CA1086644A - Phosphorus-containing fungicides - Google Patents

Abstract

ABSTRACT

Thiophosphorous acid and salts thereof of the general formula:

and derivatives thereof of the general formula:

Description

THIS INVENTION relates to fungicidal compositions and to a method for the preventive or curative treatment of plants against fungal disease.
As a result of research and experimentation it has been found that thiophosphorous acid and salts thereof of the general formula:

~ ) n and derivatives thereof of the general formula:

/ H \ ~ ~:
¦ R - O -Pl__ O~ M- ~ (II) ~ / n wherein R represents a hydrogen atom, an alkyl, hydroxyalkyl, .
haloalkyl or nitroalkyl radical, each such radical containing from 1 to 18 (preferably from 1 to 8) carbon atoms, an alkoxyalkyl radical, the alkoxy and alkyl moieties of which may contain from 1 to 8 (preferably from 1 to 5) carbon atoms, an alkenyl, haloalkenyl or alkenyloxyalkyl " , .

radical i.n whi.ch t.he al.kyl moi.ety contai.ns from 1 to 8 (preferably from 1 to 5) carbon atoms, an alkynyl or haloalkynyl rad:ical, each such. alk.enyl. or alkynyl radical or moi.ety cont.aining from 2 to 8 tpr.e.f:e~ahly from 2 to 5) carbon atoms, the cyclohexyl radi.cal, a phenyl ra.dical or a phenylalkyl radical in which the alkyl moiety contains from 1 to 3 car:bon atoms, or R represents t:he tet.rahydrofurfuryl radical, M re.presents an agriculturally or horticulturally acceptable cation, for example hydrogen, an inorganic cation (e.g. an alkali met.al, alkaline earth metal, or heavy metal, e.g.
copper, zi.nc, manganese, iron, nickel. or aluminium), or an organic cation (e.g. ammonium, ammonium substituted by one to four alkyl or hydroxyalkyl radicals each such radical containing from 1 to 4 carbon atoms or by a cyclohexyl radical, or phenyl radical, or a heterocylic cat.ion having 5 or 6 atoms .in the ring, one of which is a nit.rogen atom, e.g. pyridinium, and n is an integer equal to the valency of M, po.s~sess fungicidal activity.
The esters of general formul.a Il may be cal.led monoesters O(alkyl, a.ryl .... ) of thiophosphoni.c ac.id, although they are referred to hereinafter as monoalkyl (aryl ~ ) thiophosphites. r It will be appreciated that monovalent cations, .' -, : .

eOgO ~od.ium, form thi.ophosphite~ ~f t.he formul.a M2(HSPo~), divalent cat.i.on~, e~gO calci.um form thi.ophosphite~ of the formu.la M(HSP02), and t.r.i.val~nt. cations form thiophosph.i.t:.es of ~.he formula M~(HSP~)3~
The th:~.opho~phites~ eI~eral formula I may al.t.ernat:.i.vel.y be r~p.resent:.ed ~ ~n ~ I' wherein M and n are as~here.inbefore defi:ned.
Preferred compounds of general fo.nmulael a:nd I:r are tho~e wherei.n R repre~entY a h~d.r.ogen atom or an alkyl or hydxoxyalkyl radical, each such.r:adi.cal conta.in.i.n.g from l to 8 carbcn atoms, and more especl.ally tho~e compounds whereiin R repre3entA an alkyl radical containing from 1 to 5 c.arbon a~om~ or a hydroxyalkyl radical conta.ining from ..

2 to 5 car.bon atoms, in particular a 2 hyd:roxyethyl or

3-hydroxypropyl radi.cal, optionally substituted by, for example one or more alXyl (preferably methyl) radi.cals.
~ The symbol M preferably represent~ hydrogen, an alkali metal (eOg~ sodium), an alkaline earth metal (e.gO
magne~ium, calc.ium or ba.ri~m),an ammonlum group opt.i.onally substituted by one to four. methyl and/or ethyl radicals, or the pyr:idi.nium groupO

~ 4 Some of the compounds of formulae I and II are known, such as the ammonium and potassium thiophosphites~
and sodium ethyl and sodium butyl thiophosphite (C.A., Vol.
48, 3243 e). There is, however, no reference in the literature to the use of these known compounds as fungicides.
The novel compounds are the thiophosphites of sodium, the alkaline earth metals and heavy metals and also compounds corresponding to the general formula (II') / H
R' - O P - O ~ Mn ~ (II') \ S / n wherein R' represents an optionally substituted hydroxyalkyl radical containing from 1 to 8 carbon atoms, and M and n are as hereinbefore defined.
Preferred compounds of general formula II' are those wherein R' represents a hydroxyalkyl radical containing from 2 to 5 carbon atoms, in particular a 2-hydroxyethyl or 3-hydroxypropyl radical, optionally substituted by, for example,one or more alkyl (preferably methyl) groups.
The anion depicted in Figure II may be represented by the three tautomeric formulae:

B _ 5 _ , , 1~8664~

H
'~
R O ~ O (~) H
R - O P,-_O (B) ~r H
R ~ O - I ~ S (C) O

In this specification, by convention, formula B is uæed to repre3ent t.he anion. It is to be understood t-hat aJ.1 - .
three tautomeric forms fall within the scope of the present inventionO
.: Compounds of general formula I and II may be prepared by the complete or partial hydrolysis of secondary thiophosphites~ For example, the salts of the thiophosphorous acid monoesters of formula II may be obtained in known manner (cf: HOUBE~-WEYL, Phosphorverbindungen, Volume XII /2 page 82 ~ C.A. -48 3243 (1954)) by partial hydrolysis of the corresponding esters in accordance with the following scheme:

1~8~644 H H
~R'~0)2 P ~ + MOH -~R" - O - P~ O M + R"OH
S

whe~ei.n M is as hereinbefore def.ined and R" .is as hereillbe~ore defined for the symbol R, hut does not represent hydrogenu Hydroxyal.kyl t.hiophosphi.te3 falling within the scope of general fonmula II may be obtai.ned by the partial hydrolysis of cyclic diesters, in accordance with the reaction scheme:-(R3-C \~ +MOH-~ ~O-l-+C)m C-O P-O M

- III IV

[ Rl, R2, R3, R4, R5 and R6, wh.ich may be the same or different, represent a hydrogen atom or halogen atom, a nitro radical, an alkyl or halogenoalkyl rad.ical containing from 1 to 5 (preferably 1 to 3~ carbon atoms, or an alkoxycarbonyl radical contain.ing from 1 to 5 ~-1~ (preferably 1 to 3) carbon atoms in the alkoxy moiety, and m re.presents zero or 1, and Rl and R5 when _ is zero, i(~86644 or Rl and R3 when m is 1, may together form the residue of a phenyl or naphthyl group].
The cyclic thiophosphites of general formula III, which may be called 2-thio-2H-1,3,2-dioxaphospholanes when m is zero, and 2-thio-2H-1,3,2-dioxaphosphorinanes when m is 1, may be prepared by known methods, (cf. in particular Houben-Weyl, Vol. XII/2, pp. 84-87).
Partial hydrolysis of the 2-thio-2H-1,3,2-dioxaphospholane or dioxaphosphorinane derivatives in-accordance with the above reaction scheme gives 2-hydroxyethyl and 3-hydroxypropyl thiophosphites, respectively. The yields are good and often quantitative.
The thiophosphites of general formula I may be obtained by continuing hydrolysis in accordance with the reaction scheme:
. .

HO- I~C~C-O-P-O ~) M ~ OH

IV
; It will be appreciated that although the reaction shcemes depicted in this specification generally involve a monovalent cation, the reactions depicted may of course be effected with cations of valency greater than 1.

,.. .
i~ .

108664~
The thiophosphites of general formula I may also be prepared using barium thiophosphite, in accordance with the following "double exchange" reaction scheme:-\/,~ ~Ba2 0 +~M ~3)2 5042 ~ )M20 +Baso4 wherein M is as hereinbefore defined. Barium sulphate beinginsoluble, is easily separated from the reaction product.
Barium thiophosphite, a novel compound of general formula I, may be prepared, e.g. by the complete hydrolysis of a compound of general formula III, for example as hereinafter described in Example 2.

' : ' ' .

_ g _ 10866~4 The preparat.ion of compounds of general fo.rmulae I
and II i9 :illustrat:ed by t.he following Examples 1 to 60 -;

Sodium thicphosphit:e which i.s a novel compound of the formul.a: / O ~ \

( ~ \ O ~ ) 2 \
was obt:ai.ned by the follow.ing methodo 47 g. of 2-thio-2H 4 met.hyl-1,3,2-di.oxaphosph~lane were added dropwi.se with stirring t.o 640 cc. of lN NaOH
' solut,ion~ Stixring was then cont.inued for 2 hours. As the product is soluble in wat.er, water was di.stilled off in vacuo. The precipi.tate obtained was washed with aceton~
and then dried, to y:ield a wh.ite solid with a sulphur-like odour and cxystallised with 9% of water.
Yieldo 63%
Melting point: ~300C.
Centes.imal analysis for HP02SNa2: :
H~/o ~a% P% S%
Calculated 1.65 29.5l9o9 20~4~
Obsexved 2.48 29.36 19.8 20.55 Calcium thiophosphite, H P02S 2 ~a 2~, 1.n t,he form c~f a wh.ite powder, was obtained i.n a si.m.ilar manner:
Yi.eld~ 68%
Melt:.ing poi.nt,: ~300Co Centes.imal analysi.s for HP02S Ca 0 2H20:

~ 1~ ~ .

:. :, , :. . . .

lOBf~4 ~h Ca% ~h S%
Calculated3024 22.28 18.05 18058 Observed 3.46 22023 17.69 18021 BarilLm thiophosph.ite was chta:ined i.:n a man.ner s.imi.lar to that described i.n Example 1: the sod.ium hydroxide was replaced by a suspensi.on of 107 g. of barium hydrox.i.de i.n 400 ml. of water. After sti.rring for 2 hours, a precipitate was obtained which was washed with a little ice-wat.er and acetone and then dried to yield a product in the form of a white powder ~hich was sparingly soluble i.n water O
Yi.eld: 82% :
Melt.i.ng point: ~300 C.
Centesimal analysis for HP02S Ba 0 2 H20:
~P/O Ba% Ph S%
Calculated 1 85 51.1 llo 52 11.88 Observed 2.26 50.75 11~47 11.80 Thi9 barium salt may itself be used for the preparation of new inorganic thiophosph.ites by the'~ouble e.xchange" reaction hereinbefore described.

Magnesium 3-hydroxypropyl thiophosphite of the formula- H ~ "`
(HO CH2-CH2 - CH2 ~ ~ )2 Mg 2 was obtained by the following method:

, ,. ~ .~.--.. . .... . ..

1~86644 A ~u.~pen3i.0n in 1.~0 ml~ of water of 6 . 9 gO ~f 2~t.hi.c~2H-1,3,2-di~xaphc~phorinane and 1. g. of calci:ned magl)e9i d wa~ st.i.rred for ~ hours. The rea~tants d:i.s~o1.ved completel.y~ Evaporaticn t.o dryness yielded 8,5 g~ of a whit.e hyg:ro~cop.ic powderO
Y.;.eld: ~r l.O~/o ent.e~.i.mal an.al.ys.i9 for ~3 H8 Mg ~3PS
. ~ ~/0 M~h PYo S%
Calcu.lated 21.... 54 4079 7.2'7 1.8~55 l9c14 1~ Obse.rved 21~60 510~ 7.18 18.29 18.g9 ~he st:ru~t:ur~ of ~he product: was collf.i.r~d by nuclear magne~:;.c .resonance spæct;ro~copy (.~MR) ca.rrled out wi.t.h an NV14 Vari.~n~ apparat~ w:ith a magneti.c fi.eld equal t-o 60 mc/s usi.ng deut~rium-containing methanol as ~olverlt 1.5 and h~xamethylene di.siloxane (HMDS) as reference. The letter J stand~ for ths coupl.ing con~tant expressed in cycles p~.r ~econd, whllst ~ represents the chemi.cal d.i~placement: in ppm J P-H : .590 c/s ~ : 7.90 ppm O~her compounds of fo.rmula II were obtained in a si.mi.lar manner u~ing di.fferent dioxaphosphorinanes or d.ioxapho~pholane~ and/or d.ifferent baqes, t:he:ir formulae, yie1.ds, characterist:.ic~ a:nd centesimal ana1.yses be.ing shcwn in t~e following Table:

~086644 ,, ~ ~ ~ ~ ~ .
U~ U~ ~ 0 U~
I~ I~ ~D~
a o o ,, C~
P. ~ ~ P~
, o ~ o oD
I~ U~ t~
. . ~. . ~ . . ~ .
C~ ~ ~ ~ O O
,, ~ ,,, bq O O I~ o ~ O ~ t~
,~ u~ ~ u~ ~ ~ ~1 u~ O
~q5: . . ~. . ~ . . ~ . .
~r ~ u~ u~ ~n I
r- ~ o ~ o U~ ~ ~ ~ In U~
" o o` C) o o C~ ~, V o ~, o C~ o ~ o _ -l o o n o .~ ~1 ~ ~ ~1 ~1 ~1 ll .. :
~1 ~ ~ . o~ o~
~ ~ a) u ~ ~
O h 1~ ~ ~q u~
a ~ ~ a) o ~~1 o ~(U o ~ o a 1 ~ rl ~ 1 C ~ 1 ~ 1 ~ l ~1 3 ~ O ~ X :~ Oe~ ~ O~ ~ O ~ O
.~S U ;~ a) ~ o~ ;~ ;~ q 3 Q
q :' .
P~ ~ o~ O oo ~`i _l U~ I~ ~
-:
C~ U~ U)~
~1 0~ ~ P~1D P~ : -~ ~ 0~ ~ O O

E' ~ ~D m~, O m~

:

o l o :: :
o ~ I ~ ~ ~ ~ ~
~;
~ ~ ~ ~c ~ ~ ~
. ~ ~ ~ ~ U_ ~86644 . ~ ~ . ~ ~ , , P. ~ P~ o . ~ U5 ~ ~ ~
~:, t~ ~1 , ~ u ~ a~ n . ~ U
00~ ~ ~ ~ ~ ~
~ ~: o ~ .
..c~ O u~ 0~ . ~D ~ O O
. u~ . . c~ . . ~ I~ ~~n ~ ~ .
00 ~ ~ . tY7 .
~- ~ ~ ~- . U~ ~ ~D Ln O~ ~ . . . . ~.
r~ r~7 O ~ I~
P~ P~ . . ~ ~ ~ P.
I~ r~ u~ ~ . .
. . ,.~ U~' ~ U~ U~
U~ o 0 . . ~ . . ~ ,~ c~J O
~q. ~7 ~ ~ ~ ~ . . ~; .
~~ ~-- ~- Ul 0~ ~ ~D
~ ' I~ O ' ~ 00 ~- O U-l ~D
. . ~ 3 ~ '~ C ~' ' ~ ~ .
. ' I~ o, ~ O ~ O U~ ~D
. ~ .. ~ CO U~ ~ I~ ~
t~ ~ ~ t~ .
o o a~ oo ~ a O o~
' ~ ~. . ~ .
. , t) O , V O . V O V O
.' . ........ _ ~ ' ~ ,, ' ~ ' ~ ~
O ' . 00 O O
'Q~' . ' t) . .
8 9 ~ ~ : ~ ~ v ~ ~ ,, u ~ ~ ~ . a~ ~ ~ ~ ,1 ~ rl P~ .rl ~ ~ ~ ~ ~ ~_~ rl ~
~0 ~In ~ ~ tn- ~v) ~. O ~ . ~D ~ ' .
:~: ~. ~ ~ ~ ~
. _ . ,. ' ~ ~' '~- . ~ U)c~
~J~ P~D ' ~ : ~ ~ .
0 o. o ~ ~o.~ ~ ~ Z ~ X~;l, ~ ~ "~ S~ ::0 ~0 ~ :, ~ ~ ~Y .

l l l l . o~ m~ m'`' . o~
o ~ ~ ~ ~ m~
~ ~: t~ ~ ~ 7 ~ C~ . ~C`J . N
. O, O ~ ._ . ~;3 .,. -: . ' - ' ' ~

las6644 ATrunoni.um 2-hydroxyet.hyl and 3-hydro:xypropyl thiophosph,ites may be obtai.ned in a s.imi.La~ manne:r t:o t,hat descri.bed in. Exampl,e 3 using ammonia or an cptionally su.hst,t.t.u~.ed pri.mary, ~econdary o:r tertlary ami.ne :i.nstead of. t:he calc:ined magne~
Di.ethylan~non:ium 2,2~d.~mekhyl-3 hydroxypropyl thiop'hosphite of t,he fo:~mula:

E10 -- C~H2 -- C - CH2 - O ~ o ~H2( 2 5 2 lQ was obt:ained by the following method:
A olution of 2 g. of water and 4 g. of diethyl~
amine .in SO ccO of acetonitrile was rapi.dly introduced at ,~ !
room t:emparatur:e i.nt:o a solution of 80 3 g. of 2-thio-2H=
5,5 dimethyl~l,3,2-di.oxaphosphori.nane in 50 cc. of acetonitrileO Aft:er heating under refl.ux for 1 h.ou.r, the ~.
acetonitrile was evaporated tmder reduced pressure. A
colourle~s o.il was obtained.
Yield~ ~ 100%
n~o lo 500 CenteA.imal analysis for CgH24~03P SD
C% ~/0 ~D/o P% S%
Calculated 42.02 9034 5.45 12006 12.45 Obs0rved 41.. 99 9.20 5.30 11.98 12.40 The structu.re waq confirmed by M~-spect.roscopy:

l.S

.. . ,: . .. :

1~866~

P-H: 574 c/s o 7 n 9 3 ppm Other optionally substit;uted ammonium salts were obtained in a s.imilar manner, using differen.t dioxaphos-phor.inanes or dioxaphospholanes and/or. different nitrogen~
containing base~, their formulae, yield~, phy~ical characteristics, centesi.mal anal.ys~ and, where applicable, their ~MR charact!eristics being shown in the following Table~

~ ~ , U~
a~ ~ ~. . u~
~ ,~
O ~ ~ U~ ~ ~D
Ln ~ ~ ~ U~ ,~ U~ U~
. ~ ~ ~ P~
,, ,, O Cl~ O C~ ~n a) ~ ~
0 o~ ~ ~ ~ ~,. ..
bq ~CO ~00 ~ ~-D

~1~ O ~ ~ O~ ~I ~1 ~
~ $ ~ ~ ~ ~ o ~ ~ ~1$ 1` ~9 W 1` 1` 1` ~
~ ~ 0 1` o~ CO ~
O ~ ~ 00 c~ ~ OD ~ n In ~ O O U~ U~ ~D ~
U O ~ O ~ o o o ~ ' ~ ~ ~ a~ .
O
o .~ ~1 ~1 ~1 ?1 I'~¢) .. o $- P,` 'u~ ~ ~ ~ ~q ,1 ~
~q n u~ ~n ~1 0 . . 1 a~ u~
o ~ C: ~ ,~ s~ :>~
.. .. ~ ~ s~
~Q o ~ ~ .. ::
,1 o o ,1 ~ ~ ~1 o o ,1~ a ~ c~ o o ,,, o o ~ ~ o~ V o .
~ ~ ~ l` ~ .
n ,1 ,1 ~1 P~
o ~ o o o o ~ ~ ~o ~ . ~ ~0 ~o ~ ~ ~ ~ :
o, C) C~ I

~: , O O 0~ .C~
o~ $~$ + $~ $~ $~$ o~
~ ~ I ~~ I
o :~ ~ ~ ~ ~ m c~ ~_m ~ O O ~ ~_0 ~ ~

- ., ~ .

iO86644 U ~ U ~ U ~ U
t~ u~ ~ u~ 0~ LO ~ n (` ~ I`
~; u~ . n . LO . u ~ 11~ 1`IIX 1` 11~ 1` 11~ 1`
l 11 o o r~ ~1 ~ u~ r~
n 1` ~ ~ ~ o~ ~ 1`
U~ . U~. . V~ . U~ .
oo r~ ~ ~ Ln I
,, ,, ~ ~ ,~
o ~r I`
. . ~ . . ~ . . ~ .
~q t~
.~ ,, ,,,, ,, ~ ~ ~ ~
~1 ~I Ln I~ CD
~1 o ~ ~ o a~ o~ ~ r~
. . ~. . ~ . . ~ . .
a~ I` ~ ~ ~ ~ u~ n ~; ~ ~ ~ ct) ~ ~ ~
o~ o ~ I` oD ~ ~ o ~ C~ o ~ tO C:~ 1~ I) ~ 1~
0 ~ u~ ~n ~ o~
0 0 ~ CO
. O ~ . ~_) . ~_) .
~) ~D ~D ~ ~ Li~
U O ~ O U O O O
~ ~ '2R æ ~
~ O O O U~
O ~1 ~-1 ~ i 1`
..
a~ ~ I~ ~n ~ u~
U cq ~rl ~ U~ ,1 U~
O u~ O ul u~ (D "~
3 ~ ~ ,~ ~ ,i ~ o ~ _l o ~ ~ ' q) ~q ~ ..... o .. .c u o ..
_l O ~ ~1 0 ~ ~a ~ ~ o a~ ~ ~ o ,~ ~ ~ ,, ,, o ~1 : U ~ ~ U o ~ ~ ~ U o '.~
3 ~ ~ o .
cq u~ u~
P~ 11 P.
O
U ~ O O O
'~ ~ ~ ~o ~ 0 ~ 0 ~ ~ ~ ~0 ~ ~ ~ ~ C~ C~ .' .
_ +q,~: ~ ~ ~ ~
_ . 0~ O 0~ 0 ~ O ~ C~ ~ ~ C~ ~
P~ ~C~ ~ ~ ~
~. ~ ~ ~ .' - :: . . :

Sod:i.um ethyl thi.~phosphi.t:e of ~he fo~mula C H ~ o - ~ - o ~ Na was obt:a.i.lled hy parti.al hydrolysi.s of a secondary th:i.o-phosph.i.te, as follows.~
20 cc~ of an aqueous lG% ~aOH solution were poured wh.ile stirri.ng i.nto 7~7 g. of diethyl thiophosph.ite dissolved i.n a mixture of 20 cc~ of ethanol and 1.00 cc. of water~ The mixture wa~ left to react for one hour wi.th st~i.rring~ After evaporation of ~;he sol.vent, a greyish produ.ct cry~tallised. The product was d.issolved i.n a little acetone and precipit~ted by the addition of petroleum etherO ~he precipitate was f:i.ltered and then dried ln vacuo,~
to yield a white powderO
Yield: 60%
Melting point: 100 C~
Centesimal analysis for C2H6~aO2P S:
Ch Hh ~a% Ph Calculated 16.2 4.05 15.5 20~90 20Observed 16J2 4.16 15.5 20.95 The s~ucture was confi.~med by the ~MR result.s:
J P~H 574 C/9 ~ 7~96 ppm -- 1.9 --.XAMPLE 6 Di.eth.yl.~mmon,i~lm .isop.r~pyl. th:iophosphi.te of the f~ mlJ.l.~
H

.i90 C3H~7 ~ P~ O ~NH2 (C2H5)2 S~ ~ J
was prepar0d i~ a manner ~imilar t,o that, descri.bed in Example 50 9~1 g~ of di.i~opropyl th1.ophosphite, 5 gO of d.iethylam.i.ne (exces~) and 1 g~ of water were di~solved i.n 80 ccu of acet.onitri,le~ Afte.r heating under reflux ~o.r 1.0 5 hours, the ~olvent was evaporated under r~duced pressure, leav.i~.g lQ.5 g. of a colourless oil whi.c'h cryst:alli.sed on cool.ing to form a whit:e highly hygroscopi.c s~lid.
Yield: 100%
Centesimal analysi3 for C7H20N 02P S:
C% H% ~% P% S%
Cal.culated 39.44 8.39 6.57 14.55 15.02 Observed 39~49 8.96 6.73 14.55 15.06 The structure was confirmed by the NMR results:
J P-H- 570 c/s ~- 7.91 ppm Ot~her metal salts and other ammonium salts were obtai.lled as descri.hed in Examples 5 and 6 but usin.g di.fferent di.esters and/or bases, their formu.l.ae, yields, physicdl charact:er.i.st.i.cs, cent.esi,mal analyse~ and, where applîcable, t:~e NMR result.s bei.ng shown i.n the following Table.

108664~

U ~ ~ ~ ~ ~ ~
, ~ CO ~ C~ ~ C~ ~ ,` ~, u~ ~ Ln ~ u~ u~
, ~ 11~ ~ ~1~ ~ 0 ~1` ~ 1`
~ 11 ~ 11 ~ ~ ~
_ 11 1, 1, 11 o ~ <~, ,~ ~ ~ o~ CO ~ o U~ . . U~ . . ~q . . ~" . . U~ . ~
~ ~ ~ ~ ~ ~ O O ~ ~ ~
L~ O O ~ ~ ~D O O C~ ~ ~ O
o ~ ~ ~ o n ~ ~D ~ u~
. . ~ . . ~ . . ~ . . ~ . . ~ . .
a:~ ~ ~ ~ ~ ~ ~ o~ ~ u~ u~
tn ~ ~ o o co ~t t~ U) ~) ~ ~I ~1 u~ ,~ ~ ~D d' 0~
~1 ,a ~ t~0 ~g ,a ~ . d ~ . 1` 1~ O ~1 ~) ~ ~ ~ . ~Z; d' ~ C) ~ ~Zi . . ~Z .
~i ~1 ~1 ~ 0 ~1 ~1 ~1 ~ o~ a~ ~ 1`
0 0 o~ ~ ~ ~ ~~ 0 In ~
O O ~IO~ O O cn . . ~ . ~ ~ ~ ~ . . ~1: . . 1:~ ~
d' ~r d' ~ ~ u~ u~ ~ ~ 0 c, u~ ~ U~ ~ C~ ~ 0~ ~ U~ 0 ~ 0 u~ u~ I` r~ ~ ~ ~ ~ ~ ~D ~ ~D
0 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~7 . . . . . . . . . . . .
_ ~ O O O C~ O U O O O O O
~3 ~ ~ ~ æ æ ~ ~ :~:
~:1 ~ ~ ~ ~ ~ ~ O .:
O ~ ~ 1` 1` . 0 X~ ~.~ ~.. ~ .~ `~ 3 ~ :
~ a) ~ u ~ ~ ,~ ~ a) ~ o a) u~ ~ ~ O ~1 O a) In ~ O ~rl ~ ~ U ~ ,~ ~ ~ p rl ~
~ ~ rl d' rl ~ ~1 ~1 0 ~1 ~ rl ~ ~ 0 ~1 ~I O
~ ~ o ~ ~00 ~ ~ ~ u~ ~ o~ ~ . : ~C ~, ~ ~n U >1'0 ~dq 3 O ~g ~I (~ ~ ~
~ ~ ' U~ U~ U~
~ 0~ 0~ ~ 0~ P~ ~
o ~ ~ ~ O ~ O O
u m-~' u ~0 ~i~
~U U U U U U U

~ 1 O ~ ~a ~) ~ N N
O O ' .. ;~`
l ~ ~ l l u~ U U O O
~ U N O O N U

, The compou~d3 o.~ general formulae I a~.d Il posse-s excell.erlt f:u~g:ic.idal proper.ti.es, ~s shown ir.
t..he fol.l.owing Ex~lm~les 7 to 15, wh.i.ch demonstr~t.e t.he ~c.tivity o~ +he ~Gll.cwi.r~g compoundsu me~ d NQu ~ome~d 1. sodi.um thiopho~phite 2 calci.um th.i.opho~phit:e 3 barium thiophosphite

4 sodium 1 methyl~2-hydroxyethyl thiophosphite sodium 2~methyl~2-hydxoxye~hyl thiophosphite 6 calcium 1 methyl~2~hydroxyet:hyl thiophosphite 7 c~lcium 2~hydroxypropyl thiophosphite 8 calcium 1 methyl-2 methyl 2-hydro.xye~hyl thiophosphite 9 magnesium 1 methyl-2 methyl-2--hydroxyethyl -~
thiophosphite calcium 3~hydroxypropyl thiophosphit;e 11 magnesium 3-hydroxypropyl thi.ophosph.ite 12 sodium 2,2-dimethyl--3-hydroxypropyl thiophosphite 13 c.al.cium 2,2-dimethyl-3-hydroxypropyl thiophosphite 14 magnesium 2,2-~dimethyl 3~hydroxypropy.1 thiophosphite 2.~ 15 ammonium 2-hydrox~ethyl thiophosphite 1~86644 Compound ~o~ Compound 16 ammonium 1-methyl~2~-hydrox~ethyl thiophosphite 17 ~mo~:~.um 2 methyl 2-hydroxyeth~l +.hiopho.sphite 18 ammonium 1. methyl--2. methyl-2. hydY:oxyethyl t:h.iophosphite 19 diethylammonium 1 methyl2 hydroxyethyl thiop~osphite - 1.0 20 di.ethylammonium 2~methyl 2-hydro.xy~thyl thi.ophosphite 21 ammonium 3 hydroxypropyl thi.ophosphi.te 22 die~hylammonllln 3-hydroxypropyl t~hiophosphite ,~
23 ~mmonium 2,2 dimethyl.~3-hydroxypropyl t.hioph~sphite 24 diethylammonium 2,2-dimethyl 3~hydroxypropyl .
thiophosphite pyrid.inium 2,2-dimethyl 3-hydrox.. ~propyl thiophosphite 26 sodium ethyl thiophosphite 27 calcium ethyl thiophosphite 28 barium ethyl thiophosphite 29 magnesium ethyl thiophosphite sodium isopropyl th.iopho~phite -~ ~`
31 calcium isopropyl t~hiophosphite ~ 23 ~

:, , , ~ , 1~86644 Compound NoO Compound 32 ammonium ethyl th.iophosphite 33 d.iet;hyl.ammon.ium ethyl thiophosph.~.t:e 34 diethylammonium i.sopropyl thiophosphite 3~ cal~ium n~prcpyl thiopholsph.it.e EXA~PLE 1 _n v ~ t.est.
The compounds of the invention were examined for their effect on the following fungi: ;
(a) Colletotrichum laaenarium which belongs to the family of ascomycete and whi~h iB xesponsible fox anthrachnose of the curcubitacae e~g~ melons, (b) Piricularia o~ , which.belongs to the ~amily o~
~un~i ImE~erf.ecti and which is responsible for ri.ce bl.ast:~
The following procedure was adopted for ~ach te3t: -A gelose~containing medium MALT-AGAR-MERCK was poured into test tubes (5 cc. per tube). The tubes were plugged, sterili.sed and the medium was then kept in molten form at 60Cu Using an acetone solution containing 100 ppm of active material per 50 cc. of acetone, the required dose was injected into the gelose medium in each test ~ube~
The tubes were agitated and then left. t.o cool to permit the~r content.q to solidiy~
On the followirg day, t:he tubes were inoeulat:ed ~5 by injection, usi.ng a sYringe~ with 0O5 c~O of a suYpe~3i.0n - ~4 ~

~8~644 of ~pore~ containing lO0,000 spores/c~O or by an 8 mm~
diameter my~e1.ium im.plant~ The tl1bes were th~n le:t: t;o incu.bat.e i~ dark~e~ in an oven at 26Co ~ the r.esults heing a~e~9 on the ~th day a~er infe~t:.ati.on~
Und.er ~hese condit.iona, i~ wa3 f.ol1nd t:.~at.
.omplete irh.ibi.~.o.n o~ the funglls wa~ obt:ained.
(a) i.n the Ga~e o~ Colletot:r._ um wi.th a dose of 2.00 ppm ~o~ compound~ ~" l2, 27, 29, 33, 35 with a dose of lO0 p~m Eor compounds 8, 1.8, 21, 31 with a do~e o~ 50 ppm for compou.nd3 6 1 7 and 1.5, (b) in the ca3e o~ Piri _ aE~_2}Y~3~^
w:ith a do~e of 50 ppm for compounds 2 and 1.

In vivo te~t on la~e blight o~ tomato ( ~nfestan3, belonging to the ~amily o ~hYc~mYcetes) ~_ . _ . .
on l.iving t:omato leavesO
T~mat~o plants (Ma~mande vari.et:Y), aged about 60 day~, were tr~ated by ~praying with an acet:o~e solut.i.on of t.he active material or with an aqueous su.spen~ion of 2.0 w~t:t:able powder having t:he following compo~i.t~i.on (.by wei.ght~)~act:~ ve mat~rial t:o be t:e~t- ed 20% ~ ..
deflocculant (calcium ligno~ulphate) 5%
w~tting agent (~odi.u~ alX.ylar~lsulphonate) 1.%
fil.1.er ~alum.inium 3i1..i.~ate) 74%
2.5 in the re~ui ed dilu~:.ion ~on~.ainin~ tb.e act:.i.~0 mate~.ial.to be tested i~ the d.ose in que~t,ionO
Each test: was du.p.l.icatedO
ln thi~ Example alld following Exampl.es 9, 10, 11 and 13, w~ere a ~ungici.dallv act~ e material .is appli.ed hy spraying, but the rate of application pe~ plant i.s not:
specified it is to be understood that t.he pl.ants ~e sprayed to "run-off".

After 48 hours, the leaves were cut a~d applied t.o a wet fil~er paper covering the bot~om of. a Pet:ri d.ish.
Plugs of filter paper impregnated with a suspension of spores cont:aining 80,000 spores/cc. were t:hen applied~
After 8 days, during which time the t:est temperatu~e was kept at 16Co I the re ult.s were assessed by evaluating t;he surface area infested 'by the fungus in relation to a cont~ol treated with a composit.ion cont:ai.ring no active material.
Under these conditions, the fungus was com.pletely inhibited by compound No. 34 in a doqe of 2 g./l.
EX~MPLE 9 In vivo test or. bean blight (U.romyces phaseoli, belonging to t.he family of;basidiomvcetes) on bean pl.ant:s.
:' Using a ~pray ~m, t:he leaves of pot-gro~n bean plant:s (Contender va~iety~, aged about 10 days, were sprayed ~mderneat.h wit,h an acet.one soJut.ion or aqueous ., ~86644 ~uspension of the material to be te~ted using the same composition as i.n Example 8 Aft:er 48 hours, the leave~ were ~pt~ayed urlder:nea~ with anaqlleol~s sllspen~.io~ of spore~ ~ontaining appro~imat~ly 80,000 ~pores/ccO The pots we~e t:hen placed in incubaticn cel.~,s a+ 20C./100% relat::ive humidity or a per.iod of 48 ho~rsO
~he results wexe a3sessed approximately 10 days after in~estation by compari30n with contxol plant:~s which have to be infe~t;ed to an extent o~ at~ leas~ 7~%
of leaf areaO
Under these conditions, compound ~o. 34 comp:le~el.y pt-otect:s the bean plants in a dose of 2 g.,/l.
EX~MPLE 10 In v vo test on Plasmopara viticola (phycomycete ~mi.1y) _ _ .
on vine plant.s (a) Preventive treatme~t Usi~g a spray gun, the l.eave~ o pot-grown vine plants (Gamay variety) were sprayed underneath wi.th an aqueous suspe~sion of a wettable powder with the followi.ng compos.ition (by wei~ht)~
ac~.ive mater.ial to be tested 20%
deflocc;ll.an' (calci~Im l.ignosulphate) 5%
wett:ing agent (sodium alkylary.lsul~on3te) 1%
~ r (al~lminium ~ilicate) '74/~

~ .. . . .

1~8~644 in the requ.ired dilution ,~ont:ai~ing the aet.ive material to be te3ted in the do;ie in q~ t:.ionO
E~h te~t: wa~ repe.3.t:ed thxee t...ime~
After 48 hou~:s, ~he plants we~ co~taminated by spraying t.he leaves und.erneath with an aq-~ous suspens.Lc-~
con~:airli.ng approximatel.y 80,000 ~pore~/cc~ The po1s we~e th.en placed in incubation cells at 20Co/100% rel.at.i~e humidity fc?r a period o 48 hours.
he plants were inspected 9 days after infe.s~;~tio.n.
Under these condit:ions, it was ~ou.nd that:, in a dose of 0O5 gO/lO, compou.nds ~o~ 1 to 3, 8 to l.l., 18 t:o 21 and 24 to 31 afforded complete p~otection aI~d compound.s ~os~ 4 to 6, 16, 17 and 33 good p~otection, whil~t in a dose of l g~/l. compounds ~o~ 12, 14, 1~, ?~2., 23 and 32 afforded good protection~
In addition, it was found t:hat none of the compQunds test..ed showed the least sic3n of phytotoxici.ty.
(h) Treatment af er contaminatior The procedure used was that descr.ibed in Ex:~mple 10 (a) except that the pl.ants were first: ~ontaminated and t-.hen +.reated with the active mat.sri.al to ~e te~tedO The pl.ant.~ were in~pected 9 dayz~ after con+.am.irlat.ioI10 Under the~e ~ondit:lon~, i+ wa5 .f:ound t;hat, .in a do~e of ~ compou~d~ ~osO 16, 1.7, 1~ and 20 ~5 co~.plete.ly ~tGpped de~Jelopment.: of +he m.ildew on the vin.e ~- ~8 -10866~4 plan~
(c) Sy~t~i.c_t.e~ hy~ or~t~-on on V.lne mil wO
Several. vi.ne ~t:ccks (G~may va.riety) each a~comm.odated in a container ~illed w.ith ver~iculit:e and .~ ~ut:x~.t:.i.ve ~olut:ion, were ~prayed w.ith 40 cc. of: a O u ~ g o /1 . 901UtlOn 0~ t:hs act:.ive ma~eri.al ~:o be t.est:ed.
After 2 days, the vine was contaminated with ~n aqueous su~pen,sio~ conta.i~ing 100,000 ~pores/cc~ of .Pl_smopara vl~lc.ola. This wa~ followed by i.ncubation ~or 48 hour~
in a ~oom at 2.0C~/100% relative humidity~ The de~ree of infe~tation was i.nlspected a~ter about 9 days in ~el.at.:ion to an i~èst~d control which had been sprayed with 40 ~c.
of distilled waterO
Under t:hese conditions, it was fotmd that, i.n a dose of 0O5 g~ ! compounds ~os. 1 t.o 34, absorbed by the root~, a~forded complete prote~tion t:o the vine leaves against mildew, which clearly demonstrated the systemic nat:ure of these compound~O

.' :
2.0 T~s t on tobacco ~lants : Plots of 5 tobacco plants (PB 91) were kreated on the 15t.h June wit,h a wettable powder comprising an active material co~t,aining 80% o~ maneb in a quant:it:y of 160 gO/10, 50% of sodium ethyl thiophosphite in a quant...;.t:.y of 300 gO/10 and 50% o~ ma~ne~ium ~thyl thiop~o~ph.it.e i.n a ':

quanti.ty of 300 g./l. One plot was left untrea~ed as control O
A~t:er 48 hours, the plants were artificially cont~minated (wlth Per~r_ eora tahacina) and t;hen ~umigated. The treatment~ were then xepeated once a week.
The xe3ult~ were as3e~ed on L2th August, i.e~
after 58 days, by counting the number of mildew ~tains per plot~ ~he re3ult~ are ~et out in the following Table-_ ,_ PRODUCT ~umber of stain~ per plot _ . __ __ . __ ~.:
~ontrol 48 Mareb 4 v Sodium ethyl thiopho~phite 2 Magne~ium ethyl thiopho~phite . . ~
Other test~ have ~hown that the two compounds -- te~ted, sodium ethyl thiophosphite and magnesium ethyl thiophosphite,are also active again3t this same fungu~ in curative treatment and have a sy3temic action - ~. .
Te~t on ayocado plant~
Young avocado plant~ (Per3ea indica variety) were plant:ed in 90il infe3ted with P~hyto~hthora c~nnamomi, after ~5 whîch the ~oil wa3 sprayed with a ~olution cont:aining .. ..
. ,: . , . ... :

1~866~

3 g.~l.u of ammonium e~hyl thiophosphite. Some plants were left untreated as controls.
Under these condition~, it was found after 20 days that the root~ of the control~- were completely destro~ed whil~t 86% of those of the treated plants were healthy~
EXAMP E_13 Test o~ Pineapple Plan_ 9 `.
~oung pineapple plants were contaminated wi~h PhYtophthora ~ara~itica and then treated after 48 hours by spraying with a 005 gO/10 solution of calcium ethyl thiophoAphiteO After 30 days~ the fungus was completely inhibited in the treated plant~, whereas the controls were infestedu .Test on straw~errv ~lant~
Ten strawberry plant~ (Surprise des Halles : variety) were treated by soaking for 1 hour in an aqueous solution containing 0.2% of calcium isopropyl thiophosphite and were then dried and planted out on 14th June in soil contaminated artificially with Phyto~hthora cactorumO Immediately afterwards and then once every 8 days until 18th July, the plants were sprayed with the ~ame solution which corresponded to a total ~:
application of 005 g. of active material per plant.

-~ 31 -' '` '': :

1C~8~6~4 Plants were treated by soaking and sprayi.ngwith water to serve a~ controls.
Under the3e conditions, .i~. WdS found on the 24th July, iOe~ after ~9 day~, that the protection afforded to t,he straw})err~y plants by the act.. ive compound ; was complete, whereas 76% Of the control plant~ had diedu EX~MPLE 15 Test on sweet pe~er plants Ten sweet pepper plant~ (Yolo Wonder variety) which had been planted out were ~ransplanted on the 27~h June in pot3 of soil artificially contaminated with ~Phyto~hthora casici~ The plants were then ~prayed immediately and thereafter every 8 days until 18t:h July ~, 1~ with an aqueous solution containing calcium 1--methyl-2 hydroxyethyl thiophosphite, so as to apply 005 g./
treatment/plantO
Plants were sprayed with water to se.rve as control s O
~0 Under these conditions, it was found that the , ten treated plants were intact at the end of August, i..e.
after approximately 65 days, whereas the control plants were all dead by the 25th JulyO

~ 32 1~86644 -Examples 7 to lS clearly demonstrate the remarkable fungicidal activity of the compounds of general ..
formulae I and II on fungi belonging to families as diverse as ascomycetes, basidiomycetes, Fun~ Imperfecti and phycomycetes, and in particular ~heir systemic anti-mildew activity in preventing and inhibiting the development of fungus on the vine, and against certain phytophthora.
- The compounds of general formulae I and II have also been found to be extremely effective against other types of parasitic fungi such as: Guiqnardia bidwellii on vines, Pseudoperonospora humuli, Bremia lactucae, Phytophthora infestans, Peronospora sp., Phytophthora palmivora, Phytophthora phaseoli, Phytophthora me~asperma, Phytophthora drechsteri and other Phytophthora sp., in plants grown in temperate or tropical climates, especially the strawberry, pimento, onion, sweet pepper, tomato and bean plants and on ornamental plants, pineapples, soya, citrus trees, cacao, coconut palm and hevea.
Accordingly, the compounds of formulae I and II
are particularly suitable for use in the preventive or curative treatment of fungal disease in plants, especially against disease caused by phycomycetes, ascomycetes, basidiomycetes and Funqi ImPerfecti in the plants already mentioned.

1~86644 The compounds of general formulae I and II may be mixed with other anti-mildew fungicidal phosphorus derivatives, especially the 2-hydroxy-1,3,2-dioxaphospholanes, the ~-hydroxyethyl phosphites, the phosphonic diesters, the cyclic diphosphorus compounds, the aminophosphites, the 2-hydroxy-1,3,2-dioxaphosphorinanes and the ~-hydroxypropyl phosphites, the phosphorus-based trialkyl imides and the ,~ 2-thio-2H-1,3,2-dioxaphospholanes and phosphorinanes which form the subject of our Canadian Patents Nos. 1016454 (published 30.8.77), 1043253 (published 28.11.78), 1043254 (published 28.11.78) and 1055394 (published 29.5.79), and British Patents ~os. 1449443 (published 15th September 1976), 1494367 (published 7th December 1977) and 1494528 (published 7th December 1977).
For their practical application, the active materials are rarely used on their own. In most cases, they form part of formulations which generally contain a carrier and/or a surface-active agent in addition to the thiophosphite.
According to the present invention, there are provided fungicidal compositions suitable for use in controlling fungal disease in plants which comprise, as the active ingredient, at least one compound of general formula I or II in association with one or more carriers or adjuvants compatible with the active material and suitable for use in agricultural or horticultural fungicidal compositions. These compositions can optionally contain other compatible pesticides such as acaricides B

.. . . ~.
... .. . . ..

1~8664~ ~

or insec+:i.c:idesO Preferably t:he compos.i.t.i.on,s cont,a:in bet.w~e~ 01% and 95% by welght nf the th:i.opho~phi.te.
~h.e t:.erm "carr:i.e.r." i.n the sense of the pre~ent, descr:i.p~:ion de:not:es an organ1.c o:r inorc3ar,.i.c, n.atur~l or .~ ' synth.et.lc, mate:ri.al wit~h which ~he active mat:eri.al. i.s as~Qc.i.ated so a~ t:n fac.il.:it.ate .i.t:s appli.c.ati.on to t~he plant., t:o seeds or t.o t.~'he s~.i.l, or t:~ fac.ilitate it.s t:ran.sport or,.i.t.s handl.i.ngO The carr.ier can he so1.i.d (c1.ays such as X.aol.i.n. o.r ben~.onite, natural sil,i.cat.es such 1.0 as t:al.c, or ~yntheLi.c si.l.icates, cal.ci.ned magne.s.ia, ki.eselguhr, t.r:i.calci.~m pho.sphat.e, powdered cork, absorbe:nt cha.rcoal, reQi,ns, waxes and sol.id fert::ili.sers) or flui.d (water, alco~ols, ke~ones, pet.roleum fract,ions, chlorinated hydrocar~ns or li.quefied gases)~ When the carrier .is a common .qolvent another material should also be present, eOgO a surface--active agent, i.n order that the fungic.idal compos:ition is other than an association of the compound of general.formula I or II with a solvent. : ' -The co.mposi.t.ions in t.he form of suspensi.ons, emulsi.ons or soluti.ons ma.y contai.n a surface-act.i.ve agent.
~he surface-active agent can be an emulsi.fying, d.i.spersing or wet:t.i.n.g agent, which can be iOIl.i.C or non-i~ni.c, for example:salt.:s of polyacryl:i.c ac:i.ds and of l.i.~ni.nsl1l.ph.on:i.c 2.~ ac.;.ds, condensat~s of eth.ylene ox:i.de w.it:h fatt.y alcc,'.~o1.s, 108~644 .; fatty acids or fatty am:i.nes, product.s hased on condensates of ethylene oxide wi.th octylphenol or nonyl.phenol, or fatty ac.id e4ters of anh.ydxo-sorhit:ol.s which have been rendered soluble hy ether.i~.icat.ion of the free hydroxyl radi.cals by con.den.sat.ion wlth ethylene ox.i.dec .It ls - preferable to u.se agents of the non-ionic t.ype because they are not sens.it.ive to electrolytes~
The compositions accordi.ng to the inventi.on can be prepared in the fo~m of wettable powders, dusti.ng powders.
granules, sol.ut.ions. emuls.ifiable concentrates, emulsions, suspens.ion concentrates and aerosols.
The wettable powders are normally prepared in such a way that they contain from 20 to 95% by we.ight of act.ive materi.al, and normally contain. in addition to a solid carrier, from 0 to 5% by weight of a wetti.ng agent, from 3 to 10% by weight of a dlspersing agent and, when necessary.
from 0 to lOD/o by weight of one or more sta~ilisers and/or other ad,juvants, such as penetrating agents, adhesives or ant.i caking agents and dyestuffs.
Aqueous di.spersi.ons and emulsions. for example composit,ions obtained by diluting with water a wettable powder o~ an emulsi.flable concentrate according to the i.nvention, are i.ncluded withi.n the general. scope of t.he present i.nvent:ion. These emuls:ions may be of the water-.i.n~oil type or of the oil-i.n-~-water type and may have a thick consi.stency resembli.ng that of a "mayonnai.se".
The compositions according to t.he .invention may contain other i.ngredients, for ex~mple protective collo.i.d3, adhesives or thickeners, thixotrop.i.c agent~s, st.abi.li.sers or seqllestrantsO
Com.posi.tions ready for use .i.n a. liquid carri.er, eOgO water. will usually contain from 0O001% to 0.5%
weight/volume, iOeO from 0.01 to 5 gO per litre, of a compound of general formula I or II. Compnsitions in t.he form of concentrates for dilut.ion before use wi.ll usually contain from 10% ~-O 95% by weight of act.i.ve compound.
The doses in w~ich the compounds of general formulae I and II are u~ed may vary withi.n wide l.i.mi.ts, depend.ing both upon the virulence of the fungus and upo.n the climatic conditions~ Generally the compou.nds are used as fungicides in amounts of 0Ol to 4 kgO of active compound per hectare.
Spray volumes of 500 to 5000 litres per hectare are generally suitable.
The following Examples illustrate fungicidal cOmpoBitiOnS according to the present invention.

thiophosphite of general formula I or II 50 %
calcium lignosulphat:e (deflocculant.) 5 %
anionic wett:ing agent 1 %
anti~cak.i.ng si.li.ca 5 %
kaolin (filler) 3~ %

1(~8~i44 , , Water-~oluble powder~ are obt~i.ned by mixing from Z0 to ~5% ~y wei~ht of t:hiopho~p1lit~ of general f~rmula I or II, frQm 0 to 1~ or an ant.i-caki.n~ filler and from 0 ~o 1% of a wetti.ng agent, t.he rema~nder o~ th~ compo3i.tioll being wat.er sol~lble :iller, usual.ly ~ ~alt~
Example 17 illu~trate~ 3 fUrlqiCidal compogition ~ccvrding to the lnvan~lon ln the form of ~ wat~r ~oluhl~
po~der.
~YAMPLE 17 thiophosph:ite of general fo~mula I or II70 %
anioni.c we~tl.ng agent 0.5 %
anti-ca~lng sil.~ca 5 %
~od.it~ ~ulphate (~oluble fi.ller; 24.5 %
~le present invention also include~ within it~
scope a method for preventing or curing ~ungal disease in -~
plants which com~rises applyi.n~ to a plant or to it~
environment a ~hiophosphite of general formula I or II, or a fungicidai compo~ition ccmprising such a compound as hereinbefore descrlbed.

- ~8 . ' ~ . .

Claims (26)

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

1. A fungicidal composition suitable for use in controlling fungal disease in plants, which comprises as an active ingredient, at least one compound of the general formula:

(I) and/or at least one derivative thereof of the general formula:

(II) wherein R represents a hydrogen atom, an alkyl, hydroxyalkyl, haloalkyl or nitroalkyl radical, each such radical containing from 1 to 18 carbon atoms, an alkoxyalkyl radical, the alkoxy and alkyl moieties of which may contain from 1 to 8 carbon atoms, an alkenyl, haloalkenyl or alkenyloxyalkyl radical in which the alkyl moiety contain from 1 to 8 carbon atoms, an alkynyl or haloalkynyl radical, each such alkenyl or alkynyl radical or moiety containing from 2 to 8 carbon atoms, the cyclohexyl radical, a phenyl radical or a phenyl-alkyl radical in which the alkyl moiety contains from 1 to 3 carbon atoms, or R represents the tetrahydrofurfuryl radical, M represents an agriculturally or horticulturally acceptable cation, and n is an integer equal to the valency of M, in association with one or more carriers or adjuvants compatible with the active ingredient and suitable for use in agricultural or horticultural fungicidal composition.

2. A fungicidal composition according to claim 1 wherein the active ingredient is at least one thiophosphite of sodium, an alkaline earth metal or a heavy metal, or a compound of the general formula:

(II') wherein R' represents an optionally substituted hydroxyalkyl radical containing from 1 to 8 carbon atoms, and M and n are as defined in claim 1.

3. A fungicidal composition according to claim 1 wherein R represents a hydrogen atom, an alkyl, hydroxyalkyl, haloalkyl or nitroalkyl radical, each such radical containing 1 to 8 carbon atoms, an alkoxyalkyl radical, the alkoxy and alkyl moieties of which may contain from 1 to 5 carbon atoms, an alkenyl, haloalkenyl or alkenyloxyalkyl radical in which the alkyl moiety contains from 1 to 5 carbon atoms, an alkynyl or haloalkynyl radical, each such alkenyl or alkynyl radical or moiety containing from 2 to 5 carbon atoms.

the cyclohexyl radical, a phenyl radical or a phenylalkyl radical in which the alkyl moiety contains from 1 to 3 carbon atoms, or R represents the tetrahydrofurfuryl radical, and M and n are as hereinbefore defined.

4. A fungicidal composition according to claim 1 wherein R represents a hydrogen atom or an alkyl or hydroxy-alkyl radical each such radical containing 1 to 8 carbon atoms.

5. A fungicidal composition according to claim 4, wherein R represents an alkyl radical containing 1 to 5 carbon atoms or a hydroxyalkyl radical containing 2 to 5 carbon atoms.

6. A fungicidal composition according to claim 4 wherein R represents an optionally substituted 2-hydroxyethyl or 3-hydroxypropyl radical.

7. A fungicidal composition according to claim 6 wherein the 2-hydroxyethyl or 3-hydroxypropyl radical is substituted by one or more methyl radicals.

8. A fungicidal composition according to claim 1 wherein M represents hydrogen, an alkali metal, an alkaline earth metal, a heavy metal, an ammonium group, an ammonium group substituted by one to four alkyl or hydroxyalkyl radicals each such radical containing from 1 to 4 carbon atoms or by a cyclohexyl or phenyl radical, or a heterocyclic cation having 5 or 6 carbon atoms in the ring, one of which is a nitrogen atom.

9. A fungicidal composition according to claim 1 wherein M represents hydrogen, an alkali metal, an alkaline earth metal, an ammonium group, an ammonium group substituted by one to four methyl and/or ethyl radicals or the pyridinium group.

10. A fungicidal composition according to claim 1 wherein M represents sodium, magnesium, calcium or barium.

11. A fungicidal composition according to claim 1 in which the active ingredient is one or more of sodium thiophosphite, calcium thiophosphite, barium thiophosphite, sodium 1-methyl-2-hydroxyethyl thiophosphite, sodium 2-methyl-2-hydroxyethyl thiophosphite, calcium 1-methyl-2-hydroxyethyl thiophosphite, calcium 2-hydroxypropyl thiophosphite, calcium 1-methyl-2-methyl-2-hydroxyethyl thiophosphite, magnesium 1-methyl-2-methyl-2-hydroxyethyl thiophosphite, calcium 3-hydroxypropyl thiophosphite, magnesium 3-hydroxypropyl thiophosphite, sodium 2,2-dimethyl-3-hydroxypropyl thiophosphite, calcium 2,2-dimethyl-3-hydroxypropyl thiophosphite, magnesium 2,2-dimethyl-3-hydroxypropyl thiophosphite, ammonium 2-hydroxy-ethyl thiophosphite, ammonium 1-methyl-2-hydroxyethyl thiophosphite, ammonium 2-methyl-2-hydroxyethyl thiophosphite, ammonium 1-methyl-2-methyl-2-hydroxyethyl thiophosphite, diethylammonium 1-methyl-2-hydroxyethyl thiophosphite, diethylammonium 2-methyl-2-hydroxyethyl thiophosphite, ammonium 3-hydroxypropyl thiophosphite, diethylammonium 3-hydroxypropyl thiophosphite, ammonium 2,2-dimethyl-3-hydroxypropyl thiophosphite, diethylammonium 2,2-dimethyl-3-hydroxypropyl thiophosphite, pyridinium 2,2-dimethyl-3-hydroxypropyl thiophosphite, sodium ethyl thiophosphite, calcium ethyl thiophosphite, barium ethyl thiophosphite, magnesium ethyl thiophosphite, sodium isopropyl thiophosphite, calcium isopropyl thiophosphite, ammonium ethyl thiophosphite, diethylammonium ethyl thiophosphite, diethylammonium isopropyl thiophosphite and calcium n-propyl thiophosphite.

12. A fungicidal composition according to claim 1 in which the quantity of active ingredient is 0.001% to 95%
by weight of the composition.

13. A fungicidal composition according to claim 1 in which the active ingredient is in association with a surface-active agent.

14. A fungicidal composition according to claim 1 which contains a wetting, dispersing or emulsifying agent.

15. A fungicidal composition according to claim 1 in the form of a wettable powder, a water-soluble powder, a dusting powder, granules, a solution, an emulsifiable concentrate, an emulsion, a suspension concentrate or an aerosol.

16. A fungicidal composition according to claim 1 in the form of a wettable powder comprising from 20 to 95%
by weight of the active ingredient, a solid carrier, from 0 to 5% by weight of a wetting agent, from 3 to 10% by weight of a dispersing agent and from 0 to 10% by weight of one or more stabilisers and/or other adjuvants such as penetrating agents, adhesives or anti-caking agents and dyestuffs.

17. A fungicidal composition according to claim 1 in which the carrier is a liquid and the composition contains from 0.001% to 0.5% weight/volume of active ingredient.

18. A fungicidal composition according to claim 1 in the form of a water-soluble powder comprising from 20 to 95% by weight of the active ingredient, from 0 to 10% by weight of an anti-caking filler, from 0 to 1% by weight of a wetting agent the remainder of the composition being a water-soluble filler.

19. A fungicidal composition according to claim 1 in the form of a concentrate requiring dilution before use which contains from 10% to 95% by weight of active material.

20. A fungicidal composition according to claim 1 in which water is the carrier for the active ingredient.

21. A fungicidal composition according to claim 1 which comprises another fungicide selected from the 2-hydroxy-1,3,2-dioxaphospholanes, the .beta.-hydroxyethyl phosphites, the phosphonic diesters, the cyclic diphosphorus compounds, the aminophosphites, the 2-hydroxy-1,3,2-dioxaphosphorinanes, the .gamma.-hydroxypropyl phosphites, the phosphorus-based trialkyl imides and the 2H-2-thio-1,3,2-dioxaphospholanes and phosphorinanes.

22. A fungicidal composition as claimed in claim 1 which also contains a compatible acaricide or insecticide.

23. A method for preventing or curing fungal disease in plants which comprises applying to a plant or to its environment a compound of general formula I or II
depicted in claim 1, or a fungicidal composition comprising such a compound as claimed in claim 1.

24. A method according to claim 23 in which a composition comprising the compound of formula I or II is applied to the plant or its environment, the composition containing from 0.01 to 5 g. of compound of formula I or II
per litre of carrier.

25. A method according to claim 23 in which the compound of formula I or II is applied to a locus of fungal infestation at a rate of 0.1 to 4 kg. of compound per hectare.

26. A method according to claim 23 in which the compound of formula I or II is applied to a locus of fungal infestation to control a fungus of the phycomycete, ascomycete, basidiomycete, or Fungi Imperfecti family.