CA1062706A - 1-thiadiazolyl-5-alkylamino, arylamino and cycloimino substituted imidazolidinones - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
1-Thiadiazolyl-5-alkylamino-, arylamino- and cycloimino-substituted imidazolidinones of the formula:

are described as well as processes for their production.
These compounds have berbicidal activity. In the structural formula R1 is alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl or alkylsulfinyl; R2 is alkyl, alkenyl, haloalkyl or in which R5 and R6 are hydrogen or alkyl; and R3 and R4 are hydrogen, alkyl, alkinyl, halo-alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl or

Description

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 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 ~ 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.

~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 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 OR

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 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.

~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 .

, , ~ . , , , . . . . . . ~ .. .. ... ........ .... . . . . . . . .. .... . ... . . . . . . .. . ..

~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 `
,.
' .

~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.
'':~, '

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-'; ' 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 ~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-.... ..

~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.

.

., . , ". "

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 ~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 .
", ~"' , .~, . , , ,, ,.: . .

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.

, . ' ' . . .: ' ' ..

~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- ;
. -; ' :' ,,. .: : . .

~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.

.~ ' ' ~ ' ' ; " : ' ' , .,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 ~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 .

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.

.. .. . . .. . ..
' '. . . . .

~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 ~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-~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 ' ,' ' , ' " " ' , ', ", ' '',, '" ~, ' ' ~' ;; " , .' . ' ~ ' ' ' " .

~ ~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 ', , . . , , ' , ~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, ' ' '' ~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, ~ .

: ~: :
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~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 ~ -., .

. , ., . , . . : . .. .:
, . ~ .; , . ., . . , . .

~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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~627al6 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~

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Claims (14)

CLAIMS:

1. A compound of the formula wherein R1 is selected from the group consisting of alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl and alkylsulfinyl; R2 is selected from the group consisting of alkyl, alkenyl, haloalkyl and 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 consisting of hydrogen, alkyl of up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cycla-alkyl and wherein X is selected from the group consisting of alkyl, alkoxy, halogen, haloalkyl, alkylthio, nitro and cyano; n is an integer from 0 to 3; and m is the integer 0 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.

2. A compound of the formula wherein R1 is selected from the group consisting of alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl and alkylsulfinyl; R2 is selected from the group consisting of alkyl, alkenyl, haloalkyl and 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 consisting of hydrogen, alkyl of up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cyclo-alkyl and wherein X is selected from the group consisting of alkyl, alkoxy, halogen, haloalkyl, alkylthio, nitro and cyano; n is an integer from 0 to 3; and m is the integer 0 or 1, provided that a maximum of one of R3 and R4 is an aromatic moiety.

3. A compound of the formula wherein R1 is selected from the group consisting of alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkyl-sulfonyl and alkylsulfinyl; R2 is selected from the group consisting of alkyl, alkenyl, haloalkyl and wherein R3 and R4 are each selected from the group consisting of hydrogen and alkyl; and m is an integer from 0 to 4.

4. The compound of Claim 1, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-t-butylamino-1,3-imidazolidin-2-one.

5. The compound of Claim 1, 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hexylamino-1,3-imidazolidin-2-one.

6. The compound of Claim 1, 1-(5-trif1uoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hexylamino-1, 3-imidazolidin-2-one.

7. The compound of Claim 1, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-anilino-1,3-imidazolidin-2-one.

8. The compound of Claim 1, 1-(5-trifluoromethyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-benzylamino-1,3-imidazolidin-2-one.

9. The compound of claim 1, 1-(5-trifluoro-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-.beta.-hydroxyethylamino-1,3-imidazolidin-2-one.

10. The compound of claim 1, 1-(5-trifluoro-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-diethylamino 1,3-imidazolidin-2-one.

11. The compound of claim 1, 1-(5-trifluoro-methyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-tetramethylenimino-1, 3-imidazolidin-2-one.

12. The compound of claim 1, 1-(5-t-butyl-1, 3,4-thiadiazol-2-yl)-3-methyl-5-tetramethylenimino-1,3-imidazolidin-2-one.

13. A method of controlling weeds which comprises contacting said weeds with a herbicidal composition comprising an inert carrier and, as an essential active ingredient, in a quantity toxic to weeds, a compound of claim 1.

14. A process for the preparation of a compound of the formula wherein R1 is selected from the group consisting of alkyl, cycloalkyl, alkenyl, haloalkyl, alkoxy, alkylthio, alkyl-sulfonyl and alkylsulfinyl; R2 is selected from the group consisting of alkyl, alkenyl, haloalkyl and 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 consisting of hydrogen, alkyl of up to 18 carbon atoms, alkenyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, cyclo-alkyl and wherein X is selected from the group consisting of alkyl, alkoxy, halogen, haloalkyl, alkylthio, nitro and cyano; n is an integer from 0 to 3; and m is the integer 0 or 1, provided 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 cycloimino moiety containins from 2 to 6 carbon atoms, which comprises recacting a compound of the formula wherein R1 and R2 are as defined above, with an about equimolar or slight excess molar amount of an amine or cyclic imine of the formula wherein R3 and R4 are as defined above, in an inert organic solvent at the reflux temperature of the reaction mixture and azeotropically removing the water of reaction.