CA1076114A - 1,5-alkylene-3-aryl hydantoin derivatives - Google Patents

Abstract

Abstract of The Disclosure Novel 1,5-alkylene-3-aryl hydantoin derivatives having unique biological properties, especially herbicidal or fungicidal activities.

Description

~ 2 -- ` ~L076 : ' :
Background of the Invention --------- .. ..
.~. i .
This invention xelates to novel hydantoin derIvati~ves which have valuable bi~ological properti`es andr more particularly, to novel hydantoin deri~vatives having a substituted phenyl on the nuclear ni~trogen i~n the 3eposi~t~on.
It is already known that certain l,5ealkylene~3-aryl hydanto~n derivatives, such as 1,5-trlmethylene-3~phenyl ,. .
hydantoi~n~l,5~trimet~rylene~3eph~nyl~2-thiohydantoin, 1,5~tetramethylene~3ephenyl hydantoin, 1,5-tetramethylene-3-~2'~, 3~ or 4'~echlorophenyll~2~thi~ohydantoIn, 1,5~tetramethylene-3-~4'~etolyl~2~th~ohydantoi~n can be synthesized; however, they have not demonstrated any herbic~dal or fungicidal propert~es, ~ E. F~scher: Chem. Ber~ 34, 1460 ~19Qll;
P. Edman: ~cta Chem. Scand~ 4, 277 ~1950~; General Electri~c Co~: French Patent 1,389~841 ~1965~, and B. Stanovni~k:

Croati~ca Chemica Acta 35, 167 ~1963L~
.
We have conducted intensi~ve studi~es ~n order to show that when improved properti`es of absorption and translocation are gl~ven to the hydanto~n compounds, the herb~cidal or '~ ~ungicidal actl'vi`ty i~s also i~ncreased; at the same time, crop injury or phytotoxi~ty and envi~ronmental pollut~on are decreased. We have focused our e~orts on ~i~nd~ng a compound .: .
which i~s easily broken down by m~croorgan~sms in the soi~l, non~persi~stent i`n plantsr and composed of readi~ly bio-degradable .~ ~

-~ materials. An important structural moiety of the herbicidal ~ i, . .
' or ~ungicidal ~ dantoin derivatives according to this ~nvention - ~ is an amino ac~d such as proline or p~pecolinIc acid.
~, .
~ Proline is well known ~s one o the esse~ti~al ami`no ; acids, while pipecoli~n~c aci~d has been found in plants, such ; as apple, kidney bean and others and is also the metabolite of lysine in animals and plants.

~ ; ~ 3 ~ 10761~4 :`
,~ Therefore, the hydantoin derIvat~ves of the present inventi~on which are obtai~ned from such amino acids have :,~ already solved the dl~ffi~cuit problems occurring i~n the envi~ronment, such as pers~stence i~n the soi~l, res~dual toxicity etcO The results of our studies have shown that the novel 1~5-alkylene-3-aryl hydantoi~ns o~ the general formula I are sui~table for ~he above mentioned purposes.
,l In general, l~t i~s beli~eved that a bi~ologically active compound causes some l~nteracti~on wi~th Yi~tal t~ssues to produce . ' va~ious acti~ons~ In the case of a compound haY~ng herbicidal " -, ~ .
~, properti`es, i`t has~ bee~ noted that t~e abso~pti~on of t~e -~ compound and i~ts t~anslocati~on i~n plants and the reaction ,~ at the si~te of action are i~mportant factors and are affected by the llpophillic-hydrophillia balance of the compound ..
concerned..
.- By our detailed study of cyclic imide her~d~ides~ .we .~ ~ haYe di`scovered on the structurai characteri~st~cs necessary ,~ for herbicidal activl~ty. We hypothesize that an alkylene i`ng, electron~donatl`ng mo~ety~ i~m~de ~l~ng and aryl ri~ng are prerequi~si\tes fo~ actl~yl~ty~ The results o~ our study indicate that the. ~nai~dence of acti`vi~ty i~s very high among compounds ~; w.hose.structu~es conform to the follow~ng rules:
1, An ~mide ~ ng o~ s~mi~iar structure ~s present.
2s ~ -Ca~bon atoms i~n the alkylene group form part of planar o~ have ci`s~con~i`gurat~on agai~nst the ~mide ring, 3.. The subst~tue~t on the phenyl ring i`s of the p~ope~
.. size and proper direati`on of dipole moment, K. Wakabayashi` et al, Proceeding of The 5th Asi`an~Pacific .~ Weed Science Con~erence~ 1975 ~, .

~'~, 1C~761~

The hydantoin derivatives described in this application have a proper balance of lipophillicity and hydrophillicity based on the introduction of an alkylene group attached to the l-and 5-positions in a -els-configuration, the electron-donating moiety (~N-CH<), the cyclic imide ring, and the phenyl ring with substituents having the proper size and direction of dipole moment. These elements play an important role in the herbicidal activity of the hydantoin derivatives according to this invention. The hydantoin derivatives of .;
this invention can also be used as fungieides; e.g. 3,5-` dihalogenophenyl compounds are eXtremely useful in controlling kidney bean gray mold, rice sheath and riee brown spot diseases.
` Aeeordingly, an object of thls invention is to provide a novel hydantoin derivative having unique -- -herbicidal and/or fungicidal aetivity.
Another object is to provide an improved eommereially applicable process for producing sueh -; 20 hydantoin derivatives.
A further object is to provide a herbieidal or ., : ...... ... ~ ,, .
fungieidal composition, wherein a hydantoin derivative is the active ingredient.
- Summary of the Invention Hydantoin derivatives aceording to this invention are represented by the general formula~
. : , -, r~ ~
(CH2)n N N - R
X (I) ;~

.: .

~, ~

., . , , . , -.

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

. , ,. . ., . . ' .. .

10761~L4 ~: - 5 -~ wherein n is 3 or 4, X is oxygen or sulphur, with the -.. ; provisos that when X is oxygen R is phenyl group having at least one substituent selected from halogen, Cl-C4 ~ :
j alkyl, Cl-C4 alkoxyl, nitro, trifluoromethyl and halogenated benzyloxy group; and when X is sulphur, R is trifluoromethyl, halogenobenzyloxy or naphthyl.

' , 1 ~

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

.~, .

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

,:

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

, b~ J

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

: : \
~ 6 ~ ~076114 :, ~ Detailed Descripti~on of the Invention .
, :`, The compounds described in this appli~cation can be ~ prepared by various routes. Where X is oxygen in the general , formula (I), the compound can be prepared by e~ther Route A

;; or B.

; tl Where X i~s sulphur ~n general formu~a (I~, the compound : ~ can be prepared by e~ther Route C or D.

Route A ~
' ~ ., ~ ' The compounds o~ 1,5-alkylene-3~aryl hydanto~n are --~, : prepared according to this inventi~on by cyclizi~ng a N-(N~-substi~tuted carbamyl~ imino aci~d represented by general ~ '''1 .
'~ ~ formula (III) 1~ COOH 11 ... : / ~
(CH2)n ~ (C~2~n ] ~ - R

$~

: ~ :

:' wherein R and n have the same meaning as in formula(I).
' The compound represented by general formula (.III), which .
is a starting material of this process, can be prepared by reacting an imino aci~d such as proline or pipecolinic acid in water in the presence of an alkali such as sodium hydroxide, potass~um hydroxide, bari~um hydroxide or calcium hydroxide with an aryl isocyanate i~n an appropriate solvent such as benzene, chlorobenzene, ether or DMF at O ~ 50C
for 0.5 ~ 6 hours. The resulting ~-~N7substituted carbamylL

'', '~'~.

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

~ 7 ~ 1076~4 ;- imino acid (III~ may be purified, if desired, by recrystal-lization from an appropriate solvent such as acetone.
One embodiment of the production of N-(N!-substituted carbamyl) imino acid will be i~llustrated in the following Reference Example~

. ' Reference Example :;
To a solution of 1.73 g (0.015 mole~ of proline and 0.6 g (0.015 mole) of sodium hydroxide in 25 ml of water .:
was added 2.81 g (0~015 mole~ of m-trifluoromethylphenyl isocyanate in 20 ml of chlorobenzene. After stirring for two hours at room temperature, the reaction mixture was extracted w~th ether. Concentrated hydrochloric acid was added to the aqueous phase unti`l a pH of 4 was reached.
The resulting bulk was co;lected by filtration and washed wi~th w~ter~ After recrystallization from acetone-water, . .
4.0 g of N~NI~m~tri~fluoromethylphenyl~ carbamyl ~ proline having a melting poi`nt of 178 ~ 180 C was obtained, The elementary analysis of C13H13O3N2F3 was:

i C% H~ N%

` Calcd. 51.66 4.33 9.27 .:
~ Found 51.3~ 4.12 9.22 , - In carrying out the procedure of Route A, compound (III) ~ , ` is cycli~zed in the presence of an aci~d catalyst such as -l hydrochloric acid or sulphuric acid in an appropriate `~ aqueous solvent such as water~ dioxane and water, DMF and water,or THF and water at 50 ~ 150C for 0,5 - 6 hours.
; The cyclized product can be i~solated by filtration of the resu~ting crystals which are formed by cooling of the reaction mixture to room temperature. The product may be purified by recrystalli~zation from an appropriate solyent such as ethanol~ 2-propanol or acetone, or by column ''`

r~
iO76114 . .~
,.
. . .
~ - 8 -''~...

.. ..
~ chromatography, or by a combination thereof, .
.. ..
;. ~.. " ....
~ Route B
i ` .
, .~. In this route, an imino acid such as proline or pipecolinic acid, represented by the general formula (IV) is employed as a starting material and is reacted with .~ ..
; an aryl isocyanate. This is a conventional method, the ;l advantage of which is that the intermediate compound, ~' N-(N'-substituted carbamyl) imino acid (III) need not be isolated . . . .
:.. . .
``~'d' CGOH I '~~ r COCH ~ ~
`~ (CH2)n ~ ~ OC~-R r - - ? ~ N~ . .

~ (IV) (III) ~ ~
i. 1. ~1 ' `
~ (CH2)n ¦ ~ N - R
,.'` ~: . ' ~ 1/ '.
O

~;' wherein R and n have the same meanings defined in . .
. i formula (I).

The N-carbamylation reaction is carried out as 1`
. ~ , . described in the Reference Example of Route A, However, -a larger amount of acid is added to the extracted aqueous phase to keep the pH at 2.
,.''; . '' .. I
1, .

~'~ I

: ~ :
- ~ 9 ~(~7611~
,`:

.: The cyclization reaction is performed by heat~ng the ~` above obtained aci~di~c mixture under the condi`tions as ., descrl~bed in Route A.

! Route C
, ,~ j -~,. i ", ~ .
In this route, an imi~no aci~d (Iy~ i~s reacted wi`th an : aryl i`sothiocyanate to give a l,5.alkylene-3-aryl 2-~; thiohydantoin ~Y! in accordance with the following scheme:
-. ,., O
~ (CH2)'- r + Sc~ (CH2~n ~ / N - ~

~ (IV) (V) . ~ .
:; -.; j wherei~n R and n have the same meanings as defined i~n formula I, The formation of 2~thiohydantoin is accompli~shed by heating a mixture of an imino acid ~IY~, an aryl i~sothio~
cyanate, and a solvent under reflux conditions for 0.15 -: 2 hours. Examples of the preferred solvents which may be employed include alcohols such as ethanol, l-propanol,

2-propanol or methanol; and DMF~ THF, benzene or toluene.
~: The react;on product is obtained by filtration of the " , precipitated crystals whi~ch resulted from cooling of the reaction mixture or by evaporation of the solvent.
`~ Purification can be accompli~shed by recrystallization . . .~, :~.............. from an appropri~ate solvent such as methanol, ethanol, `
:~ ethyl acetate, acetone or water, or by column chromato- :
. graphy, ;'' .

. , , o 10761i~
. , ;,i .~;
~ Route D
,~
;, In this route, an lmino acid ester (YII i~s reacted with an aryl isothiocyanate to yield a l,5-alkylene-3 aryl-2-thiohydantoin according to the scheme:

. . .
, :., ~ .
:! .
o (Cl2)n ~ + SCN - R ~-~ (C~2)n ~ N - R

',,`',~ ~ ~I~ (Y) wherein R and n have the same meani~ngs as defined in formula T, and R' is a lower alkyl group, such as methyl or ethyl.
~ The formati~on of 2~thiohydanto~n derivatives is :. !: ::
accomplished by heating a mi~xture of an imino acid ester, an aryl isothiocyanate, and a solvent under reflux condltions

3~ -for 0.15 - 3 ~ours~ Examples of the preferred solvents which may be employed in thi~s route include an alcohol such ! ~}~ ~
` as ethanol~, l-propanol,, 2~propano~ or methanol; and DMF, THF~ benzene or toluene. The reaction product is obtained ~ ` by the filtration of precipitated crystais which xesulted '~ ~ from cooling the reaction mlxture or from evaporation of ,: ~: ~ :
,~l the solvent.

,,;,J~ Pur~fication can be accom,pli`shed by recrystallization ~ rom an appropriate solvent such- as methanol, ethanol, ',` ethyl acetate, acetone, water~ or by column chromatoyraphy or ~y a combination, thereof, , The fo~lowing examples i~lustrate the methods used in ~' preparing the compounds of the present invention. It `` should be understood that this inyention i~s not ll'mi`ted by ';' ;:,:
., ~
`
-- .
. ~'~' ' '.

-,` ~. ` ` . :
., , ~` these Examples. The letter shown in parenthesis after the Example number indicates the Route employed.
. ,i....

Example 1 (A) A mixture of 3.02 g (0.01 mole~ of N (3~trifluoromethy~ -carbamoyl proline (mp, 178 - 180C~, 40 ml of 2N hydro-chloric ac~d! and 10 ml of diox~e were heated under reflux conditi~ons for two hours with stirring. After cooling to ~` room temperature, the resulting crystals were collected by ~1 filtration, washed with water, and recrystallized from acetone-water to obtain 2,62 g ~the yield being 92.2%) of ~; 3-(3'trifluoromethyl-phenyl) 1,5-trimethylenehydantoin, having a melting point of 133 - 136C.
-"~
N _ ~`''. ~ O

The elementary analysis was:
....~
C~ H% N%

; Calcd. 54.93 3.909.86 Found 55.05 3.869.63 This corresponded to the empirical formula C13HllO2N2F3 . '.~.
~' Example 2 (B?
:: :
To a solution of 1.94 g (0.015 mole) of pipecolinic acid and 0.6 g ~0.015 mole) of sodium hydroxide in 25 ml of water was added 2.30 g ~0.015 mole) of p-chlorophenyl iso-cyanate in 20 ml of chlorobenzene. After stirring for four hours at room temperature, the reaction mixture was extracted with ether. Concentrated hydrochloric acid was added to the aqueous phase unti~l a pH of 2 was reached.
The acidic mixture was then heated under reflux conditions for one hour with stirring. After cooling to room tempera-~r Yç~

1(~76~
- 12 ~

` ture, the resulting crystals were coliected by filtration, ` washed wi~th water, and recrystalli~zed from 2~propanol to . .
obtain 3~22 g ¢the yi~eld ~ei~ng 81,1% of 3~(p-chlorophenyl\-5-tetramethylenehydantoi~n, havi~ng a melting point of 157 158 C.
.,. ~'~ , :~ O -.

~ ` ~N~ ~ Cl : . .
. . . :
~ ~ The elementary analysis was: ;
. 1, ~ C% ~ N~ Cl%
: ..... ; : .
Calcd. 58.98 4.95 10.58 13.40 Found 59.11 4.96 10.42 13.46 This corresponded to the empi~rical formula C13H13O2N2Cl.
-: ~: ~ : : : ~
Example 3 ~s) 3~
To a solution of 1.29 g ¢0.01 mole) of pipecolinic acid and 0.4 g ¢0.01 mole) of sodium hydroxide in 20 ml of water was added 2.60 g (0.01 mole~ of 4-(p-chloro~

.: , benzyloxy~ phenyl isocyanate in 10 ml of DMF. After stirring for four hours, hydrochlori~c acid was added to ~ ~, ~ the reaction mixture until a p~ of 2 was obtained. The - ~, mixture was then heated under reflux conditions for two - . .
~ hours with stirring. After cooling to room temperature, ; the resulting crystals were collected by filtration, washed : ~-with water, and recrystallized from DMF-ethanol to obtain 2.93 g ~the yield being 79.0%~ of 3~ 4'~4"-chlorobenzyloxy) phenyl_ 7-1, S-tetramethylenehydantoin, having a melting .
point of 52 ~ 53C.
~"' ' '.
;

;
,, .

; 1076~4 . j.. i !, ~
~' - 13 ~
, ~ .
~" O

\ ~ CH2--~_C

O

The elementary analysis was:
C% H% N% . Cl%
Calcd. 64.78 5.17 7.56 9.56 Found 64.72 5.01 7.43 9.55 .
This corresponded to the empirical formula C20Hlgo3N2 ;Using the procedures described in Examples 1-3, , ~
~ the compounds listed in Table 1 were also prepared.
r ~:: : : ~ - ' : .

. ~ ` :

-,.3 ~3 ~,3 ::, ' ~' ' ~'' .. ,~ '.''' :,'' .' ., .
:' .

~ ' ', ~ ~' 10761~4 i - 14 -.'"~ ,:' ,.,'`.. ~`` . ~ -I o~ ~ .
;~`,``', : - ... .' .,"', ~ ~' ~ ~_ ~ ~_ ~ ~_ ~
!, IJ ~ -- ~n _ ~n _ ~n t~ ~ '1 C ~;~ ~3 ~- ~ ~ 3; 'C~ ~0, :~ '.' . (~ I- ~D IJ ~ ~ o 1_ C~
~ ':, ~ ~ ~ ~ ~ ~ ~ ~ ~ :~ ~0 ': : ~ ~ p~, : ~ ~ . ~1 3 ~ ~

~' : ~ ~ ~ o ' l~-- o~ ~ ., ~'.

.
.:',., ~ : , . ... --,1 . ~
, ~ ~ ~ ~ ~ ~ ,~C

3i`'`;;,,`~1 :~ ~_ ~ ~ : I : g . I ~ . ~3 :
_ _ ~ _ . ___ ~ _ _ ~ . ~
~ ! ~ o~ Cr~ ~ ~ $ 0~ C~ ~J :
. ~ ~ Ir O ~ ~ ~e- 1~ 1' ; ~J: P-~ ~ ~ _ E
~ ,~ ~ ~ O~ ~ ~ n ~ ~ ~ ~ ~ .
~i~. '~ ~ ~ ~ ~o ~ ~ `o ~ _ ~ .~
`;, ~ : ~ ~ o ~ ~ ~: ~: ~ ~o ~o ~ ~ ~' ~ ;,' ~ ~0 ~o ~0 ~ ~ ~ ~ I ~.
. ~ _ : _ o~
: ~ .
~, ~ : : . ~, .,~-,i . '~ :` _ . _ _~ _ ~
~',. ~ : ~ ~ ~ ~ ~ o, ,',`' ~ : ~__ ~ . .~ .' ~. .~ . ~ ~ ~ ~ ~1, ,~
'':''~ ~ ~ ~h IJ O`
/,.. ".~. :~:,: ~n ~ O
,,; ~ : _ . Z

',', . ' _ .
~'1; ~ ~

~, ~ .. -- . . .. -_-___. __ __ . ~ ' ~

~. r i~

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

: ~
` ` ` - 15 - :~L'~'6~14 , , '~-,`, ~ ~ o, ~o o~ ,~ o~ o ', . . .
~: ~ IJ G'' ~ '- ~ I' ~,_ ~1-~. ~- ~n ~ ~ ~ ~ ^ ~
~ ~ ~ b ' l l ~,~ ' ~ ' b -` `: ~o ~ ,_ ,~ ~ ~ ~ ~' ,_ ~. '.;, :: ~ ~ ~ ~ ~s ~ ,.. ~ ,o ~ ~ ~ ,. 'i ~ ~ (D ~ ~ ~ ~ ~ ~ ~ ~ ~ .
:: ,_ ~ ~ ~ ~ ~ o ~ 'q :~ ~ ~ ~
, ,:, . ~ 1 IJ ~ ~ ~ ~ I _ I I--~D ~a ~' ~q ~D ~ tD (1~ t~) ~ ) ~ 1::
,~ `'`. ~ ~ ~ ~) 'C, ~) ~3 1 Pl' ~', ~, '~ ~. ~- ~ ~r ~- !~' ~ ~ ~- .
. ~ . _ __ _ , . ~) IJ ~ i~ ~ ~O~

~ ~ ~O . a l ~ O~ ~O ~
~ ~ ~ ..
,.~,,~ ~' __ _ _ _ .'.
: ~: ~ ~n ~ ~n ~ O~ ~n ~n ~ ~ Vl ~n ~ ~ o o o~ ~ ~ ~ o o .~ co ~ -a n ;i ~ ~n ~O ~O _~ ~ ~n ~ O~ ~ ~ *- ~D
.~ : ~ O O ~ ~ ~O . 1- ~ IJ ~ ~J ~O
~: ~ __ . _ .~ _ ,:
. . ~n ~n ~ ',~
* ~ : . o~ o~ o ~ o o~ ~o ~ --J ~_1~ : ., o o o ~ 1- ~o ~o ~o ~o ~ ~
W ~ ~ o i~ :~: 1~-.. -:1 ~ ~ ~ ~ ~n ~O O ~ O~ ~O ~O ~0 ~ _ __ _ _ _ __ ~ ..
:~ rv ~ ~ , ~ ~ ~ ~ ~ ~ ~ _, ,:
, ~ : _~ co ~. ~ . 1- ~3 ~ ~ ~ E~ , ~ . ~ .

` _ __ __~ . _ : !~
"lf`~ ~ t~ ~ t~ ~~) I_ o~ ,~ ., '~ l_ ' ~ ; _ _ _ ' ! j ;;~ _~ ~ ~ _~ ~O ~ 1~.
:.1 ~ ~ ,0 ~ _~ ~ O ~ I_ .' ':'.-~ 0;~ 1~ t~ ~- C~ . O P, '''`
, ~ ~ ' _ ,`
. ,~ ' , `': ' :,.' '"' :`-' . ~
:
,~' ~ _ :~ ~lr;;

~ ~ ',rO ~ ' ' .
:: , . :
~'' ` ` ',' '' ' ' . .
'' ' ' ' ' .

16- 1076~

~` ''~ I IJ ~ -~ ~; e--: ~
,'' ~1- 1 ~ p.~ ~ ,'~
:: ~ ~ ~ ~ ~ ~ ~ .+ ~ ~
~ ~ ~ ~ i~

':~ ' ~ ~ `- ~D
::l ~ ~l ~ ~ l ~
~- o ~ ~ l ~-~: ; ~
~ ~ -- -- ~
. ~J IJ ~ ' I_ ~J ~J X
~ O` ~ C~ O` ~d tD
: ,~ : ~ . . l l l n :~
~ ~ . ~ Cl~ C~ ~n ~o _~ 0~
--1~ - ----- - - -- -----''~} ~ ~ <~ O~ O` O~ ~n ~n ~ ~n cr~ O`
~n ~n ~ *~ ~ O~ O~ CJ~ O~ 00 C~ Q
,'``i ~ _~ ~On O ~o ~$ _~ ~ 1_ ~ i_ ~ ~
.. . . __ _ E~ .
O` ~ O` O` O` O` ~ ~ *- ~ O` O` ::1 ..
:. Ij . . . . . . . .. . . . . ~ ~
. ~; . _~ ~ 10 ~ O` O` 0~ _~ ~ ~ O` O` j~ ':
' I :. ~ ~ O O` ~ ~O O` O . ~3, ~_ ~ 1- l- 1~ ~- ~ ~1 ~ ~ 1- ~ ~
~: : : ~V ~ ~ ~~ ~ ~ ~O ~ ~ ~ ~q ; ~ ~ 1~ ~ _~ ~ ~ ~ ~o 1_ ~ ~ .. .
''.',/~ ~ ~: : _ . ._ .. ~ ~o ,~:, ~ : . . ~C ~
'-'`''~ . . .

_ _ _ ___ __ . _ ... _ _ :.
: ~ !~)h~ 10 I_ 1~) O ,~ . , ~ : I-J
~, : _ ____ ____ . _ __ ,:, : 7 . _~ _J _~ ~ c~ o~~ ~J.
.. ;~ ~n 0~ ~o IJ ~ _~ ~ ~
`,'';~' ~ _~ ' O~ ~O_ ~ ~_ ~ ' ~:
'"```, ~ :
",.
'.~ . ' '' , ,' ~

i ~ ' . . . .
.~

. ' ' ~ ' . .

~ - 17 -.``,~

.: _ __ ~o I_ O __ l_ O
'": ,_ ,_ ~ ~_ ,_ ,_ ~ ,_,_ ,_ ,_ . . ~ ~. ~ ~, ~ ~. ~...... ~
~n _ ~ _ ~ _ ~n _ ~ r~ -- ~n ~ . ~ ~+ l l '. ' l l l l l l .- ~D I'- tD ' ~ ~ (D 3' (D 1-- tD
I ~ ~ ~ 1' ~ o ~ ~--. ~ IJ ~ ~ ~ o 'O ~ o ~ o ~
:~ ~D :~ ~D ~ (D :~' tD ~ tD ~ (D
o ~ :~ ~ ~ ~ ~ ~ ~ ~ ~ ~o~
.... ~. o ~ ~ ~ l_ ~ ~ 'q ~ ~ ~ ~ ,~
~:5 ~_ ~ ~ ~ ~, ~ ,_ ~ ,_ ~ ~o . ~ ~3 ~ ~ P~ ~ ~ ~e ~ '< ~) t~
,', IJ I ~ I 0~ ~ I P :~
~ . ~` ~ O 1~. O ~ C+ .
~; ~ . !~- o, ~ ...
.~ .
~_ 0~ __ _ _ _ _~ O O` ~n i~ I_ O ~ ~
. O 1~, ,_~ _~ Cl~ ~)' _ _ _ _ ,.~S : ~n ~n ~ ,. ~ ~ ~n~n ~ ~n O~ O~
- 10 'O` ~ ~ ~ O O `O 0~ ~ 10' C~
~O i_ O~_~ ~O CO ~ ~n i- ~o ~ 00 L~
10 ~O 001~ ~O ~- 0;~ O ~ O ~O IJ
'f ~ ._ ___ _ El ~) ~ ~ ~ ~ ~ ~ ¢~ ~ ~ ~n~Jl ~1 .:
, ~o ~o ~ ~ ~
t; : Cl~ O` `O ~ _ _ ~ . -~ `O IJ IJ ~ 00 ~O O' O ~ ~ Y ~ ':' "~'J,~ , : ~_ ~ W ~ (X~ _J _~ O` ~ ~ I- I\o . ~, ~ ~
: : ~ . _ _ ~ . _ ~ t.q :: ~ ~ ~ ~ ; ~ ~ ~; ~a,' ' :
~ . ~ o~ o .K _, -:
____ __ _ _ _ _ '`:
Y ~ . ..
ro ~ ~ ~ ~ .~o',~ ~;',' ,;'`~'.-1` ' ~ ' ___ _ _ ' - -:
.. ~ ~ _~ _~ C~ C~~ _~ ~ ,. :
.''. fJ o~ ~ . ~ ~ o ~
.. ' ~n ~n ~ i~ I~O P. ' "
., '::
::, ,, . `

:' -- ::

,' ' ' . .
:- .''.'i~ 'I' , , . I
i` 1.'~ ; , , . . . .

~ :
'`~ - 18 -- 1l~76~4 ;
.`' ~' _ . . I
: ~o _~` ~ O~ ~n o ~
~
~ ~ ~' ~ ~- ~ 'C ~` '- ~ G ~J
~ " ~ ~n ~ ~v~ ~ ~n ~ ~n ~n , ~' ~ ~n ~ ~ ' ' ~ g, ~ g ~ ~ ' . I ~ P. i~ o ~ I' ~ ~ o ~ _ ~ ~ ~- ~ ~ ~ ~ ~ ~ ~ ~- ~ C~
~; o ~ o ~-- ~ - :~ ~ ~ ~ o . ~ & O ~ ~ 6 a ~ n y.

~, ~_ _, ~ ~ ~j :~ ~_ o o ~ I _, ~q 6 ~ ~ ~._ ~Z- , ~' -,,',, : ~Z ~0 I- ~ ~J IJ ~ ~:
., -, : l lZ l l l ~ c,~,~J
.
.` ~ ~o IJ ~ ZXI ~ ~ - o ~
_ ~ _ _ _ ..
~! ~" Z ~n ~Z ~ 110~ CJ~ ~Jl ~Z O~ O~ O~ ~
.. Z : ~ ZO ~) O O ~ ~ IJ ~) O O `O ~O C~Z
`~1 ~:~` : oo i~~;; \n ~ ~ $ .~~ ~ ~ c~ ~3 t, ,: : __ ~__ 3 ~ ~~) ~ ~n ~n ~ ~ ~Z ~Z _~ _~ ~D
.~ ~ ~ ~ ~ ~ -~ ~ ~ ~ ~ ~ ~ ~ k ~ ~
~,:i.,Z ~ :; _ _ . ~! ~ ~o ~o ~o ~o _~ Z c~ ~ o o lo lo '''!'''`'Z ~ J~- ~ : æ ~ ~ ~ ~ ,. ~n ~ ~ ~ ~

J)~ ~ CO i ~ , _ Z!~ ~_ ~Z ~
~: : Cl~ ~J O~ -J ~ ~J ~ IJ ~ . ;
~. ~ `. ___ ____ _ _ ~ ~ _ ' ~''`':' ~ ~ ' ~O h~Z ~ ~ .~ ~ O~, `3 ~; _ ____ - _ ~' ri~Z ~ ~ ' O _ i i ~i ,i ~ '~
`,'`;'3 '~` ' ~': . ~
';',' ~ ` ' , ' '~, ' .

," ~ ~ ~'' s, ' " '' '.'' I~i ~' '~ '' '; '' , .

~076~1~
' - 1 9 -Example 4(C) ;~ A mixture of 1.15 g (0.01 mole) of proline, 2.14 g.
.~ .. .
(0.01 mole) of p-bromophenyl isothiocyanate, and 15 ml of ethanol was heated under reflux conditions for one hour.
After cooling, the resulting crystals were collected by filtration and recrystallized from ethyl acetate-ethanol to obtain 2.60 g (the yield being 83.6%) of 3-(4'-bromo-phenyl)-1,5-trimethylene-2-thiohydantoin, the melting point ;
being 159.5 - 161C.
O

.: C~-:",~ S
The elementary analysis was:

C% H% N% S~ Br%
. .
Calcd.46.31 3.56 9.00 10.30 25.68 : Found 46.08 3.29 8.78 10.29 25.59 .
This corresponded to the empirical formula C12HllON2SBr.

Example 5(C) A mixture of 1.29 g (0.01 mole) of pipecolinic acid, 2.04 g (0.01 mole) of 3,4-dichlorophenyl isothiocyanate, and ,~ 15 ml of ethanol was heated under reflux conditions for ~j twenty minutes. After cooling, the resulting crystals were collected by filtration and recrystallized from DMF-ethanol to obtain 2.78 g (the yield being 88.3%) of 3-(3'4'-dichloro-phenyl)-1,5-tetramethylene-2-thiohydantoin, the melting point being 219 - 222C.

~ N ~ Cl .~: S

,.` ~ ,, .. . . . . . . . . .. . . ..

,~~
~: ' 1076~

~- ~
. ~, - The elementary analysis was C% H% N% S% Cl%
CalcdO 49.53 3.84 8.89 10.17 22.50 Found 49.19 3.76 8.78 10.06 22.76 This corresponded to the empirical formula C13H12ON2SC12.
` Example 6(D) .. , s ~ A mixture of 1~43 g (0.01 mole) of 2-ethoxycarbonyl-pyrrolidine, 1.49 g (0.01 mole) of p-tolyl isothiocyanate, and 25 ml of ethanol was heated under reflux conditions for ~ ~ two hours. After cooling, the resulting crystals were - collected by filtration and recrystallized from ethanol to ~,.. ~........................................................................... .
obtain 1.52 g (the yield being 61.8%) of 2-thio-3-~4'-tolyl)-1,5-trimethylenehydantoin, the meltinq point being 213-214.5C.

The elementary analysis was ;~ C% H% N% S%
~ Calcd.63.385.27 11.37 13.02 . ~
I Found63.26 5.59 11.36 13.28 -~ .
Using the procedures described in Examples 4-6, the compounds listed in Table 2 were also prepared.
., ~ i ~- This corresponded to the empirical formula s 13 14 2S' :
.-.
".~,,', .
`'.

.~-., .'.''~
.
,,~- , , 1.
.~'"' . .
' ~' i~A3 :: ~ ~ ~
: r~ ' :~: . - 21 ~ 1076114~-, . ..

:: . . .. ~ ~ ~ o e '' ..... _ .
' ~ I I l_ ~ l~ I ~ ~ ~v~

¦ L~ ~- ~ ¦ L Ll .~ S 1 .o ,~_ o l_ ~o L
~ ~ l l l l l ~SI P, ',' . I~J '.' ~; _ ; _ . ' O I_ ~-- I .J ~ I_ _ O ; J
l l l l l l O~J-`::, , __ ~ ~ _ O ~nO $ ~Al 1~ _ 0 ~U' , ~, ~; d . i-- ;O O ~) C0 0 _1 ~O C~ : .
`~`,', j: 1_1 _1 C~ IJ ~o ~ O 10 `O CO O` `O ~) .i.'~' ~1 _ __ _ ~': . : ~ . . . ~ ¢- . . . . . . . ::C t~!
. ' ;l O O ~ n ~ ~ ~ ~ O~ O~ El `'`'''~". : ~ , . ~ O ~o o~ _ \~ Co _ ~_ ~o ~ :, ~ ; ~: ~' IJ l_ C~ ~o l_ IJ l_ IJ ~J ,~ ~o `O ~ ~3 .
, ' ~ o i_ _~ O ~ ~ ~ C~ i~ ) ~ ~ P' .. ' ~ ~. O O~ ~ O _~ O ~n ~ ~o ~ ~n ~ J ..
: ~ .- ! ~ _.__ . . ._ _. . 1--~ ~ I- ~ ~ I- ~- ~ ~ ~ cn ~.
~ ~ ~ ~n r~ ~ cr~ ~ ~ ~J O ~ ~. _ ~
~ ~,1 . ~ ~ ~ . ~
. ~oo~ c~o ,` ' _ _ _ __ __ _.___ __ _ ' .
~' ~ . ~ ~ ~ O~ ~ 0~ ~
~,.. ,~ . . IJ
,: . _ _ ~-';', O~ ~ ~ _J ~J
:'~'. . O~_ O ~ ~_ ~n, P~

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

L~;6 ,, .

,~"~ .,r, ~r~
. . , ~
. . . . , ' ' ' ~ ' .

. ,~.
,' . ~, ` iO76114 ~ ~, _ I _ ... _ _ ~ . Z .
.:' ~' o ~o ~ ~ o~ o . ' . . ,.
. ~ IJ ~ I~ ~ i- ~IJ ~IJ ~lJ
~ n ~ ~ ~n ~ n ~ ~ ~n ~ n ~ W ~n . .
.. ~ ~., ~, ~, ~,, ~,, :S~, .: Io' I ID IJ. ~_ ~ o ~ ~ o' ~ ~ l' ~ ~ lOJ ~
~, ~ ~ ~ ~ . ,,, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ . .
~ P~ ~ ~ P~ o ~ ~ ~ P~ ,_ P~ o ~ 1, ~
. ::~ O <D ~ D :~ ~ tD ~ ~ ~D ~ 1~' ~ ~ :5 3' C~
g~ ~ ~ ~ 0 ~ o~ 1_ ~ 0~ ~ :J Co~ Co+ 10-~ ' ~
~g~ ~ q ~ ~ ~ ~-O ~ ~0 ; . . ~ ~~ ~ D ~_ ~ ~ ~o ~ '~' I ~ .
',' ~1 1_ ~:" . ~
.
,:', . .1 ~: _____ _ _ . _ __ _ `''~ IJ ~ ~ 1- IJ ~ ~
. O _~ . ~ . ~ ~_ ~ '; ; l . I l l l C~
"." ~ : O C~ ~ C~ O~ 0~ / .~
. _ ~n, _ _ ~,' ~ ~ ~ `O ~ ~ ~ ~ I_ I_ ~ ~ C~
:` i-- 0 ~ O O` ~Jl ~ ~n: ~ ) ~
.'.~ ~ I' ~ O` ~ C~ ~ ~ O ~ n ~ _ _ _ _ :~ ~ ~ ~n ~ O~ O~ ~ ~ ~ ~ ~ W ~
., . ~ O O `O . . O` O~ :I: ~D
.. ~, ~ . ~o W W~ ~ ~O ~ ~O O O ~ n ~
-: 1- 1- 1- 1-., ~ O O O O I' O _~ ~ `O `O !~
: -: : ~ ~ o~ O~ _~ O _~~ ~n ~ W p .~ : ~n ~ C~ O I~ O~ 1~ O~C~ 1~ ~O O P~
. ~ : ~ _ _ . _ _ "~' ~ .0 ~O ~ ~ ~ ~ ~ ~ c~ co ~ O ~ ~n' :-.: ~ ~ I-- ~ ~ ~_ W ~ CO ~
'~' ~ ~ O` ~ _ GO ~ ~ O .. _ ~
: : ~ ~ ~ ~ ~

' i O~ ~n ~ ~n O~ ~n , . : ~ : C~ CO ~' O~
_ _ _ . _ _ ~ _ '~ : .
~ ~n ~n ~n ~ J~ ~ 0~ ,~
",: . . I~D .' _ _ _ :'~' . ' CO _J CO ~ CO CO _~ ~
.~ O O~ O ~ ~ ~ ~ ~J
'` . O _ O~ Cr~ W ~ _ ~
, `
i ., '.
,.' . .~
. ;,~.1~; '. ' .
r :~ . , ' ' .' ~ ', '' ,' ~ -- - 23 -`: ~761~4 "
_ . __ .
:, ~ ~ ~ ~ ~ ~ ~, ',, ~, ,_ ,, ,_ ,~,_ ~W~ ~, ,_ ~ ~ ~ ~r~ ~ ~r~ ~wr~
~ I ~ ~

... ,. ~ . .
.... ~ ~ , ~ ..... ~ ~ ~o ~ , l r ~ r l c~g ,:.. ~ ~ ~ O .~ ~ ~ .
:. ~ ,. ___ _ _ _ .~. ~ ~ ~n ~n~ ~ ~ O ~ ~ ~ ~ C~ ..
."'~ . ~ 1~ ~O 0,C~ ~o O ~ ~0 1- 1_ ~
., . _ _ _. _ :' : . ~ ~ ~ ~o` o` o` ~. ~ ~ ~ :~
: :` :: l- ~o~, c~ o~ ~ l- ~ ~ ~ c~ lJ
::
`o `o ~o ~ `o `o oo o~ ~: ~
~ ~ ~- ~ o o` ~J ~ o~ ~o iJ --~ .~

b~~ ~ ~ `O ~t~ 1- i~ 1~ ~ ~o ~- to ~,.
;"~ ~ I_ C`~ ~) ~ ~, ~CO- -~ o` o~ o` ~ '-''''';'~ ~ ~ ~ ' . _ _ ___ _ ,,.. _ ~_ ,', -.',"'~ . ' ~' . 'i~
.:: ~ `O-.J _ _ .
-'~'``~, : . I _. I _ ., '` ~Z ~
,,.~ ~n ~n ~n ~ ~n ~ O ,~
,' . IJ
''','' . _ _ '''' CO ~3 ~ ~_ _~ ~ ~IJ
'~' . vl ~n ~O ~ ~__ ~'.' ..
,~
:~'`
_,~
, ' ' ` 'j,i~''~l`'. - '' ' "~
- ,~

'', ; ', V~' . .' ~ ' , .

; - 25 - ~076114 ,.`~.:.
~ .~ _ . .
,~-' . ~ _ ~n ~,`. .
~1 ,~ , ,_ ~ ~ ~
, . I S~ ~ n ct~~~n S ~ ~
I~ ~ ~ ~--J ~ t~ l_~ ~ l~
', 1 ~ ~ ~ ~ ~s ~ ~ ~ , .~.~,"
,, ~ ~ S (D ~ S S ~ c+ tD ~ D C~
. ~, O O S O O 1-- O ~ S O N S
.' 1'~ ~5 ~ I~ D IJ- ~_~ ~ C ~d .~' :~ O IJ :1 0 ~ ~ ~ O
;~' . ' . ~ ,~ I ~ ~ ~
'.'`' l l ~1 , .', ''! : : : . . ~J
'';''. . .
_ : ' ~ ~ ~ ~ IJ IJ 'V X
~ ~.. 1 ~ . o 1~- ~~
~`: ~ l l l l_ ~: i ~' o~ C~ o~ ~-. .
: ~ : ~o ~o . ~ ~o~ ~ l_ _ ~ i~ ~ C~ ~o ,., . : l _ i~ :- ~ , : ~ ~ ~ ~ . ~n ~n ~ ~ ~ I`
. ` ~ . _~ ~ ~0 ~ ~ `o ~n ~ ~ .
., ~ , ~ _ ~
~: : ~ Co ~ ~o ~o~o ~o ~ _~ ~ :
'`. -: : : ~ ~ ,.~ Z: P~ : '''' ~; ~ : ~ ~O _~ O ~ ~n ~ ~ :~
~,~.,. :: ~ _ . _ _ ~
:~ ~_ I_ I_ I_ ~ ~a "",', ~ 0 0 O O O O ~ ~n l ~ : _ _ . _ ~_ .. ~.i . ~ , t~ ,~ r, ~0~0 S A' . ' , ~ ~o O ~~ r . o ~J ___ ' ~ , ~ ~ . ~ ~ ,`
: ~: . .
1 ~ ~D
:~.'.' . _ _ ;; ~ ~ . o ~ ~ E;
.,: ~ ~ ~ ~n ~
., `
.
~ ~ ~:
w ~

; ~
' 1' ~ ~ ' ' 1~.; , : ~ -~~ ~ 26 ~ 10761~4 These hydantoin derivatives have valuable biological properties as herbicides or fungicides. The kind and the position of the substituents on the phenyl ring attached to `
the 3-position of the hydantoin ring have a great influence ` on the biological activity, which is brought about by the group dipole moment. Therefore, among these compounds, those which have a halogen, lower alkyl, lower alkoxyl or halogeno-benzyloxy group at the 4-position of the phenyl group exhibit excellent herbicidal properties. The 3,4-Dihalogenophenyl compounds and the 3-alkyl-4-halogenophenyl compounds also show strong herbicidal activities.
For-example, among the compounds listed in Tables 1 and 2, the following exhibit the most active herbicidal properties:
1,5-trimethylene-3-(4'-chlorophenyl) hydantoin, , .
1,5-trimethylene-3-(4'-bromophenyl) hydantoin, 1,5-trlmethylene-3-(3',4'-dichlorophenyl) hydantoin, 1,5-tetramethylene-3-(4'-chlorophenyl) hydantoin, 1,5-tetramethylene-3-(4'-bromophenyl) hydantoin, :
~ ~ 1,5-tetramethylene-3-(4'-iodophenyl) hydantoin, -~ 1,5-tetramethylene-3-(3',4'-dichlorophenyl) hydantoin, 1,5-tetramethylene-3-/ 4'-(4"-chlorobenzyloxy) phenyl 7 hydantoin, 1,5-tetramethylene-3-(3'-methyl, 4'-chlorophenyl) hydantoin, 1,5-tetramethylene-3-(3'-methyl,4'-bromophenyl) hydantoin, 1,5-tetramethylene-3-(4'-bromophenyl)-2-thiohydantoin, . .
1,5-tetramethylene-3-(4'-iodophenyl)-2-thiohydantoin, 1,5-trimethylene-3-(4'-chlorophenyl)-2-thiohydantoin, 1,5-trimethylene-3-(4'-bromophenyl)-2-thiohydantoin, 1,5-trimethylene-3-(3',4'-dichlorophenyl)-2-thiohydantoin, 1,5-tetramethylene-3-(3'-methyl-4'-chlorophenyl)-2-thiohydantoin, 1,5-tetramethylene~3-C3'-methyl-4'~bromophenyl~2~thiohydantoin, 1,5-tetramethylene-3- ~'~(4"~chlorobenzyloxy I phenyl~2-thiohydantoin, and 1,5-tetramethylene-3-(3~,4'-dichlorophenyl~-2-thiohydantoin, The herbicidal compositions which contain a hydantoin derivative as disclosed in this application possess an unique applicability to soil treatment, foliar treatment, ' ~ '':
., .

~ ~ 27 ~ 10761~4 ; and excellent herbicidal activity against grasses such as igitaria adscendens, Eleusine indica, Echinochloa crus-galli, Poa annua, Cyperus esculentus and Alopecurus aequalis and weeds ~, - .
such as Siegesbeckia pubescens, Amaranthus lividus, Polygonum persicaria, Chenopodium album, Lamium amplexicaule, Acalypha australis, Galinsoga ciliata, Plantago asiatica, Portulaca oleracea, Commelina communis, Pinellia ternata and Artemisia princeps, as well as constituting an improvement in the control of perennial weeds such as Eleocharis acicularis and others.

,:
~ The 3,5-dihalogenophenyl hydantoin compounds such as:
.:
~- 1,5-trimethylene-3-(3',5'-dichlorophenyl) hydantoin, 1,5-tetramethylene-3-(3',5'-dichlorophenyl) hydantoin, -~
.. . . .
1,5-trimethylene-3-(3',5'-dichlorophenyl)-2-thiohydantoin, and 1,5-tetramethylene-3-(3',5'-dichlorophenyl)-2-thiohydantoin show a remarkably high antifungal activity against Botrytis, Pellicularia and Chochlcobolus species. This supports the fact that these hydantoin derivatives are useful in the .. , control of Kidney bean gray mold disease, Rice sheath blight disease,~Rice brown spot disease and others.
, . -: .
l The active compound according to this invention is ,, formulated into a herbicide or fungicide by diluting it with an inert carrier or diluent which may be liquid or solid. To '~:,.: :
`~ obtain a herbicide or a fungicide in the form of a dust, f,'~l :
emulsion, wettable powder or granules, a surface active agent b may e lncorporated. It lS also posslble to add one or more other active ingredients, such as an insecticide, nematocide, ....
~; fertilizer, synergetic agent, plant growth regulator or another herbicide or fungicide to the mixture.
~`-; Examples of liquid carriers which may be used include various solvents; for example, hydrocarbons such as kerosene, benzene and xylene; halogenated hydrocarbons such as chlorobenzene and dichloroethylene; lower alcohols such as .
. :

:':
, , 7~

ethanol, and ketones such as acetone. Examples of thesolid carriers are, bentonite, kaolin, clay ! talc, activated clay, diatomaceous earth, siliceous sand and calcium carbonate.
Examples of the surface active agents which may be used in formulating the herbicidal or fungicidal compositions according to this invention include alkylbenzene sulfonates, lignosulfonates, sulfate esters of higher alcohols or of polyoxyethylene aliphatic esters, polyoxyethylene sorbitan aliphatic esters, dialkyl sulfosuccinates and alkyltrimethyl ammonium chlorides.
The amount of active ingredient to be applied is not critical so long as the intended herbicidal or fungicidal activity is achieved. It is preferable, however, that 5 to 50 g of the active ingredient be applied per 100 m2 when it is used as herbicide. The test results, as set forth below, show the herbicidal activity against various . ~ , .
weeds at the germinating and growing states when used in either foliage or soil treatment.
~; Examples of the formulations of the herbicide and }
fungicide are shown below. The number of the compound employed corresponds to the compound number in Tables 1 and ~ and "part" and "percentage" given therein are by weight unless otherwise defined.

Emulsifiable oil solution of 30 parts of compound 20 in a mixed solvent of 30 parts of N,N-dimethylformamide and 35 parts of xylene was mixed with 5 parts of polyoxyethylene napthyl ether sulfonate to give an emulsion containing . . , 30% of the active ingredient.

~ - 29 ~
10761~4 ~ Wettable Powder .~ .
A wettable powder containing 50% active ingredient was formulated by mixing and grinding 50 parts of compound 47, 10 parts of diatomaceous earth, 35 parts of kaolin and 5 parts of sodium dodecylbenzenesulfonate.
'`'~. ' Granules A mixture of 5 parts of compound 19, 27 parts of -diatomaceous earth, 66 parts of bentonite and 2 parts ,. .
~ of Aerole CT-l ~a surface active agent available from , Toho Chemical Industries Limited) was kneaded with water ;
and granulated. The resulting granules were dried at 60C for two hours to obtain a herbicide` containing 5%
of the active ingredient.
The following test examples show the herbicidal i i~ or fungicidal effect of the present invention.
`;
Test Example 1 (Paddy Field Application) Wagner's pots (1/50 m ) packed with soil from a paddy field are employed. Soil which contains the seeds of barnyard grass (Echinochloa crus~~alli) and toothcup (Rotala indica) was spread on the surface of the pots ~ i and rice seedlings (the true three leaf stage) were planted.

The depth of the water was maintained at 3 cm. After five days, herbicide in the form of granules was uniformly .. ~
applied to the surface of water in a dosage of 10 g and 30 g of active ingredient per 100 m2. The water was then drained from the bottom of the pot at a rate of three cm/day for three days. Twenty-five days after application, the herbicidal and phytotoxic effects on the rice plants were observed.

.'~ , ,.~
''' ' ----_ 30 10761~4 For the purpose of comparison, similar tests were conducted using a commercially available herbicide which contained N,N-diethyl-S-(4-chlorobenzyl) thiolcarhamate, as the active ingredient, and the results are set forth in . .
Table 3~ The means of the numbers used in the evaluation of the heFbicidal and phytotoxic effects are as follows:

Figures Herbicidal Effect Phytotoxicity ., .
;, :::
O None None 1 : Trace Trace 2 Slight Slight N :: 3 Moderate Moderate

4 Severe Severe Dead Dead "~
` 'i ~ :

''.; i~ ~ : :

, "; ,, `
.i ~ , , '"~
'~ ' " ' ''~"' ' '"
,~
'~

~:

:~ `-- - 31 -'' ' ;; 1076~
~ .
., ~: ` Table 3 ..
.~ _ . ~osage _ l~erbiciaal effect ¦ :.
. . Compd. ~o. g/lOOm2 rAs~ Toothcup Fhytotoxicity . . . _ _ . R :' . . 3 30 ~. 5 o : , lo 3 ~ o . 5 ~30 5 5 o . . 10 l~ 5 0 6 . 3o 5 5 o ` lo . 5 5 o '; : 310 3' 5 o ::
: .~2 3o 4 ~ o :~:; 10 2 4 0 . . ~ 13 30 1~ 5 o ., ~ ~ lo 3 ~ 0 ; ~ 15 30 5 5 0 :
. ~ llo ~: 5 o ~; : 16 : 3 5 5 o .
lo 5 5 o ~": ~ 17 30 5 5 o ` ~ 10 ~ ~ 5 o ~8 30 5 5 0 ~.~ ~ : 10 5 5 0 .,~ ~ 19 30 5 5 o `. : : lo 5 5 o ~ .
~` ~ 21 30 5 5 o .. .
~: . 10 5 5 .
. :: 23 30 5 5 0 . : . . lo 5 5 . 0 - '. 24 3 5 5 0 ~. _ 10 4 S

'"`.,'' ;,.~, . .
:'.
. , ,:;
."
~ ' . . .' : l- ~ ",i, "
i;
J~

~:: ` - 32 - 1076~
` . , .

: . . ._ ~os~geHerbicid~l effect ComFd. No.g/lOOm2 B~rny~rd- Toothcup Phytotoxicity - ~ _~r~s~ _ . 25 310 5 5 O

. 27 3 5 5 O
~: 10 5 5 O

. ~ 3 30 3~ 55 O

1~ 5 O

; 33 31~ 5 5 0 . O

, : l~O 30 5 5 O

.~ ~ 142 31O ~5 ~ 5 0 ,.`. ~ 43 310 5 . 5 O

~ ~ ~5 310 5 5 0 `'~ ; ~ ~,6 310 55 55 O

i~ ~ . .l~ 3 5 5 O
.~ ~ 10 5 5 O
` 51 31 4 5 O

~: ~ ~ ~2 55 5 _ ~

': . . - : ' _ __ _.
~` ~
` J`! ,~ ' . I ' :
.~ ~

., ,. , ' , ' , ' .

~ '~ ~ 33 ~ ~076114 '.,.` .. :
~ _ Herbicidal effect _ . : Co~pd. No. ~o~age ~arny~rd- l Phytotoxicity ; g/lOOmp~ asa Toothcup ~ . 5~ 30 5 5 O

'~ ~ 55 30 3 S O
.
~` . Control 10 55 5 O

.. No O . O O
.~: Application .
~.. : : . .
.
,"~ , - .
:

j ~ ~ , .
,: :, ! ' ' '.'; : .
''.`.~'~ ":
~;~; ':
i'':'~
'.~:'' :
;~ ~' '''`' ~: ~ :: - ~:
~,'" .~
` :``, ' ~ ~ ~
,''~,'-`~ ; ~ .

-. t ~ :

f~ ~

'' ''~i . .
. ~ ' ~' ' '~ '.
'~' ., ~ . ",,-:' ~

,''', ~ ' ' '` '', ' ". ' '.
. . .

Test Example 2 (Soil Application) : ~ .
Wheat, soybean and corn were seeded at a depth of 2-3 cm in 1/50 m Wagner's pots which contained seeds of crab-grass (Digitaria adscendens) and hairy galinsoga , (Galinsoga ciliata). Then aqueous di]utions of the wettable powder described in this application were applied to the surface of the pot in a dosage of 10 g and 30 g per 100 m2.
The herbicidal and phytotoxic effects were observed - twenty-five days after the application.
For the purpose of comparison, the same tests were conducted using a comercially available herbicide which contained 3-(3',4'-dichlorophenyl)-1!1-dimethylurea.
` The results are set forth in Table 4.

: , ~` Table r~ N~. g/ ~ llsrbic1~ ~l `f ~ Wheat Soybsan Corn~

2 3 ~ 5 0 l 0 3 310 3 5 o o o :~

310 ~ l55 0 o `

7 3o 5 5 0 0 0 ~ 10 5 5 0 0 0 ; g 310 55 55 0 0 0 3 ~ 5 0 0 0 3 ~ 0 0 0 , 12 3 ~ ~ 0 0 0 2 - 3 0 0 __ . . __ ~ . , '. , .

.

.-- - 107~
~l _ Dos~ge Herbici ~al eff t TtotoXiCitY
. Compd. No. g/lOOm2Crraabs9_ Hairy '~heatSoybean Corn ,,'t 1' 16 3 5 5 O O O

22 31O 5 ~55 O O O

` . . 25 30 ~ 5 5 O O O

; 26 31O 55 55 0 O O

` ~ 32 310 55 55 O O O

~. ~ 31~ 300 55 55 O O O

.I ~ 39 3o 5 5 O O O
. 1.0 3 5 O O O
, ! : 4 1 3 0 l, 5 O O O
: . 10 3 5 . O O O
: ~4 30 . 5 5 O . O O

;~ ~6 31O 5 ~ 5 ~ O O
~i ~; ~ :47 31O 5 5 00 O O

~; ~ ' 50 30 4 5 O . O o ~: 5Z 310 5 55 O . O 0 . ~, . _ ~ ~__ _ __ _ _ : ~ Control 30 5 5 1 O O
,.,, ~ . 10 4 5 O O O
:~ lio _ . O O O O
: ~Appli cation _ :`,', . , '' "''`. ~
.'''~.,1~'',''''' ' ' ' .
, '~,'~' ' .
r. . p~c . . . . ...
. ~ ,S . , ~076~14 3~

Test Example 3 (Foliar Application) , . \
sarnyard grass (Echinochloa crus-galli), crab-grass \~ ~Digitaria adscendens) and radish (Raphanus sativas) were seeded in 1/50 m2 Wagner's pots and, after growing the j plants, the foliage was sprayed with emulsions containing / 0.1~ and 0.3% of active ingredient, in an amount of 10 ; / litres per 100 m2 by a small pressurized spray-gun (0.5 -/ 1.0 kg/cm2). The herbicidal effects were observed twenty days after the application.
The herbicide was sprayed in the 2 - 3 leaf stage in : . . .
cases of bardyard grass and crab-grass and in the first true leaf stage in the radishes.
For comparison, the same tests were conducted using a commercially available herbicide which contains 3,4-dichloropropionanilide as a control. -~ . .
; ~ The results are set forth in Table 5. - ~

'.~"'''~ ~; '' Table 5 . .
H erb~,~_ef l` ec , . Compd. No. concentrAtion j Barnyard-. Crab- _ Ra~ish 0~ 3 '; :.' . .

. _ 37 _ 1~76~1~
., . ' ' '.

- _ Concentration Herl licid~l efrect Compd . No . (~) ,~rass Cr b- Rad i3h ~: . 23 031 ~ 55 0.3 5 5 5 ., -,:; : (j.l 5 5 5 ~:

` ~i35 00 3 t 5 55 55 , ~ l;l 03 ~2 3 ~3 ~ ~ ~ - 1~6 0 3 - 5 55 5 -,~ ~: ~9 03 5 . 55 ~ 5

5 0 0 31 5 . 5 5 52 0 3 5 5 3 .

~ ~ _ : _ _ ~ 1 ~ Icon~rol 031 L~ s s ~ ~
. :` Application ., : . _ __ .. ~. ..
' ::' ..
,~.

,., ~ "' ' ' ' ' ' , 1~'; ,.' ' ' ' ' , '- .

.... . .

~6~1~

'~: ' .-. Test Example 4 (Protection Test Against Kidney Bean Gray Mold Disease) Kidney bean plants in the true-leaf stage were , sprayed with a 25 ml suspension of the wettable powder " of the tested compounds, After drying, the leaves were inoculated with a 6 mm agar disc containing pathogenic -:
: mycelia of Botrytis cinerea, and the plants were incubated in the humidity chamber at 23C for four days. .
Protection value (%) was calculated according to the :
following equation. ;
~ - Protection value Disease severitVyrindYexnduntXrterataede(A~ x 100 :'~ The results are shown in Table 6.
. ~

Table 6 : ~ Concentration Protection Compd. No. (ppm) Value (%~

. ~ - .

~ 56 500 84.0 .. 57 500 78.4 ;~ Untreated 0.0 ,, ~ , .~, , , . ~
"':i :. ' ."'' '' ' .
., .
. .

~`
.

,, .

': ~S p~

` 10'76~4 . - 39 -:
; Test Example 5 ~Preventive Effect Against Rice Sheath slight Disease) Rice plants ~Cultivar; Kinmaze) in the 5-6 leaf stage, grown in the 9 cm pots in a greenhouse and cut 20-30 cm high, were sprayed with suspensions ~20 ml per pot) of wettable powder of the chemicals tested.
After drying, the plants were inoculated with pathogenic mycelia ~Pellicularia sasakii) and cultured for seven days ~, :
.~ on wheat bran medium. These pots were covered with poly f ~: : . . .
vinyl cases to retain humidity and incubated in a humid chamber ~25 - 27C). Twenty days later, the disease severity index was determined and the preventive effects -~ of the chemicals were calculated according to the following equation.

Preventive VaIue - (A~-Dlse~se s~ ir ~ ~ x IOO
Disease severlty lnoex Imtreated A) . , .
~ The results are shown in the table 7.
. ~ . .
,;
Table 7 ~: ConcentrationPreventive V~l~e - ~ Compd. ~lo. (ppm) (~) 29 500 9~.1 ., . I
; 57 500 73.2 . Untreated 0.0 .; :

, ~ ,.
.

~ - 4~ ~
; ~L076~L14 ....... ., .
Test Example 6 (Preventive Effect Test of Rice Brown~Spot ~iseaseL
., _ ~ ,.

Rice plants (cultivar: Kinmaze, 4-5 leaf stage), grown in 9 cm pots in a greenhouse, were sprayed with a suspension (20 ml/pot) of the wettable powder of the chemicals being tested. After drying, these plants were inoculated with a suspension containing pathogenic spores ~(Chochliobolus ~.
miyabeanusj. These plants were incubated in a humid chamber (25-27C). After forty-eight hours, the number of.
1 . .
~ lesions were counted and the preventive value was calcul- I :
! , ~
~: ~ ated according to the following equation.
:
(A)- number of lesions treated x 100 .. ~: Preventive value = Number of lesions untreated(A) . ~ 1 .. I .
~ . .
, The results are shown in Table 8.

:-,' :::
1. : Table 8 .. ; -- .

Compound Concentration Preventive :- ~ No. (ppm) Value (~) :
~; 28 500 91.8 .- 29 500 85.9 ....... . .

56 500 98.6 !1 Untreated 0.0 ., . ~ 1 . :
,'' , .
,, .

.,' ' ~
. I .
,~ l .';'- . I

, ,~

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A 1,5-alkylene-3-substituted hydantoin derivative of the formula wherein n is 3 or 4, X is oxygen or sulphur, with the provisos that when X is oxygen, R is a phenyl group having at least one substituent selected from the group consisting of halogen, alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, nitro, trifluoromethyl and halogenobenzyloxy group; and when X is sulphur, R is trifluoromethyl, halogenobenzyloxy and naphthyl.

2. A derivative according to Claim 1 wherein n is 3, and R is a phenyl group having at least one substituent selected from halogen, alkyl containing 1 to 4 carbon atoms, alkoxyl containing 1 to 4 carbon atoms and halogenobenzyloxy.

3. : A derivative according to Claim 1 wherein n is 4, X is oxygen and R is phenyl group having at least one substituent selected from halogen, alkyl containing 1 to 4 carbon atoms, alkoxyl containing 1 to 4 carbon atoms and halogenobenzyloxy.

4. A derivative according to Claim 1 wherein n is 4, X is sulphur and R is phenyl group substituted by halogenobenzyloxy group.

5. A derivate according to Claim 2 wherein R is a phenyl group having a halogen attached to 4-position of benzene ring.

6. A derivative according to Claim 3 wherein R is a phenyl group having a halogen attached to the 4-position of the benzene ring.

7. A derivative according to Claim 1 wherein R is 3,5-dichlorophenyl.

8. 1,5-tetramethylene-3-(4'-chlorophenyl) hydantoin.

9. 1,5-tetramethylene-3-(4'-bromophenyl) hydantoin.

10. 1,5-tetramethylene-3-(3'-methyl-4'-chlorophenyl) hydantoin.

11. 1,5-tetramethylene-3-(3',4'-dichlorophenyl) hydantoin.

12. 1,5-tetramethylene-3-(3',5'~dichlorophenyl) hydantoin.

13. 1,5-trlmethylene-3-(3',5'-dichlorophenyl) hydantoin.

14. A method for producing a 1,5-alkylene-3-substituted hydantoin derivative of the formula wherein n is 3 or 4, X is oxygen or sulphur, with the provisos that when X is oxygen, R is a phenyl group having at least one substituent selected from the group consisting of halogen, alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4 carbon atoms, nitro, trifluoromethyl and halogenobenzyloxy group; and when X is sulphur, R is trifluoromethyl, halogenobenzyloxy and naphthyl which comprises cyclizing an N-(N'-substituted carbamyl) imino acid of the general formula wherein n is 3 or 4, R is a phenyl group having at least one substituent selected from the group consisting of halo-gen, alkyl containing 1 to 4 carbon atoms, alkoxyl contain-ing 1 to 4 carbon atoms, nitro, trifluoromethyl and halogenobenzyloxy, or reacting an imino acid of the general formula with an aryl isocyanate acid of the formula OCN-R
to produce said hydantoin derivative wherein X is oxygen, or reacting an imino acid of the general formula wherein R' is hydrogen or lower alkyl, with an aryl isothiocyanate of the general formula SCN-R
wherein R is trifluoromethyl, halogenobenzyloxy or naphthyl, to produce said hydantoin derivative wherein X
is sulphur.

15. A method according to claim 14 for produaing a 1,5-alkylene-3-substituted hydantoin derivative represented by the general formula.

wherein n is 3 or 4, R is a phenyl group having at least one substituent selected ~rom the group consisting of halogen, alkyl containing 1 to 4 carbon atoms, alkoxyl containing 1 to 4 carbon atoms, nitro, trifluoromethyl and halogenobenzyloxy, which comprises cyclizing an N-(N'-substituted carbamyl) imino acid represented by general formula

16. A method according to claim 14 for producing a 1,5-alkylene-3-substituted hydantoin derivative represented by the general formula.

wherein n is 3 or 4, R is a phenyl group having at least one substituent selected from the group consisting of halogen, alkyl containing 1 to 4 carbon atoms, alkoxyl containing 1 to 4 carbon atoms, nitro, trifluoromethyl and halogenobenzyloxy, which comprises reacting an imino acid of the general formula with an aryl isocyanate acid of the formula OCN-R

17. A method according to claim 14 for producing a 1,5-alkylene-3-substituted hydantoin derivative represented by the general formula wherein n is 3 or 4, R is trifluoromethyl, halogenobenzyloxy or naphthyl.