results in the formation of a mixture ~;;
of products consisting of the des-ired compound of this
invention and dehydrated starting material of the formula
¦¦ ~C -- Nf ¦ '
X - C S / C N - R1
O ~X)
bm:
I . . . - , ~
- 10783gl
wherein X, n and Rl are as described. In these instances
the desired product can be isolated by fractional
precipitation
The compound of formula II can be readily ;~
prepared by heating a compound of the formula
H - C N ~ H OCH 3
¦¦ C - N - C - N - CH2 - ~H
X - C S/
- O R1 OCHg (IV)
wherein X, n and Rl are as heretofore described, in a
- dilute, acidic reaction medium for a period of from about
10 to about 60 minutesll Temperatures of from about 60C 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 about 0.5 to about 10 percent. Lower water-miscible
alkanols can also be suitably added to the reaction medium
to aid in the dissolution of the starting materials. After
completion of the reaction the desired product can be
recovered upon evaporation of the solvents used if soluble
therein or by filtration if formed as a precipitate.
This product can then be used as such or can further
purified by standard techniques such as trituration,
recrystallization, washing and the like.
; The ca~unds of formula IV can be prepared by
reacting a molar amount of an isocyanate dimer of the formula
0 ~ =C=O
~ 2 (V)
bm:
1078391
wherein X and n are as heretofore described, with about two
molar amounts of a dimethyl acetal of the formula
fCH9
H - N - CH 2 - CH
R~ ~CH3 (VI)
wherein Rl is as heretofore described. This reaction can
be effected by combining the isocyanate dimer of formula V, ~ ;
dissolved in an inert organic solvent such as benzene, with
the acetal of formula VI at room temperature and stirring -
the resulting mixture for a period of about ~ to about 4
hours. After this time the reaction mixture can be filtered -
and the filtrate stripped of solvent to yield the desired
product. This product can be used as such or further
purified if desired by standard tecnigues.
The isocyanate dimer of formula V can be prepared
by reacting a thiazole of the formula
H - C N
¦¦ C - NHz -~ ~
X- C--S/ '`'
(VIIl
wherein X and n are as heretofore described, with phosgene,
This reaction can be effected by adding a slurry or solution
of the benzothiazole in a suitable organic solvent such as
ethyl acetate to a solution of phosgene in a similar solvent.
The resulting mixture can then be heated at reflux for a
period of from ~ to 2 hours The desired product can then
be recovered by filtration if formed as a precipitate or
upon evaporation of the organic solvent if soluble therein. ;
- bm:
1078391
Exemplary suitable compounds of ~ormula VI for
preparing the compounds of the present invention are the
dimethyl acetal of 2-methylaminoacetaldehyde, the dimethyl
acetal of 2-ethylaminoacetaldehyae, the dimethyl acetal of
. 2-propylaminoacetaldehyde, the dimethyl acetal of 2-
allylaminoacetaldehyde, the dimethyl acetal of 2-chloro-
methylaminoacetaldehyde, the dimethyl acetal of 2-~- :
bromoethylaminoacetaldehyde, the dimethyl acetal of 2-
propargylaminoacetaldehyde and the like.
Exemplary suitable compounds of formula VII for
preparing the compounds of this invention are 2-amino- ~.
thiazole, 2-amino-5-methylthiazole, 2-amino-6-chlorothiazole,
2-amino-4, 5-dimethylthiazole, 2-amino-7-bromothiazole,
2-amino-6-methoxythiazole, 2-amino-6-fluorothiazole, 2-amino-
4-methyl-6-chlorothiazolè, 2-amino-4-chloromethylthiazole,
2-amino-5-~-bromoethylthiazole, 2-amino-6-trifluoro-
methylthiazole and the like.
Exemplary suitable compounds of formulae
VIII and IX for preparing the compounds of the present
invention are the acid chlorides or anhydrides of the
following acids; acetic acid, propionic acid, butanoic
acid! pentanoic acid, hexanoic acid, octanoic acid,
dodecanoic acid, octadecanoic acid, acrylic acid, butenoic
- acid, pentenoic acid, chloroacetic acid, bromoacetic.acid
~-chlorobutanoic acid, cyclohexylcarboxylic acid,
cyclopropylcarboxylic acid, benzoic acid, toluic acid,
4-chlorobenzoic acid, 3-bromobenzoic acid, 4-fluorobenzoic
acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4- .
chloromethylbenzoic acid, 4-trifluoromethylbenzoic acid,
3,4,5-trichlorobenzoic acid, 3-methylthiobenzoic acid,
3-ethylthiobenzoic acid, 4-butylthiobenzoic acid,
bm:
1078391
phenylacetic acid, ~-phenylpropionic acid, 4-methyl-
phenylacetic acid, pxopynoic acid, butynoic acid,
methoxyacetic acid, ~-methoxypropionic acid, y-ethoxy-
butanoic acid and the like,
The manner in which the compounds of the present
invention can be prepared is more specifically illustrated
in the following examples.
":
Example l
Preparation of 5-Bromothiazol-2-yl Isocyanate Dimer
2-Amino-5-bromothiazole ~l9.0 grams) and a
saturated solution of phosgen~ in ethyl acetate (200 ml)
; were charged into a glass reaction vessel equipped Wit}l a
mechanical stirrer, thermometer and reflux condenser.
The reaction mixture was heated at reflux with stirring
for a period of about 3 hours. After this time the reaction
mixture was cooled and filtered to recover the desired
product 5-bromothiazol-2-yl isocyanate dimer as a fine
yellow powder.
Example 2
Preparation of the Dimethyl Acetal of
2-rl-Methyl-3-(5-bromothiazol-2-yl)ureido~acetaldehyde
5-Bromothiazol-2-yl isocyanate dimer ~17.0 grams),
benzene (70 ml) and the dimethyl acetal of 2-methylamino-
acetaldehyde (13.5 grams) were charged into a glass reaction -
vessel equipped with a mechanical stirrer and thermometer. !~, '
The reaction mixture was then stirred at room temperature
for a period of about one hour. After this time the reaction
mixture was filtered, and the filtrate was stripped of solvent
under reduced pressure, leaving an oil. This oil was chro-
matographed on silica gel using ethyl acetate as the diluant.
g _
bm:
--" 1078391
- The eluant was dissolved in an ethanol-water mixture and the
solution was filtered, The filtrate was then stripped of
solvents under vacuum to yield the desired product the
dimethyl acetal of 2-ll-methyl-3-(5-bromothiazol-~-yl)
uriedolacetaldehyde as a crystalline solid having a melt
point of 72 to 73C.
Exam~le 3
Preparation of 1-(5-Bromothiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one ;~
The dimethyl acetal of 2-[1-methyl-3-(5-bromothiazol-
2-yl)ureido3acetaldehyde (10 grams), ethanol (80 ml), water
(80 ml) and concentrated hydrochloric acid (8 ml) were
charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer and reflux condenser. The
reaction vessel was purged with nitrogen gas, and the
reaction mixture was heated at reflux with stirring for a
period of about 15 minutes. After this time the reaction
mixture was stripped of solvents under reduced pressure,
and the residue was dissolved in ethyl acetate. The
resulting solution was washed with saturated aqueous
sodium bicarbonate and dried over anhydrous sodium
sulfate. The dried solution was then filtered, and the
filtrate was stripped of solvent, leaving an oil. ~his
oil solidified upon standing to yield the desired product
1-(5-bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-
2-one.
.
Example a
Preparation of 1-(5-Bromothiazol-2-yl)-
- 3-methyl-5-ethylamino-1,3-imidazolidin-2-one
1-(5-Bromothiazol-2-yl)-3-methyl-5-hydroxy-1,3- -
-- 10 --
bm:
~ 1~783~11
imidazolidin-2-one (0.1 mole) and heptane (100 ml) are
charged into a glass reaction vessel equipped with a
, mechanical stirrer, thermometer, Dean-Stark trap and re~lux ',
conaenser. Ethylamine (0,1 mole) is added to the reaction
vessel, and the mixture is heated at reflux while removing
the water as it is formed, After no more water is given
of~, the reac~ion mixture is stripped of solvent under ~,
reduced pressure to yield the desired product 1-(5- ,
bromothiazol-2-yl)-3-methyl-5-ethylamino-1,3-imidazolidin
-2-one as the residue~
Example 5
Preparation of l-(S-Bromothiazol-2-yl)~
3-methvl-5-acetvloxY-1,3-imidazolidin-2-one
_ _ . _ . ~ _
1-(5-Bromothiazol-2-yl),-3-methyl-5-hydroxy-1,3- ~'
imidazolidin-2-one (0.1 mole), acetyl chloride (0,11 mole) ,~
and pyridine (0,11 mole) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer.
The reaction mixture is stirred for a period of about 15
minutes and is then allowed to stand for a period of about ~'
2 hours. After this time water (100 ml) and hexane (30 ml)
are added to the mixture. ~he organic phase is then
separated from the aqueous phase and is dried over anhydrous ',
magnesium sulfate. The dried solution is the filtered and
stripped of solvent under reduced pressure to yield the
desired product 1-(5-bromothiazol-2-yl)-3-methyl-5-acetyloxy-
1,3-imidazolidin-2-one.
Example 6
Preparation of 5-Chlorothiazol-2-yl Isocyanate Dimer
' 2-Amino-5-chlorothiaZole (19.0 grams) and a
'~ 30 saturated solution of phosgene in ethyl acetate (200 ml) are
bm: ,
10783~1
charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer and reflux condenser. The
reaction mixture is heated at reflux with stirring for a ~-
period of about 3 hours. After this time the reaction
mixture is cooled and filtered to recover the desired
product S-chlorothiazol-2-yl isocyanate dimer,
Example 7
Preparation of the Dimethyl Acetal of
-2-tl-Ethyl-3-(5-chlorothiazol-2-yl)ureido]acetaldehyde
.
5-Chlorothiazol-2-yl isocyanate dimer (17.0 grams),
benzene (70 ml) and the dimethyl acetal of 2-ethylaminoacet- ;~
aldehyde (13.5`grams) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer.
The reaction mixture is then stirred at room temperature
for a period of about one hour. After this time the reaction
mixture is filtered, and the filtrate is stripped of sol~ent
under reduced pressure, leaving an oil. This oil is
dissolved in an ethanol-water mixture, and the solution is
filtered. The filtrate is then stripped of solvents under
vacuum to yield the desired product the dimethyl acetal
of 2-[1-ethyl-3-~5-chlorothiazol-2-yl)ureido]acetaldehyde.
ExamPle 8
Preparation o 1-L5-Chlorothiazol-2-yll.-
3-ethyl-S-hydroxy-lr3-imidazolidin-2-one
The dimethyl acetal of 2~ ethyl-3-(5-
chlorothiazol-2-yl]ureido~acetaldehyde (10 gramslr ethanol
(8Q ml)~ water (80 ml) and concentrated hydrochloric acid
~8 ml2 are charqed into a ~lass reaction vessel equi~Ped with
a mechanical stirrer, thermometer and reflux condenser. The
- 12 _
bm:
10783~1 ~
reaction vessel is purged with nitrogen gas, and the
reaction mixture is heated at reflux with stirring ~or a
period of about 15 minutes. After this time the reaction
mixture is stripPed of solvents under reduced pressure, and
the residue is dissolved in ethyl acetate. The resulting
solution is washed with saturated aqueous sodium bicarbonate
and dried over anhydrous sodium sulfate. The dried solution
is then filtered, and the filtrate is stripped of solvent
to leave the desired product 1-(5-chlorothiazol-2-yl~-3-
ethyl-5-hydroxy-1,3-imidazolidln-2-one.
-Example 9
Preparation of 1-(5-Chlorothiazol-2-yl)-
3-ethyl-5-t-butylamino-1,3-imidazolidin-2-one
1-(5-Chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-
imidazolidin-2-one (0.1 mole) and heptane (100 ml) are
charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer, Dean-Stark trap and reflux
condenser. t-Butyl-amine (0.1 mole) is added to the
reacti~n ~essel, and the mixture is hea~ed at re~ x whl1e
removing the water as it ls formed. ~fter no more water is
given off, the reaction mixture is stripped o~ solvent under ~ ;
reduced pressure to yield the desired product 1-(5-
chlorothiazol-2-yl)-3-ethyl-5-t-butylamino-1,3-imidazolidin-
2-one as the residue.
Example 10
Preparation of 1-(5-Chlorothiazol-2-yl)-
-3-ethyl-5-acryloyloxy-1,3-imidazolidin-2-one
1-(5-Chlorothiazol-2-yl)-3-ethyl-5-hydroxy-1,3-
imidazolidin-2-one (0.1 mole) acryloyl chloride (0.11 mole)
and pyridine (0.11 mole) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer.
- 13 -
bm:
10783~
The reaction mixture is stirred for a period of about 15
minutes and is then allowed to stand for a period of about 2
hours. After this time water (100 ml) and hexane (30 ml)
are added to the mixture. The organic phase is then separated
from the aqueous phase and is dried over anhydrous magnesium
sulfate. The dried solution is then filtered and striPped of
solvent under reduced pressure to yield the desired product
1-(5-chlorothiazol-2-yl)-3-ethyl-5-acryloyloxy-1,3-
imidazolidin-2-one as the residue.
_Example 11
Pre aration of 5-Fluorothiazol-2-yl Isocyanate Dimer
P
2-Amino-5-fluorothiazole (19.0 grams) and a
saturated solution of phosgene in ethyl acetate (200 ml)
are charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer and reflux condenser. The
reaction mixture is heated at reflux with stirring for a
period of about 3 hours. After this time the reaction
mixture is cooled and filtered to recover the desired
product 5-fluorothiazol-2-yl isocyanate dimer.
Example 12
Preparation of the Dimethyl Acetal of
2-!l-Allyl-3-(5-fluorothiazol-2-yl)ureido]acet-aldehyde
5-Fluorothiazol-2-yl isocyanate dimer (17.0 grams),
; benzene (70 ml) and the dimethyl acetal of 2-allylaminoacet-
aldehyde (13.5 grams) are charged into a ~lass reaction vessel
equipped with a mechanical stirrer and thermometer. The
reaction mixture is then stirred at room temperature for a
period of about one hour. After this time the reaction
mixture is filtered, and the filtrate is stripped of solvent
under reduced pressure, leaving an oil. This oil is dissolved
- 14 -
bm:
-~ 10783~1
in an ethanol-water mixture, and the solution is filtered.
The filtrate is then stripped of solvents under vacuum to
yield the desired product the dimethyl acetal of 2-[1-allyl-
3-(5-fluorothiazol-2-yl)ureido]acetaldehyde.
Example 13
Preparation of 1-(5-Fluorothiazol-2-yl)-
-3-allyl-5-hydrox~-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-allyl-3-(5-fluorothiazol-
2-yl)ureido~acetaldehyde (10 grams), ethanol (80 ml), water
(80 ml) and concentrated hydrochloric acid (8 ml) are charged
into a glass reaction vessel equipped with a mechanical -
stirrer, thermometer and reflux condenser, The reaction
vessel is purged with nitrogen gas, and the reaction mixture
is ~eated at reflux with stirring for a period of about 15
minutes. After this time the reaction mixture is stripped
of solvents under reduced pressure, and the residue is
dissolved in ethyl acetate, The resulting solution is washed
with saturated aqueous sodium bicarbonate and dried over
anhydrous sodium sulfate. The dried solution is then
2~ filtered, and the filtrate is stripped of solvent to leave
the desired product 1-(5-fluorothiazol-2-yl)-3-allyl-5-
hydroxy-1,3-imidazolidin-2-one.
~Example 1~ -
Preparation of 1-(5-Fluorothiazol-2-yl)-
3-allyl-5-allylamino-1,3-imidazolidin-2-one
1-(5-Fluorothiazol-2-yl)-3-allyl-5-hydroxy-1,3-
imidazolidin-2-one (0,1 mole) and heptane (100 ml) are
charged into a glass reaction vessel e~uipped with a
mechanical stirrer, thermometer, Dean-Stark trap and reflux
condenser. Allylamine (0,1 mole) is added to the reaction
vessel, and the mixture is heated at reflux while removing
- 15 -
bm:
-- 10783~1
the water as it is formed. After no more water is given
off, the reaction mixture is stripped of solvent under
reduced pressure to yield the desired product 1-(5- `
fluorothiazol-2-ylJ-3-allyl-5-allylamino-1,3-imidazolidin-
2-one as the residue
Exam~le 15
~ Preparation of 1-(5-Fluorothiazol-2-yl)-
3-allYl-5-~-chloroacetyloxy-l~3-imidaz~olidin-2-one
~ . . _._
1-(5-Eluorothiazol-2-yl)-3-allyl-5-hydroxy-1 ! 3~
imidazolidin-2-one (0.1 mole), ~-chloroacetyl chloride
(0,11 mole) and pyridine (0.11 mole) are charged into a
glass reaction vessel equipped with a mechanical stirrer
and thermometer. The reaction mixture is stirred for a
period of about 15 minutes and is then allowed to stand
for a period of about 2 hours. After this time water (100 ml~
and hexane ~30 ml) are added to the mixture. The organic
phase is then separated from the aqueous phase ana is
dried over anhydrous magnesium sulfate.` The dried solution
is then filtered and stripped of solvent under reduced
pressure to yield the desired product 1-(5-fluorothiazol-
2-yl)-3-allyl-5-~-chloroacetyloxy-1,3-imidazolidin-2-one
as the residue.
Example 16
. ~ . . ..
Preparation of 5-Iodothiazol-2-yl Isocyanate Dimer
2-Amino-5-iodothiazole (19.0 grams~ and a saturated
solution of phosgene in ethyl acetate ~200 ml) are charged
into a glass reaction vessel equipped with a mechanical
stirrer, thermometer and reflux condenser. The reaction
mixture is heated at reflux with stirring for a period of
about 3 hours. After this time the reaction mixture is
cooled and filtered to recover the desired product 5-
iodothiazol-2-yl isocyanate dimer~
- 16 -
bm:
`" 1078391
Example 17
Preparation of the Dimethyl Acetal of 2-[1-
Propargyl-3-(5-iodothiazol-~.-yl)llreido]acetaldehy_e
5-Iodothiazol-2-yl isocyanate dimer (17,0 ~rams),
benzene (70 ml) and the dimethyl acetal of 2-propargylamino- - -
acetaldehyde (13.5 grams) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer,
The reaction mixture is then stirred at room temperature for
a period of about one hour. After this time the reaction
mixture is filtered, and the filtrate is stripped of solvent
under reduced pressure, leavlng an oil. This oil is dissolved
in an ethanol-water mixture, and the solution is filtered,
The filtrate is then stripped of solvents under vacuum to
yield the desired product the dimethyl acetal of 2-[1-
propargyl-3-(5-iodothiazol-2-yl)ureido]acetaldehyde.
Example 18
Preparation of 1 (5-Iodothiazol-2-yl)-
3-propargyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-propargyl-3-(5-iodo-
thiazol-2-yl)ureido]acetaldehyde (10 grams), ethanol (80 ml),
water (80 ml) and concentrated hydrochloric acid ~8 ml) are
charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer and reflux condenser. The
reaction vessel is purged with nitrogen gas, and the reaction
mixture is heated at reflux with stirring for a period of
about 15 minutes. After this time the reaction mixture is
stripped of solvents under reduced pressure, and the residue
is dissolved in ethyl acetate. The resulting solution is
washed with saturated aqueous sodium bicarbonate and dried
over anhydrous sodium sulfate. The dried solution is then
filtered, and the filtrate is stripped of solvent to leave
the desired product 1-~5-iodothiazol-2-yl)-3-propargyl-5-
hydroxy-1,3-imidazolidin-2-one,
.
- 17 -
bm:
107~3S1
Exam~le 19
.
Preparation of 1-(5-Iodothiazol-2-yl)-3-propar~Yl-
5-~-chloroethylamino-1,3-imidazolidin-2-one
1-(5-Iodothiazol-2-yl)-3-proparg,yl-5-hydroxy-1,3-
imidazolidin-2-one (0.1 mole) and heptane (100 ml) are charged
into a glass reaction vessel equipped with a mechanical
stirrer, thermometer, Dean-Stark trap and reflux condenser.
~-Chloroethylamine (0.1 mole) is added to the reaction
vessel, and the mixture is heated at reflux while removing
the water as it is formed. After no more water is given off,
the reaction mixture is striPped of solvent under reduced
pressure to yield the desired product 1-(5-iodothiazol-2-yl)-
3-propargyl-5-~-chloroethylamino-1,3-imidazolidin-2-one as
the residue.
Example 20
. . .
Preparation of 1-(5-Iodothiazol-2-yl)-
-3-propargyl-5-propynoyloxy-1,3-imidazolidin-2-one
1-(5-Iodothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-
imidazolidin-2-one (0.1 mole), propynoyl chloride (0.11 mole)
and pyridine (0.11 mole) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer.
The reaction mixture is stirred for a period of about 15
minutes and is then allowed to stand for a period of about
2 hours. After this time water (100 ml) and hexane ~30 ml)
are added to the mixture. The organic phase is then separated
~rom the aqueous phase and is dried over anhydrous magnesium
sulfate. The dried solution is then filtered and stripped
of solvent under reduced pressure to yield the desired product
1-(5-iodothiazol-2-yl)-3-propargyl-5-propynoyloxy-1,3-
imidazolidin-2-one.
- 18 -
bm:
1~78391
Example 21
. .
Preparation of the Dimethyl Acetal of ~-[1-
Chloromethyl-3-(5-bromothiazol-2-Yl)ureido]acetaldehyde
5-Bromothiazol-2-yl isocyanate dimer (17.0 grams),
benzene (70 ml) and the dimethyl acetal of 2-chloromethyl-
aminoacetaldehyde (13.5 grams) are charged into a glass
reaction vessel equipped with a mechanical stirrer and ~ !
thermometer. The reaction mixture is then stirred at room
temperature for a period of about one hour. After this time
the reaction mixture is filtered, and the filtrate is stripped
of solvent under reduced pressure, leaving an oil. This oil
is dissolved in an ethanol-water mixture, and the solution
is filtered. The filtrate is then stripped of solvents under
vacuum to yield the desired product the dimethyl acetal of
2-[1-chloromethyl-3-(5-bromothiazol-2-yl)ureido]acetaldehyde.
-Example 22
~, _ -- . .
Preparation of 1- (5-Bromothiazol-2-yl)-
-3-chloromethyl-5-hydroxy-1,3-imidazolidin-2-one
Ir ~
The dimethyl acetal o~ 2-[1-chloromethyl-3-(5-
bromothiazol-2-yl~ureido~acetaldehyde (10 grams), e-hanol
(80 ml), water (80 ml) and concentrated hydrochloric acid
(8 ml) are charged into a glass reaction vessel equipped
with a mechanical stirrer, thermometer and reflux condenser.
The reaction vessel is purged with nitrogen gas, and the
~ reaction mixture is heated at reflux with stirring for a
- period of about 15 minutes. After this time the reaction
mixture is stripped of solvents under reduced pressure, and
the residue is dissolved in ethyl acetate. The resulting
solution is washed with saturated aqueous sodium bicarbonate
and dried over anhydrous sodium sulfate. The dried solution
- 19 -
bm:
1078391
is then filtered, and the filtrate is stripped of solvent to
leave the desired product l-(5-bromothiazol-2-yl)-3-chloro-
methyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 23
Preparation of 1- (5-Bromothiazol-2-yl)-3-chloromethyl-
_ 5-~-hydroxyethylamino-1,3-imidazolidin-2-one
1-~5-Bromothiazol-2-yl)-3-chloromethyl-5-hydroxy-
1,3-imidazolidin-2-one (0.1 mole) and heptane (100 ml) are
charged into a glass reaction vessel equipped with a
mechanical stirrer, thermometer, Dean-Stark trap and reflux
condenser. ~-Hydroxyethylamine (0.1 mole) is added to the
reaction vessel, and the mixture is heated at reflux while
removing the water as it is formed. After no more water is
given off, the reaction mixture is stripped of solvent under
reduced pressure to yield the desired product 1-(5- ~-
bromothiazol-2-yl)-3-chloromethyl-5-~-hydroxyethylamino- ~ -
1,3-imidazolidin-2-one as the residue.
Example 24 ~ -
Preparation of 1-(5-Bromothiazol-2-yl)-3-~-
chloroethyl-5-~-met_oxyacetyloxy-1,3-imidazolidin-2-one
l-(S-Bromothiazol-2-yl)-3-~-chloroethyl-5-hydroxy-
1,3-imidazolidin-2-one (0.1 mole), ~-methoxyacetyl chloride
(0.11 mole) and pyridine (0.11 mole) are charged into a glass
reaction vessel equipped with a mechanical stirrer and
thermometer. The reaction mixture is stirred for a period
o~ about 15 minutes and is then allowed to stand for a period
of about 2 hours. After this time water (100 ml) and hexane
(30 ml) are added to the mixture. The organic phase is then
separated from the aqueous phase and is dried over anhydrous
magnesium sulfate. The dried solution is then filtered and
stripped of solvent under reduced pressure to yield the
desired product l-(5-bromothiazol-2-yl)-3-~-chloroethyl-5-
~-methoxyacetyloxy-1,3-imidazolidin-2-one.
- 20 -
bm:
.`` ~.07a3~l .
Example 25 ~:
Preparation of 5-Methylsulfonyl-
thiazol-2-yl Isocyanate Dimer ::
A saturated solution of phosgene in ethyl acetate
(200 ml) is charged into a glass reaction vessel e~uipped
with a mechanical stirrer~ thermometer and reflux candenser, :`:`
2-Amino-5-methylsulfonylthiazole (0.1 mole) is added with
stirring, After the addition is completed~ the reaction
mixture is heated at reflux for a period of about one hour.
After this time the mixture is cooled~ and the solid product
formed is recovered by filtration. The solid is then dried
to yield the desired product 5-methylsulfonylthiazol-2 xl
isocyanate dimer~
Exam~le 26
Preparation of.the-Dimethyl Acetal of 2~ Bromoethyl-
--~3-(5-methylsulfonylthiazol-2-Yl)ureido]acetaldehvde
. _ . ~ . . _ _ .
5-Methylsulfonylthiazol-2-yl isocyanate dimer (n~l
mole) ! the dimethyl acetal of 2-~-bro~oethylami:noacetaldehyde
~0.2 molel and benzene UOO ml) are çharged into a glass
reaction vessel equipped with a mechanical stirrer and ':
thermometer, The reaction mixture is stirred at ambient
temperatures for a period of about hour, After this time ;~
the reaction mix~ure is filtered, and the filtrate is
stripped of solvent to yield the desired product the dimethyl
acetal of 2-Tl-~-bromoethyl-3-(5-methylsulfonylthiazol-2-yl~
~reido]-acetaldehyde as the residue,
~ .. .. ..
: Example-27
Preparation of 1-(5-Methylsul~on~lthiazol-
2-yll.-3-~-bromoethyl-5-hydrox~ 3-imidazolidin-2-o-ne
30 The dimethyl acetal of 2-~ -bromoethyl-3-(.5-
methylsulfonylthiazol-2-yl)ureido]acetaldehyde (15 grams),
21
bm:
1078391
water (200 ml), methanol (200 mlJ and concentrated
hydrochloric acid (10 ml) are charged into a glass reaction
vessel equipped with a mechanical stirrer, thermometer and
reflux condenser. The reaction mixture is heated at reflux
for a period of about 15 minutes. After this time the
reaction mixture is stripped of solvents under reduced
pressure, leaving a residue. This residue is recrystallized
to yield the desired product l-(5-methylsulfonylthiazol-2-yl)-
3-~-bromoethyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 28 ;
Preparation of 1-(5-Methylsulfonyl-
thiazol-2-yl)-3-~-bromoethyl-
5-methoxymethylamino-1,3-imidazolidin-2-one
1-(5-Methylsulfonylthiazol-2-yl)-3-~-bromoethyl-
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole) and heptane
(100 ml) are charged into a glass reaction vessel equipped
with a mechanical stirrer, thermometer, Dean-Stark trap and
reflux condenser. Methoxymethylamine (0.1 mole) is added to
the reaction vessel, and the mixture is heated at reflux
while removing the water as it is formed. After no more
water is given off, the reaction mixture is stripped of
solvent under reduced pressure to yield the desired product
1-(5-methylsulfonylthiazol-2-yl)-3-~-bromoethyl-5-
methoxymethylamino-1,3-imidazolidin-2-one as the residue.
Example 29
Preparation of 1-(5-Methylsulfonylthiazol-2-yl)-
3-~-bromoethvl-5-benzoyloxv-1,3-imidazolidin-2-one
1-(5-Methylsul~onylthiazol-2-yl)-3-~-bromoethyl-
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), benzoyl chloride
(0.11 mole) and pyridine (0.11 mole) are charged into a glass
:'
; - 22 -
bm:
1078391 ~ !
reaction vessel equipped with a mechanical stirrer and
thermometer. The reaction mixture is stirred for a period of
about 15 minutes and is then allowed to stand for a period
of about 2 hours. After this time water (100 ml) and hexane
(30 ml) are added to the mixture. The organic phase is then
separated from the aqueous phase and is dried over anhydrous
magnesium sulfate. The dried solution is then filtered and
stripped of solvent under reduced pressure to yield the
desired product 1-(5-methylsulfonylthiazol-2-yl)-3-~-
bromoethyl-5-benzoyloxy-1,3-imidazolidin-2-one as the residue. - -
The new compounds of this invention are ;
particularly valuable for weed control because they are
toxic to many species 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 sufficient for
good control of a light infestation of weeds growing under
adverse conditions, the application of ten pounds or more
of an active compound per acre may be required for good
control of a dense infestation of hardy perennial weeds
growing under favorable conditions.
The herbicidal toxicity of the new compounds of
this invention can be demonstrated by the following
established testing techniques known to the art, pre- and ^-
post-emergence testing,
- 23 -
bm:
~078391
The herbicidal 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
experiments 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, 1-(5-
bromothiazol-2-yl~-3-methyl-5-hydroxy-1,3-imidazolidin-2-
one (product of Example 3), 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, the soil containers were plared 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 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,a = moderate injury, 5,6 = moderately severe iniury,
7,8,9 = severe injury and 10 = death. The effectiveness of
these compounds is demonstrated by the data in Table I.
- 24 -
bm:
107839i
-TABLE I - ,
Injury Rating
Rate in
Weed Species lbs/acre: 8 4 1 1/4 1/8 1/16
Yellow Nutsedge 2 2 0
Wild Oats 10 10 10 6 0 0
Jimsonweed 5 5 4 3 0 0
Velvetleaf 10 10 10 9 0 0
Johnsongrass 10 10 7 4 0 0
Pigweed 10 10 10 10 10 0
Wild Mustard 10 10 10 10 10 6
Yellow Foxtail 10 10 9 8 4 2
Barnyardgrass 10 10 10 2 0 0
Crabgrass 10 9 7 3 0 0
Cheatgrass 10 10 10 3 0 0
Morningglory 10 10 10 9 0 0
Sprangletop -- -- -- 6 0 0
Bindweed -- -- -- 0 0 0
Quackgrass -- -- -- 10 0 0 .
The herbicidal activity of the compounds of this
invention was also demonstrated by experiments carried out
; for the post-emergence control of a variety of weeds. In ~.
. these experiments the test compound, 1-(5-bromothiazol-2-yl)-
-~ 3-methyl-5-hydroxy-1,3-imidazolidin-2-one (proauct of Example --^
3), was formulated as an a~ueous emulsion and sprayed at the
indicated dosage on the foliage of the weeds that had
~; attained a prescribed size, After spraying, the plants were
~" placed in a greenhouse and watered daily or more frequently,
Water was not applied to the foliage of the treated plants.
The severity of the injury was determined 14 days after
- 25 -
bm:
107839~
after treatment and was rated on the scale of from 0 to 10 '-
heretofore described. The effectiveness of these compounds
is demonstrated by the data in Table II.
TABLE II
. Injury Rating
Rate ln
Weed Species lbs/acre: 8 2 1 -:
Pigweed 10 10 10 .
Crabgrass 10 5 4
Barnyardgrass 10 10 10 -~
Jimsonweed 10 10 10 ::~
Wild Mustard 10 10 10
Johnsongrass 10 10 10
Morningglory 10 10 10
Bindweed 10 10 10 :
Yellow Foxtail 10 10 10
Yellow Nutsedge 4 5 o
Wild Oats 10 10 10
bm:
