Note: Descriptions are shown in the official language in which they were submitted.
6~27~6
l-THI.~DIAZOLYL-5~ALKY ~ lINO, ARYLAMINO
'AND CYCLOIMINO 'SUB'STITUTED'IMIDAZOL`IDINONES
.~
This invention r~lates to new compositions of matter
and more specifically relates to new chemical compounds of
the formula
1 4
N - R
N - N
ll ll / CH CH2
R - C C - N
S \ C ~ J _ R2 i- -
O
wherein Rl is sel~cted from the group consisting o~ alkyl,
cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl ~ .
and alkylsulfinyl; R2 is selected from thé group consisting
o~ alkyl, alkenyl, haloalkyl and
R5
~ C - C _ CH
R
wherein R5 and R6 are each selected from the group consisting
of hydrogen and alkyl; and R3 and R4 are each selected from
the group consi~ting o~ hydrogen, alkyl of up to 18 carbon -
. .
atoms~ alkenyl, haloalkyl, hydroxyalkyl, alkoxyal~yl, cyclo-
alKyl and ~:
t5-n) ..
~ ~CN2)m--(/ \
Xn ' ..
wherein X is selected from the group consisting of alkyl,
alkoxy, halogen, haloalkyl, alkylthio, nitro and cyano; n
'
27~6
is an int:eger from 0 to 3; and m is the integer a or 1, pro-
vided that a maximum of one of R3 and R4 is an aromatic moiety;
or R3 and R4 together with the nitrogen atom can form a cyclo-
imino moiety containing from 2 to 6 carbon atoms.
The compounds of the present invention are unex-
pectedly useful as herbicides.
In a preferred embodiment of this invention Rl
is selected from the group consisting of alkyl of up to 18
carbon atoms, cycloalkyl of from 3 to 7 carbon atoms, lower
alkenyl, lower chloroalkyl, lower bromoalkyl, trifluoromethyl,
lower alkoxy, lo er alkylthio, lower alkylsulfonyl and lower
alkylsulfinyl; R is selected from the group consisting of
lower alkyl, lower alke~yI,~lower haloalkyl and propargyl;
and R3 and R4 are each selected from the group consisting
of hydrogen, lower alkyl, lower alkenyl, lower haloalkyl,
lower hydroxyalkyI, lower alkoxyalkyl, cycloalkyl of from
3 to 7 carbon atoms and
(S-n)
~ (C~2)m~
Xn
wherein X is selected from the grQUp 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, provlded that a maxlmum of one of R3
and R4 is an aromatic moiety; or R3 and R4 together with the
nitrogen atom can form a cycloimino moiety containing from
2 to 6 carbon atomsO
The term "lower" as used herein designates a straight
or branched carbon chain of up to six carbon atoms.
--2--
~a)627~6
The compounds of t~e present invention can be pre-
pared ~y reacting a compound of the formula
OH
N N
~ / CH - CM2
R - C C - N
S \ C - I ~ - R2 .
O (II)
whexein Rl and R2 are as heretofore described, with an amine
or cyclic imine of the ormula
R3
1 4
H ~ N - R (III)
wherein R3 and R4 are as heretofore described. This reaction
,. ... .. ... . .
can be effected by combining the compound of formula II with ~ :
an a~ou~ equimolar amount or excess molar amount o~ the com- -
pound of formula III in an inert organic reaction medium,
such as heptane or toluene, and then heating the reaction
mixture, with stirring, at its reflu~ temperature and azeo-
tropically 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 i~ soluble
therein. ~he product can then be purified by conventional
means such as recrystallization and the like.
.
: The compounds of formuIa II can be readily prepared
by heating a compound of the formula
N - N 7
OR
R - C C - N C - N - CH2 - CH
S H O R2 ~8 (IV)
wherein Rl and R2 are as heretofore described and R7 and
R8 are methyl or ethyl, in a dilute, aqueous, acidlc reaction
.
.. ': ", .':' "
-3~
'',~' "', ' , '' . ' ,. .' """ . ." ' '' '' ' ' "',': ~'.' , " ' ," .. " . ' ' , '.
~6Z7~6
medium for a period of a~out 10 to a~out 60 minutes. Tem-
peratures of from a~out 7QC to t~e reflux temperature of
the reaction mixture can ~e utilized. The reaction medium
can comprise a dilute, aqueous inorganic acid such as hydro-
chloric acid at a concentra~ion of from about 0.5 to about
5 percent. Upon completion of the reaction the desired product
can be recovered as a precipitate by cooling the reaction
mixture. This product can be used as such or can be further
puri~ied by conventional means such as recrystallization
and the like.
The compounds of formula IV can be prepared by
reacting a molar amount o an isocyanate dimer of the formula
_ N N
L = C = N - C C Rl~ ~V)
wherein Rl is as heretofore described, with about two molar
amounts of a dimethyl acetal of the formula
oR7
H - N - CH2 - CH
R OR~ (VI)
wherein R~, R7 and R8 are as heretofore described. This
reaction can be effected by heating a mixture of the iso-
cyanate dimer and the acetal in an inert organic reaction
medium such as benzene at the reflux temperature of the
reaction mixture. ~eating at reflux can be continued for
a period o from about 2 to about 30 minutes to ensure com-
pletion of the reaction. After this time the desired product
can be recovered upon evaporation of the reaction medium and
can be used as such or can be further purified by standard
techniques in the art.
:
- :
_4_ ~
1~6;~7~6
The isocyanate dimer of formula V can be prepared
by reacting a thiadiazole of the formula
, N N
1 11 11 ' ~ -
R - C / ~ N~2
S (VII)
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
acetate, 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 remove unreacted phosgene. The desired ~ - -
product can then be reco~ered by filtration, i~ formed as
a precipitate, or upon evaporation of the organic solvent
used i~ soluble therein. This product can be used as such
or can be further puri~ied as desired.
Exemplary thiadiazoles of formula VII use~ul for
preparing the compounds of the present Lnventlon are S-methyl~
20~ 2-amino-1,3,4-thiadiazole, 5-ethyl-2-amino-1,3,4-thiadiazole,
,
S-propyl-2-amino-1~,3,4-thiadiazole, 5-t-hutyl-2-amino-l,3,4-
thiadiazole, 5-ally~ 2-amino-1,3,4-thiadiazole, 5-pent-3-
enyl-2-~mino-1,3,4-thiadiazole, 5-~-chloroethyl-Z-amino-1,3,4-
thladiazole, S-~-chloropropyl-2-amino-l,3,4-thiadiazole,
5-trifluoromethyl-2-amino-1,3,4~thiadiazole, S-methoxy-2- ~ ;
. .
amlno-1,3,4-thiadiazole, 5-ethoxy-2-amino-1,3,4-thiadiazole,
5-propoxy-2-amino-1,3,4-thiadiazole, 5~-butyloxy-2-amino-1,3,4-
thiadiazole, 5-hçxyloxy-2-amino-1,3,4-thiadiazole, 5 methylthio-
:, . .
2-amino-1,3,4-thiadiazole, 5-ethylthio-2-amino-1,3,4-thia-
diazole, 5-propylthio-~-amino-1,3,4-thiadiazole, 5-butylthio-
2-amino-1,3,4-thiadiazole, 5-methylsulfonyl-2-amino-1,3,4-
_5_ `' '"
~6;2706
thiadiazole, 5-ethylsulfonyl-2-amino-1,3,4-thiadiazole, 5-
butylsulfonyl-2-amino-1,3,4 thiadiazole, 5-methylsulfinyl-
2-amino-1,3,4-thiadiazole, 5-ethylsulfinyl-2-amino-1,3,4-
thiadiazole, 5-propylsulfinyl-2-amino-1,3,4-thiadiazole,
5-butylslllfinyl-2-amino~1,3,4-thiadiazole and the like.
Exemplary suitable acetals of formula VI 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-propylaminoacet-
aldehyde, the dimethyl acetal of 2-butylaminoacetaldehyde,
the dimethyl acetal of 2-pentylaminoacetaldehyde and the
dimethyl acetal of 2-hexylaminoacetaldehyde.
Exempla~y suitable amines of formula III are methyl-
amine, ethylamine, propylamine, butylamine, isopropylamine,
sec-butylamine, t-butylamine, pentylamine, hexylamine, heptyl-
amine, octylaminer decylaminet dodecylamine, hexadecylamine,
octadecylamine, dioctylamine, didodecylamir.e, dioctadecylamine,
dimethylamine, diethylamine, dipropylamine,~dibutylamine,
dihexylamine,. N-methyl-N-ethylamine, N~ethyl-N-hexylamine,
20. cyclopropylamine, cyclobutylamine, cyclopentylamina, cyclo-
hexylamine, cycloheptylamine, ~-chloroethylamine, Y-bromo-
propylamine, ~-chlorobutylamine, ~ dichlorobutylamine,
allylamine, but-3~enylamine, pent-4-enyIamine, hex-4-enylamine,
methoxymethylamine, methoxyethylamine, ethoxymethylamine,
methoxypropylamine, ethoxypropylamine, phenylamine, 3-chloro- :. .
phenylamine, 4-bromophenylamine, 2-methoxyphenylamine, 4-
trifluoromethylphenylamine, 3-methylthiophenylamine, 4-nitro- . .
phenylamine, 4-cyanophenylamine, 3,4-dichlorobenzylamine/: :
2-methyl-4-chlorobenzylamine, 3,4,5 trichlorophenylamine, :
N-methyl-N-(3,4-dibromoph~nyl)amine, ethylenimine, trimethylen-
imine, tetramethylenimine, pentamethylenimine, hexamethylen- .
imine and the like..
'~
P627(~6
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 S-Trifluoromethyl-
1,3,4-thiadiazol~2-y~ Isoc~_nate 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-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 precipitate. The reaction mixture was then
purged with nitrogen gas to remove unreacted phosqene. The
purged mixture was filtered to recover 48 grams of a white
solid. This solid was recrystallized from dimethyl formamide
to~yield the desired product 5-trifluoromethyl-1,3,4-thiadiazol-
2-yl isocyanate dimer.
: . ~ . '
Preparation of the Dimethyl Acetal of 2-rl-Methyl-~-(5-
~ A mixture of 5-trifluoromethyl-1,3r4-thiadiazol-
; 2-yl isocyanate dimer t9.5 grams~, the dimethyl acetal of
2-methylaminoacetaldehyde (5.8 grams) and benzene (60 ml)
are charged 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 lS minutes. After
this ~im~ the mixture is stripped of benzene under reduced
pressure to yield a solid product as the residue. Thls product
is recrystallized from heptane to yield the desired product
the dimethyl acetal of 2-[1-methyl3-(5-tri~luoromethyl-1,3,4-
thiadiazol-2-yl)ureido]acetaldehyde having a melting point
o~ 101 to 102C.
-7-
~6;Z7~6
Example 3
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
-2~ 3~-methyl-5-hydroxy-1,3-imidazo-lidin-2-one
The dimethyl acetal of 2-~1-methyl-3-(5-trifluoro-
methyl-1,3,4-thiadiazol-2-yl)ureido]acetald~ehyde (15 grams),
water (400 ml) and hydrochloric acid (4 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 filtrate was
cooled, resulting in the formation of a precipitate. The
precipitate was recovered by filtration, was dried and was
recrystalIized from an ethyl acetate-hexane mixture to yield
the de ired product l-(5-trifluoromethyl-1,3,4-thiadiazol-
2-yI)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one having a
melting point of 136 to 138C.
Example 4
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
2-yl)-3 methyl-5-t-butylamino-1,3-imidazolidin-2-one
1-(5-Tri1uoromethyll,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin2-one (13.1 grams) and heptane
(100 ml) were charged into a glass reaction vessel equipped
with a mechanical stirrer, thenmometer, Dean-Stark trap and
:'
reflux condenser. t-Butylamine (7.0 grams) was added to
the reaction vessel, and the mixture was heated at re~lux
whlle removing the water as it was formed. After no more
water was given off, the reaction mixture was cooled, resulting
in the precipitation of a crystalline solid. The solid was
recovered by filtration and was recrystallized from heptane
to yield the desired product 1-(5-trifluoromethyl 1, 3 r 4~
thiadiazol-2-yl)-3-methyl-5-t butylamino-1,3-imidazolidin-
2-one having a melting point of 113 to 115C~
''
~627~6
Example 5
Pxeparation of 5-t-Butyl-
1,3~4-thiadiazol-2-yl Isoc~anate Dimer
A saturated solution of phosgene in ethyl acetate
tlOO 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 for a period of about 16 hours resulting in the forma-
tion of a precipita~e. The reaction mixture was then purgedwith ni~rogen gas to remove unreacted phosgene. The purged
mixture was then filtered to recover the desired product
5-t-butyl-1,3,4-thiadiazol-2-yl isocyanate dimer as a solid
having a melting point of 261 to 263C.
Example 6
Preparation of the Dimethyl Acetal of 2-~1-Methyl- ~ :
3-(5`-t-butyl-1,3,4-thiadiazol-2-yl)ureido]acetaldehyde
A mixture of 5~t-butyl-1 t 3,4-thiadiazol-2-yl iso-
cyana~e dimer (6 grams), the dimethyl acetal of 2-methylamino-
acetaldehyde (3.9 grams) and benzene (50 ml~ were charged
into a glass reaction flask equipped with a mechanical stirrer
and reflux condenser. The reaction mixture was heated at
reflux, with stirring or a period of about 5 minutes. After
this time the reaction mixture was stripped of ben~ene to
yield an oil which solidified upon standing. The xesulting ~ -
solid was then recrystallized from pentane to yield the desired
product the dimethyl acetal of 2-[1-methyl~3-(5-t-butyl-1,3,4-
- thiadiazol-2-yl)ureido~acetaldehyde having a melting point
o~ 8~ ~o 82C.
E ~ ;
Preparation of 1-(5-t-Butyl-1,3,4-thiadiazol-
The dimethyl acetal of 2~ methyl3-(5-t-butyl-
1,3,4-thiadiazol-2-yl)ureido]acetaldehyde (16 gram~),
_g_
,
, . ~ ,:, . . . . . . .
~6~
concentrated hydrochloric acid (10 ml) and water (500 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 minu~es. The reaction mixture was filtered while hot,
and the filtrate was then cooled, resulting in the formation
of a precipitateO 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 o~ 133 to 134C.
Exam~e 8
Preparation of 1-(5-t-But~l-1,3,4-thiadiazol-2-yl)-
3-methyl-5-hexylamino-1,3-imidazolidin-2-one
.
1-(5-t-Butyl-I,3,4-thiadiazol-2-yl)-3-methyl-5-
hydroxy-1,3-imidazolidin-2-one (13.4 grams), hexylamine (6.0
grams) and heptane (100 ml) were charged into a glass reaction
vessel equipped with a mechanical stirrer, thermometer, reflux
condenser and Dean-Star~ trap The reaction mixture was
heated at reflux, and the water of reaction was removed as
- it was formed by azeotroping. After no more water was given
o~f, the reaction mixture was stripped o solvent to yield
an oil as the residue~ The oil was su~jected to vacuum,
whereupon it solidified. The resulting solid was then recrys-
tallized from hexane to yield the desired product 1-(5-t- -
butyl-1,3,4-thiadiazol-2-yi)-3-methyl 5-hexylamino-1,3-imid-
azolidin-2-one having a melting point of 62 to 64C.
~ ' . :
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
2-~1)-3-methyl-5-hexylamino-1,3-imidazolidin-2-one
1-(5-Trlfluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2 one (13.4 grams), hexylamine
(6.0 g~ams) and heptane (100 ml) were charged into a glass
.
--10--
, , ~ . , , , . . . . . . ~ .. .. ... ........ .... . . . . . . . .. .... . ... . . . . . . .. . ..
~L~6;~i:7~)6
reaction vessel equipped with a mechanical stirrer, thermometer,
reflllx condenser and Dean~Stark trap. ~he reaction mixture
was heated at reflux, and the water of reAction was removed
as it was formed by azeo~ropingO After no more water was
given off, the reaction mixture was stripped of solvent to
yield an oil as ~he residue. This oil was dissolved in pentane
~3~
and passed through a Florex column. The eluant was stripped
o~ solvent and dried under vacuum to ~ield the desired product
1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl~-3-methyl-5-hexyl-
amlno-1,3-imidazolidin-2-one.
Example 10
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
2--y1)-3-methyl-5-anilino-1,3-imidazolidin-2-one
1-(5-Trifluoromethyl-1,3,4-thiadiazol~2-yl-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (13.4 grams), hRptane (100
ml) and aniline (6 ml) were charged into a glas~ reaction
vessel equipped with a mechanical stirrer, thermometer, reflux
condenser and Dean-Stark trap. The reaction mixture was
heated at reflux for a period of about 8 hours, and the water
of reaction was removed as it was formed. After this time
the reaction mixture was stripped o~ so~vent leaving a solid
re~idue. This solid was recrystallized from isopropanol ~ -
tO yield the desired product 1-(5-trifluorome~hyl-1,3,4-thia- ;
diazol-2-yl)-3-methyl5-anilino-1,3-imidazolidin-2-one having
a melting point o~ 142 ~o i44C.
Example 11
Preparation of 1-(5-Tri~luoromethyl-1,3,4-thiadiazol
1)-3-methyl-5-benzylamino-lr3-imidazolidin-2-one
1-~5-Trifluoromethyl-1,3~4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one ~8 grams), benzylamine (4.5
grams) and heptane ~100 ml~ were charged into a glass reaction
vessel equipped with a mechanical stirrer, thermometer, reflux
condenser and Dean-Stark trap. The reaction mixture was
.",,~." . . . .
696~7~6
heated at re~lux, and the water of reaction removed as
it was formed. After no more water was formed, the mixture
was cooled, resulting in the formation of a solid productO
This solid was recovered ~y filtration to yield the desired
product l-(5-trifluoromethyl~1,3,4-thiadiazol-2-yl)-3-methyl
5-benzylamino-1,3-imidazolidin-2-one having a melt point
o~ 97 to 99C.
Example 12
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-
10yl)-3-meth~yl-5-~-hydrox~ ylamino-1,3-imidazolidin-2-one
1-(5-Trifluoromethyl 1,3,4 thiadiazol-2-yl)~3-
methyl-5-hydroxy-1~3-imidazolidin-2-one (8 grams), ~-hydroxy-
ethylamine (5 grams) and benzene (75 ml) were charged into -~
a glass reaction flask equipped with a mechanical stirrer,
thermometer, reflux condenser and Dean-Stark trap. The reaction
mixture was heated at reflux, and the water of reaction was
removed as it was formed. After no more water was given
off, the reaction mixture was stripped of sol~ent to yield
an oil. This oil was filtered through ~elite to yield the
desired product 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-~-hydroxyethylamino-1,3-imidazolidin-2-one.
Preparation of 1-(5-Trifluorome~hyl-1,3,4-thiadiazol~
; 2-Yl)-3-meth~1-5-diethYlamino-1,3-imidazolidin-2-one
.
1-(5-Trifluoromethyl 1,3,4-thiadiazol 2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (8 grams), diethylamine (3
grams) and benzene ~50 ml~ were charged into a glass reaction
flask equipped with a mechanical stirrer, thermometer, reflux
condenser and Dean~Starl: trap. The reaction mixture was
then heated at reflux, and the water of reaction was removed
as it wa~ formed. After no more water was given off, the
rea~tion mixture was stripped of solvent, leaving an oil.
rrhi~ 0~ 1 was dissolved in pentane, and the resulting solution
.
- E~'l
~12-
Z7~
was passed through a ~lorex column. The eluant was then
stripped of pentane, leavi.ng an oil~ This oil was dried
under vacuum to yield the desired product l-(5-trifluoromethyl-
1,3,4-thiadiazol-2-yl)~3-methyl-5-diethylamino-1,3-imidazoli-
din-2-one.
. Examl~le 14
Preparation of 1-(5-t-Butyl-1,3,4~thiadiazol-2-yl)-
3 ~ thylamino-1,3-imidazolidin-2-one
1-(5-t-Butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-
hydroxy-1,3-imidazolidin-2-one t8 grams), ~-hydroxyethylamine
(3 grams) and benzene (75 ml) were charged into a glass reac-
tion vessel equipped with a mechanical stirrer, thermométer,
reflux condenser and Dean-Stark trap. The reaction mixture .~
was heated at reflux, and the water of reaction was removed -
as it was formed. After no more water evolved, the reaction ..
mixture was stripped of benzene, leaving a solid product. ~ ~
This solid was recrystallized from ethyl acetate to yield :
the desired product 1~(5-t-butyl-1,3,4--thiadiazol-2-yl) --
3-methyl-5-~-hydrcxyethylamino-1,3-imiclazolidin-2-one having
a melt point of 128 to 130C.
Example 15
Preparation of 1-(5-Trifluoromethyl-
1,3,4-thiadiazol-2-yl)-3-methyI-
5-( methoxyisopropvlamino)-1,3-imidazolidin-2-one
1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (8 grams), 2-methoxyisopropyl-
amine (5 grams) and benzene (70 ml) were charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer,
re~lux condenser and Dean-Stark trap. The reaction mixture
was heated at reflux, and the water of reaction was removed
as it was formed. A~ter no more water was given off, the
reactio~ mixture was stripped of sol~ent, leaving an oil. .
This oil was filtered through ~elite to yield the desired ~:
~ -13- i
product l-(5-trifluoromethyl~1,3,4-thiadiazol-2-yl)-3-methyl-
5-(2-methoxyisopropylamino)-1,3-imidazolidin-2-one.
Example_16
Preparation of S-Hexyl-1,3,4-
thiadiazol-2-yl Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
(100 ml) is charged into a glass reaction vessel equipped
with a mechanical s~irrer. A slurry of 5-hexyl-2-amino-1~3,4-
thiadiazole (40 grams) in ethyl acetate (300 ml) is added
to the reaction vessel, and the resulting mixture is stirred '
for a period of about 16 hours, resulting in the formation
of a precipitate. The reaction mixture is then purged with
nitrogen gas to remo~e unreacted phosgene. The purged mixture
LS then iltered to recover the precipitate. The precipitate ' '
is then recrystallized to yield the desired product 5-hexyl- '
I,3,4-thiadiazol-2-yl isocyanate dimer.
~ . -
Preparation o the Dimethyl Acetal of 2~ Ethyl-
3-~5-hexvl-1,3,4-thiadiazol-2-vl)ure~do]ace~ald`ehvde
; A mixture of 5-hexyl-1,3,4-thiadiazol-2-yl isocyanate
~ ~ dimer (0.05 mole), the dimethyl acetal of 2-ethylaminoacet-
.
aldehyda (0.1 mole~ and benzene (60 ml) are charged into
~a glass reaction vessel equipped with a mechanical stirrer ~=
and re~lux-condenser. The reac~ion mi~ture is heated at
reflux ~or a perLod of about 15 minutes. After this time
the mixture is stripped of benzene under redùced pressure
to yield a solid product a~ the residue. The residue is " ~'
then recrystallized to yield the desired product the dimethyl
acetal of 2~ ethyl-3-(5-hexyl-1,3,4 thiadiazol-2-yl)ureido3~
3Q acetaldehyde. ;
;
'
~6Z7~6
Example 18
Preparation of 1-~5~Hexyl-1,3~4-thiadiazol-
2-vl) 3-e~hvl-5-hvdroxv-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-ethyl-3-(5-hexyl-1,3,4-
thiadiazol-2-yl)ureido~acetaldehyde (15 grams), water (400 ml)
and hydrochloric acid (4 ml) are charged in~o a glass reaction
vessel equipped with a mechanical stirrer, thermometer and
re~lux condenser. The reaction mixture is heated at re1ux
for a period of about L5 minutes. The reaction mixture is
then filtered while hot, and the iltrate is cooled to form
a precipitate. The precipitate is recovered by filtration,
is dried and is recrystallized to yield the desired product
1-(5-hexyl-1,3,4-thiadiazol-2-yl~-3-ethyl-5-hydroxy-1,3-imid-
azolidin-2-one.
Preparation of 1-(5-Hexyl-1,3,4-thiadiazol-2-yl)-
3-ethYl-5-allYlamino-1,3-imidazolidin-2-one
1-(5-Hexyl-1,3,4-thiadiazol-2-yl)-3-ethyl-$-hydxoxy-
1,3-1midazolidin-2-one (0.1 mole), allyl amine (Ooll mole)
- and benzene (100 ml) are charged into a glass,reactLon vessel
equipped with a mechanical stirrer, thermometer, reflux con-
denser and Dean-Stark txap. The reaction mixture is heated
at re~lux, and the water of reaction is remo~ed as it is
formed. After no more water is formed, the reaction mixture
is stripped of solvent under reduced pressure to yield the
desired product 1-(5-hexyl-1,3,4-thiadiaæol~2-yl~-3-ethyl-
5-allylamino-1,3-imidazolidin-2-one as the residue~
_a~æ~
Preparation of 5-Methoxy-
1,3,4-thiadia-zol-2-yl Isocyanate Dimer
A saturated solution o~ phosgene in ethyl acetate -
(100 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry of 5-methoxy-2-amino-
'
-lS-
. . .
~6;2~
1,3,4-thiadiazole (40 grams) in ethyl acetate (300 ml) is
added to the reaction vessel, and the resulting mixture is
stirred for a period of about 16 hours, resulting in the
formation of a precipitate. The reaction mixture is then
purged with nitrogen gas to remove unreacted phosgene. The
purged mixture is then filtered to recover the precipitate.
The precipitate is then recrystallized to yield the desired
produc~ 5-methoxy-1,3,4-thiadiazol-2-yl isocyanate dimer. -
Example 21
Preparation of the Dimethyl Acetal of 2-[1-Ethyl-3- ~ -
(5-methoxy-~1,3,4-thiadiazol-2-~l)ureido]acetaldehyde -
A mixture of 5-methoxy-1,3,4-thiadiazol-2-yl iso-
cyanate dimer (0.05 mole), the dimethyl acetal of 2-ethyl-
aminoacetaldehyde (0.1 mole) and benzene (60 ml) are charged
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 minutec;. Ater this time
the mixture is strippad of benzene under reduced pressure
to yield a solid product as the residue~ The residue is
then recrystallized to yield the desired product the dimethyl
acetal of 2-Cl-ethyl-3-(5-methoxy-1,3,4-thiadia~ol-2-yl)- :~
ureido]acetaldehyde. ~ ;~
Preparation of 1-(5-Methoxy-1,3,4-thiadiazol-
The dimethyl acetal of 2-~1-ethyl-3~(5-methoxy- ~ -
1,3,4-thiadiazol~2 yl)ureido~acetaldehyde (15 grams), water
(400 ml) and hydrochloric acid (4 ml) are charged into a
glass reaction vessel equipped with a mechanical stirrer, ~-
3a thermometer and reflux condenserO The reackion mixture is
heated at reflux for a period of about 15 minutes. The reac-
tion mixture is then filtered while hot, and~the filtrate
is cooled to form a precipitate. The precipitate is recovered `
,.
' .
-16-
~0162~
by filtration, is dried and is recrystallized to yield the
desired product 1-(5-methoxy-1,3,4-thiadiazol-2-yl)-3-ethyl-
5-hydroxy-1,3-imidazolldin-2-one.
Example 23
Preparation of 1-(5-Methoxy~1,3,4-thiadiazol-2-yl)-
3 ethYl-5-cyclopro~vlamino-1,3-imidazolidin-2-one
,~, .....
1-(5-Methoxy-1,3,4-thiadiazol-2-yl)-3-ethyl-5-
hydroxy-1,3-imidazolidin-2-one ~O o l mole), cyclopropylamine
(0.11 mole) and benzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer,
reflux condenser and Dean-Stark trap. The reaction mixture
is heated at reflux, and the water of reaction is removed
as it is formed. After no more water is formed, the reaction
mixture is stripped of solvent under reduced pressure to
yield the desired product l-(5-methoxy~1,3,4-thiadiazol-2-yl)-
3-ethyl-5-cyclopropylamino 1,3~imidazolidin-2-one as the
residue.
xample 24
Preparation of 5-Methylthio-
A saturated solution of phosgene in ethyl acetate
(100 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer~ A slurry of 5-methylthio-2-amino-
1,3,4-thiadiazole (45 grams) in ethyl acetate (300 ml3 is
added to the reaction vessel r a~d the resulting mixture is
stirred for a period of about 16 hours, resulting in the
formation of a precipitate. The reaction mixture is then
purged with nitrogen gas to remove unreacted phosgene. The
purged mixture is filtered to recover the precipitate. The
precipitate is then recrystalli ed to yield the desired product
5~methylthio-1,3,4-thiadiazol-2-yl isocyanate dimer.
'':~, '
-17-
6;2~06
Example 25
Preparation of the Dimethyl Acetal of 2~ Propyl-3-
~5-methylthio-1,3,4-thiadiaæol-2-yl)ureido]acetaldehyde
A mixture of 5-methylthio-1,3,4-thiadiazol-2-yl
isocyanat~ dimer (0.05 mole), the ~imethyl acetal of 2-propyl-
aminoacetaldehyde (0.1 mole) and benzene (60 ml) are charged
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 minutesO After this time
the mixture is stripped of benzene under reduced pressure
to yield a solid product as the residue. The residue is
then recrystallized to yield the desired product the dimethyL
acetal of 2~ propyl-3-(5-methylthio 1,3,4-thiadiazol-2-yl)-
ureido]acetaldehyde. ~ '
Example ?6
Preparation o 1-(5-Methylthio-1,3,4-thiadiazol-
2-yl)-3-propyl-5-hydroxy-1,3'-imid'azol'i'd'in'-2'-one
~he dimethyl acetal of 2-[1-propyl-3-(5-methylthio- ~;
I,3,4-thiadiazol 2-yl)ureido~acetaldehyda (15 grams), water
~400 ml) and' hydrochloric acid (~ ml) are charged into a
glass reaction ve~sel equipped with a mechanical stirrer,
thermometer and reflux condenser. The reaction mixture i~
heated at re~lux ~or a pexiod of about 15 minutes. The reac-
tion mixture is then filtered while hot, and the filtrate
is cooled to form a precipitate. The precipitate is recovered
by filtration, is dried and is recrystallized to yield the
desired product 1-(5-methylthio-1,3,4-thiadiazol-2-yl~ 3-
propyl-5-hydroxy-1,3-imidazolidin-2-one.
~ ~.
30Preparation of 1-(5-Methylthio-1,3,4-thiadiazol-2-yl)~
3-propyl-S-Y-chloropropylamino~1,3-imida201idin-2-one ~-
1-(5-Methylthio-1,3,4-thiadiazol-2-yl)-3-propyl- -
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), ~-chloropropyl-
-18-
'; ' I . ' ' ,'
~ ~6~0~; `
amine (0.11 mole) and benzene (100 ml) are charged into a
glass reaction vessel equipped with a mechanical stirrer,
thermometer, reflux condenser and Dean-Star~ trap. The reac-
tion mixture is heated at reflux, and the water of reaction
is removed as it is formed. After no more water is formed,
the reaction mixture is stripped of solvent under reduced
pressure to yield the desired product 1-(5-methylthio-1,3,4-
thiadiazol-2-yl)-3-propyl-5-~-chloropropylamino-1,3-imidazoli-
din~2-one as the residue.
Example 28
Preparation of 5-Methylsulfonyl-
1,3,4-thiadiazol-2-yl Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
(100 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry oE 5-methylsulfonyl-
2-amino-1,3,4-thiadiazole (50 grams) in ethyl acetate (300
ml) is added to the reaction vessel, and the resulting mixture
is stirred for a period of about 16 hours, resulting in the
~ formation of a precipitate. The reaction mixture is then
zo puryed with nitrogen ga~ to remove unreacted phosgene The
p~rged mixt~re is then filtered to recover the precipitate~
The precipitate is then recrystallized to yield the desired
product 5-methylsulfonyl-1,3,4-thiadiazol-2-yl isocyanate
dimer.
Preparation of the Dimethyl Acetal of 2-tl-Allyl-3-(5-
m~thylsulfon~ -1;3,4-thladi ol-2-yl-)ureido]acetaldehyde
A mixture of 5-methylsulfonyl-1,3,4-thiadiazol-2-yl
isocyanate dimer (0.05 mole), the dimethyl acetal of 2-allyl-
aminoacetaldehyde (0.1 mole) and benzene (60 ml) are chargedinto a glass reaction vessel equipped with a mechanical stirrer
and reflux condenser. The reaction mixture is heated at
re1ux for a period of about 15 minutes. After this time
--19--
~6;2 7~6
the mixture is stripped of benzene under reduced pressure
to yield a solid product as the residue. The residue is
then recrystallized to yield the desired product the dimethyl
acetal of 2-[1-allyl-3-(5-methylsulfonyl-1,3,4-thiadiazol-
2-yl)ureiao]acetaldehyde.
Example _30
Preparation of l-t5 Methylsulfonyl-1!3,4-
thiadiazol-2-yl)-3--allyl-5-hydroxy~1,3-_midazo-Iidin-2-one
The dimethyl acetal of 2-[1-allyl-3-(5-methylsulfonyl-
1,3,4-thiadiazol-2-yl)ureido]acetaldehyde (15 grams), water
(400 ml) and hydrochloric acid (~ ml) are charged into a
glass reaction vessel equipped with a mechanisal stixrer,
thermometer and reflux condenser. The reaction mixture is
heated at reflux for a period of about 15 minutes. The reac-
tion mixture is then filtered while hot, and the filtrate
is cooled to form a precipitate. The precipitate is recovered -
by filtration, is dried and is recrystallized to yield the i :
desirad product l-(5-methylsulfonyl-1,3,4-thiadiazol-2-yl)- :
3-allyl~5-hydroxy-1,3-imidazoli~in-2-one. . ~.
20Example 31
Preparation o 1-(5-Methylsulfonyl-
1,3,4-thiadiazol-2-yl)-3-allyl-5-(N-methyl- :
N-cy~clohexylamino)-1,3-imidazolidin-2-one~
1-(5-~ethylsulfonyl-1,3,4-thiadiazol-2 yl)-3-allyl- .:
5-hydroxy-1,3-imidazolidin~2-one (0.1 mole), N-methyI-N- .
cyclohexylamine (0.11 mole) and benzene (100 ml) are charged
into a glass reactlon vessel equipped with a mechanical stirrer,
thermometer, reflux condenser and Dean-Stark trap. The reac-
tion mixture is heated at reflux, and the water of reaction :
is removed as it is formed.. A~ter no more water is formed,
the reaction mixture is stripped of solvent under reduced .
pressure to yield the desired pxoduct 1-(5-methylsulfonyl-
.... ..
-2Q-
~627~
1,3,4-thiadiazol-2-yl)-3-allyl-5-(N-methyl-N-cyclohexylamino)-
l,3-imidazolidin-2-one.
Preparation of 5-Methylsulfinyl-
1,3,4--thiadiazol-2-vl'I'socvanate Dimer
A saturated solution of phosgene in ethyl acetate
(lO0 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry of 5-methylsulfinyl-
2-amino-1,3,4-thiadiazoIe (50 grams) in ethyl acetate (300
ml) is added to the reaction vessel, and the resulting mixture
is stirred for a period of about 16 hours, resulting in the
formation of a precipitate. The reaction mixture is then
purged with nitrogen gas to remove unreacted phosgene. The
purged mixture is then filtered to recove~ the precipitate.
The precipitate is then recrystallized to yield the desired
product 5-methylsulfinyl-1,3,4-thiadiaæol-2-yl isocyanate
dimer.
E ~
Preparation of the DimethyL Acetal of
2-[1-Methyl~3-(5-methyl~ulfinyl-
~_ ... .
A mixture of S-methylsulfinyl-1,3,4-thiadiazol-2-yl
isocyanate dimer (0.05 mole), the dimethyl acetal of 2-methyl-
aminoacetaldehyde (O.l mole) and benzene (60 ml) are charged
into a glass reactlon vessel equipped with a mechanical stirrer
and reflux condenser~ The reaction mlxture 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. The residue is
then recrystallized to yield the desired product the dimethyl
acetal of 2-[l-methyl-3-(5 methylsulfinyl-1,3,4-thiadiazol-
2-yl)ureido]acetaldehyde.
.
-21-
., . , ". "
06;~7~
Example 34
Preparation of 1-(5-Methylsulfinyl-1,3,4-thiadiazol-
_ 2-yl)-3-met~yl-5-h~drox~ 3-imidazolidin-2-one
The dimethyl acetal of 2-[1-methyl-3-(5-methyl-
sulfinyl-1,3~4-thiadiazol-2-yl)ureido]acetaldehyde (15 grams), .~ :
water ~400 ml~ and hydrochloric acid (4 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. The reac- :
tion mixture is then filtered while hot, and the filtrate
is cooled to form a precipitate. The precipitate is recovered .
by filtration, is dried and is recrystallized to yield the
desired product 1-(5-methylsulfinyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one~ ~.
E ~
Preparation.o~ 1-(5-Methylsulfinyl- ..
1,3,4-thiadiazol-2-yl)-3-methyl- : ::
: :
1-(5-Methylsulfinyl-1,3,4-thiadiazol-2-yl)-3-methyl-
20 _ 5-hyd~oxy-1,3-imidazolidin-2-one (0.1 mole), 2-methylaniline
(O.Ll mole) and benzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux condenser and Dean-Star~ trap. The reaction
mixture is heated at reflux, and the water o~ reaction is
removed as it is formed. After no more water is formed, the
reaction mixture is stripped of solvent under reduced pressure
to yield the desired product 1-(5-methylsulfinyl-1,3,4- .~. ... ..
thiadiazol-2-yl)-3-methyl-5-(2-methylanilino)-1,3-imidazolidin-
2-one as the residue.
Example~ 36
Preparation o~ 5-Cyclopropyl-
lt3,4-thiadiazol-2-~Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
(100 ml) was charged into a glass reaction vessel equipped
-22-
~627~6
with a mechanical stirrer. A slurry of 5-cyclopropyl-2-amin.o-
1~ 3r 4-thiadiazole (6 grams) in ethyl acetate (100 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
purged with nitrogen gas to remove unreacted phosgene. The
- purged mixture was filtered to recover the desired product
5-cyclopropyl-1, 3 ~ 4~thiadiazol-2-yl isocyanate dimer.
Example 37
Preparation of the Dimethyl Acetal of 2-rl-Propargyl-
3-(5-cvclo~ro~vl-1,3,4-thiadiazol-2-yl)ureido~ace~aldehyde
A mixture of 5-cyclopropyl-1,3,4-thiadiazol-2-yl
isocyanate dimer (7 ~rams), the dimethyl acetal of 2-propargyl-
aminoacetaldehyde (5 grams) and ethyl acetate (50 ml) were -.
charged into a glass reactlon vessel equipped with a mechanical
tirrer and reflux condenser. The reaction mixture is heated
at reflux for a period of about 2 hours. After this time
the mixture is stripped of solvent under reduced pressure
to yield the desired product the dimet:hyl acetal of 2-[1-
2Q propargyl-3-(5-cyclopropyl-1,3,4-thiadiazol-2-yl)ureido]-
acetaldehyde as an oil.
Example 38
Preparation of 1-(5-Cyclopropyl-1,3,4-thiadiazol-
2-yl)-3-p~E~argyl-5-hydrox~-1,3-imidazolidin-2-one
The dimethyl acetal of 2~ propargyl-3-t5-cyclo- -
propyl-1,3,4-thiadiazol-2-yl)ureido~acetaldehyde obtained
from Example 37, water (400 mI~ and hydrochloric acid (4
ml) are charged into a glass reaction vessel equipped with
a mechanical stirrer, thermometer and reflux condens~r.
The reaction mixture is heated at reflux for a period of
about 15 minutes. The reaction mixture is then flltered
while hot,. and the filtrate is cooled to form a precipitate.
The precipitate is recovered by filtration, is dried and
.
", ~"'
-23-
, .~, . , , ,, ,.: . .
6276~6
is recrystallized from ethyl acetate to yield the desired
product 1-~5-cyclopropyl-1,3,4-thiadiazol-2-yl)-3-propargyl-
5 hydroxy-1,3-imidazolidin-2-one.
Exam~le 39
j .... .
Preparation of 1-(5-Cyclopropyl-
1,3,4-thiadiazol-2-yl)-3-propargyl-
5-(2-methoxvanilino) 1~3-imidazolidin-2-one
1-(5-Cyclopropyl-1,3,4-thiadiazol-2-yl)-3-propargyl-
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), 2-methoxyaniline
(0.11 mole) and ~enzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux condenser and Dean-Stark txap. The reactlon
mixture is heated at reflux, and the water of reaction is
removed as it is formed; After no more water is formed,
the reaction mixture is stripped of solvent under reduced
pressure to yield the desired product 1-(5-cyclopropyl-1,3,4-
thiadiazol-2-yl) -3-propargy1-5- (2-methoxyanilino)-1,3-imid-
azolidin-2-one as the residue.
Example 40 :
,
Preparation of 5-Cyclohexyl-
A saturated solution of phosgene in ethyl acetate
(500 ml) is charged into a ~lass reacticn vessel equipped
with a mechanical stirrerO 5-Cyclohexyl-2-amino-1,3,4-
thiadiazole (6 grams) is added to the reaction vessel, and
the resulting mixture is stirred and heated at reflux for
a period of about 4 hours, resulting in the formation of
a precipitate. The reaction mixture is then purged with
nitrogen gas to remove unreacted phosgene. The purged mixture
is then filtered to recover the precipitate. The precipitate
i~ then recr~stallized from a dimethyl ormamide-water mixture
to yield the desired product 5-cyclohexyl-1,3,4-thiadiazol-
2-yl isocyanate dimer having a melting point of 237 to 239C.
, . ' ' . . .: ' '
..
-24
~6;2~6
E ~
Preparation of the Dimethyl Acetal of 2~ Methyl-3-
A mixture of 5-cyclohexyl-1,3,4-thiadiazol-2-yl
isocyanate dimer (12 grams), the dimethyl acetal of 2-methyl-
aminoacetaldehyde (6.9 grams) and benzene (60 ml) are charged
into a glas~ 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. The residue i5
then recrystallized from metha~ol to yield the desired product
the dimethyl acetal of 2-[1-methyl-3-(5-cyclohexyl-1,3,4-
thiadiazol-2-yl)ureido~acetaldehyde having a melt point of
133 to 134C.
Example 42
Preparatio~ of 1-(5-Cyclohexyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-hyd~y~-1,3-imidazolidin-2-on~
.
The dimethyl acetal of 2-[1-me~hyl-3-(5-cyclohexyl-
2~ 1,3,4-thiadiaæol-2-yl)ureido~acetaldehyde (15 gram ), water
(400-ml) and hydrochloric acid (4 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. The reac-
tion mixture is then filtered while hot, and the filtrate-
is cooled to form a precipitate. The precipitate is recovered
~y filtration, is dried and is recrystallized from methanol
to yield the desired product l-(5-cyclohexyl-1,3,4-thiadiaæol-
2-yl)~3-methyl-5-hydroxy-1,3-imidazolidin-2-one having a ~;
3Q melt point of 154 to 155C. -
~0627~6
Example 43
Preparation of 1-(5-Cyclohexyl-1,3,4-thiadiazol-2-yl)-
3-me~hyl-5-(3,4-dichloroanilino)~1,3-imidazolidin-2-one
1-(5-Cyclohexyl~1,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (0~1 mole), 3,4-dichloro-
aniline (0.11 mole) and benzene (100 ml) are chaxged into -
a glass reaction vessel equipped with a mechanical stirrer,
thermometer, reflux condenser and Dean-Stark trap. The reac-
tion mixture is heated at reflux, and the water of reaction
0 i5 removed as it is formed. After no more water i5 formed,
the reaction mixture is s~ripped of solvent under reduced
pressure ~o yield the-desired product 1-(5-cyclohexyl-1,3,4
thiadiazol-2~yl)-3-methyl-5-(3,4-dichloroanilino)-1,3-
... .. ... .
imidazolidin-2 one as the residue.
Example 44
Preparation of 5-Cyclopentyl-
- lr3r4--~ ,
A ~aturated solution of phosgene in ethyl acetate
tlon ml) is charged into a glass reaction vessel equipped
20 wi-th a mechanical stirrer. A slurry oE 5-cyclopentyl-2-amino-
1,3~4~hiadiazoIe (SO grams) in ethyl acetate (300 ml) is
added ko the reaction vessel, and the resulting mixture is
stirred for-a period of about 16 hours, resuIting in the
formation of a precipitate. The reaction mixture is then
purged~with nitrogen gas to remove unreacted phoagene. The
purged mixture is then filtered-to recover the pxecipitate.
,
The precipitate is then recrystallized to yield the desired
product 5-cyclopentyl-1,3/4-thiadiazol-2-yl isocyanate dimer.
: ' . ~ ' '.
30Preparation of the Dime thyl Acetal of 2~ Methyl-3-
(5-cycIopentyl-1,3,-4-thiadiazol-2-yl)ureido]acetaldehyde
A mixture of 5-cyclopentyl-1,3,4-thiadiazol-2-yl
isocyanate dimer (0.05 mole), the dLmethyl acetal of 2-methyl- ;
. -; ' :'
-26-
,,. .: : . .
~27~6
aminoacetaldehyde ~0.1 mole) and ~enzene (60 ml) are charged
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. The residue is
then recrystallized to yield the desired product the dimethyl
acetal of 2~~1-methyl-3-(5-cyclopentyl-1,3,4-thiadiazol-2-yl)-
ureido~acetaldehyde.
Exam~le 46
Preparation of 1-(5-Cyclopentyl-1,3,4-thiadiazol-
2~y1)-3-meth~1-5-hydroxy-1,3-imidazolidin-2-one
The dimethy1l acetal o 2-[1-methyl-3-[5-cyclopentyl- -
. . .
1,3,k ~thiadiazol-2-yl)ureido]acetaldehyde (15 grams), water
(400 ml) and hydrochloric acid (4 ml) are charged into a
glass reaction vess~l equipped with a mechanical stirrer,
thermometer and reflux condenser. The reaction mixture is
heated at reflux for a-period of about 15 minuteC. The reac- -
tion mixture is then filtered while hot, and the filtrate
is cooled to form a precipitate. The precipitate i5 recovered
by filtration, is dried and is recrystallized to yield the
desired product 1-(5-cyclopentyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one. -
.
~ ` : :
Preparation of 1~(5-Cyclopentyl- ~
1~ 3 r 4-thiadiazol 2-yl)-3-methyl-5- -
(4-~rifIuoromethylanllino)~ 3-imidazolidin-2-one
1-(5-Cyclopentyl-1,3,4-thiadiazol-2-yl)-3-methyl- ~- -
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), 4-trifluoromethyl-
aniline (0.11 mole) and benzene (lOO ml) are charged into
a glass reaction vessel equipped with a mechanical stirrer,
thermome~er, reflux condenser and Dean-Stark trap. The reac-
tion mixture is heated at reflux, and the water of reaction
. ,. - ' , .
~al6;~7q~6
is removed as it is formed. After no more water is formed,
the reaction mixture is stripped of solvent under reduced
pressure to yield the desired product 1~(5-cyclopentyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-(4-trifluoromethylanilino)-1,3-
imidazolidin-2-one as the residue.
Example 48
Preparation of 1-(5-Trifluoromethyl-1,3,4 thiadiazol-2-
1 (5-Trifluoromethyl-~,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2~one (8~0 grams) and benzene
(75 ml) were charged into a glass reaction vessel equipped
with a mechanical stirrer~ thermometer, Dean-Stark trap and
reflux condenser. ~-Methoxyethylamine (5.0 grams) was added
to the reaction vessel, and the mixture was heated at reflux
while removing the water as it was formed. After no more
water was given off, the reaction mixture was cooled, resulting
in the precipitation of a solid~ This solid was recovered
by filtration and was recrystallized from hexane to yield
the~desired product 1-(5-trifluoromethyl-1,3,4-thiadi~zol-
2-yl~-3~methyl-5-~-methoxyethylamino-1,3-imidazolidin-2-one
having a melting point of 82 to 84C.
.::
Exam~e 49
Preparation of 5-Allyl-
1,3,4-thiadiazol~2-vl Isoc~anate Dimer
.. ~
A saturated solution of phosgene in ethyl acetate
(100 ml) is charged into a glass- reaction vessel equipped
with a mechanical stirrer. A slurry of 5-allyl-2-amino- ;
. . ~; . . .
1,3,4-thiadiazole (50 grams) in ethyl acetate (300 ml~ is
added to the reaction vessel, and the resulting mixture is
stirred for a period of about 16 hours, re~ulting in the
formation of a precipitate. The reaction mixture is then
purged with nitrogen gas to remove unreacted phosgene. The
purged mixture is then filtered to recover the precipitate.
--28--
.~ ' ' ~ ' ' ; " : ' ' , .,1 ' ' ', ' , , '
~6;27~i
The precipitate is then recrystallized to yield the desired
product 5-allyl-1,3,4-thiadiazol-2-yl isocyanate dimer.
Example 50
Preparation of the Dimethyl Acetal of 2-~1-Methyl-
3~(5-allyl-1,3,4-thiadiazol-2-yl)ureido]acetaldehyde
A mixture of 5-allyl-1,3,4-thiadiazol-2-yl isocyanate
dimer (0.05 mole), the dimethyl acetal of 2-methylaminoacet-
aldehyde (0.1 mole3 and benzene (60 ml) are charged 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. The residue is then recrystallized
to yield the desired product the dimethyl acetal of 2~ methyl-
3-(5-allyl-1 r 3,4-thiadiazol-2-yl)ureido]acetaldehyde.
E
Preparation of 1-(5-AlIyl-1,3,4-thiadiazol-
2-yl)-3-me~h~1-5-hy~roxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-methyI-3-(5-allyl-1,3,4-
thiadiazol-2-yl)ureido~acetaldehyde (lS grams), water (400
mI) and hydrochloric acid (4 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer
and reflux conden~er. The reaction mixture is heated at
reflux for a period of about lS minutes. The reaction mixture
is then filtered while hot, and the filtrate is cooled to
form a precipitate. The precipitate is recovered by fi~tra-
tion, is dried and is recrystallized to yield the desired
product l-(5-allyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hydroxy-
1,3-imidazolidin-2-one.
E ~
Preparation of l-(S-Allyl-1~3,4-thiadiazol-2-yl)-
3-methyl-5-(3-nitroanilln_)-1,3-imidazolidin-2-one
l-(S-Allyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hydroxy-
~2~-
.
~1627~6
1,3-imidazolidin-2-one (0.1 mole), 3-nitroaniline (0.11 mole)
and benzene (100 ml) are charged into a glass reaction vessel
equipped with a mechanical stirrer, thermometer, reflux con-
denser and Dean-5~ark trap. The reaction mixture is heated
at reflux, and the water of reaction is removed as it is
formed. After no more water is formed, the reaction mixture
is stripped of solvent under reduced pressure to yield the
desired product l-(5-allyl-1,3,4-thiadiazo1-2-yl)-3-methyl-
5-(3~nitroanilino)-1,3-imidazolidin-2-one as the residue.
Example 53
Preparation of 5-Pentyl-1,3,4-
t ad azol-2-~l_Isocyanate Dimer
A saturated solution of phosgene in ethyl acetate
.
(100 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer. A slurry of 5-pentyl-2-amino-
1,3,4-thiadiazole (40 grams) in ethyl acetate (300 ml) is
added to the reaction vessel, and the resulting mixture is
stirred for a period of about 16 hours, resulting in the
formation of a precipitate. The reaction mixture is then
purged with nitroyen gas to remove unreacted phosgene. The
purged mixture is then filtered to recover the precipitate.
The precipitate is then recrystallized to yield the desired
product 5-pentyl-1,3,4-thiadiazol-2-yl isocyanate dimer~
~ ' : -~
.
Preparation of the Dimethyl Acetal of 2-[1-Ethyl- ~
A mixture of 5-pentyl-1,3,4-thiadiazol-2-yl iso- ;
cyanate dimer (0.05 mole), khe dimethyl acetal of 2-ethylamino-
acetaldehyde (0.1 mole) and benzene (60 ml) are charged into
a glass reaction vessel equipped with a mechanical stirrer
and reflux condenser. The reaction mixture is heated a~
re1ux for a period of about lS minutes. After this time
the mixture is stripped of benzene under reduced pressure
-3Q-
~6;~7~;
to yield a solid product as the residue. The residue is
then recrystallized to yield the desixed product the dimethyl
acekal of 2~ ethyl-3-(5-pentyl~1,3,4-thiadiazol-2-yl)ureido]-
acetaldehyde.
E~
Preparation of 1-(5-Pentyl-1,3,4-thiadiazol-
2-yl)-3-ethyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2-[1-ethyl-3-(5-pentyl-1,3,4-
thiadiazol-2-yl)ureido~acetaldehyde (15 grams), water (400
ml)~ and hydrochloric acid (4 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer
and re~lux condenser. The reaction mixture is heated at - ~- -
reflux for a period of about 15 minutes. The reaction mixture
is then filtered while hot, and the filtrate is cooled to
~orm a precipitate. The precipitate is recovered by filtra-
tion, is drie~ and is recrystallized to yield the desired
product l-(5-pentyl-1,3 r 4-thiadiazol-2-yl)-3-ethyl-5-hydroxy-
l,3-imidazolidin-2-one.
Example 56
Preparation of 1-(5-Pentyl-
1,3,4-thiadiazol-2-yl)-3-ethyI-5~[N-methyl-
N-(3-bromoben~zyl)amino]-1,3-1midazolidin-2-_ e
1-(5-Pentyl-1,3,4-thiadiazol-2-yl)-3-ethyl-5-hydroxy-
1,3-imidazo lidin;2-one (0.1 mole), N-methyl-N-(3-bromobenzyl)-
amine 50~11 mole) and benzene ~lO0 ml) are charged into a
glass reaction vessel equipped with a mechanical stirrer, -
.
thermometer, reflux condenser and Dean-Stark trap. The reac-
tion mixture is heated at reflux, and the water of reaction
is removed as it is formed. After no more water is formed,
the reaction mixture is stripped of solvent under reduced
pre~sure to yield the desired product 1~(5-pentyl-1,3r4-thia-
diazol-2-yl)-3-ethyl-5-~N-Methyl-N-(3-bromobenzyl)amino]-
1,3-imidazolidin-2-one as ~he residue.
'
~Q627~6
Example 57
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
2-vl)-3-methvl-5-(4-cvanoanilino)-1,3-imidazolidin-2-one
1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl- -
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), 4-cyanoaniline
(0.11 mole) and benzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer,
reflux condenser and Dean-Stark trap. The reaction mixture
is heated at reflux, and the water of reaction is removed~
as it is formed. After no more water i~ formed~ the reaction
mixture is stripped of solven~ under-reduced pressure to yield
the desired product 1-(5-trifluoromethyl-1,3,4-thiadiazol-
2--yl)-3-methyl-5-(4-cyanoanilino)-1,3-imidazolidin-2-one as
the residue. ~ - ;
Exam~le 58
Preparation of 1-(5-Trifluoromethyl--1,3,4-thiadiazol-
2-yl)-3-methyl-5-octylamino-1,3-imidazolidin-2-one
1~(5-Trifluoromethyl-1,3~4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (13.1 grams) and heptane
(100 ml) axe charged into a glass reaction vessel equipped
with a mechanicaI stixrer, thermometerj Dean-Stark trap and
reflux condenser. Octylamine (10.0 grams) 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 gi~en of~, the reaction mixture is stripped of solvent
to yield the desired product 1-(5-trifluoromethyl-1,3,4-thia-
diazol-2-yl)-3-methyl-5-octylamino-1,3-imidazolidin 2-one.
E~
Preparation of 1-(5-Tri~luoromethyl-1,3,4-thiadiazol-
2-yl-)-3-methyl-5-dodecylamino-1,3-imidazolidin-2-one
~ .
1-(5~Trifluoromethyl~1,3,4-thiadiazol-2-yl)-3-methyl-
5-hydroxy-1,3-imidazolidin-2-one (13.1 grams) and heptane
(100 ml) are charged into a glass reaction vessel equipped
.
--3 2--
i .
with a mechanical s~irrer, thermometer, Dean-Stark trap and
reflux condenser. Dodecylamine (14.0 grams) 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
to yield the desired product ~-(5-trifluoromethyl-1,3,4-thia
diazol-2-yl)-3-methyl-5-dodecylamino-1,3-imidazolidin-2-one.
Exa~Fle 6 n ~ ~
Preparation of 1-(5-Trifluoromethyl-1,3,4-thiadiazol-
102-y~ 3-methyl~5-octadecylamino-l ! 3-imidazolidin-2-one
1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl- ;
5-hydroxyrl,3-imidazolidin-2-one (13.1 grams) and heptane
(100 ml) are charged into a ~lass reac~ion vessel equipped
with a mechanical stirrer, thermometer, Dean-Stark trap and
reflux condenser. Octadecylamine (20.0 grams) is added to
the reaction vessel, and the mixture is heated at reflux
while removing the water as it is formled. After no more
water is given off, the reaction mixture is stripped of solvent ~ -
to yield the desired product 1-(5-trifluoromethyl-1,3,4-
2Q thiadiazol-2-yl)-3~methyl-5-octadecylamino~l,3-îmidazolidin-
2-one.
E ~
Preparation of 1-(5-t-Butyl-1,3,4-thiadiazol-2-yl)-
....
1-(5-t-Butyl-1,3~4-thiadiazol-2-yl)-3-methyl-5-
hydroxy-1,3-imida301idin-2-one (13.4 grams)~ dodecylamine
(12.0 grams) and heptane (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux condenser and Dean-Stark trap. The reaction
3Q mixture is heated at reflux, and the water of reaction is
removed as it is formed by azeotroping. After no more water
is given off, the reaction mixkure is stripped of solvent ~ -
~33~ '; ~
' . ~ ', '
.
, , ~ , , " ,, , .. , . , .~ , .
~6~7~6
~o yield the desired product 1-(5-t butyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-dodecylamino-1,3-imidazolidin-2-one.
Example 62
Preparation of 1-(5-t-Butyl-1,3,4-thiadiazol-2-yl)-
3-meth~1-5-octadecylamino-1,3-imidazolidin-2-one
1-(5-t-Butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-
hydroxy-1,3-imidazolidin-2-one (13.4 grams), octadecylamine
(6.0 grams) and heptane (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux condenser and Dean~Stark trap. The reaction
mixture is heated at reflux, and the water of reaction is
removed as it is ormed by azeotroping. After no more watèr
is given off, the reaction mixture is stripped of solvent
to yield the deslred product l-(5-t-butyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-octadecylamino-1,3-imidazolidin-2-one.
E_amE~ 3
Preparation of 1-(5-Trifluoromethyl-1,3,4 thiadiazol-
1-(5-Trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-
2n 5-hydroxy-1~3-imidazolidin-2-one ~13.4 grams) and heptane
0 ml) were charged into a glass reaction vessel equipped
wit~ a mechanical stirrer, thermometer, Dean-Stark trap and
reflux condenser. ~etramethylenimine (4.0 grams) was added
t~ the reaction vessel, and the mixture was heated at reflux
while removing the water as it was formed. After no more
water was given off, the reaction mixture was cooled, result-
ing in the precipitation of a crystalline solid. The solid
was recovered by filtration and was recrystallized from
heptane to yield the desired product 1-(5-trifluoromethyl-
1,3,4-thiadiazol-2-yl)-3-methy1-5-tetramethylenimino-1,3-
imid~zolidin-2-one having a melting point of 97 to 99C.
-34-
.. .. . . .. . ..
' '. . . . .
~6;~7~6
ExamPle 64
Preparation of 1 (5-t-Butyl-1,3,4-thiadiazol-2~yl)-
3-met~yl-5-tetram-t~ylenimino-l~3-imi-dazolidin-2-ohe
1-(5-t-Butyl 1,3,4-t~iadiazol-2-yl)-3-methyl-5-
hydroxy-1,3-imidazolidin-2-one t8.0 grams), tetramethylenimine
(3.0 ml) and heptane ~100 ml) wexe charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux condenser and Dean-Stark trap. The reaction
mixture was heated at reflux, and the water o reaction was
removed as it was formed by azeotroping. After no more water
was given of~, the reaction mixture was stripped of solvent
to yield an oil as the residue. The oil was subjected to
vacuum, whereupon it solidified. The resulting solid was
then recrystallized from hexane to yield the desired product
l-(S-t-bu~yl-1,3,4-thiadiazol-2 yl)-3-methyl-5-tetramethylen- ;
imino-1,3-imidazolidin-2-one having a melting point of 103
to 105C.
Example 65 ~-
Preparation of 1-~5-Hexyl-1,3,4-t'hiadiazol-2-yl)-
2~ ~
1-(5~Hexyl-1,3,4-thiadiazol-Z-yl)-3-ethyl-5-hydroxy-
1,3-imidazolidin-2-one (0.1 mole), ethylenimine ~0.11 mole)
and ben3ene (100 ml) are chaxged into a glass reaction vessel
equipped with a mechanical stirrer, thermometer, reflux -~`~
.
condenser and Dea~-Stark trap. Tha reaction mixture is
heated at re1ux, and the water of reaction is removed as
it is formed. After no more water is formed, the reaction
mixture is stripped of solvent under reduced pressure to
yield the desired product 1-(5-hexyl-1,3,4-thiadiazol-2-yl)-
b 3-ethyl-5-ethylenimino-1,3-imidaz~lidin-2-one as the residue.
' ~:
~::
,....: :-:
., ' ~ .
-35- ~
. . , . , . . : ,:, . . . . . . . .
... . . ..
~627~6
Example 66
Preparation of 1-~5-Met~oxy-1,3,4-thiadiazol-2-yl)-
3-et~ 5~-trimeth~y_ nimi`no-1_3 imidazolidin-2-one
1-(5-Met~oxy-1,3,4-thiadiazol~2-yl)-3-ethyl-5-
hydroxy-1,3-imidazolidin-2-one (0.1 mole), trimethylenimine
(0.11 mole) and benzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, reflux con~enser and Dean-Stark trap. The reaction :
mixture is heated at reflux~ and the water of reaction is
10 removed as it is formed. After no more water is formed, the
reaction mixture is stripped of solvent under reduced pressure
to yield the desired product l-(5-methoxy-1,3,4-thiadiazoI-
2-yl)-3~ethyl-5-trimethylenimino-1,3-imidazolidin-2-one as
the residue~ -
. ~
Preparation o~ 1-(5-Methylthio-1,3,4--thiadiazol-2-yl)-
. 3-pxo~yl-5 pentameth~1enim o-1,3--imldazolidin-2-one
1-~5-Methylthio-1,3,4-thiadia2O1-2-yl)-3-propyl-
5-hydroxy-1,3-imidazolidin-2-one (0.1 rnole), pentamethylenimine
(0~11 mole) and benæene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther-
mometer, re1ux condenser and Dean-Stark trap. The reaction
mixture is heated at reflux, and the water of reaction i5
: removed as it is formed. After no more water is formed, the
reaction mixture is. stripped of solvent under reduced pressure
.to yield the desired product 1-(5-methylthio-1,3,4-thiadiazol~
2-yl)-3-propyl-5-pentamethylenimino-1,3-imidazolidin-2-one
as the.residue.
~' '
Preparation o 1-~5-Methylsulfonyl-
1,3,4-thiadiazol-2-yl)-3-allyl-5-
hexamethylenimino-1,3-imidazolidin-2-one
1-(5-Methylsulfonyl-1,3,4-thiadiazol-2-yl)-3-allyl-
5-hydroxy-1,3-imidazolidin-2-one (0.1 mole), hexamethylenimine
-36-
~6~
(0.11 mole) and benzene (100 ml) are charged into a glass
reaction vessel equipped with a mechanical stirrer, ther
mometer, reflux condenser and Dean-Stark trap. The reaction
mixture is heated a~ reflux, and the water of reaction is
removed as it is formed. After no more water is formed, the
reaction mixture is stripped of solvent under reduced pressure
to yield the desired product 1-(5-methylsulfonyl-1,3,4-thia-
diazol-2-yl)-3-allyl-5-hexamethylenimino-1,3-imidazolidin-2-one. ~.
Additional compounds within the scope of the present
invention which can be prepared according to the procedures
detailed in the foregoing examples are l-(5-trifluoromethyl-
1,3,4-thiadiazol 2~ylj-3-methyl-5-amino-1,3-imidaæolidin- ;
2-one, 1-(5-t-bu~yl-1,3;4-thiadiazol-2-yl)-3-methyl-5-amino-
1,3-imidazolidin-2-one, l-(5-trifluoramethyl-1,3,4-thiadiazol-
2-yl)-3-ethyl-5-propylamino 1,3-imidaæolidin-2-one, 1-(5-
methyl-1,3,4-thiadiazol-2-yl)-3-butyl-5-(N,N-dimethylamino)-
1,3-imidazolidin-2-one, 1-~5-ethyl-1,3,4-thiadiazol-2-yl)-
3-pentyl-5-(N,N-~ipropylamino)-1,3-imicLazolidin-2-one, 1-
(5-isopropyl-1,3~4-thiadiazol-2-yl)-3-hexyl-5-(N,N-dihexylamino)-
: ... :.
1,3-imidazolidin-2-one, 1-(5-pentyl-1,3,4~thiadiazol-2-yl)-
3-but-3-enyl-5-tN-methyl-N-butylamino) 1,3 imidazolidin-2- ~:
c~ne, 1-~(5-hexyl-1,3,4-thiadiazol-2-yl)-3-pent-4-enyl-5-(N-
ethyl-N-phenylamino)-1,3-imidazolidin-2-one, 1-(5-cyclobutyl- :~
1~3,4-thiadiazol-2-yl)-3-hex-4-enyl-5-(N-ethyl-N-benzylamino)- ;~
17 3-imidaæolidin-2-one, 1-(5-cyclopentyl-I,3,4-thiadiazol-
,i, :
2-yl~-3-~-chloroethyl-5-(N me~hyl-N-but-3-enylamino)-1~3-
:
imidazolidin-2-one, 1-(5-cycloheptyl-1,3,4-thiadiazol-2-yl~
3-~ bromoethyl-5-hex-4-enylamino-1,3-imidazolidin-2-one, :
1-(5-but-3-enyl-1,3,4-thiadiazol-2-yl)-3-~-chloropropyl-5
~ ethoxyethylamino-1,3-imiclazolidin-2-one, 1-(5-pent-4-enyl~
: .
1,3 t 4-thiadiazol-2-yl)-3-~-chlorohexyl-5-~-ethoxypropylamino- : ::
1,3-imidazolidin-2-one, 1-(5-hex-4-enyl-1,3,4-thiadiazol- .. .
, ' ':
. .
~37
~116Z7~6
2-yl)-3-ethyl-5 ~-propoxybutylamino~1,3-imidazolidin-2-one,
1-(5~ff-bromoethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-~methoxy-
hexylamino-1,3-imidazolidin-2-one, 1-(5-~-chloropropyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5~cyclobutylamino-1,3-imidazolidin- :
2-one, 1-(5-~-chlorobutyl-1,3,4-thiadiazol-2-yl)-3-methyl-
5-cyclopentylamino-1,3-imidazolidin-2-one, 1-(5-~-bromohexyl-
. 1,3,4-thiadiazol-2 yl)-3-methyl-5~cyclohexylamino-1,3-imid-
azolidin-2-one, 1-(5-ethoxy-1,3,4-thiadiazol-2-yl)-3-methyl-
5--cycloheptylamino-1,3-imidazolidin-2-one, 1-(5-butoxy-1,3,4-
thiadiazol-2-yl)-3-methyl-5-~-hydroxyethylamino-1,3-imidazoli~
din-2-one, 1-(5-hexyloxy-1,3,4-thiadiazol-2-yl)-3-methyl-
5-~-hydroxypropylamino-1,3-imidazolidin-2-one, 1-(5-ethyl~hio-
1,3,4 thiadiazol-2-yl)-3-methyl-5-~-hydroxyhexylamino-1,3-
imidazolidin 2-one, 1-(5-propylthio-1,3,4-thiadiazol-2-yl)-
3-methyl-5-(2-ethylanilino)-1,3-imidazolidin-2-one, 1-(5-
hexylthio-1,3,4-thiadiazol 2-yl)-3-methyl-5-(2-propylanilino)-
1,3-imidazolidin-2-one, I-(5-ethylsulfonyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-(4-hexylanilino)-1,3-imidazolidin-2-one,
(5-butylsulfonyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-etho~y-
anllino)-1,3-imidazolidin-2-one, 1-(5-hexylsulfonyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-(4-hex~loxyanilino)-1,3-imidazoli- :
din-2!one, 1- (5-ethylsulfinyl-1,3,4-thiadiazol-2-yl)-3-methyl~
5-~4-~iodoanilino)-1~3-imidazolidin-2-one, 1-(5-propylsulfinyl- .
1,3,4-thiadiaæol-2-yl)-3-methyl-5-(4-fluoroanilino)-1,3-imid-
azolidin-2-one, 1-(5-hexylsulfinyl-1,3,4-thiadiazol-2~yl)-
3-methyl-5-(3,4-dibromoanilino)-1,3-imidazolidin-2-one, 1-
(5-t-butyl-1,3,4-thiadiazol-2~yl)-3-methyl-5-(3,4,5-trichloro- ;
anilino)-1,3-imidazolidin-2-one, 1-(5-~rifluoromethyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5~(3-chloromethylanilino)-1,3-imid- .
3Q azolidin~-2-one, 1 (5-t-butyl-1~3,4-thiadiazol~2-yl)~3-methyl-
5-(3-~-chloroethylanilino)-1,3-imidazolidin-2-one, 1-(5-tri-
fluoromethyl-1,3,4-thiadiazol-2-yl)~3-methyl-5-(4-~-chloro-
-38-
~6Z7~16
hexylanillno3-1,3-imidazolidin-2-one, 1-(5-t-butyl-1,3,4-
thiadiazol-2-yl)-3-methyl-5-(2 ethylthioanilino)-1,3-imidazoli-
din-2~one, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-
methyl-5-(3-propylthioanilino)-1,3-imidazolidin-2-one, 1
(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-(4-butylthio-
anilino)-1,3-imidazolidin-2-one, 1-(5-trifluoromethyl-1,3,4-
thiadiazol-2-yl)--3-methyl-5-(3-hexylthioanilino)-1,3-imidazoli-
din-2-one, 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-
[N-(2-methyl-4-chlorobenæyl)amino]-1,3~imidazolidin-2-one,
1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl) 3-methyl-5-~N-
ethyl-N-(2,6-dimethylbenæyl)amino~-1,3-imidazolidin-2-one, : -
1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-heptylamino-
1,3-imidazolidin 2-one, l-(5-t-butyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-octylamino-1,3-imidazolidin--2-one, l~(S-t-butyl- ~ .
1,3,4-thiadiazol-2-yl)-3-methyl-5-nony:Lamino-1,3-imidazolidin- .
2-oner 1-(5-t-butyl-1,3,4-thiadiazol-2--yl)-3-methyl-5-decyl- ~:
amino-1,3-imidazolidin-2-one, 1-(5-t-butyl-1,3,4-thiadiazol-
2-yl)-3-methyl-5-undecylamino-1,3-imidazolidin-2-one, 1-(5-
t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-tridecylamino-1,3- ~ ~ :
Lmidazolidin-2-one, 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-
3-methyl-5-tetradecylamino-1,3-imidazolidin-2-one, 1-(5-t-
butyl-:1,3,4-thiadiazol-2-yl)-3-methyl-5-pentadecylamino-1,3-
imLdazolidin-2-one, 1 (5-t-butyl-1,3,4-thiadiazol-2-yl)- :~:
3-methyl-5-hexadecylamino-1,3-imidazolidin-2-one, l-(5-t- : ~:
butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-heptadecylamino-1,3-
imidazolidin-2-one, 1-(5-trifluoromethyl-1,3,4-thiadiazol-
2 yl)-3-ethyl-5-ethylenimino-1,3-imidazolidin-2-one, 1-~5-
methyl-1,3,4 thiadiazol-2-yl)-3-butyl-5-trimethylenimino-
1,3-imidazolidin-2-one, 1-(5-ethyl-1,3,4-thiadiazol-2-yl)- ~ -
3-pentyl-5-tetramethylenimino-1,3-imidazolidin-2-one, 1-(5- -
isopropyl-1,3,4-thiadiazol-2-yl)-3-hexyl-5-pentamethylenimino- .
1,3-imidazolidin-2-one, 1-(5-pentyl-1,3,4-thiadiazol-2-yl)-
-39- .. ..
', : .
. ' , , .., , . : . ,,
31L~6;27~;
3-but-3-enyl-5-hexamethylenimino-1,3-imidazolidin-2-one,
1-(5-hexyl-1,3,4-thiadiazol-2-yl~-3-pent-4-enyl-5-ethylenimino-
1,3-imidazolidin-2-one, 1-(5-cyclobutyl-1,3,4thiadiazol-2-
yl~-3-hex-4-enyl-5-trimethylenimino-1,3-imidazolidin-2-one,
1-(5-cyclopentyl-1,3,4-thiadiazol-2-yl)-3-~-chloroethyl-5-
tetramethylenimino-1,3-imidazolidin-2-one, 1-(5-cycloheptyl-
1,3,4-~hiadiazol-2 yl)-3-~-bromoethyl--5-pentamethylenimino-
1,3-imidazolidin-2-one, 1-(5-but-3-enyl-1,3,4-thiadiazol-
2-yl)-3-~-chloropropyl-5-hexamethylenimino-1,3~imidazolidin-
2-one, 1-(5-pent-47-enyl-1,3,4 thiadiazol-2-yl)-3-~-chlorohexyl
5-ethylenimino-1,3 imidazolidin-2-one, 1-(5-hex-4-enyl-1,3,4-
thiadiazol-2-yl)-3-ethyl-5-trimethyl~nimino-1,3-imidazolidin-
- 2-one, 1-(5-~-bromoethyI-1,3,4-thiadiazol-2-yl)-3-methyl- .:
5-tetramethylenimino-1,3-imidazolidin-2-one., 1-(5-~-chloro-
propyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-pentamethylenimino-
1,3-imidazolidin-2-one, 1-(5-~-chlorobutyl-1,3,4-thiadiazol-
2-yl)-3~me~hyl 5-hexamethylenimino-1,3-imidazolidin-2-one,
1-(5- ~ bromohexyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-athylen-
imino-1,3-imidazolidin-2-one, 1-(5 ethoxy-1,3,4-thiadiazol-
2-yl)-3-methyl-5-trimethylenimino-1,3-imidazolidin-~-one,
1-(5-butoxy-1,3,4-thiadiazol~2-yl)-3-methyl 5-tetramethylen- ~
imino-1 3 imidazolidin-2-one, 1-(5-hexyloxy-1,3,4-thiadiazol- ~.
2-yl)-3-methyl-5 pentamethy~enimino 1,3 imidazolidin-2-one, ..
1 (5 ethylthio-1,3,4-thiadiazol-2-yl)-3-methyl-5-hexamethylen-
imino-1,3-imidazolidin-2-one, 1-(5-propylthio-1,3,4-thiadiazol-
2-yl)-3 methyl-5-ethylenimino-1,3-imidazolidin-2-one, 1-
(5-hexylthio-1,3,4-thiadiazol-2-yl) 3-methyl-5-trimethylen-
imino 1,3-imidazolidin-2-one, 1-(5-ethylsulfonyl-1,3,4-~hiadi-
azol 2-yl) 3-me.thyl-5-tetramethylenimino-1,3-imidazolidin- : -. .
2-one, 1-(5-butylsulfonyl-1,3,4-thiadiazol-2 yl)-3-methyl-
5-pentamethylenimino-I,3-imidazolidin-2-one, 1-(5-hexyl-
sulfonyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hexamethylenimino-
' :
~6;~706
1,3-imidazolidin-2-one, 1-(5-ethylsulfinyl-1,3,4-thiadiazol-
2-yl~-3-methyl-5 ethylenimino-1,3-imidazolidin-2-one, 1-
(5-propylsulfinyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-trimethylen-
imino-1,3-imidazolidin-2-one, l-(5-hexylsulfinyl-1,3,4-
thiadiazol-2~yl)-3-methyl-5-tetramethylenimino-1,3~imidazolidin-
2-one and the like.
For practical use as herbicides the compounds of
this invention are generally incorporated into herbicidal
compositions which comprise an inert carrier and a herbicidally
toxic amount of such a compound. Such herbicidal compositions,
whlch can also be called formulations, enable the active :~
compound to be applied conveniently to the site o~ 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-
iable 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 compound, usually dissolved in a suitable solvent, onto
and into granulated carriers such as the attapulgites or .
~ha ~ermiculites, usually of a particle size range of from - :
about 0.3 to 1.5 mm. Wettable powders, which can be dispersed
in water or oil to any desired concentration of the active . ::
compound, can be prepared by incorporating wetting agents
into concentrated dust composi~ions.
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 sol
vents. Frequently, solutions of herbicides can be dispersed
under supera~mospheric pressure as aerosols. However, preferred
-41-
' ,' ' , ' " " ' , ', ", ' '',, '" ~, ' ' ~' ;; " , .' . ' ~ ' ' ' " .
~ ~6;~7~i
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 si~e of the weed infestation. The
emulsifiers most commonly used in these concentrates are
nonionic or mixtures of nonionic with 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 ill~strated by the following example, in which
the quantities are in par~s by weight.
Example 69
Preparation of a Dust
Product of Example 4 10
Powdered Talc 90
The above ingredients are mixed in a mechanical
grinder-blender and are ground until a homogeneous, free-
flowing dust of the desired particle si~e is obtained. This
dust is suitable for direct application to the site of the
weed infestation.
The compounds o~ this invention can be applied
as herbicides in any manner recognized by the art. One method
or 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 present invention. The concentration of the new compounds
of this in~ention in the herbicidal compositions will vary
greatly with the type of formulation and the purpose for
-42-
', , . . , , ' ,
~L60 627~
which it is designed, but generally the herbicidal composi-
tions will comprise from about 0~05 to about 95 percent by
weight ~f the active compounds of this invention. In a pre-
ferred embodiment of this invention, the herbicidal composi-
tions will comprise from about 5 ~o about 75 percent by weight
of the active compound. The compositions can also comprise
such additional substances as other pesticides, such as insecti-
cides, nematocides, fungicides, and the like; stabilizers,
spreaders, deactivators, adhesives, stickers, fertilizers,
activators, synergis~s, and the like.
The compounds of the present invention are also
usefuI when combined with other herbicides and/or defoliants,
dessicants~ growth inhi~itors, and the like in the herbicidal
compositions heretofore described. These other materials
can comprise from about 5~ to about 95~ of the active ingre-
dients in 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~ion~ which are more effective in controlling
weeds and often provide re~ults unattalnable with separate
-compositions of the individuaI herbicides. The other herhi- -
cides t defoliants, dessicants and plant growth inhibitors,
with which the compounds of this inventio~ can be used in
the herbicidal compo~itions to control weeds, can include
chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB,
4(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-
TES, 3,4-DA, silvex and the like; carbamate herbicides such
as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like;
thiocarbamate and dithiocarbamate herbicides such as CDEC,
- 30 metham sodium, EPTC, diallate, PEBC, perbulate, vernolate
and the like; substituted urea herbicides such as norea,
siduron, dichloral urea, chloroxuron, cycluron, fenuron,
' ' ''
-43-
~6~
monuron, monuron TCA, diuron, linuron, monolinuron, neburon,
buturon, trimeturon and the like; symmetrical triazine herbi-
cides such as s~mazine, chlorazine, atraone, desmetryne,
norazine, ipazine, prometryn, atrazine, trietazine, simetone,
prometone, propazine, ametryne and the like; chloroacetamide
herbicides such as alpha-chloro-N,N-dimethylacetamide, CDEA,
CDAA, alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropyl-
acetanilide, 4-(chloroacetyl)morpholine, l-(chloroacetyl)-
pip~ridine and th~ like; chlorinated aliphatic acid herbi-
cides such as TCA, dalapon, 2,3-dichloropropionic acid, 2,2,3-
TPA and the like; chlorinated benzoic acid.and phenylacetic .
acid herbicides such as 2,3,6-TBA, 2,3,5.,6-TBA, dicamba,
tricamba, amiben, fenac,- PBA, 2-methoxy-3,6-dichlorophenyl-
acetic acid, 3-methoxy-2 r 6-dichlorophenylacetic acid, 2-methoxy-
.3,5,6-trichlorophenylacetic acid,. 2,4-dichloro-3-nitrobenzoic
acid and the like; and s~ch compounds as aminotria~ole, maleic
hydrazide, phenyl mercuric acetate, endothal, biuret, technical
chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat,
erbon, DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin,
: 20 triflurali~, solan, dicryl, merphos, DMPA, DS~A, MSMA, potassium
axide, acrolein, bene~in, bensulide, AMS, bromacil, 2-(3,4-
dichlorophenyl~-4-methyl-1,2,4-oxadiazolidine-3,5-dione,
bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA,
dichlone, diphena~ril, DM~T, DNAP, EBEP, EXD, HCA, ioxynil,
. IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH,
molinate, NPA, OC~, paraquat, PCP, picloram, DPA, PCA, pyrichlor,
sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-l,
H-732, M-2901, planavin, sodium tetraborate, calcium cyanamid,
DEF, ethyl xanthogen.disulfide, sindone, sindone B, propanil
and the like. Such herbicides can.also be used in the methods
and compositions of this invention in the form of their salts, ~ .
: ~: :
~ ~ .
-44-
,. , . , , : ~
~i2~
esters, amides, and other derivatives whenever applicable
to the particular parent compounds~ ~-
Weeds are undesirable plan~s growing where they
are not wanted, having no economic value, and inter~ering
with the production of cultivated crops, with the growing
of ornamental plants, or with the welfare of livestock~
Many types o~ weeds are known, including annuals such as
pigweed, lambsquarters, foxtail~ crabgrass, wild mustard,
field pennycress, ryegrass, goose grass, chickweed, wild
oats, velvetleaf, purslane, barnyardgrass, smartweed, knot-
weed, coc~lebur, wild buc]cwheat, kochia, medic, corn cockley
ragweed, sowthistle, coffeeweed, croton, cuphea, dodder,
fumitory, groundsel, hemp nettle, knawel, spurge, spurry, -
emex, jungle rice, pondweed, dog fennel, carpetweed, morning-
glvry, bedstraw, ducksalad, naiad, cheatgrass, fall panicum,
iimsonweed, witchgrass, switchgrass, watergrass, teaweed,
wild turnip and sprangletop; biennials such as wild carrot,
matricaria, wild barley, campion, chamomile, burdock, mullein,
roundleaved mallow, bull thistle, hounds-tongue, moth mullein
and purple star thistle; or perennials such as white cockle,
perennial ryegrass, quackgrass, Johnsongrass, Canada thistle,
hedge bindweed, Bermuda grass, sheap sorrel, curly dock,
nutgrass,~field chickweed, dandelion, campanula, field bind-
weed, Russian knapweed, mesquite, toadflax, yarrow, aster,
gromwell, horse~ail, ironweed, ~esbanla, bulrush, cattail,
winter-cressl horsenettle, 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 dama~ing beneficial plants
or livestock.
The new compounds o this in~ention are particularly
valuable for weed control because they are toxic to many
.
. .
-~5-
.
7~1~
species and groups of weeds while they are relatively non-
toxic to many ~eneficial 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 applica~ion, 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 infesta-
tion of weeds growing under adverse conditions, the application
of ten pounds or more o~ an active compound per acre may
be required for good control of a dense infestation of hardy
perennial weeds growing under favorable conditions.
The her~icidal toxicity of the new compounds of
this invention can be illu~trated by many o the established
testin~ techniques known to the art, such as pre- and post-
emergence testing~
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
~20 experiments small plastic greenhou~e pots filled with dry
. .
90il 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 compounds formulated
as aqueous emulsions of acetone solutions containing emulsi-
fiers were sprayed at the indicated concentrations on the
surface of the soil.
After spraying, the soil containers were placed
in the greenhouse and provided wi~h supplementary heat as
required and dally 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 ~ -
., .
-46-
. , ., . , . . : . .. .:
, . ~ .; , . ., . . , . .
~1627~i
10, as follows: O = no injury, 1,2 = slight injury, 3,4 =
moderate injury, 5,6 = moderately severe injury, 7,8,9 = severe
injury and 10 - death. The effectiveness of these compounds
is demonstrated by the data in Table I. ..
. .
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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 compounds to be tested were formulated
as aqueous emulsions and sprayed at the indicated dosage on
the foliage of the weeds that have 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 de~ermined 14 days after treatment and was rated
on the scale of from O to 10 heretofore described. The
effectiveness of these compounds is demonstrated by the data
in Tables II--and~
-51-
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