PHOSPHORUS-CONTAINING FUNGICIDES

FONGIDIDE CONTENANT DU PHOSPHORE

English Abstract

ABSTRACT
Thiophosphorous acid and salts thereof of the
general formula:
<IMG>
and derivatives thereof of the general formula:
<IMG>
wherein R represents hydrogen, an alkyl, hydroxyalkyl,
haloalkyl, nitroalkyl, alkoxyalkyl, alkenyl, haloalkenyl,
alkynyl, haloalkynyl, or alkenyloxyalkyl radical, the
cyclohexyl radical, a phenyl or phenylalkyl radical or the
tetrahydrofurfuryl radical, M represents an agriculturally
or horticulturally acceptable cation and n is an integer
equal to the valency of M, some of which are novel compounds,
are useful as fungicides.

Claims

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:
<IMG> (I)
and/or at least one derivative thereof of the general
formula:
<IMG> (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
- 39 -

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:
<IMG> (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.
- 40 -

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.
- 41 -

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
- 42 -

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
- 43 -

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.
- 44 -

Description

1086644
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
" , .

11D86644
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,
.'
-, : .

1086644
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

1086644
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:
- 6 -

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
R5 R6
- 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 -;
EXAMPLE 1
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
EXAMPLE 2
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.
EXAMPLE 3
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:
12

~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_
-- 13 -

~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
EXAMPLE 4
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:
CH3 H
E10 -- C~H2 -- C - CH2 - O ~ o ~H2( 2 5 2
CH3 S
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~

1086644
~ ~ ,
U~
a~ ~ ~. . u~
~ ,~
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- ., ~ .

iO86644
U ~ U ~ U ~ U
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a~ ~ I~ ~n ~ u~
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-- 18 --
- :: . . :

1086644
EXAMPLE 5
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 --

1086644
.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.
- 20 -

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 ~ ~ ~
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. . ~ . . ~ . . ~ . . ~ . . ~ . .
a:~ ~ ~ ~ ~ ~ ~ o~ ~ u~ u~
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~ U N O O N U
,
-- 21 --

1086644
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.
EXAMPLE 8
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
25 -

1086644
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/~
27 -
~ .. . . .

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
EXAMPLE 11
.' :
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
29
':

1086644
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
EXAMPLE 12
- ~. .
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
EXAMPLE 14
.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
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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,
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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
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1086644
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.
EXAMPLE 16
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.
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