CA1049547A

CA1049547A - Soil fungicidal phosphorothioate

Info

Publication number: CA1049547A
Application number: CA217,814A
Authority: CA
Inventors: Toshiro Kato; Mitsuru Sasaki; Tadashi Ooishi; Kunio Mukai
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 1974-01-14
Filing date: 1975-01-13
Publication date: 1979-02-27
Also published as: DE2501040A1; PL94954B1; GB1467561A; DK137761B; DE2501040B2; CH612943A5; HU172092B; NL7500293A; DK5675A; FR2257598A1; CS181284B2; SU701517A3; IT1036863B; ES433737A1; TR18202A; IL46427A0; DK137761C; NL157309B; FR2257598B1; IL46427A

Abstract

ABSTRACT OF THE DISCLOSURE
Novel phosphorothioates represented by the formula,

Description

~49S47 1 This invention relates to a novel organic phosphoric acid ester compound represented by the formula~
S Rl . .' / ~ (I) CH O

wherein Rl a~d R3, which may be same or different,~ are individually a chlorine or bromine atom, and R2 is a : .
methyl or ethyl group; to a process for preparing the samei and to a soil fungicide containing said compound as an active ingredient.
.
Plant diseases derived from plant pathogenic fungl, wh1ch exist in soil to give great damage to agricultural and horticultural crops by~infection, have heretofore been feared as~a kind of the most ~
di~icultly controllable dieseases. Although several soil fungicides are being actually used to control said diseases, these fungicides have no sùfficient controlling effects.
- On the other hand, environmental pollution - due to agricultural chemicals has come to be a serious problem in recent years, and there has strongly been .
desired the advent of agricultural chemicals which are less toxic to mammals and fishes, do not show phytoto-xicity to crops~ do not remain in crops and have ~ sufficient controlling effects.
j ~In consideration of the above-mentioned .
points, the present inventors~conducted extensive ...
.

- . ~ , . , ~

~049547 i ~1 examinations from various viewpoints on organic phosphoric acid ester compoundsO As the result, the inventors have been successful in developing entirely novel soil fungicides which show sufficient controlling effects, are markedly less toxic to mammals and fishes, show no phytotoxicity to crops and do not remain in cropsO
~ The compounds of the present invention have markedly excellent controlling effects on substantially all of soll-borne plant diseases such as damping-off and "Bakanae" disease of rice plants, damping-off of seedlings~ and damping-off, Fusarlum wilts~ yellows~
Verticillium wilts, southern blight, rot, late blight of agricultural and horicultural crops. At the same time, the compounds have actions~to promote the spread of root portions of crops to rnake the growth o~ the crops vigorous, and particularly show prominent effects against damping-off of seedlings and foot rot of crops which are diseases derived from fungi belonging to the genus Rhizoctonia. It-is needless to say that they have no phytotoxicity on every crop.~
On the other hand~ the compounds of the present invention are extremely low in toxicity to warm-blooded animals such as mice, rats~ dogs and chickens, and~fishes such as carps and gold-fishes. Furthermore, the .
compounds scarcely remain in crops.
The~above-mentioned.facts indicate that the compounds of the present invention are ideal soil fungicides capable of promoting the growth of agricul~
tural crops without causing any enviromnental pollution.

- 2 -~049S~7 : -:
.
1 The present inventors sufficiently examined '-ln detail the soil-borne disease-controlling effects of many organlc phosphoric acid ester compounds9 but no effects of controlling soil-borne'diseases could be seen even in those which were quite similar in structure to the present compounds.' The compounds disclosed in Australian Patent . , .
' 294,072~ which is a prior art to the present invention, are relatively similar in chemical structure to the 10- present compounds, but did not show any soil-borne .- .
disease-controlling effects (refer to Test Examples 1, -' 2 and 3)0 Furthera 0-2,4,6-trichlorophenyl 0,0~
. : ~
dimethyl thiophosphate disclosed in United States Patent 2~5999512 as parasitic1des, which compound is quite similar to the present compounds, shows strong neurotoxicity to chickens, and hence cannot be a suitable : ~ , soiI fungicide. On the other'hand, the present~compounds~
show no neurotoxicity to chickens at all, and are extremely'hlgh in safety.
The excellent controlling effects and~low toxicity of the present compounds are ascribable to such specific structure and substituents thereof as ~ ~ ' represented~by the formula (I).
In spite of there existing many organic ' ~ ' phosphoric acid ester compounds hitherto 9 the present -inventors have found that only the compounds represented b~ the formula (I) can show excellent effects of ~' preventing soil-borne diseases. Thus, the present '' invention, which is based on the'above~finding, is not only extremely high in inventive~ idea but~al'so ~ 3 ~
:: ~ . , . ' - ! 1049547 ~ ~

1 entirely different from the prior art~
.; The present compounds can be prepared with ease and in high yields by rea.cting a. 2,4,6-trisub-stituted phenol represented by the formula9 Rl R2 ~ - OM

' ~3 ' ~:~

wherein Rl and R3, which may be same or different, are individua.lly a chlorine or bromine a.tom; M is a hydrogen : . atom, an alkali metal or an a.mmonium group; and R2 is a methyl or ethyl group~ with O,O-dimethylthlophosphoryl .
chloride preferably in the presence of an a.~cid bindin~ ' agent~ or by reacting a salt of said 2,'496-trisubstituted .
phenol with O~O-dimethylthiophosphoryl chloride. :~ .
:' ' The above-mentioned reaction is pr`efera.bly' : :~
.
carried out in an inert organic solvent, which may be any o~, for example, aliphatic or aromatic hydrocarbons ,:
(including halides) such as benzene~ toluene and chloroform; ethers such as dieth~l~'ether, dioxane and : t~trahydrofuran; and allphatic alcohols and ketones such as methanol, acetone and methylisobutylketone. ~ ..
; Examples of the acid binding agent are ~ ~
20 sodium hydroxide; potassium hydroxide; alkali metal -.
carbona.tes and bicarbonates such as potassium ca.rbonate ~':
and sodium carbonates;:sodium or potassium methylates~
and ethylates; and aliphatic, aromatic or heterocyclic :: tertiary bases such as pyridine, triethylamine and ~ ' ~ 2~ N,N-diethylaniline.
- , ' .

-.. .. ,. , .~ ., " , : :~ . , ,. , ,.:.. .. .. .. . .

!: io 49 547 . i . 1 Alternatively~ the said reaction ma.y be ~effected~by converting the aforesaid 2~4~6-trisubstituted phenol into a salt~ preferably an alkali metal or ammonium salt~ and then reacting the said salt with -: 5 O~O-dimethylthiophosphoryl chloride.
~ Each o~ the above-mentioned reactions may be :~ : carried out at a temperature in a considera.bly broad . ~ range9 but is ordinarily effected at 20 to 110C., :prefera.bly 70 to 100C. The reactions may be represented :;-by the following reaction scheme 1 Reaction scheme 1~

~: : R~ S ~ R: S ~ `
1 U ," OCH ,_~ 1 ll ~ OCH
R2~ 0 ~OM -~ CL-P ~ 3 ~--~ R2~ 0-P ~ 3 OC~ R 3 wherein ~19 R2, R3 and M are~as defined previou~ly.
: Alternatively~ the present compounds may be :prepared by rea.cting the a.foresaid 2~6-trisubstltuted~
- . ~
phenol with phosphorus trichloride at an elevated temperature in the presence of an acld~ binding a~8ent and an inert solvent~ and then with thiophosphoryl : .trichloride at about room temperature in the presence -o~ a~ inert solvent to form a 2~476-trisubstituted 20 phenyl thiophosphoryl dichloride~ and then reacting : ~
the said dichloride:with sodium or potassium methylate,:: : ~-: ~or with methanol in the presence of an :acid bindlng .
agent~ in the presence of an inert~solvent at a :. temperature ranging from room temperature to the : -~
Z5 boillne~polnt of the sol~ent. This reaotlon may be ;:

5 -- ~ ~ :
.

~0495~7 .
1 represented by the following reaction scheme 2:
Reaction scheme 2:

R2~0H ~ PC13 Heating R2~0-P~ + HCl R3 R `

' --P\ + PSC13 ~ R2 ~ 0-P~ + PC13 R3 temp. ~ R3 Rl 1I Cl ` OM 'R ~ Rl O ~ O C1~3 2~ \ Cl 3Room 2 ~ ~ OCH3 R3 ~ temp. R3 ~ `~
. ~

:- + 2M~Cl wherein R1, R2 and R3 are a.s defined above9 and M~ is a ; ~ hydrogen atom or an alka.li metal.
:` :
: ~ 5 : Further~ the present compounds may be obtained also by reacting the aforesaid 2,4,6-trisubstituted ~`
~henol with thiophosphoryl trichloride in the presence o~ an acid bi~ing agent under cooling conditions to form a dichloride~ and then reacting the said dlchloride with sodium or potassium methylate, or with methanol in the presence of an acid binding agent~ in the presence .. .
of an inert solvent at a temperature ranging from room~
~ temperature to the boiling point of the solvent. This : reaction may be represented~by the following reaction scheme 3 ` - 6 .

-;

49S~7 1 Reaction scheme 3:
Rl Rl S
R ~ OH + PSC13 - ~ R2 ~ o_p~ + HCl 2 Under Cl . -.
R3 cooling 3 ..
S
R ~ O-P + 2CH OM' _ 2 ~_~ ~ Cl 3 Room R3 : tempO

,OCH3 -R2~ ~ ~~P~ + 2M'Cl y OCH

- ~' , .
-: wherein ~ , R27 R3 and M' are as~defined in the :: ~
- ~ .
. reaction scheme 2. - :
: Chemical structures and physical constants ~: : 5 of the present compounds are as shown in Table 1. ~

: ~ . . . . , ~ , .
: . ~
- Table 1 .
: Compound Chemical Physical No. - ~ structure constant - . , -- ,. . . .
: ~ : S Cl CH30 ~ P-- ~ 3 m-p- 79-79.5C

S Cl (2) ~:3 ~ P-O ~ -CH3 m.p. 73-7~C .

3 Br Cont'd -. . ~ , .

-. :
i049S47 !
S Br (3) 3 ~ P-0 ~ CH m;p. 81-83C
3Br .

CH30 ~ ~ 2 5 n18 0 ~: 1.5500 S Cl~ ~ :
(5) 3~p_o~C2H5 n20-0~ ~ 1.5620 3Br .

.
S Br .
(6) ~ 3 ~P- ~ C2H5 n2 ~: 1.5672 In actual application, the present compounds ;~
.
: , ~ma~ be used as they are or in the form of any conventio~
nal preparations such as granul.es, dusts, fine gr~anules,~ .~. .
: -~ wettable powders and emulsifia.ble:concentrates. In : :~ 5 these preparations, the present compounds may be conta1ned ..
, , as active in~redients in an amount~of O.l to~about 90%~
~ preferably 5 to 60%. It is-~desirable that these : preparations are used properly according to thsir appl1ca~
tlon purposes. The prep~rations may be:applied by any such procedure as sprinkling, dusting, spra.ying, : granule-sprinkling, soil-mixing, injection,~irr1gatio~
~ : seed dressing and dipping, and prominent fungicidal :~
: - effects~of the preparations can be displa~sd~by a.dopt1on~ of suitable a.pplication procedure.

- 8 ~

~049S6~7 ~ . .
1 In rormulating the above-mentioned prepara-. tions7 there may be used any of solid ca.rriers~ liquid carriers and emulsifiers. Examples of the solid carriers include talc~ bentonite, clay~ kaolin~ .
diatomaceous earth~ vermiculite and slaked lime;
examples of the liquid carriers include benzens, alcohols~ acetone, xylene, dioxane, methylnaphthalene a~d cyclohexanone; and examples of the emulsifiers :include alkyl sulfuric acid esters, alkyl sulfonates, aryl.sulfonates, polyethylene glycol ethers and . ~ polyhydric alcohol esters.
When the present compounds are used in admixture with one or more~of other fungicldes : and the resulting compositions are applied in proper .
~ ~: 15 forms to soil, effects of controlling soil-borne : g : . diseases can be fa.r more increased. Chemicals which ` ~ : .
~ ca~ greatly increase the controlling effects when used~
:. ~ in admixture with the present compounds are~N-trichloro-methylthio tetrahydrophthalimide,:sodium p-dimethyl-. .
20~ aminophenyl diazosulfonate,`5-ethoxy:-3-trichloromethyI~
2~4~thiadiazole~ 5-methyl-3-hydroxy-1,2-oxazole and ; 1,4-dichloro-2,5-dimethoxybenzene. ::It is needless to ~ :
:~ ~ say that the present compounds can be used in~
admixture aIso with fungicides other than those - .~
: ~ 25 mentioned above, insecticides, nematocides, herbicides........ ~ ~ .
and~fertilizers~ and the resulting compositions can greatly contribute to the~simultaneous control of . ~. diesases and injurious insects and to the promotion ~ ~.
- : of growth of:cropsO `~
; 30 ~ The present invention is explained in more . ,. . ,. .
- . , i . ~ . .

~049547 ::
1 detail below with reference to examples9 but the examples are by way of illustration and not by way of limitationO
Example 1 (Compound No. 1): .
To a solution Or 17.7 g. of 2,6-dichloro-4-methylphenol in 50 ml. of toluene was added 6.9 g. of potassium carbonate. Into the resulting mixture, 16.0 g.
of 0~0-dimethylthiophosphoryl chloride was dropped at 50 to 60Co with stirring. After completion of the dropping, the stirring was further continued at 80 to 85C. for 3 ' hours. Thereafter~ the reaction liquid was cooled to 20 to 2 ~Cc and then charged with water~to separate the liquid into water and toluene lay'ers. The toluene layer -was dried with 5 g. of Glauber's salt.~ Subsequently, ~' ' ' the Glauber's salt was separated by filtration, and the 'toluene was removed by distillation, whereby a solid residue was formed; This residue was`recrystallized ~ ~' from methanol to obtain 20.3 g. of whi'te crystals of 090-dimethyl-0-2,6-dichloro-~-methylphenyl phosphoro~
thioate having a melting point of 79~to 79. ~C.`
Example 2 (Compound No. 2)~
To a solution of 22.0 gO of 2-bromo-~-methyl- ' - 6-chlorophenol in 50 ml. of methyl isobutyl ketone was~ ' ' ' .
~ added 5.3 g. of sbdium carbonate. Into the resulting - ' 25 mixture, 16.0 g. of 0,0-dimethylthiophosphoryl chloride was dropped at 70 ~to 75C. ~After completion ~
of the dropping, the mixture ~as heated with stirring ~ ' . ,. . ~ .
at 100 to 105C. for 2 hours. Thereafter, the ~ ' ~; reaction liquid was allowed to cool,~and then charged '' with water to separate the liquid into water and methyl ~' .

:
.
1a~49547 .
1 isobutyl ketone layers~ Subsequently, the methyl iso-. butyl ketone was removed by distillation, and the residue was quickly cooled to form a. solid. This solid was recrystallized from n-hexane to obtain 18.0 g~ of white crystals of 0~0-dimethyl-~-2-bromo-

4-methyl-6-chlorophenyl phosphorothioate having a melting point of 73 to 74C.
: Example 3 (Compound No. 3):
To a sodium methylate prepared by reactlon lO of 406 g. of metallic sodium with lO0 ml. of metha.nol : .: was added 26.4 gO of 2g6-dibromo-4-methylphenol. ~ ~
- ::
From the resulting mixture, the methanol was emoved -by distillation to form a sodium;salt of 2,6-dibromo-4-methylphenolO This sodium salt was gradually added -.
to a solution of 16.0 g. of 0,0-dimethylthiophosphoryl .
~: ~ chIoride in 100 ml. of toluene. After stirring at;
said temperature for 2 hours,.the~reaction liquid was charged with water to separate the liquid into water and~toluene layers. The toluene layer wa.s dried with Glauber's salt. Subsequently the Gla.uber's salt wa.s sepa.rated by filtration and the toluene was removed by distillation, whereby a solid residue was formed.
This residue was recrystallized~from methanol to obta.in 18.0 gO of white crystals of 0,0-dimethyl-0-2,6-dibromo- . ~:
: 25 4-methylphenyl phosphorothioate having a melting point of 81 to 83C.
Example 4 (Compound No. 4)~
. ~ ~ In the same manner as in Example l, 0,0- -; dimethyl-0-2,6-dichloro-4 ethylphenyl phosphorothioate was obtained, nl8 = 1.5500.

;

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

~L~49S47 1 Example 5 (Compound No. 5):
In the same manner as in Example 2, 0,0-dimethyl-0-2-bromo-6-chloro-~-ethylphenyl phosphoro-thioate was obtained, n2D0'0 = 1~56200

-5 Example 6 (Compound NoO 6): ~ ' ~ In the same manner as in Example 3, 0,0-`~ dimethyl-0-2,6-dibromo-4-ethylphenyl phosphorothioate wa~ obtained, n200 - 1.5672.
(Provided that no recrystallization was required ~i ~ . : . .. .
in each of Examples ~, 5 and 6.)~
~Example 7 (Compound No. 1): ' '' . .
~ 1707 Grams of 2,6-dichloro-4-methylphenol was added to 27O5 g. of phosphorus trichloride with stirring at 20 to 25C. The resulting mixture was allowed to stand at 7 ~ to 80C. for 3 hours, and then .
subjected to fractionation to collect 19.~ g. o~
' fractions having a boiling point~of 120 to 125C at 0.6 mmHg. `The~collected fractlon was mixed with~16.9 g. ~ -o~ thiophosphoryl trichloride,~and the resulting~mixture~
., 20 was refluxed for 2 hours. ~Thereafter, the mixture~was ~ ' fractionated to obtain 28.2 g.~o~ fractions having~a boiling point of 90 to 92C at 0.01 mmHg. To a solution ~' -o~ said fractions in 300 mlO of toluene;, 10.0 g. of '~ sodium methylate was gradually added at 20 to 2'5 C.
: :
After stirring at said temperature for 3 hours, the . : . . .
reaction liquid was charged with water to separate the liquid into water and toluene layers. The toluene layer was dried with-Glauber's salt. Subsequently, .
; the Glauber's saIt was separated by fil~ration, and the ~
toluene`was removed by distillation, whereby a solid ~'' - - 12 - ~
- . : .

~04~547 .... , . : .
1 residue was formed. The residue was recrystallized .
from methanol to obtain 23.0 g. of white crystals of ~0~0-dimethyl-0-2~6-dichloro-4-methyl-phenyl phosphoro-thioate having a melting point of 79 to 79.5C.
- 5 Example 8 (Compound No. 1): -Into a solution of 28.0 g. of thiophosphoryl trichloride and 17.7 g. of 296-dichloro-4-methylphenol i~ 50 g. of toluene was dropped at~0 to 5 C. 13.3 g.
of triethylamine. The resulting mixture was maintained -at 20 to 25C. for 2 hours9 and then charged with 50 ml.
of a 5 % aqueous ECl solution to separate the reaction~
- liquid into water and toluene layers. After washing ~ ~ -twice with 50 g. of water~ the toluene layer was dried~
with Glauber's salt. Subsequently, the Glauber's salt was separated by filtration and the toluene was removed by distillation~ whereby a solid residue was formed.
` This residue was subjected to fractionation to collect 25aO g. of fractions having a boiling point of 90 to 92 C
at OoOl mmHg. To a solution of sàid fractions in 300~ ml.
: . ~ , - . , Or toluene~ 8.7 g. of sodlum methylate was gradually added at 20 to 25C. After stirr mg at said temperature for 3 hours, the reaction liquid was~charged with , ~ .
water to separate the liquid into water and toluene layers. Tha toluene layer was dried with Glauber's salt. Subsequently~ ~he Glauber's salt was separated ~, by filtration, and the toluene was removed by distilla-tion~ whereby a solid residue was formed. This residue was recrystallized from ~ethanol to obtain 14.6 g. of ~

`~ white crystals of 0,0-dimethyl-0-2,6-dichloro-4-methyl-, phenyl phosphorothioate having a melting point of 79 ~;
- 13 - ~
, - : :
:: -.

.. .
.

~049547 'l ~o 79.5C~ , . , Procedures for compounding the present i compounds into fungicidal compositions are expla,ined in detail below with reference to compounding examples, 5 but the kinds and proportions of additives for the ~:
present compounds are va.riable within broad scopes without being limited to those shown in the exa,mples. :, In the examples~ all the parts are by weight. , -- ` Compounding Example 1 ~ust~
A mixture comprising lO parts of the present ' ~ '.
compound (l) and 90 pa,rts of clay was sufficiently . .
pulverized to obta.in a dust conta,ining 10% of active -ingredient. In appli,cation, the dust was dusted as ~' it was~or thoroughly kneaded with~so Compounding Example 2 Wettable powder:
A mixture comprising 50 pa.rts of the present ,,~
, compound (4), 5 pa.rts of a wetting agent (a,lkylbenzene- ,:
,: sulfonate type) and 45 parts of dia.tomaceous ea.rth ::
was sufficiently pulverized to obtain~a wettable powder ~.'' 20 oontaining 50% of active ingredientO In applica,tion,~ ' , - the wettable powder was diluted with wa,ter, and the ''' resulting dilution was irrigated into water. ; . "~
. .
: Compounding E.xample 3 .Emulsifiable concentra,te:
A mixture comprising 20 parts of the present 2~ compound (3), 60 parts of xylene and 20 parts of an ~ , ~: emulsifier (polyoxyethylene phenylphenol polymer type) ;,"'' ' ;
was sufriciently kneaded to obta m an emulsifiable concentra,te containing 20% Or active 'ingredient. In , - ,, ; application, the concentrate wa,s diluted with water, ~' ', -and the resulting.emulsion was irrigated into soil. ~ ,, .

14 - :
, 1 Compounding Example 4 Cranule:
. A mixture comprising 10 parts Or the present compound t5)~ 85 pa.rts of silica powder, ~.95 parts of calcium lingnin sulfate a~d 0.05 parts of sodium alkyl-benzenesulfonate wa.s sufficiently pulverized, knea.dedwith water, granulated, and then dried to obta.in a granule containing 10% of active ingredient. In application, the granule was sprinkled as it was or kneaded with soil.
Compounding Example 5 Compounded dust:
A mixture comprising 2 parts of the present compound (1) 9 3 parts of N-trichloromethylthio tetra~
.
hydrophthalimide and 95 pa.rts of talc wa.s sufficiently ~ ~
. .. pulverized to ob.tain a compounded dust containing 5% . ;
of active ingredient.
. Compounding Example 6 Compounded dust~
; . A mixture comprising 2 parts of the present compound (6), 3 parts of sodium pa.radimethylaminophenyl diaæosulfonate and 95 pa.rts of clay wa.s sufficiently :
20 pulverized to obtain a compounded dust conta.ining 5% :
Or active ingredient.
Compounding Example 7 Compounded dust:
A mixture comprising 2 parts of the present compound t4)~ 3 parts of 5-ethoxy-3-trichloromethyl-1, 25 2,4-thiadiazole and 95 parts of~:clay was sufficiently pulverized to obtain a compounded dust conta.ining 5 o~ active ingredient.
~ . , Compounding Example 8 Compounded dust~
A mixture comprising 2 parts of the present compound (1)~ 1 part of 5-methy1-3-hydroxy-1~,2-oxazole -.

. ,:
.
, !, , ' , , 104~547 1 and 97 parts of clay was sufficiently pulverized to obtain a compounded dust containing 3% of active ingredient~
Compounding Example 9 Compounded dust~
A mixture comprising 2 parts of the present compound (~)~ 8 parts of 1,4-dichloro-2 9 5-dimethoxy-benzene and 90 parts of clay was sufficiently pulverized to obtain a compounded dust containing 10% of active ingredient.
In order to substantiate excellent so~
fungicidal effects of the present compoundsg typical ;;
test results are described below with reference to test examples, but the test examples are part of typical tests, and it is needless to sa~ that the present .: , : , ~ -compounds have extremely broad application scopes as soi~l fungicides.
Test Example 1 Cucumber damping-off-controlling effect (Pot test):
Farm soil was filled in 9 cm-diameter flower pots. On the surface of said s~o~l was uniforml~
- spread and inoculated 10 ml. per pot of pathogenic : . ~
soil in which Rhizoctonia so~lani had been cultured.
Subsequently, each of aqueous dilutions of test chemicals~
~ ~ .
in the form of emulsifiable~concentratès was irrigated ~ -- 25 into the thus treated soil in a proportion of 15 ml.
per pot. After 2 hours, lO seeds per pot of cucumber ~variety: Kaga-Aonagafushinarl) were sowed in the soi~ ~
and~ 5 days thereafter~ the disease severity of cucumber `
- seedlings~was investieated to calculate the percentage~
Or healthy seedlings. The said percentage was calculated - 16 ~
:. : ~

~ 9547 ~

1 according to the ~ollowing formula.:
Number of healthy seedl-Perce tage Or _ ngs in ~rgerminated seeds seedlings in non-trea.ted and non- -inocula.ted area As the result, the present compounds showed markedly excellent effects over the control similar : compounds as shown in Table 2.
, ~ Table 2 . ~--:
. : ..
Active Percentage ~:~
ingredient of healthy Compound concentra.tion seedlings (p.p.m~) (%) __ . _ _ , . ~ ' -7 Cl 250 lO0 ~(CH30)2P-0 ~ CH3 ~ 125 lO0 Cl 62.5 9 Compound No. (l) . . . _ _ _ ._ S~ C ~ ~ 250 ~ 100 ~

- .~.(CH30)2P-0 ~ 3 62.5 100 ~ .
: Compound No. (2) i _ , _ _ . , ~- (CH30)2P-0 ~ -CH3 ~ 125 ~ l00 Br ~ 62r 5 ~` 60 ~ ~ .
Compound No. ~3) ~ .
_ _ _ .. _ : ` ll Cl 250 100 (CH30)2P-0 ~ C2 5 125 lO0 Cl 62.5 ~ 80 .
.Compound No. (~) ~
_ _ . _ _ ~ ~:
~ - Cont'd - :
.

~ ~7 , ..
: . ~ ; ~: , , .

~49547 Il Cl ~50 100 (CH30 )2P-0~ 2 5 125 90 Br 62. 5 60 Compound No. ( ~) _ S Br 250 100 (CN30)2P-0~ 2 5 125 90 Compound No . ( 6 ~ 62 . 5 50 L ~ [3 * 1 250~ 1 10 ~ ~ ~ ~ CI3 250 ~r~ 10 1 : ~ ~

250 ~ ~ O

(CN30 )2P-0~3Cl : 250 ~ . .
. ~ ~ ~ -, L~ ;250 ~ 0 ~1*- 250 ~ 0 - 3 --~ P~- O ~ C l 2 50 0 ' iC3~170 Cl :
. - - : . :
Cont ' d - ;`

- 18 ~

~C~4~59~7 O Br ~* . 250 ~ O

-, _. .......... . ., S **. . . ~;
(CH30)2P-0 ~ N02 250 O

~/H2-SCX3 , ~ .
. .
' S . *** .
ll 250 O -(C2H50)2-p 3 _ Cl~ /Cl **** ~ ~

~ ~ 250; 30 : Fungus inoculated9 ~ ~
Non-treatment _ ~ .
._ .
Non-inoculation, Non-treatment _ 100 . . ..

.
1 Notes~
* Control compounds synthesized for comparison by the present inventors. `
~` ** Compounds disclosed in Australian~Pàtent~
294,072. ~ -*** Compound disclosed in Belgian Patent 648,813.
****~ Commercially available soil fungicide.
(The same sh~ll apply hereinafter.) Test Example 2 Gucumber damping-off controlling effect (Vat test):
~ Farm soil was fille~ in plastic-made vats of 0.1 m2 in size. On the surface of said soil was : .
~ uniformly spread-and inoculated pathogenic soil in which .
.
- : ~

. ~ ~
- . ~ .

.. . . . . ..
:, .

.

- ! 1049547 hizoctonia sola.ni ha.d been cultured9 and the pa.tho- "
.. genic soil wa,s sufficiently mixed with the farm soil , .:.
to a depth of 3 to 5 cm from its surface. Subsequently, each of aqueous dilutions of test chemica.ls in the 5 form of emulsifiable concentrates was irriga.ted into the thus treated soil in a. proportion of 300 ml. per .
vat. After 2 hours, 30 seeds per vat of cucumber ~ (variety: Kaga-Aonagafushinari) were sowed in the soil and~ one month thereafter, the disease severity of ' ~ '' 10 cucumber seedlings was investigated to calculate ths ,`'- :
percentage of healthy seedlings. -The said percentage ~ .
was calculated according to the same formula as in~ ' ' Test Example 1. : ~ .
As the results~ the present compounds showed .. .
' 15 markedly excellent controlling sffects ovsr the control ~ -'~ ~ ' slmilar compounds as shown in Table 3.

Table 3 _ .
Active Percentage ' Compound concentration seedlings , . : (p,p.m.) (%) . . . _ . . ; ~ . , ¦ (CH30)2P-0 ~ 3 ¦ 200 ¦ 9O ¦
: . Compound No. (1) .
. . . : .
¦(CH30)2P-0 ~ 3 ¦ Z ~¦~ 9 :~ . Compound No. (2) : . . . : `
~ : ' : ~ :: : . ~ : "
- Cont ' d - ~ ~

: : ~ ~ - .:
- 20 ~

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

:
- -~04g54~

:..~ ..

¦. (CH30)~P-0 ~ H3 200 97 Compound No. (3) ' ' IICl - , ..

(CH30)2P-0 ~ -C2 5 200 97 Compound No. (4) H5 ~200 97 Compound No. (5) . :~
. ..... _.. ___, . .

¦ (CH30)2P-0 ~ C2H5 ¦ 200 ¦~ 95 ~: . Compound No. (6) :
. : _ , , ~
: ¦ ~ 3 )2P ~ H3 ¦ 200 ~ ¦ 8 ¦

: ........ .. _ , ......... .

(C2H50)2P-0 ~ CH3 200 5 Cl ~ :
~ . .... . . :..... :.

~ ~ Cl ~200 l _ ..... ~. _ . . . .

~CH30)2P-0 ~ -Cl 200 .
., , ~, , _ -- --- ~ .__ .;
Cont'd -, , .:
;. .... .

:~L049547 `, .
,' ' : ' . ", ' 0 ~* I 200 ¦ 0 ¦

. - . ... , ~` ¦3 ~ p_ ~ Cl l 200 ¦ 2 ¦
. . . . . _ . o Cl **
CN30 1l-O ~ -C1 200 . , . _ . . . _ _ _ .
0 Br *~ ¦ 200~ ¦~

, ~ , . , (CH3~)2P-0 ~ N02 ~ 200 CH2-SCH3 ; ~ - ~ ~ ~ ~
, ~ . , .. .
: ~ . S *** 200 ~: 0 - .
. (C2Ns)2 P H3 ~ ` . . _ ~ Cl C1 **** ~ ~ ::
: ~ ` : Cl ~ 2 ~ ~200~ ~
, . . . . -:~ : Fungus inoculated~ ~ : O ;
: Non-treatment :
,, . _ _ Non-inoculation, : _ : .
: Non treatment _ : .:

Test Example 3 `~
Japanese raddish Fusarium wilt-controlling effect ;
(Vat test)~
Farm soil was ~illed in plastic-made vats of :

' '` '`: . ' : ~ . :, ` , ' ` ' ., : . , : ' ' ' , ' . : ' ' . . . ' .. ' 1 O.l m2 in size. Subsequently~ pathogenic soil~ in ~- which Fursarium oxYs~orum f. ra~hani had been culkured~
....
was mixed with and inoculated into the farm soil to a depth of 5 cmO from the surface thereof. On the - 5 thus treated soil, 30 seeds per pot of Japanese raddish (variety: Wase ~O-nichi) were sowed, and the seeds were covered with soil. After 3 hours, each of aqueous - .
dilutions of test chemicals in the form of emulsifiable concentrates was irrigated into the soil in a proportion - 10 of 300 ml. per vat. After culturing the raddish for one month in an air-controlled greenhouse at 26 to 28C~
the disease severity of raddish seedlings was investi-gated to calculate the percentage of healthy seedlingsO
The saicl percentage was calculated according to the same formula as in ~est Example 1.
-:
; ~ As the result~ the present compounds showed markedly excellent controlling effects over the control -~compounds as shown in Table 4.

` Table ~ ;~
~, : . .
Active Percentage ~`
ingredientof healthy Compound concentrationseedlings - (p.p.m.) (%) ~3 I 500 9 Compound No. (1) - ~ ~
. ' ' , . ~ :
; - Cont'd -: ~ . .

: :,, ., , . , ,. ,. . .. , .. .: ., ~ . , 1~49547 : :
.
S Gl 500 95 ~ Compound No. (2) .
: ¦(CH30)2P-0 ~ 3 ¦ 500 ¦ 97 Compound No. (3) _ ~ .
1l Cl ~ . ;

(CH30)2P-O~ C2 5 500 92 :
Compound No. (4) . ~ ~ .
.: . 1l Cl . :

(CB30)2P-O~C2H5 ~ ~ 5 ; : ~
: ~Compound No. (5) : ~ ~ .
: S Br ~:. ~: -- (CH30)2P-O~ C2 5 500 ~ ~ 97 Compound No. (6) ~ :

¦(CH30)2P-O~ H3 ¦ 5 ~ ¦ ~ 8 ¦
. ~ . .

¦( 2H50)2P-O~ `H; ¦~ 5~ 10 .. . _ .

¦(CH~30)2P-0~ 1 ¦ 500 ~ ¦ ~ 12 ¦
:~ . . ., ~ ., : :;
: ~ ~
~ - Cont'd ~
- 2~

`~: . -~- .
: . ~ . , ~. :
.

1049547 ~ I
,, , S Cl * . .
(CH30)2P-0 ~ Cl 500 14 .
_ ~ ** :
2 5~ P-O ~ Cl 500 . . 8 CH30 .
Cl o Cl ** ~ .
P O ~ Cl 500 ~ 15 C2H50 Cl ~ . .
. _ O Cl ** ~ . .
CH30~ 11 O-~¢Cl . 500 :
iC3H70 >~ : ~ . i Cl -:~` . .
`
-e Br ** ; : ~ :
.
(C2H50)2P-0 ~ Cl 500 ~ :
Br CH3 -~ ~
.
,, . ..................... .
: ~ S ** . : ~ . . ~ ' ~ ~:
; ~(CH30)2P-0 ~ N 2 5 ~ ~ ; 12 . ~ CH2-SCH3 ~ ~ .
i . S *** :~ ~ .~ :; ' 500 : : 7 .
(C2H50)2-P-SCH3 ~
: CONH-n-C4H9 **** ~ :~ :
N 500 ~ 78 ~ ..
: ~ ~ NHCOOCH3 ~ .
: , : : .
~: Fungus inoculated, ~ 7- ;
Non-treatment _ ~ .
. . . . ~: .:
Non-inoculation, . 98 Non-treatment ~ :. -: :
. . ,~

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

Claims

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

1. A phosphorothioate of the formula, (I) wherein R1 and R3 are each chlorine or bromine atom and R2 is methyl or ethyl group.

2. A phosphorothioate of the formula, wherein R1 and R3 are as defined in Claim 1.

3. A phosphorothioate of the formula,

4. A phosphorothioate of the formula, .

5. A phosphorothioate of the formula,

6. A process for preparing a phosphorothioate of the formula given and defined in Claim 1 which includes (1) reacting 2,4,6-trisubstituted phenol derivative of the formula, (II) wherein R1, R2 and R3 are as defined in Claim 1 and M
is hydrogen, an alkali metal or ammonium group, with 0,0-dimethyithiophosphoryl chloride;
(2) reacting 2,4,6-trisubstituted phenol of the formula (II) with phosphorus trichloride in the presence of an acid-binding agent and then with thiophosphoryl trichioride, and reacting 2,4,6-trisubstituted phenyl-thiophosphoryl dichloride thus obtained with an alkali metal alcoholate or reacting said dichloride with methanol in the presence of an acid binding agent; or (3) reacting 2,4,6-trisubstituted phenol with thio-phosphoryl trichloride in the presence of an acid binding agent, and reacting the dichloride thus obtained with an alkali metal alcoholate or reacting said dichloride with methanol in the presence of an acid binding agent.

7. A method for controlling soil fungi which comprises applying a phosphorothioate of the formula given and defined in Claim 1, 2 or 3 to the soil fungi.

8. A method for controlling soil fungi which comprises applying a phosphorothioate of the formula given and defined in Claim 4 or 5 to the soil fungi.

9. A method for controlling soil fungi of the Rhizoctonia species which comprises applying a phosphorothioate of the formula given and defined in Claim 1, 2 or 3 to the soil fungi.

10. A method for controlling soil fungi of the Rhizoctonia species which comprises applying a phosphorothioate of the formula given and defined in Claim 4 or 5 to the soil fungi.