5Z~
. , ,
The invention concerns novel metal complexes of
antimicrobic eFfect, havlng the g3neral formula I, whlch
are mixed lig~d metal complexes of 8-oxyquinollne and
diethyl-dithiocarbamic acid. In the fo~rnula M is a
S divalent metal atom, such as Mg~ Mn~ Fe, Ni, Cu, Zn,
Cd~ Sn.
The invention also concerns the product of the
matal complexes of general formula Iq
The formula is:
,.
.. ~0~'
,r~ I
C~13
S C ~ N
! CH
The metal complexes of dialkyl ~ ~
acids and of alkylene-bis-dithiocarbamic acids have become
known, and various derivatives of them are widely used as
funqicides in plant protection (UOS. Pa~ent Specifications
No50 1,972.961, 2,317~765, 2,4S7~674, 2,~04~404 and
2,710.822). The most widely u~ed, as leaf fungicides,
are the zinc complexes (~Ziram~, ~Zineb~, ~Propinebl~, the
manganese complexes (tManeb~) and a product containing
~ . ~
a mlxture of the two (~Mancoseb~). In spite of widespread
u~e, however, they do not provide adequate protection
agein9t many species of Fungi, e~gO against Botrytis.
In another connection, 8-oxychinoline and its metal
salts have also been known for a long time and several
publications describe their fungicidal effect~ The
possibilities of prac~ical application against fungus
.~
- 2 - ~ ~
'~' .. ' " :
.
, ... , , ... . .. .:~ . . . . . .. .
~4~35Z15
diseases of plants have also been studied by many authors.
(D. Powell9 Plant Disease Reporter, 38, 76-79, /1954/;
E.M. Stoddard, Plant Disease Reporter, 41, 536 /1957/;
E.M~ Stoddard, and RoM~ Miller, Plan~ Disease Reporter,
46l 258-259. /1g62/? ~
8-Oxyquinoline has mostly been investigated in
the form of its salts. In one class of these, 8-oxy-
quinoline plays a cationic role (oxyquinoline sulphate~
citrate, salicylate etc.) v~hile in another class the
8-O~ I~ anion for:ms a salt with some metal cation,
such as copper, cobalt, zinc etc. (C.L. Mason, Phyto-
pathology, 38, 740-751 /1948/; A~ Albert, S.D. Rubboo, R.J .
Goldacre, and B~C~, Balfour, Brit. J. Phytopathol. 28, 69-87,
/1947/; A~ Manten, HoL~ I<lopping, G.~.M. van der l<erlc and
Antonle van Leeuwenhoek, J. Microbiol. Serol.~ 17, 58-68
/1951/), Investigations of the structure of the metal
salts have proved that they are complexes wherein two
8-oxyquinolinate anions form the ligands of a central
metal atom. It has been ascertained that of these metal
complexes only copper(II)-oxyquinolinate has a fungicidal
effect worth mentioning (D. Powell, Phytopathology, 36,
572-573 ~1946/), and for this reason only this compound
has become knownJ under the nama 'Oxin~
In view of the fact that the metal comple>~es of
dialkyldithiocarbamates and of alkylene-bis-dithiocarbamate
have not proved to be sufficiently effective against
many fungus diseases, there has been widqspread research
into further possibilities of protection against such
fungus diseases. Thus Patent Specification NoO 1 ~288J358
of the Feder~iL Rapublic of Germany describes a fungicicle
. .
. . .
.. . .
sz~
for protection against sotrytis which consists of a mixture
of zinc dimethyl-dithiocarbamate and copper-8-oxyquinolinate.
We have found that the novel mixed ligand metal com-
plexes of 8-oxyquinoline and dimethyl-dithiocarbamate having
the general formula I - M in the formula being a divalent
metal atom, e.g. Mg, Mn, Fe, Ni, Cu, Zn, Cd, Sn - or mixture
of such mixed ligand complexes containing two metal atoms,
exhibit a strong microbiotoxic, primarily fungicidal, effect.
The novel complexes are characterized by containing two bio-
logically active anions that are different from each other, -
as mixed ligands.
Further, we have found that the metal complexes of
general formula I can be produced by reacting an alkali metal
salt of 8-oxyquinoline in a polar organic solvent or in an
aqueous solvent with an alkali metal salt of dimethyl-dithio- -
carbamic acid and a metal halogenide MHal2 - where M has the
meaning given above and Hal is a halogen atom, most suitably
a chlorine atom - or simultaneously with two such metal halo-
genides. The reaction is carried out at room temperatureO
generally at a temperature below 30 C, expediently in an
alcoholic or an aqueous-alcoholic medium. As a result of
the reaction the desired complex or mixture of complexes
separates out from the medium, normally in a crystalline form.
The separated product is filtered, washed and dried.
In accordance with one aspect of this invention there
is provided a compound selected from the group consisting of
metal complexes of the general formula I given hereinbefore
A: `
,~` wherein M is a divalent metal atom, and mixtures thereof.
. . .
In accordance with another aspect of this invention
there is provided a process for inhibiting the growth of a
microorganism comprising the step of contacting the organism
:
with an amount sufficient to inhibit its growth of the compound
hereinbefore noted.
.~
~ 4 -
,; . . . .
~4~5Z~3
In accordance with another aspect of this invention
there is provided a process for the production of the herein-
~ before noted compound characterized in that an alkali metal
`: salt of 8-oxyquinoline is reacted in a polar solvent or aqueous
solvent medium with an alkali metal salt of dimethyl-dithio-
carbamic acid and with a metal halide having the general
formula MHal , where M is a divalent metal atom and Hal is a
halogen atom, or simultaneously with two metal halides of
said general formula MHal2, then the thus obtained product is
separated.
Surprisingly, we have found that the mixed ligand
; complexes according to the invention are considerably more
effective than single-ligand metal complexes of 8-oxyquinoline
or dimethyl-dithiocarbamic acid, taken by
, :
. ,
;., .
.. ' '
" :
.~
~ .
...
: ~ .
. , .
:
"
~, ::- :
; .
," .,: ,:
, ~ :
' 4a~ :
` j;a~ ..., !
1~4~5Z~
- themselves or in their mixtureJ
.~ The greater effectiveness manifests itselF both ~n
a requirement for s signlfi.cantly lower concentration of
active substances and in suitability~the metal complex~s
according to the invention for inhibiting the germinatlon
and proliferation of fungus species against which single-
ligand complexes have been practically ineffective (e~g.
wheat smu~
In the course.of calorimetric tests we have
ascertained that the enthalpy change in formation of the
mixed-ligand complexes according to the invention is
greater than the sum of the enthalpy changes in formation
of single-ligand complexes; consequently the complex
according to the invention has greater çhemical stability
than a physical mixture of the two corresponding single-
ligand complexesD It is presumed that the increased
effectiveness can be functionally related partly to the
greater stability and partly to the asymmetric charge
distribution of the complex.
The novel~ mixed-ligand cornplex of general formula
I may be produced by reacting an alkali metal salt of
8-oxyquinoline in a polar solvent at room temperature with
a stoichiometric quantity of an alkali metal salt of di-
`, b ethyl-dithiocarbamic acid and a halogen salt MHal2 of a
divalent metal, the solid produot separating out being
filtered, washed and dried.
In the course of production one can pro~eed also
;' ' ' O ~c~ q L~ o l J~q ~e
1. by reacting an alkali metal salt of 8~ hi~iLui~ and an
alkali metal salt of dimethyl-thiocarbamic acid, not with
a staichiometric quantity of the halogeh salt of one metal,
,, ~
~ . .
:'''' '. ' . - : ,
5~ ~
but simultaneously in one reaction step with the
: cornbined stoichiometric quantity of two.metal haloyan
s a l t s O
The invention further relates to antimicrobic,
principally fungicidal, prepara~ions which contain at
least one compound having the general formula I as
the active substance.
In certain cases, mi~tures of compounds of general
formula I containing different metal atoms exert a
'~ 10 stronger effect~ and are therefore preferred in certain
areas of appllcation.
The~biological effectiveness of the novell mixed-
ligand metal complexes of general formula I were
' investigated by comparison with the fungicidal effects.
of commercially available single-ligand zinc dimethyl-
~ dithiocarbamate (~Ziram~) and'zincc 8-oxyquinolinate, as
'` wel~l as the equally well-known 1-butylcarbamyl-benzimida-
zole-2-yl-carbamic acid-methyl ester~ (~Benomyll).
' ': ' In the t.est: a modified'McCallan method was used
''. 20 (American Phytopha~hological Society, Committee of
` . Standardization pH fungicidal Tests, Phytopha~hology,
, - . .
'` 33, 419 /1943/~. According to thisl predetermined
. .
- . quantitles of~a concentration series prepared from
'. aqueous suspensions of the fungicides to be investigated
~ 25. were~applied to :plates, the water was evaporated and to
.~ ~the~locations of the dried residue a spore suspension of
.; the test ~fungus:was added dropwise~ The plates were kept.
$or~Z4 hours in a humid chamber at constant temperature,
' then the p:ercentages of the germination and growth were
'~' 30 read'off microscopically~ . . '
,
' '
.' .
,~ , , , , . , ;
~ . . . . . . . . .
~o~sz~ ~
The results are given in a percentage concentration
ensuring a 50% spore-inhibiting effect (ED50)q Alternaria
tenuis and Botrytis cinerea being used as test fungi, for
oolnparative experiments and the results are shown in
Table 1 D
rable 1
Number Active fungicide Alternaria tenuis Botrytis cinerea
.. . .. ~
germination g~wth germination growt~
, _
nece~sary concentration for 50% in-
hibition
~ . . .. . . ... . . . . . . . . . , . .
1- Mixed ligand Zn
8-oxyquinolate-di-
methyl dithiocar- 10-5 1o-1o 10-10 10-~l
bamate
2~ Single~ligand Zn
8-oxyquinolate 10-5 2x10 7 9x10 55x10 6
3~ Single-ligand Zn
dimethyl-dithio-
carbamate 2x10 3 7x10-4 9x10 5 5x10 5
4~ Equimolar mixture
of the compounds of
2~ and 3~ ebove 2x10 4 7x10 5 5x10 9 10
5 ~ 1 -Butylcarbamyl-
: benzim id azole-2-yl-
carbamic acld-methyl ~x10 1 3x10 1 7x10 6 3~1~ 6
e3ter
.
- 7 -
. - .
, ., : ~ - . ~ :
1~495~1!3
The results in the Tahle prove that the ef-fect
of the mixed-ligand metal comple~xes according to the
invention exceed both tha effect of the single-ligand
metal complexes (2l 3) and the eFfect of a physical mixt~re
of the two single-ligand metal complexes~ It can also
be seen that the fungiGidal effect of the commercially
very widely used 1-butylcarbamyl-benzimidazole-2-yl-
carbamic acid-methyl ester (~8enomylr) is also very
considerably exceeded~
We investigated the fungicidal eFFect of the mixed-
ligand metal complexes having the general Formula I and
containing a central metal atom~ and of mixtures of such
cemplexes, for eight fungus species by using the well-
I<nown agar diffusion process~ The inhibition 'zone'
was investigæted by means of a dilution series of the
complexes, or rather the threshold concentration tn
ppm where the complex still inhibited the grow~h of
the spores was found (Table 2)~
S ; .,
. f . - 8 ~
' : ' , . "
~L~9~SZ~3
Table 2
A ~ B ' C D t
m J
where there is still inhibition
1~ Zn-8-oxyquinolinate ~ 2 < 2'~4
dimethyl-dithiocarbamate
2~ Mn-8-oxyquinolinate ~ 2 > 2~<2 ~2
dimethyl-dithiocarbamate
,.~_
3. Cu-8-oxyquinolinate ~ 4 7 80720 74
dimethyl-dithiocarbamate
4. Cd~8-oxyquinolinet,e 6~40 ~2000 ~200 8
dimethyl-dithiocarbamate
5. A mixture of:
Zn-8-oxychinolinate
dimethyl-dithiocarbamate ~ 2. ~4 ~c2 ~C2
Mn-8-oxychinolinate
dimethyl-dithiocarbamate
6. A mixture of:
Zn-8-oxyquinolinate ~ 4 720~ 4 ~2
', dimethyl-dithiocarbamate
Cu-8-oxyquinolinate
dimethyl-dithiocarbamate
.~ ~
7. A mixture of: ' '
Mn-8-oxyquinolinate,
, dimethyl-dlthiocarbamate~2 ~4 ~2 /~2
- Cu-8-oxychinolinate
, dimethyl dithiocarbamate
.; ~ .
Stan- 'zineb' ~2000 ~80;72000 ~80
,~
dard Gopper-8-oxyquinolate 40 1000400 100
~ .
A : Al~ernaria ~enuis
B : ~spargillus niger
, ~ : Aspergillus tenuis
O i;`- Botrytis cinerea
:
.
'
: _ g _
;:
- , :
,:
lQ4~S2~3 ~
~, ~ con t inued~
._,
Example Fungicide Fungus species
E F G H
threshols concentration in ppm ~
where there is ~till inhibition
(inhibition zone)
1~ Zn-8-oxyquinolinete
dimethyl-dithiocarbamate C 2 ~ 4 ~2 7 4
2~ Mn-8-oxyq~inolinate ~ 2 ~4 2 2
dimethyl-dithiocarbamate ~~ ~ C ;7
3~ Cu-8-oxyquinolinate 7 20 ~40 ~20 ~20
dimethyl~dithhacarbamata
4~ Cd-8-oxyquinolinate
dimethyl-dithiocarbamate ~ 80 ;740 ~40 ~8
- 50 A mixture of~
Zn-8-oxyquinolinate
dimethyl-dithiocarbamate ~ 2 ~4 ;~ 2 ~4
Mn-8-oxyquinolinate
dimethyl-dithiocarbamate
~ A mixture of:
: Zn-8-oxyquinolinate
dimethyl-dithiocarbamate C 2 ,~20 ~2 ~ 20
Cu-8-oxyqwinolinate
dimethyl~dithiocarbamate
,_ , , ,
7. A mixture of~
Mn-8-oxyquinolinate
dimethyl-dithiocarbamate.g 2 > 4~ 20 ~ 2
Cu-8-oxyquinolinate
dimethyl-dithiocarbamate
. .
~tan- lZineb~ 40 ~-80 ~40 ~20
dard copper 8-oxyquinolinate 100 100 20 100
E ~ Botrytis allii
F : Fusarium culmorum
G : Helminthosporium turcicum
H : Tricho~hecium roseum
- 10
.. . . . .
~195Z~3
The data of the Table unambiguously show ~he
excellent fungicidal effect of the mixed-ligand metal
complexes accordlng to the invention, since all seven
complexes Or mixtures shown inhibit the proliferation of
6 the spores of the eight fungus species at a concentration
ji` of less than 200 ppm, - with the exception of one case -
and in the overwhelming proportion in a concentration
of less than 40 ppm. The complexes according to Example5 1,
2, 5 and 7 inhibit spore proliferation even under 4 ppm,
i.e. are eff~ctive in exceptionally low concentrations,
and their fungicidal effect considerably exceeds that of
' known fungicides.
Further, we investigated the effect of the novel
mixed-ligand metal complexes according to the invention
` 15 on the very resistant smut fungi (Tilletia spp.), wheat
~' seed being dressed by means of an'80% dust dressing
~ ~ .
:material containing as active substances the mixed-ligand
metel oomplexes or N-methyl-mercury (II)-p-toluene- '
sulphonyl-anilide a a standard"(i~ranosan~). .
~:~ Tho wheat sesds used for'our experiments were
. ' artL~f1c1ally infected with spores of Tillet.i3 caries and
. Tilletia foetidaO The seeds were then dres6ed ln the usual
manner with a dose of 200 g/q and the tests were performed
. by the well-known seed impression method. A nutrient
~'` 25 medium applied in a Petri dish in the form of a slurry
was dried until its surface became~dull and thereafter a
~ed impre~sion was made by imprjessing S0-50 dressed
seed, with the aid of tweezers. The impressed medium was
'` kept at 12-18 C and on the 5th, 7th, and ~th day 'the
, . '!. '
'proportions of impressions with g.erminatlng spores ware
.. . .
,
: - ;................... - ~.
.
~ ~ ~9 5
read offO
In parallel with these 9eed impression experimentsO
the treated and untreated seeds were planted in cultivation
boxes fillsd with garden soil and the effects of the traat-
ments on the sprouted plantslwere investigated on the 5thand 'lOth days after sprouting by measuring the average
of the plants.
The results of the t~sts are shown in Table 3.
Table 3
. ~ . . .
Sprquting Plant height Spore
% expressed as germination
perOEentage of % of
height of un- impréssions
drsssed in-
- fected con~rol
Days 5 ~10 5 10 5 7
Dres~ed with Zn
3-oxyquinolate ; 66h5 69.0 146.713220 Nil Nil 0.
dimethyl-dithiocarba-
mate
Dressed with N-methyl-
Hg(II)-p-toluene- 50~5 5505 106.210508 Nil 6-3 10~2
sulphonyl-anilide
(?~rano~an~)
:Undressed inFected
eeed : 49.0 ' 53~0 100 100 79~5 94.6 ~7JO
.. . .
: Uninfected, control
seed . 55~0 56~5 115.2118 -
,
:: Accord~ng to the result~ af the me36urements the noval
mixed-ligand metal complexes provide, on the onè hand, a more
effectiva protection egainst smut than the known dressing
30 agent containing mercury and on the other hand, going beyond
' . .
,, . . :, . .
--1 2 - . .
.
.
9 Sz ~
that, exert a plant~growth stimulating effect~ Thus the1r
use as a dressing agent affords a double advantage.
After ascertaining that the novel mixed-ligand metal
complexes exhibit a strong fungicidal effect, we carried
out further investigations in the case of three complexes
to ascertain on what fungi they exert an effect, in
addition to those shown in Tables 1 and 2.
From Table 4 it can be seen that the three in-
vestigated mixed-ligand complexes generally exert a well-
defined inhibiting effect even at a concentration of 10ppm in the cases of all seven fungi namedO
: Table 4
Investigated fungi 1 2 3
Zn-8-oxyquino- A mixture Mn-8-oxy-
linate di- of Zn and quinolinate
. methyl-dithio- Mn-8~oxy- dimethyl-
carbamate quinolinate dithio-
- dimethyl-- carbamate
dithio-
carbamate
tnresnol~ conc~ntration ppm
Cercospora beticola 10 10 10 .
Fusarium gramineorum 1o2 10 10
Nigrospora oryzae 10 . 10 10
Septoria lycopersica 10 10 10
Stemphylium botryceum 10 10 10
Verticillium sp. 2 x 10 10 10
Aspergillus niger 10 10 10
25
Further, mixtures of metallic complexes were in-
vestigated wherein the ratios of Zn and Mn were chosen
in different ways in order~to observe.the effect of the ratio
to each other of the metals; the meaeure of the fungicidal
30 activity of mixtures of 8~oxyquinollne-Zn-dlmethyl-di-
- 13
SZ~
:
thiocarbamate and 8 oxyquinollnete-~n-dimethyl-dithio~
carbamate can he read off in 9equen~e fro~ tho graph~
~ ~ The hori.zontal axis is the ~ position and
; the vert~cal axis ~9 tha threshold or limit concentra~ion
in ppm. The individual curves show ehe effect on the
following fungi:
- 1. Fusarium culmorum
2~ Trichothecium roseum
. 3. Helminthosporium turcicum
4. Botrytis e~b~
With the exception of fusarium culmorum, l~rge inhlbition
zones were found f.or the chosen fungi even at vsry low
concentrations, and it may be observed that the effect
of complexes of one metal, containing Zn only or Mn only,
is smaller than that containing both me:~als~ The~r~tio
of the two metals is expediently between 3:7 - 7:3.
In parallel wlth the fungicidal effect, an in-
vestigation was conducted to show a bacttericidal effect.
Bacillus subtilis and Pseudomon3s tabacl were employed,
and the invastigation was carried out in a B, subtilis
nutrient medium, i~e, 1% maat broth (Oxoid "L~b-Lam~o" . -
beef extract) which was solidifled with 2% agar-agar.
The method of the tast was an agar-agar diffuslon proce~8.
. The result is shown in Table 5, from which it can : -
be seen~ that tha novel mixed~ligand matal complexes
according to the invention have a pronounoed bactericidal
effect also~ ~
,
.. . . .
- 14 -
: ,.
- : . .
~9 ~
Table 5
Active substanceBacillus subtilis ~ tabacl
.: ~
.limit concentra- limit concentra-
tion ppm tion ppm
Zn-8-oxyquinolinate
dimethyl-di~hiocarbamate 1o2 104
Mn 8-oxyq~inolinate
dimethyl-dithiocarbamate 1o2 1~2
~0
A mixture of: -
Zn~8-oxyquinolinate
dimethyl-dithiocarbamate 1o2 102
Mn 8~oxyquinolinate
dimethyl-dithiocarbamate
;
; A mixture of:
Cd 8-oxyquinolinate
dimethyl-di~hiocarbamate ~o2 . 102
:Mn 8-oxyquinolinate
dimethyl-dithiocarbamate
After demonstrating the fungicidal activity of the
novel mixed-ligand metal complexas according to the in-
jn
vention we describahthe following Examples ~ proceRsss
for their preparation and formulation into fungicides~
The Examples about to be described do not limit
the scope of the invention~
145 g (1 mole) of 8~oxyquinoline wera added under
stirring to 40 g (~ mole~ of sodium hydroxide di~solved in
.
- 15
~ ~ 4~ 52 ~
1500 ml of methanol. The mixing was carried ou,~ at room
tempera~ure un'til solution was complete, then a 25%
, aqueous solution of 143 g (1 mola) of ~vdhor dimathyl~dithio~
carbamate was added to the solution., To the homogeneous
solution obtained a solution of 136 g (1 mole) of zinc
chloride dissolved in 700 ml methanol was added at a
temperature below 30 C, with stirring. After the
,' addition had been completed and the mixture had been left
standing for a short timeJ a thiclc yellow precipitate
separated out which was separated by filtering, washed
with water and dried. 331 g,of yellow crystalline
material was obtained which did not melt or dissociate
below 300 C0
Yield: 100% of the theoretical yield of the product,
,, 8-oxyquinolinate-zinc-dimethyl-dithiocarbamate.
, The structure of the mixed ligand metallic
complexes according to the invention was examined using the
product obtained according to Example 1 as a model
, compound wi~h the,following four methods: ,~
~ a) Elemental analysis
b) pH measurements
; ~ c) Calorimety ,'
d) Derivatographic measurements
In the tabulated compilati,on the 8-oxyquinoline is
`, ~5 designated as oxin while dimethyl-dithlocarbamate i5
' designa~ed as DD~.
a~ Elementa ~_Q~y~
Found: N: 8.10%~ 8~02%, S~ 8%, Zn: 2001%,
, Calculated: N: 8.46% 5: 19.3%, Zn: 19~8%~
. .
, ' ~ 16 - ,
~ 52
b) ~H ~o _ '
The basis of the determlnation is the experimental
fact that in.an acidic me,dium the pH of the equilibrium
system containing Zn(II)~DDC changes with time, hence
the H -ion can expel the metal ion,~rom the complex.
Accordingly, a pH measurement method based on the
competition between the metal ion and the proton can be
usad for the equilibrium investigation. By utilizing
the measured pH value's the stability'constant was
calculated by a modified S~OGS programme, as was the
concentration distribution of the individual molscular
parts of the complex~ The results ~re shown in the table
below~
Table
: 15 ~ ,
spec'ies
pH . . l9111
.
4,88 14~63 0066 34.4
5.02 14053 0.56 26.2
; 5.47 14.47 0.50 21~8
5.86 14.70 ~ 0.73 . 12.6
- pH~ Zn(oxin) Zntoxin)2 (Zn/DDC),\ Zn(DDC)2 Zn(DDC)
25 4088 2~1 0.1 -25.7 24.2 23~5
i ~
S,02 5.1 0.7 Z1.~ ' 21.4 25.6
5.47 5c7 1~0 ' 19~5 22.0 ~ 3~.0
; 5786 . . 5.4 1~6 12.1 1406 53~8
30In the table 19111 represents the stabillty con~tant of the
- 17 -
95i28
mixed complex defined below:
zn2 ~ oxin ~ DDC ~ Zn(oxin) (~DC)
11'1 =~
- LZn2 ~ .~oxin ~ [DDC]
The mixed-ligand complex formation appropriate
to the statistical case can be calculated from the
constants of the prime complexes
lgB11~ ~ 2 (lg 2 ~ lg 2 ) ~ lg 2
The difference between these constant~ is the
so-called stabilization constant: ,
19~111 ' 19~3111 - 19fl1'~1 '
On the basis of the va~ues tabulated in the ,.
table~
lgB111 = 14.6 ~ 0~.5 /~lgB111 = 006 ~ 092
Thus, thè'increase in s~ability in ~he course
of formation of the mixed-ligand Zn(oxin)(DDC) i~ quite
significant.. It can be seen further tha~ the procesa of
'~; ~ e ~orma~tion becomes complete in the pH range of~
approximately 4 to 7, and in this way in the ~ystem
at biological pH always the mixed'complex iB pre9en~ ~
:Und~er such circumstances the relation between the mixed
ligand and the prime co'mplexes is expressed by the
equilibrium constant l<
Zn(oxin)2 ~ Zn(DDC)2 ~ 2 Zn(oxin)(DDC3
K
M Zn(oxin)2 Zn(DDc)2
.
,
. - . . : '
9 ~Z ~
The value of KM on the basis of thé above data 1s
: ~l< = 60 ~ 30.
, M
5) ~
: The investigations were carried out in an alkaline
medium at pH = 11, where the dissociation of the complex
no longer occurs and the formation of hydroxo-complexes
exerts no disturbing effect eitherO ~or the investigations
. an Ll<B~8700 precision calorimeter was usedO In every ca~e
; ~he solution contained an equal amOUnt of Zn(II~ while
the all<aline oxin, and NaDDC, or rather, a mixture there-
of were placed in the vial,
As a result of our investigations it can be
ascertained that the change in enthalpy of formation of
: the product according to the invention is greater than the
average values obtained in the formation of the prime
complexes, which can also be a~certained by calculations~
The greater change in enthalpy indicates D on the one
; hand, the favoured character of the formation of the
:~ mixed ligand complex, and on the other hand, an increase
in the bonding strength~
. d) ~
Under identical conditions the derivatograms of
the product according to the invention and of Zn(oxin)2
and Zn(DDC~2 were prepared. The data are summarized
; 25 in the tables below:
, ' ' ' ~
., .
: .
; ~ 19 -
:~ f
. . .
,
: ~ :
. ~ :
~495Z~3
TQb 1 ~
Zn(o~in~2, Zn(DDC~2 and Zn(DDC~(oxin~
Zn(oxin)2
C ~ Weight loss
100 exotherm~c 20.3
180 endothermic
420 endothermic 13.2
Total: 33.5
C Character of dissociation Wei~ht 105s
100 endothermic ~ 2.44
170 endothermic 2,40
270 endothermic 5.87
15 290 endothermic .42~07
455 ~ exothermic
520 exothermic
Total: ^ 52,79
~ Table
( Z l ~ ~ ~n~ ~ t
C Character of_dissociation ~g~
110 ; exothermic 1.30
180 endothermic 6nS0
260 endothermic 5.20
295 endothermlc S.20
295 endothermic 6.50
320 endothermie 9~10
390-520 many ~light endothermic _~
Totals 4505
.
- 2V -
, . . .
.:.: - :. , .
sz~
It can be seen that the derivatogram of the material
obtained by a simultaneous precipitation cannot be produced
by the superimposition of the derivatograms of the two prime
complexes, from which it can with justification be inferred
that the formation of the mixed complex in the solid phase
is complete.
The unambiguous and similar results of the investiga-
tions performed with three different methods verify without
any doubt that the product described in the invention is a
novel compound and not a physical mixture of complexes already
known from the literature.
Among the results obtained by the three different
investigative methods the calorimetric results are to be
highlighted, because in addition to their significance as
proving the structure they also show that the product accord-
ing to the invention is more stable than the physical mixture
of the complexes. This extra stability is very significant
from a practical view point since it results in a reduction
in the rate of dissociation of the product in storage and on
application to the plant surface and thus causes an increase
in the duration of its effect.
Example 2
..
145 g (1 mole) of 8-oxyquinoline was added with
stirring to 40 g (1 mole) of sodium hydroxide dissolved
in 1550 ml of methanol and stirred until solution was
; complete. Thereafter, under stirring, the solution was
~' mixed with a 25% aqueous solution of 143 g (1 mole) of
sodium dimethyl-dithiocarbamate and a solution of 198 g
(1 mole) of crystalline manganese chloride (MnC12.4H20).
.' ;
-21-
:' ' . . : '
,
52~
dissolved in 750 ml of methanol was added, w~th cooliny,
at 20-25 C~ After further mixing the solid complex
separated out~ and was recovered by Filtering, washing
and drying~
300 g of light brown powdery crystalline material
was obtained which did not melt or dissociate up to
3~0 C
A~J Yield: 94% of the theoretica1 yield of the product,
~e 8 oxyquin~linate-Mn-dimethyl-dithiocarbamateO
~o Analysis:
Calculated: N 8.77%, S: 20~%, Mn: 12.7%.
Found: , N 8.32%, S: 20~12%, Mn: 13.1%.
Ex_~e~
145 g (1 mole~ o~ 8-oxyquinoline were added under
stirring to a solution of 40 9 (1 mole~ of sodlum
hydroxide dissolved in 1500 ml of methanol~ and stirred
until completely dissolved. ThereaFter, with stirring
tho solution WflS mixed with a 25% aqueous solution of
143 9 (1 mole) of sodium dimethyl-dithiocarbamate, and
was`added under cooling to a solution of 170.5 9 (1mole~
of crystalline copper~ chloride (CuCl2q2H20) in
750 ml methanol. After the addition, the mixture was
stirred for another hour. On termination of the stirring
a solid powdery crystalline complex separated out~ It
was recovered by filtering, washed and dried~ 310 9
of chocolate-brown crystalline material was obtained which
did not melt or dissociate up to 300 CO
t~le 0~
Yield: 94.5% of~theoretical yield~the product
8~ rrnv~ Gu(II)~dimethyl-dithiocarbamate.
Analysis:
- 22 -
, . . . ...................................................... . .
~495~ .
Calculated: N: 8064%9 S: 19~56%~ Cu: 19~38%~
~ound: N: 8~58%, S: Z0~0 %, Cu: 19~60%.
145 9 ( 1 mole) of 8-oxyquinoiine was added with
stirring to 40 9 (1 mole) of sodium hydroxide dissolved in
1500 ml of methanol and stirred until completely dissolved~
Thereafter~ under stirring the solution was mixed with
143 9 (1 mole~ of sodium dimethyl-dithiocarbamate as a
25% aqueous solution, and 18303 9 (1 mole) of cadmium
chloride dissolved ln 760 ml methanol were added, with
: 10 cooling~ at 20 25 OCD After stirring for an`hour and leaving
the mixture to stand~ a crystalline material was separated
by filtering, washed with water, and dried. 300 9 of light
: brown powdery crystalline material were obtained which did
not dissociate or melt up to 300 C.
Yield: 95.5% of the theoretical yield of the
product~ 8-oxyquinolinate-Cd-dimethyl-dithiocarbamate~
.
Analysis:
Ca~l¢ulated: N: 7~44%, S~17.03%, Cd: 29~92%J
Found: N: 7035%, S:17.30%, Cd: 30~10%.
~ e~
i 145 9 (1 mole2 of 8-oxyquinoline were added with
stirring to 40 g (1 mole) of sodium hydroxide dissolved
.~ ln ~500 ml methanol and stirred until completely
dissol~ed.~~Theraafter the solut~ion was mixed with stirring
with 143 g (1 mole) of sod~um dimethyl-dithiocarbamate
` ~ as a 25% aqueous solution, and then under cool$ng mixed
with 176 95 9 (0~9 mole~ of crystalline manganese chloride
., ~
:: (MnCl2.4H20) and 13.5 9 (001 mole~ of zinc chlocide
dissolved in 700 ml of methanol~ ~iAfter stirring for an
23 ~
;
.
; . , , . ~ ~ , . ~
SZ~
hour t separated powdery crystallins material was filtered
ofF, washed with water and dried.
295 9 of green-brown crystalline material were
obtained whieh did not melt or dissociate up to 300 C.
Yield: 92% of the theoretical yield of the product,
a mixture~ in a molar ratio of 1:9, of 8-oxyqulnolinate-Zn-
dimethyl-dithiocarbamate and 8-oxyquinolina~e-Mn-dimethyl-
dithiocarbamate.
Analysis:
Calculated: N: 8075%, S: 20.03%, Mn: 16~42%~ Zn: 2p9%.
Found: N: 8.58%, S: 19O80%, Mn: 15.30%, Zn: 2~11%o
~ .
145 g (1 mole) of B-oxyquinoline~ were added undsr
s~irring to A0 9 (1 mole) of sodium hydroxide in 1500 ml
of methanol and stirred until completely dissolved. There-
after, under stirring, the solution was mixed with 143
(1 mole) of sodium dimethyl-dithiocarbamate as a 25%
.. ~ aqueous solution, then mixed with cooling with ~3 9 (0.9
mole) of zinc chloride and 17 9 (0.1 mole) of crystalline
copper chloride (CuCl2.2H20~ dissolved in 750 ml of methanol,
at 20-25 C. After stirring for an hour, crystalline
material separated out during standing was filtered off~
washed wi~h wa~er and dried~
... .
312~5 9 of a brown crystalline powdery material
were obtained which did not melt or dissocia~e up to
~i 300 ~.
-~ Yield: 95% of the theoretical yield of the produc~
a mixture of 8-oxyquinolinate-~n-dimethyl-dithiocarbamate
and 8-oxyquinolinate~Cu~ dimethyl-dithiocarbamate in a
:~ .
.` 30 molar ratio of 9:1.
. . - 24 -
.. . .
~. . ~ . . . .- .. ~ .... .
. . , . , . ~
1~4~52~ .
Analysis:
Calculated: N: 8.49%, S: 19~43%, Zn: 17088%, Cu: 1092%~
Found: N: 8.40%~ S: 19.60%, Zn~ 17i60%7 Cu: Z.10%~
Example 7
145 g (1 mole) of 8-oxyquinoline were added with
stirring to 40 g (1 mole~ of sodium hydroxide dissolved in
1500 ml of methanol and stirred until Gompletely dissolved.
Thereafter the solution was mixed with stirring with 143 9
(1 mole) sodium dimethyl-dithiocarbamate as a 25% aqueous
solution, and then under cooling and at a temperature of
20-25 C added to 178~1 9 (0.9 mole) of crystalline
manganese chloride (MnCl2~ H20) and 17 9 (0.1 mole)
of crystalline copper chloride ~CuCl2.2H20~ in 750 ml o~
methanol. Mixing was continued for,an hour then the
crystalline material separated during standing was filtered
- off, washed with water and dried. 310 9 of brown
crystalline powdery material was obteined which did not
,melt or dissoc,iate up to 300 C.
Yield: 9605% of the theoretical yield of the product,
' 20 a mixture of 8-oxyquinolinate-Mn(II~-dimethyl-dithio-
;' earbamaee and 8-oxyquinolinate-cu(II)-dimethyl-dlthi
carbamate in a molar ratio o~ 9:1. ,
~- Analysis:
' Calculated: N: 8.75%, S: 20.04%, Mn: 15.42%, Cu: 1.99%~
25Found~: N: 8.62%, S: 20.10%, Mn: 15~38%, Cu: 2~05%o
.~ . , ,
- Example 8
' 80 hg of ~-oxyquinolinate-Zn-dimethyl-dithio-
,` carbamatel 20 kg of ~alc and 1 kg of paraffin oil were
,'' mixed in a ball~mill for~an hour and ground. 100 ~ of
3~ product contalning 80% of active substance wera obtain0d~
~ ~5
'.
~ ~ , ., ,. . , - ~,.
. . . ., ~ . .
~4~52~3 :
utilizable for dust dressing with a dose of 200 g/100 kg of
seed.
Example 9
50 kg of 8-oxyquinolinate-Mn-dimethyl dithiocarbamate,
41 kg of 'Tensia N-300' 2 kg of 'Aerosil' 3 kg of 'Totanin
B' , 2 kg of 'Tensiofix LX Spec' and 3 kg of 'Tensopol SP -
USP' were added to a ball-mill and ground for three hours.
100 kg of wettable powder were obtained containing 50~ of
active substance, utilisable as a fungicide, sprayed in water,
for protection against Botrytis cinerea.
Example 10 --
A mixture of 20 kg of 8-oxyquinolinate-Zn-dimethyl-
dithiocarbamate and 8-oxyquinolinate-Mn-dimethyl-dithio-
carbamate was charged into a ball-mill together with 2.5 kg of
'Poliglikol' 1000`, 10 kg of 'Emulsogen' N and 67.5 kg of
'Vaseline' oil and ground for 2.5 hours. 100 kg of an oily
suspension containing 20~ of active ingredient were obtained.
Example 11
A mixture of 45 kg of 8-oxyquinolinate-Mn~dimethyl-
dithiocarbamate and 8-oxyquinolinate-Cu(II)-dimethyl-dithio-
carbamate were charged into a ball-mill together with 10 kg
of 'Emulsogen Ml, 10 kg of ethylene glycol and 35 kg of water
~ .
~ and ground for three hours. 100 kg of an aqueous suspension
^~ was obtained which contained 45% active substance and which
..
could be sprayed when diluted with water.
The materials used in Examples 8 to 11:
a. carriers: 'Tensia N-300'
'Aerosil'
i b. dispersing agents: 'Totanin B' -
.~ .
'Tensiofix LX Spec' `
-26-
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Emulsogen
A ~Poliglikolt 1000
c. wetting agents: ~ rensopol SP-USP~
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- 27
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